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Commission of the European Communities

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Edited by
G.L. FERRERÒ
Κ. MANIATIS
A . BUEKENS
A.V. BRIDGWATER

E1S E VI ER A P P L I ED S C H N E I
PYROLYSIS AND GASIFICATION
Proceedings of an international conference held in Luxembourg, 23-25 May
1989.
PYROLYSIS AND
GASIFICATION

Edited by

G. L. FERRERÒ
Commission of the European Communities, Brussek, Belgium

K. MANIATIS
pert to the Commission of the European Communities, Brussels, Belgium

A. BUEKENS
Vrije Univ ersiteit Brussel, Belgium

Α. V. BRIDGWATER
University of Aston, Birmingham, UK

ELSEVIER APPLIED SCIENCE


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Pyrolysis and gasification.
1. Energy sources: Biomass. Thermochemistry
I. Ferrerò, G. L.
662'.6
ISBN 1-85166-449-1

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PREFACE

Thermochemical processing of renewable resources and solid fuels has become a


strong contender to partially replace the energy dependance of the European
Community on imported hydrocarbon fuels and the Commission is supporting R & D as
well as Demonstration projects In this field. Similarly in the US, Canada and the
Developing Countries numerous projects have been carried out on fundamental as well
as industrial scale projects on Pyrolysis and Gasification. Such technologies are
therefore of increasing importance worldwide, not only because they can provide a
source of energy but also because they can be utilized to dispose off various industrial
wastes in an environmentally acceptable way.

Though interesting results and experiences have certainly been achieved, several
problems still remain and their solution will strongly influence the commercialisation
of Pyrolysis and Gasification all over the world.

It was the need to critically evaluate the progress achieved in this field and to draw
up recommendations for future work which prompted the Directorate General for
Energy of the Commission of the European Communities to organise this International
Conference with the assistance of the Directorate General for Information, Marketing
and Innovation.

While invited speakers from the Commission, EC countries, US, Canada and the World
Bank presented overviews on all aspects of Pyrolysis and Gasification processes such
as Feedstock Pretreatment and Characterisation, Gasification and Pyrolysis
Technologies, Products Upgrading and Utilization as well as Environmental and
Economic aspects, researchers and industrialists from 20 countries presented their
results and views in oral as well as poster presentations. The Workshops and Panel
Discussions gave the opportunity to all participants to express their opinion so that
realistic recommendations for future R & D and Demonstration activities could be
drawn up.

About 200 participants representing Administrations, Governmental Institutions,


Universities and mainly the Industry attended the Conference. This is a fresh proof of
the significance in recent years of Pyrolysis and Gasification technologies.

The Editors express their graditute to all the participants for their contributions as
well as to the Chairmen and Rapporteurs who assisted in making this a successful
Conference and we are confident that the contents of this proceedings will be a
valuable tool and source of information to all those working in the field.

G.L. FERRERÒ Κ. MAN I ATIS Α. BUEKENS A.V.BRIDGWATER


vu
CONTENTS

PREFACE

SESSION I

OPENING SESSION AND COUNTRY OVERVIEWS

ACTIVITIES AND RESULTS OF THE COMMISSION DEMONSTRATION


PROGRAMME IN THE SECTOR OF GASIFICATION AND PYROLYSIS
G.L. FERRERÒ, General Directorate for Energy, Commission
of the European Communities, Brussels, Belgium 3

COMMUNITY R&D STRATEGY IN THE FIELD OF BIOMASS PYROLYSIS


AND GASIFICATION
G. GRASSI, Directorate General for Science Research and
Development, Commission of the European Communities 7

PROGRESS IN PYROLYSIS AND GASIFICATION OF BIOMASS:


AN OVERVIEW OF RESEARCH IN THE UNITED STATES
J. DIEBOLD, D. STEVENS, Solar Energy Research Institute,
Golden, Colorado, USA 14

OVERVIEW OF THERMOCHEMICAL CONVERSION OF BIOMASS IN CANADA


R.D. HAYES, Bioenergy Research and Development Technology
Branch, Energy, Mines and Resources Canada, Ottawa, Canada 28

RAPPORTEUR'S REPORT ON SESSION I


OPENING SESSION AND COUNTRY OVERVIEWS
C H . NELS, Federal Office for the Environment, Berlin 40

SESSION II

PRE-TREATMENT AND CHARACTERIZATION

PRETREATMENT AND CHARACTERIZATION OF FEEDSTOCKS


C.P. MITCHELL, Forestry Department, Aberdeen University,
Aberdeen, UK, A.V. BRIDGWATER, Chemical Engineering
Department, Aston University, Birmingham, UK 43

PROCESSING OF URBAN WASTE TO PROVIDE FEEDSTOCK FOR


FUEL/ENERGY RECOVERY
J.R. BARTON, Warren Spring Laboratory, Department of
Trade and Industry, UK 57

CHARACTERIZATION OF CARBON CONTAINING MATERIALS WITH RESPECT


TO PYROLYSIS AND GASIFICATION
H.J. MÜHLEN, W. WANZL, K.H. VAN HEEK,
Bergbau-Forschung GmbH, Essen, FRG 72
VIU

KTI ACTIVITIES IN THE FIELD OF BIOMASS PYROLYSIS


L. ANTONELLI, Vice President, Director of Alternative Energies
Department, Kinetics Technology International SPA, Rome, Italy 85

BIOMASS FUELS AND GASIFICATION


J. CARRE, L. LACROSSE, Y. SCHENKEL, Center for Agronomical
Researches (CRA), Gembloux, Belgium
F. RURIHOSE, Université Catholique de Louvain (UCL),
Louvain-la-Neuve, Belgium 93

USAGE OF CARBON BLACK AND ACTIVATED CARBON IN RELATION TO INPUT


AND TECHNICAL ASPECTS OF THE PYROLYSIS PROCESS
B. BILITEWSKI, G. H K R D T L E , K. MAREK, Intecus, Associated
Engineers for Environmental Protection Technologies, Berlin 98

RAPPORTEUR'S REPORT ON SESSION II


PRE-TREATMENT AND CHARACTERIZATION
C. ESNOUF, Cemagref, Antony Cedex, France 106

SESSION III

PYROLYSIS, GASIFICATION AND LIQUEFACTION TECHNOLOGIES

BIOMASS GASIFICATION: PAST EXPERIENCES AND FUTURE


PROSPECTS IN DEVELOPING COUNTRIES
M.S. MENDIS, Industry and Energy Department,
The World Bank, Washington DC, USA 111

GASIFICATION AND PYROLYSIS OF BIOMASS IN EUROPE


A.A.CM. BEENACKERS, Department of Chemical Engineering,
University of Groningen, Groningen, The Netherlands
A.V. BRIDGWATER, Chemical Engineering Department,
Aston University, Birmingham, UK 129

A SURVEY OF BIOMASS LIQUEFACTION PROCESSES


R. CAPART, A. ELAMIN, S. AMMAR, M. GELUS,
Department of Chemical Engineering,
University of Technology, Compiègne, France 158

THE GEORGIA TECH ENTRAINED FLOW PYROLYSIS PROCESS


R.J. KOVAC, D.J. O'NEIL, Georgia Institute
of Technology, Atlanta, Georgia, USA 169

PILOT PLANT DEMONSTRATION OF USED TIRES VACUUM PYROLYSIS


C. ROY, Université Laval, Department of Chemical
Engineering, Quebec, Canada
J. UNSWORTH, Petro-Tire Inc., Hamilton, Ontario, Canada 180

FLUIDIZED BED PYROLYSIS OF SEWAGE SLUDGE


U. BELLMANN, A.B. KUMMER, Y. YING, W. KAMINSKY,
Institute for Technical and Macromolecular Chemistry,
University of Hamburg, FRG 190
IX

RAPPORTEUR'S REPORT ON SESSION III


PYROLYSIS GASIFICATION AND LIQUEFACTION TECHNOLOGIES
A.V. BRIDGWATER, Aston University, Birmingham, UK 195

SESSION IV

PYROLYSIS CASE STUDIES

SUGARS FROM CELLULOSICS BY THE WATERLOO FAST PYROLYSIS PROCESS


D.S. SCOTT, J. PISKORZ, D. RADLEIN, S. CZERNIK,
Department of Chemical Engineering, University of Waterloo,
Waterloo, Ontario, Canada 201

PRODUCTION OF BENZOLES AND ACTIVE CARBON FROM WASTE RUBBER AND PLASTIC
MATERIALS BY MEANS OF PYROLYSIS WITH SIMULTANEOUS POST-CRA CKING
R. CYPRES, B. BETTENS, Université Libre de Bruxelles (ULB),
Brussels, Belgium 209

CHEMICALS FROM ALMOND SHELLS BY PYROLYSIS IN FLUIDIZED BED


R. FONT, A. MARCELLA, E. VERDU, J. DEVESA, División de
Ingenieria Química, Universidad de Alicante, Spain 230

BIOMASS PYROLYSIS IN MOLTEN SALTS FOR FUEL PRODUCTION


J.Κ. MAUND, D.M. EARP, Department of Chemical Engineering
and Applied Chemistry, Aston University, Birmingham, UK 238

FLASH PYROLYSIS OF SULCIS COAL


L. CONTI, G. SCANO, Dipartimento di Chimica,
Università' di Sassari, Sassari, Italy 246

RAPPORTEUR'S REPORT ON SESSION IV


PYROLYSIS CASE STUDIES
D.J. O'NEIL, Georgia Institute of Technology,
Atlanta, Georgia, USA 250

SESSION V

GASIFICATION CASE STUDIES

PERFORMANCE OF A PILOT SCALE FLUIDIZED BED GASIFIER


FUELLED BY RICE HUSKS
HARTINIATI, A. SOEMARDJO, M. YOUVIAL,
LSDE-BPP Teknologi, Indonesian Energy Research
Laboratory, Puspiptek - Serpong, Indonesia 257

ELECTRICAL ENERGY FROM BIOMASS'


F. FONZI, Italenergie S.p.a., Sulmona AQ, Italy 264

FLUIDIZED BED GASIFICATION OF WOOD: PERFORMANCE OF A


DEMONSTRATION PLA NT
K. MANIATIS, A. BUEKENS, Department of Chemical
Engineering and Industrial Chemistry, Free University
of Brussels, Belgium
A.V. BRIDGWATER, Department of Chemical Engineering,
Aston University, Birmingham, UK 274
A NATIONAL PROGRAM ON IMPLEMENTATION OF BIOMASS GASIFICATION
PROCESS IN INDONESIA. SCENARIO, PROGRESS AND ECONOMIC EVALUATION
H. SUSANTO, S. REKSOWARDOJO, Department of Chemical
Engineering, ITB, Bandung, Indonesia 282

GASIFICATION AND PYROLYSIS OF STRAW - RESEARCH IN DENMARK


G. OLSEN, P.H. PEDERSEN, O. HENRIKSEN, E. KOFOED,
Laboratory for Energetics, Technical University of
Denmark, Lyngby, Denmark 290

AN INVESTIGATION INTO THE GASIFICATION OF LOW QUALITY


COAL WITH OXYGEN ENRICHED AIR IN A FIXED BED GASIFIER
A.D. ENGELBRECHT, Division of Energy Technology,
CSIR, Pretoria, South Africa 296

PRESSURIZED FLUIDIZED BED GASIFICATION OF PEAT


E. KURKELA, P. STAHLBERG, W. MOJTAHEDI, M. NIEMINEN
Technical Research Centre of Finland, Laboratory of
Fuel Processing Technology, Espoo, Finland 304

RAPPORTEUR'S REPORT ON SESSION V


GASIFICATION CASE STUDIES
K. MANIATIS, Free University of Brussels, Belgium
A.A.CM. BEENACKERS, Groningen University, The Netherlands 312

SESSION VI

UPGRADING, CLEAN OP AND UTILIZATION OF PRODUCTS

GAS PURIFICATION: A REVIEW OF THE AVAILABLE


METHODS OF GAS CLEANING
P. GUIGON, J.F. LARGE, Université de
Technologie de Compiègne, France 317

WHAT CAN WE DO WITH PYROLYSIS OILS?


E. CHURIN, B. DELMON, Université Catholique de Louvain,
Louvain-la-Neuve, Belgium 326

COMPOSITION, PURIFICATION AND USE OF PRODUCER GAS


J. VAN DER WEIDE, J.J. SEPPEN, TNO Road-Vehicles
Research Institute, Delft, The Netherlands 334

RAPPORTEUR'S REPORT ON SESSION VI


UPGRADING, CLEAN UP AND UTILIZATION OF PRODUCTS
J. DIEBOLD, SERI, Colorado, USA 342

SESSION VII

ECONOMIC, ENVIRONMENTAL AND LEGAL ASPECTS

ECONOMIC AND MARKET OPPORTUNITIES FOR BIOMASS DERIVED FUELS


A.V. BRIDGWATER, Energy Research Group, Chemical
Engineering and Applied Chemistry Department,
Aston University, Birmingham, UK 347
XI

ENVIRONMENTAL PROBLEMS IN THE USE OF BIOMASS FUELS


GLOBAL AND LOCAL ASPECTS
P. GIRARD, Centre Technique Forestier Tropical,
Nogent-sur-Marne, France 372

WASTE MANAGEMENT AND PYROLYSIS:


CURRENT SITUATION, TRENDS AND PROSPECTS
C H . NELS, Federal Office for the Environment, Berlin 379

RAPPORTEUR'S REPORT ON SESSION VII


ECONOMIC, ENVIRONMENTAL AND LEGAL ASPECTS
R. FABRY, Commission of the European Communities,
Brussels, Belgium 387

WORKSHOPS

WORKSHOP 1 - PRETREATMENT AND CHARACTERIZATION


Chairman: J. BARTON
Rapporteur: J. PISKORZ 391

WORKSHOP 2 - PYROLYSIS
A.V. BRIDGWATER, Energy Research Group, Chemical
Engineering Department, Aston University, Birmingham, UK
C. ROY, Université Laval, Département de génie chimique,
Quebec, Canada 394

WORKSHOP 3 - GASIFICATION TECHNOLOGY AND ECONOMICS


Y. SOLANTAUSTA, Laboratory of Fuel Processing
Technology, Technical Research Centre of Finland
A.A.CM. BEENACKERS, Department of Chemical Engineering,
University of Groningen, The Netherlands 396

WORKSHOP 4 - PYROLYSIS AND UTILIZATION


E. CHURIN, Université Catholique de Louvain,
Louvain-la-Neuve, Belgium 399

POSTERS PRESENTED

SECTION I

PRE-TREATMENT, PRODUCTS AND OTHER ASPECTS

FULL-SCALE DEMONSTRATION PROJECTS OF THE EUROPEAN COMMUNITY


IN THE FIELD OF PYROLYSIS, GASIFICATION AND CARBONISATION OF
BIOMASS AND WASTE
R. FABRY, G.L. FERRERÒ, Directorate General for Energy,
Commission of the European Communities, Brussels
K. MANIATIS, Free University of Brussels, Belgium 405

THE USE OF WOOD AS FUEL IN MALAYSIA


W.K. HOI, Forest Research Institute of Malaysia,
Kuala Lumpur, Malaysia
A.V. BRIDGWATER, Department of Chemical Engineering,
Aston University, Birmingham, UK 411
XU

SELECTED ASPECTS, EXPLANATIONS AND STATEMENTS IN ACCORDANCE AND


ANALOGY TO THE BIT GRANULATION-TECHNOLOGY
J.M. DISS, F.W. HOCHHEIM, Directorate General and General
Management of the incorporated company B.I.T. SA, Luxembourg 417

THERMOCHEMICAL DENSIFICATION OF BIOMASS


- A KINETIC APPROACH TO PROCESS DEVELOPMENT
D.P. KOULLAS, N.S. ABATZOGLOU, E.G. KOUKIOS,
Department of Chemical Engineering,
National Technical University of Athens, Greece 420

PREPARATION AND USE OF CHARCOAL : WATER SLURRIES


C. ESNOUF, S. GAUDEMARD, Cemagref, Antony Cedex, France,
G. ANTONINI, O. FRANCOIS, Université de Technologie
de Compiegne, Compiegne Cedex, France,
C. MEZERETTE, CTFT, Nogent-sur-Marne, France 425

TREATMENT OF PYROLYSIS OIL WITH COMPRESSED CARBON DIOXIDE


V. BRANDANI, G. DEL RE, G. DI GIACOMO, D. FLAMMINI
University of L'Aquila, Department of Chemistry
Chemical Engineering and Materials., L'Aquila, Italy 430

ACTIVATED CARBON FROM EUCALYPTUS KRAFT LIGNIN


J.J. RODRIGUEZ, T. CORDERO, J. RODRIGUEZ-MIRASOL,
A. SIMON, A. BATALLER, Departments of Chemical
Engineering and Mechanical Engineering, University of
Malaga, Malaga, Spain 435

ACTIVATED CARBONS FROM CHROMIUM-TANNED LEATHER WASTE


M.A. MARTINEZ-SANCHEZ, C. ORGILES-BARCELO, Asociación de
Investigación de las Industrias del Calzado y Conexas,
Alicante, Spain
J.M. MARTIN-MARTINEZ, F. RODRIGUEZ-REINOSO, Departamento
de Química Inorgánica e Ingenieria Química. Universidad
de Alicante, Alicante, Spain 439

MOTOR FUELS FROM PYROLYTIC LIGNINS


J. PISKORZ, P. MAJERSKI, D. RADLEIN, D.S. SCOTT,
Department of Chemical Engineering, University of
Waterloo, Ontario, Canada 444

ROLE OF CHROMIUM OXIDE IN THE TEXTURE OF CARBONS FROM LEATHER


J.M. MARTIN-MARTINEZ, F. RODRIGUEZ-REINOSO, Departamento
de Química Inorgánica e Ingenieria Química, Universidad
de Alicante, Alicante, Spain
M.A. MARTINEZ-SANCHEZ, C. ORGILES-BARCELO, Asociación de
Investigación de las Industrias del Calzado y Conexas,
Alicante, Spain 452

INFLUENCE OF THE POROSITY OF CARBON IN Fe/Carbon CATALYSTS


J.M. MARTIN-MARTINEZ, Departamento de Química
Inorgánica e Ingenieria Química, Universidad de
Alicante, Alicante, Spain
M.A. VANNICE, Department of Chemical Engineering,
The Pennsylvania State University, Pennsylvania, USA 457
XIII

DEVELOPMENT AND CONSTRUCTION OF A SAMPLING LINE FOR WOOD


PYROLYSIS EMISSIONS
J. LACHENAL, J.M. TOLEDO, Laboratoire National d'Essai,
Trappes, France
C. MEZERETTE, A.M. VERGNET, Centre Technique
Forestier Tropical, Département du CIRAD,
Nogent-sur-Marne, France 462

FURNACE FOR BIOFUELS THERMAL UTILIZATION


W. BLASIAK, B. ZETHRAEUS, R. COLLIN, Royal Institute of
Technology, Department of Heat and Furnace Technology,
Stockholm, Sweden
W. GAJEWSKI, J. ZAJDEL, Technical University of
Czestochowa, Institute of Heat Machinery, Poland 468

INVESTIGATION OF TOXIC COMPONENTS IN PRODUCTS FROM MUNICIPAL


WASTE - SEWAGE SLUDGE PYROLYSIS
H. RÖSSLER, U. PRÖSCH, W. KAMINSKY, Institut für
Technische und Makromolekulare Chemie, Universität
Hamburg, Hamburg, FRG 473

RESEARCH ON TAR CRACKING AND APPLICATION OF TAR


G. OLSEN, Laboratory for Energetics, Technical
University of Denmark 479

THE FUEL PROPERTIES OF HYDROCARBON LIQUIDS DERIVED FROM


PYROLYSIS OF WASTE
P.T. WILLIAMS, D.T. TAYLOR, Department of Fuel
and Energy, The University of Leeds, Leeds, UK 486

ENVIRONMENTAL AND PUBLIC HEALTH ASPECTS OF GASIFIER SYSTEMS


J. WILLOCX, Consultant, Londerzeel, Belgium
A BUEKENS, Professor, Vrije Universiteit Brussel,
Brussels, Belgium 492

CHARACTERIZATION OF WOOD CONSTITUENTS BY PYROLYSIS


- FIELD IONIZATION MASS SPECTROMETRY
H.R. SCHULTEN, Fachhochschule Fresenius, Department of
Trace Analysis, Wiesbaden, FRG 497

CHARACTERIZATION OF WOOD BY PYROLYSIS


- FIELD IONIZATION MASS SPECTROMETRY
H.R. SCHULTEN, Fachhochschule Fresenius, Department of
Trace Analysis, Wiesbaden, FRG
J.M. HALKET, Department of Chemical Pathology, Queen
Charlotte's and Chelsea Hospital, London, UK 505

SECTION 2

PYROLYSIS TECHNOLOGY

PYROLYSIS OF HAZARDOUS WASTE OIL


U. STEFFENSEN, J. FRANCK, R. RAHNENFÜHRER, W. KAMINSKY
Institute for Technical and Macromolecular Chemistry,
University of Hamburg, FRG 517
XIV

ENERGAS SEWAGE SLUDGE PYROLYSIS


H.F. HINRICHS, H. MULLER, ENERGAS, Gesellschaft zur
Energiegewinnung aus Müll und Kohle mbH, FRG 522

COGENERATION PYROLYSIS
G. BONINO, Biomass Energies Integrated Systems, Turin, Italy 527

CARBONISATION OF LARGE WOOD PIECES IN A LABORATORY RETORT:


PRODUCT ANALYSIS AND ENERGY A SSSESSMENT
N. SHAH, P. GIRARD, Energie Division, CTFT,
Nogent­sur­Marne, France
R. CAPART, Departement Genie Chimique, UTC,
Compiegne, France 530

MILD PYROLYSIS PROCESS IMPROVES STEAM CYCLE EFFICIENCY


P. GRAVERSEN, R.M. HUMMELSHØJ, Κ. JENSLEV, COWIconsult,
Consulting Engineers and Planners AS, Virum, Denmark 536

FLASH PYROLYSIS OF BIOMASS FOR LIQUID FUELS


S.A. BRIDGE, A.V. BRIDGWATER, Energy Research Group,
Department of Chemical Engineering and Applied
Chemistry, Aston University, Birmingham, UK 541

GASIFICATION OF REFUSE, A PROCESS OF SFW


H. HUMMELSIEP, Η. FUNK, Saarberg­Fernwärme GmbH,
Saarbrücken, FRG 547

A CATALYTIC GASIFICATION PROCESS OF BIOMASS


J. MUNCK, Dansk Termo Industri/I. Krüger AS, Soborg, Denmark 551

AGRICULTURAL WASTES FOR ELECTRICITY GENERA TION


C. ESNOUF, M. HEERAH, Cemagref, Antony Cedex, France 554

PYROLYSIS PROCESS FOR RECYCLING FOREST AND AGRICULTURAL WASTES


FOR RECUPERATING BIOMA SS ENERGY
B. GROUX, R. GUIOL, Ph. POUSAZ, Bio­Alternative, S.A .
Engollon, Switzerland 559

PYROLYSIS OF GREEK LIGNITES


A.A. LAPPAS, I.A. VA SA LOS, Aristotelian University of
Thessaloniki, Thessaloniki, Greece 563

DIRECT MASSS SPECTROMETRIC STUDY OF PYROLYSIS BEHAVIOUR OF BIOMASS


AND ITS CONSTITUENTS UNDER DIFFERENT IONIZATION CONDITIONS.
MS AND MS­MS STUDY OF THE PRIMARY PYROLYSIS MECHANISMS
P.L. DESBENE, M. ESSAYEGH, B. DESMAZIERES, C. LANGE,
J.J. BA SSELIER, Laboratoire de Chimie Organique Structurale,
Université" P. et M. Curie, Paris, France 568

A TWIN BED PYROLYSER­COMBUSTOR FLUID BED SYSTEM FOR THERMAL


PROCESSING OF URBAN WASTE
H. MASSON, Seghers Engineering, Willebroek, Belgium
A. BUEKENS, Κ. MANIATIS, Free University of Brussels, Belgium,
J. SCHOETERS, Groep Τ, Leuven, Belgium 574
XV

PMMA PYROLYSIS FUNDAMENTALS AND EXPERIMENTAL INVESTIGA TION


Α. BUEKENS, F. DE WOLF, Free University of Brussels, Belgium
J. SCHOETERS, KIH Groep Τ, Leuven, Belgium 580

PYROLYSIS OF EXHAUSTED OLIVE HUSKS COUPLED WITH TWO­STAGES


THERMAL DECOMPOSITION OF AQUEOUS OLIVE OIL MILLS EFFLUENTS
G. DI GIACOMO, G. DEL RE, University of L'Aquila, L'Aquila,
Italy, E. BONFITTO, S. IACOBONI, Regione Abruzzo, Avezzano,
Italy, Ν. BRUNETTI, E.Ν.E.Α., Centro Ricerche Casaccia,
Rome, Italy 586

SECTION 3

GASIFICATION TECHNOLOGY

STUDY OF BIOMASS GASIFICATION UNDER PRESSURE


R. CAPART, M. GELUS, N. LESGOURGUES, Z. LI,
Department of Chemical Engineering, University of
Technology, Compiegne Cedex, France 593

GASIFICATION OF CHARCOAL IN MALAYSIA


W.K. HOI, Forest Research Institute of Malaysia,
Kuala Lumpur, Malaysia
A.V. BRIDGWATER, Department of Chemical Engineering,
Aston University, Birmingham, UK 598

UPDRAFT GASIFICATION OF WASTE FUELS


P. STÂHLBERG, E. KURKELA, VTT, Laboratory of Fuel
Processing Technology, Espoo, Finland
H. FILEN, Κ. SALO, Bioneer Oy, Hämeenlinna, Finland 603

PEAT ΑΜΟΝΙΑ PLANT IN OULU ­ SYNTHESIS GAS PRODUCTION FROM


PEAT BY FLUID­BED GASIFICATION
K. SIPILÄ, C. WILÈN, E. KURKELA, A. MOILANEN, VTT
Laboratory of Fuel Processing Technology, Espoo, Finland
J. KOLJONEN, Kemira Oy, Oulu, Finland 608

DEVELOPMENT OF A DOWNDRAFT MOVING BED BIOMASS GASIFIER


R. BILBAO, J. LANA, P. GARCIA, J. ARAUZO,
Department of Chemical Engineering, University of
Zaragoza, Zaragoza, Spain 613

STEAM GASIFICATION OF BIOMASS IN FLUIDIZED BED.


EFFECT OF THE TYPE OF FEEDSTOCK
J. CORELLA, J. HERGUIDO, J. GONZALEZ­SAIZ, Chemical
Engineering Department (Faculty of Science),
University of Zaragoza, Zaragoza, Spain 618

STEAM GASIFICATION OF BIOMASS IN FLUIDIZED BED WITH A


SECONDARY CATALYTIC REACTOR ­ I. RESULTS WITH THE
SECONDARY REACTOR EMPTY AND WITH SAND
J. CORELLA, M.P. AZNAR, Ν. CEBRIAN, J.I. IGLESIAS,
M.P. MARTINEZ, Chemical Engineering Department,
University of Zaragoza, Zaragoza, Spain 624
XVI

STEAM GASIFICATION OF BIOMASS IN FLUIDIZED BED WITH A


SECONDARY CATALYTIC BED. - II. TAR CRACKING WITH DOLOMITE(S)
IN THE SECONDARY REACTOR
M.P. AZNAR, J. DELGADO, J. CORELLA, J. LAHOZ,
Chemical Engineering Department, University of
Zaragoza, Zaragoza, Spain 629

FIXED BED GASIFICATION OF LIGNOCELLULOSIC BIOMASS


THE CEMAGREF PROCESS
S. GAUDEMARD, J.J. BECKER, Cemagref, Antony Cedex, France 635

STUDY ON MARKED PRODUCTS OF WOOD GASIFICATION MECHANISMS


WITH THE AIM OF PRODUCING CLEAN GASES
S. CASTILLO, S. BENNINI, G. GAS, J.P. TRAVERSE,
Université Paul Sabatier, Toulouse, France 640

REDUCTION ZONE HEIGHT DETERMINATION IN SOLID WASTE


GASIFICATION PROCESS IN A SHAFT FURNACE
J. WANDRASZ, K. WALECZEK, The Silesian
Technical University, Poland 646

COMPUTER MODELLING OF FLUIDIZED BED GASIFICATION


J.M. DOUBLE, E.L. SMITH, A.V. BRIDGWATER,
Energy Research Group, Department of Chemical
Engineering and Applied Chemistry, Aston
University, Birmingham, UK 651

THREE-PHASE WOOD GASIFIER SYSTEM EASIMODR


H. MICHEL-KIM, Efeu GmbH, Research and
Development for Energy and Environment, Schwelm, FRG 656

LIST OF PARTICIPANTS 661

INDEX OF AUTHORS 677


SESSION I

OPENING SESSION AND COUNTRY OVERVIEWS


ACTIVITIES AND RESULTS OF THE
COMMISSION DEMONSTRATION PROGRAMME IN THE SECTOR OF
GASIFICATION AND PYROLYSIS

G.L. FERRERÒ
General Directorate for Energy
Coma I ss Ion of the European Communities
200 rue de la Lol
Β ­ 1049 Brussels ­ Belgium

Summary

The demonstration programme In the "Blomass and energy from waste" sector
Is outlined In general, with particular reference to the subject of
"Pyrolysls and Gasification".

Comments are made on certain results obtained In the Member States and
general trends can be concluded.

The results of finished projects and of measures still In progress


Indicate that these technologies, especially pyrolysls, will develop In
Mediterranean countries where the conditions of blomass supply lend
themselves better to conversion of the blomass In the form of stockable
fuels.

The Energy Demonstration Programme Introduced In 1978 by the Directorate­


General for Energy of the Commission of the European Communities provides
financial support for demonstration projects of an Innovatory nature and
Industrial scale in respect of energy saving, renewable energy sources
and substitutes for hydrocarbons.

Demonstrations projects are defined as any project which on a real scale


amounts to the application of an Innovative technology or a new
application of a proven technology and helps to establish the technical
and economic feasibility of a process before advancing to commercial
exploitât Ion.

These projects form the link between the research and development phase
upstream, possibly backed by a pilot project, and the commercial
exploitation phase downstream.

Since 1978 an Invitation to submit proposals for demonstration projects


has been published each year In the Official Journal of the European
Communities, and each year a certain number of projects considered to be
of considerable technological and economic Interest are provided with
finance by the Commission to cover part of the technical and economic
risks Inherent In the project.
From 1978 to 1988 (Table 1) some 1631 projects have been selected from
the huge number put forward In response to the annual Invitation to
submit proposals Issued by the Commission and financial support totalling
841 Mio ECU (1 007 Mio $) has been awarded. This Community programme,
which Is the largest In the world, Is accompanied by national programmes
In the Member States of the European Community.

T A B L E

DEMONSTRATION PROJECTS 1978-1988

Total proposals S 176

Total accepted projects 1 631

CEC support 841 Mio ECU - 1 007 Mio $

Under the Βiomass and Energy from Waste Sector of this Programme some 191
projects (Table 2) have been awarded support totalling 87,4 Mio ECU
(101,6 Mio $ ) .

TAB L E

BIOMASS AND ENERGY FROM WASTE

Total accepted projects 191

CEC support 87,4 Mio ECU - 101,6 Mio $

Total cost of projects 311 Mio ECU - 361,8 Mio $

Some of these projects will be described to you In the course of the


Seminar's technical sessions. The projects which have been selected can
be divided Into 11 sub-sectors shown In Table 3. For the most part they
fall Into one of the two main catagorles, "biological conversion" and
"thermochemlcal conversion" of blomass and waste.
T A B L E

BIOMASS ANO ENERGY FROM WASTE

SUBSECTORS PROJECTS

01. Biomass Harvesting 4


02. Energy crops 3
03. Treatment of waste 18
04. Biogas 70
05. Refuse Derived Fuel 14
06. Direct combustion 40
07. Gasification and Pyrolysls 24
08. Compost 7
09. Fuels and chemicals (biol. treat.) 1
10. Fuels and chemicals (thermo-chem. treat.) 9
11. Proteins 1_
Total 191

Some 90X of biological conversion projects selected, 66 out of 70


projects, concern the production and use of biogas from animal litter,
urban waste or effluent from the agro-food Industry. This Is a major sub-
sector of the programme.

Some 50X of the 87 thermochemlcal conversion projects selected are


concerned with direct combustion, 27% with gasification and
carbonization, and 16% with the production and use of refuse-derived
fuels (RDF).

In each sub-sector the projects In progress or completed are designed to


establish the technical feasibility of new concepts and to evaluate the
economic profitability of the projects, and In each of these sub-sectors
projects successfully completed have or will give rise to multiplication,
with considerable impact In terms of energy and the environment.

Treatment by gasification and pyrolysls of solid urban waste still seems


to present certain problems whereas the pyrolysls and gasification of
wood seems set for reasonable success.

In the short term It seems unlikely that these technologies are destined
for extensive application, and there is clearly a need for demonstration
measures before maximum use of their Interesting potential can be
achieved.

The results obtained so far In the demonstration programme, although in


no great quantity, nonetheless allow certain basic observations to be
made on the technologies of gasification and pyrolysls.

The first point to be made is the growing interest In pyrolysls in most


southern European countries, with Italy to the fore due to the numerous
R&D activities tied up with the Leben-Abruzzo project.
In Germany various gasification of wood and wood waste techniques have
had success although marketing of these facilities has not always had
equally positive results.

In France some experiments Into the pyrolysls of solid urban waste have
encountered technical and economic problems whereas wood gasification and
torefactlon projects have demonstrated the reliability of these
techniques.

In Belgium, finally, certain ongoing experiments have had problems due


mainly, as In other countries elsewhere, to the low cost of oil.

For other Community countries too few data are available for any
conclusions to be drawn.

The feeling remains, however, that the technologies of gasification and,


to a greater degree, pyrolysls are becoming particularly attractive, and
the possibilities opened In future by the release of cultivated land for
non-food uses may Increase to some extent the use of these processes.

However, there Is still the problem of their profitability.

Studies currently In progress and environmental requirements, which are


still difficult to quantify, should provide a better Idea of the
economics of these technologies, taking Into account not only the energy
value of the products to be treated but also the far more general Impact
that the use of blomass for energy purposes can generate.

The demonstration project of the Commission's Directorate-General for


Energy will draw to an end In 1989. An Invitation to submit proposals has
been published recently in the Official Journal, and projects on the
pyrolysls and gasification of biomass and waste in general may still be
submitted and accepted. However, regardless of the results of projects
still to come. It can already be said that this sector of the
demonstration programme has made a solid contribution to the spread of
the technologies of gasification and pyrolysls. The projects In process
and the results obtained, even though negative In some cases, have shown
the way and pinpointed the problems on which greater effort should be
concentrated.

We are now starting to reap the benefits of this vast programme, which,
complementing measures taken at national level In the individual Member
States, has led to technological maturity and process reliability in
every respect.

The Directorate-General for Energy is proud to have contributed, and to


continue to do so, to solving the common problem, which is not
exclusively an energy one, of Increasingly efficient use of blomass and
waste In an overall context reflecting nature protection, the use of
local resources and the conservation of Jobs.

This conference will be different from many others being held elsewhere
on this subject through Its mainly demonstration nature of the results
obtained and the guidelines that should emerge for future action In
Commission programmes.
COMMUNITY RSD STRATEGY IN THE FIELD OF BIOMASS PYROLYSIS
AND GASIFICATION

G. GRASSI
Directorate General for Science Research and Development,
Commission of the European Communities

1. INTRODUCTION

The immense stock of chemical energy, represented by vegetal matter


(biomass) , constantly produced on the earth will play the role of a
strategic and the only renewable industrial energy resource in the long term
future. Its exploitation on a large scale will offer supplementary important
benefits such as rural development, environmental land and atmosphere
improvement, better climatic stability etc.
The biomass potential in the European Community is estimated at around
600 million ton/year (dry matter) and its likely utilisation is as follows:

Energy utilisation 300 million ton/year


Industrial utilisation 80 million ton/year
Chemicals and organic fertilisers 220 million ton/year

So, the energy sector should get the largest share of the resource. Of
course, the development and speed of penetration of the bio-energy sector
will depend largely on the future supply cost of biomass (30/60 ECU/ton (dm)
actually in Europe); on the cost of the conversion technology; and (mainly)
on the cost of imported oil.
Among the several conversion technologies so far developed in the
Community (direct combustion, air gasification, advanced gasification,
pyrolysis, liquefaction, catalytic conversion, bio-gasification) pyrolysis
today appears very promising and best suited to the implementation of large
biomass schemes like the LEBEN - Industrial projects. In fact pyrolysis or
synthetic-oil can be competitive on a relatively small scale of production.
This may also allow for large-scale biomass exploitation, the adoption of
modular conversion units with capacity in the range of 2:10 ton/hr, to match
in the most convenient way, the more or less productive and/or dispersed
resource available.

2. BIOMASS CONVERSION INTO FUELS

The energy content (fixed carbon) of biomass can be exploited by


direct combustion or after conversion (and eventual upgrading) into a more
valuable fuel by physical, biological or thermochemical processes. My
presentation today will be limited to these last conversion methods ; in
particular to the state-of-the-art and the future development of pyrolysis
and gasification technologies.
In Table 1, Table 2 and Figure 1 a summary of the main characteristics
of thermochemical conversion processes and products is presented (Ref:
A. Bridgwater, Aston University - workshop on LEBEN-PROJECTS/ Feb. 1989,
Brussels).
TABLE 1. Thermochemical Conversion Technologies and Products

Technology Primary Product A pplication

Pyrolysis generally gas fuel gas


liquid oil or liquid fuel substitution
solid char solid fuel or slurry fuel

Flash pyrolysis liquid mostly oil or liquid fuel substitution

Slow pyrolysis solid char mostly solid fuel or slurry fuel

Liquefaction liquid oil or liquid fuel substitution

Gasification gas fuel gas

Combustion heat heating

TABLE 2. Secondary Products and Sources

Secondary Product Source Process

Oxygenate Fuels
Methanol Gasification Synthesis
Fuel alcohol Gasification Synthesis

Hydrocarboη Fuels
Gasoline Pyrolysis Hydrotreating
Pyrolysis Zeolites
Liquefaction Hydrotreating
Gasification via methanol MTG

Diesel Pyrolysis Hydrotreating


Pyrolysis Zeolite + MOGD
Liquefaction Hydrotreating
Gasification via methanol MCGD

Fuel oil Pyrolysis Stabilisation


Liquefaction Stabilisation

Power
Power Pyrolysis Turbine
Gasification Engine or turbine

Chemicals
Ammonia Gasification Synthesis
Speciality chemicals Pyrolysis Extraction and/or Conversion
Liquefaction Extraction and/or Conversion
• • • / • / , / • • •
CONVERSION I . V . PRIMARY A ' ;i PROCESSING Χ \ \ \ Ύ Ε Ο Ο Ν DAR Y V S \ \ ' .
: TECHNOLOGY s '/,- PRODUCTS . V I TECHNOLOGY -/// \ \ \ ν \ \
PRODUCTS '.-'/Α-';
• • • / • / • / / • •
\ f/t \/•/ \•.S\•/ \•f \f/ \\ .. Ν Λ Ν Χ \ */ \ /S\SS\ t/ '
V• S Ν Χ Κ Κ \
S Ν• • • • /
\ \ S \ \ S
MOONQ Slurry fuel

LIQUEFACTION

Fig. 1. Primary and secondary products from thermochemical


biomass processing

Primary Products

The primary products can be gas, liquid and/or solid char, depending
on the conversion technology employed. Most of the present interest centres
on liquid products due to their high energy density and potential for
premium liquid fuel substitution.
As far as biomass conversion is concerned, I would like to recall here
that:

(a) the basic strategic considerations for the present and future R&D
programmes of the Commission suggest the production of two types of liquid
"biofuels":
Bio-ethanol from sugar or starch (by advanced technologies and new
crops) for the transportation market and which should develop at a
significant rate after the year 2000 (presently given low emphasis by
the Commission) ;
- Synthetic-oil (pyrolytic-oil) from lignocellulosic material for
general thermal application, as a real substitute for the extensive
oil import market, which could be conveniently produced (technically
and economically) in the medium term (five years).

All other types of biomass fuels can, of course, be regarded as being


of interest and deserve consideration, but only as a tactical means to solve
local and time limited problems, or due to the particular characteristics of
residues (i.e. municipal wastes, manure, sludges, etc.).
10

(b) In the EC the potential displacement by these two types of fuels is very
large and it has been estimated at:

2.2 million barrels OE/day for Europe (about 24% of total oil
imports).

(c) Biofuels should then be considered an important element in the


Community's energy mix, whether viewed from the security perspective
(domestic renewable feedstock), socio-economic impact (source of
competitive, intensive manpower activity), rural development contribution,
market dimensions (not saturable demand), environmental improvement (new
uses for agricultural and marginal land, no sulphur, CO2, better climatic
conditions etc.) or technological (industrial) competitiveness.

International collaboration could speed up the progress of pyrolytic


biomass conversion technologies for the following reasons :

(a) Within the framework of the general EC-Canada Agreement, DG XII has
proposed a collaborative programme on "pyrolysis and up-grading of pyrolytic
fuels". Furthermore, an international industrial consortium has been
constituted for the implementation of the first "fast pyrolysis pilot plant"
in Spain, the construction being foreseen at the end of 1989. This
technology should be able to convert lignocellulosic biomass into 60% oil +
10% charcoal + gas (energy efficiency > 80%).

(b) DG XII is joining efforts with DG XVII and DG I for a collaboration with
Brazil and other countries in the bio-energy sector.

(c) In parallel, transfer of technologies to and from Europe is now under


consideration and specific negotiation has already been carried out.

Importance of Regional Biomass Schemes

Biomass is a diluted dispersed resource, therefore there is a need to


implement large projects, probably on a regional scale, to appreciate the
importance and full value of these benefits.
There is general consensus that large-scale exploitation of biomass by
multi-sectorial, innovative and integrated technologies will constitute a
real instrument of rural development.
The involvement of regional/national authorities then becomes
essential, as a guarantee for large investments as well as their ability to
ensure the continuity of supply, the control of the cost of biomass
resources in the long term, and to facilitate the market development of this
renewable natural resource.
At present, several regions in Europe are considering the possibility
of implementing major activities in the sector of biomass and of synthetic
oil (pyrolytic fuel) production, as well as other kinds of conversion for
energy and industry.
For these types of project, multi-sectoral integration of large market
industrial activities with the bio-energy sector makes them more attractive
and profitable in terms of economics.

Pyrolysis

Pyrolytic fuel (synthetic oil) has a strategic value because, as a


liquid, its handling, storage, transportation and utilisation are similar to
that of bunker-oil; its heating power is fair (above 6 000 kcal/kg) and its
11

specific gravity higher (1.2 gr/cm) . As it can be used immediately in the


existing utilisation systems, this does not require expensive actions for
market promotion and it can be considered as a fuel for general thermal
applications (steam and electricity production).
Preliminary research results show the possibility of modern bio-energy
technologies reaching promising markets which are:

general thermal applications (heat-steam production);


thermal power stations for electricity production ;
gas-turbine/steam-turbine electricity plant (combined cycles);
conventional refineries.

Through this technology, the penetration and exploitation of biomass


for energy production could be accelerated and implemented on a very large
scale, by the adoption of modular standardised plants for synthetic liquid
fuel production. Furthermore, such a conversion product could also be
utilised at a later stage as a raw material for chemicals.
Another activity, inspired by the Commission and already considered of
interest by important industrial groups (Mannesmann, VEBA, etc.), is the
development of mobile pyrolysis plants, mounted on tracks. These plants are
aimed at the production of pyrolytic fuels from biomass harvested by small-
holders. This could also allow the creation of service companies, which
could contribute to a rapid expansion of this activity.
Concerning the state-of-the-art and the progress of pyrolysis
technology, we can confirm that:

This old technology disappeared by and large during the last 40 years.
Up to now only a low level of activity in Europe (seven years).

However, the general situation in Europe is now improving solely as a


consequence of the RSD programme initiated and managed by DG XII of the
Commission. Several experimental activities have been carried out over the
past seven years or are now under implementation in several countries (F, I,
FRG, B, E, GR) . Large industrial organisations (mainly German, i.e.
Mannesmann, Preussag, VEBA, Bayer) are interested.
In some cases European industry has offered a full guarantee of this
technology. As a consequence, it was possible to perform on a realistic
basis an initial techno-economic evaluation for the bio-energy sector of the
LEBEN-Projects (see Figure 2 ) .
It is important to note that advanced pyrolysis technologies also
exist outside Europe and in particular in Canada and the USA. These,
however, are only at a laboratory stage. European advanced commercial
technology can be made available in five to ten years through a continuous
R&D effort focussed on conversion efficiency, quality of products and
reduction of specific investment.
The forecast on conversion investment costs evolution, is as follows:

at present: 7 US$/barrel OE
in 1993: 4 US$/barrel OE
around 2000: 2 US$/barrel OE

For comparison, specific investment costs for oil exploration (1987)

North Sea: 8-10 Ş/barrel


Middle East: 2 Ş/barrel
5o $/BARREL OF OIL EQUIVALENT
- $5 (Social and
salaries)
- $1.8 (Exchange)

III

+ $ 8 / b a r r e l for
dssulphurisation to

ECU/t (dm)

F i g . 2.
13

An interesting development concerns pyrolytic oil upgrading, through


the adoption of ZSM-5zeolite conversion directly on pyrolysis vapours. A 20%
yield of gasoline on wood looks feasible. Assuming a cost for biomass of
35 ECU/t, the gasoline could be produced at a cost of around 175 ECU/t
(actual market price: 150 ECU/t), if the phenolic fraction was to be
recovered (to obtain phenolic raw material for phenolformaldehyde type of
resin) and sold at 335 ECU/t (actual cost 670 ECU/t).
Small capacity decentralised gasoline production plants could result
from such activity and would be of great interest especially for remote
areas in developing countries.

CONCLUSIONS

Biomass for energy has great potential in the Community (around


300 Mt/year); thus biofuel production should be seriously considered a
significant element in the Community's energy mix.
Large-scale exploitation of biomass presents the following benefits :

(1) potential energy contribution: around 1 0 % of primary energy needs;


(2) contribution to industrial needs: possibility of covering 100% of the
EC deficit, around the year 2000;
(3) social impact: 600 000 new jobs in the Community for the bio-energy
sector alone;
(4) large exploitation of biomass could constitute an important instrument
for rural development
(5) improvement of environment and quality of life;
(6) stimulation of industrial competitiveness in this new sector of
activity;

Multi-sectoral integration of large market activities improves the


economic results of a comprehensive massive exploitation of biomass.
Integrated projects on a regional level appear to be the correct
dimension for an optimal exploitation of biomass.
As far as the bio-energy by-sector is concerned, the production of
synthetic liquid fuels (pyrolysis), as a substitute for oil, for refineries
and for general thermal application (heat and electricity production) looks
very promising and better suited in the short and medium term in the frame
of agro-energy-industrial projects (LEBEN).
By means of integration of markets, progress of technology and
development of crops, production of this type of synthetic fuel will, in a
relatively short term, become competitive in southern Europe and in five to
ten years also in northern Europe.
14

PROGRESS IN PYROLYSIS AND GASIFICATION OF BIOHASS:


AN OVERVIEW OF RESEARCH IN THE UNITED STATES

J. DIEBOLD and D. STEVENS


Solar Energy Research Institute
Golden, CO 80401

Summary

The United States Department of Energy (U.S. DOE) is conducting


research to produce liquid transportation fuels from biomass and
municipal waste. Research in the thermochemical conversion area
includes production of both methanol and gasoline. Methanol is
produced by gasifying the biomass feedstock to produce a medium-
energy synthesis gas, which then can be cleaned, conditioned, and
catalytically converted to methanol. Gasoline is produced by first
generating biocrude oils through high or low pressure pyrolytic
processes. Catalytic upgrading of the intermediate, biocrude oil
product yields hydrocarbon products, which can be used directly
as gasoline or as octane enhancers depending upon the catalytic
process employed. A summary of the thermochemical program within
the U.S. DOE is presented.

1. INTRODUCTION
Until the discovery of large quantities of low cost petroleum and
natural gas in the early 1900's, wood supplied a significant proportion
of the energy requirements for heat and power. Combustion of wood in
various sized boilers produced steam to heat buildings, power industrial
machinery, and even power transportation vehicles such as ships, trains,
and farm machinery.
Today, it is estimated that biomass provides about 3 quadrillion
BTU's of energy per year in the United States. This corresponds with
about 4% of the annual U.S. energy demand. This energy comes primarily
from the combustion of wood and other forms of biomass to provide steam
and process heat. This contribution is very significant in relation to
other energy resources. Nuclear energy generation, for example, provides
about 4 to 5 % of the nation's energy supply. With proper resource
management and the development of efficient conversion processes, it has
been estimated that biomass resources can provide an even greater
fraction of this nation's energy supply. (1)
Liquid fuels derived from biomass are expected to contribute
significantly to this energy potential. As an abundant, renewable,
domestic energy resource, biomass can help the United States reduce its
dependence on imported oil. Biomass is the only renewable energy source
capable of supplying liquid transportation fuels. Thermochemical
conversion processes offer efficient methods for converting biomass to
liquid hydrocarbon fuels through a variety of processes. At present,
thermochemical research sponsored by the U.S. DOE is focussed on the
production of methanol or gasoline. Thermal conversion processes are
well suited to the conversion of wood and crop residues, which account
15

for the vast majority of the biomass resources in the United States.
These processes can convert all of the organic materials in the
feedstocks to liquid fuel products, with water and carbon dioxide as
byproducts. In addition, the thermochemical processes and their products
are relatively insensitive to variations in the feedstock.
Harvested biomass is typically a solid material having a low energy
density, as well as a tendency to biodegrade during storage. With the
advent of petroleum fuels, society has become very dependent upon fuels
which can be conveniently stored in a form having a very high energy
density and which can be transported and metered into a combustor as a
fluid. For example, the energy contained in a volume of aromatic
gasoline is equivalent to that in 4 volumes of solid softwood or 8
volumes of sawdust. Relative to coal, biomass is extremely easy to
liquefy or gasify due to its high reactivity. This characteristic makes
biomass a prime candidate for the production of liquids or synthesis
gases, which may be upgraded to transportation fuels. The diversity of
biomass suggests that fairly small conversion plants would be very
desirable, which can be quickly developed and constructed. Thus, the
conversion of biomass to liquid transportation fuels would favorably
impact local economies by the creation of employment opportunities in
rural areas.
Although the extent of the world's petroleum resources have been
traditionally underestimated, it is generally agreed that petroleum is
a finite resource and the only real question is when, not if, will
alternate sources of liquid transportation fuels be needed. However,
most of the world is dependent upon oil fields which are remote from the
consumer and upon long shipping routes and/or pipelines which will prove
to be very difficult to protect. Consequently, the next oil shortage
will most likely be caused by political decisions or by accidents, rather
than to depletion of the world's petroleum resources. Biomass resources
provide a secure fuel source, which is immune to these types of
disruptions.
Biomass also provides a method to help ameliorate carbon dioxide
emissions to the atmosphere. Recent concerns about the rising levels of
carbon dioxide in the atmosphere, implicate the widespread combustion of
fossil fuels. Since the use of biomass as a fuel involves the recycling
of atmospheric carbon rather than the conversion of fossilized carbon to
atmospheric carbon, future methods to reduce carbon dioxide emissions
should include the increased use of biomass as a source of fuel. This
implies the need for the development of technology related to the
conversion of biomass to more conventional forms of fuel.
The U.S. Department of Energy is sponsoring research on the
production of fuels through its Biomass and Municipal Waste Technology
Division. This research includes the development of energy crops and
their conversion to fuels using biological or thermochemical processes.
The biological processes typically produce plant oils, methane, or
ethanol. The thermochemical processes produce: a) methanol from
synthesis gases having a medium energy content; or b) biocrude liquids
for subsequent refining to a hydrocarbon gasoline, via catalytic cracking
or hydrogénation. The potential impact of this research would be a
seven-fold increase in the contribution of biomass to the energy consumed
in the United States from the current level of about 3% to a little over
20%. (1) For this large a contribution to the energy supply, successful
research must be completed in biomass production, as well as in the
conversion processes. Actual deployment of the several thousand biomass
16

refineries would require a major industrial investment, which will not


take place until the economics are made more feasible through research.
This paper is an overview of research and development sponsored by
the U.S. DOE in the technology area of the pyrolysis and gasification of
biomass and municipal-refuse-derived fuel (RDF). This research includes
the upgrading of these intermediate liquids an/or gases to methanol or
gasoline. The reader is referred to the proceedings of four recent major
symposia (1-4) for additional detail in specific areas discussed in this
paper.

2. CONVERSION OF BIOMASS TO METHANOL


The conversion of biomass to methanol first involves the
gasification of the biomass to a gas which is primarily composed of
hydrogen and carbon monoxide, with very little inert gases such as
nitrogen or methane, and virtually no sulfur compounds nor tars. Once
these synthesis gases have been generated in the proper proportions, the
technology to convert them to methanol is commercially available.
Therefore, the development of the conversion of syngases to methanol has
been left to industry. The gasification of biomass to produce a clean
synthesis fuel gas has been studied extensively over the last eight years
with the successful development of four process development units (PDU's)
involving quite different reactor designs. Two of these used partial
combustion with oxygen to directly supply the heat needed for
gasification including: a downdraft fixed bed (SERI/Syngas) and a single
fluidized bed (IGT). The other two used heat which was transferred
indirectly to the gasification zone from separate combustion processes,
including: a dual-fluidized bed (Battelle-Columbus) and a single
fluidized bed (University of Missouri-Rolla). To better understand
pyrolysis and gasification, DOE is continuing research into the
mechanisms involved and the catalytic removal of residual tars. DOE is
completing limited work on gasification development.

Gasification research Research into the actual mechanisms involved


during the gasification of biomass and pelletized RDF is being carried
out at SERI and also at the University of Washington. This research will
be valuable to the design and operation of fixed-bed or slow-moving-bed
gasifiers. In the SERI research, a single cylindrical particle of
biomass or pelleted RDF is instrumented and placed in a preheated
reactor, which is swept by a flow of a mixture of nitrogen and oxygen.
The pellet is heated from all sides. The temperatures of the surface and
the center of the particle, the weight, and the energy flux are all
measured in real time during the pyrolysis and/or flaming combustion of
the single particle. A very thin, visually transparent coating of gold
on the glass reactor wall acts as an infrared radiation shield to reduce
heat losses to a low level, while allowing the pellet decomposition to
be visually observed and photographed. Empirical equations have been
derived which predict the time of pyrolysis (or flaming combustion), the
heat required for pyrolysis, and the ash content as a function of
temperature, initial moisture content, oxygen in the carrier gas, and
relative amounts of plastics, metals, and newspaper in RDF pellets. A
mathematical model based on scientific principles was shown to predict
the temperatures and weight loss of the pellet quite well. (5-7)
In complimentary research at the University of Washington, a single
pellet of biomass or RDF is radiantly heated from only one surface to
result in a one-dimensional heat flux. The surface and several internal
temperatures of the pellet are monitored during the test, and the
17

pyrolysïs products collected. Empirical equations have been derived


showing the interactions of the process variables for both softwood
pellets of varying density and for RDF pellets. Mathematical models,
based on scientific principles, are in progress involving heat transfer
considerations and global chemical kinetics. (8,9)

Gasification development U.S. DOE is completing research on one of


the promising pyrolysis reactor designs, a fluidized bed. A major
technical area, which has been addressed with the past gasification
research is how to transfer the necessary heat into the bed that is
required to pyrolyze the biomass. In addition to oxygen-blown gasifiers,
DOE has examined indirect methods of providing heat. Indirect heating of
the fluidized bed through heat-exchange surfaces immersed in the bed has
the potential of operational simplicity and possibly a smaller reactor
size.
Research into the heat transfer between heat-exchange tubes immersed
in a fluidized-bed gasifier at the University of Missouri-Rolla showed
that the factor limiting the heat transfer to the bed was the heat
transfer between the inside of the tube and the hot combustion gases.
Recent research by MTCI, Inc. has been directed toward the improvement
of this limiting heat transfer. Rather than merely increasing the hot
gas velocities to increase the heat transfer rates (which requires more
input of mechanical energy to the blower on the combustor) , MTCI
replaced the conventional pressurized combustor with a pulsed combustor.
The pulsed combustor concept is over 50 years old, but some of the
benefits are only now being realized. The pulsed combustor consists of
a combustion chamber fitted with a long exhaust pipe which is sized to
produce a resonating, traveling pressure wave. Valves open when the
combustor pressure is low to allow a fresh charge of fuel and air to
enter without the need for a mechanical blower. In the MTCI design, the
mechanical valves are replaced by aerodynamically sized inlet and outlet
ports. In the resonance tube, the combustion gases experience very high
velocities because the forward and backward velocities of the resonating
gases are superimposed upon the net gas velocity. This resonating gas
flow resulted in an increase in transfer of heat to a fluidized-bed
gasifier by a multiple of between four and five times greater. Data in
the literature suggest that an order of magnitude increase in heat
transfer over that attained with conventional turbulent flow can be
attained through the use of resonating gaseous heat transfer. (10) With
the use of calcium carbonate as the fluidized-bed material, relatively
high hydrogen and low tar yields were obtained, apparently due to
catalytic effects of the calcium. With funding from the Office of
Industrial Programs in DOE, this system has also been used to gasify
black liquor from the Kraft pulping process in steam. This resulted in
gases containing very high levels of hydrogen and carbon dioxide and low
levels of tars and carbon monoxide, apparently due to catalytic effects
of the sodium present in the black liquor and in the sodium carbonate bed
material. (11)
Catalytic reduction of tars in gasification The use of synthesis
gases in conventional methanol synthesis systems requires that the levels
of pyrolytic tars be very low. Research at the Pacific Northwest
Laboratory (PNL) has investigated the use of catalysts to reduce tars.
A primary fluidized gasifier was operated, followed by a secondary
fluidized bed in which the catalysts were placed. The catalysts appear
to function by reacting with the tars to form coke and then to promote
the oxidation of that coke to form gases. Inputs to this secondary bed
18

were steam-gasification vapor products and enough air to prevent catalyst


deactivation by oxidizing the coke deposits as they formed. The
oxidation very specifically gasified the coke on the catalysts to result
in greatly increased the gas yields. Even with 0.4 g of air added to the
secondary reactor per g of wood feed, the nitrogen composition in the
gaseous products did not change significantly from the original value in
the dirty gases. The remaining hydrocarbons in the gases were primarily
volatile aromatic compounds, which were not be expected to be troublesome
for most applications. (12) Using the MB/MS, SERI will soon be
initiating a study to screen different catalysts for the reduction of
residual pyrolytic tars.

3. CONVERSION OF BIOMASS TO GASOLINE


The U.S. DOE is also sponsoring research to convert biomass to
gasoline hydrocarbons. This research is focussed on first converting the
biomass to a biocrude oil or vapor and then upgrading the intermediate
to gasoline. Gasoline is completely compatible with the existing
distribution and vehicle systems; it naturally produces low aldehyde
emissions; and it has a greater energy content. With the modern
computer-controlled automobile engines coupled with catalytic mufflers,
hydrocarbon gasolines would be expected to produce very low levels of
pollution in the form of carbon monoxide, aldehydes, and unburned
hydrocarbons.
These considerations have led to the development of processes to
convert biomass to gasoline. Three process routes have been investigated
to make gasoline intermediates from biomass: a) liquefaction in a
pressurized solvent to produce a biocrude oil having a low oxygen
content; b) liquefaction of biomass at low pressures with slow pyrolysis;
and c) fast pyrolysis of biomass at low pressure to form a biocrude oil
having a high oxygen content. Two upgrading processes have been
investigated: a) catalytic deoxygenation of the biocrude oils with
pressurized hydrogen; and b) cracking and deoxygenating the biocrude
vapors with zeolite catalysts at atmospheric pressures.

Liquefaction of biomass in pressurized solvents The liquefaction


of biomass in pressurized solvents was demonstrated at Albany, OR in the
late 1970's. This process was operated at 20.8 MPa pressure, 20 minutes
residence time, and with a sodium carbonate catalyst. Since the early
1980's, research in this area was shifted to the University of Arizona
and has focussed on improving the solids content of the slurry of biomass
solids fed into the high pressure reactor. Higher contents of biomass
in the feed, allow a smaller, more economical reactor vessel to be used
for a given throughput. Mixtures containing as much as 60% wood flour
in product oil have been pumped into pressurized containers, using a
modified extruder originally designed to extrude plastics. With this
technique, early liquefaction experiments at the University of Arizona
were conducted at 375 to 400 C, 5.5 to 21 MPa pressure, 40% wood flour
in Albany oil with a residence time of between one and four hours, and
both with and without carbon monoxide and sodium bicarbonate catalyst.
Recent experimentation was directed toward the recycling of the product
oil containing approximately 40% fresh wood flour, along with water and
carbon monoxide to result in a carrier oil composed primarily of material
made at the University of Arizona. The fluid product distilled from the
carrier oil had a heating value of 37 MJ/kg (16,000 BTU/lb), a residual
oxygen content of 7 to 10%. The oil yield was close to that
theoretically attainable. (13)
19

Liquefaction of biomass at low pressures with slow pyrolvsis The


product slates from the slow heating of loose mixtures of RDF materials
at atmospheric pressures in a retort swept with helium has been
researched at Argonne National Laboratory. Final temperatures of 475 C
were used. Sample sizes were varied between 1 and 50 g. The yields of
tar and solid residue from newsprint were reported to be 25 to 30% and
21 to 26% respectively at heating rates of 5 C/m. The effect of heating
rates between 5 and 30 C/m were found to be negligible. The influence
of polyethylene in the feed was seen only in the tars collected after the
first of a series of condensers, as deduced through the use of IR
spectral analysis. The presence of polyethylene in a kraft paper feed
decreased the low viscosity of the tars by a third. (14) The yields
of condensates are consistent with those reported for RDF components
previously reported by the New York University with similar sample sizes
and slow heating rates of between 12 and 136 C/m. (15) It appears that
slow heating rates of around 136 C/m and slower in a retort produce lower
yields of organic condensates from RDF compared to other processes which
use faster heating rates.

Liquefaction of biomass at low pressure with fast pyrolvsis Fast


pyrolysis processes can be used for biomass liquefaction at atmospheric
pressures, vapor residence times of less than a second, and intermediate
temperatures of around 500 C. The fast pyrolysis condensates have about
the same oxygen content and energy per unit weight as the feedstock.
However, when produced with only the water of pyrolysis present, they are
very fluid at room temperature and have a specific gravity of about 1.25.
Due its relatively low projected cost, fast pyrolysis is currently
thought by the International Energy Agency's Liquefaction Activity to be
advantageous depending upon the end use of the product. (16)
Basic research into the pyrolysis of biomass and RDF has been
recently studied at the Solar Energy Research Institute (SERI) using the
molecular beam mass spectrometer (MB/MS) to study the pyrolysis vapors
and gases in real time as they evolve from the pyrolyzing particles.
Over 50 different samples of biomass and RDF were pyrolyzed and analyzed
by the MB/MS scanning over the mass ranges of 10 to 250. Multivariate
analysis of this very extensive data set was used to determine that there
were 13 factors that explained over 90% of the variance in the data.
Interpretation of the data resulted in the identification of six major
chemical compound classes to explain the 13 factors. To determine the
effect of process variables, a statistically designed set of experiments
was conducted to look at the effects on the six compound classes
identified in the feedstock screening tests. Empirical equations were
fitted to the data and used to generate parametric plots showing the
effect of different variables. In addition, a set of 50 different
pyrolysis oils, most of which were part of the IEA set of pyrolysis and
gasification oils, were analyzed on the MB/MS. Multivariate analysis was
also used to reduce this data set to a similar set of six major chemical
compound classes. An empirical equation was fit to the data which
predicted the size of the distillable fraction based on the relative
amounts of the various compound classes. (17,18)
Applied research in fast pyrolysis at the Georgia Tech Research
Institute has used an entrained-flow reactor. In this system, powdered
wood (0.30 to 0.42 mm) is entrained in a straight tube by a flow of
stoichiometrically combusted flue gases. The heat for pyrolysis is
supplied by these carrier gases. If the carrier gases are too hot,
20

significant losses from the first-formed vapors take place to result in


higher overall gas yields. Consequently, fairly large amounts of
tempered carrier gases at 745 C were used at a carrier-gas-to-biomass
weight ratio of about 8 to supply the heat of pyrolysis to maximize the
yield of pyrolysis oils. The diameter of the entrained-flow reactor is
currently 15 cm and the length is 4.4 m, which results in a residence
time of one to two seconds. This residence time is a compromise between
the length of time needed to pyrolyze the size of particles fed on a
once-through basis and the need to minimize the time which the pyrolysis
vapors spend in the reactor. Feeding rates are typically about 15 kg/hr
and have resulted in reported yields of 58% organic condensates (moisture
free) and 12% char (maf feed) with a total mass closure of 101%
(including the large amount of carrier gases). The pyrolyzate is
recovered along with the water formed in the combustion used to directly
heat the carrier gases, as well as any water formed during pyrolysis,
or which was present as moisture in the feed, resulting in condensates
containing about half water. (19,20)
A different type of entrained-flow reactor has been developed at
SERI specifically for the fast pyrolysis of biomass. In this reactor,
the feed is entrained at very high velocities (calculated to be about 400
m/s) in a tube having an inside diameter of 1 cm into a vortex reactor
having a diameter of 13 cm and a length of 0.69 m. The feed particles
are forced to slide on the hot cylindrical wall in a helical path as they
pass through the reactor. The sliding contact of the particles on the
wall results in very high heat transfer to the particle so that ablative
pyrolysis is thought to take place. Partially pyrolyzed particles exit
the reactor tangentially, are mixed with fresh feed, and are recycled
back to the carrier gas ejector, where they are re-accelerated by the
supersonic carrier gas. The recycle loop decouples the residence times
of the solids and the vapors, which allows the vortex reactor to be
insensitive to the particle size of the feed. The small amount of char
which is formed is also recycled until it is attrited to a fine powder
(-50 micrometer). (21) A mathematical model based on first principles
suggests that the typical 2-mm thick feed particle will make about 30
passes during a total residence time of 1 to 2 seconds through the
reactor before it is completely pyrolyzed. Operation of this small
reactor is typically at 13 to 20 kg/hr of dry sawdust (-3 mm) with a
carrier-gas-to-biomass weight ratio of 1 to 1.5. Yields on a dry feed
basis have been 67% condensates (55% moisture-free organic liquids), 13%
char, 14% net pyrolysis gases, and 12% water of pyrolysis for a mass
closure of 94% of the feed (a 98% mass closure, if the nitrogen carrier
gas is included in the calculations) . (22) This reactor has recently
been modified to allow it to pyrolyze RDF, which contains tramp metals
and other inert solids. Preliminary operation with RDF indicates that
the plastic derived condensates interact with the lignocellulosic derived
condensates to form an asphalt appearing material. (23,24) The asphalt
nature of these condensates contrasts with the low viscosity reported as
a result of slow pyrolysis. (17)
An alternate approach to effect the sliding contact between a hot
surface and the biomass to be rapidly pyrolyzed has been under
development at the Colorado School of Mines (CSM). The CSM reactor uses
two specially grooved disks made of copper, which are stacked one on top
of the other. The biomass or RDF is centrally fed between the heated
disks. As the bottom disk is rotated at 4 to 80 rpm, the feed particles
make their way to the circumference of the disks in a spiral path and are
allowed to fall to a cooler zone. The vapors and gases pass between the
21

heated disks and also exit at the circumference of the disks and pass out
of the reactor to the condensers. The disks had a diameter of 6.4 cm.
Feeding rates were 13 to 210 g/h. Maximum reported liquid yields from
sawdust were 54% (including moisture) at disk temperatures of 600 C, a
flow of nitrogen purge gas of 0.5 g N2 per g of sawdust, and a feeding
rate of 13 g/h. (25,26) If the developmental challenges can be met, the
CSM pyrolysis reactor offers a greater decoupling of the purge or carrier
gas flow rates than is possible with other fast pyrolysis reactors, e.g.
entrained flow, vortex, or fluidized bed reactors.

Characterization of organic condensates formed by thermochemical


processes The pyrolysis and gasification processes mentioned above
produce condensates which vary in their characteristics depending upon
the nature of the process. In particular, time spent at high
temperatures increases gas formation, but also changes the nature of the
surviving organic condensates. A recent study by PNL of condensates made
with short residence times at temperatures from 450 to 900 C revealed
that the primary pyrolysis condensates which form at 450-500 C do not
contain polycyclic aromatic hydrocarbons (PAH's) and are not carcinogenic
to mice. However, as the pyrolysis temperatures are raised, the amount
of PAH's increases along with the carcinogenicity to mice. In fact, the
tars formed above 800 C appeared to be slightly more carcinogenic to the
mice than was the reference material, benzo(a)pyrene. (27)
The nature of the oxygenated oils and tars formed by the various
pyrolysis processes is such that they are not equivalent to a petroleum
crude oil and they require different refining techniques to be developed.
The oils formed in pressurized solvents have tended to have a high
phenolic content, whereas, the oils formed by fast pyrolysis have a very
high oxygen content. These biocrude oils could be used as boiler or
turbine fuels without refining. However, neither of the biocrude oils
can distilled into usable gasoline or diesel fractions, rather both of
them must be deoxygenated to be converted hydrocarbons and usable
transportation fuels. Two such deoxygenation processes have been under
development: a) hydrogénation with cobalt-molybdenum catalysts at high
pressures, and b) cracking with zeolite catalysts with no added hydrogen
at atmospheric pressures.

Upgrading of pyrolysis products by hydrogénation The upgrading of


pyrolysis oils, formed at both high and low pressures, through catalytic
hydrogénation has been under investigation at PNL. Early work used oils
formed at high pressures in the Albany (PERC) process with a sulfided
cobalt-molybdenum catalyst at 13.8 MPa hydrogen pressure, 350 to 450 C,
and a liquid hourly space velocity (LHSV) of 0.1 volume of oil per
volume of catalyst per hour to produce a hydrocarbon product boiling
primarily in the gasoline range. (28) More recently, this work has been
expanded to oils formed by the fast pyrolysis of biomass at atmospheric
pressures made at Georgia Tech, SERI, as well as those from Canada and
peat derived oils from Finland. The fast pyrolysis oils must first be
stabilized by deoxygenation in the presence of hydrogen at low
temperatures to avoid polymerizing the feedstock. After stabilization,
the fast-pyrolysis oils are partially deoxygenated and have many
properties in common with the oils formed at high pressure. The
stabilized pyrolysis oils can then be hydrodeoxygenated at higher
temperatures to form a gasoline product similar to that made from the
high pressure oils. Originally, this two-step process was conducted
separately at a pressure of 13.8 MPa hydrogen, temperatures of 275 and
22

350 C, and liquid hourly space velocities of 0.6 and 0.1 in the first and
second reactors, respectively. Yields on a dry wood basis from pyrolysis
oils made by Georgia Tech were about 25 wt% of hydrocarbon product
containing only 1.3 wt% oxygen. More recently, this two-step process was
combined into a single, non-isothermal reactor at 13.8 MPa, which
maintained the inlet temperature at around 260 C and the outlet
temperature at around 375 C. With a LHSV of 0.1 volume of oil per volume
of catalyst per hour, the fast, pyrolysis oil from SERI was converted into
a product which contained only 1.3 wt% oxygen, a hydrogen-to-carbon ratio
of 1.68, and 73 vol% boiling in the gasoline range (C5 to 225 C ) . Liquid
product yields of about 20 wt% were reported based on the dry wood feed.
The cause for the difference in yields has not been addressed. (29)
Octane tests of the gasoline products, combined from several preliminary
hydrogénation experiments of the Albany oils, indicated a research octane
of 77. (29,30) Based on the fairly high hydrogen-to-carbon ratio and the
medium octane value, it is highly probable that the octane level could
be raised by optimizing the process or by removing some of the hydrogen
in a subsequent reforming step to increase the aromatic content, as is
commonly done in a typical petroleum refinery, i.e. with "Platforming".

Zeolite upgrading of pyrolysis oil vapors at low pressures An


alternate method to the high pressure upgrading of the pyrolysis oil is
with the use of zeolite catalysts at atmospheric pressures without added
hydrogen. These catalysts were introduced to the petroleum industry
about 30 years ago and have found widespread use in the catalytic
cracking of heavy petroleum fractions to increase the yield of gasoline.
More recently, Mobil has developed zeolite catalysts which have pore
sizes small enough to allow production of toluene and similar gasoline
compounds. This H-ZSM-5 catalyst is now in commercial use in New Zealand
to convert methanol to gasoline. Although the molecular weight of the
condensed pyrolysis oils has been found to be typically between 500 and
2000, researchers at SERI determined that the pyrolysis vapors had much
lower molecular weights of typically less than 200. The molecular size
and shape of most of the identified compounds were small enough to enter
the H-ZSM-5 pore. Preliminary experiments with H-ZSM-5 catalyst
furnished by Mobil confirmed that a small amount of catalyst was
sufficient to change the product slate from the oxygenated pyrolysis
vapors to a highly aromatic gasoline product. This process has been
studied extensively using the MB/MS which allowed the product slate to
be examined in real time as the catalyst aged in a fixed bed of 10 g of
H-ZSM-5 catalyst. A process variable study was conducted to identify
optimum operating conditions, which were found to be quite different from
those used to convert methanol to gasoline. Empirical equations were fit
to the data to result in parametric contour plots illustrating the
effects of the process variables on the yields. (31,32,33) Concurrently,
research has been conducted with a larger fixed-bed reactor having 100
g of catalyst and fed a small slipstream of fresh pyrolysis vapors
directly from the vortex reactor at SERI. (34,35) Hydrocarbon product
yields, including olefins, have been around 15 wt% of the dry feed, when
using steam as the carrier gas and a weight hourly space velocity of
between 1 and 4 g wood per g catalyst per hour at 525 C. Recent research
has been directed toward recovery of the gaseous olefins as part of the
gasoline product. The gasoline produced consists primarily of alkylated
benzenes, e.g. toluene, xylenes, ethyl benzene, and isopropyl benzene
(eumene). These compounds are present in today's commercial gasolines
and their effect is to raise the octane value. (36,37) Similar impure
23

streams (mixed xylenes) in a petroleum refinery are typically worth one


and a half times the value of unleaded gasoline. The upgrading of fast-
pyrolysis oils with zeolites has also been studied at Georgia Tech
Research Institute, but detailed results have not yet been released.
(19,20)

Technoeconomic assessments (38) Technoeconomic assessments were


recently made by Science Applications, Inc. (SAI) to compare two methods
of upgrading fast pyrolysis products to gasoline. Each of the two
processes were evaluated at their present stage of development, as well
as, at the expected future stage of mature development. In the process
being studied at PNL, the condensed fast pyrolysis oils, made by an
entrained-flow process similar to that of Georgia Tech, are fed to a high
pressure reactor where in the present case the oils are first
deoxygenated in the presence of hydrogen at relatively low temperatures
to stabilize the oils to prevent polymerization reactions. The
stabilized oil is then treated with hydrogen at higher temperatures to
complete the hydrodeoxygenation process. Hydrogen is made by steam
reforming and shifting of the byproduct gases. This hydrogénation process
is relatively complex and capital intensive, but is said to have the
potential of very high hydrocarbon yields of about 32% by weight of the
dry feed. Liquid hourly space velocities of 1.0 and 0.1 were assumed for
the "current" two-step hydrogénation process. A LHSV of 0.5 was assumed
for the "future" non-isothermal hydrogénation process in a single
reactor.
The other process, which is being studied by SERI, is based on the
immediate conversion of the hot organic vapors, formed by fast pyrolysis
in the vortex reactor, before they are allowed to cool and condense. In
this process at atmospheric pressures, the hot carrier steam, pyrolysis
gases, and vapors are passed through a catalytic cracking reactor loaded
with H-ZSM-5 catalyst. With a gas residence time of a few seconds, an
equivalent LHSV of 2.5 was assumed to give complete conversion of the
oxygenated organic pyrolysis vapors to the hydrocarbon products, water,
and oxides of carbon. The process stream was then condensed and the
olefinic gases adsorbed from the off-gases and recycled. This process
is thought to have lower potential gasoline yields of 24% of the dry
biomass feed, but is less capital intensive per unit weight of biomass
fed than high pressure hydrogénation.
The present technoeconomics of both processes were examined in light
of the state-of-the-art as it existed at the time of the beginning of the
study: a 15 wt% yield for hydrogénation; and 10% yields for zeolite
cracking. The annual cost assumed for the capital was equivalent to a
simple amortization over 20 years of the total capital investment at 15%
annual interest without any subsidies or tax considerations. The assumed
cost of the feedstock was $27.50 per dry tonne. As expected, the
research on these processes is only partially completed and established
research goals have not yet been reached. For this reason, projected
production costs in a plant fed 908 tonnes of dry biomass per day were
not economically attractive at $2.64 per gallon via hydrogénation and
$2.92 per gallon via catalytic cracking. Incorporation of more recent
yields and process information would result in lower predicted production
costs for both processes.
If future research and development are successful, the economics
improve substantially. The future hydrogénation process is projected to
require a capital investment of $74.4 M to result in a cost of $0.96 per
gallon of medium octane gasoline. The future zeolite cracking process
24

was projected to require a capital investment of $47.8 M to result in a


cost of $1.05 per gallon of high octane gasoline blending stock. These
projected production costs are very sensitive to the relative success of
research and development to achieve the gasoline yields assumed. Within
the accuracy of the study, the projected production costs are equivalent
for the two different gasolines.

4. COMMERCIALIZATION OF DOE DEVELOPED TECHNOLOGY


There are several private firms which are involved with the
commercialization of biomass gasification in the United States. Most of
this work has involved air blown, low-energy gasifiers for fuel purposes.
Approximately 20 gasifiers are currently in operation including, for
example, a unit which provides boiler fuel for a hospital in Rome,
Georgia. Other units are being planned. Technology based on a downdraft
gasifier developed by the DOE program at SERI is being used by Syngas,
Inc. to develop gasification systems to produce electricity in New York.
Another gasifier, based on the vortex reactor is being planned by
Pyrotech to operate in California.
There currently are no firms with commercial gasifiers to produce
a medium-energy gas, which could be utilized as a synthesis gas. To
encourage such a development and to facilitate the commercialization of
a process to make methanol from biomass, the U.S. DOE has recently
announced that it is looking for an industrial partner to share the cost
of the scale-up of a gasifier system to produce a medium-energy gas.
This would be at the 15 to 25 tonne per day size. A formal request for
proposal is soon to be issued to those U.S. companies indicating an
interest to share at least 50% of the cost of the project. The U.S. DOE
funding for this project is projected to be about $5M over the life of
the development. (42)

5. FUTURE TRENDS IN THERMOCHEMICAL CONVERSION IN THE U.S.


The DOE funding available for thermochemical conversion has steadily
declined in recent years. Cutbacks in the research program during the
current fiscal year resulted in the cancellation of all thermochemical
programs, except those at SERI. The research and development of the
zeolite upgrading of the pyrolysis oils to improve yields at lower cost
and the pyrolysis of RDF in the vortex reactor to optimize organic vapor
yields will continue at SERI, but at reduced levels compared to prior
years.
This funding decline is at a time when the world is looking for
methods to reduce the emission of carbon dioxide through the curtailment
of the use of fossil fuels. Since the use of biomass as a fuel recycles
carbon dioxide over the course of a few years, it will not be a net
contributor to the "greenhouse" effect. In future years, the funding for
alternate sources of methanol and gasoline may be more optimistic.

6. CONCLUSIONS
The U.S. DOE has successfully transferred the technology for
gasification to produce low-energy gases and commercialization of this
technology is underway. Gasification of biomass to produce medium-energy
gases for methanol synthesis is still being researched at a low level of
effort and a pilot plant demonstration project is planned, in which the
U.S. DOE will share the cost of development with a private firm. Most
thermochemical research in the last few years has been directed toward
the production of liquid hydrocarbon fuels, i.e. gasoline. Using
pyrolysis oils formed during the fast pyrolysis of biomass, two promising
25

processes to make gasoline have been researched concurrently. This work


will also examine the use of RDF feedstocks to produce gasoline.

REFERENCES

(1) SCHIEFELBEIN, G., ed. (1988) Thermochemical Conversion Propram


Annual Meeting. June 21-22. 1988. Solar Energy Research Institute,
Golden, CO 80228, SERI/CP 231-3355, DE 88001187.
(2) BRIDGWA TER, A .V., and KUESTER, J.L., eds. (1988) Research in
Thermochemical Biomass Conversion. Proceedings of the IEA
Conference held in Phoenix, AZ in May 2-6, 1988, Elsevier Applied
Science, London and New York.
(3) SOLTES, E.J. and MILNE, T.A., eds. (1988) Pvrolvsis oils from
Biomass. Producing. Analyzing, and Upgrading. Proceedings of the
symposium held in Denver, CO on April 5-10, 1987, ACS Symposium
Series 376, American Chemical Society, Washington, D.C.
(4) KLA SS, D., ed. (1989) Proceedings of the symposium on "Energy from
Biomass and Solid Wastes XII", held in New Orleans, LA February
13-17, 1989, Institute of Gas Technology (in press).
(5) LEVIE, B.E. (1988) Pvrolvsis of Refuse Derived Fuel Pellets. Ph.D
thesis, University of Colorado.
(6) LEVIE, B.E. and DIEBOLD, J.P. (1988) "Pyrolysis of single pellets
of refuse derived fuel" in Ref. (1), pp. 259-269.
(7) LEVIE, B.E., DIEBOLD, J.P., and WEST, R. (1988) "Pyrolysis of
single pellets of refuse derived fuel" in Ref. (2), pp 312-327.
(8) LA I, W. and KRIEGER-BROCKETT, B.B. (1988) "Single Particle RDF
Pyrolysis Properties and Products-Initial Results" in Ref. (1),
pp.269-280.
(9) KRIEGER-BROCKETT, B.B. and GLA ISTER, D.S. (1988) "Wood
Devolatilization - sensitivity to feed properties and process
variables" in Ref.(2), pp. 127-142.
(10) DURA I-SWA NY, K. , WARREN, D.W., and CHE, S.C. (1988) "Pulse-
enhanced biomass gasifier for production of medium-BTU gas" in
Ref. (1), pp. 77-86.
(11) DURA I-SWA MY, K. , WARREN, D.W., A GHA MOHA MMA DI, B. , and MANSOUR,
M.N. (1989) "Pulse-assisted gasification of black liquor and
organic wastes for medium-BTU gas" in Ref. (4).
(12) MUDGE, L.K., GERBER, M.A ., and WILCOX, W.A . (1988) "Improved
gasification by catalytic destruction of tars in biomass-derived
gases" in Ref. (1), pp. 87-100.
(13) WHITE, D.H. and WOLF, D. (1988) "A dvances in direct biomass
liquefaction by the extruder-feeder method" in Ref. (1), pp. 57-
66 and Ref. (2), pp. 827-853.
(14) HELDT, J.E. and MALLYA, N. (1988) "Experiments on basic mechanisms
of pyrolysis" in Ref. (1), pp. 221-236.
(15) KA ISER, E.R. and FRIEDMAN, S.B. (1968) "The pyrolysis of refuse
components", Combustion. May, pp. 31-36.
(16) ELLIOTT, D.C, BA KER, E.G., BECKMA N, D., SOLA NTA USTA , Y.,
TULENHEIMO, V., OSTMA N, Α., GEVERT, S.B., HORNELL, C , and
KJELLSTROM, B. (1989) "A technical and economic analysis of direct
biomass liquefaction" in Ref. (4).
(17) EVA NS, R.J., MILNE, T.A ., and FILLEY, J. (1988) "Mass
spectrometric studies of municipal solid waste pyrolysis" in Ref.
(1), pp.209-219.
26

(18) EVANS, R.J., and MILNE, T.A. (1988) "Mass spectromctric studies of
the relationship of pyrolysis oil composition to formation
mechanisms and feedstock composition" in Ref. (2), pp. 264-279.
(19) KOVAC, R. (1988) "Production and upgrading of biomass pyrolysis
oils" in Ref. (1), pp. 5-20.
(20) KOVAC, R. (1989) "Liquid biofuels production by an entrained
pyrolysis process" in Ref. (4).
(21) DIEBOLD, J.P. and SCAHILL, J.W. (1988) "Production of primary oils
in a vortex reactor" in Ref. (3), pp. 31-40.
(22) DIEBOLD, J.P. and POWER, A.J. (1988) "Engineering aspects of the
vortex reactor to produce primary pyrolysis oil vapors for use in
resins and adhesives" in Ref. (2), pp. 609-628.
(23) SCAHILL, J.W. and DIEBOLD, J.P. (1988) "Adaptation of the SERI
vortex reactor for RDF pyrolysis" in Ref. (1), pp. 237-246.
(24) DIEBOLD, J.P., EVANS, R.J., and SCAHILL, J.W. (1989) "Fast
pyrolysis of RDF to produce fuel oils, char, and a metal-rich by-
product" in Ref. (4).
(25) REED, T.B. (1988) "Principles and operation of a novel "pyrolysis
mill" in Ref. (1), pp.247-258.
(26) REED, T.B. (1988) "Contact pyrolysis in a pyrolysis mill" in Ref.
(2), pp. 192-202.
(27) ELLIOTT, D.C. (1988) "Relation of reaction time and temperature to
chemical composition of pyrolysis oils" in Ref. (3), pp. 55-65.
(28) BAKER, E.G. and ELLIOTT, D.C. (1988) "Catalytic hydrogénation of
biomass-derived oils" in Ref. (3), pp. 228-240.
(29) BAKER, E.G. and ELLIOTT, D.C. (1988) "Catalytic upgrading of
biomass pyrolysis oils" in Ref. (2), pp. 883-895.
(30) ELLIOTT, D.C. and BAKER, E.G. (1988) "Catalytic hydrotreating
processes for upgrading biocrude oils" in Ref. (1), pp. 45-56.
(31) EVANS, R.J. and MILNE, T.A. (1988) "Molecular-beam mass-
spectrometric studies of wood vapor and model compounds over an H-
ZSM-5 catalyst" in Ref. (3), pp. 311-327.
(32) EVANS, R.J., FILLEY, J., and MILNE, T.A. (1988) "Molecular beam
mass spectrometric studies of H-ZSM-5 activity during wood
pyrolysis product conversion" in Ref. (1), pp. 33-43.
(33) MILNE, T.A., EVANS, R.J., and FILLEY, J. (1988) "Molecular beam
mass spectrometric studies of H-ZSM-5 activity during wood
pyrolysis product conversion" in Ref. (3), pp. 910-926.
(34) DIEBOLD, J.P. and SCAHILL, J.W. (1988) "Biomass to gasoline:
upgrading pyrolysis vapors to aromatic gasoline with zeolite
catalysts at atmospheric pressure" in Ref. (3), pp. 264-276.
(35) DIEBOLD, J.P. and SCAHILL, J.W. (1988) "Conversion of wood to
aromatic gasoline with zeolite catalysts", Energy Propress. Vol.
8, No.l, 59-65.
(36) SCAHILL, J.W., DIEBOLD, J.P., and POWER, A.J. (1988) "Engineering
aspects of upgrading pyrolysis oil using zeolites" in Ref.(2), pp.
927-940.
(37) DIEBOLD, J.P. and SCAHILL, J.W. (1988) "Zeolite catalysts for
producing hydrocarbon fuels from biomass" in Ref. (1), pp. 21-32.
(38) WAN, E.I. and FRASER, M.D. (1988) "Economic assessment of
producing liquid transportation fuels from biomass" in Ref. (1) ,
pp. 111-121.
(39) GRABOSKI, M.S. (1989) Private communication with J.P. Diebold on
April 21.
(40) AYRES, W. (1987) "Commercial application of wood derived oil",
Enerpv Propress. Vol.7, No. 2, 77-79.
27

(41) AYRES, W. (1989) Private communication with J.P. Diebold on April


21.
(42) ANON,(1989) Commerce Business Daily. Jan. 6.
28

OVERVIEW OF THERMOCHEMICAL CONVERSION OF


BIOMASS IN CANADA

R.D. HAYES
Bioenergy Research and Development
Technology Branch
Energy, Mines and Resources Canada
Ottawa, Canada K1A 0E4

Summa ry

Thermochemical conversion of biomass in Canada has undergone a


considerable transformation in approach and expectations over the
last ten years. A decade ago, the promise of early
commercialization quickly evaporated and was replaced by a more
realistic assessment that the potential would likely not materialize
except over the longer term. More recently this outlook has been
modified slightly in the wake of unanticipated research progress and
the surfacing of some special near term market applications.

1. INTRODUCTION AND HISTORY

During the late 1970's and early 80's there was a short-lived
perception of panic in energy security accompanied by exaggerated claims
of technical readiness of thermochemical conversion applications. Several
premature commercial demonstrations in the U.S.A. of pyrolysis and
gasification failed technically and financially. Governments and
investors became understandably cautious therefore when further approached
by technology vendors. American communities that once considered
gasification and pyrolysis of municipal solid wastes as environmentally
attractive alternatives to relieve pressure on decreased availability of
landfill sites for urban refuse, turned their attention to mass
incineration and refuse derived fuel (RDF) combustion applications.
Though environmentally less attractive in terms of emissions, combustion
offered less technical and financial risk than did the more exotic
thermochemical conversion options.

Canada was somewhat behind the U.S.A., having felt less apparent
impact from the energy supply disruptions of 1973 and 1979. In those days
also there was less pressure to find alternatives to landfilling of wastes
than there was in many U.S. cities, or, as there is in some Canadian
cities today. Canadian thermochemical conversion research, then in its
infancy, therefore focussed its effort on the long term. It assumed a
lengthy timeframe to mature innovative process developments. In theory,
this new breed of technologies would presumably become technically ready
for the 1990's or 2 1 s t century, in a world eager to embrace bioenergy,
particularly from wood, as a sustainable and environmentally attractive
energy resource.
29

The ultimate vision of some researchers was to refine biomass in a


manner analogous to petroleum that would eventually lead to alternative
transportation fuels, preferably high quality gasoline, plus a host of
high value byproduct specialty chemicals. As the bubble burst on high
world oil prices, the sense of urgency to accelerate RSD diminished.
Admittedly, severe federal budget reductions for energy RSD also had its
predictable effect on the "sense of urgency". Except for one major
project, gasification research in Canada all but disappeared by 1984. The
pyrolysis/liquefaction research community collectively agreed to back off
from upgrading studies, and concentrated instead on perfecting their
processes for primary oil production.

Over the past decade, the science has become better understood and
technical advances have actually surpassed earlier expectations. Some
laboratories have begun to re-activate their upgrading research.
Scientists and engineers have broadened the scope of experimental
conditions and gained a much deeper understanding of the chemical
transformations of complex feedstocks to multiple products.

A new vision of conversion and product opportunities has begun to


reshape our view of the timeframe for commercialization. The long term
perspective remains paramount, and perhaps even more so since the global
call for environmentally sustainable economic development by the
Brundtland Commission report, "Our Common Future"l·

In addition to the long-term vision, technical progress in the


identification of several high valued specialty chemicale in wood
pyrolysis oil may be the market hook (albeit a small market) required to
help finance the high costs of staged scale-up from laboratory, process
development unit, pilot plant, small commercial demonstration and
eventually to full-scale commercial reality.

Several other near term opportunities have also surfaced.


Environmental pressures have influenced the trial experimentation of
biomass pyrolysis liquefaction technologies on non-woody feedstocks such
as used tires, petroleum sludges, sewage sludge, and, once again,
municipal solid wastes. Impending environmental regulatory controls on
waste incineration and increasing costs for landfilling may create a
climate more ideal for fully contained emission-free thermochemical
processes.

Researchers, industry and government have all become more creative in


building a diversified, yet comprehensive, portfolio of thermochemical
conversion opportunities for the commercial world. Though nothing
thoroughly new has emerged, the past ten years have seen an evolution from
a subject of technical curiosity to one of concerted effort toward cost
effective products for the marketplace, some sooner than others.

2. PROSPECTIVE APPLICATIONS OF TECHNOLOGY (PAT)

A broader diversified portfolio, as referred to above, presents a


major challenge to the RSD planner. Added to this challenge is the ever-
present restraints in government RSD funding. This challenge has
necessitated a major overhaul in organizing RSD priorities in the context
of assessing a balance in both near and long term commercialization and
environmental opportunities and needs.
30

The commercialization process for a new technology as defined within


the Energy Diversity Division of Energy Mines & Resources Canada includes
everything germane including opportunity identification, the actual
research, development, technical evaluation, and demonstration as well as
the determination of current and projected economic feasibilities, current
and future market, expected timeframes for commercialization, standards
development, and many other factors affecting market introduction and pene­
tration. Once these elements have been assessed and analyzed for the
various feedstock/conversion' technology pathways, priorities could be estab­
lished with respect to activities that government can, should, or must, do
and those that government should not, or cannot afford, to support.

The first step in the process is to organize the four basic elements
of a technology by resource (eg. biomass, wastes, peat etc.), process(es),
product(s), and market application. The particular feedstock combined
with specific conversion processes and a particular market application of
products result in what we define as a Prospective Application of
Technology or PAT. The picture can become rather complex especially
when considering combinations of thermochemical, biochemical and
fractionation technologies that might be otherwise overlooked during
conventional analysis. In order to illustrate many of the various
combinations pictorially, we have constructed a 'PAT map.'

Figure 1 is a simplified version of a 'PAT map' for thermochemical


technologies. One can visualize perhaps one hundred or more probable
combinations of resources, processes, products, and market applications.
The product possibilities alone include a vast array of oils, gases,
chars, carbon black, sugars, fermentation products, high value specialty
chemicals, medium value commodity chemicals, olefins, gasoline and
gasoline components, diesel fuel, and other materials. Figure 2 is a more
general PAT map encompasing most bioenergy technologies.
FIGURE I

Prospective A pplications of Technology


< Thermochemical)

IzBüfffla.·,!!
ition
Thermochemical ­
Processes;
Thermochemie al "Τ Τ attractive*/
pyrolysis and/or χ y Ian s lionln votatile«
hydrotreating biochemical
catalytic
solvent pressurized
partial oxidation
oxygen gasification
Processes
TvTvl
soivoiyss Various combinations of thermochemical,
hydrothermolysis biochemical, ex tract lon/fract Jona tion and
product separation derlvatlzatlon processes
etc.

CMA
oletins "* BTX acetic acid
diesel /urt
phenolic denVaoVes
synthesis gas gaso/ine components aahe¡áve¡¡lb¡nders lm, mol. m lignns
carbon 'llavoursl aromas
black charcoal
31

Figure I I

PROSPECTIVE APPLICATIONS OF TECHNOLOGY

| MATERIALS PREPARATION]

JPRETREATMENT FRACTIONATION |

THERMOCHEMICAL
COMBUSTION EXTRACTIVES
GASIFICATION
PYROLYSIS
CATALYSIS
HYDROTHERMOLYSIS
SOLVOLVSIS. ETC...
VARIOUS COMBINATIONS OF BIOCHEMICAL
THERMOCHEMICAL. FRACTIONATION, EXTRACTION
AND D ERIVATIZATION PROCESSES

| THERMOCHEM-UPGRAOING |

FUEL OIL GAS CMA ACETIC ACID RESINS FIBERS SUGAR ENZYMES
OLEFINS BTX METHANE CARBON BLACK GASOLINE AD D ITIVES OLIGOMERS
FURFURAL D IESEL FUEL SYNTHESIS GAS HEAT ALCOHOLS A
D HESIVES'BIN
D ERS
PHENOLIC D ERIVATIVES CHARCOAL GASOLINE FLAVOURS/AROMAS LOW MOL WT. LIGNINS
MANY FERMENTATION PROD UCTS ETC.

RESIDENTIAL. COMMERCIAL INSTITUTIONAL AND IND USTRIAL BLOGS.. PULP AND PAPER , AGRICULTURE &
FISHERIES. UTILITIES. FOOD AND BEVERAGE. FOREST PROD UCTS IND USTRY. NORTHERN COMMUNITIES
TRANSPORTATION. INTERNATIONAL AID AND EXPORT. REFINERIES
HEAVY IND USTRY. BRICK. LIME AND CEMENT ETC.

Our view of the world of thermochemical conversion of biomass is no


longer limited to merely the pyrolysis or gasification of wood to heating
oil and gas. Thermochemical conversion is not treated in isolation from
biochemical, fractionation or derivatization processes. Even considering
a single process technology, the variation in process conditions,
catalysts, reactants, or feedstocks can impact the range and output of
possible product combinations.

The second step will be to select a handful of promising PA T■s, and


perform an analysis of expected technical progress, economic feasibility,
market penetration, and timeframe for commercialization. In theory, this
should provide government (and industry) with a rationale for desirable
government (and industry) activities in those PA T's such as research,
development, demonstration, detailed engineering, market studies, economic
and financial analysis, information dissemination, standards formulation,
etc.

Some of the so-called 'thermochemical PA T■s' that are not typically


represented at thermochemical conversion of biomass conferences, but which
are included or planned for in Energy, Mines and Resources' Bioenergy R&D
program planning include the following:

thermochemical treatment of plant oils (oilseed, tall oil) to produce


high cetane diesel fuel.
biochemical and thermochemical derived lignin that is thermally or
thermochemically treated with or without catalysts to produce gasoline
and other chemicals.
32

c
product derivation of thermochemical and biochemical lignins (eg.
resins, adhesives, cement dispersants).
° thermochemical treatment of the steam fractionated cellulose component
of biomass.
° direct steam (thermal) production of adhesives with a fibre byproduct
suitable for molding, pelletizing, or thermochemical or biochemical
processing.
0
calcium magnesium acetate (CMA) production a3 a road de-icer from
aqueous effluents (ie. dilute acetic acid) of pyrolysis and biochemical
processes.
° investigation of wheat chaff as a thermo- or biochemical conversion
feedstock.
° methanation of pyrolysis aqueous effluents.
° separation of short and long fibers of hardwoods where pulp would be
processed from the long fibers and fuels processed biochemically or
thermochemically from the lower value short fibers.
° source separated and/or prescreened, or raw, municipal wastes that
undergo thermochemical or biochemical conversion with or without
pretreatment/fractionation.

3. EMR's BIOENERRY DEVELOPMENT PROGRAM

Table 1 shows the historical trend in Canadian federal government


spending on bioenergy RSD including biomass production and conversion.
Table 2 is a breakdown of thermochemical R&D expenditures relative to
other conversion technology areas.

3.1 BRIEF REVIEW OF NON-THERMOC.HEMICAL R&D

The following is a cursory view of Canadian R&D activities in


technical areas other than thermochemical.

The combustion area's main focus of effort is the evaluation and


improvement of industrial and residential combusto! performance and
emissions. Also included has been support to Environment Canada's
National Incinerator Test and Evaluation Program (NITEP) and the
development of standards for performance, safety and emissions of
residential wood burning appliances.

The biomass handling/preparation area includes research in


biomass materials handling, storage, drying, beneficiation, and
preparation. This research is seen to provide necessary infrastructural
support for all biomass conversion processes, but more importantly, to
improve biomass fuel quality with objectives to improve biomass combustion
performance and to reduce emissions. Examples of developments include a
bin, silo and non-consolidating feeder system that regulates the
controlled and non-disrupted feeding of hog fuel and chips to burners, a
device to exclude frozen lumps of hog fuel and chips to burners, a
continuous moisture sensor to provide improved combustion control of
biomass of varying water content, and a low energy grinder to powder wood
suitable for suspension-fired boilers.

The biochemical area receives the largest allocation of funds, in


part due to increasing industrial leverage provided by cost-shared R&D.
Much of the impetus for this area comes from mid-term (1990's) competitive
potential to enter the transportation fuel market with biomass derived
33

Table I
S/MILUONS
25
Federal Bioenergy R&D Funding
r™™^ , m ^
20

ÏS-

IO-
BPsTţjs man

82 83 84 85 86 87 88 89 90

Table II

1988/89 Bioenergy R&D


Expenditure Forecast

35.4%

Combustion Biomass Thermo­ Bio­ Infor­


Handling/ chemical chemical mation
Preparation Tech/
Transfer
34

ethanol based blends and oxygenates and the longer term potential of neat
ethanol fuel along with value added byproducts. The program is divided
into a number of areas including enzymatic and acid hydrolysis of
lignocellulosics, steam and extrusion pretreatment and biomass
fractionation, novel fermentation engineering, biotechnology of enzymes
and microorganisms, anaerobic digestion, characterization and
derivatization of lignin, and the development of non-ethanol byproduct
streams, among others. The rate of achievements in this area over the
past four years rivals that in the thermochemical area. The lure and
promise of biotechnology and the recent accelerated progress are likely
the major factors in attracting industry participation in an area that
was viewed by our program as very long term as of only five or six years
ago.

3.2 CANADA'S MAINSTREAM BIOMASS THERMOCHEMICAL CONVERSION RSD

An approach has evolved in Canada whereby, unlike earlier efforts, a


whole range of products and reactants are now considered. Products
include gases and oils of varying quality, sugar solutions in high yield,
chemicals (olefins, phenolics, as well as high value specialty chemicals),
gasoline or diesel fuel, and higher value carbon products.
Diversification of reactants include whole biomass, fractionated biomass
components, peat, and muncipal solid waste, including source-separated
wastes such as used tires. Another area of research is the treatment, and
especially, the conversion, of waste aqueous effluents from thermochemical
conversions into value-added co-products. Left unprocessed, these
effluents would otherwise incur a cost for waste treatment.

3.2.1 GASIFICATION

Canadian developments in biomass gasification for the production of


low, medium and high energy gases have enjoyed world technical acclaim
over the past decade, but there has been a disappointing uptake by
Canadian industry. The cautious attitude of our industry appears to have
been due largely to premature and unsuccessful attempts in the US to
commercialize immature technologies during the latter '70s and early '80s.
A possible revival of interest in gasification technology applications
appears to be for replacing industrial boilers that use oil and for
municipal energy from waste projects. The work to complete ongoing
projects will continue, although at a reduced level, and any impetus for
an expanded government program will likely wait for stronger industry
confidence, interest, and cost share. Application of Canadian technology
in developing countries may hold some promise.

Large scale (10 tonnes/hour) gasification technology, developed


through the Biosyn project offers a world leading technology in
pressurized, air or oxygen fed, fluidized-bed gasification that can be
adapted to the production of synthesis gas for methanol production or low
energy gas for other applications such as space heating, gas turbines or
industrial diesel engine operation.

Another portion of the gasification research funds is directed to the


development of a small scale gasifier that is designed to use wet wood and
produce a clean gas. The Heuristic gasifier is a two-stage reactor that,
in principle, operates similarly to a downdraft design. The first stage
is an updraft gasifier where producer gas and condensible vapours (tars)
35

are routed through a hot char bed below. The tars are to be cracked in
the second stage. The project now underway is to modify the gasifier,
optimize the operating parameters, and enhance cracking in the second
stage.

3.2.2 LIOUEFAC.TION/PYROLYSIS

In 1985, research in the direct liquefaction of biomass was expected


to wind down because the rapid commercialization that was expected to
occur in the early '8 0s did not materialize. The plan was to conclude as
much of the work as possible, revert to lower cost basic research, and
pursue a strategy of chemicals from liquefaction. Then in 1986 there
appeared to be a turnaround in commercial interest. Unprecedented
technical achievements started to renew aspirations and industry interest
in exploiting selected market niches for pyrolysis products. The
following is a brief review of current projects.

McGill University

Over the past several years researchers W.J.M. Douglas and D.G.
Cooper at McGill University have been studying an interesting
thermochemical approach to wood liquefaction using aqueous hydrogen iodide
at fairly mild conditions of pressure and temperature (125°C) . Still far
from certain is the exact nature of the liquid products and the
techno-economic practicality of hydrogen iodide recovery and recycle. On
the positive side, in addition to the low severity conditions of reaction,
the process removes about 80% of the oxygen in the wood, and the char
yield is low.

University of Toronto

D.G.B. Boocock and co-workers at the University of Toronto have


undertaken the investigation of steam pyrolysis or hydrothermolysis of
wood. Based on their earlier work, they recently designed and constructed
a laboratory scale cascade autoclave which can accommodate up to 100 g of
wood chips or 170 g of a single larger piece (3.8 cm reactor I.D., 600ml
volume). It is rated at 24.1 MPa (3500 psi.) at 350°C allowing for 7.6
MPa (1100 psi) gas overpressure above the vapour pressure of water at that
temperature. Replicated results indicate that oil yield increases with
increased chip size. Dry product oil yields are high (up to 50%) with no
solids contamination, and the oil is easily separable from the aqueous
phase. Coupled with an upgrading process, this technology may someday
lend itself well to commercialization.

In addition to their process development work, Professor Boocock's


group has contributed greatly to the basic understanding of biomass
liquefaction, especially through their scanning electron microscopic
studies. The group at the University of Toronto is also performing
upgrading studies through the catalytic hydrotreatment of model compounds.
Of potential interest too is their discovery in 1984 that a particular
clone of hybrid poplar yielded 6% phenol. This discovery raises the
prospect of matching processes more closely with specific feedstocks in
the interest of optimizing a particular product slate. Efforts are now
beginning to genetically engineer trees that are designed for specific
process/product applications.
36

Université de Sherbrooke

E. Chornet, R.P. Overend and co-workers at the Université de


Sherbrooke have been working on a liquefaction process in pressurized
solvent for some years. Their approach involves an overall integration of
biomass pretreatment, fractionation, acid processing, thermochemical and
biochemical treatment.

Funding for research at Sherbrooke in the areas of peat and wood


conversion is provided by a number of sources, including Energy, Mines &
Resources. The program there involves a comprehensive variety of
fundamental studies, product engineering and technology development at
laboratory and pilot plant levels. Examples of approaches under
investigation include a thermo-mechanical-chemical treatment to
fractionate and liquefy biomass including steam treatment, thermocatalytic
conversion of fractionated products such as lignin to monomers, ethylene
glycol solvolysis/liquefaction, acid/thermal/shear treatment of biomass
and cellulose, and a variety of biochemical investigations in combination
with thermochemical techniques. In association with other laboratories,
the chemical engineering laboratory of Professor Chornet is especially
well equipped for analytical characterization of products derived from
their various reaction systems.

University of Waterloo

D.S. Scott, J. Piskorz, D. Radlein and co-workers at the University


of Waterloo are well known for their fluidized bed flash pyrolysis
development, also known as the WFPP (Waterloo Fast Pyrolysis Process). A
number of companies and the European Economic Community have indicated
their interest in collaborating with the Waterloo group. The WFPP
actually includes five process options as follows :

1. Direct thermal processing at 450-550°C, atmospheric pressure, and


about 500 ms vapour residence time. They report high liquid yield
(80% including water, based on input wood) that is a suitable fuel for
conventional boilers.

2. By varying the process conditions and adopting a mild sulphuric acid


pretreatment of wood followed by fluidized bed thermopyrolysis, the
WFPP produces a high yield and concentration of anhydro-sugars rather
than oil products. Their reproducible yields of sugars from pure
cellulose are about 80% of theoretical in a concentrated form. One
can easily speculate whether this development could challenge some of
the equally exciting biochemical conversion methode of converting
lignocellulosics to fermentable sugars.

3. Waterloo's hydrogasification work has been technically highly


successful, resulting in 75% conversion of wood carbon to methane via
pyrolysis over a nickel-alumina catalyst with hydrogen at about 550°C
and 440 ms vapour residence time.

4. Under current investigation is a fourth process option of producing


polyolefins from wood in a catalyzed reaction. Apart from the use of
catalysts, the process equipment and operating conditions are very
similar for all of the above process options.
37

5. The Waterloo group is also performing upgrading research by


catalyticly hydrotreating pyrolysis oil fractions, especially lignin,
in a continuous pressurized reactor.

University of Western Ontario

Although not currently funded by Energy, Mines & Resources, M.


Bergougnou, R. Graham and co-workers have developed an Ultra-Rapid
Pyrolysis or Ultrapyrolysis process at the University of Western Ontario.
Although there are similarities in this work and the research at the
University of Waterloo, there are important differences. Whereas the
Waterloo process utilizes fluidized-bed heat transfer. Professor
Bergougnou employees a very rapid (30ms) mixing and heat transfer in a
vortical contactor or vortactor followed by a plug-flow entrained-bed down
flow reactor (50-900ms) and quenching (30ms) with cryogenic nitrogen in a
cryovortactor. Dissimilar to the Waterloo process are the process
conditions (650-1000°C, 50-900 ms residence time), and the main product at
these temperatures is gas rather than liquid. Since pyrolytic fuel gas
production has not been of high priority in Canada's bioenergy RSD
strategy, the current objective, in collaboration with Ensyn Engineering,
(see below) is the production of chemicals and, in particular olefins.

It is interesting to note here that the Universities of Waterloo and


Western Ontario conducted an extensive data comparison from each of their
reactor systems. Using selected data from both groups at around 500 ms
residence time, liquid and gas production data were plotted vs
temperature. The temperature ranges were as follows: Waterloo at
400°-750°C, and Western Ontario at 650°-900°C. With combined data for
each of the gas yield vs temperature and liquid yield vs temperature
respectively there was remarkable agreement of data in overlapping
regions. A simple first order kinetic model is able to describe the oil
yield over the temperature range of both experiments.

Ensyn Engineering

Ensyn Engineering is a recently formed company whose principal


investigator, R. Graham has scaled up the University of Western Ontario
Ultrapyrolysis reactor by a factor of 20 to a 5-10 kg/hr capacity RTP
(Rapid Thermal Processor). The reactor is designed to accept any
carbonaceous feed (solid, liquid, or gas) by injecting it into a turbulent
cloud of hot solids. The mixed feed plus solids is carried through a
tubular transport reactor to an inerţial separator where vapour products
are removed. This project is co-sponsored by the private sector.

Work planned for 1989 involves thermal cracking and catalytic


treatment of pyrolysis oils and various lignin preparations including
steam exploded biomass derived lignin.

Laval University

Multi-stage vacuum pyrolysis was developed by C. Roy and co-workers,


initially at the Université de Sherbrooke and, currently, at the
Université Laval. The technology consists of a 40 kg/hr multiple hearth
vacuum pyrolysis process development unit located near the Université
Laval. There is aleo an industrial cost-shared pilot demonstration of a
38

single-stage process at St-Amable, Quebec. The unit has a capacity of


200 kg/hr and is designed for used tires.

Although the multiple hearth concept suffers from low heat transfer
relative to other pyrolysis processes, and, at first glance, is capital
cost intensive, it has a number of redeeming features that show commercial
promise as follows:

1. A high yield of pyrolysis oil (50% based on wood).


2. The production of co-product carboxylic acids and high value
chemicals.
3. Reactive charcoal at 25% of input wood.
4. The aqueous phase is recovered separately as vapour or liquid as an
integral part of the process leaving a low water content water-free
pyrolysis oil ready for upgrading.
5. The multiple hearth performs a product fractionation function that
could reduce extraction costs of high value chemicals.

Centralized Analysis

One final work of interest in Canada is a Centralized Analysis project


at B.C. Research. In 1984, a trial project was set-up whereby different
Canadian bio-oils could be compared in a standard manner. The project
embraced a three-pronged approach. Under the guidance of J. Howard and J.
McKinley, B.C. Research performed and/or coordinated the centralized
analyses of optimized oils produced by each researcher. Individual
researchers also did some of their own analyses to obtain immediate
experimental feedback.

The second prong of the approach was that all researchers were
provided with a standard wood sample, Populus deltoides, by Forintek
Canada Corp. The idea was that when each process development became
somewhat optimized, the researcher would submit oil from the standard wood
sample to the centralized analysis team.

The third prong was a computer communications network link called


CoSy, through the University of Guelph, to provide fast communication of
analytical data. It was also used to encourage multilateral and bilateral
collaboration and problem solving.

The centralized analysis project has entered Phase II. Learning from
the successes and pitfalls of the first two and one half years, the scope
of this project has changed somewhat. Phase II has two major tasks.

Task 1 is a set of analytical techniques along the same lines as the


initial project except the methods that were considered to be less
interesting to the entire group are not included. The basic analyses of
task 1 include the following:

- Elemental Analysis
Water Content
Density
Carboxylic Acids
Gas Liquid Chromatography
Carbon-13 NMR
Gel Permeation Chromatography
39

Task 2 consists largely of special analytical projects to meet the


special needs of individual researchers, Energy, Mines and Resources
Bioenergy Development Program or groups of thermochemical conversion
researchers that may arise over the next two years.

4. INTERNATIONAL VIEW - IEA

Under the International Energy Agency, eleven countries signed a three


year Bioenergy Agreement on Cooperative R&D, effective January 1, 1986 to
December 31, 1988. This Agreement has since been extended by another
three years. Canada, USA, Sweden and Finland agreed to collaborate on a
project entitled Direct Biomass Liquefaction (DBL). A Working Group of
engineers and other specialists are preparing a detailed
technical-economic assessment (TEA) at commercial size scale-up and
operation of the most promising high and low pressure
pyrolysis/liquefaction processes. Both primary oil production and
upgrading are considered in the TEA. The upgrading work on Canadian
atmospheric and vacuum pyrolysis oils has been conducted by D. Elliot at
Battelle Pacific Northwest Laboratories. Yields of products in the
gasoline boiling range have so far reached 35% of primary oil by
hydrotreating. The Working Group is attempting two types of analyses, one
based on current state of the art and the second based on projected
improvements and developments in the technologies.

ACKNOWLEDGEMENTS

The author wishes to acknowledge the various researchers in North


America without whose ideas, open discussion, and dedication to research
in thermochemical conversion of biomass, this paper would not have been
possible. Each has contributed to this paper, either directly or
indirectly. The following list is not complete, but includes the
principal investigators in Canadian laboratories and other notable
international collaborators. In alphabetical order, many thanks to
Narendra Bakhshi, Dave Beckman, Dave Boocock, Jean Bouchard, Maurice
Bergougnou, Michel Bertrand, Esteban Chornet, Maurice Charron, Helena
Chum, Jim Diebold, Allan Dolenko, Murray Douglas, Guy Drouin, Dick Eager,
Doug Elliot, Bob Graham, guy Gravel, Michele Heitz, Ed Hogan, John Howard,
Serge Kaliaguine, Björn Kjellstrom, Bill Lowe, Tom Milne, Hugh Menard, Jim
McKinley, Ralph Overend, Hooshang Pakdel, Jim Pepper, Jan Piskorz, Desmond
Radlein, Tom Reed, Joe Robert, Christian Roy, Tom Tidwell, Don Scott, and
their many colleagues, staff, and students.

REFERENCES

This paper contains technical contributions including progress reports


from all the Canadian and other workers mentioned here. The reader is
referred to these individuals or their published papers as primary
references.

1. Brundtland, Gro Harlem. 1987 "Our Common Future". World Commission


on Environment and Development.
40

RAPPORTEURS REPORT ON SESSION I


OPENING SESSION AND COUNTRY OVERVIEWS

C.H. NELS
Federal Office for the Environment, Berlin

The following report covers the first session of the conference.


The papers delivered during this session dealt mainly with :

Activities and results of the demonstration program of the Commission


in the areas of gasification and pyrolysis as well as European
activities planned for the future.
International research and development in this area presented by the
United States, Canada and Japan.

Because of time constraints follow-up discussion was limited to the EC


papers. Topics included details for the forthcoming planned EC research
program, how technologies already proven in laboratory and bench scale could
be transferred/tested in the field, how many test plants currently exist in
the EC and when results will be ready for general use. Special interest was
given to problems of developing countries. Issues included how demands of
developing countries could be taken into consideration in future RSD
programs and whether direct or indirect help could be given by the EC to
strengthen their own efforts in this area. Environmentally related issues
were also discussed dealing with critical emissions caused by extended
agricultural production of biomass, its thermal or chemical conversion and
finally the question of its potential for use as a fuel or raw material.
The papers as well as the subsequent discussion led to the following
conclusions :

Any future research commitment should have long term orientation.


Since funding resources are limited research should be directed toward
those types of biomass "crops" which are most widely applicable.
Alongside biomass research there should always be an environmental
impact assessment.
Because of the global nature of the problem there are numerous biomass
research programs underway internationally. To avoid duplication and
enhance information transfer more conferences such as this one should
be organized to coordinate international efforts.
Efforts in international cooperation should begin at the earliest
stage while planning research programs such as that currently underway
in the EC.
Such exchanges also provide the missing link to developing countries
giving them vital information; the importance of such exchanges should
be recognized.
SESSION II

PRE-TREATMENT AND CHARACTERIZATION


43

PRETREATMENT AND CHARACTERIZATION OF FEEDSTOCKS


C Ρ MITCHELL and A V BRIDGWATER
Forestry Department Chemical Engineering Department
Aberdeen University Aston University
Aberdeen AB9 2UD Birmingham B4 7ET
UK UK
SUMMARY
Feedstocks generally considered for thermochemical conversion are wood and wood
waste, energy crops, agricultural waste and refuse. The main technical criteria for
suitability for thermochemical processing is low moisture content, and ash content and
characteristics. The main economic criteria are cost which includes production,
collection and transport, and quantity which includes availability. Wood will be
available from processing residues, unmanaged woodlands, conventional forestry and
short rotation forest biomass plantations. Harvesting, processing and transport
systems for delivering wood fuel either already exist or are under development.
Delivered fuel costs will be between £28 - £36/dt from conventional forestry and in the
order of £41/dt from short rotation.

Agricultural wastes, such as cereal straw, can be delivered to the end-user for £22/dryt.
Domestic and commercial refuse is widely available and can attract disposal credits of
£10 - £20/wet t which has a significant effect on the conversion economics.

1 INTRODUCTION
Feedstocks generally considered for thermochemical conversion are wood and wood
waste, energy crops such as short rotation forestry and sweet sorghum, agricultural waste and
refuse (1). The main technical criteria for suitability for thermochemical processing are low
moisture content, and ash content and characteristics. The main economic criteria are cost
which includes production, collection and transport, and quantity which includes availability.
There is also the question of competing uses such as pulp and board manufacture, combustion,
recycling or material recovery rather than energy recovery.
2 FEEDSTOC K S
2.1 Wood
Wood will be potentially available as a feedstock from residues generated within the
wood processing industries, presently unmanaged woodland, conventional forestry and from
plantations specifically grown to produce raw material for the biomass industries.
Processing Residues
Residues are generated within the forest products industry itself. Processing residues
are produced primarily in sawmills; these consist of slabs and blocks of wood, chips and
sawdust. However, with the increasing demand for raw material in the pulp and board mills
much of these residues go to these industries and are therefore unlikely to be available in large
quantities to the energy industry.
Unmanaged Woodland
There are several million hectares of woodland within Europe which is currently not
managed and which could be brought into production for biomass. In France and Italy alone
there are some 5 million hectares of overmature coppice. The maquis systems in the
mediterranean region and several other categories of natural vegetation offer good prospects to
be brought into management for biomass production (2). In the UK, the potential for
production of fuelwood from presently unmanaged woodlands is around 0.15 million wet t/y
(3).
44

Conventional Forestry
Conventional forestry practice gives several opportunities for harvesting wood for fuel.
Firstly, under current harvesting practice only the merchantable stemwood is removed from the
forest. The tops and branches, roots and stumps are left in the forest. The roots and stumps
can be harvested but it is a costly operation and there are potentially severe environmental
problems which limit their use. However, the tops and branches, so-called forest residues are
available for harvest. Secondly, early thinnings can be harvested using whole tree harvesting
techniques. A third opportunity lies in adapting harvesting systems to remove both the
stemwood and the "energy component" at the same time. These integrated harvesting systems
are attracting a great deal of interest world-wide because the overall harvesting system costs are
reduced.
Modified conventional forestry management systems involve planting trees closer
together initially, taking heavy early thinnings using whole tree harvesting techniques, and
using integrated harvesting systems for later thinnings and clearfell.
For the UK alone by the year 2020 the total annual sustainable production of fuelwood
from conventional forestry could amount to some 4.8 million wet tonnes. In the longer term
modified conventional forestry could provide an additional 8 million wet tonnes per year (4).
Short Rotation Forest Biomass Plantations
Woody biomass can be purpose grown for energy in short rotation coppice biomass
plantations. These are intensively cultivated plantations using fast growing broadleaved trees
which coppice readily and are harvested every 3 to 5 years. The main species used are from
the genera Eucalyptus, Populus (Poplars) and Salix (Willows). Growth rates are high
giving productivities of around 10 to 15 dry tonnes per hectare and year (dt/ha/y) in commercial
operations. Coppice crops need to be grown on good fertile soils. Within Europe the
agricultural surpluses problem coupled with the revision of the CAP is leading to land being set
aside from agricultural production. Such land is well placed for coppice plantations. Of the 40
million hectares of land coming out of production in the CEC some 5 million hectares has been
conjectured to be available for energy plantations (2). In the UK, it has been estimated that if
0.82 million hectares of land currently in agricultural production were to change to short
rotation forestry then this would give an annual production of some 2.72 million wet tonnes
(4).

2.1.1 Harvesting of Wood Fuel


Conventional Forestry
The actual harvesting system chosen for conventional forestry is heavily dependent on
the crop, species, size, terrain and the requirements of the end-user. Most current harvesting
systems operating in Europe are designed to supply raw material to the pulp, board industries
and sawmills. Harvesting systems can be categorised into one and two pass systems. One
pass systems are applicable to whole tree operations in either integrated or whole tree
comminution, and two pass systems to residue collection and comminution following
conventional methods for harvesting the stem wood. The harvesting options available are
shown in Figure 1.
Two pass residue harvesting systems are perhaps those that are the most appropriate
with short wood harvesting systems. The residues can either be chipped in the stand with
mobile machines (terrain chipping) or the residues are collected and extracted to a central point
for chipping (landing chipping). Terrain chipping is appropriate to the dryer load bearing
mineral soils and landing chipping to the wetter organic soils.
Yields of fuel chips from terrain chipping will reflect the predominance of pine species
and are likely to be in the lower end of the range 50-100 wet tonnes per hectare (wt/ha).
Production costs for terrain chipping are in the range of £10 - £15/wet L
Yields of fuel chips from landing chipping systems reflect the higher potential of spruce
crops and are likely to be in the lower half of a range from 100 - 200 wet tonnes per hectare.
Production costs for extraction of residues to landing are estimated to be in the region of £3.00/
wet t and chipping costs in the region of £7.00/wet t
Whole tree comminution systems are appropriate to smaller tree sizes, either in early
thinnings or premature clearfell situations where the tree stem size is insufficient to warrant
45

conventional utilization or in clearance or cleaning operations in hardwoods. Chipping can take


place either at landing or at the stump (terrain chipping) and the choice of systems will be a
factor primarily of the suitability of the terrain and extraction distance.
In landing chipping systems the whole trees are extracted to landing. In the smaller
tree sizes appropriate to whole tree chipping, the use of forwarder extraction of whole trees or
tree sections, is favoured to reduce extraction costs. Whole tree chipping at landing requires the
use of larger chippers with infeeds capable of handling and feeding the whole tree by grapple.
Terrain chipping can be used where the ground conditions permit. Small scale
equipment such as small tractor mounted chippers can be used. A self propelled chipper and an
infeed at the front fed by a grapple crane can be used in line thinning operations with the chips
blown over the chipper into a chip bin at the rear.
Yields of fuel chips from whole tree comminution systems has been found to be in the
region of an additional 50 -100% expressed as a percentage of stem wood. Production costs
for fuel chips from whole tree comminution systems will vary on the scale of the operation,
and as for integrated systems, on the tree size and the terrain. Landing chipping costs will be
around £4.80/ wet t and £5.60/ wet t for terrain chipping.
In integrated harvesting systems the whole tree is extracted to landing for processing
and product separation. Landing processing, involving delimbing and crosscutting, can be a
manual system with the use of chain saws, or be partly or fully mechanised, the availability of
equipment and landing size being the factors taken into consideration when deciding the
method to be adopted. The residue material on the landing can be chipped in a continuous (hot)
system closely following the processing, or, can be allowed to accumulate on the landing for
chipping in a separate process (a cold system). The chipping equipment used will be primarily
decided by the scale of operation, the use of hand fed tractor mounted chippers will be
appropriate to only the smaller operations. Given a sufficient scale of operation, the use of
trailer mounted chippers feeding with a grapple crane will give higher outputs, particularly in
working a cold system where there are no limiting factors in the processing line. The chipped
material can be accumulated on the landing for later loading on to road transport, or, more
commonly the chips can be blown directly into containers or lorry trailers for road transport.
Yield of fuel chips from integrated harvesting systems has been found to be in the
region of an additional 30% expressed as a percentage of stem wood. Production costs for fuel
chips from integrated harvesting operations vary considerably with tree size, terrain and the
harvesting system used. On the assumption that integrated systems can produce the traditional
assortments as efficiently as comparable shortwood systems, the cost of fuel chips will reflect
the "free ride" that they get to landing. The cost of production then amounts to the chipping
element which can be as low as £5.10/wet tonne.
Short rotation forestry
Current harvesting technology for short rotation crops is limited. The two coppice
harvesters currently working are both prototypes; there are no machines commercially
available. The principle on which these machines work is for the coppice to be severed by
circular saw(s) and the cut coppice rods tied together in bundles before being ejected from the
machine. The Loughry coppice harvester produces 300 kg (wet) bundles, the Swedish
machine 2.5 wet tonne bundles. The rationale for this approach is to produce bundles which
can be left in the field to dry. Coppice willows and poplars are around 55% moisture content
(wet basis) at harvest. By stacking the bundles of cut material in the open or with a tarpaulin
cover there will be some natural drying. Once stored for 3 months or so the moisture content
will drop to around 40% and the bundles are then chipped.

2.1.2 Transport of Wood Fuel


The transport system of the raw material to the conversion plant is of utmost
importance. In many respects it is no different from any other wood delivery system to the pulp
and board industries which are designed to handle chips. In addition, delivery and reception
systems have been developed in Sweden for handling wood fuels to the mill and district
heating plants (5).
Converted pulp wagons, containers, tippers and curtainsiders can all be used for
transporting wood fuel. Converted pulp wagons show the most potential for use in the present
UK situation ie with a small wood fuel market and existing road transport legislation. These
46

allow self loading and unloading, a wide range of available loads and the ability to revert to
conventional pulp haulage.
Container systems are used in the UK for several commercial operations. Tippers and
curtainsiders showed potential for use in the future when demand for industrial fuelwood will
be high allowing full utilisation of independent loaders. It is not feasible to use lorry transport
of whole trees and forest residues over long distances without compaction equipment.
Transport costs amount to some £0.07/wet tonne/km.
2.1.3 Storage of Wood Fuel
Storage of wood fuel will be necessary to bridge the gap between supply and demand
with due allowance made for the time required for drying and pretreatment. The storage can be
done in the open, under cover to protect it from rain or an enclosed space such as silos and live
bottomed bins which have to be linked to the gasifier feeding system. The type of storage is
strongly influenced by scale of operation and climatic factors. The most common type of wood
fuel is chipped wood.
If storage is required then it has to be carefully considered. Whole tree chips, due to
their high moisture content and foliage content, decompose rapidly (1 - 5% per month) during
storage. Such materials also present a fire risk because of heating during decomposition. A
further problem associated with the storage of wood fuels in enclosed spaces is the
development of microfungi the spores of which represent a serious health hazard (6). From
experimental experience, drying during storage will give a moisture change from a delivered
55% to an outgoing 40%. Costs of storage have been calculated to be of the order of £5/wet
tonne (7) (Table 1).

2.1.4 Drying of Wood Fuel


Flash pyrolysis requires a feedstock at <5% moisture content and gasification <15%
but there is an optimisation to be carried out between moisture content and conversion
efficiency. The actual moisture content required for the conversion process will therefore vary
somewhat between conversion facilities. Biomass as received will have a moisture content
typically in the range 50 - 60% (wet basis).
Passive drying during summer storage can reduce this to perhaps 30%. Active silo
drying can reduce the moisture content down to 12% (8). Drying can be accomplished either
by very simple means such as near ambient/solar drying or by waste heat flows or by
specifically designed dryers operating on solid or hydrocarbon fuels. The selection of the most
appropriate system depends on the location, climate, level of sophistication required and scale
of operations. Commercial dryers are available in many forms and sizes but the most common
are the rotary kilns and shallow fluidized bed dryers.

2.1.5 Costs of Supply of Wood Fuel


The costs of supply of wood for fuel have been examined for UK conditions (3, 9).
Short rotation coppice crops biomass can be grown on a four year cutting cycle, harvested,
stored, chipped and delivered to the end-user at a cost of £40.83/ dry t (Table 1) for a farmer
operated system. In such a system the farmer carries out all the operations to do with growing
and tending the crop and uses contractors to carry out the harvesting and chipping operations
much as he may use contractors for other specialist farming operations.
Calculation of the costs of harvesting wood for fuel from conventional forestry is not
so simple as there are are conventional forest products produced along with the fuelwood
assortment. The costs of supply of wood fuel from forestry and the contribution of the
elements in the chain are illustrated for a number of options in Figure 1 and for the optimal
systems in Table 1. Delivered costs of wood fuel at 40% moisture content range from £28.17/
dry t for integrated harvesting systems in clearfell to £36.33/ dry t for a whole tree chipping
operation in an early thinning. Forest residue chips can be delivered for £34.33/ dry L
47

S H O R T ROTATION F O R E S T R Y SYSTEM
Stumpage (3.60) COST

FELL/BUNDLE ÏXTRACT CHIP TRANSPORT STORAGE


(2.60] ~* (4.70)
- 24.50
(6.70) (2.10) (6.00)

RESIDUES
Stumpage (1.00)

COLLECT EXTRACT CHIP TRANSPORT STORAGE


(3.30) (6.30) (4.70) (6.30)

CHIP TRANSPORT STORAGE


(10.30) (4.70) (6.40) 21.40

WHOLE TREE CHIPPING


Stumpage (6.00)

FELL/BUNCH EXTRACT CHIP TRANSPORT STORAGE


(1.60) (4.30) (4.80) (4.70) (6.60)

TERRAIN \ CHIP TRANSPORT STORAGE


(6.60) (4.70) (6.00)

INTEGRATED (THINNING)
Stumpage - residue» (1.00)

FELL EXTRACT_ PROCESS^ ROUNDWOOD


(1.20) (3.30)

CHIP T R A N S P O R 1 _ STORAGE
(6.10) (4.70) (6.30) 20.60

INTEGRATED (CLEARFELL)
Stumpage - realduea (1.00)

FELL EXTRACT PROCESS^ ROUNDWOOD


(0.10) (1.10)

CHIP TRANSPORT. STORAGE


(6.10) (4.70) (4.90) 16.90

Figure 1 Harvesting supply options and costs ( £ / w t ) .


48

Table 1 Total Cost of Wood Fuel,


ŞRF Residues Whole Integrated
tree chip clearfell
£/wett £/wett £/wett £/wett
Stumpage* 3.50 1.00 5.00 1.00
Felling 6.70 1.50 0.10
Extraction 2.10 1.10
Comminution 2.50 10.30 5.60 5.10
Transport 4.70 4.70 4.70 4.70
Storage 5.00 5.30 5.00 4.90
Total £/wet t 24.50 20.60 21.80 16.90
£/dryt 40.83 34.33 36.33 28.17
* raw material cost at stump
Assumptions: 1 Moisture content of 55% (wet basis)
2. Transport distance of 70 km one-•way
3 Covered storage at end user, moisture content reduction to 40%
4 Integrated systems costed on the residue component only.
5 Particle size of chips 5-35 mm.

3 AGRICULTURAL WASTE
Considerable quantities of agricultural waste, such as straw, bagasse, corn cobs, and
rice hulls, arise in agriculturally based economies where there may be no ready market for solid
fuels. In many cases this material is free and may even have a credit or negative cost of up to
£-20/t because of the cost of disposal if it cannot be used. Particular features of agricultural
waste are that is is often already collected at one site and has often been subjected to extensive
pretreatment such as size reduction and drying. There will also usually be some storage and
material handling facilities. In addition such waste often creates a disposal problem with an
asociated cost. F or all these reasons, agricultural waste can be a very attractive feedstock for
conversion and upgrading, since the costs are low or even negative, i.e. attract a disposal
credit, and disposal problems can be solved. A summary of a variety of waste arisings in
several countries in Europe in given in Table 2.
In the UK, about 7 million t/y of surplus straw arise for which no ready market is
available, out of a total arising of about 14 million t/y. Comparable figures pertain to Europe.
Prices vary by location from £5 to £50/t, but representative costs have been estimated at about
£17/t on-site or £22/t delivered [10].
The wide variety of materials suitable for processing precludes consideration of each
individually, and the range is indicated in Table 3.
4 REFUSE
4.1 Resources
Considerable quantities of domestic and commercial refuse are produced from any
society which require disposal at a significant cost. Processes that utilise this waste, therefore,
can often justify a credit from the disposal authority, as a result of saving the disposal cost.
Raw waste attracts the highest credit but requires the most preparation. There is again the
advantage of "free" collection as with agricultural wastes. The largest arisings of waste that
also attract the greatest disposal credit often occur close to the potential market for the energy
products. Estimated arisings for Europe are shown in Table 4.
49

Table 2 Estimated overall national arisings of potential energy from


principal agricultural residues, 1979 (11)
(millions of GJ/year unless otherwise stated)
Cereal. Livestock Green Plant Total Total in
Maize & Rice Wastes Matter Mtoe
Residues fa) ibi
Belgium & Luxemburg 27.1 27.3 12.3 66.7 1.52
Denmark 98.7 29.2 6.4 134.3 3.05
France 556.6 171.2 59.3 787.1 17.89
Italy 233.7 81.7 37.3 352.7 8.02
Holland 16.4 45.6 17.7 79.7 1.81
Ireland 21.9 38.1 3.3 63.3 1.44
UK 191.4 99.2 20.7 311.3 7.08
West Germany 327.1 129.7 40.0 496.8 11.29
1 472.9 662.0 197.0 2 291.9 52.10
Notes
(a) Presented as biogas available from pig, cattle and poultry by anaerobic digestion,
not as gross energy, animal bedding excluded.
(b) Presented as biogas availabe by anaerobic digestion: other conversion routes are
available. No data are available for Greece, Spain and Portugal.

Table 3 Agricultural Wastes that have been Thermochemically


Processed
Alfalfa straw Almond shells Bagasse Bamboo
Barley straw Bark Brazil nut husks Cocoa husks
Coconut husk Coconut shells Coffee grounds Cotton gin trash
Cotton gin stalks Flax Ground nut shells Maize cobs
Olive pits Paper Peach pits Prune pits
Rice hulls Safflower straw Straw Sunflower husks
Tobacco dust Vegetable fibre Walnut shells

Table 4 Estimated Arisings of Wastes in the EEC in 1982 (12)


Component million tonnes/year
Household waste 120
Agricultural waste 950
Industrial waste 160
Sewage sludge 300
Waste from extractive industries 250
Demolition waste and debris 170
Consumer waste (used vehicles, tyres, etc.) 120

Some thermochemical processes have been devised that accept whole raw waste with
minimum pretreatment, such as the now abandoned Purox and Andco-Torrax processes.
Current thinking, however, is that some separation of inerts and pre-processing is necessary
for reliability and control in handling, feeding and conversion. Pretreatment of refuse to
50

produce a material acceptable for conversion would follow conventional refuse sorting
technologies, employing screening, shredding and classification. The products can range from
"fluff' (loose, low density material) through "crumb" (ie partially densified material) to pellets.
There are many proprietary systems on the market that have been proven for production of
refuse derived fuels.
Domestic refuse
In the UK, about 18 million t/y of domestic refuse are produced with a heating value of
about 9 GJ/t, and containing about 11 million t/y of combustibles, ie about 300 kg/head/y of
raw refuse or 150 kg/head/y daf waste. The average cost of disposal in the UK is claimed to
be about £6/t but these are believed to be very conservative with average costs of disposal
nearer £12/t, over a range of £5/t to as high as £40/t (13). In Europe, disposal costs are much
higher by a factor of up to 5, with typical figures at around £30/t. In some parts of the world,
disposal costs can exceed £70/t raw refuse. These figures will have a significant effect on
conversion economics if translated into credits. Further details of costs are given below.

Commercial refuse
In the UK, arisings of commercial solid waste have been estimated as 8 million t/y (dry
basis) with a heating value of around 16 GJ/t (dry basis) ie about 130 kg/head/y. The material
is generally cleaner and drier than domestic refuse with a higher proportion of packaging ie
paper, plastics, wood, etc. This is mostly handled by the private sector with a paucity of data
on quantity, quality and cost.
Industrial refuse
In the UK, combustible waste arisings from the UK industrial sector have been
estimated at 9 million t/y (dry basis) with a heating value of 16 GJ/t (dry basis), i.e. about 150
kg/head/y. This is also mostly handled by the private sector with a paucity of data on quantity,
quality and cost.
Other Wastes
Sewage sludge is another resource that is being investigated for thermochemical
processing. In the UK, sludge is generated at the rate of about 25 kg dry solids/head/y. A
disposal credit of up to £50/dry t is potentially available.
4.2 Refuse Processing
Most refuse processing or pretreatment processes are based on refuse separation for
RDF production in which the raw material is shredded to reduce particle size, screened to
separate inerts such as dust and glass, demetalled to remove cans, and classified as a refining
stage, giving a wet low bulk density (fluff) RDF product, although the sequence of these steps
can vary. The fluff can be dried, or pelleted then dried, and an intermediate step in the
production of pellets is a partially densified and dried material known as crumb. Each of these
operations has a cost associated with it which includes all capital and operating costs. This
permits the total cost of production of any RDF product to be estimated as shown below.
There will invariably be a residue after recovery of the fuel product which consists of nonfuel
materials and inerts, and which will have a much higher bulk density than the raw refuse. This
residue would normally be landfilled, and since the bulk density is so much higher, the cost of
this operation would be expected to be significantly less than for raw refuse due to the reduced
transport and handling costs.

4.3 Costs of Refuse Processing


The total cost of the unit operations encountered in refuse processing is summarised in
Table 5. Figure 2 shows a processing flowsheet and mass balance for various levels of
separation from which the cost of refuse derived fuels has been estimated in Table 6.
Refuse is normally disposed by landfill or incineration at a cost that reflects the
economic, social and environmental constraints. Disposal of residue, as explained above,
would be expected to be less than the disposal of raw refuse as costs are usually based on
51

volume rather than weight. It has been assumed that the disposal cost of the residue after
processing is half therawrefuse disposal cost.
From the methodology employed in the example in Tables 5 and 6, a general cost
model has been derived in Table 7 for the estimation of fuel costs for any raw refuse disposal
cost/disposal credit. This has been applied for a range of disposal credits in Table 8 to estimate
fuel costs at various levels of disposal cost/credit. This data is used in another paper at this
conference to estimate fuel gas and fuel oil costs from gasification and pyrolysis processes
(14).

Table 5 Cost of Refuse Processing Operations


Basis
Disposal cost £10/t raw refuse assumed
Operations
Shredding £2.75/t raw refuse
Demetalling £2/t raw refuse (self financing)
Screening £2.75/t raw refuse
Air classification £1.5/t raw refuse
Disposal of residue £2.75/t raw refuse (50% disposal cost of raw refuse)
Drying -fluffor pellets £3/t raw refuse or £10/t product fuel
Pelleting £3/t raw refuse or £10/t pellets

Table 6 Cost of Refuse Derived Fuel Products


A Gross
The gross cost of products are as follows:
Wet "fluff' RDF (25% water) £9.75/t raw refuse or £24.40/t product
assuming 40% yield of fuel
product (with demetalling being
self-financing)
Dry "fluff' RDF (10% water) £12.75/t raw refuse or £37.50/t product
assuming 34% yield of fuel
product (with demetalling being
self-financing)
Pelleted RDF (10% water) £15.75/t raw refuse or £46.30/t dried pellets
Β Nett
A disposal credit may be set against these costs, of, for example, £10/t raw refuse as used
above. This gives the following net costs:
Wet "fluff' RDF (25% water) -£0.25/t raw refuse or -£0.60/t product
Dry "fluff (10% water) £2.75/t raw refuse or £8.10/t product
Pelleted RDF (10% water) £5.75/t raw refuse or £16.90/t dried pellets.
52

Raw refuse
d.a.f. RDF 0.25 te
ash 0.05 te
water
waste, d.a.f.
mme
0.34 te
ash 0.07 te
water 0-14 te
metal, d.a.f. 0.05 te
Total 1.00te

I
Shredding " " " £2.75 Metals 0.05 te Credit £2.00
Demetalling £2.00
Screening £2.75
Air classification £1.50
Total £9.00 Waste 0.55 te Disposal£0.275 D

Wet "fluff"
τ RDF
d.a.f. RDF 0.25 te
ash 0.05 te
H20 0.10te
Total 0.40 te
JL
Drying £3.00 H20 0.06 te To atmosphere

ι
Dry "fluff' RDF
d.a.f. RDF 0.25 te
ash 0.05 te
H20 0.04 te
Total 0.34 te^
Έ
Pelletising £3.00

Σ
Pelleted RDF
d.a.f. RDF 0.25 te
ash 0.05 te
H20 0.04 te
Total 0.34 te

Note: Raw refuse disposal cost = £ D / te


Processed refuse disposal cost = £ 0.5 / te
Figure 2 Refuse Processing Flowsheet, Mass Balance and Build-up of
Cost
53

Table 7 Product Cost as a Function of Disposal Cost


Example of build-up of processing costs.
Basis
Wet "fluff RDF (see Figure 2)
Assumptions
Assume disposal cost = £ D / te.
Assume disposal cost of residue after processing is half disposal credit value, as bulk density is
much higher thus reducing transport and handling costs, = £ 0.5 D/te
Cost Model £
Cost of shredding, demetalling, screeening and air classification (Table 5) +9.00
Cost of waste disposal, 0.55 * 0.5 D +0.275 D
Credit from sale of metal -2.00
Disposal credit -D
Total cost per tonne of raw refuse 7.0 - 0.725 D
Cost per tonne of wet "fluff' RDF (7.0-0.725D)/0.4 17.5- 1.81 D
Cost per tonne of wet "fluff RDF, d.a.f. basis (7.0 - 0.725D) / 0.25 28.0 - 2.9 D
Cost of RDF
£/te raw refuse £/te product £/te product
daf basis
Wet "fluff RDF 7.0 - 0.725 D 17.5- 1.81 D 28.0 - 2.9 D
Dry "fluff RDF 10.0 - 0.725 D 29.4-2.13 D 40.0 - 2.9 D
Pelleted RDF 13.0 - 0.725 D 38.2-2.13 D 52.0 - 2.9 D

Table 8 Product Cost for Various Disposal Options


Costs derived from cost model in Table 7
Product Disposal Cost per tonne Cost per tonne Cost per tonne
credit raw refuse product d.a.f. product
Wet "fluff RDF 5 3.38 8.45 13.50
10 -0.25 -0.60 -1.00
15 -3.88 -9.63 -15.50
20 -7.50 -18.70 -30.00
Dry "fluff RDF 5 6.38 18.75 25.50
10 2.75 8.10 11.00
15 -0.88 -2.55 -3.50
20 -4.50 -13.20 -18.00
Pelleted RDF 5 9.38 27.55 37.50
10 5.75 16.90 23.00
15 2.13 6.25 8.50
20 -1.50 -4.40 -6.00
Note: All costs and credits are expressed as £/tonne
54

CHARACTERISTICS
The basic characteristics of biomass are summarised in Tables 9 and 10. Particular features
are the fairly high moisture content, low bulk density and wide particle size range.

Table 9 Typical Properties of Biomass


Forest Processing Whole SRF MŞW Straw
residues residues trees (fluff)
Moisture content 30-60% 20-60% 40-60% 40-60% 15-40% 10-20%
(wet basis)
Mean particle size 5x20 5x2C1 5x20 5x20 50 5x200
(mm)
Size range 2-150 2-75 2-100 2-50 up to 500 5-1000
(mm)
Bulk density 300 350 300 350 100 200
(wet kg/m3)

Table 10 Analyses of Feedstocks


Ultimate analysis Moisture
Mass %. drv basis %,
Feedstock C H 0 Ν S Ash wet basis
Douglas Fir 52.3 6.3 40.5 0.1 0.0 0.8 30-60
Beech 51.6 6.3 41.5 0.0 0.0 0.6 30-60
Douglas Fir bark 56.2 5.9 36.7 0.0 0.0 1.2 25-75
Wood shavings 16-40
Sawdust 25-40
Sander dust 2-8
Charcoal 80.3 3.1 11.3 0.2 0.0 3.4
Paper 43.4 5.8 44.3 0.3 0.2 6.0
Rice hulls 38.5 5.7 39.8 0.5 0.0 15.5
Straw 48.1 5.9 40.2 1.0 0.1 4.7 16-20
Refuse (UK) 30.7 4.2 20.5 0.3 0.5 43.8 § 20-35
Municipal solid waste (USA) 33.5 4.6 22.4 0.7 0.4 38.4 § 15-30
For comparison
Peat 58.4 5.4 26.0 - 0.5 9.7
Lignite 68.4 5.8 17.8 - 0.4 7.6
Bituminous coal 73.1 5.5 8.7 - 1.2 11.5
Notes § Ash includes metals, glass etc.

6 CONCLUSIONS
Wood, municipal solid waste and agricultural residues are all potential feedstocks.
Wood will be available from processing residues, unmanaged woodlands, conventional
forestry and short rotation forest biomass plantations. Harvesting, processing and transport
systems for delivering wood fuel either already exist or are under development. Delivered fuel
costs will be between £28 - 36/ dry t from conventional forestry and in the order of £41/ dry t
55

from short rotation. Agricultural wastes, such as cereal straw, can be delivered to the end-user
for £22/dry t. Domestic and commercial refuse is available and can attract disposal credits of up
to £20/wet t which has a significant effect on the conversion economics, even after extensive
processing to separate the fuel rich fraction. Once at the plant, conventional handling,
screening and sorting systems can be utilized for all feedstocks. All aspects of the supply chain
are under active research and development which should result in reduced feedstock costs.

7 ACKNOWLEDGEMENT S
The work on wood as fuel (CPM) was supported by the UK Department of Energy and
the Biomass for Energy Programme of the CEC. The views expressed are those of this author
and not necessarily those of the sponsors.
Much of the data reported in this paper on refuse costs (AVB) were generated for the
Energy Technology Support Unit at the UKAEA, Harwell, UK, as an update of earlier work
(13). They are intended to be published in due course in a strategic review of thermochemical
conversion technologies for biomass and wastes (15). All opinions and statements are the
views of this author and in no way reflect any views of the UKAEA or the UK Department of
Energy.

8 REFERENCES
1 BRIDGWATER, A V and MITCHELL, C Ρ 1987. Interfacing biomass production and
biomass conversion. In 4th EC Energy from Biomass Conference. Ed Grassi et al.
Elsevier Applied Sci ρ 1174 -1178.
2 MITCHELL, C Ρ 1987. European forest energy scene. In Proc 4th EC Energy from
Biomass Conference. Ed Grassi et al. Elsevier Applied Sci ρ 54 - 58.
3 HARE, Ρ M; MARTINDALE, L Ρ and MITCHELL, C Ρ 1989. Supply and Use of
Wood Fuel in the UK. Energy Technology Support Unit, Harwell. In press.
4 MITCHELL, C Ρ; TRANTER, R B; DOWNING, P; BRANDON, O; PEARCE, M L;
BUNCE, R G H; and BARR, C J 1987. Growing wood for energy in Great Britain.
ETSUB-1102.
5 DERLER, R 1988. Measurements of tree fuel at eleven district heating plants in
Sweden. IEA/BE Report ρ 52.
6 JJIR IS, R 1988. Microfungi problem - health aspects. In Production, storage and
utilization of wood fuels. Proc IEA/BE Conference, Uppsala, Sweden Dec 6-7,1988.
2 Vols. Ed B O Danielsson and O Gislerud. Swedish University of Agricultural
Sciences, Department of Operational Efficiency. Research Notes No 133/134 1988. ρ
163 - 167.
7 MITCHELL, C Ρ; HUDSON, J B; GARDNER, D Ν A and STORRY 1989. Storage
and drying of comminuted wood fuels. In Proc IEA Task VI Workshop "Wood
preparation, storage and drying". Lind, Denmark May 16 -18,1989. In press.
8 GUSTAFSSON, G 1988. Forced air drying of chips and chunkwood. In Production,
storage and utilization of wood fuels. Proc IEA/BE Conference, Uppsala, Sweden Dec
6 - 7, 1988. 2 Vols. Ed B O Danielsson and O Gislerud. Swedish University of
Agricultural Sciences, Department of Operational Efficiency. Research Notes No
133/134 1988. ρ 150 -162.
9 MITCHELL, C Ρ; MARTINDALE, L P; HARE, Ρ M; HUDSON, J B; GARDNER, D
Ν A and STORRY 1988. The potential for harvesting fuelwood in the United
Kingdom: A systems approach. In Proc IEA Workshop "Economic evaluations of
biomass oriented systems for fuel". Ed G Lonner and A Tornqvist Swedish University
of Agricultural Sciences, Department of Forest Industry Market Studies, ρ 211 - 217.
10 CLEGG, J M et al., The acquisition and utilisation of straw as fuel, Silsoe College,
Report to ETSU, 1985.
11 BUNGAY, H R, "Thermochemical Processes", in Energy: The Biomass Options,
(Wiley-Interscience Publication, New York, 1981).
12 BOURDE AU, P H and FERRERÒ, G L, "Introduction and general presentation of the
R&D programme on recycling of urban and industrial waste", in Anaerobic digestion
and carbohydrate hydrolysis of waste; Eds. Ferrerò, G L, Ferranti, Μ Ρ and Naveau,
U, (Elsevier Applied Science, 1987).
56

13 BRI
D GWATER, A V; DOUBLE, J M and EARP, D M 1986. Technical and market
assessment of biomass gasification in the UK. Report to ETSU 1986.
14 BRI
D GWATER, A V, Economic and market opportunities for biomass derived fuels,
these proceedings.
15 BRI
D GWATER, A V and STRONACH, Ν J, "A Review of Thermochemical
Conversion Technologies", Report to ETSU, Department of Energy, 1989.
57

PROCESSING OF URBAN WASTE TO PROVIDE FEEDSTOCK


FOR FUEL/ENERGY RECOVERY

J R Barton
Warren Spring Laboratory
Department of Trade and Industry

Summary

The UK has over ten years experience in the design, operation and
monitoring of Refuse Derived Fuel (RDF) production plants and
combustion of the products. Although most plants recover the fuel
in pelletised form for use on conventional industrial solid fuel
boilers, shredded fuels are also made and used. The paper reviews
the technology adopted for fuel recovery and, given the
composition and processing characteristics of UK refuse, comments
on best practice based on the experience of commercial plants.
Brief comment is made on the combustion characteristics of RDF
based on laboratory research and practical experience in order to
highlight problem areas. The paper concludes that much better
guidance can now be given to designers of thermal treatment
processes on the role waste pretreatment can play in developing
more effective energy from waste systems, whether these involve
direct combustion or the application of pyrolysis or
gasification.

1. INTRODUCTION
Mechanical sorting systems, by separating, concentrating and
altering the physical nature of the waste, permit more effective
application of subsequent thermal, biological or other treatment and
recovery processes. They also offer the opportunity for improved
control over the environmental problems associated with waste treatment
and disposal. However, experience of sorting plants for MSW has been
mixed and full scale processes have generally not fulfilled
expectations. Often equipment capacity and availability has been lower
than expected and marketing problems have been experienced with the
products due to quality deficiencies, competition from alternatives or
the introduction of more stringent regulations governing use. Despite
these difficulties, significant progress has been made in terms of
achieving reliable plant operation and, more importantly, in
understanding the limitations and potential inherent in the approach
to permit better matching of feedstock characteristics with process and
58

market requirements. Warren Spring has been closely involved in


designing, commissioning and monitoring refuse derived fuel plants in
the UK and abroad and this paper summarises the key factors that need
to be considered when adopting a pretreatment stage prior to thermal
treatment. Obviously sorting waste for fuel recovery results in
residues which must be disposed or further treated to recover values.
However, whilst effective treatment of these residues is an integral
part of the overall concept and influences process selection, it is a
subordinate consideration. Fuel and energy recovery is the major
weight and volume reducing stage and if this is not effective,
extending recovery processes to residues can rarely be justified.

2. SEPARATION AND RECOVERY OF THE FUEL RICH COMPONENTS


2.1 Refuse composition and process selection
Table 1 gives a typical composition for UK refuse along with the
ash, moisture and calorific value of the components 'as received', ie
as delivered to a processing plant. This input data dictates the mass
yield, energy recovery and quality achievable by physical sorting
alone. Fig. 1 illustrates the effect of ideal separation (eg by hand
sorting) assuming categories are removed in order of increasing fuel
value eg starting at point A with raw refuse, removing glass, metals
and inert categories first (point Β ) , then unsorted fines (­10 mm)
(point C ) , next putrescibles (point D) and so forth. The effect on
mass yield (x axis) energy loss (y axis) and fuel quality at any point
can be assessed. Obviously mechanical sorting systems are not so
systematic nor are they 100% efficient at removing separate categories
but this graph,does provide target values for process designers and
a baseline against which to assess plant performance. Theoretical
separation efficiences can be calculated at each point using accepted
efficiency formulae. The values given on Fig. 1 are calculated using
the following formula derived by Douglas'1':

« p £
Separation efficiency = ioo­C i00­f x 100%

where R = % of available energy recovered in concentrate


C = weight % of concentrate
c = % assay of concentrate (in terms of calorific value)
f = % assay of feed (in terms of calorific value)

To obtain values for c and f, an arbitrary maximum calorific value


must be selected to represent 100% 'pure' fuel. In this case the
average calorific value of the combined plastics categories,
ie 28.5 MJ/kg, has been selected. The low values calculated using this
formula mainly reflect the unrealistically high target CV for 'pure'
fuel which, by definition cannot be reached without rejecting
categories such as paper. However, considering the relative changes,
these data show that whilst the separation efficiency gains from the
removal of non combustibles, fines and putrescibles reach a maximum
value and conform to expectations, selective recovery of the plastics
alone is equally efficient; this is because the formula used gives
equal weight to maximising fuel quality as it does to maximising fuel
59

Table 1. Composition of UK refuse

As ree'd Moisture Ash content Gross calorific


assay content (as ree'd) value (as ree'd)
wtZ wtZ wtZ MJ/Kg

Paper 33 30 8 12
Plastic film 4 25 9 27
Dense plastics 4 15 6 30
Textiles 4 25 8 15
Misc. combustibles 5 25 12 13
Misc. non-combs 5 15 85 -
Glass 8 20 90 -
Ferrous 6 15 85 -
Non-ferrous 1 10 90 -
Putrescibles 20 65 8 6
Fines -10 mm 10 40 40 4

TOTAL 100 33 28 9.1

20 40 60 80 100
YIELD OR WEIGHT OF FUEL AS A PERCENTAGE OF INPUT

FIG. 1 EFFECT OF 'IDEAL' SORTING OF REFUSE FOR FUEL RECOVERY


60

recovery. Obviously many other criteria, particularly options for the


residues, need to be taken into account when determining an optimal
solution but this assessment does highlight that, for refuse, a wide
range of fuel yields is compatible with maintaining a high separation
efficiency from a strict technical viewpoint.
Even from the fuel viewpoint alone the chemical composition,
particularly of elements which cause environmental problems in thermal
treatment (eg chlorine, heavy metals), has a significant effect on the
costs of converting the 'fuel' to usable energy. Thus to select the
optimum fuel recovery and grade for a system and to determine how to
achieve it requires more detailed data. Such information has become
available from testwork undertaken by WSL and other workers'^)").
For example, size distributions of each category have been measured at
10, 20, 40, 80, 160 and 320 mm and for each sized-category fraction (eg
-80+40 mm paper fraction) further analysis gives moisture, ash,
calorific value and chemical composition. These data have proved
invaluable for optimising plant equipments and process flowlines. At
WSL the information is kept on database and manipulative software has
been written to permit selection and averaging of sample data and the
application of "process function" matrices which represent either real
separations achieved by specific process equipments or 'ideal'
separations. This work, along with the potential to develop mathematic
models of the processes, has been detailed previously^*'; for the
purposes of this paper it is sufficient to know that given a
specification or requirement based on the thermal treatment step, a
rapid assessment of whether this is achievable using sorting technology
alone can now be made.
2.2 Practical considerations
Many options can be selected for a process flowline but practical
considerations and experience have narrowed these down, particularly
during the early treatment steps. Thus whilst the simplified flowline
illustrated in Fig. 2 represents a good option for achieving fuel
qualities and yields close to the theoretical values given in Fig. 1,
variations on the theme, particularly in the latter stages for a more
refined fuel with controlled physical characteristics (eg pellets), are
entirely acceptable. For discussion purposes, the four stages selected
are (i) preliminary liberation and screening, (ii) magnetic separation
and coarse shredding, (iii) a refining separation stage and finally
(iv) processes to control the physical characteristics of the fuel.
The following sections are not intended to be a comprehensive review of
the requirements for each stage but to illustrate, with examples, why
certain processes are effective, where the major problems are and to
indicate where the balance between pretreatment and preparation costs
and the costs of the energy raising unit is likely to be in any given
circumstances.
2.2.1. Stage 1 liberation and screening
Experience in the U K ' ^ ) has clearly identified that screening
prior to size reduction has significant benefits in terms of process
reliability and fuel quality. It can remove materials which
contaminate the fuel categories during shredding as well as problematic
items which adversely effect the performance of shredders. The key
equipment item is a rotary screen or trommel and, whilst a separate
61

RAW WASTE

wt = 100%
cv = 9.1 MJ.Kg" 1 -· - -
ENERGY = 100%

50mm FINES wt = 32%


LIBERATION AND SCREENING cv = 4M J. Kg"1
STAGE 1 FINES REMOVAL (^50mm) ENERGY= 14%
OVERSIZE REMOVAL (^500mm) +500mm wt = 2%
OVERSIZE cv = 13 M J Kg"1
ENERGY= 3%

wt = 66%
c v = 11.5 M J. K g " 1 * - - I
ENERGY= 83%

MAGNETIC SEPARATION
STAGE 2 AND -FERROUS METAL w t = 6%
COARSE SHREDDING c v = 1 MJ.Kg"1
ENERGY= 1%

wt = 60%
cv = 12.5 MJ.Kg"1-»-
ENERGY = 82%

REFINING (SEPARATIONS)
AIR/BALLISTIC „HEAVY AND wt = 12%
STAGE 3 CLASSIFIERS FINE REJECT cv = 9 MJ.Kg"1
FINES REMOVAL (<10mm) ENERGY= 12%

wt = 48%
cv = 13.4 MJ.Kg 1 '
ENERGY = 70%

REFINING (PHYSICAL)
SHREDDING
MOISTURE wt 12%
STAGE 4 DRYING
LOSS
PELLETING
COOLING

wt = 36%
cv = 18MJ.Kg- 1 -*-—I
ENERGY = 70%
RDF PELLETS

FIG. 2 STAGES IN PRODUCTION AND REFINING OF REFUSE-


DERIVED FUELS
62

liberation stage to open bags and release refuse component (eg at the
Byker plant) is advantageous, a trommel can be designed and operated in
a manner which ensures sufficient liberation and breakage of friable,
non-fuel components (such as glass) to achieve efflicient screening.
Effective design criteria for fine screening duties have been
developed*·"', the equipment is simple and robust, designs for
feedrates up to 40 teh-* for a single unit are proven and scale up
for higher feedrates is possible. Running costs are low with specific
power consumptions below 1 kWh per tonne of raw waste processed. For
UK refuse the aperture size selected for fine screening is normally
between 40 and 60 mm, a size which ensures minimal loss of identifiable
combustibles categories ( 5%) whilst achieving removal of over 65% of
the putrescible category, over 90% of the -10 mm fines and over 85% of
the glass. Most metal reports to the topsize, fuel rich fraction, but
items such as small batteries and foil from wine bottles tend to report
to the fines and this results in reduced heavy metal contamination of
the recovered fuel.
One action of a trommel which is detrimental to downstream
processes is the tendency to 'create' ragtails; these are sausage like
composites of wire, string, textiles and plastics up to several metres
in length. Such items, along with the bulky items which 'naturally'
occur in refuse (eg matresses, dustbins etc) are difficult to size
reduce effectively. Some pulveriser designs, such as vertical shaft,
non gridded hammer mills are capable of coping with such materials but
the effect on gridded mills can be extremely damaging in terms of
throughput and availability. Fortunately a coarse screen section
installed in the trommel can reject such items with minimal loss of
fuel values and is strongly recommended. Table 2 shows the dramatic
improvement achieved at the RZR Herten plant by modifying the trommel
to scalp out items above approximately 500 mm in size. Close attention
needs to be given to the design of the screen plate to minimise
blinding and to ensure easy access to the external surface for cleaning
purposes. Experience suggests that downtime for cleaning can be kept
to below 10 minutes per 8 hour shift without adversely effecting
screening efficiency. Removal of coarse materials also improves the
efficiency of subsequent magnetic separation when this is carried out
before shredding in Stage 2.
The importance of trommel screening as the first fuel-non fuel
separation process is now well established, even without magnetic
separation, screening alone proved effective in terms of increasing
energy output and boiler efficiency for a conventional mass burn
incinerator at Sheffield*·''.
For UK waste, Stage 1 should result in a yield of 60% wt fuel rich
material, reporting a calorific value of approximately 11.5 MJ/Kg and
containing 83% of the original energy content.
63

Table 2. RZR Plant, Herten - Effect of coarse aperture screening


on plant performance

Before coarse aperture After scalping out


scalping oversize at
approx. 500 mm*

Steady state -1
throughput
22 teh 27 teh"1

Plant
72% 96%
availability

Hammer mill
specific power 25 kWh/tonne 18 kWh/tonne
consumption

* weight of oversize removed was less than 2% of the refuse feed.

2.2.2. Stage 2 Magnetic Separation and Coarse Shredding


Assuming the fuel rich topsize has been scalped to remove coarse
items, the preferred magnetic extraction system is an overband unit
positioned at a head pulley in line with the refuse flow. Recoveries
of at least 90% are common but the magnetic product will contain up to
15% contrary materials (eg paper, plastics). Cleaner products are
obtained if magnetic separation is delayed until after the shredding
operation; however prior metal removal can be considered a protective
measure, reducing the risk of explosion damage from volatiles (eg paint
thinners, butane) present in cans, aerosols and gas bottles.
Irrespective of the sequence, shredders need to be sited in 'explosion
proof' housings and preferably fitted with an explosion suppression
system. Hammer mill designs are preferred for coarse shredding due to
their robust nature and, if scalping has been carried out, a gridded
design does assure topsize control for downstream operations is
maintained irrespective of hammer wear (hammer condition will still
need attention for maintaining desired size distribution and
throughputs). Specific power consumptions and flow rates will depend
on mill design and feed composition. Values between 15 and
25 kWh/tonne are not untypical. A major pitfall to be avoided is to
believe that the size and power of a mill can be significantly reduced
by stream splitting. For example, when a trommel was installed before
the pulveriser at Byker, the weight throughput to the pulveriser
reduced from 30 teh-^ to 20 teh-·'- due to removal of
10 teh -1 of fines. It can be seen from Table 3 that the effect on
power usage was minimal as the specific power requirement for the
remaining topsize increased from 12 to 17 kWh/tonne. This is not
surprising, the volumetric flowrate was largely unaffected and the
weight of materials that actually required size reduction, ie the
paper, plastics and textiles had not been reduced. Similar experiences
at the secondary shredding stage have occurred when little benefit has
64

resulted from prior removal of materials already below the desired


shred output size.
From the fuel quality and yield data given on Fig. 2, it can be
seen that the bulk of the fuel-non fuel separation has been achieved by
the trommelling and magnetic separation stages. Again, without
shredding, current testwork on a conventional mass burn unit (at the
Edmonton incinerator) is showing encouraging results and the shredded
product is similar (but of better quality) to the fuel used at
Courtaulds'"' in Grimsby on a large water tube chain grate boiler
and the fuel used in the cement kilns at Westbury by Blue
Circle'"'. Restricting pre treatment to this stage and using
circulating fluid bed combustore is also being given serious
consideration in the UK.
For UK waste, Stages 1 and 2 should result in a yield of 60% wt
fuel rich material, reporting a calorific value of approximately
12.5 MJ/Kg and containing 82% of the original energy content.

Table 3. Effect of fines removal on hammer mill performance

Hammer mill power


Throughput Size reduction consumption
Wt. Volume (d,, mm) Total Specific
From To kWh kWh/te
teh m h

Raw refuse 30 165 80 11 355 11.8

Screened
refuse 20 155 150 24 335 16.8
(-50 mm fines
removed)

2.2.3. Stage 3. Light-heavy separations and fine screening


The separations in Stage 3 are primarily to refine the fuel
product. Useful improvements in terms of reducing ash and metal
contents can be achieved but residues often report relatively high
calorific values. Of equal importance, Stage 3 separations protect
more vulnerable downstream equipment such as knife mills and
pelletizers by removing heavy or dense items irrespective of
composition.
Light-heavy separations for refuse materials have been subject to
a number of detailed studies'"''™' and many different designs have
been tested at full scale'"'. Products other than fuel from refuse
have also been recovered (eg plastics, composts, paper). The
separation characteristics of ballistic units are different from air
classifiers, for example in certain designs 'bounce' is a more
important characteristic than particle density and shape. Such
differences can be worth exploiting, eg PVC bottles tend to 'bounce'
into the heavy reject for one ballistic design and this can reduce
chlorine levels in the fuel. On the other hand fuel quality and fuel
flow rates tend to be easier to control in air classifiers
(particularly under variable feedrate or surge conditions) and this can
65

bring important benefits in terms of process efficiency of downstream


equipment.
Further fines removal is often carried out during this stage to
reduce ash content and screening can be incorporated into the
light-heavy separation unit or carried out separately. Both trommels
and flat bed units have been used, but if a flat bed unit is selected,
vibration amplitude should be larger and frequency lower than is
normally adopted for screening minerals (eg coal, sand, gravels). To
prevent excessive loss of fuel values on aperture size of 10 mm or
below is usually selected.
Energy inputs for Stage 3 separations equipments are not
particularly high and rarely exceed 10 kWh/tonne for most fuel recovery
applications. Careful consideration should be given to the
requirements of downstream equipments and the thermal conversion
process when designing this section of the plant. Specific problem
materials can be rejected and there is scope for more development in
the equipments but it must be recognised that in strict energy
efficiency terms the separations undertaken are in a regime of
diminishing returns.
For UK waste, Stages 1, 2 and 3 should result in a yield of
48% fuel rich material reporting a calorific value of approximately
13.4 MJ/Kg and containing 70% of the original energy value.
2.2.4. Stage 4 Processes to improve the physical properties of the
fuel
This stage is concerned entirely with tailoring the fuel to suit
the combustion or thermal treatment stage. By further shredding,
drying and pelleting, the fuel storage, handling and combustion
properties are improved. This stage also lends itself to blending in
additives specifically to enhance combustion properties. In terms of
capital, maintenance and operating costs per tonne of material
processed, the processes in this stage tend to be the most expensive in
the plant. Hence, high plant availability is essential and this
requires much improved monitoring and control of flowrates, feed
composition and equipment. The shredding stage normally requires in
excess of 25 kWh/tonne to reduce a coarse shred (say approximately
100 mm) to below 25 mm (mean size approximately 10 mm). The
evaporative heat requirement for successful pelleting (reducing
moisture levels from approximately 30% to below 12%) is approximately
700 MJ per tonne of fuel and as drying efficiencies are between 50 and
65%, a thermal input of over 1200 MJ per tonne is needed (ie +£4/tonne
at natural gas prices or up to 10% of the plants fuel output if an RDF
fired combustor is used). For good quality pellet production a
specific power consumption of +35 kWh/tonne for the pellet mill alone
is typical. Although no physical separation processes are undertaken
during Stage 4, moisture removal during drying, pelleting and cooling
increases calorific values to around 18 MJ/Kg and the bulk density from
approximately 100 Kg m~3 for coarse shred to over 600 Kg m--*
for pellets.
There are many views on the best equipment designs and of best
process sequence for the production of pellets. There are certainly
advantages and disadvantages to all with different plant designers
preferring knife mills to hammer mills, cascade dryers to pneumatic
66

dryers, fixed die pelletisers to rolling die machines, single stage


pelleting to two stage densification etc. Suffice it to say all
systems initially developed failed to meet design objectives, flowrates
of half the anticipated levels were not unusual and dedicated effort to
modify and improve the process, often by the plant operators rather
than individual equipment manufacturers has been needed to achieve
satisfactory performance. Today there is no excuse for installing
equipments which don't fulfill the process requirements but new plants
would be strongly recommended to buy proven systems rather than put
together separate units that haven't previously been tested in
sequence. Quite simply "the art" in preparing and pelleting waste
fuels is as important as the scientific and engineering knowledge of
the individual unit processes.
An important consideration in the drying stage is abatement of
particulate emissions and odours from the dryer gas. This has caused
problems with existing UK plants whether the drying heat has been
provided by gas burning or burning RDF. Although satisfactory retrofit
solutions have been found (eg increasing chimney heights, increasing
efflux velocities, adding odour counteractants and oxydising chemicals
to scrub waters, adding additional particulate removal systems etc),
this is an area where further investigation is needed to define the
problems more closely and develop optimal solutions.
There is undoubtedly scope in Stage 4 processes for significant
improvements to be made. The design of pelleting processes has been
based mainly on achieving similar handling, storage and feeding to
small coal. This has proved expensive but as experience with using
waste fuels increases, user requirements will become more specific and
this should stimulate development of more cost effective Stage 4
systems.
For UK waste, Stages 1 to 4 should result in a yield of 36% by wt
fuel, reporting a calorific value of approximately 18 MJ/Kg and
containing 70% of the original energy content. Electrical energy
inputs for the full plant are likely to be up to 70 kWh/tonne of refuse
input, approximately 200 kWh/tonne of pelletised fuel.
2.1.5. Other processing factors
Before considering fuel characteristics against combustion
requirements, brief comment on storage and handling systems is
warranted. Within a production plant, short term storage systems have
advantages from a design viewpoint in smoothing out flows and matching
capacities in different sections of the circuit. However they have
frequently resulted in more problems than they have solved. Blockages
and uneven discharge characteristics have been experienced with most
shred bunker designs, particularly push floor bunkers and bunkers with
screw discharge systems. The reasons for failure vary, hopper size and
shape is critical (it must diverge), push floor designs generally do
not provide sufficient positive motion to be effective if the depth of
shred exceeds 1 or 2 metres, the design of screws and discharge outlet
must avoid compressing the shred. Recent work at WSL on a multiscrew
discharge hopper proved blockages could be avoided by careful design,
but even with a fine sized ( 25 mm), relatively dry shred suited for
pelleting, fluctuations of 25% about the mean discharge flowrate still
occurred. Bunkers with screws that move position within the mass of
67

the shred (eg by traversing the bottom of the hopper or rotating


eccentrically within the hopper) largely overcome blockages and a novel
design based on a slow moving plate conveyor floor and a rotating rake
device to tear off the shred as the mass moved toward the .open
discharge side worked successfully at the Rolls Royce plant' 11 '.
Thus progress has been made but problems in this area are still a
frequent occurrence at sorting plants and for all new systems or
systems to feed shred to a combustion unit, particulary attention needs
to be paid to this aspect of plant design.
Handling, storage and feeding of pellets is less of a problem;
small amounts, kept in dry and well ventilated conditions, show little
sign of degradation after a year or more, but prolonged storage in deep
bunkers or piles would not be recommended. There are many examples of
localised heating, sweating and fungal growth leading to break up of
pellets in bulk storage and potential fire/health hazards. Whilst some
of these problems can be attributed to poor control of moisture content
during production, changes in climatic conditions (temperature and
humidity) also affect pellet stability. Hence storage should be
limited to a few months. For undried RDF, a few days is preferable
although longer periods can be tolerated if the subsequent handling
system is designed to cope with 'lumpy' materials.
The above comments cover a few of the practical difficulties
experienced on UK plants. Generally solutions have been found but
further progress and experimentation with plant design is still
required and to aid this, a few thoughts are given below based on over
10 years of problem solving on RDF plants.

. Reliability is more important than technical efficiency


. Reject problematic materials as soon as possible
. Exploit the natural separation characteristics of the waste first
. Delay energy intensive stages as long as possible
. Ensure the basic processing and separation principles of the
equipments are understood
. Volume, not weight throughput tends to be the rate limiting
factor
. Once refuse stops moving, it needs a positive kick to start again
. Always remember it is waste until a marketable product is
recovered, irrespective of the degree of processing

3. RDF and thermal treatment


Although this paper is primarily concerned with production of RDF,
UK experience with combustion of RDF (pellets in particular) is
beginning to feed back into the production process and consideration
can be given to whether problems are better tackled during feed
preparation or by developments in the thermal conversion stage.
Table 4 gives basic information on composition and properties of RDF
pellets and a typical UK bituminous coal but many of the comments made
below are based on more detailed characterisation studies undertaken by
WSlA"). Th e objectives to be realised for an effective energy
from waste plant are as follows:
1. Maximum heat release for minimum grate size.
2. Minimising clinker formation.
68

3. Minimising boiler fouling


4. Minimising emissions (acid gases and heavy metals in
particular).

Table 4. Properties of RDF pellets and bituminous coal

RDF (Byker) Coal

Gross calorific value MJ/kg 18.5 27

Proximate analysis

Moisture content Zwt 8 8


Ash content Zwt 15 10
Volatile matter Zwt 67 26
Fixed carbon Zwt 10 56

Ultimate analysis (DAF)

Total carbon Zwt 55 84


H Zwt 7 5
0 Zwt 36 8
Ν Zwt .6 1.6
Cl Zwt .9 .1
S Zwt .3 1

Bulk density Kg m" 600 900


Size of fuel mm 16 mm diameter 10 to 25 mm

1 Heat release
From Table 4 it can be calculated that almost twice the volumetric
throughput of pellets is required to match the same thermal input of
coal. This affects fuel handling and feeding equipment more than the
combustion appliance because the higher volatile content of RDF and the
higher reactivity of RDF char compared to coal greatly reduces the
residence time requirements within the combustor for complete burn out.
Pellet density, size and shape will affect this but, to date, it has
not proved necessary to exploit the ability to change these properties
to increase (or reduce) heat release rates.
It is pertinent to note the difference in heat release
characteristics of RDF pellets compared to raw waste; the residence
time for pellets on a chain grate is approximately 15 minutes compared
to approximately 60 minutes for MSW on an incinerator grate. As
pellets have approximately 7 times the energy content per unit volume
compared to raw waste this suggests a 30 fold advantage over raw waste
in terms of grate area required to achieve the same heat release
rates.
3.2 Minimising clinker formation
Although clinker formation was a problem experienced on a number
of stoker/grate systems during early firing trials^^',
69

improvements in processing technology, particularly the use of front


end screens, have reduced ash contents in RDF and reduced clinker
formation. At Byker, for example, RDF ash contents reduced from
approximately 17Z to below 14% on a dry weight basis^) and much of
the reduction was due to removal of components with a low fusion
temperature such as glass. Most of the remaining ash is inherent in
the combustible categories; paper extracted from refuse for example
normally assays approximately 10% ash (dry wt basis) and the IDT
(initial deformation temperature) is between 1000'C and 1050°C compared
with 1150°C for coal. Hence RDF will always report lower ash fusion
points than coal but, given efficient processing, clinkering on most
commercial systems is not a problem. For systems which still
experience problems (eg ram stokers), recent work at Warren Spring has
indicated that addition of chemical compounds can increase fusion
temperatures and hence offer a potential solution. Obviously for lower
temperature thermal processes, eg pyrolysis or gasification, the
possibility of clinker formation is much reduced.
3.3. Minimising boiler fouling
Severe fouling of boiler surfaces has been experienced with both
raw waste incineration and RDF combustion. The deposits have a high
concentration of alkali metals, for example tube entry deposits on a
chain grate unit burning pellets assayed over 90% alkali sulphates.
The problem is more severe than coal simply because RDF contains ten
times more sodium and potassium and these metals are also present in a
more easily volatilised form. Alkali salts are added as fillers to all
forms of paper and there is no physical separation technique capable of
removing these deposit forming chemicals from the feedstock. One
processing step that could contribute to some deposition control is the
addition of a chemical that reacts with the alkali to form a more
stable compound which will not volatilise at the temperature
experienced on the fuel bed. Kaolin has been proved effective in
retaining alkalis as alumino silicates in the past'^' but is
unlikely to offer a complete or cost effective solution. In the longer
term, control of deposition will probably lie with the design and
operation of the combustion and boiler unit. Boiler fouling has been
substantially reduced on a chain grate by a combination of selecting
fuel bed depths and grate speeds to reduce the time of the high
temperature ash burn out phase (and hence reducing volatilisation),
reducing the temperature of the flue gas prior to the first boiler pass
(at the cost of reduced boiler efficiency) and use of soot blowers.
Again adoption of lower temperature gasification processes as opposed
to full combustion would make a significant impact on this problem by
retaining the alkalis in the fuel ash residues.
3.4 Minimising emissions
Coal combustion particulates are mainly coarse fly ash entrained
through the system and relatively easy to abate using conventional
basic units, ie grit arrestors. In RDF combustion a larger proportion
of the particulates are sub micron which can only be removed
efficiently by more expensive abatement units such as electrostatic
precipitators or bag filters. Test work in chain grate stokers has
shown RDF particulate emissions are high in metallic chlorides (eg Na,
K, Pb, Cd and Zn). As mentioned, the alkali metals are constituents of
70

paper; lead, cadmium and zinc also appear in combustible categories.


For combustion processes, improved abatement equipment is the
established solution though again lower temperature thermal processes
should certainly reduce the emission of these metal chlorides.
For acid gas emissions, SO2 is not a problem compared with coal
combustion but HCl emission certainly is. In the UK, combustion of RDF
pellets typically gives rise to HCl concentrations of 800 to 1000 mg
Nm - 3 (9% CC-2). Up to 60% of chlorine in RDF is present in
chlorinated plastics (PVC) and this is totally converted to HCl in all
forms of thermal treatment.
As discussed previously there is some scope for removing PVC
bottles during RDF production but this by itself is unlikely to make a
substantial reduction in emission levels. Thus controlling HCl
emission from combustion processes requires the appropriate downstream
flue gas clean up technology (eg scrubbing). Lower temperature thermal
processes may offer more cost effective methods of retaining chlorine
within the system, for example gasification with injection of lime is
reported' " ' to retain approximately 90% of the fuel's chlorine.

5. Conclusions
Whilst burning waste and waste derived fuels for energy recovery
has and continues to be an effective waste treatment option, problems
with clinkering, boiler fouling and emissions still occur under full
combustion conditions. Whilst some cost effective solutions are
available by improved production methods and improved combustion
control, other solutions will significantly increase the costs of using
RDF on conventional coal fired plant, particularly where stricter
emission limits are applied to RDF as compared to coal. Lower
temperature processes such as gasification or pyrolysis are looking
increasingly attractive as a means of reducing these costs.
In terms of preparing waste for thermal treatment, full scale RDF
plants have proved the potential for significantly increasing calorific
value, energy density and the provision of fuels with consistent
handling, feeding and combustion properties. These are all factors
which lead to substantial reductions in the cost of building and
running the thermal treatment plant compared to mass burn incineration.
The energy loss on converting raw refuse to an RDF can be restricted to
30% by effective plant design and for a range of RDF types there are
positive experiences to report on a variety of combustion plant.
Equipment requirements and processing costs for the various forms of
RDF are established in broad terms and matching fuel characteristics
with requirements for the thermal treatment stage is facilitated by the
availability of detailed analysis data and improved understanding of
the separation processes.
Raw refuse cannot be considered to be the optimum form or
composition for thermal treatment and energy recovery. There may be
arguments as to the degree of separation and processing warranted for
the most effective overall system, but there is no doubt that
pretreatment offers excellent opportunities for improving the thermal
treatment stage as well as the opportunity to recover additional values
from the residues by more appropriate, non thermal processing methods.
71

REFERENCES
(1) DOUGLAS, E. Derivation of basic efficiency formula for
concentration operations. Trans. Inst. Mining and Metallurgy 71
(1961-2), pp697-704.
(2) LORBER, K.E. Incineration of RDF and incineration of total waste
- comparison of emissions. Paper to EC Seminar, Sorting of
household waste and thermal treatment of waste, Luxembourg,
Sept. 84. Applied Science, Elsevier 1985 pp208-225.
(3) VAN ROOSMALEN, G.R. et al. Heavy Metal Sources and Contamination
Mechanisms in Compost Production. Paper to MER 3 Conference,
18-20 March 1986, Antwerp. Belgium.
(4) BARTON, J.R. et al. The Use of Database and Modelling Techniques
in Furthering Developments in Solid Haste Processing in the UK.
Paper to 23rd intersociety Energy Conversion Engineering
Conference (ECEC), 31 July-5 August 1988. Denver, Colarado, USA.
(5) BARTON, J.R., WHEELER, P.A. The Benefits of Front End Trommelling
in Processing Municipal Solid Wastes. Trials at the Byker Plant -
June 1987. WSL Report LR661(MR)M, Sept. 1988, 39pp.
(6) WHEELER, P.A. et al. An Empirical Approach to the Design of
Trommel Screens for Fine Screening of Domestic Refuse to be
published, Resource, Conservation and Recycling (1989).
(7) BARTON, J.R., POLL, A.J. Preparation and Incineration of Screened
Refuse: Preliminary Trial, Sheffield, November 1986. WSL Report
LR592(MR), March 1987, 49pp.
(8) BARTON, J.R., POLL, A.J., WEBB, M., WHALLEY, L. Waste Sorting and
RDF Production in Europe. A report prepared for the Commission of
the European Communities R and D programme - Recycling of Urban
and Industrial Waste, Barking, England. Elsevier Applied Science,
Publishers Ltd, 1985, 209pp.
(9) BARTON, J.R. Development and Application of a Method for
Predicting and Assessing Performance of Operating Air Separators
in the Processing of Municipal Solid Wastes. Paper to EC Seminar
on Sorting of Household Waste and Thermal Treatment of Waste,
Luxembourg, 25-27 September 1984, London: Elsevier Applied
Science, 1985 ppl09-119.
(10) ROSENBRAND et al. The Separation Performance and Capacity of
Zig-Zag Air Classifiers. Paper to EC Seminar, Sorting of
Household Waste and Thermal Treatment of Waste, Luxembourg,
September 1984. Elsevier Applied Science, 1985, pp208-225.
(11) ENERGY EFFICIENCY OFFICE. Combustion of Shredded Industrial and
Commercial Waste in a Circulating Fluid Bed. Project Profile 206,
Energy Technology Support Unit, Harwell Laboratory, May 1985.
(12) RAMPLING, T.W.A., HICKEY, T.J. The Laboratory Characterisation of
Refuse Derived Fuel. WSL Report LR643(MR), Dec. 1987, 186pp.
(13) BURNLEY, S.J. The ETSU/WSL Refuse Derived Fuel Combustion Trials
Programme: A Review of Progress. WSL Report LR595(MR),
Sept. 1987, 33pp.
(14) BRINSMEAD, K.H. and REAR, R.W. The Formation of Alkali-Bonded
Deposits. Laboratory Studies of the Behaviour of Sodium Chloride
during Combustion. BCURA Inf. Circular No. 134, Doc. No. C/4950.
(15) HOS, J.J. et al. Gasification of Organic Solid Wastes in
Co-current Moving Bed Reactors. Energy from Biomass and Wastes
IV, Florida 1980.
72

CHARACTERIZATION OF CARBON CONTAINING MATERIALS WITH RESPECT


TO PYROLYSIS AND GASIFICATION
H.­J. Mühlen, W. Wanzl, K.H. van Heek
Bergbau­Forschung GmbH, Essen, FR of Germany

Summarv
From the broad use of thermochemical conversion of coal
and other solid fuels various methods have been estab­
lished for their characterization with respect to pyro­
lysis and gasification. The experimental techniques and
theoretical methods including those for reactor modeling
are reviewed, taking as examples those in use at Berg­
bau­Forschung. Typical results achieved for coal and
lignites are shown, demonstrating how the experimental
devices and the theoretical background can be used to
characterize other carbonaceous materials like biomass
and wastes. The final aim is the design of new or the
optimization of existing processes with respect to the
feedstock available and the products desired.

1. INTRODUCTION
As it is expressed in the introduction to the programme
of this conference, thermochemical processing is most impor­
tant amongst the available technologies for biomass conver­
sion. Such processes like pyrolysis, gasification and also
combustion have been since ever the basis for industrial con­
version of coal. Therefore the purpose of this contribution
will be to review the main techniques for the characteriza­
tion of coal with respect to pyrolysis and gasification,
thereby showing their importance also for the treatment of
other feedstocks.
2. CONVERSION PROCESSES AND RELEVANT FEEDSTOCK PROPERTIES
First of all it has to be noticed that the term "conver­
sion" is used differently in science and technology. As illu­
strated in fig. 1, taking as an example gasification, it
stands in a narrow sense for the heterogeneous reactions of
carbon with gasifying agents such as Η,Ο, C0 2 , H 2 and 0 2 · In
a broader meaning it denotes the gasification reactor, that
means, it includes additional processes such as heating up,
drying and pyrolysis. In some reactors, in which heat has to
be provided for conversion, also combustion may be enclosed.
Finally, conversion means the whole process, starting with
the storage of the feedstock, its preparation and ending up
with valuable products at the one hand and the disposal or
utilization of the undesired residues on the other /!/.
73

GASIFICATION PROCESS
Storage
Grinding

GASIFICATION REA CTOR


Pyrolysls

Resultant
GASIFICATION REA CTIONS
Feed
Propertles m C ­ H20
C ­ CO2 53
Char
and A sh
C ­ H2 Properties
Combustion

Gas Cleaning
Residue Disposal

Fig. 1: Different steps of a thermochemical conversion


process taking as an example g a s i f i c a t i o n
Table 1; Correlations between coal properties and t h e i r
changes in the s i n g l e process steps
PROCESS RELEVANT P0SS8LE »PACT ON
STEPS PROPERTES EFFECTS PROPERTES
­ro* ­ self ¡onrtion ­ oging
STORAGE ­ ODOQuOn ­ reduction of size
­ reduction of swefing

­ra* ~ bea hooung ­ reduction in V i l


— mocera composition ­ release of hydrocarbon ­ changes in surface area
GRNDNG — mineral content oases aid carbon oxidei
­grnMtfty

­ra* ­ 90s ond tor evolution ­ shape


PYROLYSS ­ mocera composition ~ char formation ­ kitema) surface
~ demonta composition — ÜHHiMjtjtastictty ­ reactivity
­ elomental composition

­ asmen tol composition ~ partial consvnption ~ ash enriched residue


­ sirfoce and porosity ­ changes η minerals ­ reactivity
GASFCATION ­ intrinsic reactivity ­ changes in physical structure
­ minora composition

­ strfoce and porosKy ­ bum out ­ physical and chemical


­ reactivity ­ partial combustion constitution
COMBUSTION ­ minora composition

— minera composition ­ eh/tion of traces


DISPOSAL ­ seJubïty of ash elements

Considering characterization of the feedstock i t has t o


be taken into account that although the properties of the s o ­
l i d s influence the reaction in the s i n g l e process s t e p s , they
themselves do undergo changes in them. Under t h i s aspect
74

table 1 tries to summarize the effects of the reactions du­


ring storage, grinding, pyrolysis, gasification, combustion
and disposal, and the interactions with the relevant proper­
ties of the in­ and outgoing solids. Without going into de­
tails it can be stated, that there is a wide number of pro­
perties to be considered as relevant to the different process
steps. Taking as an example pyrolysis these are rank, maceral
composition and elemental composition of the ingoing feed­
stock. During the process condensable products (tars) gases
and char are formed. A lso thermoplasticity has to be taken
into account for a proper operation of the reactor. The con­
ditions in the pyrolysis process influence shape, internal
surface, reactivity and elemental composition of the outgoing
char. In a similar way also the other process steps have to
be discussed.
To sum up: the solid feedstock must be characterized
with respect to every process step, in which generally diffe­
rent properties are relevant. However, the following part
will mainly concentrate on the conversion step.
3. EXPERIMENTAL AND THEORETICAL METHODS
Course and product yields during pyrolysis and gasifica­
tion of carbonaceous solids are mainly influenced by such pa­
rameters as final temperature, residence time, rate of hea­
ting, gas atmosphere and pressure. Most important is the
timetemperature history, which can be described by the rate
of heating. As it is shown in table 2 the technical reactor
types differ widely by the rates of heating applied.

Table 2: Classification of heating rates in coal conversion


Heating Rate Heating Time to 1000°C Technical
K/s dp = 100 μπι Reactor Types

Coke Oven
slow « 1 *· 20 min
Fixed Bed Gasifier

medium 5 ­100 10 s ­ U min LR­Carbonization

Entrained Phase
fast 500 ­ 100.000 10ms ­ 2s
Fluidized Bed

flash > 105 < 1ms Plasmareactor

Relativly slow values of some K/s are achieved in cokeovens


or fixed bed gasifiers. There the reactions occur in hours.
Medium rates of heating are found in carbonizers like the
75

Lurgi/Ruhrgas (LR) type. Much faster heating rates are achie­


ved in entrained phase and fluidized bed reactors, where the
reactions occur in less than one second. Plasma reactors ap­
plying temperatures up to 3000 Κ lead to very fast heating
rates.
In order to characterize the behaviour of the feedstocks
in thermochemical processes under these very different hea­
ting rate conditions we operate three types of apparatus at
Bergbau­Forschung as shown in table 3. In the thermobalance
apparatus a sample of about 1 g is heated up with several
degrees per minute to a final temperature of 1000 " C A s a
result from the continuous measurement of the weight loss and
gas analysis the formation of products like Ho, CO, CO,,
CJJHJJJ, BTX or tar is described, from which the kinetic
parameters can be determined as will be mentioned lateron.
For higher heating rates up to 1500 K/s the grid heater
technique is used. About 10 mg of the sample are heated on a
metallic wire net. Besides the determination of the product
formation and yields we use a high speed camera to study the
mechanical behaviour of the particles and other visible phe­
nomena like ignition, duration of plasticity phases etc. Very
high rates of heating of 10.000 K/s at an adjustable final
temperature can be achieved using the Curie­point­technique.
About 5 mg of the solid is housed in a metallic cylinder
which is heated up by electrical induction.

Table 3: Laboratory equipment for pyrolysis, hydropyrolysis


and gasification; pressure 0.1 ­ 30 MPa
thermobalance wire­net­technique Curie­point­technique

dt t i f i
apparatus

Th
"t tilt t
Th

sample size mg 1.500 5


heating rote K/s 0.05 10.000
final temperature °C 1.000 adjustable
isothermal experiments

results kinetics of kinetics of kinetics of


product formation particle swelling product formation
from high speed
E.ko.n.Vo E.ko.n.Vo
camera studies
for Hi.COx.CxH». for Hï.COx.CxH».
BIX and tar BTX and tar

product yield product yield

At its Curie­temperature the metallic cylinder loses its


ferromagnetic properties and does not take up energy any
longer. Thus it stays at this temperature. From this
technique we get similar results as in the apparatus men­
tioned above.
76

As a next step to scale-up we operate process develop-


ment units (PDU) where the solids can be converted in kg-
scale. As given in table 4 these are: fluidized bed reactors
operating semi-continuously with a feed of solids between 100
g/hour and 1 kg/hour. Reactions can be performed at a
pressure of 1 to 40 bar in steam or air at maximum
temperatures up to 900'C. - For pyrolysis, gasification and
combustion entrained phase reactors operated as free-fall-
reactors have been built up for the same amount of coals.
With respect to hydropyrolysis the pressure goes up to 200
bar, other gasifying agents are steam and air. Also inert gas
like nitrogen can be used. The maximum temperature is 950°C.
Finally, a plasma reactor is used for the conversion of
solids in the presence of hydrogen at 1 bar. The temperatures
are here extremely high up to 3000-C.

Table 4; Experimental methods applied at Bergbau-Forschung to


characterize solid feedstocks for pyrolysis and
gasifications processes
apparatus mode of sample size conditions
operation lappr.)
laboratory :
Curie-Point pyrolysis batch 5 mg 0.1 - 200 bar (N 2 ,H 2 I
500 - 950 e C
ca. 5 > 10 4 K/s
grid heater batch 10 mg 0.1 - 90 bar (N2,H2,air)
20 - 1000"C
ca. 103 K/s
TGA batch 1000 mg 1.0 - 100 bar (N2,H2,H20,airl
20 - 1150eC
1 - 100 K/min
PDU :
fluidized bed seml-contlnuous 100g/h - 1kg/h 1 - 40 bar IH 2 0,airl
600 - 900 e C
entrained phase semi-continuous 100g/h - Ikg/h 1 - 200 bar (H 2 0,N 2 ,iirl
- pyrolysis up to 950°C
- gssification
• combustion

plasma reactor semi-continuous lOOg/h - Ikg/h 1 bar (H2I


up to 3000°C
105 K/s

For the evaluation of the results in laboratory scale


isothermal and non-isothermal reaction kinetics are used
/2,3/. From the poduct formation as a function of time and
temperature kinetic data are established. Also the product
yield can be determined for pyrolysis and gasification. These
are the input data for reactor models at hand both for
fluidized bed or entrained phase reactors. The throughput and
degree of conversion calculated can be proven first in kg-
scale in the process development units and then be used for
the scale-up to industrial reactors.
77

4. RESULTS
The following examples for the results on coal characte­
rization with respect to thermochemical conversion are mainly
taken from thermogravimetric measurements, which in combina­
tion with product gas analysis has been proven to be a very
powerful method on laboratory scale. As an example for the
process development units a result from the plasma pyrolysis
reactor is shown lateron also.

4.1 PYROLYSIS
Fig. 2 presents results obtained during the pyrolysis of
a hard coal in the thermogravimetric analysis device /4/. As
can be seen from the upper diagram on the left the sample was
heated at 3 K/min from room temperature to approximately
1000'C within approx. 6 hours. The primary measuring curve
relates to the mass left in the reactor. The coke formation
per unit time can be derived from this by differentiation.
The curves of gaseous product formation are obtained by gas­
chromatographic analysis performed simultaneously to the TGA­
measurements. The release of higher hydrocarbon gases leads
to rather simple curves so that it may be assumed that only
one reaction is involved in their formation with possibly 3
reactions at the most in the case of CH 4 . Obviously several
reactions contribute to the generation of Η,Ο, CO and CO,.
The formation curve of tar is obtained by subtraction of the
gas formation rates from the loss of mass. Obviously tar is
formed mainly in one reaction.

moss ioss dGimgl


dllg­lj
tar

Λ
ι CCI *

water
gaseous HC

ο ώ ώ 600 m ião 200 too sfa ώ


irci rrci

Fia. 2; Product formation during pyrolysis of hard coal


(coal: 32 % V.M. daf; 3 K/min; 1.1 MPa, N 2 )
Fig. 3 shows how the formation of gases during pyrolysis
of coal varies with rank, ranging from anthracite to high vo­
latile bituminous coal. In the cases of CH 4 , C 3 H g , CO and N 2
78

the gas formation is reduced when rank increases. Thereby the


beginning of the curves is shifted torwards higher temperatu­
res indicating that during coalification functional groups
with weaker bonds are preferably reduced. H 2 0 and CO 2 show a
different behaviour: The H 2 0 curves indicate less gas forma­
tion with rank. Thereby the comparison leads to the conclu­
sion that all relevant groups had been reduced equally during
coalification. The CO2­curves show no remarkable differences
with rank /3/.

5?Is >]cmll

CHt
C

0.4·

O.l·

ftD
1,Ψ
L· V
à ώ

500 700 WO
Temperature I'C I

Coals : •/.V.M, maf


a Heinrich 10.0 c Gustav 29.0
b Dickebank 19.5 d Fürst Leopold 39.5

Fia. 3; Formation of gases during pyrolysis of coal of


different rank
These gas formation curves can be fitted by a mathemati­
cal model on the basis of non­isothermal reaction kinetics.
This is rather easily done if the curves are representing one
reaction e.g. in the case of C3H8. A good fit is also possi­
ble if one has to assume more than one reaction. In the case
shown in fig. 4 the fitting of the measured CH4­formation by
3 reactions of second order leads to the lowest least square
deviations /5/. In this way kinetic parameters for the
different products and for various solid feedstocks have been
determined. Table 5 gives as examples values describing the
kinetics of pyrolysis of a coal at 1 and 100 bar. For the
condensable products tar and benzene and the gases CH 4 , C2H6
and C 2 H 4 the values for the activation energy E, frequency
factor k o and order of the reaction η are given. Without go­
ing into details it can be said, that these can be well
interpreted by the mechanism of pyrolysis assuming as a first
step the thermal breaking of bonds between the aromatic
structural elements and in the case of η = 2 a following
bimolecular radical reaction as rate controlling. Practical
use of these data is made in reactor modelling. Thereby the
sound physico­chemical basis allows a high security for
79

extrapolation from the laboratory scale into the next higher


and, finally into the industrial one.
dV/dt
[cmV(gK|]
0.3η
3 reactions 1. order
S = 0,01

3X SOO TOO

o measured
3 reactions 2.order
— single reaction 1 . . . .
S = 0,003 i calculated
— total J
Westerholt

CH4

inert gas 10 MPa N2

S: standard deviation

Fig. Different kinds of mathematical description of


measured CH 4 formation curves of a h.v. bit. coal
Table 5; Overview of kinetic parameters measured in the ther­
mobalance at 3 K/min (Coal Zollverein, 32.9 %VM)
N2 pressure
0.1 MPa 10 MPa
E ko E ko
8
tar n=1 138 7.6 χ 10 174 1.5 χ 10 11

1) n=1 140 2.1 χ 10 11 136 2.0 χ 1011


7
benzene 2) n=2 142 6.0 χ 10 115 2.0 χ 10 6
7
3) n=2 150 1.0 χ 10 149 8.0 χ ΙΟ 6

1) n=2 204 7.8 χ 1 0 " 214 7.8 χ 1 0 η


7
CH 4 2) n=2 158 2.7 x 10 141 5.3 χ 10 5
3) n=2 ­ ­ 257 1.8 χ 10 11

C2H6 n=2 210 1.5 χ 10 1 3 224 2.2 χ 10 1 3

C2H4 n=2 205 2.7 χ 10 1 3 218 7.1 χ 10 1 3


Ε in kJ/mol ; k0 for n = 1 in 1/min ; k 0 for n = 2 in g / ( c m 3 min)
80

4.2 GA SIFICA TION


At first an example shall be shown, how temperature and
pressure influences the rate of the carbon­H20­reaction. The
diagram in fig. 5 is based on experimental results measured
in a TGA /6/ taking coal char. As to the influence of tempe­
rature an exponential increase of the rate of reaction can be
noticed following the A rrhenius­law. A s to the influence of
pressure the reaction rate increases in the range between 1
and 10 bar, afterwards the curves come into saturation. This
behaviour can be explained by the Langmuir­Hinshelwood­mecha­
nism, which assumes an adsorption step in the overall reac­
tion /7,8/.
Fig. 6 compares the reactivities of lignites, coals,
chars, metallurgical coke and pitch coke against steam at 40
bar depending on temperature. In all cases the rate of reac­
tion is increasing with temperature as has been seen in the
previous figure. However, great differences are found for the
different solid fuels. The reactivity of the lignite is
highest, those of coals and chars have been found in a
relatively narrow range, whereby rank is not significant.

950 Í
92
0 5
90Θ
Fia. 5; Rate of C­H20­gasification depending on pressure and
temperature
Finally, coke and pitch coke, that means carbonaceous mate­
rial which is treated at high temperature significantly exee­
ding 1200'C, show lowest reactivity. As main factors influen­
cing the scattering of reactivity, chemical structure, physi­
cal structure and catalytic influence of the ash constituents
have to be taken into account. Especially the coke, treated
at high temperatures shows very low reactivity as the active
81

6Û0 650

Fio. 6.; Chemical reactivity against H 2 0 (40 bar) depending


on coal rank and pyrolysis conditions

10" 2 g/g­min

30­
10 bar, 10 Κ /min
* Kosovo
• Schwarze Pumpe
a Rhenish
20­ χ Kolubara
° Spanish

10­

temperature

Fia. 7: H,0­reactivity of lignites depending on their earth­


alkaline content
sites, i.e. the rand atoms of the microcristallite structu­
res, their dislocations and the hetero atoms are annealed at
high temperature. Responsible for the high reactivities of
lignites are the catalytic active constituents of their
ashes. Às Fig. 7 shows some correlation exists between the
reactivity of the different types of lignites and their con­
tents of earth­alcaline compounds. It is known, that these
82

are found finely dispersed in the raw samples as salts of hu­


mic acids. This is a precondition for the catalytic activity
of these compounds /9/. It should be noticed, that reactivi­
ties of other materials such as biomass generally are found
to be less than those of lignites. This is understandable as
catalytically active compounds are not generally found in
these materials.
4.3 PLA SMA PYROLYSIS
Plasma pyrolysis for solids has been developed in order
to produce acetylene from coal, which is thermodynamically
the only stable gas at temperatures exceeding 2500"C. Within
a project together with an industrial partner we have built a
laboratory scale plasma pyrolyser as shown in fig. 8. Between
cathode and anode an electric arc is produced. It rotates in
a field of a magnet and produces a hydrogen plasma at
temperatures up to 3000"C. Into this coal is injected and
pyrolysed. Fig. 9 summarizes some results for different
coals. The left handdiagramme shows that the acetylene yield
is rising with the specific energy input and goes up to 40 %
of the feed coal. Besides acetylene small amounts of ethylene
and CO are formed, also tar and char are obtained /10/.
Plasma pyrolysis is generally a simple technique to produce
directly acetylene from carbonaceous materials. A lso it
should be taken into account that it could be a tool to de­
stroy organic compounds from e.g. liquid wastes, which are
not acceptable for environmental reasons.

cathode 0.1 - 1 bar


2000 - JO O O 'C
m w, s 10 kg coal/h
cool s Wm„JH2A
anode■ s 30 MW

t plasma generation
A
magnetic coil
plasma pyrolysis

V
H20—­=i quench

products
C2H2
Fia. 8; Laboratory reactor for the pyrolysis of solid
feedstock in a hydrogen plasma
83

acetylene yield
In w t - X of
feed cod (ar.)
coal: Cape Breton
50-1
Cape Breton^
(Canada)
40·

30-
/ / \S N Luisenthal
20· ffi\ (Saar)
Westerholt
10- (Ruhr)

1 1 1 -
2 4 6 8 4 6
specific energy input in kWi/tcg cool

Fia. 9: Results from laboratory experiments of plasma


pyrolysis for different coals
5. CONCLUSIONS
With respect to the aims of the Conference to improve
pyrolysis and gasification of biomass in the future the fol-
lowing may be concluded:
From the broad use of thermochemical conversion of coal
and other solid fuels experimental and theoretical methods
are established for their characterization with respect to
their use in pyrolysis and gasification processes. Especially
it is possible to determine the course of the formation of
different products with temperature and thereby to investi-
gate the influence of the conditions in the reactor i.e.
pressure and kind of atmosphere and rate of heating on the
amount and composition of the product. Mathematical models
are available to improve the design of reactors and pro-
cesses.
All these methods and results can be used to characte-
rize other carbonaceous material like biomass and wastes for
the design of new or the optimization of existing processes,
with respect to the feedstock available and the products
desired.

REFERENCES
( 1) VAN HEEK, K.H. and H.-J. MÜHLEN, Effect of Coal and
Char Properties on Gasification. Fuel Processing Tech-
nology, 15 (1987 ), p. 113/133
( 2) JÙNTGEN, H. and K.H. VAN HEEK, Reaktionsabläufe unter
nicht-isothermen Bedingungen. Fortschritte der chemi-
sehen Forschung 13 (1970), p. 601/99, Springer Verlag,
Berlin
( 3) JUNTGEN, H. and K.H. VAN HEEK, An update of German non-
isothermal coal pyrolysis work. Fuel Processing Techno-
84

logy, 2 (1979), p. 261/93


( 4) ARENDT, P. and K.H. VAN HEEK, Comparative Investiga-
tions of Coal Pyrolysis under Inert Gas and H, at low
and high Heating Rates and Pressures up to 10 MPa. Fuel
60 (1981), p. 779/788
( 5) VAN HEEK, K.H., P. KASSLER and W. WANZL, Übertragung
von Laborergebnissen zur Pyrolysekinetik von Kohlen auf
in situ-Reaktionen. Erdöl, Erdgas, Kohle 102 (1986),
p. 200/205
( 6) MÜHLEN, H.-J. and A. SULIMMA, High temperature, High
Pressure Thermogravimetry of Coal Gasification - Appa-
ratus, Data Acquisition and Numerical Evaluation. Ther-
mochimica Acta 103 (1986), p. 163/168
( 7) MÜHLEN, H.-J., K.H. VAN HEEK and H. JÜNTGEN, Kinetic
Studies of Steam Gasification of Char in the Presence
of Hydrogen, Carbon Dioxide and Carbon Monoxide.
Fuel 64 (1985), p. 944/949
( 8) VAN HEEK, K.H., H.-J. MÜHLEN and H. JÜNTGEN, Progress
in the Kinetics of Coal and Char Gasification. Chem.
Eng. Technol. 10 (1987), p. 411/419
( 9) VAN HEEK, K.H. and H.-J. MÜHLEN, Effect of Coal and
Char Properties on Gasification. Fuel Processing Tech-
nology, 15 (1987), p. 113/133
(10) BAUMANN, H., D. BITTNER, H.G. BEIERS, J. KLEIN and
H. JÜNTGEN, Pyrolysis of Coal in Hydrogen and Helium
Plasma. Fuel 67 (1988), p. 1120
85

ΚΤΙ ACTIVITIES IN THE FIELD OF BIOMASS PYROLYSIS

L. ANTONELLI
Vice President - Director of Alternative Energies Department
Kinetics Technology International SPA , Italy

Summary
Solid fuels use is becoming more and more difficult because of the
environmental problems connected with their handling and burning.
Strong efforts are carried on to develop suitable pretreatments to
overcome handling, combustion and pollution problems.
Slurrification of fossil coal (coal-water mixture, CWM) is starting
to have a significant role in the industrial installations. The
production of slurries based on charcoal from biomasses pyrolysis
shows specific difficulties and requires sophisticated technologies
and know-how. The ^critical factors and the results obtained with
our production process are illustrated. The production of charcoal
slurries on semi-industrial scale and their physical and
rheological behaviour is discussed. Evaluations of energy
consumption in slurry production and comparison with pit-coal
slurries is also analyzed.

1. GENERAL
Figure 1 shows the programs developed by KTI in fuels production
from biomasses pyrolysis. A ll the aspects of the production of these
alternative fuels was investigated including the ecological impact.

Figure 1 :
1. Pyrolysis process development
2. Charcoal and bio-oil utilization as fuels
3. Ecological impact (pyrolytic waters etc.)
4. Economics

In this paper the charcoal use as industrial fuel is presented.

2. CHARCOAL UP-GRADING
The use of solid fuels is becoming more and more difficult because
of the environmental problems connected with their handling, sulphur and
ashes content.
A system to overcome these drawbacks has been the up-grading of the
coal transforming it in a coal-water slurry (CWM). The advantage is to
transfer the coal in a liquid fuel eliminating the pollution problems
connected with the storage, transport and handling.
The pollution due to SOx and ashes require further treatments. The
advantages are significant and a number of large industrial plants have
successfully adopted this system of burning coal and many others are
considering this possibility.
With the target of the maximum flexibility in the use of the
pyrolysis fuels, we started a program to develop the same system of
using charcoal.
86

The difficulties of obtaining a char-slurry with acceptable solid


content are well known and are mainly due to:
- high porosity
- high surface area
- high oxygenated groups concentration on the surface area with
consequent hydrophilic characteristics
- low bulk density
On the contrary, there are interesting positive points due to the
absence of sulphur, to the relatively low ashes content and to the good
reactivity.
The program was developed in three phases:

2.1) Phase 1
Laboratory tests have been started using two different categories
of char produced in the Raiano pyrolysis plant from wood chips and olive
husks. The tests were oriented to investigate the following:
- grinding techniques
- granulometry distribution influence on the viscosity and
stability
- dispersion and stabilization agent selection and dosing
- influence of the oxygen during char milling
- influence of the char pretreatment at high temperature.
The results of this first phase were:
a) The max. solid content of the char based CWM has been as high as
52% by weight, with a slurry viscosity below 1000 cP.
b) The bimodal size distribution curve of the pulverized char is
producing an unstable slurry.
c) By using a very finely ground char powder with a monomodal size
distribution, the same solid content and the same viscosity, as
for the bimodal distribution, was obtained but with the
advantage of a very good slurry stability. Another advantage is
the simplicity of the process to obtain the monomodal slurry.
d) None of the programmed surface modifications of the char
(heating treatment, wetting, ash leaching) resulted successful
in increasing the solid content in the char-water slurry.
e) The grinding of char under controlled atmosphere of nitrogen
increases the solid content of the char based CWM by 5 to 10J
with respect to the grinding in presence of air.
It is worth noting the peculiar behaviour of the char slurries with
respect to the granulometrie distribution. Monomodal is better than
bimodal which gives unstable mixtures. This is due to the surface
physico-chemical characteristics which are not modified by the thermal
and chemical treatments tried during the tests.
Figures2 and 3 summarize the results obtained for four typical
mixtures prepared from wood chips char and olive husks char.
Figure 4 shows the Theological behaviour of char slurries compared
with pit-coal conventional slurries.
Figure 5 shows the Theological behaviour of two typical slurries
with micronized char. The sample containing olive husk char has a lower
viscosity.
Figure 6 shows the trend of viscosity against the temperature.

2.2) Phase 2
At this stage of the program, the experimental work was transferred
from laboratory to pilot plant. The main targets were:
- Reproduction of the best lab results;
87

Mixture type Mixture no.1 Mixture no.2 Mixture no.3


(*) (")

Coarse particles/fine p. 60/40 60/40 60/40


Char theoretic content in
the final mixture (% weight) 44,9 46,7 49,7
Dispersing agent (J weight) 0,7 0,7 0,7
Char content in the final
mixture (% weight) 46,9 48,8 51,9
* grinding in air
** grinding in nitrogen atmosphere

Fig. 2. Solid Content in the Different Aqueous Slurries


Obtained from Wood Chips Char

Mixture type Mixture no.4


(»)

Coarse particles (wt) /fine p. (wt) 60/40


Char theoretic content in the final mixture (% weight) 46,7
Dispersing agent (% weight) 0,7
Char content in the final mixture (J weight) 48,7
* grinding in nitrogen atmosphere

Fig. 3. Solid Content in the Olive Husks-Char Water Mixtures

2.0

1.8

1.6
\ TOTBWTUTC « 20 ' c
1.4 ^\
ArøU53
1.2 ^ - W R T W T " ^ ™m rø απ« β , . „ „.„, Α Ι Β

1.0
-
* * * * * * auwr « Μ ΤΗ« κ« w.tr saio
0.8
-
0.6
AQUEOUS SLURRT WITH OUR FRUI CLIVE HJSKS (48.TTC U.CF SOLIDI

0.4
-
0.2 -
n.n
ι
20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 *
9€AR RATE 1/S

Fig. 4. Charcoal Based Aqueous Slurry and Pit-Coal Water Conventional Slurry
88

- Better understanding of the influence of the granulometry;


- Investigation of the influence of the milling equipment when
operating at a scale which can be correlated to the industrial
dimension;
- Acquisition of data related to the energy consumption for the
milling and mixing stages;
- Definition of the best conditions for increasing the solid
content above the limits reacted during the lab tests.
A campaign of tests was carried on using a wet milling in single
stage. The simplicity of this scheme is very attractive for an
industrial application.
The investigation on the bimodal distribution can be done adding a
coarse fraction prepared separately. The additive is the same used in
lab tests. The milling is done in the presence of air. Characterization
of typical samples can be summarized as follows:

Solid content
Values higher than those on lab scale are obtained, concentration
around 55-56J can be produced with micronized char.

Slurries viscosity
The samples produced in the campaign have a viscosity in the range
600-2000 cP at 30 deg.C, compatible with the pumpability requirements.
Furthermore the behaviour is pseudoplastic with significant advantages
in industrial application.
Figures 5 and 6 show the Theological behaviour of some samples.
Figures 7 and 8 Show the granulometry distribution of the same
samples.

Slurries stability
A series of slurries produced during the tests have been stored in
drums and the tendency to solid décantation and water separation checked
every 2/3 days. With the same frequency all samples have been roughly
mixed by hand. After forty days, the Judgement on the most significant
sets of samples can be summarized as follows:
E1 very good
E3 excellent
Ek very good
E5 good
E12 acceptable
In any case, thé analysis of the results shows that all the
products can be used in an industrial plant if midly mixed with a daily
frequency as it is normally done in all the installations using CWM.

2.3) Phase 3
Since the max. content of solid obtained using only char was 55-
56J, even using micronized powder, another line of investigation was set
up trying to produce slurries with char and pit-coal.
The basic concepts at the basis of this approach are:
- The pit-coal can be used for CWM production having solid content
up to 65-70J.
- The combination of the two coals makes possible to reconsider the
utility of the bimodal distribution using the pit-coal only for
the coarse function.
- The dilution of the polluting components (sulphur) makes possible
89

2.0
TEM"ERATURE ■ 20 ' c
1.8 SOLID CONTENT IN BOTH SLURRIES ■ 52Z W.

1.6

1.4
MONOMODAL (FINE SIZE} CHA R POVCER FROM WOOD CHIPS
1­2

1.0

0.8 ­

0.6
ItïICtCOAL (FINE SIZE) CHA R POWDER FROM OLIVE HUSKS
0­4

0.2

0.0

—1 1 1 1 1 1 1 1 1 1 1 1 1 1 1

0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300
SHEAR RA TE 1/S

Fig. 5. Water­Charcoal Mixtures Viscosity

1.6

1.4

1.2 SHEAR RATE· 100 m'

1.0

0.8

0.6

0.4

0.2

­1— ­i— ­ 1 —
20 40 60 80 100
TEMPERATURE "c

Fig. 6. Viscosity Related to Temperature for Water­Wood Chips Char Mixture


90

the utilization of large quantities of pit­eoai remaining in the


limits imposed by the antipollution regulations.
The new system consists in incorporating a fossil charcoal having
an average granulometry of about 45 microns in a micronized pyrolytic
coal slurry (dm. 12­16 microns). Such procedure will permit to obtain
the following advantages:
­ Higher solid content in comparison with the pyrolitic carbon
slurry only.
­ Lower energy consumption in comparison with the completely wet
procedure.
­ Better fluidity with the same concentration, due to the bimodal
distribution.
­ Lower sulphur and ash content in comparison with the two separate
components.
It is also possible to foresee advantages in the plants operations;
for example the char slurry production will be done in the pyrolytic
plants spread in the territory, the fossil carbon grinding and its
incorporation in the micronized char slurry will be centralized close to
the power station which uses the fuel.
The operative diagram of such production is the following:

PYROLYSIS PLANT POWER STATION

Production of Grinding of fossil


micronized char coal at 45 microns
at 50*
I ^
Transport to the > ■

power station
Mixer

High concentration
slurry ■
'
Burner

Experimental work
A first campaign of samples production was carried on obtaining
slurries with 60J of char and pit­coal. The ratio between the two coals
is 60 and 40? char. The coarse pit­coal is added to the char slurry
(50Í). The behaviour is Newtonian, the resulting slurries have a LHV
of 4000 Kcal/kg and are usable as fuel in a burner.
A second campaign aiming to increase the solid content to 65J is
carried on with a ratio char/pit­coal 40/60; 50/50 and 54/46. Analysis
of the produced samples show increasing viscosities. With small
adjustments on the additive quantity, which is increased to almost 1J
the slurries obtained are good and usable in a burner. The HV is higher
than 4500 Kcal/kg.
In conclusion, this second group of samples confirm the possibility
of producing mixed slurries with 65Í solid and good viscosity stability
and comparable with the pit­coal slurries.
The final experiments tried to increase furtherly the solid content
above 65%. The result was that it is still possible to reach 69/70% but
the viscosity is high and at the limits of acceptability for industrial
applications.
91

3. ENERGY CONSUMPTION
The energy consumption registration shows that during all the tests
the milling process was regular without big variation in power
absorption. Indications were also obtained for the consumptions
expected on industrial mills with capacity 10/100 times higher. Figure 7
summarizes the results obtained on pilot plant:

Figure 7

Run Energy consumption Slurry flow Char flow Consumption KWh/t


KW Kg/h Kg/h a b A B

E1 2,2 15,3 7,81 86 170 43 85


E3 2,1 20,4 10,52 62 120 31 60
EU 2,2 18,2 10,51 73 125 37 63
E5 1,9 16,7 10,75 68 106 34 53
E12 (35? di E1 + 65? di E2) 58 114 29 57

Legend: pilot mill a = consumptions referred to slurry


b = consumptions referred to char
A = consumptions referred to slurry
B = consumptions referred to char

The experience matured on pit­coal allows to foresee a reduction of


40­60? of the figures shown in A and B when using industrial scale
equipment.
A further reduction can be obtained using multisector ball mills
for which the above experimental results allow a forecast of 25­40 KWh/t
of slurry which with a solid concentration of 56? gives a consumption of
only 45­70 KWh/t of dry charcoal.

1500 ­
E­12

E­2o

1000 ­

E­1,
500 ­ *^^«^_
*» ^^*^^

E­3.

0 1 ι ι 150 200 250


50 100

Fig. 8. Different Samples Viscosity at 30°C


92

4. CONCLUSIONS
The case of the process investigated in this program allows the
production of excellent slurries with a solid content of 65>. Higher
concentrations are technically possible but not usable in industrial
burning systems. The resulting slurries have roughly 50J char, 50Í pit-
coal with a LHV above 4000 Kcal/kg.
Figure 8 shows the Theological behaviour of some typical products.
Energetic consumption: taking into condlderation the products with
solid (char/pit-coal 50:50), the energy consumption is 35 KWh/t of
slurry or 54 KWh/t of solid including the milling stage. The same value
for slurries with only pit-coal is 70 KWh/t of slurry with 70J solid or
114 KWh/t of coal. This calculation are relative to a slurry production
of 20 t/h.
93

BIOMASS FUELS AND GASIFICATION

J. CARRE, L. LACROSSE, Y. SCHENKEL


Center for Agronomical Researches (CRA)
Unité."Biomasse"
5800 GEMBLOUX, Belgium

F. RURIHOSE
Université Catholique de Louvain (UCL)
Unité "TERM"
1348 LOUVAIN-LA-NEUVE, Belgium

Summary

Fixed bed downdraft gasifiers have specific requirements on fuels .


This paper considers the different fuels characteristics that are ne-
cessary to obtain an optimal gasification : moisture, mineral and vo-
latiles contents, size, bulk density,...
The densified products quality is also considered, particularly their
cohesion . Specific testing methods have been developped at the CRA .
They allow to fix quality limits for these products .

1. INTRODUCTION
Many important studies have been carried out on gas producers designs.
The gasified fuel has often been neglected . Indeed, a well-designed gasi-
fier will never work with fuels that do not have a minimum quality .
This paper presents the quality limits that fuels must have to be suc-
cessfully gasified in fined bed downdraft gasifier .

2. FIXED BED DOWNDRAFT GASIFIERS REQUIREMENTS ON FUELS


2.1. Moisture content
The fuel moisture content is of prime importance for the success of
the gasification process . The negative influence of water can be noticed
at different levels :
- the lower heating value (LHV) of lignocellulosic material decreases when
the moisture content increases .
Considering that ashfree dry biomass LHV is about 18.8 MJ/kg, the LHV of
wet biomass becomes :

THV -IflS 100 2 c H (1)


LHV 1 8
H - ·8 100 + H 2
· 5
100 + H
LHV = wet biomass lower heating value (in MJ/kg)
H = moisture content (% dry basis)
For instance, ashfree biomass containing 20% moisture content (dry basis)
would have a LHV :
LHV H = 18.8 y|g - 2.5 - ^ = 15.25 MJ/kg
94

water in excess induces the hearth cooling . The resulting temperature does
not allow the cracking of the heavy hydrocarbons coming from the pyroli­
sis zone of the gasifier . Moreover, the water itself is not cracked and
will condense later in the cooling and cleaning system .
it must also be said that, thermodynamically, it is always more interes­
ting to gasify as dry as possible fuels .
Indeed, the gas LHV and the gasification efficiency quasi­linearly de­
crease from 0 to 50% moisture content (see fig. 1) .
The hydrogen and methane gains in the gas do not compensate the carbon
monoxide losses (see fig. 2) .

100 40
o CO
35
90­
30 • CO,

80
Q 25

70­ g 20
ω
Η

1 15
M 60

10Η
50­
5
_Δ_Δ_Λ_Λ_­Δ­Λ_Λ­*­*
40 0
10 20 30 40 50 10 20 30 40 50
MOISTURE CONTENT (%, d.b.) MOISTURE CONTENT (%, d.b.)
Fi g . 1 : Gasification efficiency Fig.2 : C0,H , CH4 and C0 2
and gas LHV as functions
contents in the gas as
of moisture content
functions of moisture
content

2.2. Mineral content


The fuel mineral content must be as low as possible . It also affects
the LHV . Introducing the mineral content in relation (1), it becomes :
100 ­ MC Η
LHV,, 18.8 2.5
Ή 100 + Η 100 + Η
MC = mineral content (% dry basis)
For instance, biomass containing 20% moisture content and 10% ash con­
tent, would have a LHV :
100 ­ 10 20
LHV„ = 18.8 2.5 y|^ = 13.68 MJ/kg
Η 120
95

Moreover, the mineral content can make the gasification impossible .


Indeed, the temperatures that are reached in the hottest zone of fixed bed
downdraft gasifiers are often higher than the biomass ashes melting points.
When the mineral content is too high, clinkers will progressively appear
in the hearth . They will finally prevent the gas from passing through .
Usually, it is considered that higher than 5% mineral content, it is
nearly impossible to avoid clinkers formation . But it is dangerous to ge-
neralize : following the mineral composition, melting happens at more or
less high temperatures . For instance, the presence of alkali oxides can
induce eutectics formation at relatively low temperatures .
For exemple, the mineral content of rice husks is about 20-25% with
more than 90% silica (Si0„) . The latter has a melting temperature of
about 1700°C . If it was alone, the risks of melting would be very little.
Unfortunately, it is principally accompanied by kalium oxide (K.0) but al-
so by Mg, Al, Ca, Fe, Na oxides . It results a much lower melting tempera-
ture .
2.3. Volatiles content
The biomass volatiles content may not be considered as a limiting
factor . Fixed bed downdraft gasifiers must actually be designed in order
to crack the tars and heavy hydrocarbons liberated in the pyrolises zone .
However, it must be noticed that thermodynamically, biomass must not
only be as dry as possible (cfr supra) but should also ideally undergo a
thermal treatment (torréfaction) .
The gasification efficiency is optimal for dry biomass having lost an
equivalent of 20% moisture content (see fig. 3) i.e. biomass with a for-
mula of about C L . 0. , .
0.9 0.4
100

Gasification efficiency and gas LHV


evolutions as functions of moisture
content or pyrolisis level
96

2.4. Size
The optimal size for a fuel that has to be gasified depends on the
gasifier hearth dimensions . It must be such as to allow an optimum air/
fuel contact .
It is generally considered that the length of the fuel must be between
1/10 and 1/5 of the hearth diameter . Out of these values, problems of ir-
regularities in the gasification process can occur :
- too long fuels can generate bridges preventing the fuel from flowing down
to the gasifier hearth . The gasification reaction can tend towards com-
bustion by air excess .
- too small fuels cause high pressure drops by forming a kind of airproof
cake .
For small size fuels (sawdust, agricultural residues,...) densification
can be a solution but the densified products must be of prime quality
and answer some criteria (see below) .
2.5. Bulk density
The fuel bulk density directly influences the gasification velocity
and the residence time of the fuel in the gasifier hearth . If the bulk
density is too low, it is difficult to maintain gasification reactions .
The air excess also turns gasification into combustion .
2.6. Ultimate analysis and heating value
If the only organic material is considered, it may be said that the
different kinds of dry biomasses more of less have the same composition in
carbon, hydrogen and oxygen : C = - 50%
H = I 6%
0 = - 44%
It corresponds to a formula of CH. ,, 0. .. and a lower heatingö value
c ίο α U T Λ 1.44 0.66
of 18.8 MJ/kg .
The latter mainly varies with the moisture and mineral contents (cfr
supra) .
2.7. Densified products quality
Densified products generally answer the above quality criteria .
Indeed, their moisture content is low (<10%) and their density is high .
Moreover, it can be possible to adapt their size to the gasifier hearth
dimension .
But another quality must absolutely be satisfied : cohesion
Researches carried out at the CRA allowed to develop testing methods
in order to determine this parameter .
This methods are described by Carré et al. (1984) .
The most important are the ones concerning the measurement of :
­ the density after different conditionings
­ the rate of volume change in immersion
­ the friability index after different conditionings
­ the elongation and swelling at 20"C 95% RH
Table 1 give the quality limits corresponding to these tests .
97

800 1200
Density at 20°C 65% RH (kg/m3)
Υ//Λ
3
Density at 20°C 95% RH (kg/m ) 77Δ50 100
Rate of volume change in immersion (% min)
0-5
ΊΖΖΔ
0­75
Friability index at 20°C 65% RH
y/A0 3 \
05
Friability index at 20°C 95% RH ΈΖΣΖ.
10 25
Elongation at 20°C 95% RH (% initial length)
10
VM
25
Swelling at 20°C 95% RH (% initial diameter)
WZÅ
Bad ////// Acceptable Good

Table 1 : technical prescriptions for densified


fuels to be gasified

3. CONCLUSIONS
When a gasification unit does not work properly, the gas producer,
i.e. the technology is more or less always suspected .
Actually, the operators are very often responsible for the problems
that occur . One of the reasons is that they are careless about the fuel
characteristics : the gasified biomass is too wet, or bad calibrated, or
contains too much inorganics .
They too often forget that downdraft fixed bed gasifiers require very
good quality fuels .
It may be said that the respect of the above prescriptions must allow
to avoid many important problems and to have a good working of the gasifi­
cation installations.

REFERENCE
CARRE, J., HEBERT, J. and LACROSSE, L. (1984) ­ Critical analysis of the
dry process improvement of ligneous materials for energy­producing pur­
poses . Final report CEC (DG VIII)­CRA, 245p.
98

USAGE OF CARBON BLACK AND ACTIVATED CA RBON


IN RELATION TO INPUT AND TECHNICAL ASPECTS
OF THE PYROLYSIS PROCESS

B. Bilitewski, G. Härdtle, K. Marek

­ intecus ­
associated engineers for environmental protection technologies
­ Berlin ­

SUMMARY

A variety of pyrolysie char made of domestic waste, biomass, sewage


sludge, plastics, rubber etc., has been examined in regard to its
usage as combustible, carbon black and activated carbon (1).
Pyrolysis char made of plastics and waste tyres has a high content
of carbon and a low content of ash and thus it is very suitable as

­ carbon black to enrich low and medium rubber qualities


­ a colour pigment in printing ink, colour­ and plastics­industry
­ activated carbon for waste water purification

But in spite of the different possibilities to be used pyrolysis


char still has not been produced and commercially sold. The
examination shows that the raw material cannot be sold without a
further treatment, for example the enlargement of the BET­surface.

1. INTRODUCTION

The degasification of waste tyres produces char with a greater or


lesser carbon content. It is essential to find a suitable method of re­
utilizing this product if the pyrolysis process is to be applied
economically. Particularly the pyrolysis char obtainded from waste tyre
degasification appears to offer a number of interesting possibilities.
With a pyrolysis temperature of 700 °C and a retention time of 50
minutes, we obtain a residual char content of more than 40 Ζ by weight,
with an upper heating value of approx. 31,400 KJ/kg and a carbon content
of approx. 87 Ζ by weight. Co­combustion trials of this char with
mineral coal have yielded positive results, although the high sulphur
content (2.8 Ζ by weight) constitutes a considerable problem. Orienting
tests to determine the suitability of the char for application as acti­
vated carbon, as carbon black for vulcanisâtes, as pigment or in the
printing ink industry have shown that the pyrolysis char cannot be
satisfactorily re­utilized without further treatment.
99

2. ACTIVATED CARBON AND ITS APPLICATION

Pyrolysed waste tyre char can be effectively activated with steam


in a temperature range of 750 °C ­ 950 °C. Fig. 1 shows the internal
surface area of the different sorts of activated carbon as a function of
burnoff. By burnoff, we mean the gasified portion of the carbon in the
char, expressed as a percentage (1). The symbols used mean: A700, A700P­
A ­ waste tyres, 700 ­ pyrolysis temperature (°C), t ­ 10 pyrolysed for
10 minutes, t ­ max pyrolysed for 2 hours, where no retention time
given, pyrolysed for 50 minutes. Ρ ­ in powder form, AH ­ waste tyre
char from the fluidized­bed reaktor at the University of Hamburg, Prof.
Dr. V. Kaminsky, K ­ sewage sludge, Sp ­ paper mill waste.
tm^/g] infernal surface area
600
A70o',f=10
A700V \ /
i^A700P
400 ¿yv
A550
A700.t= max
Sp700
TV^r·
200
r\AH K 700
^ ■ ^

20 40 60 80 1001%]
burnoff
Fig. 1 Internal surface area of the different sorts of activated carbon
as a function of burnoff (Nz isotherm) (1)

It is evident that neither sewage sludge nor paper mill waste are
suitable for the production of activated carbon. Other important factors
for the possibility to use char as activated carbon are temperatur,
reactor type and the retention time of the pyrolysis of waste tyre.
Temperatures around 700 °C and retention times around 10­15 minutes
during the pyrolysis process are advantageous for the production of
activated carbon. The fluidized bed reactor (AH) however produces char
which is not as suitable as the char in a rotation drum.
Our results show that the theoretical considerations borrowed from
coal gasification (2) are applicable to the partial gasification of
waste tyre char within the limits of permissible variation. This means
that the characteristics of the activated products can be calculated as
a function of burnoff, where the cavity structure of the feed char is
known. The correctness of the postulate can also be verified qualita­
tively by the change in the pore distribution in the adsorption and
macro pore structure as a function of burnoff.
Fig. 2 shows the differential radius distribution of the adsorption
pore structure for activated carbon from waste tyre char with varying
burnoff characteristics.
To begin with, the char has narrow pores which expand to produce
larger pores in the course of partial gasification at higher burnoff
values. The maximum number of pores is reached at about 200 A.
Comparable samples of activated carbon from mineral coal have their
maximum number of pores at 100 A and less. For this reason, such
commercial activated carbon has a considerably greater internal (BET)
100

surface area (Hydraffin BS 12 - 1200 m z /g) with the same total pore
volume as activated carbon from waste.

radius [Ál
Fig. 2 Differential pore radius distribution for activated carbon from
waste tyres with varying burnoff characteristics

Activated carbon was contacted with the test substance phenol dis-
solved in water until an equilibrium condition was reached. As phenol
frequently occurs in waste water, it constitutes an interesting test
substance for waste water treatment. There are two standardized methods
for tests using phenol: the DIN standard test method 19 603, which
governs the determination of the isotherms using powdered activated
carbon in a mechanical shaker with an input concentration of 10 mg/1;
and the AWWA standard test method, according to which the phenol
adsorption of a layer of granulated activated carbon is determined when
subjected to a phenol solution flow.
The adsorption equilibrium was determined by contacting phenol dis-
solved in water at a fixed input concentration with a predetermined
quantity of activated carbon. If the carbon remains in equilibrium with
the solution for a sufficiently long period, and no further changes in
the adsorption behaviour are detectable, we speak of an equilibrium ad-
sorption. The concentration corresponding to this state is known as the
equilibrium concentration. The equilibrium adsorption Q Q is defined as
the quantity of the test substance in mg that can be adsorbed from the
solution per g activated carbon:
101

(CA. ­ Ce) (mg/g)


M
Qo ■ equilibrium adsorption (mg/g)
V ­ volume of solution (1)
M ­ quantity of carbon (g)
CA. ­ input concentration (mg/1)
Ca ­ equilibrium concentration (mg/1)

As adsórbate a phenol solution with an input concentration of 10


mg/1 and a bath volume of 10 litres was used. The char sample weighed 1
g and was subjected to a constant flow of phenol solution. The concen­
trations of the solutions were measured continuously with an ultraviolet
spectrometer, and the adsorbed quantities calculated in accordance with
equation above. Generally speaking, phenol adsorption is increased by a
factor of 8 through an activation process (850 °C and 30 minutes). By
way of comparison, the commercial activated carbon Hydraffin BS 12 was
also tested. The equilibrium adsorption condition is reached between 16
and 20 hours, whereas Hydraffin reaches an equilibrium condition after
only 6 hours.
The slope of the equilibrium isotherms, at the same input concen­
tration and with a constant quantity of solution, is determined by
altering the weight of the samples of activated carbon and plotted in
terms of log­log coordinates (fig. 3 ) . Fig. 3 shows the phenol
adsorption capacity of activated carbon from waste tyre with different
burnoff characteristics as a function of the residual concentration.

lwt­%) phenol adsorption


5.0

2.0 5,0 10 (mg/Il


residual concentration of phenol

Fig. 3 Representation of phenol adsorption as a function of the residual


concentration in terms of log­log coordinates
102

twt %] DC­adsorption
5
:
A 700,til0
BŞ12, • Ι O­W
3

2
Sjp*
fop

1 ÍÍA700F

0,7
0,5
η »

0,3
Γ ι1
0,2
30 50 100 200 300
[mgDC/l]
Fig.4 Dissolved carbon adsorption from waste water as a function of the
residual concentration in terms of log­log coordinates

Taking, on the basis of this figure, the phenol adsorption capacity


(in 2 by weight) for a residual phenol concentration of 1.0 mg/1 as a
criterion for assessing the activated carbon, the high quality of the
waste tyre char is confirmed by increasing burnoff. The capacity of the
carbon increases with higher burnoff as the almost parallel moved slope
became steeper and the adsorption capacity went down.
The reference carbon samples Hydraffin 214 and BS 12 showed very
good results. With a residual phenol concentration of 1.0 mg/1, we ob­
tain, a phenol adsorption capacity of 9.8 Ζ for Hydraffin 214 and 4.6 Ζ
for Hydraffin BS 12. Because of a steep gradient both of these activated
carbon samples can only be applied successfully in a relatively narrow
concentration range.
Adsorption tests designed to demonstrate the characteristics of
activated carbon cannot be limited to the adsorption of suitable test
substances. An orienting study was therefore carried out in which
granular and powdery carbon samples were produced from waste tyres and
tested together with two commercial activated carbon samples. In a
laboratory­scale sewage treatment plant the carbon was added to the
activated sludge tank in accordance with the biocarbon process. First of
all, the isotherm was plotted on the basis of tests using a mechanical
shaker. Fig. 4 shows the adsorption isotherm for waste water which has
not been subjected to biological pre­clarification, when tested in con­
junction with the four different carbon samples. The input concentration
of the waste water measured CA. ­ 145.3 mg DC/1. The curves obtained are,
as far as the gradient is concerned, comparable with the results
obtained by Franke et.al. (3) for activated open­hearth carbon and waste
water treatment carbon.
103

η [%] reduction IJ [%) reduction


100 100

90

A700P
80
... A 700,*10 °

70
214 ,' y~)
' . °­
» BS12 \ · o 2­
* X ^
60
without carbon y^ « Χ
Χ

50
30O[mgO2/l] 1000 1500 2000 2500 3000 [mg/I]
BSB5­input K2&2O7­input

Fig. 5 Percentage BOD reduction Fig. 6 Percentage COD reduction


plotted against BOD input with plotted against COD input with
and without carbon and without carbon

On the basis of the gradient, it is possible to describe the be­


haviour of the carbon in activated carbon filters. Gradients greater
than 1 result in separating factors of more than 1, and thus cause an
unfavourable equilibrium. In the case of isotherms such as those in fig.
4, complete removal of the substances in a filter is likely to prove
difficult owing to the unfavourable equilibrium. However, it is obvious
form the curve that the powdery activated carbon A700P from waste tyres
demonstrates the most favourable characteristics.
In fig. 5 and 6 the performance of the carbon sample A700P is con­
firmed. Here the percentage BOD and COD reduction is plotted against the
BOD and COD input and compared with the biological BOD and COD
reduction. With the help of the activated carbon, the biological BOD and
COD reduction can be increased by approx. 10­25 Ζ depending on the type
of carbon tested.

3. CARBON BLACK AND ITS APPLICATION

The utilization of residues of the pyrolysis of waste tyre as a


filler in the rubber industry is very important. Their utilization as
industrial black carbon for low technical rubber articles is undeniable,
but the most important field of application would be the utilization of
residues as enrichment fillers in the production of tyres. We examined
the following possibilities at the TU­Berlin:
black carbon from the pyrolysis process as half­enrichment
black carbon SRF or GPF
black carbon from the pyrolysis process as full­enrichment HAF
black carbon, as it is for example used for the top surface of
tyres
Fig. 7 shows the characteristics of black carbon of the pyrolysis
of waste tyres in comparison with normal black carbon as it is used for
the vulcanisation of tyres. The mechanical­technological results are re­
presented as a function of the temperature. The statement can be made
104

that the property of all used black carbon don't correspond to the
standard. The same results have been achieved in Japan by Kobe Steel,
Ltd. (4).
But in case of lower temperatures the black carbon quality
generally became better.
Another field of application which we examined concerns the black
carbon pigment in the production of printing inks. In a company for
printing ink in Berlin we examined the possibilities of utilization of
black carbon from the pyrolysis process of waste tyres for book­,
offset­, newspaper rotary­ and heliogravure­ink. Only one examined black
carbon met the requirements for the newspaper rotary print. The particle
size distribution, the adsorption capacity of oil, the set behaviour and
the swelling time corresponded the usual commercial requirements. The
ink proved to be slightly more blue than normal printing ink. The
intensity of ink of black carbon usually becomes better the smaller the
particle size granulation is and can be improved by a corresponding
treatment.

tear strength abrasion


[ Κ « N/m] [ mm ]

•HAF Χ·
QPF
S
χ

HAF
> τ 1 I I ■» »
500 600 700 800 BOO f C] 900 600 700 βΟΟ 900 f C]

elongation tensile strength


[ Χ]
[ M * N/m]
15,

­HAF
­GPF

500 eoo 700 eoo eoo


I* C]

Fig. 7 Impact of pyrolysis temperatur on the physical property of vul­


canisation products in comparison with two commercial(HAF, GPF) carbon
blacks.
105

REFERENCES

1. Bilitewski, Β.: Gezielte Herstellung von Adsorptionskoksen aus Abfäl­


len für die Abwasserreinigung, Dissertation, TU­Berlin, 1980
2. Juntgen, H.: Gezielte Herstellung von Adsorptionskoksen für die Was­
ser­ und Luftreinigung, Habilitationsschrift, Universität Heidelberg,
1966
3. Franke, F. H., Motadi, M., Bohnke, B.: Forschungsbericht des Landes
Nordrhein­Westfalen, Nr. 2678, Westdeutscher Verlag, 23 pp.
4. Kawakami, S. ; Inone.K.; Tanaka.H.: Pyrolysis Process for Scrap Times
in American Chronical Society 1980
106

RAPPORTEURS REPORT ON SESSION II


PRE-TREATMENT AND CHARACTERIZATION

Catherine Esnouf
Cemagref
B.P. 121
92164 Antony Cedex
France

PRESENTATIONS

Introduction
This session was concerned with feedstock variety and its adaptation to
thermochemical processes; two very different examples of charcoal valorization
were also presented.

Feedstock Characteristics
The diversity of feedstock was emphasised as being the most important
point, as the feedstock determines the process used and the products obtained.
This was clearly shown throughout the conference.

Feedstock diversity
Not only do different raw materials have to be considered, such as
agricultural waste, wood, refuse etc., but also the different characteristics of those
raw materials. Wood, for instance, is affected by the type of forestry it comes from,
the parts of the tree that are collected, and the harvesting techniques, giving rise to
as many products as there are processing lines.
This gives very different costs: wood from 48 ECU/dry t to 70 ECU/dry t;
agricultural waste 25 ECU/dry t; and municipal solid waste from 34 ECU/dry t (wet
fluff) to 53 ECU/dry t (dry fluff) and 65 ECU/dry t (pellets:RDF) without considering
disposal credits.

Feedstock influence on thermochemical processes


A detailed study has been conducted on coal, showing the influence of
chemical and physical structure, as well as mineral matter content. Experimental
and theoretical methods have been developed to link feedstock composition to
process, and the use of such methods has been proposed for biomass and wastes.
The main parameters influencing biomass gasification were presented, for
example moisture and mineral content, size and bulk density, volatile content, and
their effects on gasification were emphasised.

Pretreatment
Feedstocks may need pretreatment to improve the subsequent process, but
it must be remembered that it involves additional cost. With regard to biomass, a
critical study on densification for gasification was presented, showing that good
and bad methods exist. The minimum cost of pelletisation is US$100/t.
107

Municipal solid wastes (MSWÌ


Pretreatment of municipal solid wastes (MSW) should include as few steps
as possible as set by the feedstock and the required output of the plant. In this
respect, several critical steps are recommended for any plant recovering energy:
liberation and screening; magnetic separation; and coarse shredding - these
operations give separation of the fines, oversize putrescibles and ferrous materials.
These are steps with high mass and energy efficiency which provide better plant
performance and improved energy recovery. Their viability is due to the low cost of
implementation.
The manufacture of refuse derived fuels (RDF), however, is often much more
questionable: it entails a high cost and complex process and a market for the
products has to be found.

Charcoal valorisation
Two different strategies for charcoal valorisation were reported:
(i) A large scale biomass project was presented in which charcoal-coal-water
slurries have been manufactured for burning in power stations. Compared to
coal slurries, the reduced energy needs and absence of sulphur are
advantages. The production cost was reported as US$25/t.
(ii) A project using wastes as feedstock for the specific markets of carbon black and
activated carbon was also presented. The effect of products specifications on
pyrolysis conditions and the importance of the feedstock were reported as major
considerations. An acceptable activated carbon was obtained in a three-step
process, but the carbon black produced was not of an acceptable standard so
that new markets had to be sought for the product.
Strategies of the latter type are more short-term as they provide answers to
environmental concerns and could therefore quickly prove profitable. Short-term
opportunities for pyrolysis and gasification mean, therefore, that diversification is
necessary such as looking for feedstocks that could match market needs through
appropriate processes.

DISCUSSION

Feedstock characteristics
A discussion took place on moisture content relating to the presentation by
Dr Lacrosse: what is the influence of water?
Is it the same on every process?
Is it right to suggest zero moisture content as the optimum?

It was agreed that it depended on the process: gasification uses water for the
shift reaction and the performance improvement versus cost of removal of the last
remaining moisture is disputable. For pyrolysis, with water being produced in the
reaction, the less moisture content in the feed the better. On the optimum
gasification efficiency presented for partially carbonised (torrified) wood, Dr
Lacrosse said that it was the result of a theoretical computation, no experiments
having been performed. Mr Bonino stated that this was confirmed by his own
experiments.
108

Pretreatment
The discussion focussed on the briquetting technology for gasification where
it was asked what technologies had produced "good" and "bad" briquettes. Dr
Lacrosse replied it was very difficult to give a general answer, the methods being
as important as the equipment used. Generally screw extruders gave the best
results, but a small number of tests in a piston extruder in carefully controlled
conditions proved to be better on one occasion. It was suggested that a good
characterisation method for pellets was the measurement of mechanical strength at
high temperature.
Questions were asked on the cost of such pretreatment. Dr Lacrosse replied
that it depended greatly on the feedstocks, whether it had to be dried and/or ground
before compression. Whichever method was used, a minimum cost of US$100/t
was incurred reaching up to US$150-200/t.

Charcoal Characteristics
Questions were asked on lignite behaviour and whether the evolution of
reaction rate as a function of temperature and pressure were the same as those
presented for coal char? Mr van Heek replied that no systematic study had yet
been conducted, but that one has to be very cautious on extrapolations from one
feedstock to another. For instance in the case of ash content, carbonate formation
in the case of lignite leads to a reaction rate decrease with pressure increase.
With reference to the specific uses of carbon as higher value products,
questions were put forward concerning the value of the carbon black. Mr Bilitewski
stated that for an acceptable carbon black to be obtained, specific reaction
conditions had to be used in tire pyrolysis. The cost of making good carbon black
was 200-350 DM/t (1985 figures). For activated carbon, the process is more
complex and results in a production cost of 1200-1400 DM/t. Dr Roy, from the
University of Laval, indicated that in his process of vacuum pyrolysis, the resulting
char from tires had a better homogeneity but that the steel should be eliminated in
order to avoid catalytic formation of pyrolytic carbon.
Examples were requested of large scale uses of char-water slurries as well
as information on the economics of the process. Mr Antonelli stated that current
slurry usage concerned coal slurries; two large scale boilers in the petrochemical
industry presently use these slurries in Italy. Huge projects for coal slurry use exist
in the USSR, as slurries allowing the transport of coal in pipelines. As for the
economics, the last evaluation indicates a total production cost of 30-40 Lit/kg, i.e.
US$25/t; with the cost approximately equally distributed into operating cost, capital
cost amortization and energy cost. It was emphasised that charcoal use in
combination with coal in slurries permits a reduction in sulphur content.

Economics
In conclusion, the chairman asked Dr Bridgwater whether he could give a
breakdown of the biomass costs presented into labour, capital, and energy costs,
so that this could be extrapolated for developing countries as very high costs in
Europe compromise short-term energy uses through pyrolysis and gasification. It
was explained that the major costs are labour and capital and therefore
extrapolation must be carried out cautiously because if labour is expected to be a
lower cost, equipment could cost more or even be unavailable, even without
considering maintenance problems.
SESSION III

PYROLYSIS, GASIFICATION AND LIQUEFACTION TECHNOLOGIES


Ill

BIOMASS GASIFICATION:
PAST EXPERIENCES AND FUTURE PROSPECTS
IN DEVELOPING COUNTRIES

Matthew S. Mendis
Industry and Energy Department
The World Bank

Summary
This paper presents an overview of the history, technology and use of
small-scale biomass gasification systems in developing countries. The
experiences to date have been mostly disappointing due to several
reasons including: inappropriate technology and standards for developing
countries; use of unacceptable biomass fuels; lack of trained operators
and infrastructure support; lack of adequate user incentives; and
finally, marginal economics. Recent developments in utilizing
ferrocement instead of metal to fabricate biomass gasifiers have led to
drastic reductions in the cost of production and significant increases
in reactor service life. The resulting economics present a more
favorable picture for the future of small-scale gasification systems.

1. HISTORY
The basic principles of biomass gasification have been known since
the late 18 th century and commercial applications of the principles were
first recorded in 1830. By 1850, large parts of London had gas lights and
there was an established gas industry manufacturing "producer gas" from
coal and biomass fuels. The use of producer gas to run an internal
combustion engine was first tried around 1881. By the 1920s, producer gas
systems were being used to operate trucks and tractors in Europe. While
it was demonstrated that it was possible to operate engines with producer
gas, it was not convenient or reliable and producer gas systems for
operating mobile or stationary engines did not gain wide acceptability.1
Biomass gasification systems reappeared with a force in Europe,
Asia, Latin America and Australia during World War II as a result of the
scarcity of petroleum fuels. In Europe alone, almost one million gasifier-
powered vehicles helped keep basic transport systems running during the
War. In most cases, the gasified biomass fuels were either wood or
charcoal. Gasifier systems were generally abandoned with the reemergence
of relatively inexpensive liquid fuels after the War.
The "energy crisis" of the 1970s sparked a renewed interest in
biomass gasification systems. The technology was perceived as a relatively
cheap indigenous alternative for small-scale industrial and utility power
generation in those developing countries that suffered from high world
market petroleum prices and had sufficient sustainable biomass resources.
By the early 1980s over 15 (mainly European and North American)
manufacturers were offering small-scale wood and charcoal gasifier power
plants (up to approximately 250 kWe). In addition, at least four
developing countries (Philippines, Brazil, Indonesia and India) had started
gasifier implementation programmes based on locally developed technologies.
As a result of developing country interests and the possibilities for
export earnings, a large number of biomass gasification systems were
112

installed in several developing countries for testing and demonstration


mostly through donor financed projects. In some cases such as Brazil,
China, India and Thailand, the technology was even developed and promoted
by local entrepreneurs. At present, biomass gasification systems have
found only limited commercial applications in several developing countries
including Brazil, China, India and Thailand.

2. TECHNOLOGY
Chemistry. Biomass gasification is the process of conversion
through thermal decomposition of a solid biomass feed material to
combustible gas. Gasification is achieved in the presence of heat and a
limited supply (less than stoichiometric) of oxygen resulting in incomplete
combustion of the feed material. The result is a combustible gas. When
air (as opposed to pure oxygen) is used as the gasifying agent, the product
gas mainly consists of carbon monoxide (CO), nitrogen (N 2 ), hydrogen (H 2 ),
small amounts of methane (CH4) and other higher hydrocarbon gases. Due to
the nitrogen dilution, the product gas has a low energy or calorific value
in the range of 3.8 to 5.6 MJ/m3 as compared to natural gas which is the
range of 38 MJ/m3. Thus, producer gas from air gasification is suitable
for combustion in adjacent internal combustion (IC) engines, boilers or
kilns but is too dilute for economic transport in pipelines over long
distances.
Equipment. Biomass gasification systems consists of four principal
components :
(a) Fuel preparation, handling and feed system;
(b) Gasification reactor vessel;
(c) Gas cleaning, cooling and mixing system; and
(d) Energy conversion system (e.g., IC engine with generator or pump
set or gas burner coupled to a boiler or kiln).
Power Gasifiers. Gasification systems that are coupled to IC
engines to produce shaft power are called power gasifiers. When the gas
is to be used in an IC engine it is important that it is cleaned of all
particulate, tars and moisture and cooled to near ambient conditions to
ensure reliable and efficient operation of the engine. As such, power
gasifiers require elaborate gas cleaning, cooling and mixing systems and
in general have stricter fuel quality and reactor design criteria. An
example of a typical power gasifier system is shown in Figure 1.
Heat Gasifiers. Gasification systems that are used to fuel
external burners such as those found in boilers, kilns or driers are
referred to as heat gasifiers. Heat gasifiers differ from power gasifiers
in one important aspect. Heat gasifiers generally don't require elaborate
gas cleaning and cooling systems because the producer gas is usually
combusted externally in close proximity to the gasifier. Heat gasifiers
are also more energy efficient because they tend to utilize the sensible
heat and tars in the producer gas. As a result of the less critical gas
quality requirements, heat gasifiers, in general, are simpler to design,
construct and operate than power gasifiers and are more versatile in the
fuels they can utilize. Figure 2 illustrates a typical heat gasifier
system.
Reactor Designs. The vessel or reactor used to convert biomass
fuels to gaseous fuels are called "gasifiers". These gasifiers are usually
characterized by the design of the "fuel bed" and the method in which the
biomass fuels are brought into contact with air and heat for the process
113

of gasification. Three principal fuel bed designs can be identified: fixed


bed; fluidized bed; and entrained bed. Fluidized bed and entrained bed

biomass

t
air —*~—

GASIFIER
gas cooler/
cleaner engine power

1
ι' '

ash dust condensate

Fig. 1 Typical power gasif ier system

biomass

GASIFIER

process
heat

ash

Fig. 2 Typical heat gasifier system


114

designs, while more robust and versatile in their operation are generally
more difficult to design , build and operate, are more expensive and are
presently not considered appropriate for small scale (less than 1 MWe) ,
developing country applications. As such, fluidized and entrained bed
gasifiers are not considered in this study.
Fixed Bed Gasifiers. The most common type of gasifier reactors
used in developing countries are the fixed bed type because of their
relative simplicity of design, low cost of fabrication and ease of
operation. Fixed bed gasifiers can be further characterized by the
direction of the flow of biomass fuel and gasification air within the
reactor. The principal fixed bed gasifier types are:
(a) Down-draft or co-current;
(b) Up-draft or counter-current;
(c) Cross-draft or cross-current; and
(d) Open-core.
Several variations exists within the four principal fixed bed
gasifier types. The exact choice of gasifier design is more a function of
the type of fuel to be gasified and the end use of the producer gas (for
power or heat). For example, power gasifiers fueled with unprocessed
biomass tend to be of the down draft design because of the ability of down
draft gasifiers to produce low tar gas. Heat gasifiers tend to be more of
the up draft or cross draft design. Charcoal fueled gasifiers can be
either up draft, down draft or cross draft. Open-core gasifiers are
designed for gasification of rice husks. Simplified block diagrams
illustrating the main types of biomass gasifiers considered in this study
are presented in Figure 3.
Fuel Characteristics. Given the state-of-the-art of commercially
available fixed bed gasifier systems and based on data obtained from the
UNDP/World Bank Biomass Gasifier Monitoring Program, at present, only wood,
charcoal, rice husks and coconut shells are considered suitable biomass
fuels for gasification. Biomass fuels such as wood wastes, coconut shells
and rice husks can generally be used with minor processing such as drying,
sizing and screening. The typical characteristics of these bioraass fuels
are presented in Table 1.
In order to ensure reliable and efficient operation, biomass fuels
for gasification must meet certain specifications. All gasifier types have
fairly strict fuel requirements with respect to size, moisture content and
ash content. Inadequate fuel preparation is an important and frequent
cause of technical problems associated with gasification and therefore a
strict organization and control of fuel preparation procedures is of utmost
importance. Table 2.2 presents a generalized overview of the most
important fuel requirements for the different types of gasifiers considered
in this study.
115

fuel air fuel qas

up-
draft

fuel

open-
core

Figure 3 Main types of biomass gasifiers


116

Table 1: TYPICAL CHARACTERISTICS OF BIOMASS FUELS

Biomass Moisture Ash Volatile Bulk Average


Fuel Content Content Matter Density Higher
% Wet % Dry % Dry kg/m3 Heating
Value
MJAg
dry basis

Charcoal 2 - 10 2 - 5 5 - 30 200 - 300 30

Wood 20 - 40 0.1 - 1.0 70 - 80 600 - 800 20

Rice husks 3 - 5 15 - 25 60 100 15

Coconut
shells 25 0.8 79 20

Table 2: FUEL REQUIREMENTS FOR DIFFERENT GASIFIER TYPES

Gasifier type: Up-draft Down-draft "Open Core" Cross Draft


Fuel: (Wood) (Wood) (Rice Husks) (Charcoal)

Size (mm) 20 - 100 5 - 100 1 - 3 40 80


Moisture (%db) < 25 < 60 < 12 < 7
Ash (% db) < 6 < 25 approx. 20 < 6

Producer Gas Utilization Systems


IC Engines. One of the most attractive uses of producer gas is its
use in internal combustion engines for the production of shaft power which
in turn can be used for generating electricity, pumping water, milling
rice, running compressors, motive power, etc. Although producer gas can
be combusted in gas turbines, its application in this area has not been
adequately demonstrated to warrant serious consideration in this study.
Producer gas has been widely used in reciprocating IC Diesel (compression
ignition) and Otto (spark ignition) engines. However, several issues
regarding the resulting engine performance, efficiency, output, and life
need to be closely evaluated to determine the trade-offs of utilizing the
relatively low quality producer gas in engines that are essentially
designed to operate on high quality liquid fuels.

Spark ignition engines can be run entirely on gas. The maximum


power output of an Otto engine on producer gas depends on the gas heating
value, the setting of ignition timing and specific engine characteristics
and is normally considerably less then the equivalent value on petrol or
natural gas. Diesel engines can only be partly operated on producer gas
117

(dual fuel operation) and therefore always consume a certain amount of


diesel fuel. The maximum power output of such an engine depends on the gas
heating value, the injected diesel fuel amounts and specific engine
characteristics.
Direct Combustion Burners. Producer gas can also be directly
combusted in external combustion systems such as boilers, kilns, driers,
ovens, etc. In most cases little or no modification to the existing
equipment is necessary especially if the system is designed to burn a
gaseous or atomized liquid fuel. As in the case of IC engines, a close
evaluation of system performance, efficiency, output and life as a result
of the use of producer gas needs to be accounted for. However, given the
fact that direct combustion systems generally involve no internal moving
parts, the impacts of producer gas on these systems is usually minimal.

Safety and Environmental Aspects


Operation of gasification systems may give rise to the following
types of hazards :
(a) Toxic gaseous emissions;
(b) Fire and explosion hazards; and
(c) Toxic liquid effluent.
However, with care and proper safety precautions, biomass gasification
systems can be made to operate without incident. This requires full
recognition of the potential dangers associated with the system and
operation by only trained personnel.
Toxic Gases. An important constituent of producer gas is carbon
monoxide (CO), which is an extremely toxic and dangerous gas because of its
tendency to combine with blood haemoglobin and rob the body of normal
oxygen intake. Fortunately, normal power gasification systems work under
suction, so that even in case a gas leak occurs in the system, no dangerous
gas will escape from the equipment during actual operation. If CO
emissions do occur, they are only of concern in the immediate vicinity of
the gasifier plant as the CO will quickly react with ambient 0 2 to form

The situation is different during start-up and shut-down of the


installation. During start-up the gas is generally vented and it is
necessary to ensure that the vented gases cannot be trapped in an enclosed
room. As a rule a suitable chimney will provide sufficient safety. During
shut-down of the installation a pressure build-up will occur in the
gasifier, caused by the remaining hot and pyrolysing fuel. As a result, for
a short period (approximately 15 minutes) carbon monoxide containing gases
will be released. Therefore gasifier systems should always be installed
in well ventilated buildings, or, if possible, installed externally covered
only by suitable roofing.
Fire and Explosions. Fire hazards may result from high surface
temperature of equipment; risks of sparks during refueling; and flames
emerging from gasifier air inlets. In most cases, burn risks can be
eliminated by relatively simple safety measures such as insulation of hot
parts, installation of double valve fuel feeding system, installation of
back-fire valve in gasifier inlet, etc.
Gas explosions may occur in case the hot gas is mixed with a
sufficient amount of air to trigger spontaneous combustion. Air leakage
into the system will generally not give rise to explosions, but will lead
to local zones of gas combustion resulting in higher gas temperatures and
lower gas quality. Pyrolytic gases in the bunker section when mixed with
118

air (as may happen during refueling) may form an explosive mixture. It is
not unusual for this to burn in a relatively harmless manner, especially
when the fuel level in the bunker is low. Risks to the operator can be
obviated by burning-off the gases in the bunker through introduction of a
piece of burning paper or the like. Also double sluice fuel feeding systems
prevent this type of risks. The major explosion risk lies in the lighting
of an un-vented cold gasifier. An explosive mixture may still be present
in the equipment and be ignited. Therefore cold systems should always be
carefully vented before ignition.
Toxic Effluent. A biomass gasification system produces ashes and
tar/phenol containing condensates. Ashes do not constitute an
environmental hazard and can be disposed of in the normal way. Condensates
amounts from down-draft gasifiers are normally small and also tar/phenol
contamination is relatively minor. The situation is different with the
large quantities of heavily contaminated condensates from up-draft and
"open-core" systems. Although no hard data are as yet available on
biodegradation of phenolic and tarry constituents from condensates of such
systems, it is clear that untreated disposal of such condensates is
environmentally unacceptable and can result in contamination of drinking
water, fish kills and other related effects. Therefore, this disposal
problem needs careful study before introduction of gasifier systems that
produce large quantities of condensate are considered.
Positive Impacts. The primary positive impact of biomass
gasification systems is the possibility of effectively utilizing a waste
biomass material such as wood residues, rice husks, coconut shells, etc.,
which could otherwise pose disposal problems and create localized fire
hazards, insect infestation, vermin breeding or odor during the decay
process. Air emissions from IC engines fueled with producer gas are
marginally cleaner than emissions with petroleum fuels. The main
advantages are the absence of lead and sulphur emissions with producer gas.
Additionally, gasification systems, by virtue of utilizing a biomass fuels,
do not contribute to the net increase of C0 2 in the environment as would
liquid fossil fuels.

3. CURRENT COMMERCIAL STATUS


Commercialized Power Gasifiers. There are a small number of strictly
commercial power gasifiers currently operating globally. No accurate
inventory is available, but rough estimates would be in the range of one
to three thousand. However, the vast majority of these would be small
charcoal gasifiers located in Latin America, primarily Brazil. It is
estimated that less than one hundred commercial non-charcoal power
gasifiers are currently in operation globally. Of the commercial non-
charcoal gasifiers, most are either fueled with wood or rice husks.
Down-draft Charcoal Gasifiers. Several hundred commercially
operating down-draft charcoal gasifiers are reported in operation
throughout the globe. Most are located in Brazil. About a dozen are
located in the Philippines as a result of a major government program to
promote the technology in the early and mid 1980s. It should be noted,
however, that of nearly one thousand down-draft charcoal gasifiers
disseminated through a government subsidy program, none are presently in
operation. The gasifiers that are in operation were purchased by the
private sector without government subsidy and, in many cases, were modified
to meet the users needs. The technical performance of most down-draft
charcoal gasifiers have been satisfactory, especially where operator
119

training and maintenance support have been provided. However, rising


charcoal prices and lower petroleum prices have resulted in the
decommissioning of many of these units.
Down-draft Wood Gasifiers. A few commercial down-draft wood
gasifiers are reported to be operating in India and Latin America. The
units in India are small scale (5 hp - 100 kW) units used primarily for
water pumping and isolated power generation. The seemingly most successful
commercial down-draft wood gasifiers are located in the Mennonite community
of Loma Plata, Paraguay. The gasifiers are part of a power plant used to
supply electricity to the Loma Plata community. It is reported that there
are three gasifier units each coupled to a 420 kWe gas engine/generator
set. The wood gasifiers are used to meet the base load demands while
stand-by diesels are used to meet peak loads. The first unit was installed
in 1983. After initial technical problems and after extensive
modifications of the gas cleaning section, the system is now reported to
function to the satisfaction of the user.
At least one gasifier manufacturer (in France) can point to a small
number of commercial projects presently operating in developed countries
(primarily Europe). Most of these gasifier systems are situated at
isolated sawmill sites. However, operational and financial details with
respect to these plants are not available.

Up-draft Gasifiers. A few commercial up-draft wood gasifiers are


known to be operating primarily in Latin America. The situation was
completely different in the 1940s and 1950s when both in Europe and
elsewhere a considerable number of systems were functioning on a diversity
of fuels including wood residues and agricultural wastes. The last
European updraft power gasifier (in Germany) operating on sawdust was
closed down recently for environmental reasons (water pollution resulting
from disposal of tarry effluent). Up-draft gasifier plants currently in
operation perform technically satisfactory on fuels of a fairly wide range
of specifications. However, as explained earlier, updraft gasifiers
produce large quantities of tar, with potentially serious health and
environmental hazards. As such, their commercial applications have not
been aggressively pursued.
Cross-draft Gasifiers. A large number of cross-draft charcoal
gasifiers have been in commercial operation in Brazil and other Latin
American countries. Two such installations were systematically monitored
under the UNDP/World Bank BGMP.2 The results indicated that the units
experienced considerable operational problems primarily due to
inexperienced operators, sensitivity to fuel quality, operation of the
gasifier below minimum loads and inconsistent maintenance of the plant and
equipment. In cases where these issues were addressed and where plant
utilization factors were high, the charcoal cross-draft gasifiers were
commercially attractive.
Open-core Gasifiers. A number (at least twenty) commercial open
core rice husk gasification plants have been in operation in the Peoples
Republic of China (PRC) for decades. Since 1967 identical units were
installed at a rice mill in Dogofiri, Mali. The performance of these units
were monitored under the UNDP/World Bank BGMP.3 It was concluded that
plants operate technically satisfactorily and, at given locations are able
to produce electricity at marginally lower financial cost than equivalent
diesel engines. As a result of the general success of these units in Mali,
it was recently (1986) decided to install an additional unit in Mali.
120

However, it should be borne in mind that the units, as presently designed,


produce considerable amounts of potentially harmful tars which are a
problem to dispose in an environmentally acceptable manner.
Over the past five years a number of locally designed and
manufactured open core gasifiers have been commercially installed at rice
mills in Thailand. No performance data, other than that the systems
generally work to the satisfaction of the users, are available on the
Chinese and Thai rich husk gasifiers.

Commercialized Heat Gasifiers. By far the most successful


commercialization of gasification technology has been with heat gasifiers
of varying capacities, designs and applications. Most of the heat
gasifiers currently on the market have output capacities in the range of
0.1 to 10 MWt. Heat gasifiers operating on fuels of widely differing
specifications have been used commercially to produce process heat for use
in kilns; ovens; driers; boilers; heaters; etc.
Heat gasifiers have been manufactured and applied in Europe and
North America as well as several developing countries of the Pacific,
South-East Asia and South America. During the mid-1980s, Brazil had over
dozen active heat gasifier manufacturers and over 50 known commercially
operating heat gasifier installations.* Heat gasifiers have also been
locally manufactured and commercially adopted in Malaysia, the Philippines,
Indonesia and India as well as several other Asian and Latin American
countries. New Zealand manufactured heat gasifiers are reported to be
commercially operating in significant numbers in Papua New Guinea and
several other Pacific Island countries. Attempts are now being made to
promote similar heat gasifier technology in several African countries.
There appears to be no significant technical problems associated
with heat gasifiers. Unlike power gasifiers, the gas produced by heat
gasifiers is combusted externally, generally in close proximity if not
directly adjacent to the gas outlet of the gasifier. Therefore, heat
gasifiers usually do not require elaborate gas cleaning systems, are more
efficient because they utilize the sensible heat and condensible tars in
the gas and do not produce any toxic effluent. An exception are heat
gasifiers applied in situations where the gas has to be transmitted long
distances or a clean flame is required as is the case in food drying or
baking or ceramic production.

4. RESEARCH. DEVELOPMENT AND DEMONSTRATION PROJECTS


Donor Financed Proprams. Over the past decade there have been numerous
donor organizations that have financed biomass gasification research,
development and demonstration (RD&D) projects in developing countries. It
is beyond the scope of this report to outline the extent or results of
these efforts. However, a few key points can be summarized. Most donors
have concentrated on demonstrating down-draft power gasifier systems for
applications in isolated power generation, irrigation, water pumping or
rural industries. In a majority of the cases, the gasifiers being
demonstrated were designed and manufactured in the donor countries and
exported to the developing countries. In many cases, a wide variety of
fuels were experimented with, however, positive results were achieved
primarily with the well established fuels of charcoal, wood, coconut shells
and rice husks. In all cases, the donor financed projects are important
121

to review as their history and experience are usually much better


documented than the strictly commercial operations.
The donor projects were, for the most part, designed on the assumption
that the technology would work in the developing country context and
therefore had the objective of demonstrating economic and social viability
while simultaneously promoting the technology for wider use. In reality,
most of these demonstration projects failed to achieve normal, reliable
operation due to several diverse reasons including those listed below:
(a) Use of biomass residues that were unacceptable for down-draft power
gasification systems;
(b) Use of equipment that was previously untested in developing country
environments ;
(c) Mismatching of gasifier system capacity to energy demand profiles
resulting in systems operating at turn-down ratios below
specification or systems being made to respond to rapid and wide
load changes ;
(d) Insufficient training of operators and provision of competent
technical back-up resulting in initial operating errors and damage
to equipment;
(e) Lack of sufficient incentives to motivate operators to accurately
perform additional, and usually time consuming, laborious and dirty
tasks, associated with gasification systems;
(f) Poor system design including mismatching of imported and local
system components, inattention to local operator skills and biases
and little or no documentation or operation manuals; and
(g) Finally, disappointing economics due to poor system performance,
accounted costs or simply disregard for economic criteria at the
outset of project design.

Nationally Financed Programs. In addition to the donor financed gasifier


demonstration projects, there have been several nationally initiated
efforts over the past decade. The most notable in the developing countries
include: The Philippines; Brazil; India; Thailand; and Indonesia. Brief
highlights of the key points associated with each program are presented
below.
The Philippines. A government backed and United States Agency for
International Development (USAID) supported program to commercialize
locally designed and manufactured charcoal gasifiers was initiated in the
early 1980s. The program was aimed at providing options for rural
irrigation water pumping, rural electrification and motive power for
jeepneys and bancas (trucks and boats). Nearly one thousand charcoal
gasifiers were manufactured under the program. The program, terminated in
1986, was a failure for several reasons including poor design and quality
of the gasifier systems, no control on input fuel specifications,
inadequate operator training, no manufacturer technical and maintenance
back-up, and, perhaps most importantly, disregard for the normal economic
incentives necessary to assure success. The Philippine program was
subsidized. Gasifiers were essentially given away by the government to
local farmer cooperatives without instilling adequate economic incentives
to ensure commitment by the farm cooperatives to the overall success of the
systems. It is interesting to note that of the few gasifier systems that
did succeed in the Philippines, almost all were purchased and operated by
the private sector without any subsidy or other form of government
assistance.
122

Brazil. Unlike the Philippines, the Brazilian government program


to promote gasifiers was essentially passive and relied on demand side
incentives rather than on the supply side subsidies. In addition to
instituting phased in quotas of petroleum consumption for certain
industries and thereby creating a demand for alternative technologies, the
Brazilian government also sponsored a few select research efforts to help
develop appropriate gasification systems for Brazilian needs. However, no
subsidies or direct government assistance were provided for the promotion
of gasification systems. The results were dramatic. By 1985 there were
between 15 to 20 commercial gasifier manufacturers and well over a thousand
power and heat gasifiers that were privately purchased and in operation.5
While gasification activity in Brazil has declined somewhat recently, this
has been primarily in reaction to easing of petroleum quotas and prevailing
lower petroleum prices.
India. Recently (1987) a government-backed commercial down-draft
wood gasification programme was started in India, based on locally
developed and manufactured technology and aimed at small-scale irrigation
applications. To date a total of 2.5 MWs of capacity, mainly in 5 kW size
units (i.e., approximately 500), has been installed. The programme is
heavily subsidized. A recent evaluation concludes that approximately 60 %
of the units are not in regular operation for technical, organizational and
financial reasons. A more detailed evaluation quantifying the above
factors is presently underway.
Thailand. Relatively independently from several donor and private
sector efforts to promote gasification in Thailand, the Thai Ministry of
Interior, through its Department of Public Works (DPW) has, for the past
few years, undertaken a program to promote rural electrification using
biomass gasification technology. With a budget of approximately 25 million
Bhats (one million USŞ) , the DPW has installed 143 - 15 kW charcoal
gasifiers throughout Thailand. DPW's objective were to install 4000 units
by 1991.6 Like the Philippine government's program, the Thai DPW program
has run into several difficulties including technical problems with the
design of their gasifier system as well as economic, social and
institutional issues that have hampered the program.
Indonesia. The potential for biomass fuelled gasifiers to
substitute petroleum consumption has attracted much attention in Indonesia.
In 1987, the President of the Republic of Indonesia (ROI) mandated that 10
Indonesian manufactured biomass gasifiers be placed in field operations,
to help demonstrate the technical and economic viability of such systems.
Over the past decade several donor financed activities in Indonesia have
also promoted gasification systems. A s a result of these activities, there
are at present over 20 power gasifiers and several heat gasifiers installed
in Indonesia. The power gasifiers, all for demonstration and testing
purposes, are widely spread over the different provinces of Indonesia.
Three units are fueled with rice husks while the rest are fired with
different types of wood. Most projects aim at demonstration and/or testing
of the technology. To date no truly commercial power gasification systems
are in operation in Indonesia. Most of the heat gasifiers are situated in
Java or Sumatra and operate on coconut shells or other similar types of
residues. These units represent the only truly commercial applications of
biomass gasification technology in Indonesia to date.

5. ECONOMICS
The economics of small scale power gasifiers hinges on the savings
that can be realized by switching from high-cost liquid fuels (i.e.,
diesel) to low-cost biomass fuels. These fuel cost savings must be
measured against the additional capital costs of the gasifier, the increase
in operation and maintenance costs, and the reduced reliability of the
123

system. One way to evaluate the tradeoff between capital costs and
operating and maintenance costs is to compare the levelized costs of
electricity generated by each system. This has been done in a study based
on data collected under the UNDP/World Bank Biomass Gasifier Monitoring
Program (BGMP).7 The study compared generic wood and charcoal gasifiers to
diesel stand-alone systems from 5 kWe to 1 MWe.
The study evaluated commercially available power gasifiers in the
following ranges:
o Manual feed charcoal gasifiers from 5 - 200 kWe;
o Manual feed wood gasifiers from 5 - 200 kWe;
o Automatic feed wood gasifiers from 100 kwe - 1 MWe.
Figure 4 presents some of the principal findings of the study. The
analysis indicates that power gasifier economics is most strongly affected
by system size and by the relative cost of petroleum and biomass fuels.
Under the baseline economic price of diesel at US$ 0.20/1, charcoal
at US$80/t and fuelwood at US$20/t, none of the gasifiers evaluated in the
BGMP were economic. However, if economic price of diesel were assumed to
rise to US$ 0.40/1, as is the case in many isolated rural areas of
developing countries, then the manual feed charcoal gasifiers and wood
gasifiers above 30 kW become competitive. With the current low economic
prices of petroleum fuels, it is clear that power gasifiers will have a
niche only in remote applications where the economic cost of diesel is high
(due to transport costs and unreliable supplies) and the cost of biomass
fuels is low (due to surplus availability).

6. RECENT BREAKTHROUGH
Recent work at the Asian Institute of Technology (AIT) in Bangkok
has resulted in a radical departure from conventional gasifier systems.
Due to the high costs of metal, fabrication of a 10 kWe charcoal gasifiers,
even when locally manufactured, is in the range of US$500/kW. As such, the
economics of gasification are marginal given current petroleum prices.
Under the leadership of Dr. Bob Reines, the AIT has developed a 10 kWe
"ferrocement" open-core charcoal gasifier with the resultant costs of only
$50/kW for the gasifier. The reactor is lined with refractory brick to
manage the normally high temperatures encountered in this zone. The
ferrocement components are water cooled which provides a relatively uniform
temperature gradient over the ferrocement surface minimizing thermal
stress. The water also serves as heat transfer fluid for gas cooling. As
a result, the ferrocement approach solves many of the material (thermal
stress and corrosion) as well as economic constraints associated with
conventional metal gasifiers. To date, ferrocement gasifiers have only
been demonstrated for small (less than 18 kWe maximum output) charcoal
gasifiers.

New Economics
The ferrocement gasifier presents the possibility of a ten fold
decrease in the capital costs of a gasifier. A brief comparison of the
economics of a diesel generator set, conventional charcoal gasifier system
and a ferrocement gasifier system is presented to illustrate the impact of
this new approach. Table 3 outlines the basic assumptions used in the
analysis. Figure 5 shows the resulting levelized electricity costs (in
cents/kWh) of the three systems. At the current economic price of diesel
of US$0.25/1 and charcoal at US$40/t, the conventional gasifier is not
economic with a diesel system. However, the ferrocement gasifier has
levelized electricity about 11% lower than the diesel system. Figures 6
to 8 show a sensitivity analysis on charcoal and diesel prices, installed
124

Costs of Electricity Production


Small Stand-Alone Systems
Electricity Costs ($/kWh)

1000
INSTALLED CAPACITY (kW)

POWER SOURCE
— · — Diesel I 40c/l Diesel θ 20c/l -*- Clmrgns θ $BD7mt
-β- Woodgas/m $2Q/mt Woodgas/a $20/mt

m = manual / a = automatic

Figure 4: Electricity Costs: Diesel vs. Gasifier Systems

capital costs (ICC) and annual operating hours. In all cases, the $50/kW
ferrocement gasifier significantly increase the range in which the
technology is economically competitive with diesel systems

7. SUMMARY
Based on the above discussion, the current status of biomass
gasification technology can be broadly summarized as follows:

(a) Commercially proven power and heat biomass gasifiers are available
especially when the fuels are charcoal, wood, coconut shells and
rice husks. Heat gasifiers are more tolerant of other types of
biomass fuels. However, only limited experience with "non-
conventional" biomass fuels is available for small-scale power
gasifiers.

(b) The economics of biomass gasification, at present, are at best


marginal. When compared to the counterpart petroleum system, the
economics of heat gasifiers are more favorable at present than
conventional power gasifiers.

(c) The recent developments in ferrocast charcoal gasifiers could help


change the negative picture for biomass power gasifiers. However,
further testing especially in field applications are necessary to
confirm the viability of this technology.
125

Table 3: BASIC MODEL OF THE ANALYSIS

LHV (MJ/unit) Energy Cost (c/MJ)


Diesel Price (c/1) 25.00 36.00 0.69
Charcoal Price (cAg) 4.00 30.00 0.13
ICC Diesel/Gas ($AW) 600.00 500.00 50.00
Ann.Op. Hours (hrs) 3000.00

PARAMETER DIESEL CONV. CHAR FEROCEMENT


SYSTEM GASIFIER CHAR GASIF

Capacity (kW) 10.00 10.00 10.00


Ann. Op. Hours (hrs) 3000.00 3000.00 3000.00
Avg. Op. Load (%) 0.80 0.80 0.80
Annual Output (;kWh/yr) 24000.00 24000.00 24000.00

Installed Capital Cost


Eng/Gnenset ($) 6000.00 7500.00 7500.00
Gasifier ($) 5000.00 500.00

Total ICC ($) 6000.00 12500.00 8000.00


Expected Lif (yr) 6.00 4.00 4.00
Discount Rat (%) 10.00 10.00 10.00
Annual ICC ($/yr) 1377.64 3943.39 2523.77
ICC/kWh (cents) 5.74 16.43 10.52
ICC A « ($) 600.00 1250.00 800.00
ANNUAL O&M
Fuel
System Eff. (%) 20.00 15.00 15.00
Annual ($/yr) 3000.00 768.00 768.00
Unit Costs (cAWh) 12.50 3.20 3.20
Labor
Monthly Wage ($/mo) 50.00 50.00 50.00
Operators 1.0 1.5 1.5
Labor Costs ($/yr) 600.00 900.00 900.00
Unit Costs (c/kWh) 2.50 3.75 3.75
Maintenance ($AWh) 0.015 0.025 0.025
Maint. Costs ($/yO 360.00 600.00 600.00
Unit Costs (cAWh) 1.50 2.50 2.50
Total Ann. O&M ($/yr) 3960.00 2268.00 2268.00
Tot Ann. O&MA (c) 16.50 9.45 9.45
COST/KWH 22.24 25.88 19.97
126

cents/kWh
25.881
19.966

□¡•«•I Sytten »εοθ/kW Qatifier »60/kW Qasifier

Maint Costa/kWh 15 2.5 2.5


Labor Costa/kWh 2.5 3.75 3.75
Fuel Coata/kWh 12.5 3.2 3.2
Cap. Coata/kWh 5.74 16.431 10.516

■>■ Cap. Costs/kWh 22 Fuel Costs/kWh


EZ] Labor Costs/kWh ! S i Maint. Costs/kWh

Figure 5. E l e c t r i c i t y C o s t Components

Cost of Electricity
vs. Charcoal Price
Coat of Electricity (c/kWh)

3 4 5 6 7 8 10
Charcoal Price (c/kg)
$eo/kW »200/kW »600/kw
Diesel · 20 e/l Diesel · 40 c/l

Figure 6. Sensitivity to Charcoal Price


127

COST OF ELECTRICITY
vs. ICC of Gasifier System
[c/kWh]
35

100 200 300 ­400 500 600 700 BOO


ICC of Gasifier System ($/kW)
25 c/l Diesel 40 c/1 diesel S20/t Charcoal
S40/t Charcoal 380ft Charcoal

Figure 7: Sensitivity to Installed Capital Costs

Cost of Electricity
vs. Operating Hours
Cost of Electricity ( c / k W h )
130

1000 1500 2000 2500 3000 3500 40GG ­450G 5000 5500 6000
Annual Operating Hours
^ D i e s e l System — ι ­ »50/feW Gasifier ­ * ­ 1500/kW Gasifier

Figure 8: Sensitivity to Operating Hours


128

1. Reed, T.B., Biomass Gasification: Principles and Technology. Noyes


Data Corporation, Park Ridge, NJ, 1981.

2. Furtado, P. et.al., Biomass Gasifier Monitoring Proiect in Brazil.


Final Report, prepared by Cetec under World Bank/UNDP contract,
January 1987.

3. S tassen, H., et.al., Biomass Gasifier Monitoring Project in Hali.


Report prepared by Twente University of Technology, Biomass
Technology Group, under World Bank/UNDP contract, 1987.

4. Mendis, M.S., "Biomass Heat Gasifiers: Status and Potential",


Internal Working Paper, New and Renewable Energy Unit, The World
Bank, Washington, DC, May 17, 1984.

5. Furtado, P. and Antunes, R. , "Commercial Applications of Biomass


Gasifiers in Brazil", Presented at the Second International
Producer Gas Confernece. Bandung and Jakarta, Indonesia, March 19
-23, 1985.

6. Coovattanachai, N., "Final Report on the Assessment of the


Performance and Identification of Technical Problems of DPW's
Gasification System", Prince of Songkala University, Haadyai,
Thailand, January 28, 1988.

7. Terrado, E., Mendis, M. and Fitzgerald, Κ., "Impacts of L ower Oil


Prices on Renewable Energy Technologies", Energy Series Paper
No.5. World Bank, Washington, DC, 1988.
129

GASIFICATION AND PYROLYSIS OF BIOMASS IN EUROPE

A A C M Beenackers A V Bridgwater
Department of Chemical Engineering Chemical Engineering Department
University of Groningen Aston University
Nijenborogh 16 Aston Triangle
9747 AG Groningen Birmingham B4 7ET
The Netherlands UK

ABSTRACT
Biomass, as the only renewable source of fixed carbon, has attracted
considerable attention as a renewable energy resource after the oil crises of the last 15
years. Thermochemical processing has attracted considerable attention from the variety
of technologies available for converting biomass into more useful and valuable energy
products. As pyrolysis, gasification or liquefaction, this technology has been
researched and developed for the economic production of fuel products that may be
readily integrated into the energy infrastructures of both industrialised and developing
countries.
The characteristics of the generic types of thermochemical conversion -
gasification, pyrolysis and liquefaction - are described in this paper. The range of
products derivable from each system are discussed and related to each technology, and
the applications that have been researched to date are reviewed.
Current interest lies in relatively simple conversion technology to produce low
Joule gas and basic liquid fuels. Longer term possibilities include gaseous and liquid
hydrocarbon fuels, petrochemicals, bulk organics such as methanol and ammonia, and
chemical specialities.

1 INTRODUCTION
The potential offered by biomass and solid wastes for solving some of the world's
energy problems is widely recognised. The energy in biomass may be realised either by direct
use as in combustion, or by upgrading into a more valuable and usable fuel such as fuel gas or
fuel oil or higher value products for the chemical industry. This upgrading may be by
physical, biological, chemical or thermal methods to give a solid, liquid or gaseous fuel. This
paper is concerned with thermochemical conversion, and it reviews the state-of-the-art in
gasification, pyrolysis and liquefaction of biomass.

2 THERMOCHEMICAL TECHNOLOGY
Except for direct combustion which is outside the scope of this paper, there are three
thermochemical methods of converting biomassrgasification, pyrolysis and liquefaction. Each
gives a different range of products and employs different equipment configurations operating in
different modes. These are summarised below in Table 1, and the characteristics of the
technologies are described in Table 2. The basis of a fuel or chemical production system is that
the feedstock is converted to a useful primary energy product in a sequence of operations:
pretreatment, conversion, and primary upgrading by simple physical processing such as gas
scrubbing. Secondary higher value products may be produced by additional processing as
shown overall in Figure 1.
130

Table 1
Thermochemical Conversion Technologies and Products
Technology Primary Product Application
Pyrolysis generally gas fuel gas
liquid oil or liquid fuel substitution
solid char solid fuel or slurry fuel
Flash Pyrolysis liquid mostly oil or liquid fuel substitution
Slow Pyrolysis solid char mostly solid fuel or slurry fuel
Liquefaction liquid oil or liquid fuel substitution
Gasification gas fuel gas
Combustion heat heating

Table 2
Characteristics of Thermochemical Conversion Technologies
Figures quoted are typical, and can vary considerably according to technology and operating
conditions
Pvrolvsis Liquefaction Gasification
Slow Flash
FEEDSTOCK
Feed size any small small mixed-large
Moisture content low very low very low 50% max
PARAMETERS
Temperature, °C 500-700 500-900 250-350 800-1500
Pressure, bar 0.1-1 1 100-200 up to 30
Maximum throughput, t/h, 5 0.05 0.1 20
achieved so far
PRODUCTS
Gas yield, %wt on dry feed up to 40 up to 70 20 100-250
heating value, MJ/Nm3 5-10 10-20 2-6 5-15
Liquid yield, %wt on dry feed up to 30 up to 70 up to 50 up to 5
heating value, MJ/kg 22 22 27 22
Solid yield, %wt on dry feed 30 up to 20 up to 25 nil (ash)
heating value, MJ/kg 30 30 30 -

Feedstocks generally considered for thermochemical conversion are agricultural waste,


wood and wood waste, energy crops, and refuse (MSW). The main technical criteria for
feedstocks in terms of their suitability for thermochemical processing are low moisture content
and low ash content The main economic criteria are cost and quantity available, both of which
have a considerable influence on costs.
3 PRODUCTS
3.1 Introduction
The possible primary products and their processing origins are summarised in Table 3.
This primary product can be used directly, or it may be subjected to further chemical
processing to give a higher quality fuel or chemical product as shown in Figure 1. The
131

technologies for upgrading and likely viable size ranges are summarised in the relevant sections
below.

CONVERSION /·'/■'·· ' PRIMARY '\,\<


TECHNOLOGY SSS PRODUCTS ν Λ
S S S S S S S S S -

V A . V WATER ^ . V >

Figure 1
Primary and Secondary Products from Thermochemical Biomass Processing

Table 3
Primary Thermochemical Conversion Products and Technologies
Product Form Components Source
Fuel gas LHV CO, H2, C02, CH4, N2 Pyrolysis, Air gasification
MHV CO, H2, C02, CH4, Pyrolysis, 02 gasification
higher hydrocarbons
Liquid OU Water insoluble Pyrolysis, Liquefaction
oxygenates of high
boiling point
Char-oil slurry Charcoal and oil Pyrolysis
Char-water slurry Charcoal, water and Pyrolysis
stabiliser
Aqueous Waste water water soluble } Pyrolysis
oxygenates of low boiling j Liquefaction
point.eg acetic acid } Gasification
Solid Charcoal Pyrolysis
Heat Hot gas Combustion
132

3.2 Primary products


The primary products can be gas, liquid, and/or solid char depending on conversion
technology employed. Much of the present interest in thermochemical conversion centres on
liquid products due to their high energy density and potential for premium liquid fuel
substitution.
The gas is a low to medium heating value fuel gas that may be used as such, or
physically and chemically upgraded to higher value products, including liquid products such as
gasoline. This is depicted in Figure 1 above.
The liquid, when formed, approximates to biomass in elemental composition, and is
composed of a very complex mixture of oxygenated hydrocarbons. The complexity arises
from the degradation of lignin, and the broad spectrum of phenolic compounds that result from
uncontrolled degradation. The liquid is often referred to as "oil" or "bio-oil", but is more like
tar. This also can be upgraded to liquid hydrocarbon fuels. Utilisation of this material is
discussed later.
The solid product from pyrolysis processes is char, which has limited application in
developed countries for metallurgical and leisure industries. Water is also produced from
moisture in the biomass feed and as a reaction product from pyrolysis. An alternative approach
to a liquid product lies in grinding the char and slurrying it with water with a stabiliser as in
coal-water mixtures. A slurry can also be made from the bio-oil and char The significance of
the energy density is shown in Table 4 below.
3.3 Secondary Products
These include power, fuels and chemicals and are summarised in Table 4.
Table 4
Secondary Products and Sources
Secondary product Source Process
Oxygenate Fuels
Methanol Gasification Synthesis
Fuel alcohol Gasification Synthesis
Hydrocarbon Fuels
Gasoline Pyrolysis Hydrotreating
Pyrolysis Zeolites
Liquefaction Hydro-treating
Gasification via Methanol MTG
Diesel Pyrolysis Hydrotreating
Pyrolysis Zeolite + MOGD
Liquefaction Hydrotreating
Gasification via Methanol MOGD
Fuel oil Pyrolysis Stabilisation
Liquefaction Stabilisation
Power
Power Pyrolysis Turbine
Gasification Engine or turbine
Chemicals
Ammonia Gasification Synthesis
Speciality chemicals Pyrolysis Extraction and/or Conversion
Liquefaction Extraction and/or Conversion
133

4 GASIFICATION
Of the conversion technologies discussed in this paper, biomass gasification by now is
the most widely applied technology, except for charcoal production. However, relative to the
already significant contribution of biomass combustion to energy generation, the impact of
gasification of biomass for energy generation is still fairly limited. The main reason for this is
probably that the technology still has not reached full maturity. However, research efforts to
develop improved biomass gasification technologies have been impressive during the last 15
years. This is likely tö result in an increasing number of successful commercial biomass
gasification applications in the future and justifies a review of recent developments including
low joule and medium joule gasification and the role of catalysis in gasification.

4.1 Low Joule Gasification


If air is used as the gasifying agent, a so called low joule gas or producer gas is
obtained having a heating value of typically 5MJ/Nm3.
Wood based gasifiers for heat applications have operated successfully for many years.
Both updraft moving bed gasifiers and (fast) fluidised bed gasifiers have been installed.
European plants have been described by Bierback et al. [1] McKeough et al. [2] and Salo [3].
New American plants were listed annually in the reviews of Klass [4, 5] but are no longer
published. A thermochemical biomass conversion database has been established through the
IEA Bioenergy Agreement which includes over 300 gasification activities around the world in a
total database of 650 thermochemical activities [6].
Recent progress at 150 kg/h dry biomass has been realised by Framatome with high
carbon conversion. Carbon to gas efficiencies as high as 96% have been obtained by
introducing secondary air above the bed and recycling char to the bed from the first cyclone (of
a set of two). In this way the char content in the ash collected from the second cyclone could
be as low as 0.7%.
Gasification of wood wastes followed by power generation via a steam cycle has been
investigated by the Florida Power Corporation at a scale of 2 MWe in an updraft moving bed
gasifier [7]. Some problems were encountered with handling the condensibles which were
separated from the wood gas on its way to the boiler by centrifugation. Initial problems to
combust the liquids in the burner could be solved. The project confirmed that adapting a
gasifier to an existing boiler can be accomplished with only minor effort. The economic break-
even point of the facility was determined at $16 per ton of raw fuel with actual fuel wood prices
at the time varying between $13 and $25/ dry tonne.
Figure 2 gives an overview of the capacities of the units constructed in the
industrialised world during the last five years and implemented in both the industrialised world
and in developing countries. As can be seen, typical capacities in Europe and North America
nowadays are in the range of 80 to 300 kW whilst for developing countries these are slightly
smaller typically from 40 to 200 kW. Further, the maximum capacity presently is in the range
of 1 to 5 MW. Despite the commercial availability of the technology, only limited operating
experience is available from the open literature. There is no doubt, however, that significant
scope still exists to improve the available technology. To show this in more detail, a diagram
of these systems is presented in Figure 3.
Although some counter current moving bed gasifiers have been installed, nearly all
modern systems for power generation are of the downdraft moving bed type. This is because
of the cleaner gas produced by downdraft gasifiers resulting in a relatively less complicated
cleaning process and less environmental problems with respect to waste water. However,
downdraft gasifiers show little flexibility with respect to feedstock moisture content (15-20%)
and feedstock size. Well defined chips or pellets with a moisture content not exceeding 25%
are necessary to produce a gas that has a really low tar content. Most commercial systems
operate on wood chips while maize cops and coconut shells can be successfully gasified too.
Loose materials such as straw, rice hulls and MSW are difficult to gasify at a small
scale. Pelletisation has been successfully applied but increases costs of the feedstock to $25
per tonne. A potentially very large market exists for small scale rice hull gasification. Initial
efforts by Kaupp to gasify it continuously at a scale of 30-60 kWe in a downdraft gasifier were
unsuccessful [8]. The main problems are:
134

poor flow due to low density and swelling in the pyrolysis zone
poor oxygen distribution due to small particle size
sintering arising from poor oxygen distribution
lack of a well designed continuous ash removal system.

Figure 2
Typical Distribution of Gasification Based Electrical Power Generation Units
Manufactured in the Industrialized World.
I - operating in industrialized world
II - operating in developing countries
III = I + II

Biomass Air (Pilot diesel)

Air-
Hot,
* Β Cool
D Exhaust
dirty clean
product gas
gas
Tar, Electricity
ash,
soot,
water
Figure 3
Gasifier-Reciprocating Engine Systems
A = Gasifier C = Gas-air mixer
Β = C leaning and cooling section D = Engine-generator set
135

Recently Manurung and Beenackers succeeded in solving all these problems by


developing a new type of gasifier optimally designed for rice hulls [9]. The system is shown
in Figure 4. Smooth flow of rice hulls is obtained by eliminating the throat of conventional
down draft gasifiers. Hot spots, causing ash sintering, is avoided by eliminating the
conventional local air inlets. Air is sucked into the gasifier over the whole cross section of the
surface of the bed resulting in a uniform combustion zone over the cross section close to the
top of the bed. Finally, a scraper slowly rotating over a grate effectively continuously removes
the ash from the gasifier.

GASIFIER

ASH FLUSHING
VESSEL

WATER SEAL

Figure 4
Small Scale UT/ITB Downdraft Rice Husk Gasifier with Ash Removal System
[9]
Such a device is essential because the rice hulls keep their original shape after
gasification. After successful trials both at Twente University, The Netherlands and the
Institute of Technology, Bandung, Indonesia, the first field unit of 10 kWe was installed at a
rice mill in an Indonesian village in 1986. It is operated by trained but otherwise unskilled
people. Now, after more than a year of successful operation the conclusion is that this
technology is promising and the Indonesian government has decided to start an implementation
programme.
On a larger scale, at 1-10 MWe, gasification of loose waste materials with relatively
high ash contents such as straw and rice hulls may be successfully gasified in fluidised beds.
For rice hulls van den Aarsen et al. have demonstrated this on a pilot scale [10]. Two methods
136

of gas cleaning are available: dry and wet. Dry dust removal can be carried out, for example,
by two cyclones in series followed by an impingement separator, filtration with high
temperature resistant fabrics and a cooler-condenser for tar and water removal [11]. The wet
method also uses cyclones followed by a wet scrubber, either of conventional or venturi type
design [12].
4.2 Low Joule Fuel Gas Utilisation
Gasification is a method to transfer the heating value of solid biomass into the heating
value of a combustible gas (and some sensible heat) while in combustion the heating value of
the solids is completely transferred into sensible heat. In principle, gasification offers some
advantages over combustion. Firstly, a gas has better burning properties relative to a solid.
The burning process is easier to control, it needs less excess air, it allows for simpler burner
construction, it causes no particle emissions, less air pollution and less fouling of the heat
exchange equipment. Further, gases can be burned in internal combustion engines (gas
turbines or reciprocating engines) and can be applied easily in combined cycles. Basically,
there are three main routes for combustion of the fuel gas produced (see Figure 5):
A) external combustion for heating or drying purposes or for electricity
generation with a steam cycle
B) combustion in a gas turbine
C) internal combustion in either a diesel engine or a spark ignition engine, both
for shaft power and electricity generation.

ELECTRICITY

STEAM
CENERATOI!

ELECTRICITY

GAS TURBINE

DUST
DIESEL . ELECTRICITY
ENGINE
COOLING
+
TAR CLEANING

ELECTRICITY

Figure 5
Low Joule Gas Production and Power Applications
4.2.1 External Combustion of Producer Gas
The direct use of the gas in a furnace (route A in Figure 5) is the simplest application
and this generally requires little or no gas treatment except for dust removal. For efficiency
reasons it is important to preserve the sensible heat of the product gas which requires close
coupling of the gasifier and the furnace. In many cases it is possible to convert an existing
natural gas or fuel oil fired facility to biomass firing by adding a gasifier. This requires some
137

repiping and change of burners etc., but not necessarily a derating of the facility. If a
completely new installation has to be constructed the situation is somewhat different and clearly
direct combustion is a competing alternative.
It should be realised that in many wood combustion installations some gasification
occurs, and complete combustion is realised by the introduction of secondary air. Thus, two
stage gasification with combustion and direct combustion systems are essentially the same.
There remains, however, a difference in controllability, especially under varying load
conditions. Generally it can be said that in gasification units combustion of the product fuel
gas can be expected to have less impact on the environment than in direct combustion. In
retrofitting an existing unit special attention must be paid to the burner. In most cases natural
gas or fuel oil will be replaced by a hot dirty gas of low heating value. The characteristics of an
ideal burner to cope with such a gas were defined recently as follows [13]:
• the burner should maintain stable combustion over a wide range of gas compositions and
gas energy content and should be adjustable without modification to accommodate different
gas types
• it should have low pollutant characteristics
• the burner should be able to handle dirty gas without clogging or frequent servicing
• the burner should be able to operate at low gas pressures
• if possible, the burner should be able to simulate the heat release patterns of a natural gas
burner so that retrofit modifications could be attempted.
Many types of commercially available burners for low Joule gases have been tested by
the Canadian Gas Research Institute but none were found entirely satisfactory, mainly because
of susceptibility to clogging or erosion/corrosion with dirty tar laden gases [13]. Therefore,
the Canadian Gas Research Institute has developed a modified two stage burner which,
reportedly, meets the characteristics described above. It can handle a gas with a calorific value
as low 3 MJ/Nm·' standard cubic meter which is heavily laden with dust and tar as results from
counter-current updraft moving bed gasification systems.

4.2 2 Combustion in a Gas Turbine.


This is shown as route Β in Figure 5. The favourable properties of gas turbines such as
long running periods between overhaul, low cost of maintenance, potential high inlet
temperatures favouring high thermodynamic efficiencies and the possibility of using the
exhaust gas in a steam generation cycle (combined cycle), make turbines potentially very
attractive for use in combination with a gasifier. F urther developments in turbine technology
are probably needed such as in prevention of corrosion by alkaline metal vapours, improved
tolerance to trace amounts of dust, and in control technology of the gasifier-engine system.
For an optimally integrated system the gasifier has to be pressurized [14-16]. F or an air blown
gasifier the optimum pressure will be in the range of 10-30 bar. Operation under pressure
increases the complexity of both the gasifier, the reeding and the ash removal system and can
probably only be done economically for relatively large capacities. Efficient filtering,
preferably at high temperature, will be required to protect the gas turbine.

4.2.3 Internal Combustion in Engines.


A gasifier/engine system is currently the most attractive way of generating shaft power
or electricity from biomass in the power range from a few kilowatts to several megawatts.
This option is made attractive by the simple arrangement of a gasifier/engine system with the
relatively high overall efficiency in producing shaft power at different loads (with diesel
engines up to 30%), and the possibility of immediate use of other fuels. The technology is
already relatively old, having started in the 1890's. The wide spread application in the second
world war was caused by a shortage of liquid fuels and its moderate revival in the last two
decades was stimulated by sharply increased crude oil prices. Re-introduction of this
technology for traction will probably remain a curiosity in the industrialised world, unless a
dramatic shortage of liquid fuels arises. F or stationary applications, however, particularly for
electricity generation, the R&D work of the last 15 years has resulted in a commercially
successful technology which now is being implemented, especially in the developing countries.
A major problem is that minimum gas quality requirements for engines are still unclear.
138

For dust, values vary from <0.5 to <20 mg/m^ whilst for tar a maximum value of 100 rng/m^
is quoted. There is much uncertainty on the efficiency of the gas cleaning methods. On dust
filtration some results have been published recently [17]. Primary cyclones were found to be
not effective for particles below 5 micrometer, Barrel filters not effective for diameters in the
range 0.3-3 micrometer and bag house filters not efficient for particles between 0.3 and 1.0
micrometer. However, two stage or two sleeve fibre glass filters were found to be effective for
any particle size. Tar removal seems to remain the major problem, particularly at the small scale
below several MWe where secondary gasification is not economical. Under specific, but
poorly understood conditions, particularly with respect to specifications on fuel size,
downdraft gasifiers can produce a relatively tar free gas. However, with irregular solids or
with no-throat gasifiers as developed for rice hulls, tar removal still requires further additional
R&D.
Control devices for optimizing the fuel/air ratio to the engine under varying loads are
proven technology, as are the engines [18]. Whether to choose for a diesel engine or a spark
ignition engine will vary from application to application. For a discussion on this topic see
Kohan [19] for example.
For biomass based power stations of capacities of 10 MWe and higher, direct
combustion of biomass is technically proven and an economically feasible technology in some
applications [20]. It follows that there is still a need to develop biomass based power
generating systems in the capacity range of 1-10 MWe. It is here that gasification in fluidised
beds and/or in fast circulating fluidised beds may have potential. Both atmospheric gasification
and pressurised gasification may be considered, with the latter option probably in combination
with route B of Figure 5 (power generation by gas turbines).
For biomass based power generation in engines Fritz Werner has sold units up to 1
MWe [21] and Ahlstrom Oy in Finland has developed units for combined heat and power in the
range of 2-28 MWe + 3-35 MWt [2]. European operating experience both with a counter-
current Smaus system and a two-stage Michel Kim (Easimod) gasifier each at a capacity of 500
KWe have been collected by Friedrich Wahl GmbH. [22]. For operating experience in
developing countries, reference should be made to the reports of the World bank [23].
4.2.4 Gasification for Ammonia Production
A pressurised high temperature Winkler fluidised bed gasifier is operated in Finland for
ammonia production [24]. The feed is 23 ton peat per hour and the pressure is up to 4 bar.
The longest uninterrupted operation time so far has been 31 days.
4.3 Medium Joule Gasification
Medium Joule gas can be produced if oxygen instead of air is used as the gasifying
agent. Alternatively, steam can also be used as the gasifying agent but then some provision
should be made to supply sufficient heat to the gasifier because steam gasification is an
endothermic process. Various options are available as indicated in Table 5. The so called
Oxygen Donor Gasification process may lead to a Medium Joule Gas using air as the gasifying
agent. For a review of the various process principles and technologies, see Beenackers and
van Swaaij [25, 26].
Although none of these medium Joule processes are commercial yet, much
development work has been done during the past decade, particularly in the European
Community under the second E C Biomass Development Programme "Methanol from Wood".
An overview of the companies involved in medium joule gasification and of the process types
they selected to develop is presented in Table 5 above. Under the E C programme four pilot
plants were operated at design capacities ranging from 4.8 to 12 tons dry wood/day. An
overview of the results is presented in Table 6; a more comprehensive analysis of the results of
this programme has been published elsewhere [27]. The main result of this programme is that
atmospheric gasification with oxygen both in a classical fluid bed (Framatome) and in a fast
circulating fluid bed (Lurgi) are technically proven.
139

Table 5
Principle Gasification Routes for Medium Joule Gas from Biomass
Gasifying Agent Process Types Processes
Oxygen Downdraft SERI
Updraft SFW-Funk
Purox
Simplex
Cross flow Foster Wheeler
Huid bed Framatome*
ΜΓΝΟ
IGT
Omnifuel
Circulating fluid bed Lurgi*
Entrained bed Texaco
Steam With heat carrier (doublefluidbed) Baillie
Battelle
TNEE Compiegne*
AVSA*
C02 Acceptor
With indirect heat supply (fluid bed) ALI 'bN/ltaienergie*
With recycle of synthesis gas (fluid bed) ΚΉ
Air With heat and oxygen carrier John Brown/Wellman*
(double fluid bed)
* Sponsored by the Commission for the European Communities.

Table 6
Main Characteristics of Pilot Plant Projects for EC Methanol from Wood
Programme
Organ- Press:. Capacity Reactor Gasifying Duration H'carbon Reagent
isarion bars kg dry ţy£S agent of test in svngas. use. kg/
wood/h run vol % kg wood
Framatome 1 350 fluid bed+ 2° 0 2 & H 2 0 24 hrs 0.6 02:0.57
empty tube for 1° & 2° H20:0.08
gasifier gasifier
Lurgi 1 200 circulating 02&H20 36 hrs 6.5 02:0.453
(fluid) bed H20:0.02
John Brown 1 400 double fluid Air 9.5 hrs 12.5 Air only
/Wellman bed + chemically
active solids
Italenergie 1 500 1° fluid bed steam H20 for 1° 100 hrs 12.4 N/A
/AGIP gasifier heated gasifier, 02
through wall + 2° for 2° gasifier
fluid bed
140

Progress on circulating fluidised beds has been realised with both the AVSA process
[28] (G4) and the TNEE-Compiegne [29] (G5) dual fluidised bed. Due to significant
improvements in the slot designs of the former, the early problems of excessive gas-leakage
between the compartments have been largely eliminated.
The EC programme aimed to develop the large scale methanol from biomass
technology. With present oil prices below US$20/bbl this technology is not economically
feasible. However, application for power generation is already a viable option, depending on
site specific conditions. Prospectives for large scale power generation via pressurised
gasification of coal using low cost oxygen enrichment techniques such as membrane
technology, means that medium joule gas might also be viable from biomass. If so, there is an
extra incentive for pressurisation of the gasifier because of the increased flow ratiorproduct
gas/gasifying agent, in oxygen gasification relative to air gasification. This conclusion holds
for either methanol synthesis or power generation. In the latter technology the use of gas
turbines seems to be particularly attractive because of efficiency considerations. Although this
route is not commercially available yet, significant development work on pressurised medium
joule gasification is in progress; particularly in fluidised beds (see Table 7).
The Framatome project [30] (Gl, Gil) is the only pressurised pilot plant within the
EC. Operating results will probably become available from 1990 onwards. In parallel,
fundamental research is carried out by Gelus et al, on the kinetics of gasification under pressure
[31] (G10). This is considered to be essential research for pressurised units because hardly
any information is available on the influence of pressure on pyrolysis and gasification but for
the fact that such an influence exists.
Table 7
Pressurised Oxygen-Wood Fluid Bed Gasification Projects [30, 32-35]
Company Pressure CaDacitv Moisture Temperature
bar kg drv wood/hr wt% Ώ
Framatome 5-30 2500 15-40 800-1000
MINO 10-30 300 50 700-850
Biosyn/Omnifuel 14 1400 5-45 —
IGT 20 400 — ~

4.4 Catalysis in Medium Joule Gasification


Results obtained outside the E C have shown that a potential exists for catalysis both in
enhancing gasification rates in double fluidised bed processes and in improving the synthesis
gas quality, reviewed in [26]. A major conclusion of the Venice Workshop on thermochemical
conversion routes in 1985 [36] was that also the E C should take up fundamental research in
this area. As a result, the third C E C . R&D subprogramme Energy from Biomass, which
started in 1986 included several topics such as the project of TNEE on the improvement of the
dual fluidised bed wood fast pyrolysis/gasification process by use of catalysts [37] (G5). The
project consists of:
• fundamental studies on the catalytic activity of dolomite;
development of a catalyst with favourable characteristics under operating conditions in a
double fluidised bed (sintering, erosion, poisoning);
• solids circulation studies on a fluidised bed gasifier - fast circulating combustor system;
• pilot unit tests at a capacity of 10-20 kg/hr.
A special feature of the TNEE process is a counter-current gas-solids trickle flow
contacting device above the fluid bed. Here pyrolysis gases are heated with the hot solids from
the combustor raining down into the bed over a packing. The main challenge of the project is
in finding suitable catalysts for product gas composition improvements and/or reduction of the
solids circulation flow rate. The main problems here will be catalyst deactivation, particle
attrition and catalyst effectivity to produce a hydrocarbon free gas. As far as the project
concentrates on alkali carbonates as catalysts still much work remains to be done at the
141

fundamental level on a small scale.


A second project is at the University of Zaragoza [38] on catalyst steam gasification,
which includes testing catalysts on activity, selectivity, deactivation rates and attrition risks.
Results obtained with a single fluid bed are reported at this conference [39]. Future work will
be directed towards a circulating multi-solids fluid bed such as developed by Battelle Columbus
[40].
4.5 Hydrogen From Producer Gas
Traditionally, the E C "Energy from Biomass" Programmes have also supported the
exploration of speculative new ideas on a laboratory scale to explore long-term potential. An
example is the recovery of pure hydrogen from low joule producer gas by a slurry of
hydridable metal alloys. Under the previous programme very reactive metal alloy slurries have
been developed [41] (G3).
The objective now is to select suitable reactors to apply the technology at a continuous
scale, and to evaluate the design rules for scaling-up and to optimise the process conditions.
Opportunities are in synthesis gas production from simple single bed air gasification, in
providing the hydrogen both for pyrolysis oil upgrading and direct hydro-liquefaction of
biomass, and, who knows, in cold fusion if it ever becomes practical.
5 PYROLYSIS
5.1 What is Pyrolysis?
Pyrolysis is thermal degradation either in the complete absence of oxidising agent, or
with such a limited supply that gasification does not occur to an appreciable extent which may
be described as partial gasification. Relatively low temperatures are employed of 500-800°C,
compared to 800 to 1100°C in gasification. Three products are usually produced: gas, liquid
and char, the relative proportions of which depend very much on the pyrolysis method and
reaction parameters. Fast or flash pyrolysis is used to maximise either gas or liquid products
according to the temperature employed.

5.2 Why is Pyrolysis Interesting?


Pyrolysis is attractive because solid biomass and wastes which are difficult and costly
to manage, can be readily converted to liquid products. These liquids, as crude bio-oil or
slurry of char and water or char, have advantages in transport, storage, combustion, retrofitting
andflexibilityin production and marketing. The energy density advantages are summarised in
Table 8.
Table 8
Energy and Density Characteristics of Biomass and Derived Products
Bulk Heatine value Enerev
density drv basis densitv
Feed kp/m3 GJ/t GJ/m3
Straw -100 20 2
Woodchips -400 20 8
Pyrolysis liquid -1200 25 30
Char -300 30 9
Char-water slurry (50/50) -1000 15 15
Char-oil slurry (20/80) -1150 23 26

The crude pyrolysis liquid is a black fluid which is often referred to as bio-oil,
pyrolysis oil, or just "oil". The other main liquid product is a slurry which can be made from
water and ground charcoal with chemicals added to stabilise the suspension. Stable and mobile
concentrations of up to 60% wt charcoal have been reported. Slurries can also be made from
the oil and char.
In pilot plant work to date the gas is usually flared but in a commercial process it would
142

be used to drive the process or use it as a fuel gas for fuel drying or power generation [42].
In transport bulk density is important, and some estimated values are given in Table 8
above. Oil and slurry mixtures have a clear advantage over woodchips and straw in transport
bulk densities and notably in energy density. For longer distances this difference may be a
decisive factor.
Storage and handling may be important because of seasonal variations in production
and demand and some storage will always be required [43]. Apart from the bulk density and
energy density considerations, it is important to appreciate that crude biomass (such as wood
chips and straw) will deteriorate during storage due to biological degradation processes. Char,
however, is very stable and will not deteriorate. Another important factor is handling, in which
liquids have significant advantages over solids.
Potential disadvantages can arise from the chemical and physical instability of bio-oil,
bio-slurries and mixtures, although there are mixed reports on such problems. These are
discussed later, but unless the properties of these fluids can be completely controlled, the
advantages of liquid fuels cannot be fully realised.
Combustion, retrofitting, market flexibility. Generally liquid (or gaseous) products are
easier to handle in the combustion process and this is important in retrofitting existing
equipment. Existing oil fired burners cannot be fuelled directly with solid biomass without
major reconstruction of the unit, which may not be attractive in uncertain fuel markets.
However bio-oils, char-oil slurries and char-water slurries are likely to require only relatively
minor modifications of the equipment or even none in some cases [44]. Powdered coal fired
furnaces can relatively easily accept charcoal as a partial fuel replacement, as long as the volatile
content is compatible with the furnace design.
It is likely that gas turbines can be readily fired with bio-oil and slurry fuels although
care is needed with the alkali ash residue in the char content of the slurry [45]. Modified diesel
engines may also be modified to accept upgraded char/water slurries or related products, but
there is little recent practical experience as yet. In most countries there is a small market for
charcoal lumps and briquettes for leisure and industrial applications and small regional markets
for firewood, usually as logs. There is reported to be a growing demand for charcoal for
specialist steel and non-ferrous metal production [46].

5.3 Pyrolysis Technologies


The heat required for pyrolysis can be added indirectly in a variety of ways such as
indirect firing, hot gas, or hot liquid such as metal or molten salt [47](PI2), or directly by
partial gasification with limited addition of oxidising agent such as air to give direct heating
[48KP5).
Pyrolysis has been practiced for centuries for production of charcoal. This requires
relatively slow reaction at low temperatures to maximise solid char yield (P6). More recently,
studies into the mechanisms of pyrolysis have suggested ways of substantially changing the
proportions of the gas, liquid and solid product. This is achieved by changing the rate of
heating, and the final temperature (P7).
High heating rates, of up to a claimed 1000°C/s or even 10 000°C/s, at temperatures
below about 650°C and with rapid quenching, causes the liquid intermediate products of
pyrolysis to condense before further reaction breaks down higher molecular weight species into
gaseous products. These high reaction rates also minimise char formation, and under some
conditions no char is apparently formed. At higher maximum temperatures the major product is
gas. Pyrolysis at these high heating rates is is known as fast, flash, or ultra pyrolysis
according to the heating rate and residence time, although the distinctions are blurred. Other
work has attempted to exploit the complex degradation mechanisms by carrying out pyrolysis
in unusual environments. The variations are summarised in Table 9.
A wide range of processes based on flash pyrolysis have been researched and
developed in these various modes in the last few years either to produce liquid bio-oil in high
yield, or to produce chemicals. In a few cases a reactive environment has been included to
influence the type of products. Examples of the main technologies and reactor configurations
employed are listed in Table 10, which is not intended to be exhaustive but indicative of the
variety of processes under development [50].
143

Table 9
Characteristics of Pyrolysis Technologies [49]
Residence Heating Temp. Maior
time rate °Cmax product
Slow pyrolysis
Carbonisation hrs-days very low 400 solid
Conventional 5-30 m low 600 gas,, liquid & solid
Fast pyrolysis
Fast 0.5-5 s fairly high 650 liquid
Flash - liquid <1 s high <650 liquid
Flash - gas <1 s high >650 gas
Ultra <0.5 s very high 1000 gas
Vacuum 2-30s medium 400 liquid
Reactive pyrolysis
Hydropyrolysis <10s high <500 liquid
Methanopyrolysis

Table 10
Examples of Pyrolysis Technologies [50]
Pvrolvsis technology andI main product(s) Reactor Organisation. Country
Liquids
Conventional for liquids Stirred bed Alten (KTI + Italenergie), Italy
Cyclonic for liquids and gases Cyclone Ensyn Engineering, Canada
Fast entrained flow for liquids Entrained upflow Georgia Inst Tech., USA
Vacuum for liquid fuels and chemicals Multiple hearth Laval University, Canada
Ablative for liquids and chemicals Vortex Solar Energy Research Inst., USA
Low temperature for liquids & charcoal Auger Tübingen University, West Germany
Flash fluid bed for liquids Fluid bed Waterloo University, Canada
Solids
Conventional for charcoal & liquids Downdraft Bio-Alternative SA, Switzerland
Gases
Molten salt Batch Aston University, UK
Methanopyrolysis for gases & chemicals Entrained flow Brookhaven National Lab., USA
Hydropyrolysis for gases & hydrocarbons Autoclave Toronto University, Canada
Twin fluid bed fast pyrolysis Twin fluid bed TNEE, France
Fluid bed Fluid bed University of Zaragoza, Spain
Chemicals
Vacuum for liquid fuels & chemicals Multiple hearth Laval University, Canada
Ablative for liquids & chemicals Vortex Solar Energy Research Inst., USA
Molten salt for gases & chemicals Batch Aston University, UK
Methanopyrolysis for gases & chemicals Entrained flow Brookhaven National Lab., USA
Hydropyrolysis for gases & hydrocarbons Autoclave Toronto University, Canada

One of the more innovative processes being developed is based on the principle of
ablative pyrolysis in which biomass "liquifies" if it is pressed onto a hot moving surface at
below about 650°C [51]. At these temperatures the liquid vapourises and if it is removed
sufficiently rapidly from the high temperature zone and quenched, high liquid yields with very
144

low char yields result The most advanced research of this type is being earned out at the Solar
Energy Research Institute [52] and a diagram of the equipment is shown in Figure 6. Other
processes based on a range of technologies are also well advanced [50] and await a suitable
opportunity for larger scale demonstration [53].

To liquid condensation
train and collection
Biomass pins

Char
cyclone

Screw feeder
Char
400 to 750 °C Vortex receiver
Steam reactor
Steam
ejector

Figure 6
Vortex Ablative Pyrolyser at SERI [52]
5.4 Pyrolysis Products
5.4.1 Liquid Product
The process of pyrolysis is complex, but a recent theory is that primary vapours are
first produced, the characteristics of which are most influenced by heating rate. These primary
vapours then further degrade to secondary tars and gases, the proportions and characteristics of
which are a function of temperature and time [54]. Yields of liquids from pyrolysis can thus
be influenced by the rate of reaction, with fast or flash pyrolysis at lower temperatures of
typically 450-650°C giving the highest liquid yields.
This liquid product may be readily bumed [44] and has been employed for this purpose
[55]. There are, however, some precautions which have to be taken in handling, storage and
combustion due to the water and high oxygen content (P6). For these reasons, pyrolysis
liquids cannot be directly assimilated into a conventional fuel marketing infrastructure and some
conversion or upgrading is necessary to give a product that is compatible with conventional
fuels. Upgrading technology is not well developed with most attention being paid to either
hydrotreating or zeolite decarboxylation to give synthetic gasoline and other hydrocarbons.

Characteristics and Utilisation


The liquid product is a highly oxygenated hydrocarbon with an appreciable proportion
of water from both the original moisture and reaction product. Solid char may also be present
Raiano). These properties can make it relatively unstable in both chemical and physical terms
and have been reported to cause some problems in utilisation and upgrading. It is readily
combustible, but care has to be taken in storage, handling and atomisation. Some of the other
characteristics are discussed below [56].
Water content is important as it has several effects: it reduces the heating value, affects
the pH, reduces the viscosity, influences both chemical and physical stability, reduces potential
pollution problems from waste water disposal and could affect subsequent upgrading processes
[57]. The interactions are poorly understood. The water is difficult to measure and remove,
since evaporation or distillation at normal temperatures of around 100°C can cause significant
145

and potentially deleterious physical and chemical changes in the liquid. Lower temperature
drying is not successful due to the nature of the relationship between water and the organic
component in which the water seems to be chemically combined, analogous to water of
hydration. This phenomenum makes claims of water content and consequently oxygen content
of liquids on a dry basis subject to some uncertainty. Water appears to be completely miscible
up to 20% by weight of total liquid, but above which an aqueous layer separates. Any water
that does separate must be carefully managed and this is discussed further below. Utilisation
and consideration of oil on a "wet" basis therefore seems to be more sensible. A much more
attractive approach appears to be to not condense the water by maintaining the pyrolysis
vapours above the dew point of water i.e. above about 110°C. The principle has been tried by
Roy in his vacuum multiple hearth pyrolyser [58] and successfully practiced by Bio-Altemative
[59].
Particulate levels may be high from char and ash carry-over. Separation of solids and
liquids is poorly understood with reliance placed on primary separation in the vapour phase
downstream of the reactor before condensation. Efficient separation inevitably causes some
condensation or precipitation and careful design is essential. Solid separation in the liquid
phase is not believed to have been studied, but is very likely to be troublesome. However, it is
clear that a fairly high level of charcoal can be assimilated in the liquid product, for example
Alten reported up to 15% [48] although some lumpiness was evident in the bio-oil. Both char
particle size and proportions will influence the liquid product quality. This is why research into
char-oil mixtures could prove valuable.
Oxygen content of the pyrolysis liquid is very high, at up to 40% wt. When produced
from dry or low moisture content feeds it typically has a heating value a little above that of the
biomass feed in the range 20 - 25 MJ/kg, which has caused it to be referred to as "liquid
biomass". The oxygen content arises from oxygenated compounds including phenols and
polyphenols, which can be recoveered as a valuable chemical fraction [60].
Low pH arises from the organic acid content (e.g. acetic and formic acids), and is
therefore corrosive. Mild steel is not suitable for handling or storage. Polypropylene piping
has been used to overcome this problem.
Polymerisation or deterioration of the liquid can be caused by temperatures above
around 100°C which adversely affect physical properties such as viscosity, phase separation,
and deposition of a bitumen-like substance. Heating the liquid to reduce viscosity for pumping
or atomisation needs to be considered carefully and thoroughly tested. Exposure to air also
causes deterioration, but at a slower rate than temperature increase. Maintenance in a sealed
enclosure has been claimed to cause substantial pressure increases, so some minimal venting is
necessary to avoid pressure build-up, but minimise exposure to oxygen. Pyrolysis liquid has
been stored in this way in a useable form for up to two years without problems (P6). Liquids
produced from refuse/MSW appear to be much more unstable [52, 61, 62].
Health hazards associated with pyrolysis liquids are also poorly understood. It has
been claimed that these are no worse than coal tar or crude oil [63].
Compatibility with conventional fuels is variously reported as immiscible but
compatible (P4). Pyrolysis liquids cannot be expected to be assimilated into a conventional
fuel marketing infrastructure without some conversion or upgrading to give a product that is
compatible with conventional fuels. One alternative is to feed to crude pyrolysis liquid into a
refinery for upgrading in orthodox refinery operations, utilising the hydrogen availability and
blending opportunities [64]. The alternative is to create a discrete pyrolysis liquids storage,
distribution and utilisation system, that is managed by experts who understand the special
problems of this fuel.
Some properties that have been reported are summarised and compared in Table 11.
Stabilisation
The crude liquid product can be used directly if in a single phase. If more than about
20% water is present, it can be processed to overcome some of the above problems by
emulsification with the water content if this separates (at typically above 20%wt water).. This
controls the stability of the liquid to a certain extent, and also enables the contaminated water to
be effectively disposed of, but at the expense of a lower heating value product. The cost is
relatively high with additives costing about half the value of the product as fuel [46,48].
146

Table 11
Comparison of Pyrolysis Technologies - Typical Data [1]
Conventional Fast Flash
Alten * GIT Waterloo
Temperature, °C 500 480 510
Products, yield on daf feed
% wt gas 68 10
% wt liquid (dry) 21 51 66
% wt water 26 29 10
% wt char 21 20 14
Liquid characteristics
oxygen (raw product), % wt - 53 -
oxygen (dry product), % wt 15 42 39
water, % wt 14.6 17 18
viscosity, cps@40°C 300 220 40
pour point, °C 27 -23 -
density, g/cm^ 1.195 1.26 1.19
pH 2 2.4
HHV, MJ/kg raw product 26.3 18.3 16.3
HHV, MJ/kg dry product - 22.1 -
Elemental analysis, dry product
Cwt % 61.9 52.2 54.7
Hwt % 6.0 6.3 6.4
Owt % 14.9 41.5 38.9
H:C molar ratio 1.16 1.45 1.40
0:C molar ratio 0.18 0.60 0.53
Char content, % wt 9.2
* (P5).

Upgrading
Upgrading technology is based either on orthodox hydrogénation technology to
produce successively lower oxygen content hydrocarbons, or the evolving zeolite technology
to produce hydrocarbon fuels directly.
Hydrotreating is based on technology that is established in the petroleum industry and
is in principle readily adaptable to reducing or removing the oxygen content of the bio-oil.
Preliminary results indicate that conventional hydrotreating processes may be readily adapted to
pyrolysis liquids [65](P8) and [66]. An alternative approach is to send the crude bio-oil to a
conventional refinery for upgrading with fossil oil. This has not yet been examined.
Zeolite based synthesis of hydrocarbons has been extensively demonstrated for alcohol
feeds. Some experience has been gained on upgrading products of cellulose pyrolysis by
decarboxylation [52, 67, 68], but there is concern over the problems of coking which would
require aregenerativeprocess. No reliable results are yet available.
Neither technology is yet available commercially, nor have robust mass balance and
performance data been produced, although a comprehensive technoeconomic assessment
suggests that atmospheric flash pyrolysis gives gasoline costs approximately double that of
conventional fuels with the potential to reduce this considerably in the medium term [69]. The
zeolite decarboxylation route gives potentially higher quality products due to preservation of the
aromatic structures resulting in high levels of benzene, toluene and xylene.
An alternative approach is to reduce the oxygen content to a sufficiently low level that it
may be satisfactorily blended with conventional fuels. This might be achieved by less complete
hydrogénation, or by simple distillation over activated clay such as bentonite which is claimed
to give a stable and storable product in one low cost step. No work on blending requirements
is known to have been carried out, but has been considered as a possible route to utilisation
[64].
147

5.4.2 Gas product


The gaseous product from pyrolysis is usually a MHV fuel gas around 15-22 MJ/Nm3,
or a LHV fuel gas of around 4-8 MJ/Nm3 from partial gasification depending on feed and
processing parameters. It has a high level of hydrocarbons, particularly methane, and saturated
and unsaturated hydrocarbons from the complex thermal dgradation processes. The heating
value is enhanced if the gas is used and kept hot, from the sensible heat, and the relatively high
tar content. The gas may be used to drive the pyrolysis process if an indirectly heated process
is used, or it can be employed to dry the feed, or generate power.
5-4.3 Solid product
When pyrolysis is optimised for charcoal production, yields of up to 30 or 40% wt on
dry feed are obtained. This occurs in slow pyrolysis with reaction times of hours or days.
Partial carbonisation gives the higher yields, when the product contains a high level of
volatiles, and this is also referred to as torrified wood. At the very high heating rates
encountered in fast and flash pyrolysis, very low char yields result, and have been reported as
approaching zero under some process conditions. This avoids the marketing and design
problems of a multiple product process, since the associated byproduct - gas in the case of
liquid production for example - can be used as process heat [46, 53](P5). Char yields can be
optimised for production of material for char-water slurries, although an integrated approach is
necesary for maximum energy recovery.

5.4.4 Slurries
A possible outlet for the char is slurrying with the oil, or with water, or with both oil
and water. Only a limited amount of char can be introduced into oil as unacceptably high
viscosities result from a char concentration higher than about 30% wt [46] (P4, PIO). The
maximum concentration of char in water that can be handled is about 60% to retain mobility
[42]. Costs of the additive are significant at about 1/3 of the slurry preparation cost [46].
Three phase slurries of bio-oil, char and water or waste-water are not feasible.
Coal-water slurries are increasingly used in large boilers and these slurries can be
simply and/or partially replaced by char-water slurries. The char/water slurry cannot,
however, be an outlet for pyrolytic waste water as unstable sludge formation results. The ash
content of the char is an important consideration in developing liquid fuels, and de-ashing
processes are being examined [70] (P6).
Although in principle it seems to be attractive to remix all products of pyrolysis process
into one single liquid biomass derived fuel, this does not currendy seem possible.
5.4.5 Chemicals
Several hundred chemical constituents have been identified to date, and increasing
attention is being paid to recovery of individual compounds or families of chemicals [52, 58,
71] (P7). The potentially much higher value of speciality chemicals compared to fuels could
make recovery of even small concentrations viable. An integrated approach to chemicals and
fuels production offers interesting possibilities for shorter.term economic implementation.
5.4.6 Water
A key feature of the pyrolysis process is that water is produced in significant quantities
of typically between 20 and 40% wt on the feed, depending on feed moisture content. The
water phase is highly contaminated with dissolved and suspended organics, with a COD of
typically 150 000. This therefore represents a major problem of disposal or utilisation. In the
selection of the primary pyrolysis products this waste water must be considered (PIO). If
biological treatment is not appropriate or too expensive, part of the heat of combustion of the
products will be required for incineration of this heavily contaminated water fraction. The
pyrolysis gas should primarily be used for this purpose but this may not be enough in cases
where the primary feedstock has a high water content and the gas is required for feed drying.
A potentially more attractive alternative route than incineration is oil condensation above
the dew point of water, i.e. about 110-120°C. The water then stays in the vapour phase and
can be burned with the product gas [59].
148

5.4.7 Secondary Products


The range of secondary products derivable from pyrolytic oil and char is summarised in
Table 12. The secondary products obtainable from the gas are not different from those
obtained by gasification (see Section 4).
Table 12
Secondary Products from Pyrolytic Oil and Char
Primarv Process Secondary Process Market Size ranee
product product \Jh input
LHVgas - - - Fuel gas 0.1-5
Engine Power - Electricity 0.1-5
Turbine Power - CHP 1-10
Conversion Ammonia Conversion Fertilisers 2-20+
MHVgas _ _ . Fuel gas 1-5
Engine Power - Electricity 1-5
Turbine Power - CHP 1-10
Conversion Methane - SNG 10+
Conversion Methanol Refine Methanol 10+
Conversion Methanol Conversion Gasoline 10+
Conversion Hydrocarbons Refine Gasoline, 10+
diesel, fuel oil
Liquid Hydrogénation Intermediate Refine Gasoline, 5-20+
diesel, fuel oil
Zeolites Hydrocarbons Refine Gasoline, 5-20+
diesel, fuel oil
Char (briquetting) Solid fuel 0.2-5

Notes: + upper size limited by feed supply

5.5 Pyrolysis Implementation


Bio-oil is claimed to be a relatively easy fuel to use, provided the viscosity is not too
high. Preheating to reduce viscosity is not usually favourable due to thermal degradation of the
bio-oil. The water content can be considered an advantage both for the combustion process
and because it reduces the viscosity of the liquid. Therefore the oil can be considered an outlet
or disposal route for some of the pyrolysis water. Phase separation is likely to occur at water
concentrations greater than 20% which could only be counteracted by costly emulsifiers.
Moreover the water could render the oil more unstable and more corrosive. Methanol has been
suggested as a possible additive [42].
An alternative to upgrading bio-oils on a relatively small scale is to introduce them into
some sector of mineral oil refining operations [64]. Bio-oil has a relatively large oxygen
content however, and oxygen is not easy to remove, being placed in this respect between
nitrogen and sulphur contaminants in oil. In a refinery biomass oil would profit from the
economics of large scale processing used in mineral oil refining as well as the ready availability
of low cost hydrogen. Research is planned in this area. One problem is that the resultant value
attributed to the bio-oil by the refinery may be too low to justify implementation.

5.6 Pyrolysis Status in Europe and North America


A demonstration plant of 500 kg/h is currently operating in Italy for liquid bio-oil
production with plans for a series of small commercial units there, in Spain and in Greece. A
number of demonstration plants for flash pyrolysis for bio-oil production are operating in
149

North America at a scale of up to 25 kg/h with plans for several commercial developments
ranging up to 20 t/h, including a commercial installation planned for California based on the
SERI ablative pyrolyser [72]. In addition to conventional and well established units for
charcoal production, a number of new carbonisation processes have become available for
production of slurry fuels from the charcoal and also recovery of the oil as a liquid fuel [73,
74]. These are, however, slow pyrolysis processes that give a low liquid yield. Examples of
current activities are listed in Table 13, all of which are orientated to liquid or slurry fuels
production.

Table 13
Examples of Pyrolysis Processes
Status Reactor type Example, (country')
Pilot Cyclonic reactor Ensyn (Canada)
Cyclonic reactor SERI (USA)
Entrained flow GIT (USA)
Fluid bed Waterloo (Canada)
Multiple hearth Laval (Canada)
Demonstration Auger kiln Waste Water Treatment Centre (Canada)
Fixed bed Cemagref (France)
Fluid bed Waterloo (Spain)
Fluid bed or stirred bed Alten (Italy)
Rotary kiln Kiener (West Germany)
Commercial Fixed bed Bio-Alternative (Switzerland)
Horizontal moving bed Pyrosol (USA)
Cyclonic reactor (planned) Pyrotech (USA)

5.7 Pyrolysis Costs


Of major importance in implementation of pyrolysis technologies is the economics of
production. A preliminary economic analysis is given in Figure 7 to show the effect of scale of
operation and feedstock cost on product price [49].
Current typical fuel oil prices are around 125 ECU/t, which is equivalent to 80 ECU/t
of pyrolysis oil on an equivalent heating value basis of 25 MJ/kg although it is not yet
established what conventional fuel product can be equated to bio-oil. This is shown as the
lighter shaded part of Figure 7 which identifies the plant capacities and feed costs that can be
justified at this price level. The larger darker shaded area represents an oil price 50% higher,
showing the sensitivity of production costs to scale of operation and feed cost. Special credit
might be given to bio-oil because of the extremely low sulphur content and possibly low NOx
production. Thus pyrolysis oil could be competitive on a relatively small scale of production.
A more comprehensive assessment of bio-oil and bio-slurry fuel costs has recently been
completed [AVB 164/165].
6 LIQUEFACTION
6.1 What is Liquefaction?
Liquefaction is low temperature, high pressure thermochemical conversion in the liquid
phase, usually with a high hydrogen partial pressure and also a catalyst to enhance the rate of
reaction and/or to improve the selectivity of the process. This approach gives a more
physically and chemically stable liquid product requiring less upgrading to produce a
marketable hydrocarbom product. Catalysts are also employed to provide enhanced
hydrogénation and de-oxygenation, as well as some selectivity in product formation.
The attractions of this technology include heat transfer to a liquid phase which is more
effective than to a gas phase, the liquid phase reduces the reactor and ancillary equipment
volume requirements, and the product is a higher quality liquid than from pyrolysis processes
in terms of higher heating value and lower oxygen content.
150

Pyrolysis Liquid Production Cost ν F eed Cost

400-
Product
cost, ECU/t

300'

2t/h
3t/h
200' 5t/h
20 Vh
100t/h

100'

40 50 60
Feed cost, ECU/t

Figure 7
Pyrolysis Oil Production Cost in relation to Fuel Oil Prices now &+50%
The high cost of high pressure processing, and unresolved problems of feeding
biomass slurries at high pressure, product separation from solvent if used, and use of high
pressure hydrogen have all caused significantly less activity in this area of thermochemical
conversion. Most work has been on a batch scale of operation (for example [75, 76] in
Europe, with only a few examples of continuous processing, including a 25 kg/h plant that was
built at Albany in the USA but has now been dismantled; a 1 kg/h plant in the USA [77] and
another in the UK [78].
More activity has concentrated on black liquor as a feedstock in recent years due to the
adverse economic situation for biomass derived fuels, and the economic and environmental
attractions of reducing the waste management problems surrounding black liquor [79].
The potential processing and reaction advantages of this conversion route should not be
ignored for longer term possibilities
6.2 Why is Liquefaction Interesting?
The particular interest of liquefaction is that a lower oxygen content product is produced
that is more stable and requires less upgrading to a hydrocarbon product. There are also
processing advantages with a liquid phase system that requires a lower volume reactor and
ancillary equipment, and also lower reaction temperatures that result in lower heat losses and
easier materials of construction problems.
A particular disadvantage is the high pressure requirement which is costly and
potentially more hazardous. This gives rise to feeding problems associated with slurries.
Hydrogen is often added to effect reducing reactions which increases problems and costs, and
In addition catalysts are often employed to improve yields of desired products which can lead
to more complex catalyst recovery systems or high costs from catalyst losses. A solvent is also
necessary as a solid carrier which requires separation and recovery and this also increases
process complexity and cost.
151

6.3 What products are produced?


The main product from biomass liquefaction processes is a low oxygen content oil
(around 10-15% wt oxygen on a dry basis), with a heating value of around 35-40 MJ/kg. The
byproduct gas may be used to generate hygrogen or used a low heating value fuel gas. Water
and a small proportion of char and ash residue are also usually formed. Similar products are
derived from black liquor. The oil product may be used directly as a liquid fuel to substitute
for fuel oil, or may be upgraded by hydrotreating to hydrocarbon fuels followed by refining for
assimilation into the transport fuel market.

6.4 Liquefaction Technologies and Status


Most work has concentrated on small scale batch type experimentation (L2), but some
work has also been carried on continuous flow systems (LI). Compared to gasification and
pyrolysis, there is comparatively little activity currently due to the high cost of establishing a
research facility and low conventional fuel costs. Examples of current activities are listed in
Table 14.
Table 14
Examples of Liquefaction Processes
Status Reactor type Example, (country)
Bench Autoclave Inst Wood Chemistry (West Germany)
Autoclave VTT (Finland)
Autoclave University of Toronto (Canada)
Flow reactor T.U.Berlin (West Germany)
Fluid bed UMIST/MANOIL (UK)
Pressure screw University of Arizona (Canada)

Related to liquefaction is solvolysis in which biomass is dissolved in a solvent at high


pressure and elevated temperature, such as [80, 81] and supercritical extraction in which a
similar effect is carried out more selectively in a solvent under supercritical conditions, such as
[82]. Both technologies are at a relatively early stage of development.
8 CONCLUSIONS
8.1 Gasification
Low joule gasification of biomass for heating applications is a technically proven and
often viable technology, provided that the scale of operation is sufficiently large, and that
feedstock is available in sufficient quantities at an acceptable cost.
• Low Joule gasification of wood for shaft power presently is commercially proven at
capacities up to a few MWe. Smaller units below 0.5 MWe have promising economic
potential in developing countries. The economics of retrofitting diesel fuel generator
sets with a biomass fueled gasifier can also be attractive in the industrialised world in
site specific situations.
Significant progress has been made in the field of medium joule gasification.
Demonstration projects now have reached the scale of 2-10 tons wood/day operating at
pressures up to 30 bar.
• Short term opportunities for medium joule biomass gasification are probably in power
generation rather than in methanol production but this remains an interesting long term
opportunity.
• The potential for catalysis both in enhancing gasification rates in double fluidised bed
processes and in improving synthesis gas quality has been recognised in the E C with
fundamental research at bench scale and larger scale applications. There is still much
progress to be made [83, 84].
• The most likely short term markets for industrial use of fuel gas from biomass and
wastes are where gas quality specifications are undemanding such as in boiler
retrofitting and direct firing (in the production of lime, cement, bricks and unglazed
152

pottery). Current and short term economic applications lie in utilising wastes and
residues to produce power, and fuel gas where quality requirements are less
demanding. There is potential for the production of transport fuels and chemicals in the
longer term, particularly in less developed countries and those with few indigenous
conventional energy resources.
8.2 Pyrolysis
Pyrolysis offers the potential to convert solid biomass into a high energy density
product that is easy and inexpensive to transport and that may be readily utilised in existing
installations. The recent EC Energy from Biomass Programme actively examined many
aspects of the production, upgrading and utilisation of pyrolytic liquid fuels which will be
continued in the successor programme. There are still problems to be resolved, however, if the
potential of biomass pyrolysis is to be optimised, including product yield improvement,
product quality improvement, new upgrading methods, product testing and utilisation and
resolution of environmental problems [84, 85].

8.3 Liquefaction
Liquefaction produces a higher quality product in terms of heating value and physiscal
properties, but at the expense of the higher costs of pressurised processing and use of
hydrogen. Waste conversion, such as black liquor, is a potentially interesting option.
8.4 General C omments
The production of higher value products in combination with fuel production would
enhance the economic viability of the processes. An objective comparison of the various
technologies for different applications would be useful.
In general, there are still some technical gaps between biomass production and
conversion, and between conversion and application. These will need to be resolved as
attention continues to turn to renewable energies.
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156

APPENDIX 1
RECENT EC SPONSORED RESEARCH IN EUROPE
References to all these projects may be found in Proceedings of EC Contractors Conferences,
including the Biennual ENERGY FROM BIOMASS Conference Proceedings published by
Elsevier Applied Science. Projects are identified in the text by the reference numbers below.
Gasification
G1 Air gasification of biomass for J. M. Lemasle FRAMATOME, France
fuel-gas production
G2 Catalytic steam gasification in fluidized J. Corella University of Zaragoza
bed of some biomasses existing in Spain
Spain to obtain a methane rich gas
G3 D evelopment of a new method for hydrogen W.P.M van Svaaij Twente University
recovery from lean gas mixtures using metal Netherlands
hydride slurries
G4 Further developments of the AVSA biomass H.A.Masson INIEX, Belgium
gasfication process
G5 Improvement of the dualfluidizedbed wood A. Le Lan T.N.E.E, France
fast pyrolysis gasification process; use of
catalyst and optimization of particulate solids
circulation techniques
G6 Modelling and application of biomass J.Heaton Energy Options Ltd., UK
gasification based power plants
G7 Modelling of biomass conversion processes B. Rhodes CHAM Ltd., UK
G8 Production of synthesis gas from biomass A.Bernardini ALTEN, Italy
gasification. Final data gathering.
G9 R&D of gasification module complete with G. Bonino B.E.S., Italy
filters for rice husk & Biomass residue
energy conversion
G10 Study of biomass gasification kinetics M.Gelus Université de Compiégne
under pressure France
G i l Syngas production from wood; the J Carré A.S.C.A.B, France
pressurised gasification unit of Clamecy
Pyrolysis
Ρ1 Accoustic agglomeration to clean G. Botti Progettazioni Industriali, Italy
pyrolysis gas
P2 D evelopment of a biomass utilization F.Cherubini Consorzio Cooperative
system at the power plant in Avezzano della Marsica, Italy
P3 Evaluation of potential penetration of F. Uccelli Italy
pyrolysis conversion technologies in
the mediterranean areas of Italy
P4 Improvement of pyrolysis emulsion/slurry, L Antonelli and F Fonzi, Alten, Italy
P5 Improvement of pyrolysis conversion F Fonzi and L Antonelli Alten, Italy
technology utilizing agricultural and
forestry wastes,
P6 New process of suspension pyrolysis M Ρ Chassin GRADT, France
and use of charcoal slurry, F Cailliez CIRAD, France;
C Esnouf Cemagref, France
P7 Production and utilization of synthetic IA Vasalos CPERI, Greece
liquid fuels
P8 Quality improvement of pyrolytic B Delmon UCL, Belgium
oils from biomass L. Leonardini CRITA, Italy
P9 Study on the production of charcoal slurry G. Salvi COGIS, Italy
based on biomass pyrolysis products
157

PIO Study on biological degradation of the F.Fonzi ALTEN, Italy


acidic condensates coming from L.Antonelli
pyrolysis of biomass
P i l Study of optimisation of the use of biomass C. Erbaggi Società Cooperativa Agricola
derived from forest for pyrolysis oil. Forestale "Collelongo", Italy
production
P12 Thermal conversion of biomass JKMaund Aston University, UK
in molten salt media
Liquefaction
LI Direct liquefaction of wood and H Meier zu Köcker Technical University
solid agricultural waste Berlin, West Germany
L2 Production of synfuels and chemical O Faix Institute of Wood Chemistry
feedstocks by direct hydroliquefaction of West Germany
ligno-cellulosic biomass,
158

A SURVEY OF BIOHASS LIQUEFACTION PROCESSES

R. CAPART, A. ELAMIN, S. AMMAR, M. GELUS


Department of Chemical Engineering
University of Technology - B.P. 649
F - 60206 - COMPIEGNE

Summary

From the 1970's, the liquefaction of wood or biomass has been


extensively studied in order to provide a liquid product easily
pumpable and stockable, very like to gasoline or fuel produced from
petroleum Industry. In this paper are exposed different methods to
obtain this liquid (oil) at a laboratory scale or from process
development units working in a continuous mode.
The oil from direct liquefaction or pyrolytic processes are often
ameliorated by a subsequent catalytical treatment which makes use of
either hydrocraking catalyts (CoMo, NiMo, Pd, etc....) under
reductant atmosphere or zeolite - type catalysts (HZSM-5) without
reductant gas.

1. INTRODUCTION
Thermo-chemical conversion of biomass produces always gases, liquids
and solids. How the products share between these three states depends on
the process and temperature is the more important parameter.
Pyrolysis is the breakdown of biomass by heat in the absence of air
or oxygène. If pyrolysis is run at slow rates and temperatures less than
500°C, then the process yields a maximum of solid residue, the charcoal.
In flash pyrolysis as in fast pyrolysis, heating rates are very high. The
solid residue is very small and the production of high quality gases is
very important, due to thermal craking of pyrolytic oils.
Liquefaction processes are related to direct high pressure
hydrotreatment. The aim is to maximize the liquid yield, with a low
oxygen content. It is obvious that liquids, because of their energy
density, appears to give the only way to use biomass in transportation. A
high yield of liquids could be obtained not only by liquefaction, but
also by pyrolysis and upgrading of pyrolytic oils.
There is no clear definition of the different processes of
thermochemical conversion. Neither the mass balance, nor the operating
conditions could bring a clear understanding of the lot of terms used in
the field of thermal biomass valorization. That could be a problem for
people in charge of reviewing the state of art of liquefaction.
In liquefaction processes, it is not obvious to evaluate the mass
balance and the results depends on the analytical methodology. Oil could
be the part which is extracted by a solvent as acetone or benzene or
159

methylene chloride and oil yields depend on the solvent, which is often
acetone. In this paper, conversion is evaluated as :

weight of wood - weight of solid residue


weight of wood

Water is always produced during thermochemical conversion of wood.


So, we can roughly consider that liquefaction leads to form fractions :
- gases
- oil
- water
- solid residue
and comparison of yield could be interesting from an economical point
of view.

2. DIRECT LIQUEFACTION OF WOOD - PROCESS DEVELOPMENT UNITS IN CONTINUOUS


Appell (1) first studied the liquefaction of lignocellulosic
material at the Pittsburg Energy Research Center (PERC). He obtained a
heavy oil by reaction of wood at 350°C in the presence of H 2 and/or Co in
aqueous Na 2 C0 3 . This preliminary work encouraged the PERC to. pursue
development of studies leading to the conversion of wood into liquid in a
single step.
A pilot demonstration unit (PDU) has been constructed in the 1970's
at Albany (Oregon) (2). This PDU being able to work following two
different processes which have been developped by the PERC and the LBL
(Lawrence Berkeley Laboratory).
The PERC process consisted of converting dried wood flour in an
anthracene oil, between 300 - 370°C in the presence of N a 2 C 0 3 as catalyst
(2 - 8 wt * based on dry wood), under reductant gas, mixing C0/H 2 in the
proportion 60/40 and at 200 bar of pressure. Anthracene oil was
progressively replaced by recyling the oil produced. The original PDU was
submitted to many modifications to improve its working capacity and wood
treatment. In the best case it has been working during 572 hours with an
average flow rate of 8.75 kg/hour of produced oil. However, the wood
concentration in the slurry is dramatically low, no more than 8 * by
weight. In addition, serious technical problems due to undissolved solid
and increase of oil viscosity prevented the Albany PDU to work after
1981.
In order to increase the wood concentration in the slurry as well as
its pumpability, the LBL induced a pretreatment of the wood prior its
liquefaction. The pretreatment consisted to a mild hydrolysis in diluted
H 2 S 0 A at 180°C. After milling, an aqueous suspension containing 30 * of
undissolved lignocellulosic material is obtained. The liquefaction
reaction is performed from this suspension, the pH of which being
increased to 8 by adding N a a C0 3 . Contrarily to the PERC configuration
process, the LBL process did not require the recycling of produced oil.
The experimental difficulties encountered with the Albany pilot plant
conducted the LBL to study the liquefaction through a bench scale
laboratory unit (BLU) of much smaller capacity. From litterature data,
the LBL process operating either in PDU or in BLU mode provides no
advantage with regard to the PERC process. The working time and the oil
yield are inferior to those of the PERC process obtained in its best
configuration.
160

OPERATING CONDITIONS PERC (Run 12) LBL (Run 7) Univ. ARIZONA


TYPE OF REACTOR PLUG FLOW STIRRED P.F. EXTRUDER
REACTOR TEMPERATURE 330 345 400
PRESSURE (bar) 210 210 210
WOOD FEED RATE (Kg/h) 17,4 7,7 3,6
SLURRY FEED RATE (Kg/h) 245 71 54
Na 2 C0 3 /Wood 0,1 0,12 0
REACTANT GAS (Nm/h) 14,9 4,5 0
H 2 % IN REACTANT GAS 39,2 37,7 0
SLURRY VEHICLE ANTHRACENE OIL WATER WATER

CHARACTERISTICS OF CRUDE OIL

GHV (Kcal/Kg) 8236,2 8025,3 8325


OIL YIELD 53,3 25,1 27
(wt % on Wood Basis)
VISCOSITY (CPS) 135 142 103
ANALYS] S (ON DRY BASIS)

C 79 79,2 80
H 8,5 7,8 8,4
0 12,5 14,4 10

Table 1 DIRECT LIQUEFACTION OF WOOD


CONTINUOUS PROCESS DEVELOPMENT UNITS

The major difficulties encountered with the Albany process plant was
the pumpability and the transfer of the slurry througout the
installation. To overcome these difficulties, some searchers such as
Eager (3) and White (4) used a screw-feeder or an extruder-feeder which
allow a certain defibration of the woody Material and a good circulation
of the slurry. The experimental device designed by Eager and al consisted
of an horizontal tubular reactor with an internal screw (Auger) which
vehicles water-wood slurry from a pressurized container through the
reaction zone. The liquefaction technique was not different from that of
LBL (catalyst Na 2 C0 3 , reductant gas : CO). The wood/water ratio being
about 0.4, Eager obtained good yields in produced oil (37 - 42 %)
nevertheless with a certain formation of wood char (1 - 15 * ) . Different
types of Auger have been tested. They were all subjected to serious
erosion or corrosion problems.
White and Wolf, at the University of Arizona have developped an
extrusion technique which permits a good feed and the pressurization of
the reactor as well as a mechanical pretreatment. The vertical reactor,
of plug flow type, was feeded with steam and CO so that H 2 was formed in
161

situ by water gas shift reaction catalysed by Na 2 C0 3 . Various tests up to


52 hours have been performed, covering a range of pressures from 50 to
210 bar and temperatures from 350 to 430°C. Crude oil containing 6 to
10 % of residual oxygen were obtained and nothing was mention about char
formation, probably prevented by steam injection in the reactor.

3. DIRECT LIQUEFACTION OF WOOD WITH REDUCTANT GAS AT LABORATORY SCALE


A lot of research works has been devoted to the direct wood
liquefaction in order to prove the feasibility of a process and to define
the best experimental conditions, i.e temperature, pressure, choice of
carrier solvent or catalyst from numerous repetitive experiments
conducted in batch autoclaves generally of small capacity.
Early works due to Appell and the Bureau of Mines were exclusively
based on the use of very cheap catalysts such as Na a C0 3 . Boocock (5) (6)
has particularly studied the liquefaction of wood in aqueous suspension
and discussed the effect of various Ni basis catalysts as Ni Raney, Ni
salts or oxydes, at temperatures around 350°C and initial pressures of
hydrogen in the range 17 - 100 bar. He obtained relatively low yields of
oil containing about 10 wt % of residual oxygen. No noticeable difference
was observed between the different Ni - basis catalysts upon the oil
yield.
Rogers (7) investigated the catalytic effect of different salts of
transition metals in the presence of steam and CO. The nature of chemical
bonds on the metal are determinant : the chloride, sulfate, acetate and
nitrate are not efficient. Only the oxyde and cyanid have a real
catalytic effect.
Soyer (8) liquefied wood sawdust in water suspension by using
various Fe basis catalysts under pressure of reductant gas H 2 or neutral
He at 340°C and 40 - 60 bar. Among all the tested catalysts, finely
divided iron powder revealed the more efficient, but its activity is
decreasing during the reaction. With a sufficient initial quantity of
iron powder (14 wt * based on wood), Soyer obtained a total conversion of
wood and observed that the nature of gas (H 2 or He) has no significant
effect on the yield (about 40 %) and the quality of the oil produced.
From systematic experiments of wood liquefaction in organic solvents
(anthracene recycled-oil, pyrolysis oil) under hydrogen pressure, Meier
and Faix (9) have tested many current catalyts of hydrocraking. Because
of the high wood content in the carrier solvent, total wood conversions
were rarely reached and wood char was formed. Meier and Faix concluded
that only Pd on activated charcoal support and iron powder meet important
requirements of the liquefaction process such as complete recovery of the
carrier with simultaneously high yields on the net product oil. The use
of iron powder is preconized because of its very low cost. About the
influence of pressure, a minimum of 100 bar is necessary to recover the
whole carrier oil and to obtain low char formation. Gupta and Weiss (10)
made an extensive study of the nickel promoted hydrogénation of
celluloslc materials. Using both powdered newspaper and pure cellulose as
feedstock, they demonstrated the feasibility of converting celluloslc
materials into liquid hydrocarbons by reaction with hydrogen at 425°C and
70 atm in a slurry phase with paraffinic oil and in the presence of
0.2 wt * Ni OH catalyst. Oil yield of 45 % was reported.
Delmon (11) and al. have used mainly tetralin as solvent and the
sulfided CoMo as catalyst. They have emphasized the role of CS a to
maintain the catalytic activity of CoMo during the reaction.
Araya (12) and al. compared the effect of gas, neutral or reductant
162

on the liquefaction in a typical hydrogen donor solvent : the tetralin.


The production of lighter organic liquid is favoured under an atmosphere
of hydrogen and with CoMo catalyst, particularly if the catalyst is
finely ground and dispersed in the reacting mass.
In the case of liquefaction of pure cellulose, Vasilakos and Austgen
(13) have obtained good oil yield for that type of catalyst in
conjunction with tetralin as solvent. When using 2-propanol, the best
catalyst is the Ni-Raney, giving very good yield in net product oil,
about 75 wt % (on the basis of cellulose), with an oxygen content
comparable to that of the cellulose derived oil in the tetralin/palladium
series (24 - 27 * ) .

4. LIQUEFACTION OR SOLVOLYSIS OF WOOD WITHOUT REDUCTANT GAS


In the early 1970 s' the Bureau of Mines (14) conducted some
interesting experiments using formic acid or sodium formate in place of
carbon monoxyde. This lowered the operating pressure at 250°C to the
range 1000 - 1100 PSIG and still gave good oil yields as shown by the
table.

Water Catalyst: g. Oil yield Conversion


ml Type Amount
HCOaNa HC0 2 H
100 1 5 60 99.6
100 5 1 55 99
100 2.5 2.5 55 99.8
50 2.5 2.5 41 90

Table 2 : LIQUEFACTION OF WOOD WITHOUT REDUCTANT GAS

The products obtained at these mild conditions were pitches instead


of oils and revealed to be instable. The Bureau of Mines studied the
effect of recycling wood derived oil. A series of run at 250 to 275°C
showed that the product become too viscous to use after only 4 cycles.
Without using catalyst and reactant gas, Yan (15) in 1980 liquefied
a variety of wood species and paper in aromatic solvents with high
boiling point (340 - 484°C). Various experiments at temperature of
320 - 400°C in batch or semi continuous reactor give yields of oil, gas
and water around 60 Ss, 17 % and 23 * based on the original wood. Yu (16)
selected organic solvent such as phenol and ethylene glycol and used them
with an acid catalyst H 2 S 0 4 at temperatures lower than in most
liquefaction processes i.e 180°C and 250°C. Almost complete conversion of
wood into oil was obtained nevertheless with high oxygen content
(20 - 30 %).
Continuous liquefaction in mineral oil has been performed by Kaufman
and Weiss (17) using a finely divided paper slurry with 20 wt * solid
content.
Vanasse, Chornet et Overend (18) have tested two different solvents
in a continuous process (known as the UDES-S process) ethylene glycol and
creosote oil rich in by-phenol compounds. The reactor of plug flow type
was feeded by a wood-solvent slurry in the concentration range 14 - 18 S>.
The slurry was obtained after a pretreatment which associates an heating
163

up to 240°C with a mechanical defibrating of the suspension through an


homogeneizing valve placed in a recirculation loop. The results are
clearly different from a solvent to another. With the creosote oil, the
yield in final oil is in the range 61 - 51 % and the wood conversion is
almost complete. With the ethylene glycol, the conversion is limited and
plateau 65 *. Nevertheless the yield in produced oil between 40 - 55 * is
satisfactory. The cellulosic fraction is relatively resistant to the
solubilization by ethylene glycol and can be isolated by this way. In
both cases, the oxygen content of the produced oil (ranging 21 - 29 %)
was much higher than that of the PERC process.
A recent study (19) has been reported about the dissolution of a
tropical prototype wood (eucalyptus) in various organic solvents. Simple
alcohol (C 2 to C Ä ) , ethylene glycol, water, phenol and phenolic
compounds : guaiacol and cresol. The experiments have been conducted in
batch autoclaves, heated up to 250°C. Discussed in term of a kinetical
parameter, termed severity, the results show that an almost total
conversion of wood is obtainable with ethylene glycol and like phenol
products, only for a high degree of severity. Selective dissolution of
hemicellulose, lignin and cellulose are observed only with the polyol and
phenolic solvents.
Recently Boocock (20) has given up the use of Ni-Catalysts with
reductant gas and performed the liquefaction of wood samples of different
sizes by rapid steam injection at temperature between 335 and 355°C. He
obtained good oil yields, around 50 wt % based on the original wood.
Some interests exist to process the biomass with solvents in their
supercritical state. As explained by Modell (21) in the case of water
(T — 374°C), the hydrogen bonds are weaken in critical conditions and
the solvent behaves very much like a polar organic solvent which leads to
prevent char formation by keeping intermediates highly solvated and well
dispersed. At the same time the presence of hydrogen, a product of
reforming can aid in stabilization of the intermediates. In supercritical
water, pure cellulose is completely degraded, after Modell. Supercritical
methanol has been employed by Grandmaison et al. (22) to perform
selective extractions on wood material.

5. THE CATALYTIC HYDROREFINING OF WOOD DERIVED OIL


Soltes (23) compared the activity of 20 different catalysts for the
upgrading of the oil produced from wood pine pyrolysis. The catalysts
were either metal transition oxydes or noble metals such as Pd, Pt, Rh.
The experiments were conducted with decaline or methylcyclohexane as
solvent at 400°C and initial pressure of H 2 of 66 atm. The formation of
water and hydrocarbons are enhanced by noble metal, however the
increasing in temperature leads to coke formation, a decreasing in light
products and an increasing in aromatic compounds.
Baker and Elliot (24) have successfully converted both high pressure
liquefaction oils and pyrolysis oils to a highly aromatic gasoline range
fuel. Their studies were conducted in a one liter continuous flow reactor
system. From Baker and Elliot, the production of high quality gasoline
boiling range liquid requires hydrodesoxygenation without saturing the
aromatic rings in the oil and the sulfided CoMo catalyst is the best
choice which satisfy this constraints. As shown by table (3) good quality
of oil have been obtained by BAKER particularly in the case of LBL
process oil leading to a final product with a 0-content near to zero.
164

PROCESSING LIQUEFACTION PROCESS PYROLYSIS PROCESS


CONDITIONS OIL OIL

Source of oil LBL (N° 7) PERC (n° 12) GEORG TECH. LAVAL SERI
Temperature 398 397 353 258-400 259-376
YIELDS
Total oil 0.99 0.92 0.43 0.42 0.37.
1/1 feed oil
Aqueous phase 0.20 0.20 0.61 0.57 0.51.
1/1 feed oil
H_ consumption 616 548 457 711 689.
171 feed oil
Carbon conver- 14.1 9 17 35.5 25.
sion to gas wt %
PRODUCTS
INSPECTION
Oxygen % 0.0 (14.4) 0.8 (12.5) 2.3 (52.6) 0.8(44.2) 1.3 (43.)
H/C ration 1.65(1.18) 1.5 (1.3) 1.67 (2.2) 1.7(1.77) 1.7 (1.7)
CS-225°C Vol. * > 87 37 72 87 73.

Table 3 - HYDROREFINING OF CRUDE OIL (BAKER and ELLIOT)


CATALYST CoMo/Al a 0 3 - PRESSURE 140 BAR
( ) Value related to feed oil

Various pyrolysis processes can produce oil at a lower cost than


high pressure liquefaction but the oils have a lower quality. The
pyrolysis oils have the tendency to form coke quite rapidly and to plug
the reactor bed. The Pacific Northwest Laboratory (24) has developped a
method to upgrade these oils and produce hydrocarbon fuels similar to
those obtained from high pressure liquefaction oils by increasing the
reaction temperature from a low value (about 280°C).
GEVERT (29) upgraded PERC-process oil in a batch reactor in the
presence of sulfided CoMo finely ground and decahydronaphtalin as
solvent. All the distillation products of the upgraded oil i.e lights,
heavy gas oil and residue have an oxygen content less than 1 wt % as
indicated by table 4.
The pyrolysis oil obtained from wastes of olive industry can be
valorized by hydrotreatment. DELMON and CHURIN (30) preconized the same
methodology as BAKER and ELLIOT i.e. to avoid the coke formation, the
bio-oil must be pretreated at low temperature (< 300°C) before to be
heated at the reaction temperature, around 380°C. They reported also a
good recovery of the solvent (tetralin) by distillation and the
possibility to replace tetralin by the distilled fractions from the
produced oil.
165

Fraction Boiling 0 C H H/C


range

Lights < 60 0.6 14 85.4 2.0

Heavy gas oil 250


50 - 350 0.7 14 85.2 2.0

Residue > 350 0.8 9.5 89.7 1.3

Table 4 : ELEMENTAL COMPOSITIONS OF HYDROGENATED PRODUCTS Wt %


GIVEN BY GEVERT (29).

6. THE UPGRADING OF WOOD DERIVED OIL BY ZEOLITE CATALYSTS


Another approach to valorize the wood derived oils is to convert
these oils by using an appropriate catalyst in absence of reductant gas.
The appropriate catalysts can be classical cracking catalysts such as
silica/alumina bust the most used are zeolites known as ΖSM-5 and
particularly HZSM-5 in pellet form with silica/alumina as binder. This
type of catalyst was already known to have a good efficiency for the
upgrading of alcohols, phenolic and many other oxygenated compounds. It
has a middle size pore structure and is constituted by cristallites of
various oxydes, principally Na a 0, Al a 0 3 , Si0 a , TiO a and eventually ZnO or
MnO.
The conversion reaction with zeolite is conducted at atmospheric
pressure, under neutral atmosphere, at temperature ranging from 400°C to
550°C. The feeding material can be either a condensed oil or the vapor
emitted from a pyrolysis process plant whithout condensation. In the
1980's several laboratories have studied a variety of
pyrolysis/liquefaction oil over HZSM-5, the feedstock ranging from high
pressure oil (31) (32) to low pressure pyrolytic oils and vapor (33) (34)
(35) (36) (37). A review of upgrading possibilities for pyrolytic oils
from wood was prepared by Kaliaguine (38).
As for the simple model of oxygenated compounds, the upgrading
action of the ZSM catalyst consists of an almost complete removal of the
oxygen in the feed material under the form of H 2 0, CO and C0 3 . The
upgraded product is particularly rich in C, - C 1 0 gasoline fraction,
characterised by boiling points ranging from 70 C to 213°C.
The components of the gasoline fraction are essentially aromatic and
are of a great economical interest due to the expected high octane
number, between 115 and 135, as reported by Diebold and Scahill. The main
compounds identified by mass spectrometry are :

Benzene Indene/Indane
Toluene Cresol
m, ρ, o Xylene Xylenol
m, ρ, Ethylbenzene Naphtalene
1, 2, 4 and 1, 2, 3, 4 Méthyl-Benzene

Milne and al. (39) have established a summary of hydrocarbon yields


reported from different works based on the use of HZSM-5. The yield in
hydrocarbon C + 2 (in wt * of original wood) is ranging from 12 % to 21 *
while the gasoline fraction C s - C 1 0 is ranging from 7.8 to 15 Ss,
depending on the method of pyrolysis which gives more or less char. The
166

ratio of aromatics (benzene, toluene, xylene) to olefin (ethylene,


propylene, butene) ranges from 3.8 to 8.3.
However, the zeolite catalysts are rapidly deactived by coke
formation which is more important for wood tar or derived oil than for
simple model compounds. Different solutions are suitable to reduce the
coke formation as the injection of steam in the bed of catalyst or the
coprocessing of the wood derived oil with methanol.
Till now, experiments have been performed in microreactor at a
laboratory scale. Scahill and Diebold (36) have proposed a technoeconomic
study about an industrial process-plant which would include :
- a continuous regeneration of the zeolite in a fluidised bed burner
- a separation step of the produced olefins.

7. CONCLUSION
Numbers of studies have been carried with different thermochemical
processes, i.e. pyrolysis, direct liquefaction and solvolysis show that,
liquid-oil can be obtained from a variety of wood materials. The yield of
this oil is in the range of 30 - 70 wt % based on the original solid
material. Whatever the type of the process, the oil produced is very
oxygenated compared with the petroleum products. The pyrolysis have an
oxygen content around 30 - 40 %; solvolysis oil in organic solvent
20 - 30 wt * and the oil obtained with direct liquefaction at high
pressure have a less oxygen content about 10 wt %.
Oxygen removal and molecular weight reduction are necessary to
produce usable hydrocarbon fuels. This can be actived either by catalytic
hydrotreatment on catalytic cracking. Catalytic hydrotreatment if often
carried in the presence of catalysts based on transition metals such as
CoMo, CoMos, MiMo, NiMos supported on alumine on in the presence of
Raney-nickel and noble metals like Pd, Rh under hydrogen pressure around
100 bar and at temperature range of 330 - 400°C. Catalytic cracking could
be realized with zeolite supported on silice-alumine at high temperature
450 - 550°C, zeolite such as HZSM-5 could eliminate the need of hydrogen
in the upgrading process and can effectively deoxygenate biomass oil to
produce hydrocarbons.
We can conclude that, for the feasibility of a liquefaction process
for producing hydrocarbon fuels, the research should be oriented to :
- regeneration of the solvent which gives maximum oil yield for
continuous liquefaction process ;
- catalysts development for cracking and hydrogénation of the higher
molecular weight components.

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169

THE GEORGIA TECH ENTRAINED FLOW PYROLYSIS PROCESS

R. J. Kovac and D. J. O'Neil


Energy and Materials Sciences Laboratory
Georgia Tech Research Institute
Georgia Institute of Technology
Atlanta, GA 30332, USA

Summary

The Georgia Tech Research Institute has developed an atmospheric flash


pyrolysis process for the conversion of biomass to liquid fuels. The
successful demonstration of pyrolysis oil production of 60Z (moisture-
and ash-free) has been achieved in a large-scale Process Development
Unit (1.4 DRY TONNE/DAY). Nearly fifty steady-state trials have
confirmed the technological reliability of the process. The liquid
biofuel product is a uniform mixture of oxygenated hydrocarbons and
modest levels of stably bound water. Char and non-condensable gases are
ancillary products. Gross product thermal efficiency of 94Z and a net
thermal process energy efficiency of 73Z are achieved. Oil and char
recovery exceeds 70Z (moisture- and ash-free). A conceptual manufactur-
ing process and an economic analysis for oil production for a 200 TPD
plant is presented. The plant proves to be profitable even at current
fuel costs and investment costs (June, 1989 basis). Rate of return on
investment is 39.AZ. The payout period is 2.1 years. Total capital
investment is $2.28 million. Manufacturing cost per GJ is $2.70. The
process is being prepared for further scale-up from the PDU stage to a
commercial prototype.

1. OVERVIEW
During the 1960's the Georgia Institute of Technology (Georgia Tech)
began the successful design and development of a patented Moving-Bed
(Vertical-Bed) Pyrolysis System for the conversion of biomass, municipal
wastes and sludge to high-energy density, transportable fuels (pyrolysis oil
and char) and a low-energy process gas which was used on-site for drying of
feedstocks (1). In the 1970's the Georgia Tech Moving-Bed Pyrolysis Process
was licensed to the Tech-Air Corporation (which became a subsidiary of
American Can Company) which, through a sub-license to American Carbons Co.,
has commercialized the technology. This technology was developed by Georgia
Tech and Tech-Air in four large-scale pilot plants and a commercial prototype
of fifty tonnes per day (TPD) which was operated continuously at a sawmill,
around the clock (24 hours per day) over a period of eighteen months before
the demonstration was terminated. That research, development and demonstra-
tion program, spanning 1968-1978, confirmed the reliability and high
efficiency of pyrolysis technology with biomass and municipal wastes, and the
economic viability of vertical-bed pyrolysis plants of 50-250 TPD. That
170

Georgia Tech Moving Bed Pyrolysis Process, in commercial form, remains the
standard for commercial biomass pyrolysis technology.
The design for the Georgia Tech Entrained Flow Pyrolysis Process
originated in 1978 with an internally-sponsored project for the development
of an innovative process for the thermochemical conversion of biomass to
synthesis gas via a combined pyrolysis-gasification process. Following a
contract award from the U.S. Department of Energy in 1980, and after
completion of bench-scale studies and the construction of a preliminary
conceptual design and preliminary economic studies, which indicated very high
potential for an economically viable, stand-alone process for liquid biofuel
production, continuing research and development focused on the design and
development of a new pyrolysis process. With the revised objectives, the new
Georgia Tech Entrained Flow Pyrolysis Process was focused on the maximal
production of the liquid biofuel, pyrolytic oil. A 1.5 TPD Process
Development Unit (PDU) was designed and installed in 1983. The purpose of the
experimental PDU was to investigate the entrained pyrolysis of wood under
steady-state conditions. The experimental parameters which have been studied
included feed material characteristics, particle size, pyrolysis temperature
and residence time. The data was analyzed in parallel and interactively, to
develop mathematical models of the kinetic and transport processes occurring
in the pyrolysis process. By this methodology the process model was
progressively refined and improved process parameter predictions were
developed for maximal oil production. In the later stages of program
development, after identification of key parametric parameters, oil yields
(dry basis) consistently in excess of 552 and achieving 602 were demonstrated
in steady-state operation of the PDU. Modeling indicates that 632 oil yields
are achievable in the PDU. The prospect of reaching 702 yields was indicated
with process design modification in future prototypes. The program
consistently demonstrated mass and energy closures of 100 ± 52 in which all
elements of the applicable equations were measured. The validity of
engineering data is unlike that of most other pyrolysis projects. It is of
significance that the excellent closures have been achieved in a large-scale
process demonstration unit. The experimental results have demonstrated a
gross product thermal efficiency of 942 and an overall process efficiency of
732. Oil and char yields (dry mass) exceed 702. A detailed summary of the
development of the Georgia Tech Entrained Flow Pyrolysis Process has recently
been presented (2) . This paper will focus on the conceptual design for a
manufacturing process using the proprietary Georgia Tech Process for the
production of liquid biofuel and co-products. The results of a detailed
economic analysis for a 200-dry TPD plant will be presented.

2. PROCESS DESCRIPTION
A manufacturing flow diagram which highlights the key pieces of
equipment and systems for commercial scale operation of the Georgia Tech
Entrained Flow Pyrolysis Process is given in Figure 1. There are three
principal sections to the manufacturing process: feed preparation, pyrolysis,
and product collection. A process flow block diagram is presented in Figure
2. The incoming feed and outgoing product streams are identified in
relationship to the key process operations of a 200-dry TPD plant. By
reference to both figures, the manufacturing process may be described.
Green wood chips at 502 moisture (wet basis) are brought from a
receiving and storage area and conveyed to a wood-burning dryer using a front-
end loader. The dryer is a fan-circulatory design fitted with a metering bin
and a particle collector. The burner is a co-fuel design and uses wood and
product gas. (The exhaust gases from the wood dryer burner will be passed
through, and air-cooled in, a heat exchanger and used as a conveying carrier
171

ROTARY
SEPARATORS

«AT
EXCHANGE*
ELOWBl A H)
AND PYROLYBB
REACTOR

FEED PREPARATION PYROLYSIS PRODUCT


COLLECTION

FIGURE 1 MANUFACTURING FLOV DIAGRAM

gas for the reactor feedstock.) The wood chips are dried to less than 10Z
moisture (wet basis) and are transferred to a storage bin which supplies feed
to the pyrolysis unit on demand and provides surge capacity. The feed is next
comminuted in a hammer mill, fitted with a vibratory screening circuit, where
grinding reduces the average particle size of the wood and the moisture
content to 6 Ζ (wet basis). The dried feedstock is screened to segregate
oversized pieces which are recycled to the hammer mill for re­grinding. The
screened dry wood feedstock is transported to an enclosed feed bin mounted on
a loss­in­weight feeder. The particulate feed is dropped into a conveying
"inert" (non­reacting) gas carrier stream which consists of the combustion
products exhausted from the dryer­burner. This stream is fed into the
pyrolysis reactor mixing zone where the wood and conveying gas are mixed with
the entraining hot, inert (non­reacting) combustion gases of a wood­fired
burner. The wood is rapidly transported upwardly through the vertical
pyrolysis reactor and is completely pyrolyzed before exiting the reactor. For
a 200 TPD plant the entrained flow reactor will consist of a cluster of five
vertical tubes. The stream leaving the pyrolyzer consists of newly­formed
char, pyrolysis gases, water vapor (water of reaction, feedstock­associated
water, and combustion product water), and conveying/entraining combustion
gases. The char is removed by cyclone separation and is cooled before being
discharged into a sealed conveyor, whence it is fed via a rotary airlock to
a char conveyor. The char is conveyed to a storage bin from which it may be
retrieved by gravity flow for subsequent shipment. The char bin incorporates
a pressure­relief system. The hot pyrolysis gas and vapor stream passes
through a multiple organic spray (pyrolysis oil) quencher system to condense
vapors. The pyrolysis oil is collected in a series of patented high­
efficiency, Georgia Tech proprietary rotary separators (3) as a relatively
narrow molecular­weight fraction. This oil consists of a total liquid product
in total yield of 70.6Z with moisture content of 15Z (60Z dry oil yield).
172

Wood Recycled go Recycled gas


ractmng
Recycled gas
«id storage

X Exhaust gai Gas to


co-sited
pstøår ^Juntar
users
Dried st n a M
ground
wood Grinding
and
itary 1©
Dried
ground
wood Pyrotyw
Char Oil
Exhaust

® ®
Oried
ground

Char Oil
storage storage

Dried
ground Dried
wood ground
wood

PRODUCT MASS AND ENERGY YELDS FOR A MIXED HARDWOOD FEEDSTOCK

DRYOLYELO TOTAL CHAR TOTAL OL (15%HO) TOTAL GASEOUS


Kg dry ol/ FUEL (DLUTED)
KgrraffMd ® ® ©
MASS ENERGY MASS BBK3Y MASS ENERGY
Ko/hr OVrr Ko/rr OVtir Kp/lr QJ/rr

0.6 1056 28.8 5837 111.4 15003 13.3

FIGURE 2 GT ENTRAINED FLOW PTROLYSIS SYSTEM; 200 dry TPD

N.B. The water is uniformly dispersed and bound in the pyrolysis oil fraction.
Maintenance of operating conditions above the dew point of water prevents
4

3. DESIGN BASIS
Mass and energy balances were calculated for a 200-dry TPD in support
of the economic analyses. The product mass and energy yields for a 200-dry
TPD plant, based on a mixed hardwood feedstock, is included in Figure 2.
173

The product yields and other design conditions for purposes of


performance of the economic analyses are given in Table I.

TABLE I DESIGN BASIS - GT ENTRAINED FLOW PYROLYSIS PLANT 200-dry TPD

Location Southeast USA

FEEDSTOCK - (MIXED HARDWOODS)


Average Moisture Content, Wet Basis 50Z
Ash Content, Moisture Free 0.77Z
Higher Heating Value, Moisture Free 19.5 MJ/kg

PRODUCT YIELDS
Pyrolytic Oil, Dry Wt/Wt Dry Wood 0.60
Char, Dry Wt/Wt Dry Wood 0.12
Pyrolysis Gas, Dry Wt/Wt Dry Wood 0.10
Water of Reaction, Wt/Wt Dry Wood 0.18

PRODUCT SPECIFICATIONS
Pyrolytic Oil
Specific Gravity 1.10
Higher Heating Value, Moisture Free 22.4 MJ/kg
Product Oil Moisture Content, Wet Basis 15Z

Char
Higher Heating Value, Moisture Free 29.0 MJ/kg

Pyrolysis Gas (Diluted)


Higher Heating Value, Dry Basis 0.9 MJ/kg
COOLING AND COMBUSTION AIR
Temperature 25°C
Relative Humidity 40Z
Pressure 1 bar

PYROLYSIS REACTOR CONDITIONS


Temperature 550°C
Pressure c.l bar
Throughput, kg/hr-m2 2200

4. ECONOMIC ANALYSIS
For purposes of the economic analysis, the entrained flow pyrolysis
system was divided into six sections according to the operations performed:
wood delivery, wood drying, size reduction and storage, entrained pyrolysis
in the reactor, char removal, handling and storage, and oil removal, handling
and storage.

4.1 Capital Costs


Both purchased and installed capital equipment costs were specified
(Table II) . A number of sources of information were used to arrive at capital
equipment costs. For some of the equipment the requirements were discussed
with manufacturers and vendors and direct quotes were obtained. The most
accurate information was used for critical items, that is, the ones which had
a major influence on the total cost. A rotary separator had been recently
specified and purchased, giving accuracy to that estimate. The installation
cost for each item was determined separately rather than by using a uniform
174

rate of the capital equipment cost to determine installation costs.


Installation costs were obtained by estimating material and labor requirements
directly for each capital item or by using estimated installation material and
labor for various classes and types of equipment. The major reference for the
economic analysis was the monograph of Peters and Timmerhaus (4).

TABLE II EQUIPMENT COSTS 200-dry TPD

Purchase Installed
Cost ($) Cost (S)
WOOD DELIVERY
Front-End Loader 100,000 100,000
Conveyor 10,000 11,700

DRYING
Metering Bin 1,650 2,250
Dryer (with Fan) 119,800 166,600
Dryer Particle Collector 9,700 13,500
Dry Wood Storage Bin 34,650 38,100
Dryer-Burner System 15,500 21,600

SIZE REDUCTION
Hammer Mill (with Screening) 141,650 198,300
Feed Storage Bin 105,900 116,500

PYROLYSIS
Pyrolysis Reactor System 41,400 55,700
Feeder system 22,000 27,500
Gas Blower 26,950 35,050

CHAR REMOVAL
Cyclone Separators 43,600 60,600
Storage Bin 71,100 78,200

OIL COLLECTION
Rotary Separators 30,500 42,450
Quench Spray System 12,000 16,650
Hold-Up Tank 19,000 22,850
Oil Storage Tank 73.600 91.250

TOTAL $ 879.000 SI.098.800

The total capital investment for the 250-day TPD plant (60Z dry oil
yield) is given in Table III. No land cost is estimated since (a) the
pyrolysis process is based on a rural location where purchase cost is minimal,
(b) land may be leased at modest cost, (c) land is provided, and/or (d) the
plant only occupies A,460 sq.m. (48,000 sq.ft.) on a 1.0 ha (2.5 acre) site
which accommodates a thirty-day supply of wood feedstock.
The total direct plant cost amounts to $1.35 million and the total
capital investment (TIC) amounts to $2.3 million for the 200-dry TPD pyrolysis
plant. The total purchased cost of equipment was $0.88 million and the
installed equipment cost, as noted in Table II, amounted to $1.1 million.
175

TABLE III TOTAL CAPITAL INVESTMENT 200-dry TPD

DIRECT COST
Installed Equipment Cost 1,, 0 9 8 , ,800
Building and Services (5Z of Total
Purchased Equipment Cost) 44, ,000
Yard Improvements (4Z of Total
Purchased Equipment Cost) 35, ,200
Service Facilities (14Z of Total
Purchased Equipment Cost) 1 2 3 , ,100
Land: 1.0 ha (2.5 acres) N.C.

TOTAL DIRECT PLANT COST 1,, 3 0 1 , ,100

INDIRECT COST
Engineering and Supervision (15Z of
Total Purchased Equipment Cost) 131,900
Construction Expense (10Z of Total
Direct Plant Cost) 130,100

TOTAL INDIRECT PLANT COST 262,000

TOTAL DIRECT AND INDIRECT PLANT COST 1.563.100

CONTRACTOR'S FEE (5Z of Total Direct Plant Cost) 65,100

CONTINGENCY (8Z of Total Direct and Indirect Cost) 125.000

FIXED CAPITAL INVESTMENT (FCH 1.753.200

WORKING CAPITAL (3 months total labor expenses +


2 months, all other operating expenses +
1 month feedstock supply) 389,200

START-UP COSTS (8Z of FCI) 140.300

TOTAL CAPITAL INVESTMENT (TCI) S2.282.700

4.2 Manufacturing (Product) Costs


The total manufacturing costs for a 200-dry TPD plant amounted to $3.25
million as described in Table IV. The operating labor cost is based on four
men per shift, three-shift operation, and a labor rate of $8.00/hr.

4.3 Sales Revenue


The total annual sales revenue for the products of 200-dry TPD (Table
V) wood pyrolysis plant includes sale of the pyrolytic oil, the char, and the
sale of product pyrolysis gas to a co-sited commercial or industrial user.
The oil-revenue was based on a selling price indexed on an energy-equivalence
basis to a barrel of crude oil at $21.00/barrel, i.e. $0.132 per liter
($0.50/U.S. gallon). This is clearly a conservative value for the pyrolysis
oil since petroleum heating fuel derivatives of crude oil, for which it will
substitute, will have a higher value than the crude oil itself. No. 2 fuel
oil was priced in the market at $0.93/U.S. gallon in 1981 (Wall St. Journal,
Oct. 12, 1981). Current inventories, based on earlier cheaper supplies of
crude oil, have a depressed current market price. At an expected mid-1990
176

TABLE IV TOTAL MANUFACTURING (PRODUCT) COSTS 60Z OIL YIELD

200 MT/d

RAW MATERIAL ($24.25/DT) 2,1*5,400

OPERATING LABOR 268,800

OPERATING SUPERVISION (15Z of Operating Labor) 40,300

UTILITIES 252,300

MAINTENANCE AND REPAIRS (4Z of Fixed Capital


Investment 70,100
OPERATING SUPPLIES (15Z of Maintenance and

Repairs 10,500

LABORATORY CHARGES (10Z of Operating Labor) 26,900

DIRECT PRODUCTION COST 2.814.300.

FIXED CHARGES (Depreciation, Taxes, Insurance,


Rent; 10Z of Total Product Cost) 325,300
PLANT OVERHEAD COSTS (30Z of Operating Labor,
Supervision, Clerical and Maintenance + Repairs) 113,800
TOTAL MANUFACTURING (PRODUCT) COST S3.253.400

TABLE V ANNUAL SALES REVENUE 60Z OIL YIELD 200-dry TPD

OIL PRODUCTION (15Z Moisture)


liters per annum 44.6 million
gals (US) per annum 11.8 million

CHAR PRODUCTION
Tonnes per annum 9,325
Tons (short) per annum 10,260

GAS PRODUCTION
GJ per annum 94,750
MMBTU per annum 89,800

OIL REVENUE $3,167,200

CHAR REVENUE 820,500

GAS REVENUE 449.000

TOTAL REVENUE S4.436.700


177

1990 stabilization price of $25.00 per barrel of crude oil, No. 2 fuel oil could
range from $0.63 ­ $0.75/U.S. gallon (i.e. $0,166 ­ $0.20 per liter). The
char revenue was based on a market price of $80/ton for briquette charcoal
(the sales price of the Tech­A ir charcoal in 1976­78). The gas revenue is
based on a value of $5.00/MMBTU ($4.74/GJ) which is significantly less than
liquid propane which it would displace ($9.25/MMBTU; $8.77/GJ). The total
projected sales revenue is expected to be $4.44 million per annum at current
market prices.

4.4 Profitability A nalyses


Three methods were used for the evaluation of profitability: (a) the
(engineering) rate of return (ROR) on investment expressed on an annual
percentage basis, (b) payout (payback) period, and (c) discounted cash flow
(DCF) rate of return (ROR) on investment for the book life of the plant (taken
as ten years, based on depreciation).

TABLE VI A NNUA L RATE OF RETURN ON INVESTMENT 200­dry TPD

Years 1­5 Years 6­10

SALES REVENUE $4,436,700 $4,436,700

MANUFACTURING COST 3,253,400 3,253,400

GROSS PROFIT 1,183,300 1,183,300

DEPRECIATION 374,300 4,400

TAXABLE INCOME 809,000 1,178,900

INCOME TAX
Case I Tax at 35Z 283,150 412,615
Case II No tax
NET ANNUAL PROFIT
Case I (A fter tax) $ 525,850 $ 766,285
Case II (No tax) $ 809,000 $1,178,900

Cash Flow* χ 100


Engineering Return on Investment = _ , . , „ ·_ιτ
° ,,. , ­. Total Capital Investment
v
(Years 1­5)
= 39.4 Ζ (A fter Tax)

= 51.8 Ζ (No Tax)

* Cash Flow ­ Net Annual Profit + Depreciation

The engineering rate of return on investment analysis is presented in


Table VI. Both a "before income tax" and an "after income tax" case were
used.
178

The before­tax case could arise in subsidized situations. The after tax case
assumed a net income tax rate of 35Z. The plants were depreciated over ten
years with an accelerated rate applicable in years 1­5 per U.S. Internal
Revenue Service directives. The law provides for depreciation of plant
equipment over a five­year period and, for buildings and services, over a ten
year period. The results for both cases demonstrate excellent rates of return
on investment: 39.42 (after tax), 51.8Z (without tax). The respective net
annual profits were $526,000 and $809,000.
The payout period analysis and the discounted cash flow­rate of return
analysis (DCF­ROR) are summarized in Table VII. Both "before tax" and "after
tax" cases were used as cited above.
The results of payout period analysis indicate that the capital
investment can be "paid back" in 1.6 years in the case of no income taxes, and
in only 2.1 years for the "after tax" case. The payout period corresponds to
the minimum length of time necessary to recover the original capital
investment in the form of cash flow to the project based on total income, less
all costs excepting depreciation.

TABLE VII PAYOUT PERIOD AND DISCOUNTED CASH FLOW­RATE OF RETURN ON


INVESTMENT 200­dry TPD

PAYOUT PERIOD DCF­ROR

Case I (Tax at 352) 2.1 years 30.32

Case II (No tax) 1.6 years A


A .9Z

„ .. r> · j ,v, · ,. ^ u > Depreciable FCI


Payout Period (No interest charge) = —ττ* r : :—
Avg. Profit A vg. Depreciation
per year per year
DCF­ROR ­ i, where i is calculated from

___ _ A nnual Cash Flow to Γ 1 1 . . . 1 "I


Project After Taxes [_1+ί d+i)2 d+i) 5 J

Γ Working Salvage"] Γ 1
1 5
^Capital Value J [d+
" i) J

5. SUMM
A RY
The Georgia Tech Entrained Pyrolysis Process is a technically­proven and
cost­effective method for the production of liquid biofuels and related
bioenergy products. Based on a detailed economic study for a 200­dry TPD wood
pyrolysis manufacturing process the Georgia Tech process should be scaled­up
to a commercial prototype scale and be actively commercialized. A summary of
the results of the economic analysis is given in Table VIII.
179

TABLE VIII SUMMARY OF ECONOMIC ANALYSIS 200-dry TPD Plant 60Z Oil Yield

TOTAL CAPITAL INVESTMENT $2.2 million

MANUFACTURING (PRODUCT) COST (ANNUAL) $3.25 million

SALES REVENUE (ANNUAL) $4.44 million

AVERAGE ANNUAL RATE OF RETURN 39.4Z (51.8Z)*

PAYOUT PERIOD 2.1 (1.6)* years

DISCOUNTED CASH FLOW RATE OF RETURN 30.3Z (44.9Z)*

MANUFACTURING COST, PER GJ $2.56

FIXED CAPITAL INVESTMENT, PER GJ $1.38

* Before (or no) tax case.

ACKNOWLEDGEMENT

This work was supported by the U.S. Department of Energy through the
Biomass Thermochemical Conversion Program, managed by the Battelle-Pacific
Northwest Laboratories, under subcontract B-C5863-A-Q.

REFERENCES

(1) BOWEN, M.D. et al. (1978). A Vertical-Bed Pyrolysis System. Chapter 6


in Solid Wastes and Residues: Conversion by Advance Thermal Processes
(ed. Jones, J.L. and Radding, S.B.), ACS Symposium 76, Americom Chemical
Society, Washington, D.C.
(2) O'NEIL, D.J., KOVAC, R.J. and GORTON, C.W. (13-17 February 1989). Liquid
Biofuels Production by an Entrained Flow Pyrolysis Process. Paper
presented at Energy from Biomass and Wastes XIII. New Orleans, Institute
of Gas Technology.
(3) ELSTON, W.E., KOVAC, R.J. and O'NEIL, D.J. (7-9 October 1986).
Proceedings of the Fourth Southern Biomass Energy Research Conference.
University of Georgia, Athens, Georgia.
(4) PETERS, M.S. and TIMMERHAUS, K.D. (1980). Plant Design and Economics
for Chemical Engineers. Third Edition. McGraw-Hill Book Co., New York.
180

PILOT PLANT DEMONSTRATION OF USED TIRES VACUUM PYROLYSIS

CHRISTIAN ROY
Université Laval, Dept. of Chemical E n g i n e e r i n g , Ste-Foy, Québec, GIK 7P4
and
JOHN UNSWORTH
P e t r o - T i r e Inc., Hamilton, Ontario, L8P 1X1

Summary

Tire r e c y c l i n g has become a n e c e s s i t y b e c a u s e of t h e h u g e piles of t i r e s


which r e p r e s e n t a t h r e a t to t h e environment. By and l a r g e , t h e r e is
a b o u t one worn t i r e p r o d u c e d p e r y e a r and p e r p e r s o n in t h e developed
c o u n t r i e s . However t h e used t i r e s r e p r e s e n t a s o u r c e of e n e r g y and
valuable chemical p r o d u c t e . By vacuum thermal decomposition of r u b b e r ,
it is possible to r e c o v e r t h e initial compounds which c o n s t i t u t e a t i r e .
We have used a s t e p - t o - s t e p a p p r o a c h , from bench scale batch s y s t e m s ,
to p r o c e s s development u n i t and finally pilot plant u n i t to experiment
and develop vacuum p y r o l y s i s of used t i r e s . Vacuum p y r o l y s i s of r u b b e r
yielded 55% oil, 25% c a r b o n black, 9% eteel, 5% fiber and 6% g a s . The
maximum r e c o v e r y of oil was performed at 415* C below 2 kPa (abe.
p r e s s u r e ) . The specific g r a v i t y of t h i s oil was 17.8"API and i t s g r o s s
heating value was 43 000 J / g with a total sulfur content of about 0.8%.
It was rich in benzol and o t h e r petrochemical components. The carbon
black favorably compared with the s t a n d a r d g r a d e s and will p r o b a b l y find
s e v e r a l applications as a semi-reinforcement or reinforcement c a r b o n in
r u b b e r p a r t s . I t s main limitation comes from t h e high level of impurities
(ash) it contains. The heat of p y r o l y s i s for the reactions is low and has
been estimated to be a r o u n d 706 k J / k g . The p r o c e s s has been t e s t e d in
a 200 k g / h pilot plant which positively demonstrated the possibility to
continuously feed u n d e r a vacuo l a r g e c h u n k s of r u b b e r . Work is p r o -
g r e s s i n g to optimize t h e r a t e of heat t r a n s f e r in t h e pilot plant r e a c t o r .
The p r o c e s s feasibility looks promising, with r e t u r n s on t h e investment
of a b o u t 50% after t h r e e y e a r s of operation.

1. INTRODUCTION
Tire recycling h a s become a n e c e s s i t y b e c a u s e of t h e h u g e piles of t i r e s
which r e p r e s e n t a significant environmental r i s k . Each y e a r 24 million t i r e s
(220 kt) a r e disposed of in Canada and a b o u t 250 millions (2.3 Mt) in the
U.S. Table I r e p r e s e n t s c o n s e r v a t i v e estimates of used t i r e s for t h e EEC
and o t h e r c o u n t r i e s . While some of t h e s e t i r e s a r e recapped or g r o u n d u p
for special u s e s , most a r e simply dumped in r u r a l farm land or in landfill
s i g h t s . When buried in landfills t h e y eventually float to the surface, and if
piled t h e non biodegradable r u b b e r will cause serious harm if ignited by
l i g h t n i n g or v a n d a l s .
However, t h e t i r e s r e p r e s e n t a source of e n e r g y and raw chemicals for
t h e production of r u b b e r p a r t s . By thermal decomposition of r u b b e r , it is
possible to r e c o v e r to a c e r t a i n extent the initial i n g r e d i e n t s which c o n s -
t i t u t e a t i r e . T h e r e have been numerous a t t e m p t s to i n t r o d u c e economically
viable t e c h n i q u e s of t i r e p y r o l y s i s . It is beyond the scope of this p a p e r to
d e s c r i b e the v a r i o u s tire p y r o l y s i s v e n t u r e s worldwide and the many
181

a d a p t a t i o n s of t h e technology. A detailed review was published in 1983 b y


Dodds e t al (3) for t h e US Department of E n e r g y . To o u r knowledge t h e r e
a r e only a few s c r a p tire commercial p y r o l y s i s p l a n t s in t h e world, which
mainly o p e r a t e in J a p a n a s indicated in Table II.

Table I . T o t a l A r i s i n g s of Used T i r e s i n D i f f e r e n t C o u n t r i e s
Country Tonnage/Year Reference

EEC 1 500 000 (1)


USA 2 300 000 (2)
JAPAN 579 000 (1)
CANADA 220 000 (2)

Table II. Existing Commercial Scrap Tire Pyrolysis Plants


Process or Company Capacity Location Start-up Date

Hyben Recycler Batch Britain, Japan 1977

Kobe Steel 1 t/h Aioi, Japan 1978

Onaharaa Smelting 4 t/h Iwaki, Japan 1981


and Refining
Kleenair 1 t/h Centrali a, Wash. 1986 (discontinued?)

Of all t h e s e p l a n t s , t h r e e o p e r a t e on a c o n t i n u o u s feed mode and one is


batch. Typical yields from the Kobe plant a r e 31% oil, 29% c a r b o n black,
14.5% gas and 10% steel. The oil is sold to a cement kiln company. The
p r o d u c t s do not overall a p p e a r to have met earlier expectations. The e c o n o -
mics of the plant was r e p o r t e d to be only marginal (1).
The Kleenair p r o c e s s was developed by Conrad I n d u s t r i e s back in 1986
for the recycling of used r u b b e r in g a s , oil and c a r b o n black. The plant
capacity was 1000 k g / h , similar to t h e Kobe plant. In both c a s e s , t h e
feedstock consisted of s h r e d d e d t i r e s . C u r r e n t l y the plant operation has
ceased.
The distinct feature of t h e Onahama plant is t h a t whole t i r e s a r e used
as feedstock to the r e a c t o r . The major saleable p r o d u c t s a r e a heating oil
(25-30%), c a r b o n black (35-40%) and steel (10%). The carbon black is used in
the adjacent copper smelting plant (4). The economics of t h e p r o c e s s is
good, although it has been r e p o r t e d to be less profitable t h a n b u r n i n g t h e
t i r e s at the plant site.
Here a r e some of t h e conclusions we have reached after visiting t h e s e
plants:
• The most successful recycling p r o c e s s e s a r e those which use whole
t i r e s a s feedstock. S h r e d d i n g t i r e s is expensive. It also r e s u l t s in materials
which a r e difficult to handle inside the r e a c t o r , eventually giving rise to the
so-called "ballmilling" problem.
• The quality of the carbon black p r o d u c t g r e a t l y determines its e n d - u s e
and as a consequence, i t s value on the market.
• The plant operation should be s u p p o r t e d by a h i g h - q u a l i t y control lab
which should be o p e r a t e d by low-level technicians. In addition, t h e company
should maintain a s t r o n g R and D activity for p r o d u c t improvement and
discovery of new m a r k e t s . None of t h e p l a n t s t h a n we visited afforded such
182

technical s u p p o r t .
• The p r o c e s s is cost sensitive to the s u p p l y of r u b b e r feedstock. The
p r o c e s s will be more profitable if t h e r e is a tipping fee or management cost
a t t a c h e d to the reception of a t i r e .
• Attempts should be made to replicate t h e p l a n t s elsewhere n e a r l a r g e
piles t h r o u g h licensed or franchise a g r e e m e n t s , in o r d e r to s h a r e t h e risk
and optimize t h e i n v e s t m e n t . Marketing of the p y r o l y s i s technology is
r e q u i r e d , s t r e s s i n g t h e a d v a n t a g e s of t h e p r o c e s s in terms of t h e e n v i r o n ­
mental r e g u l a t i o n s . The p y r o l y s i s r o u t e has been low­profile compared to
the o t h e r thermochemical t e c h n i q u e s so far, and it is a b o u t time t h a t a more
a g r e s s i v e marketing a p p r o a c h be launched in o r d e r to b r i n g to light the
d i s t i n c t a d v a n t a g e s of t h e p r o c e s s from an environmental point of view.
Our p u r p o s e is to meet a s many of t h e s e goals u s i n g t h e vacuum p y r o ­
lysis concept. This p a p e r will explain how t h i s can be done.

2. VACUUM PYROLYSIS PROCESS


Vacuum p y r o l y s i s is an old concept. It e n a b l e s t h e production of l a r g e
q u a n t i t i e s of p y r o l y s i s oils from an o r g a n i c s u b s t a n c e . When a vacuum pump
is a t t a c h e d to t h e p y r o l y s i s r e a c t o r , t h e g a s and v a p o r molecules a r e
immediately removed from t h e reaction chamber. This minimizes t h e e x t e n t
of s e c o n d a r y r e a c t i o n s s u c h a s thermal c r a c k i n g , repolymerization and r e c o n ­
densation r e a c t i o n s , g a s p h a s e collision, catalytic c r a c k i n g and r e d u c t i o n and
oxidation r e a c t i o n s . If t h e v a p o r p h a s e p r o d u c t s a r e p r o p e r l y q u e n c h e d , the
yield of o r g a n i c liquids s u c h as p y r o l y s i s oils is dramatically i n c r e a s e d a t t h e
expense of solid r e s i d u e s and g a s e s . B esides, t h e physicochemical p r o p e r t i e s
of t h e end p r o d u c t s a r e specific. For i n s t a n c e , t h e c a r b o n black p r o d u c e d
u n d e r a vacuo is more easily d i s p e r s e d t h a n t h e atmospheric p r e s s u r e p y r o l y ­
sis black which is a n important c h a r a c t e r i s t i c in reinforcing r u b b e r p a r t e .

3. B ACKGROUND DATA
L a b o r a t o r y t e s t s were performed in a bench scale r e a c t o r to s t u d y t h e
influence of t e m p e r a t u r e a n d p a r t i c l e size d u r i n g p y r o l y s i s . For t h e s e t e s t s
approximately 1 k g of feedstock was p o u r e d into t h e r e a c t o r v e s s e l . P r e s ­
s u r e was maintained below 3 kPa d u r i n g t h e whole r u n . Experiment was
stopped when the final d e s i r e d r u b b e r bed t e m p e r a t u r e was r e a c h e d . A
detailed d e s c r i p t i o n of t h e a p p a r a t u s and p r o c e d u r e u s e d will be found
elsewhere (5). Regular t i r e s with no steel belt were u s e d for t h i s s e r i e s of
r u n s . The t i r e s had been p r e v i o u s l y s h r e d d e d to 1/4" ­ 1/2" Tyler sieves
(6.35­12.70 mm). The chemical composition of t h e r u b b e r feedstock is given
in Table III.

Table III. Chemical composition of the used tires

Elemental Composition Proximate Analysis Gross Calorific Value

81.5% C 65.2% Volatile matter 36800 J/g


7.1% H 28.7% Fixed C
3.4% O 6.1% Ash
0.5% Ν (Moisture 0.5%)
1.4% S
(6.1% ash)

The yield of oil, c a r b o n black, p y r o l y t i c water and g a s p r o d u c e d d u r i n g


p y r o l y s i s a t v a r y i n g final t e m p e r a t u r e s a r e summarized in Table IV of t h e
183

paper. The temperature shown is that of the bed of shredded tires. The
maximum oil yield was reached at a plateau temperature of about 415*C as
appearing in Table IV. At 415"C the yield of oils was 56.6%.

Table IV. Effect of temperature on product y i e l d during vacuum p y r o l y s i s


of used t i r e s (wt. %, t i r e a s - r e c e i v e d b a s i s ) .

Temperature C C ) Oil (%) Carbon black Gas (%) Water (%)


and
fibers (X)

250 7.2 91.1 Traces 1.7


310 17.7 79.4 0.3 2.6
335 27.2 68.8 1.7 2.3
363 48.3 45.6 2.9 3.2
415 56.6 36.6 2.2 4.6
500 56.2 35.5 4.3 4.0

The gas phase was mainly composed of Ha, CO, COj and a few HCs. At
415'C, the gas has a g r o s s calorific value of 36800 J g - 1 with an average
molecular weight of 28.3. No H2S could be detected in the gas phase. If
any, its concentration must be low since a partial mass balance on the sulfur
gave 70.4% for the solid residue while 27.4% of the initial S found its way in
the oil, leaving 2.2% for l o s s e s and gases.
Two runs were also conducted at identical temperature (420 ± 5'C), one
with pieces of rubber sieved between 6.35 and 12.70 mm, and the other run
with larger chunks of old rubber of 150 to 400 mm. According to Table V
there was no significant difference between the two runs on the product
yields:

Table V. Influence of size in product yields during vacuum pyrolysis of


used tires at 420'C (wt. %, rubber as-received basis)

Size (mm) Oil (%) Solid residue (%) Gas (%) Water (%)

6.4 - 12.7 56.6 36.6 2.2 4.6


150 - 400 58.4 34.8 2.1 4.7

Similarly vacuum pyrolysis at 450'C of a steel belt (17.6% fiber + steel)


tire sample gave 59.0% oil, 33.8% carbon black, 5.2% gas and 2.0% water on
an organic rubber basis which was in line with the results shown in Table V.

4. PROCESS DEVELOPMENT UNIT STUDY


These preliminary results were further investigated using a vacuum
pyrolysie Process Development Unit. The system operated on a semi-con-
tinuous feed mode using shredded (regular) used tire material sieved to 6.4-
12.7 mm mesh size. The reactor was a six hearth furnace, 2 m in height
and 0.7 m in diameter. It was externally heated by electric elements s u r -
rounding the reactor chamber. The maximum throughput reached with this
unit during this study was 13 k g / h . A schematic of the P.D.U. is shown in
Figure 1 below and a detailed description of this unit will be found e l s e -
where (5).
At a maximum flowrate and reactor temperature of 513 *C, the oil yield
184

was 54%, 37.8% carbon black and fiber, 4.2% gas and 4.0% water. These
results were in straight correlation with the previous bench scale data.
An important engineering parameter to be considered when designing a
full scale pyrolysis plant is the quantity of energy required for the pyrolysis
reactions. This value has been empirically determined using the P.D.U.
described in this paper, and the detailed procedure has been published else-
where (5).
Figure 1. Schematic of the Vacuum Pyrolysis Process Development

Scrubber 1 Scrubber 2

Chen-
tank Flore
leter I lv Filters
Ice P1™?
trap

The quantity of heat required to decompose rubber ( Hr) will depend on


the operating conditions used and the extent of reaction which has been
reached. Under normal carbonization conditions, the reactions are exother-
mic. Under vacuum, the reactions were found to be slightly endothermal,
reaching 706 kJ/kg. We concluded that the secondary reactions (e.g.,
thermal and catalytic cracking, repolymerisation, recondensation, oxidation
and reduction reactions) which occurred under higher pressure conditions,
released heat and hence contributed to the overall exothermicity.

5. PILOT PLANT STUDY


The experimental system was a further scale up to the pilot plant stage.
The new system was designed to continuously decompose 200 kg/h of steel
belt tires below a pressure of 1.3 kPa. Large chunks of rubber were con-
tinuously fed across a column of water which connected a tank on the
ground and the top of a horizontal reactor which was elevated 14 m in the
air (see Photograph I). The reactor was externally fired with gas and a
small portion of the pyrolysis oil. The vapors were sucked at the outlets of
the reactor and immediately quenched by two scrubbers set in series. The
carbon black was recovered at the bottom of another water head which
connected the bottom of the reactor and the ground. A sharp separation of
the fiber, steel and carbon black was made in the water phase. The process
schematic is illustrated in Figure 2 of the paper.
The objective of the pilot plant phase study was to demonstrate the
feasibility of the vacuum pyrolysis process using semi-industrial scale equip-
ment under continuous operation during several hours. The reactor con-
figuration and the reliability of the downstream equipment including the
scrubbers, gas cleaning system and pumps were tested. The results obtained
so far with this unit are the followings:
• Continous feeding of tires under a vacuo was practicable.
• Separation of steel, fiber and carbon black at the reactor outlet is
feasible.
185

• The equipment designed for the condensation and r e c o v e r y of the


p y r o l y s i s oils well performed.
• The overall thermal efficiency of t h e p r o c e s s is high, exceeding 80%.
• The optimum t e m p e r a t u r e and p r e s s u r e conditions to p r o d u c e large
yields of oils have been found.
• The t h r e e major p r o d u c t s , oil, c a r b o n black and steel, a r e saleable and
marketable.
• No major problem is expected with the quality of the g a s e o u s emis­
sions.

Photograph I: Vacuum P y r o l y s i s Pilot Plant in Saint­Amable, Quebec

Figure 2. Schematic of the Saint­Amable Pilot Plant


12
~1 l.Feed conveyor
ψ 2.Vacuum r e a c t o r
Heat for
3.Cooling screw
reactor
8 f 4.Discharge screw
1 5.Crusher
6.Vibratory s c r e e n
7.Magnetic s e p a r a t o r
8.Heavy oil q u e n c h e r
9.Light oil q u e n c h e r
10. Decan ter
11.Vacuum pump
12.Flare stack
13.Carbon black
handling system
14.Steel r e c o v e r y bin
D L »^^ "■» a.
15.Heavy oil s t o r a g e
16.Light oil s t o r a g e
Ώ %
The main limitation with this system was t h e low r a t e of heat t r a n s ­
f e r r e d to the r e a c t o r for each s q u a r e meter of surface a r e a . Actually the
r e a c t o r o p e r a t e d at less t h a n half of its t h r o u g h p u t capacity, due to ineffi­
186

cient heat exchange in the reactor chamber. Another improvement on which


we are working at the present time is a better system for handling the
rubber-material inside the reactor, using large rubber chunks as feedstock.
The pilot plant unit was built and tested during fall 1987 in Saint-
Amable near Montreal. Unfortunately the project was momentarily stopped
during early 1988 because of the bankruptcy of the licensed company (Petrc—
Sun Intern. Inc.) due to facts unrelated to this project. With the financial
support of both Université Laval and Energy, Mines and Resources Canada
(Bioenergy Development Program), the project wae continued at the P.D.U.
level during 1988 up to now. The pilot plant phase will be continued during
the second half of 1989 under the auspices of the new licensed company,
Petro-Tire Inc., Hamilton, Ontario.

6. OIL AND CARBON BLACK ANALYSIS


The two main products obtained from the pyrolyeis of tires are carbon
black and oil. Samples of each of these products obtained in the pilot plant
unit were tested in our laboratory and by different customers. Some of the
analytical results are reported in this paper.
The oil has a g r o s s heating value of about 43000 J g"1. It has a
specific gravity of 0.95 (17.8'API) with a pour point of - 6 ' C . Its initial
boiling point is 112'C with a 50% cut at 376"C (simulated distillation). The
residual metal content is < 0.1% for Va, 0.1% for Ni and 0.6% for Na. A
typical elemental analysis for thie oil gave 87.3% C, 10.5% H, 0.8% S, 1.2% 0
and 0.2% N. It yielded upon distillation 8% (by vol.) of heavy naphtha, 16%
kerosene, 24% light gas oil, 35% cat. feed and 17% bunker. The PONA
analysis of the fraction boiling below 204'C which constituted 26.8% of the
crude oils gave 24.9% paraffins, 43.3% olefins, 6.6% naphthenes and 25.4%
aromatics.
This oil can be used as a heating oil and would be classified as a
number 4 ASTM bunker oil. It can alternatively be refined as a crude oil by
the petroleum industry and it has also several other potential applications
which are under development in our laboratories. As an example, Table VI
constitutes a partial list of the major compounds which have been detected
in vacuum pyrolysis oils. There is no doubt that some of these compounds
have a potential value as petrochemical feedstock.

Table VT. Examples of compounds found in vacuum pyrolysis oils


Compound Yield
(wt. %, as-received rubber basis)

Limonene-ld 2.26
Toluene 1.05
Xylene (o-,m-,p-) 0.93
Styrene 0.82
Benzene 0.38
Dimethylcyclopentadiene 0.24
Methylpentene 0.23
Dimethylpentane 0.16
Cyclopentanone 0.15

Table VII summarizes some of the main characteristics of the carbon


black produced at 550° C and 1.3 kPa. Pyrolysis carbon black was compared
187

with two reinforcement commercial blacks, N­234 and N­330, which price on
the market varied between 960 and 1040 Can $. As indicated in Table VII,
carbon derived from vacuum pyrolysis of used tires has an iodine number
greater than the standard blacks. The main disadvantage of the recycled
carbon is its high inorganic content (ash). Work is progressing in our
laboratory to purify the material in order to increase its potential value on
the market. It has numerous usages including reinforcement or semi­rein­
forcement for bicycle tires, shoes, auto flaps, footwear, conveyor belts, dock
fenders. The carbon black acts primarily to strengthen and increase the
impact on abrasion resistance of rubber. Other uses also include pigments
for ink and reduction for ore refining.

Table VII. Physicochemical properties of used tire­derived carbon black


compared with standard blacks

Physicochemical N­234 N­330 Obtained after pyrolysis


properties at 550 'C and 1.3 kPa

Iodine index (rag/g) 112.7 80.5 144.5


pH 4.2 7.3 7.9
Volatile material {%) 4.2 3.3 4.4
Ash (%) 0.6 0.3 14.5
Composition (%)
C 94.8 96.0 79.2
H 0.84 0.66 0.76
Ν 0.77 0.60 0.71
0 2.98 1.98 2.10
S 0.68 0.74 2.80

7. PROCESS FEASIBILITY
Based on the background and engineering data reported in this work, a
preliminary feasibility study of the process was performed. The assumptions
used are summarized in Table VIII below.
Table VIII. Assumptions used for the process f e a s i b i l i t y study
Product Yield Price
Oil 55% Regular grade: 18.0 $/bbl
Improved grade: 19.4 $/bbl
Carbon black 25% Regular grade: 100 $/t
Improved grade: 485 $/t
Steel 9% 90 $/t
Fiber/Kevlar 5% 2 $/t
Gas 6% Used for make­up heat

Prices are in Can. $. All metric u n i t s .


188

Other assumptions
Tipping fee/Lean-up fee 1 $/tire
Tires per ton 110
Rate of inflation 5%/year
No credit given for re-usables or re-caps

Table IX shows that the profitability of a 3 tons per hour or 20 000


tons/year plant with a capital investment of 7 M $ ie attractive if a tipping
fee can be collected for the recycling of tires.
Table EC. P r o f i t a b i l i t y of a 20 000 t / y plant for vacuum pyrolysis of used
tires
Sales/Revenues
Year 1 Year 2 Year 3
Oil, regular 733 000 1 538 000
improved 1 615 000
Carbon black, regular 250 000 525 000
improved 2 425 000
Steel 81 000 170 000 179 000
Fiber 1 000 2 000 2 000
Tipping fees/Clean-up 1 100 000 2 200 000 2 200 000
Re-usables NIL NIL NIL
Re-caps NIL NIL NIL
Total Sales/Revenues 2 165 000 4 436 000 6 421 000
Cost of sales 479 000 1 160 000 1 329 000
Gross margin 1 686 000 3 276 000 5 092 000
Adm. and Comm. Expenses 136 000 192 000 244 000
Depreciation 675 000 675 000 675 000
Financial Expenses 675 000 675 000 675 000
Taxes NIL NIL NIL
Profits (loss) of the year 200 000 1 734 000 3 498 000
Undivided profits (deficit) at
the commencement NIL 200 000 1 934 000
Undivided profits (deficit) at
the end 200 000 1 934 000 5 432 000

8. CONCLUSIONS
A process for the recycling of used tires has been developed from bench
scale, to process development and pilot plant units. The project which is
still under development at Université Laval under contract with Petro-Tire
Inc. has great potential. There is a market for the oil, the carbon black
189

and steel which c o n s t i t u t e t h e t h r e e main p y r o l y s i s p r o d u c t s . The p r o c e s s


feasibility would justify t h e c o n s t r u c t i o n of a l a r g e demonstration p l a n t (10
000 t / y ) which we foresee in t h e n e a r f u t u r e . This p r o c e s s would simulta-
neously r e p r e s e n t an e l e g a n t solution for t h e disposal of the tire piles.

REFERENCES
(1) Dufton, P.W. The Value a n d Use of S c r a p T y r e s . Rapra Technology
Ltd. England. Report dated 26 November 1987.

(2) The Rubber Association of Canada, Mississauga, Ont. 1989.

(3) Dodds, J., W.F. Domenico and D.R. Evans. S c r a p Tires: A Resource and
Technology Evaluation of Tire P y r o l y s i s a n d Other Selected Alternate
Technologies. N.T.I.S. Report # EGG-2241. P r e s e n t e d to t h e U.S. Dept.
of E n e r g y . November 1983.

(4) Kono, H. Onahama Smelting and Refining Co., Ltd. Iwaki City,
Fukushima. P r i v a t e communication. (1987).

(5) Labrecque, B. Etude du t r a n s f e r t de chaleur p a r radiation thermique


d a n s u n r é a c t e u r de p y r o l y s e sous vide des v i e u s p n e u m a t i q u e s . M.Sc.A.
Thesis. Université de S h e r b r o o k e , S h e r b r o o k e , Qué. 1987. (In F r e n c h ) .

ACKNOWLEDGMENT
This work has been s u p p o r t e d by the National Research Council of
Canada, the Natural Science and E n g i n e e r i n g Research Council of Canada,
E n e r g y , Mines and Resources Canada, Energie et Ressources Québec, U n i v e r -
sité Laval and P e t r o - T i r e Inc.
190

FLUIDIZED BED PYROLYSIS OF SEWAGE SLUDGE


U. BELLMANN, A.B. KUMMER, Y. YING, and W. KAMINSKY
Institute for Technical and Macromolecular Chemistry
University of Hamburg, FRG

Summary
Digested, thermally conditioned and dried sewage sludge
has been pyrolyzed in an indirectly heated fluidized bed
reactor at temperatures ranging from 620°C to 750°C. A
quantity of up to 40 kg of sewage sludge per hour has
been converted into pyrolysis gas, oil, product water and
carbonaceous residues in a continuously working pilot
plant. The pyrolysis gas has a calorific value of approx-
imately 23 MJ/m3. The main constituents of the pyrolysis
gas are hydrogen, methane, ethane, ethene and propene as
well as carbon monoxide and carbon dioxide. The oil frac-
tion yielded contains up to 30% aromatic compounds. The
heavy metals from the sewage sludge become to a large ex-
tent enriched into the solid residue on account of the
reducing conditions of the pyrolysis process.

1. INTRODUCTION
More elaborate and refined purification methods in the
treatment of communal and industrial crude waste water are
leading to a continuous increase of the amount of sewage sludge
to be produced. The expected annual amount of sludge is esti-
mated to rise up to 320-430 mio m 3 in the EC in 1990 (1). At
present, the whereabouts of sewage sludge is distributed as
follows (2):

- agriculture + decompostion 32%


- sanitary landfill 59%
- incineration 9%.
The utilization of sewage sludge as fertilizer seems to be re-
stricted because of the harmful components in the sewage
sludge, such a heavy metals, polyaromatic hydrocarbons (PAH)
and the polychlorinated biphenyls (PCB).
There are certain requirements to be met prior to the de-
position of sewage sludge in landfills with the intention of
avoiding any kind of emission. In addition, neither the biolo-
gical potential nor the chemical energy content are sufficient-
ly exploited. In future, deposition of sewage sludge will be
made more difficult resulting from a decreasing deposition ca-
191

pacity on the one hand and increasing cost of deposition on the


other hand.
Thermal conversion processes such as combustion or pyro-
lysis, offer alternative waste disposal concepts. The combus-
tion process yields a considerable amount of sulphur and ni-
trogen compounds. Expensive precautions as regards flue gas
purification have to be taken for the purpose of running com-
bustion plants on an environmentally tolerable scale. In addi-
tion to that, problems arising from the increased elution ca-
pability of heavy metals out of the ashes from the oxidizing
treatment have to be solved.
The pyrolysis of sewage sludge according to the HAMBURG
PROCESS (3) seems to be advantageous as to the minimization of
emission due to a closed gas cycle in connection with an indi-
rectly heated fluidized bed and the reduced volume of the de-
pyrolyzed sewage sludge.
2. PYROLYSIS RESULTS
Figure 1 shows the flow scheme of the fluidized bed pilot
plant by means of which the pyrolysis of sewage sludge has been
investigated.
Core of the plant is an indirectly heated fluidized bed,
450 mm in diameter. Right at the start of the pyrolysis, the
fluidization material consists of quartz sand with particle
sizes between 0.3 and 0.7 mm. In the course of the run the sand
is gradually replaced by depyrolized sewage sludge. In order to
ensure a constant height of the fluidized bed of approximately
650 mm during continuous input of sewage sludge an overflow
vessel has been attached to the reactor.
Next to the reactor, a cyclone separates carbon and solid
particles from the product gases. The cyclone is followed by
three quench coolers where the pyrolysis oils are subsequently
quenched. At the end of the third cooler the temperature goes
down to 0-5°C. During the last condensation stage the product
gas is freed from aerosols and entrained droplets in an
electrostatic precipitator.
The gas is then conveyed into five membrane compressors,
connected in parallel, and stored in three gas tanks. One por-
tion of the gas is used to fluidize the sand bed, whereas the
rest of the gas may be used as fuel for the radiation heating
tubes, thus allowing an autothermal operating mode of the
plant.
As feed stock for the pyrolysis experiments all kinds of
digested or thermal conditioned and dried sewage sludge from
different communitities or industries could be used (4). The
water content of the sludge has to be 5-10 weight percent.
The pyrolysis experiments were carried out at temperatures
of 620°C, 690°C and 750°C. The sewage sludge was acontinuously
and directly fed into the reactor from a silo via two crew con-
veyors. The conveying capacity was 25-40 kg/h and the whole
charge of converted sludge amounted to more than 360 kg.
The product fractions obtained consisted of gas, pyrolysis
oil, product water, soot and pyrolysis residue. This solid re-
sidue contained the formed pyrolysis coke together with the an-
organic fraction of the sludge.
Fig. 1. Flow Scheme of the Fluidized Bed Pilot Plant for Sewage Sludge

d e s t i l l i n g columns
cryostat —■

~=H,0
cyclone 1 uench c
°°l<=r quench cooler electrostatic :H,O
quench cooler precipitator
silo η
■tí 3,
lock Π Η,Ο
Θ
steam «­_,,_. steam
ϊΗ,Οΐ
=1 I
ν o i l Ί.,­ΐ, j . η — ­,

r-ςπ
l^' Kigh­
bollinj Xylene Toluene Benzene
fraction fractlor fraction fraction

compressed a i r ¡

πι
overflow vessel
tìafitì
propane
gasooeter compressor
pjrolysis gas/l

Γ heat exchanger

flare
n


193

Table 1 shows the composition of the organic pyrolysis


products obtained at three different reaction temperatures.

Table I Product Fractions of the Pyrolysis of Digested Sewage


sludge (% by Mass of Organic Dry Matter

Temperature ("CI 620 690 750


Sludge mass Çkq) 361.2 126.6. 118.7
Organic dry matter (kg) 185.5 62.9 60.0
Product fraction (m%)
Pyrolysis gas 22.7 30.7 40.8
Oil 40.1 34.3 21.1
Product water 12.6 10.8 8.0
Soot 3.7 3.1 4.9
Pyrolysis coke 20.0 19.2 22.3
Loss 0.9 1.9 2.9
100 100 100

The main contents of the pyrolysis gas are carbon mon-


oxide, carbon dioxide, hydrogen as well as C1-C4 hydrocarbons.
Small amounts of carbonoxysulfide and hydrogensulfide are
likely to be found. The calorific value of the pyrolysis gas
amounts to 23 MJ/m·*, that means up to about 70% of the calor-
ific value of natural gas.
The gaseous portion of the pyrolysis products increases
with rising temperature from 620°C to 750°C from 22.7% to
40.8%.
The pyrolysis oil contains hydrocarbons and, in addition
to that, some amounts of nitriles, phenols and heterocyclic
compounds. With rising reaction temperature the oil yield de-
creases from 40.1% at 620°C to 21.1% at 750°C. The major por-
tion of the pyrolysis oils is still tar after all, especially
at low temperature down to 620°C amounting to 75.5%. This tar
consists of substances which cannot be separated by destilla-
tion. The increase of pyrolysis temperature leads to a rising
percentage of aromatic components due to progressing defunct-
ionalization.
Investigations of the pyrolysis residues, composed of the
anorganic residue and the pyrolysis coke, show that the heavy
metals originated from the sewage sludge are enriched in this
fraction. This enrichment holds quantitatively true in the case
of all relevant heavy metals except the volatile elements mer-
cury and cadmium which are condenced at the carbon black in the
eyeIon.
Elution experiments with water resulted in the finding
that heavy metals are evidently stronger incorporated in the
matrix of pyrolysis residue than in the incineration ash, pro-
duced at 1200°C, or in the sewage sludge itself. Table II shows
that chromium, for instance, is more than 250-fold less liable
to be eluted from pyrolysis residue than from incineration ash.
Moreover, chromium is dissolved from ash essentially in the
oxidation state VI as compared to chromium II from pyrolysis
residues.
194

Table II Elutions According to DIN 38.414 T4


Sample Sewage Sludge Incineration Pyrolysis Re-
Ash (1200°Ci sidue (750°C)
Element ^ g / k g ) :
Cadmium 8 14 < 3
Chromium 100 7750 30
Copper 8150 100 50
Nickel 3860 125 25
Lead 350 55 50

The investigations have shown that sewage sludge can be


pyrolyzed according to the HAMBURG-PROCESS. The gas/oil-ratio
is adjustable in a large extent by means of varying the reac-
tion temperature. The use of the aromatic oils for petrochem-
ical application seems to be promising
The reduction of volume and the strong incorporation of
the heavy metals in the matrix of the pyrolysis residue cases
the problem of sludge decomposition. This shows that the pyro-
lysis of sewage sludge can be looked upon as environmentally
tolerable alternative to the conventional sewage sludge utili-
zation.
This research is sponsored by the BMFT, Federal Republic
of Germany.
3. REFERENCES
(1) L'HERMITE, P., OTT, H. (1982). Recycling International,
Freitag Verlag Berlin, 342
(2) BLICKWEDEL, P.T., SCHENKEL, W. (1986). Korrespondenz Ab-
wasser 33, 680
(3) KAMINSKY, W. (1985).J.Anal. & Appi. Pyrolysis 8, 439
(4) KAMINSKY, W., KUMMER, A.B., BELLMANN, U. (1986). Phosphat-
entfernung und Klärschlammnutzung. Hoechst Symposium,
Frankfurt
195

RAPPORTEURS REPORT ON SESSION III


PYROLYSIS GASIFICATION AND LIQUEFACTION TECHNOLOGIES

A V Bridgwater
Energy Research Group
Chemical Engineering and Applied Chemistry Department
Aston University
Aston Triangle
Birmingham B4 7ET
UK

INTRODUCTION
This overview provides what were seen to be the significant points and conclusions
from the papers presented in this session, some recommendations and à report on
the questions and discussion. It is hoped that the views of the authors are fairly
represented, and further details are contained in the individual contributions.

BIOMASS GASIFICATION IN DEVELOPING COUNTRIES


Dr M S Mendis

A summary of the World Bank monitoring programme has shown that biomass
gasification for heat applications has generally been successful, but for power
applications where gas quality is of prime importance, much less success has been
realised. Most projects have failed due to unacceptable fuels, untested equipment,
mismatch of system to application, poor training, lack of incentives and poor
economics. Proven fuels are charcoal, wood, rice husks and coconut shells.

Gasifiers cannot economically compete at present with diesel due to high capital
costs. Gasifier capital costs for charcoal are $500/kW, and for wood, $750/kW.
Total system costs for power generation for charcoal fuel are $1250/kW, and for
wood $1600/kW. A major breakthrough has recently been achieved at AIT in
Bangkok, Thailand with a ferrocement gasifier which costs about $50/kW compared
to $500 for a fabricated metal gasifier.

The economic attractiveness of biomass gasification systems for fuel and power is
very sensitive to fuel prices. The most interesting market is in the 10-300kW size
range, operating at more than 60% utilisation. Major inhibitions to development
are a lack of trained personnel, poor equipment maintenance, poor incentives for
implementation and environmental factors.

Recommendations
1 Continue support for monitoring to obtain better field data.
2 Learn from experiences to date and provide more technical and social
support for any new initiatives.
196

BIOMASS GASIFICATION & PYROLYSIS IN EUROPE


A A C M Beenackers and A V Bridgwater

Gasification
Low heating value gas production Systems are commercially available, but
generally not economic. Applications include process heat, for example drying,
and power from engines where considerable experience has been obtained. An
interesting system size for Europe is around 1MWe. Turbines offer considerable
potential but ideally require pressurised gasification and a particularly clean gas
both of which currently present problems.

Medium heating value gas production Considerable experience was gained in the
EC sponsored Methanol from Wood pilot programme. The Framatome pressurised
fluid bed oxygen gasifier at Clamecy is planned to be restarted which will provide
more data. Genedrally the technology is fairly well developed but uneconomic.

Catalytic gasification Good progress has been made in Spain and France on
catalytic gasification and in Sweden on secondary processing for gas quality
improvement.

Recommendations
1 Obtain more field experience and data from operational gasifiers,
2 Initiate work on gasifier driven turbine power generation,
3 Continue R&D on product gas quality improvement.

Pvrolvsis
Pyrolysis has been carried out in diverse processes to produce a wide range of
products including liquids, slurries, gases and solids. The technologies are less
developed, but there is more potential for production of liquid fuels as either fuel oil
substitutes, or by upgrading as synthetic hydrocarbons. More experience is
needed at pilot plant scale in Europe for pyrolysis processes and upgrading
technologies. Utilisation of the variety of liquid fuels that can be derived from
pyrolysis requires assessment and testing.

Recommendations
1 Improve the performance of pyrolysis processes,
2 Build pilot plant scale pyrolysis processes for liquids production at high
efficiency,
3 Continue liquids upgrading, particularly through zeolite synthesis of
hydrocarbons,
4 Provide wider experienceof utilisation of all pyrolysis products.

BIOMASS LIQUEFACTION PROCESSES


Prof M Gelus and Dr R Capart

Liquefaction and the related processes of solvolysis, hydrolysis and supercritical


extraction are the least developed of the thermochemical conversion technologies.
The processes are generally low temperature, high pressure processes which can
produce chemicals as well as higher quality oil liquids with a lower oxygen content
than pyrolysis oils.
197

Recommendations
As this is the least well developed conversion process, research should be
continued into as many variations as possible to more fully evaluate the technical
and economic opportunities for both chemicals and fuels production.

THE GEORGIA TECH FLASH PYROLYSIS PROCESS


Dr D O'Neill

The entrained flow flash pyrolysis process has been subjected to continued
development and 60% weight yield of liquids (dry basis) has now been achieved.
A robust computer model has been derived and developed which predicts that
yields of more than 70% oil by weight could be achieved in the optimum
circumstances.

A 200 t/d commercial plant has been designed and assessed which gives an oil
yield of 60% wt at an energy efficiency of 73%. No waste water would be produced
by maintaining the vapour temperature above the dew point of water. The 200 t/d
plant has a total capital cost of $2.28 million and, with the product oil valued the
same as crude oil on a heating value basis, gives attractive profitabilities even in
the current economic environment with a payback time of around 2 years and a
discounted cash flow rate of return of around 30%.

Development will continue on the piolt plant and opportunities for demonstration
will be sought.

VACUUM PYROLYSIS OF SCRAP TYRES


Prof C Roy

A novel tyre vacuum pyrolysis proces has been developed based on the
application of a biomass conversion technology to alternative feed, and a 250 kg/h
pilot plant has been built and operated This provides a more commercially
attractive opportunity than a biomass based process in the short term and enables
R&D activities to be maintained and provides valuable operating experience. The
products are oil, charcoal and carbon black, gas and steel. A 60 t/d (20 000 t/y)
plant has an estimated capital cost of CAN$ 7 million, and has been shown to be
profitable under current conditions. Development will continue and further
opportunities for this technology will be sought.

FLUID BED PYROLYSIS OF SEWAGE SLUDGE


Dr W Kaminsky

Fluidised bed pyrolysis of waste materials has been researched since 1970,
including earlier work on rubber and plastics which resulted in a demonstration
plant of 1 t/h operating in Southern Germany. This has been recently shut down
due to poor economics. Recent work on sewage sludge has given oil yields up to
40% by weight at lower temperatures of around 650°C, which reduce as the
temperature of pyrolysis increases, while the gas yield increases. Considerable
data has been collated but commercial feasibility has not yet been assessed.
198

QUESTIONS and DISCUSSION

QUESTION ANSWER or COMMENT

How does gasification compare with Gasification gives complete conversion


pyrolysis in terms of costs and benefits? to a single product - gas - which is difficult
to transport and can only be readily used
locally. Pyrolysis gives multiple products,
some which are liquid and can be
transported and used remotely. Capital
and operating costs are similar, and the
only difference, therefore, lies in the
product worths.

What hazards are involved Pyrolysis oils are no worse than coal tar
with pyrolysis oil? or crude oil.

How is water managed in the GTRI Water would be maintained in the vapour
process? phase in a commercial plant. This has
been achieved in a fixed bed operation
and is planned for the entrained flow
process.

What chemicals can be produced Lambiotte operating but with little interest.
from carbonisation plants? Extensive recoveryis practised in Brazil.

How does atmospheric tire pyrolysis. Vacuum increases the oil yield, and
compare with vacuum pyrolysis? improves the carbon black activity.

What are the power costs in As whole tires or 1/4 tires are processed,
tire shredding? power costs are very low.

What happens to the sulphur in the Sulphur is fixed by CaO & ZnO present in
products from tire pyrolysis? the tires

How are products from sludge This is not a problem.


processing denitrified?

What is the cost of the sludge A 20 000 t/y dry solids process would
conversion process? cost $2million+ buildings + special costs

What is the conversion efficiency and The process is not economic without a
economics of sewage sludge pyrolysis? disposal credit for the sewage sludge.
SESSION IV

FYROLYSIS CASE STUDIES


201

SUGARS FROM CELLULOSICS BY THE WATERLOO FAST PYROLYSIS PROCESS

D.S. Scott, J. Piskorz, D. Radlein and S. Czernik


Department of Chemical Engineering, University of Waterloo
Waterloo, Ontario, Canada

Sunarna T-y

It has been found that fast pyrolysis in a fluidized bed of sand at


atmospheric pressure can convert cellulose into anhydrosugars and
other sugars if certain characteristics are present in the feed.
Normally some pretreatment will be required to condition the feed so
that high yields of sugars can be obtained. For example, for wood,
treatment with 5% sulphuric acid at 100°C will give a product which
on pyrolysis will result in a sugar yield corresponding to about an
80% conversion of the cellulose to glucose. Wood pretreated in this
way and then pyrolyzed also yields a pentose solution, and an aroma-
tic fraction derived from lignin which has numerous possible uses.
The sugar produced by fast pyrolysis would be in the form of a syrup
with a concentration of 150 to 200 grams/liter. Results are also
given for pyrolysis of wood pretreated by steam explosion, and for
some agricultural wastes such as wheat chaff.

1. INTRODUCTION
Over the last several years, the Waterloo Fast Pyrolysis Process
(WFPP) has been developed to maximize yields of liquids by the rapid ther-
mal decomposition of lignocellulosic biomass. The process operates at
atmospheric pressure and the reaction is carried out in a fluidized bed of
sand as a heat transfer medium. Optimal conditions for woody biomass are
450 C to 550 C and about 0.5 seconds gas residence time. The nature of
the fluidizing gas has little influence on yields.
Liquid yields from wood at optimal conditions are 70% to 80% of the
dry feed, with the organic liquid yields being 60% to 65% of the dry wood
fed. A description of the process and the yields obtained with various
types of biomass has been published previously by the authors (1)(2). Ex-
tensive identification and quantification of many of the individual com-
pounds present in these pyrolytic oils has also been reported (3)(4)(5).
It has been known for many years, as described in the extensive lit-
erature on the subject, that slow heating of cellulose under vacuum can
lead to significant yields of anhydrosugars, principally levoglucosan.
However, pyrolysis of wood, whether slow or rapid, normally gives very low
yields of levoglucosan. Instead, lower molecular weight oxygenated com-
pounds are the major products, and, as pointed out by the authors in a
previous publication [6], if fast pyrolysis is employed, then hydroxyacet-
aldehyde will be one of the principal products. In that publication, a
mechanism was also proposed to account for the formation of hydroxyacetal-
dehyde, in which it was assumed that levoglucosan was a precursor, and
202

that lower molecular weight products were formed in successive sequential


decomposition steps. However, more recent work has led us to believe that
levoglucosan and hydroxyacetaldehyde are produced in parallel reactions, a
mechanism which has also been proposed recently by Richards (7).
Shafizadeh and Stevenson (8) suggested that the yield of levoglucosan
from wood could be increased by pretreatment of the wood to remove hemi­
celluloses prior to vacuum pyrolysis. Radlein et al. (9) in 1987 reported
the results of preliminary experiments which showed that a mild acid
hydrolysis of wood followed by fast pyrolysis at atmospheric pressure
completely changed the product spectrum, and, in particular, greatly in­
creased the yields of levoglucosan and other sugars. A dditional experi­
mental results are given here of investigations of the effects of various
pretreatments of wood on the yields of anhydrosugars obtained in the WFPP.

2. EXPERIMENTA L
Samples tested included poplar woods, both untreated as well as sub­
jected to a variety of pretreatments, and a pretreated pine.
The St. Lawrence poplar was prehydrolysed with 0.5% HCl at 165°C for
6 minutes in a plug­flow reactor ­­ a procedure which led to substantial
hemicellulose removal. Wayman poplar was whole wood pretreated with 2%
SO2 at 200°C for 45 seconds in a Wenger extruder. Biohol pine was auto­
claved with 3% S 0 2 at 110°C for 2 hours. Hemicelluloses were partially
removed by this treatment. Stake poplar was steam­exploded wood after
digestion at 322 psi for 2 minutes.
The acid­hydrolysed samples were prepared by boiling the ground wood
meal in 5% H2SO4 for 2 or 6 hours as indicated in the tables, except in
the case of the Stake wood which was treated with cold (21°C) 5% HOSOA for
21 hours. Following the acid treatment the samples were washed with de­
ionized water till acid­free. "De­ionized" wood was prepared by percolat­
ing 10 cm g of cold 0.1% H J S O A through a column of clean wood meal at a
rate of about 2 cm hr (g wood) , followed by washing with distilled
de­ionized water at a similar rate until the wash was acid­free.
Analysis of acid hydrolysate and of the water extract of the pyroly­
sis oils was done by HPLC (A minex ΗΡΧ­87Η column at 65°C, eluent 0.07N
H 3 P0 4 , eluent flow rate 0.32 χ 2.25 ml/min).
Except where otherwise noted, pyrolysis of raw or treated wood or
cellulose was carried out at standardized conditions near optimal for the
Waterloo Fast Pyrolysis Process for all runs, that is at 500°C, 0.46 to
0.50 seconds apparent gas residence time, nitrogen atmosphere, employing
the bench scale fluidized bed unit which has been described in detail
elsewhere (1).
Ash analysis was carried out by slow controlled combustion of biomass
in a muffle furnace at 650°C to prevent loss of volatile inorganic salts.
It was estimated that this method gave ash values accurate to 0.01 weight
percent.
Cellulose content was determined by gravimetry of the residue remain­
ing after hemicelluloses and lignin were dissolved in a mixture of acetic
and nitric acids according to the procedure of Updegraff (10).
A sample of wheat chaff, both untreated and acid pretreated in the
same manner as the wood samples, was also pyrolyzed. Pyrolysis conditions
and analytical methods were the same as for other samples.

3. RESULTS ­ WOOD
The "commercial" feedstocks were pyrolysed without further pretreat­
ment with the results shown in Table 1. Results for untreated clean IEA
poplar are included for comparison. Pyrolytic lignin is the water
203

insoluble portion of the tar (5). Only the (anhydro) sugars and hydroxy-
acetaldehyde from among the water-soluble components are listed. Total
liquid yields (water + organics) for the pretreated materials range from
-61% (Biohol) to 81% (St. Lawrence) compared to 78% for the un-treated
wood. Sugar yields were in all cases relatively low. In the best case
(Wayman) 35.5% of the cellulose was converted to sugars.
Some of these materials were then subjected to hydrolysis with HoSO^
as described in the experimental section. This procedure causes extensive
hemicellulose removal resulting in an enhanced cellulose content. Ash
levels are also reduced. The results of pyrolysis of the hydrolysed sub-
strates are listed in Table 2. In all cases there is a sharp increase to
>66% conversion of cellulose to sugars. It should be pointed out that the
"char" in these cases is not solely primary but includes a fused material
accumulated at the reactor outlet and having the appearance of a carbon-
ized sugar.
An attempt was made to identify the important variables controlling
sugar yields. Clean IEA poplar was hydrolysed with f^SO^ in the manner
already described and pyrolysed at different temperatures and feed rates,
with varying water content and, in one case, with an additive (NHo). The
results are summarized in Table 3 which includes a detailed breakdown of
the compositions of the gas and the water-soluble organics. In some cases
a distinction is made between the primary char and fused materials
("coke"). In all cases primary char yields are nearly zero. Liquid
yields are uniformly high and gas yields correspondingly low as would be
expected from the pyrolysis of similarly treated substrates (cf. Table 2 ) .
In the case of Run S#l, following hydrolysis the lignocellulose was
steeped in dilute NHj for one hour, washed till ammonia free and dried.
Only in this case is the sugar yield significantly suppressed. Otherwise
no clear trends emerge of the effects of hydrolysis time, moisture con-
tent, pyrolysis temperature, particle size or feed rate.
We have also made a preliminary investigation of the feasibility of
obtaining high sugar yields from wood without preliminary hydrolysis of
hemicelluloses. For this purpose "de-ionized" IEA poplar was prepared in
the manner already described. In some cases 0.1 wt% of (NH^^SO^ or H2SO4
was added to the de-ionized wood by dissolving in a sufficient amount of
water to saturate the wood then drying at 105 C for one hour. The results
of these tests are shown in Table 4. Sugar yields are good with a presum-
ably catalytic enhancement by small amounts of (NH^^SO^ or H2SO4. Though
less than those from lignocellulose (i.e. acid hydrolysed wood) they are a
great deal better than those from untreated wood. To our knowledge they
are the highest ever reported from whole wood.
Fermentation tests were carried out by an independent consultant on
the liquid products produced by pyrolysis of acid treated poplar in a
pilot plant scale reactor (3 kg/hr feed). The anhydrosugars as produced
can be fermented only slowly, if at all, by the common ethanol producing
yeast strains. After hydrolysis of these anhydrosugars to glucose, how-
ever, fermentation proceeded to completion at a normal rate with common
bakers yeast, that is, in about 24 hours. If the hydrolyzed sirup of
hexoses was treated with activated carbon before fermentation, quantita-
tive conversion to ethanol occurred in 1.5 hours.

4. RESULTS - WHEAT CHAFF


Wheat chaff was investigated as a typical agricultural waste avail-
able in large quantities which might be a source of fermentable sugars.
It is a very different type of biomass from wood, having a lower cellulose
content (22.5%) and very substantial amounts of minerals, mainly silica,
204

which are not removed by acid pretreatment. lhe chaff was given two
different acid pretreatments, 5% H^SO^ for 20 hours at 20°C, and 5% f^SO^
at 100°C for 2 hours. A summary of these pretreatment results is given in
Table 5.
Results of the pyrolysis tests at 500°C for the untreated and the two
pretreated wheat chaff samples are given in Table 6. Unlike wood, very
substantial amounts of a solid product were collected, which was in a
great part probably due to the high ash content of wheat chaff. However,
even if calculated on an ash free basis the amount of char product
obtained from acid prehydrolyzed wheat chaff was almost twice as high as
that from pretreated wood.
The composition of the liquid product obtained from pyrolysis of the
untreated wheat chaff was similar to that from wood. Similarly, the in-
fluence of acid pretreatment on the change of concentrations of main com-
ponents of the pyrolytic tar was much the same, that is, a very signifi-
cant increase was observed in the yield of sugars, mainly levoglucosan,
and a drastic drop in the yield of monomer fragmentation products such as
hydroxyacetaldehyde and acetol. The pretreatment of wheat chaff with
sulphuric acid at room temperature was more efficient in the enhancement
of the yield of pyrolytic sugars than was the hot acid pretreatment, in
contrast to the behaviour observed for raw poplar wood, but similar to
that of steam exploded wood. The conversion of cellulose into anhydro-
sugars reached a value of about 71% (glucose equivalent), which is a
little less than that for prehydrolyzed wood.
In view of these preliminary and non-optimized results, the processes
for the pretreatment and pyrolysis of wheat chaff appear to merit further
investigation.

5. DISCUSSION
The factors which determine the yield of levoglucosan from cellulose
pyrolysis have been extensively studied. Apart from the hydrodynamic and
temperature regime, various intrinsic factors like cellulose morphology
and degree of polymerisation have been cited. Definitive evidence has
been hard to come by but one of the most clearly established effects is
the role of certain types of cations, especially alkaline and alkaline
earth, in even trace amounts, in catalysing fragmentation and charring
reactions and suppressing levoglucosan yields. Most of the published
studies of cellulose pyrolysis relate to slow, low temperature vacuum
conditions. The results from de-ionized wood indicate that the deleteri-
ous effects of cations persist in the case of fast high temperature pyrol-
ysis of whole wood (cf. Runs A-2 and S#3 in Tables 1 and 4 respectively).
This cation effect appears to be one of the principal reasons why the
commercial pretreated wood samples gave only poor to modest yields of
sugars. It will be noticed from Table 2 that acid hydrolysis of these
samples caused substantial reductions in ash content. (Most of the re-
maining ash is likely to be inert material like silica.) In fact the data
suggest that a mild cold de-ionization of these samples is likely to
cause substantial enhancement of sugar yield. The best results in Table 1
are for the SOn treated materials (Wayman poplar and Biohol pine). It is
possible that this treatment causes other changes which are conducive to
sugar formation. On the other hand the Stake wood gave excellent results
after a cold acid wash.
Acid hydrolysis under the conditions used also causes hemicellulose
removal. Our data (Table 4) confirm an earlier observation by Shafizadeh
and Stevenson [8] that, provided soluble ionic substances are removed, the
presence of hemicellulose in wood is not, per se, detrimental to
205

levoglucosan production. (Cations in fact would be expected to associate


with carboxylic groups in hemicellulose.) The best results with de-
ionized wood are not quite ás good as those with lignocellulose but no
definite conclusion can be drawn as the degree of de-ionization has not
been optimized.
The other principal question addressed by our data concerns the pre-
cise role of acids. Apart from cation and/or hemicellulose removal, the
data in Table 4 clearly show what appears to be a positive catalytic
effect. Such an effect has been previously postulated by Shafizadeh [8].
(NH 4 ) 2 S0 4 decomposes at 235°C to free H 2 S 0 4 (b.p. 338°C and volatile NH3
gas which probably readily escapes. By this strategy the timing of the
release of acid is controlled and the problems of drying samples contain-
ing HOSOA are avoided. (When the substrate of Run S#7 was dried some
surface charring was clearly visible - - a fact which might be contributory
to the lower sugar yields.) There remains a great deal of scope for opti-
mizing the chemical nature, the quantity and the manner of incorporating
acid into wood or lignocellulose.
One final point concerns the completeness of the characterisation of
the water-soluble portion of the organic liquid. We are able to identify
by HPLC an average of only 73% for the wood samples in Table 4 compared
with 85% to 95% for the lignocelluloses in Table 2. GCMS showed the pre-
sence of significant quantities of two unidentified components in the wood
tars which were absent from the lignocellulose, suggesting a hemicellulose
origin. Preliminary work indicates they are anhydro-xylan substances but
positive identification has not yet been established.
The preliminary tests carried out on wheat chaff indicate that the
cellulose content of a wide range of biomass materials could be converted
to fermentable sugars in good yield by pyrolysis after an appropriate
pretreatment. The wheat chaff results, together with other work done in
our laboratory (unpublished) show that of the cations naturally present
only the alkali and alkaline earth cations appear to have a specific cata-
lytic effect in promoting ring fragmentation rather than depolymerization
of the cellulose.
We summarize our principal conclusions as follows
(a) It is possible to obtain good yields of anhydro-sugars from wood and
agricultural lignocelluloses by fast high temperature pyrolysis.
(b) The highest yields were obtained when the feedstock was pretreated in
a suitable way. Acid hydrolysis or acid washing proved to be very
effective leading to over 70% conversion of cellulose to sugars in the
most favourable cases.
(c) The acid appears to play at least two critical roles; to remove harm-
ful cations and to catalyse anhydrosugar release.
(d) However, much more fundamental work remains to be done to gain a full
understanding of the effects of both pretreatraent and pyrolysis
variables on sugar yields.

ACKNOWLEDGEMENTS
The authors would like to acknowledge the financial support for a
portion of this work by the Renewable Energy Division of Energy, Mines and
Resources Canada, and by the Natural Sciences and Engineering Research
Council of Canada.
The valuable assistance of Peter Majerski as operator of our pyroly-
sis pilot plant is also acknowledged with pleasure.
206

REFERENCES

(1) Scott, D.S. and Piskorz, J., "The Flash Pyrolysis of Poplar Wood",
Can. J. Chem. Eng., 60, 666­674 (1982).
(2) Scott, D.S., Piskorz, J. and Radlein, D. , "Liquid Products from the
Fast Pyrolysis of Wood and Cellulose", Ind. Eng. Chem. Proc. Des
Devei., 24, 581­588 (1985).
(3) Piskorz, J. and Scott, D.S., Symp. on Production, A nalysis and Up­
grading of Pyrolysis Oils from Biomass, ACS Meeting, Denver, April 5­
10 (1987).
(4) Radlein, D. , Grinshpun, Α., Piskorz, J. and Scott, D.S., "On the
presence of anhydro­oligosaccharides in the sirups from the fast
pyrolysis of cellulose", J. Anal. Appi. Pyrolysis, 12, 39­49 (1987).
(5) Radlein, D. Piskorz, J. and Scott, D.S., "Lignin derived oils from
the fast pyrolysis of biomass", J. Anal. Appi. Pyrolysis, 12, 51­59
(1987).
(6) Piskorz, J., Radlein, D. and Scott, D.S., "On the mechanism of the
rapid pyrolysis of cellulose", J. A nal. A ppi. Pyrol., 9, 121­ 126
(1986).
(7) Richards, G.N., "Glycolaldehyde from pyrolysis of cellulose", J.
Anal. Appi. Pyrol., 10, 251­256 (1987).
(8) Shafizadeh, F. and Stevenson, T.T., J. Appi. Polymer S c , 27 4577­
4585 (1982).
(9) Radlein, D., Piskorz, J., Grinshpun, A. and Scott, D.S., "Fast pyrol­
ysis of pretreated wood and cellulose", ACS Preprints, Div. of Fuel
Chemistry, 32, No. 2, 29­36 (1987).
(10) Updegraff, D.M., A nal. Biochem. 32, 420­424, 1969

Table 1

Pyrolysis of Raw and Pre­Treated Wood

Run No. A­2 1­SL 18 20 38

IEA St.Lawrence Wayman Biohol Stake


Feedstock Poplar Poplar Poplar Pine Poplar

Cellulose Content, X mf 49.1 65.4 43.1 54.9 47.0


Ash, X mf 0.46 0.85 1.8 1.0 0.67
Temperature, °C 497 488 500 500 500

Yields, wt X mf
Gas 10.8 7.6 14.0 7.5 13.0
Char 7.7 10.1 11.9 23.0 12.4
Water 12.2 2.9 8.5 10.6 3.2
Organics 65.8 78.4 63.2 51.0 58.9

Total Recovery 96.5 99.0 97.6 92.1 87.3

Levoglucosan 3.0 4.5 6.7 10.3 2.9


Other Sugars 6.1 5.1 8.6 4.7 1.1
Hydroxyac etaldehyde 10.0 9.1 7.4 Trace 7.5
Pyrolytic Lignin 16.2 18.8 19.3 21.9 18.0

X Cellulose 18.5 14.7 35.5 29.1 8.5


Converted to Sugars
207

Table 2

Pyrolysis of Some Acid­Hydrolysed Woods

Run No. 10 14 46

IEA St.Lawrence Stake


Feedstock Poplar Poplar Poplar

Celluiose Content, X ffl£ 65.5 70.6 66.5


Ash. X mf 0.02 0.30 0.16
Hydrolysis Time, hours 6 2 2
Temperature, C 480 480 490

Yields, wt X mi
Gas 6.9 6.4 6.6
Char S.2 10.5 6.7
Water 2.2 5.2 3.2
Organics 80.9 75.0 82.1

Total Recovery 98.2 97.1 98.6

Levoglucosan 30.0 30.1 25.3


Other Sugars 13.2 18.8 20.2
Hydroxyacetaldehyde 0.9 0.9 4.3
Pyrolytic Lignin 21.0 17.9 18.8

X Cellulose Converted 66.0 69.3 68.4


co Sugars

Table 3

Pyrolysis of IEA Ligno­Cellulose Under Varying Conditions

Run Ho. A­1 ST­10 ST­11 S#ll S«*

Temperature, 'C 501 480 475 501 485


Feed Rare, g/hr 46.9 71.5 116 86.9 41.6
Hydrolysis Tiae, hr 6 6 2 6 2
Moisture, wt Ζ 16.5 6.5 6.0 3.5 13.7
Particle Size, aa ­0.25 ­0.5 ­0.5 ­0.5 ­0.5

Yields, wt % mf
Gas 6.4 6.9 6.4 4.4 4.3
Char 0.0 ]1 0.0 0.0
8.2 11 6.3
Coke 6.7 | 6.2 4.2
Organics 79.6 Ι 80.9 ι173.6 77.0 78.1
Water 0.9 2.2 6.3 10.0 9.6

Total Recovery 93.6 98.2 92.6 97.6 96.2

CO 2.79 2.13 2.5 2.00 1.96


co2 3.07 2.29 1.9 1.96 1.93
cnu 0.38 0.6 0.4 0.33 0.33
c2+ 0.10 0.10 0.11

Oligosaccharides 1.19 0.69 0.89 0.50 2.56


Cellobiosan 5.68 4.74 4.77 3.71 6.05
Glucose 1.89 1.34 1.96 Tr Tr
Fructose (?) 3.89 2.21 2.12 0.50 2.01
Glyoxal 0.11 0.28 0.28 0.65 2.32
1,6­Anhydroglucofuranose 4.50 •3.90 3.89 1.96 2.40
Levoglucosan 30.42 30.0 28.7 25.56 18.80
Hydroxyacecaldehyde 0.37 0.9 0.9 1.62 3.96
Formic Acid 1.42 ) . ,, 4.96
Formaldehyde 0.8 2.36 1.06 ...
Acetic Acid
Acecol
0.17
0.06
2.32 1.03 1 »·" 0.70
0.07 0.12 ... ...
Pyrolytic Lignin 19.0 21.0 21.8 23.7 23.9

*NH 3 treated. See text.


208

Table 4
Pyrolysis of De-ionized IEA Poplar
Run No. S#3 S#4 S#5 S06 S#7
Temperature, "C 530 -530 -530 493 495
Feed Rate, g/hr 8.0 22.3 18.3 23.6 27.1
Additive (wt X ) * 0 Ν (0.1) Ν (0.1) Ν (0.1) Η (0.1)
Moisture, wt Ζ 0 3.0 28.9 11.4 7.0
Particle Size, mm -0.5 -0.5 -0.5 -0.5 -0.5
Yields, wt X mf
Gas 14.13 7.35 6.63 2.61 3.22
Char 2.5 1.66 3.93 0.67 0.72
Coke 2.77 4.68 5.41
Organics 60.50 66.07 75.24 75.93 66.10
Water 18.25 16.20 5.70 13.96 -17
Total Recovery 95.38 94.05 91.50 97.85 92.45
CO 4.86 3.86 2.94 trace 0.61
CO 2 8.75 2.90 3.09 2.37 2.27
CH,, 0.38 0.60 0.47 0.24 0.29
C 2+ 0.13 0.13 0.05
Oligosaccharides
Cellobiosan 4.92 1.35 1.92 1.68
Glucose 0.94 0.81 1.12 1.00
Fructose (?) 1.81 1.22 1.92 1.84
Glyoxal 2.86 2.34 2.65 2.26
1,6-Anhydroglucofuranose 1.12 2.24 2.87 2.72
Levoglucosan 9.33 18.73 16.53 17.11 15.52
Hydroxyacetaldehyde 3.35 3.36 2.57 1.95 1.65
Acetic Acid 0.67 1.41 1.15 1.34 1.17
Pyrolytic Lignin 17.8 -21 18.9 22.4 23.1
X Cellulose 37.1 53.9 45.1 50.8 46.4
Conversion to Sugars
* Ν ■ (NH 4 ) 2 S0 4 , Η

Table 5
Properties of Raw and Pretreated Wheat Chaff, mf basis
Pretreatment Feed removed A sh content Cellulose content
X X X
None 0 22.5 22.5
5X H 2 S0 4 , 15.6 28.8 26.0*
room temp., 20 h
5X H 2 S0 4 , 31.6 34.2 33.5*
b.p. temp., 2 h
Average of four tests

Table 6
Pyrolysis of Prehydrolyzed Wheat Chaff
Run # 57 56 66
Temperature, "C 502 500 495
Feed Wheat Chaff Wheat Chaff Wheat Chaff
acid washed acid washed untreated
at room temp.
, at 100'C
App. res. time, s 0.5 0.5 0.5
Feed rate, g/h 49.1 83.7 86.8
Amount fed, g 36.8 41.8 36.2
Moisture, w/w X 5.7 3.9 6.1
Particle size, mm -0.25 -0.25 -0.25
Yields, w/w X mf maf mf maf mf maf
Gas 8.7 12.2 8.4 12.7 11.0 14.1
Char 40.5 16.4 44.0 14.9 43.9 27.6
Water 6.0 8.4 7.7 11.7 8.6 11.1
Organics 42.4 59.6 38.4 58.4 37.2 47.9
Total 97.6 96.6 98.5 97.7 100.7 100.7
Levoglucosan 10.5 14.7 13.7 20.8 0.9 1.2
Other sugars 6.3 8.8 5.5 8.4 0.6 0.8
Hydroxyacetaldehyde tr tr tr tr 2.5 3.2
X Cellulose converted 70.8 63.1 7.3
into sugars (glucose
equivalent)
209

PRODUCTION OF BENZOLES AND ACTIVE CARBON FROM


WASTE RUBBER AND PLASTIC MATERIALS
BY MEANS OF PYROLYSIS WITH SIMULTANEOUS POST-CRACKING

PROFESSOR R. CYPRES and DR B. BETTENS


Universite Libre de Bruxelles (ULB), Centre de Transposition
Semi-Industrielle de la Recherche Appliquée (Centre for the
Semi-Industrial Transposition of Applied Research) TSIRA,
Charleroi, and the Association pour l'Incinération,
la Collecte et la Destruction des Immondices de la Region de
Charleroi (Association for the Incineration, Collection and
Destruction of Waste for the Charleroi Region) ICDI

Summary

The pyrolysis of' rubber has long been the subject of study. The
initial aim was to regenerate isoprene, the monomer of natural rubber.
Then, after 1967, research was carried out into cracking at
temperatures of between 300 and 1 000°C. Temperature was seen to have
a marked influence on the kind of products obtained by cracking. At
low temperatures, aliphatic hydrocarbons predominate in the liquid
phase. At high temperatures, aromatic hydrocarbons, BTX and
naphthalenes are formed to the exclusion of all other products.
Pilot installations have been constructed in various countries -
by Goodyear and Interco Inc. (37.5 tonnes per day) in the USA, Kobe
Steel (20 t/d) and Energy Recovery Research (20 t/d) in Japan, Foster
Wheeler in Great Britain, Deutsche Reinfen- und Kunstoffpyrolyse
(15 t/d) and Mannesmann Veba Umwelttechnik (48 t/d) in the Federal
Republic of Germany, to name but a few.
The process developed by the ULB and the TSIRA Centre is based
on two-stage pyrolysis. During the first stage, rubber is
depolymerized at a relatively low temperature (around 500°C). During
the second stage, the volatile substances thus obtained are
post-cracked at temperatures of between 750 and 800°C. This process
exploits the fact that aromatization can take place only above 700°C,
whereas deploymerization and the formation of mainly C4 olefins
produces maximum yields at low temperatures. The aromatization
mechanism was studied in great depth by subjecting butane, butene and
butadiene to thermal cracking. These are aromatized mainly into
benzene, toluene and xylene as a result of Diels Alder cyclization
reactions, with two molecules being converted into C4, followed by the
dehydrogenation of cyclohexenes into benzene and its derivatives.
Pyrolysis with simultaneous post-cracking maximizes the yield of
benzoles. It is also possible, by varying the period of time for which
volatiles are retained in the post-cracking zone, to obtain high
yields of naphthalenes. This makes for flexibility of operation, as
the process can be made to function according to the market prices of
benzoles and naphthalenes.
Research was carried out into a full working plant consisting of
a pyrolysis furnace with a conveyor belt, a depolymerization zone and
a post-cracking zone. The furnace is charged with whole car tyres
(lorry tyres are first sheared) and the solid residue is eliminated in
the lower section of the furnace.
210

Economic studies showed that it was not profitable to treat more


waste tyres than are available within a limited radius of a
conurbation. Collection costs become prohibitive if tyres must be
collected outside the area covered by municipal collection services.
This is why we explored the possibility of setting up units capable of
processing approximately 500 t of waste tyres per annum within
existing refuse treatment centres. Similar units could be set up in
all conurbations. In the case of large or very large cities, where
much more waste could be collected, larger installations could
obviously be constructed using the same model.
The process is technically feasible and would be highly
profitable. The capacity of the installation must correlate with the
quantity of tyres available within a radius not exceeding that of an
urban centre together with its adjacent centres of population.
Treatment of such waste must be combined with that of household waste
within existing centres, and suitable arrangements made for its
collection.
From an environmental point of view, the dumping of tyres in
quarries or elsewhere is not only detrimental to the sites in
question, but also encourages the proliferation of rats. The
incineration of tyres leads to atmospheric pollution unless expensive
devices are installed to clean the fumes. Pyrolysis is the only method
which produces aromatic hydrocarbons in the form of benzoles and
naphthalenes, together with solid carbon (from the carbon used to
reinforce tyres), which can either be converted into active carbon or
used for other industrial purposes. The scrap tyre is a unique source
of energy in that the only real cost involved is that of collection.
The price of benzole and naphthalene fluctuates according to the price
of oil.

1. INTRODUCTION AND LITERATURE SURVEY

Like any other organic compound, rubber decomposes when it is heated.


Natural rubber is a polymer of 1,3 methyl butadiene. Generally speaking,
pyrolysis is governed by the following parameters: temperature, retention
time at the reaction temperature, pressure, and type of gaseous atmosphere.
There are two stages to pyrolysis: primary cracking and post-cracking.
Post-cracking occurs at higher temperatures and enables primary products to
be converted into compounds which may have a higher market value.
Work on the pyrolysis of rubber first began in the 1920s. Initial
research was carried out with a view to regenerating the monomer of natural
rubber, isoprene. Williams (1) used atmospheric distillation to obtain a
distillate containing approximately 5% isoprene. The effect of pressure was
subsequently explored by Standinger and Fritschi (2) . These two authors
showed that distillation at temperatures of between 275 and 350°C and at a
reduced pressure of 0.1 mm Hg yields 63.5% of liquid phase, approximately
half of which consists of isoprene and its dimer, dipentene. Standinger (3)
went on successfully to distil rubber in an inert atmosphere at atmospheric
pressure. Using this method, he managed to increase the weight of the liquid
phase, which consisted mainly of isoprene dimers such as limonene and other
monocyclic terpenes.
The author also reports the presence of cyclohexadiene and methyl-
cyclohexadiene in the liquid phase. The rapid decomposition (4) of a crepe
211

of natural rubber at 700°C produced olefins, dienes, cyclohexadiene, as well


as aliphatic and aromatic hydrocarbons.
Japanese authors (5) pyrolysed a solution of rubber in heavy oils at
temperatures of between 310 and 390°C and at pressures of between 50 and 200
atmospheres. Reaction products consisted mainly of cracked oil, bitumen,
carbon and gas.
Since then, research has started up in a number of new areas, in an
attempt to discover ways of converting rubber waste into liquid combustibles
and fuel. One method is the aromatization of products generated by primary
pyrolysis. This has prompted a considerable number of researchers to carry
out investigations into the pyrolysis of isoprene and its dimers. Oro, Han
and Zlatkis (6), for instance, pyrolysed isoprene at temperatures of between
300 and 1 000°C. The influence of temperature on the composition of the
reaction products is very marked. Whilst aliphatic components predominate in
the liquid phase at low temperatures, at high temperatures decomposition
products are entirely aromatic; they consist principally of naphthalene,
methylnaphthalenes, xylenes and trimethylbenzenes, together with toluene.
Pyrolysis produces optimum yields of aromatic components at temperatures of
between 700 and 800°C.
It was not until 1974 that interest in the solid phase really
developed. Most studies concentrated on the recovery of the solid phase with
a view to using it in the treatment of waste water once it had been
activated. Mention should be made of the work of Tanaka and Gomyo (7), Jo
and Yoda (8), Sanga (9), Ishibashi and Noda (10) and Kudo (11).
A number of pyrolysis methods have been, or are being, developed at
pilot or industrial scale.
In 1977, Goodyear carried out tests using a rotary drum in which
ceramic beads were heated to 650°C and used to pyrolyse shredded tyres.
Results showed that the profitability threshold for this type of reactor,
which had been developed previously for processing bituminous shale, was of
the order of 150 tonnes per day, which was too high.
Two plants came into operation in 1979, one in Japan and the other in
the USA. The Japanese plant has a capacity of 20 t per day and is run by
Kobe Steel Ltd. It consists of a rotary kiln with scraper blades to remove
carbon from the walls. The American plant has a capacity of 37.5 t per day,
is situated in Houston, and is run by Intenco Inc.
A third plant with a capacity of 20 t per day was set up in Osaka by
the American company Energy Recovery Research Group.
In Great Britain, Foster Wheeler Power Products Ltd uses a process
developed jointly by the Warren Spring Laboratory and the National Research
Council. Pieces of waste tyre are held in place between two parallel
vertical grills and heated by a horizontal stream of hot flue gas from an
auxiliary furnace. Some of the gases thus generated are burned in the
furnace to produce the hot flue gas.
In the Federal Republic of Germany, Deutsche Reifen- und Kunststoff-
pyrolyse GmbH set up a fluidized bed plant with a capacity of 15 t per day
in Hamburg in 1982. In this process, which was developed by the University
of Hamburg, whole tyres are used as a feedstock for the reactor. These
gradually sink into a fluidized bed of sand and carbon black as pyrolysis
progresses. The steel casings are collected on a grill and removed.
Mannesmann Veba Umwelttechnik GmbH (Federal Republic of Germany) is
currently planning to construct a rotary kiln with a capacity of 48 t per
day for pyrolysing rubber, plastics and resins.
Dunlop Holding Ltd has financed a research project at the University
of Aston (Great Britain) with a view to using molten carbonate salts as a
source of heat for pyrolysis.
212

With the help of subsidies from the US Department of Energy, Rockwell


International Corp. has carried out pilot-scale tests into pyrolysis at
Canoga Park, California, using molten sodium carbonate salts. Pieces of tyre
react with the sodium carbonate at temperatures of between 900 and 1 000°C
and produce a combustible gas rich in hydrogen and carbon monoxide when
exposed to a reducing atmosphere fuelled by a fixed amount of air.
USBM Firestone pyrolyses scrap tyes in an electric furnace at
temperatures of between 500 and 900°C and at a pressure of 150 bars. In
spite of the high pressure, products are not qualitatively different from
those generated by other processes, nor is the yield.
The Herbold process treats pieces of waste tyres and plastics
measuring between 30 and 40 mm at temperatures of between 430 and 450°C. A
24 t/d installation would cost approximately $1 000 000 (1978 prices).
In the Reprox process (Japan), pieces of waste tyre which have been
reduced to a size of between 50 and 100 mm are pyrolysed in a fluidized bed.
Retention time is less than one minute. Gases from the furnace are burned
off after desulphurization, whilst the oils are used as commercial fuel.
Research is currently being carried out into the residual carbon which is
produced.
In the H. Rubber process, rubber undergoes catalytic hydrogénation
after it has been pulverized to a grain size of approximately 0.1 mm and
suspended in oil. A desulphurization and hydrogénation catalyst such as
cobalt molybdate is used on an aluminium support. Hydrogénation takes place
at 450°C and at a pressure of between 35 and 200 bars. Investment for a
plant with a capacity of 270 000 t per annum would be of the order of
$30 000 000 (1977 prices), and production costs (including hydrogen, labour,
energy and maintenance) around $76 per tonne.
In the DSR Firestone process, rubber is heated in aromatic oil to
induce depolymerization. The aim is to produce carbon black suspended in the
oil, the mixture then being used to make new rubber compounds. Particle size
is 35 mesh at a temperature of between 250 and 275°C and after a reaction
time of between 12 and 24 hours, unfortunately, the suspension produced by
this method is not of a sufficiently high quality to permit its use in the
rubber industry.
The H Oil process is also designed to recover high-quality carbon
black and fuel oil. Waste is pulverized and then dissolved in oil before
being depolymerized. This is done at a temperature of 200°C and a pressure
of 3 bars.
Mention should also be made of the low-temperature process (around
300°C) developed at the university of Compiegne.
The Tyrolysis method used in Wolverhampton (GB), is based on thermal
decomposition at temperatures which are carefully selected to give the
maximum yield of fuel oil. The Wolverhampton plant began operating in 1984.
It is designed to treat 50 000 t of waste tyres per year, producing 20 000 t
of fuel, 17 500 t of carbon and 7 000 tonnes of steel. It is a
self-sustaining process, burning preheated pyrolysis gases. Tyres must be
shredded twice in succession before the reactor can be fed with ground
feedstock.
Although this list of waste tyre pyrolysis plants is far from
exhaustive, it does show that the pyrolysis of waste tyres is widely
developed throughout the world. Methods vary according to the technology
used.
At low temperatures (below 500°C), fuel oil is produced but not much
gas. At high temperatures, light aromatics and lavjer quantities of gas are
produced.
213

In our process, advanced depolymerization of rubber takes place at low


temperatures. The C3 and C4 olefins thus produced are continuously aroma-
tized into BTX at high temperature.

2. EXPERIMENTAL RESULTS

The results of our laboratory research were published in 1981 (12) and
were the subject of a feasibility and development study (13) which was
financed by the Walloon region and carried out jointly by the following
bodies working together on a temporary basis: the TSIRA Centre, the ICDI,
the Centre de Transposition Semi-Industrielle de la Recherche Appliquée
(Charleroi), and the Intercommunale de Collecte et de Destruction des
Immondices de la Région de Charleroi.
We studied a two-stage process comprising an initial low-temperature
pyrolysis phase followed by continuous post-cracking of resultant volatile
materials at a higher temperature. This concept is based on a fact revealed
by previous studies into the aromatization of short-chain olefins (14, 15,
16), namely that aromatization begins to take place at 750°C as a result of
the cyclization of olefins into C2, C3 and C4. Post-cracking at a carefully
chosen temperature effectively allowed an additional fraction of the gases
corresponding to these ethylene compounds to be aromatized.

2.1 Pyrolysis with Post-cracking

The material to be pyrolysed is heated to a temperature of between 400


and 450°C. The gaseous phase thus produced is entrained by a vector gas
stream into a second post-cracking furnace (600 to 800°C). The large
isothermal zone in this furnace ensures that the gas remains in the reaction
zone for a sufficient length of time to enable aromatization to take place.
The composition of mass balances for the different phases is given in
Figure 1. The composition of the gaseous phase is given in Figure 2 and that
of the liquid phase in Figure 3.
It will be seen that the ethylene compounds disappear at higher
temperatures. They are aromatized, producing H and CH in accordance with
the following general reactions :

C
4H8 + C
2H4 - C6H6 + 3H
2
and
C
4H8 + C
3H6 - C6H6 + CH
4 + 2H
2

In the liquid phase, isoprene quickly disappears above 600°C. At high


temperatures, naphthalene and plenanthrene seem to be most common, whereas
the concentration of BTX does not vary significantly above the 600°C
threshold.
The heating of elastomers induces depolymerization reactions. These
depolymerization mechanisms are very complex and are described differently
by various authors; they can lead to the formation of dipentene (17), or of
numerous dienes of lighter molecular weight. In the case of rubber,
butadiene and its methylated derivative probably account for an important
fraction of such dienes.
As has been seen, the pyrolysis of rubber leads to the production of
ethylene, propene and 1,3 butadiene. These induce aromatization as a result
of Diels Alder reactions, which have been amply described in the relevant
literature (18, 19, 20). These reactions can be represented as follows:
Moles

Liquid
Weight
60
%
70 ■ BTX
X ■^--^^Styrene

50 ■

30
20 to
l—i
Phenanthrene

20 \ o / •^Naphthalei

20
10

0 \
^ Isoprene

6O0 700 800 C 600 700 800 C 600 7O0 800 C


P o s t - c r a c k i n g temperature P o s t - c r a c k i n g temperature Post-cracking temperature

Fig. 1. Mass balance for tyre Fig. 2. Molar percentages of Fig. 3. Weight percentage of
pyrolysis with 450°C hot charge constituents of the gaseous phase constituents of the liquid phase
obtained by tyre pyrolysis with obtained by tyre pyrolysis with
45cPC hot charge 450°C hot charge
215

2 C 2 H 4 + 1 C 4 H 8 - 1,3 C 4 H 6 + ^

.11—0
1.3 butadiene ethylene cyclohexene

C- r — O 4-methyl-l-cyclohexene

4-vinyl-l-cyclohexene

Dehydrogenation causes cyclic compounds with six carbons to produce


aromatic derivatives corresponding to one cycle. As a result of subsequent
associative reactions, these may lead to the formation of polycyclic
compounds such as naphthalene and phenanthrene.

2.2 Influence of Contact Time

Pyrolysis was carried out three times, with the contact time being
varied by changing the rate of flow of vector gas (N ) . Three values were
used: 20, 40 and 60 ml per minute.
Michelin X tyres were used in all the tests. The results are given in
Tables I, II and III.

TABLE I. Mass balance produced by tyre pyrolysis,


as a function of contact time (% weight)

Rate of flow of nitrogen in ml/min

20 40 60

Gaseous phase 13.96 15.12 13.42


Liquid phase 34.44 36.54 41.58
Solid phase 51.60 48.34 45.00
216

TABLE II. Molar % of constituents of the gaseous phase as


a function of the rate of flow of carrier ga:

Rate of flow of nitrogen (ml/min)

20 40 60

H
2 23.28 23.30 30.65
CH 56.15 53.85 47.36
4
C 14.95 16.78 13.56
2H4
C 3.21 3.56 4.51
2H6
C
3 R H 0.15 - 0.32
C 2.26 2.52 3.60
3H6

TABLE ill. Percentage weight of the constituents of the


liquid phase as a function of the rate of
flow of carrier gas

Rate of flow of nitrogen in ml/min

20 40 60

Octene + lights 3,.55 1.04 2.89


Benzene 33..85 36.41 30.57
Toluene 14..55 16.78 15.66
m + p-xylenes 4,.16 4.83 5.22
p-xylene 1..24 1.35 1.48
Styrene 4..17 4.58 5.83
Indane 1..27 1.68 2.18
Indene 2..60 2.47 3.26
Naphthalene 11..21 9.15 7.97
2-methylnaphthalene 3..41 2.42 2.71
1-methylnaphthalene 1..87 4.06 5.43
Acenaphthene + ... 7..47 4.35 6.13
Plenanthrene 4.,58 3.19 2.98
Heavy fraction 6..08 7.68 7.69

An increase in the flow rate N2 appears to improve the yield of liquid


phase but somewhat diminish the benzene content. This is because depolymer-
ization products are entrained more rapidly at lower temperatures, whereas
at high temperatures aromatization is less marked owing to the reduced gas
retention time in the hot zone.

2.3 Pyrolysis of Various Tyres and Brands of Tyres

Different brands of tyres were pyrolysed at temperatures of between


450 and 800°C. The results appear in Tables IV to VII.
There do not appear to be any significant differences, although it
should be pointed out that the yield of liquid is greater when V 10 tyres
are used.
217

TABLE IV. Mass balances produced by pyrolysing various types of tyre

Michelin Michelin Uniroyal Uniroyal Kleber Kleber


Rad. X Rad. XAS-P Rallye Rallye V 10 V 10GT
Wet Weather

Gaseous phase 16.77 17.55 16.05 19.47 16.98 16.16


Liquid phase 38.46 37.15 39.72 37.02 41.34 42.17
Solid phase 44.77 45.30 44.23 43.51 41.68 41.67

TABLE V. Molar percentage of constituents of the gaseous phase

Michelin Michelin Uniroyal Uniroyal Kleber Kleber


X XAs Wet Weather V 10 V ÎOGT

H 31.69 26.50 29.01 15.75 32.91 39.49


2
CH 54.88 53.25 54.61 63.84 56.60 46.98
4
C 10.06 12.72 11.89 14.90 7.18 . 10.99
2H4
C 2.54 4.38 3.51 3.96 2.75 2.12
2H6
C
3H8
- - - 0.06 - -
C 0.84 3.18 0.97 1.49 0.57 0.42
3H6
C
„ o H _ 0.18 _ _ _ _
4 8

TABLE VI. Weight percentages of the constituents of the liquid pha se


after pyrolysis at 450°C- 800°C

Michelin Michelín Uniroyal Uniroyal Kleber Kleber


X XAS-P Rallye Wet Weather V 10 V ÎOGT

Non-aromatic
c6c7 +
isoprene 0.04 0.07 0.06 0.05 - -
Octene 0.16 0.27 0.25 0.09 0.15 0.07
Benzene 42.07 34.43 41.51 30.42 41.89 33.93
Toluene 15.32 15.06 17.14 14.25 15.55 13.04
Ethylbenzene 2.84 3.95 3.52 3.28 2.88 2.61
m + p-xylenes 0.62 0.82 0.69 0.66 0.65 0.46
o-xylene 0.10 0.11 0.11 0.10 - 0.09
Styrene
(intermediate
fraction,
propylbenzene,
indane, indene,t
etc) 2.35 2.42 2.98 2.69 1.87 2.10
Naphthalene 12.67 11.69 10.72 12.96 11.19 14.17
Methyl-
naphthalenes
(diphenyl,
fluorene, etc) 12.97 14.59 9.79 15.85 10.10 12.29
Phenanthrene +
anthracene 5.59 5.38 3.92 5.62 5.04 5.89
Heavy fraction 1.41 8.47 5.74 9.52 7.32 12.41
218

TABLE VII. Comparison of various mass balances

Average over Average over Pyrolysis of a


6 pyrolyses 6 pyrolyses mixture of all 6
450-800°C 500-750cC tyres 500-750°C

Gaseous phase 17.16 lb.87 13.82


Liquid phase 39.31 39.02 39.23
Solid phase 43.53 45.11 46.95

Mixtures of tyres give approximately the same results as those


obtained for one type of tyre, as can be seen from Table VIII.
TABLE VIII. Comparison of the different phases obtained by pyrolysing
a mixture of 6_ tyres with that obtained from an average
of 6 pyrolyses of the same tyres

Analysis of the liquid phase as % of weight

C
3H6' C4H8' C
5H10
C
5 H 8 ' C 5 H 6 ' C 6 H 12
C 7 H 1 4 , Isoprene
Cyclohexadiene 4.10 3.59
Octene 1.88 2.06
Benzene 26.15 27.80
Toluene 17.27 17.81
Ethylbenzene 6.42
m-xylene + p-xylene 1.86 8.27
o-xylene 0.61 1.94
n-propylbenzene 0.11
Styrene 5.97 6.51
Ol -methylstyrene (unidentified) 2.34
Indane 2.42 3.23
Indene (unid.) 2.47 4.00
Methylindene (unid.) 1.35
Naphthalene 5.08 5.52
unid. 0.21
2-methylnaphthalene 2.66 2.72
1-methylnaphthalene 2.18 5.81
Diphenyl (unid.) 2.67
Acenaphthene (unid.) 2.62 4.71
Dibenzyl (unid.) 2.25
Fluorene (unid.) 2.91
Phenanthrene 2.37 2.25
m-phen., pyr., benzanth., H.F. 4.81 3.69

Analysis of the gaseous phase as a % of volume

H 21.05 22.37
2
CH 51.66 53.63
4
C 13.92 12.10
2H4
C 7.48 6.66
2H6
C 0.82 0.59
3H8
C 5.06 4.64
3H6
219

3. EXPLOITATION OF RESIDUAL CARBON

Carbon residue accounts for between 35% and 40% of the weight of a
pyrolysed tyre. Its minimum value is that of a good smokeless fuel, since
all the organic matter has been decomposed thermally and the combustion
fumes no longer contain tar.
We studied the adsorption properties of various types of residual
carbon obtained from tyre pyrolysis after they had been activated by steam
and so converted into active carbon. This is an excellent adsorbent and is
well known on the market as a purification medium. Its high price does,
however, make it unsuitable for large-scale use as a water purifier.
There is clearly an interesting potential in being able to convert 40%
of a particular type of waste, in this case the scrap tyre, into active
carbon.
Overall results are given in Figure 4, which shows isotherms of phenol
adsorption by carbon, where q represents the amount (in mgs) of phenol
adsorbed by a quantity g of carbon.
Activation is by steam heating at approximately 900°C. Activation time
is about 30 minutes. Under these conditions, the weight loss of carbon is of
the order of 30-40%. The test solution had a phenol concentration of
100 mg/1.
Some types of active carbon obtained from tyre pyrolysis (550, 600,
700°C) have adsorbent qualities which are very similar to those of
commercially-produced active carbon. Other types, obtained at pyrolysis
temperatures of between 450 and 500°C could also be used provided the higher
residual concentration of phenol is acceptable. Carbon produced by pyrolysis
could even be used "raw" for the pretreatment of heavily polluted water.
It will be seen from the isotherms that carbon obtained by pyrolysis
at 550°C is the best.
As far as abatement rates are concerned (Figure 5) , it will be seen
that in the case of high weight concentrations of active carbon (approxi-
mately 5 g ) , carbon obtained at 600°C adsorbs all molecules of phenol (rate
= 100%). For other types of carbon, the abatement rate is approximately 95%.
At lower concentrations (approximately 1 g) , carbon obtained at 500°C
adsorbs the most molecules (90%), followed by carbon obtained at 600°C and
700°C. Rates for carbon obtained at the latter two temperatures are of the
order of 75% to 85%.
In order to improve classification of the various types of active
carbon obtained, we also studied their adsorption properties vis-a-vis
methylene blue and iodine.
The solid phases used in these tests were obtained by steam or carbon
dioxide activation. Figures 6 and 7 show the adsorption capacity of these
types of carbon vis-à-vis methylene blue (curve a) and iodine (curve b ) , as
a function of activation time.
The specific surfaces of the various types of carbon derived from tyre
pyrolysis were measured both before and after activation. The specific
surface before activation, of the order of 60 m 2 /g, is the same whatever the
speed of pyrolysis. Steam activation creates specific surfaces of around
390 m 2 /g for slow pyrolysis and 290 m 2 /g for rapid pyrolysis.
To sum up, it can be said that this method, in which waste tyres are
used as a feedstock, produces oils with a high BTX content and carbon with
good adsorbent properties as a result of pyrolysis at a low temperature
(450°C) and simultaneous post-cracking at a high temperature (700 to 800°C).
Figure 8 shows the mass balance produced by treating one tonne of used
tyres.
220

Abatement rate
A Commercial
Β 550°
C 70O°
D 600°
E 500°
F 450°
G Non-active

Residual concentration

Amount of carbon (in g)


Fig. 4. Isotherm of phenol
adsorption by carbon
Fig. 5. Rate of phenol adsorption
by active carbon

Methyle Iodine
blue

100.

80 ■·

60 ·- .3

.. .2

20

10 15 20 min

Fig. 6. Steam activation Fig. 7. CO? activation


221

1 t TYRES

Pyrolysis Post­cracking
450­500°C 75O­80O°C

"2 3.8
CH4 O. 35
C 2 H„ 32
C H
2 6 18.6
c
3 20.1
Mise. 3.15

148

_^ LIGHT B 105.8
BTX 2 6 0 kg T 68.6
Χ 37.4
Sty. 24.4
Misc. 29.8

.HEAVY Naphth. 21.2


Phen. 18.0
1 3 2 kg

carbon 359
SOLID
steel 70
4 6 0 kg ash 31

Fig. 8. Mass balance produced from the pyrolysis of 1 t of used tyres

4. STRATEGY FOR THE COLLECTION OF WASTE TYRES

4.1 A vailability of Used Tyres

ICDI and TSIRA, working together on a temporary basis, carried out a


detailed study into the amounts of used tyres available in Belgium, and the
cost involved in collecting these. They considered the Charleroi region for
the purposes of the study.
This study, which cannot be described in detail here, concluded that
between 45 000 and 50 000 tonnes of scrap tyres are available each year in
Belgium. They are the main source of rubber waste. Table IX gives a very
approximate breakdown of the different ways in which this waste is used.
222

TABLE IX. Use of waste tyres

Retreading 20%
Ground feedstock 0.5%
Export 10%
Pyrolysis 0%
Artificial reefs 0%
Incineration 25 to 30%
Tipping + 35% (difference)
Regeneration 3%
Marginal users 5%

At least 65% of all waste tyres are incinerated or dumped.

Incineration

Incineration exploits the energy content of tyres. They have a


calorific value of between 6 000 and 9 000 Kcal/kg, and are thus ideal for
this purpose.
Free-air incineration is banned, but has in any case several obvious
drawbacks :

it produces large quantities of black, acrid and highly noxious smoke;


it produces high concentrations of SO;
the considerable calorific value of tyres is wasted.

The main pollutants produced by the combustion of tyres are sulphur


oxides, nitrogen, carbon, zinc, very fine "carbon black" dust (carbon black
is used to reinforce tyres), and condensed polyaromatic hydrocarbons, which
are carcinogenic.
Tyres are incinerated in furnaces specifically designed for the
purpose (types include LUCAS, UHDE, CEC-CEA, etc.). Conventional furnaces
can also be used if incineration plants are modified by means of scrubbers,
electrostatic dedusters, desulphurizers, etc. but appliances such as these
are expensive.

Tipping

In many countries, tipping is the most common form of waste tyre


disposal.
In Belgium, as in many other European countries, waste disposal sites
are becoming increasingly rare. Tyres cannot continue to be disposed of in
this way if the environment is to be protected. Because they are not
biodegradable, they simply accumulate. Tyre dumps constitute a fire hazard
and make the ground spongy and soft, thus creating problems if the site is
ever redeveloped. Rats proliferate in dumps which are either poorly covered
or left completely uncovered, and this clearly presents a health threat to
the general public.
As has been pointed out, tyres have a high calorific value. Tipping
does not exploit this potential energy, nor does it exploit the hydrocarbon
and carbon content of used tyres.
The cost of tipping varies according to the method used: a simple
tipping costs between Bfrs 300 and 400 per tonne, controlled tipping with
tyres shredded at the site costs Bfrs 2 500, and controlled tipping with the
tyres shredded before they are transported costs Bfrs 4 000.
223

4. 2 Cost of Collection

An evaluation was made both of the cost of collecting tyres in the


Charleroi area, and of the scrap tyre potential of the region.
Most used car tyres are located in the main distribution outlets for
new tyres. These are, in descending order of importance:

tyre specialists: 57%


garages, service stations and dealers: 30%
hypermarkets: 13%

Used lorry tyres are mainly found at the following places :

tyre specialists : 60%


end users (army, haulage firms, etc.): 35%
major distributors: 5-10%

ICDI carried out a detailed investigation into the cost of collecting


1 000 tonnes of used tyres per year in the Charleroi region. Collection is
carried out using Berliet Saviem refuse lorries with GDA skips with a
capacity of 20.4 m 3 . Normal manning costs are assumed. When all expenses are
taken into consideration, the total cost of collecting one tonne of used
tyres is approximately Bfrs 1 550 (1984 prices). This figure assumes that
used tyres can be taken away free of charge, and that there are no
collection fees.

The remaining tonnage treated at the plant comprises tyres which are
delivered to the treatment centre, and for which payment is made. This is
the system used for incineration. In 1984, the CBR cement works at Lixhe
paid Bfrs 600 for each tonne of tyres delivered to the plant. This figure is
much lower than that quoted above for specific collection (Bfrs 1 550 per
tonne) . In the case of incineration, it is not possible to increase this
price without making it economically unviable to use old tyres as fuel.
Higher prices can, however, be paid for pyrolysis, although these must still
remain well below the cost of collection if there is to be a real advantage.
It has been estimated that, on the basis of the Lixhe experience, 45% of
used tyres in the Charleroi region could be obtained for Bfrs 600 per tonne
delivered to the plant.
The ICDI study showed that collection price increases rapidly in
proportion to distance from the treatment plant, particularly since there
are much fewer tyres to be collected near the outer limits of the region
concerned.
The conclusions drawn by the ICDI led us to develop a new strategy for
the pyrolysis of used tyres. We do not think it reasonable to construct one
large plant in Belgium with an annual capacity of between 20 000 and 25 000
tonnes. (This figure corresponds more or less to the quantity of scrap tyres
which are not used for other purposes. ) Tyres would have to be collected
over long distances and the cost would soon become prohibitive. Moreover,
the need to guarantee the supply of tyres to the pyrolysis plant would leave
the plant in a weak position vis-à-vis collectors. The price of used tyres
would inevitably rise.
If, however, existing centres for the incineration of household refuse
were made to include small-scale, "sub-regional" units (i.e. units
corresponding to the amounts of used tyre waste produced by any one urban
area), this would constitute an extension of existing activities carried out
by such bodies. The collection of tyres would be carried out by the same
bodies responsible for collecting household waste.
224

5. 2 OOP TONNES PER YEAR PLANT

5.1 Description of the Plant

The tonnage of tyres available in the Charleroi region was used as a


basis for designing a 2 000 tonne per annum industrial plant to carry out
pyrolysis with simultaneous post-cracking. The plant design is illustrated
in Figure 9. The main element is the furnace, the design and dimensions of
which were drawn up by EUROFOUR. This consists of a conveyor belt within the
horizontal part of the oven, which is heated to between 450-500°C.
The tyres, which are left whole, are fed into a charging chamber,
which is kept free of air by circulating nitrogen. It is thus not necessary
to cut up the tyres. The estimated saving is between Bf rs 1 000 and 1 500
per tonne.
Depolymerization and primary cracking take place progressively.
Volatile material is entrained by the stream of nitrogen into the vertical
post-cracking furnace at 700-800°C, where olefins are converted into light
aromatics. The post-cracking furnace is heated by radiant tube burners
(automatic heat recuperators), which are fitted with fins. These can easily
be removed or replaced.
Gases are separated from oils in the condenser. Light oils are drawn
towards the top of the fractional condensation column, whilst heavy oils are
drawn to the bottom.
To sum up, this installation has the following features:

1. Whole-tyre feedstock, which cuts down on shredding or cutting costs.


2. Depolymerization and primary shredding by heating the tyres to between
450 and 500°C.
3. The aromatization of volatile products produced at low temperatures by
continuous and simultaneous post-cracking.

5.2 Investment and Running Costs

Investment will be of the order of Bfrs 31 million (1984 estimate),


divided up as follows :

1. Specific equipment for the plant, comprising the following:

Pyrolysis and post-cracking furnace;


Containers for solids;
Oil condensers ;
Compressors, vibrating separators and other
accessories.
22 370 000
2. Installation 800 000
3. Electricity 600 000
4. Miscellaneous (safety, civil engineering,
maintenance , engineering etc.) 6 980 000
TOTAL Bfrs 30 750 000

Running costs including personnel, supply of tyres, electricity and


nitrogen, have been estimated at approximately Bfrs 6 000 000 per annum
(1984 prices), or Bfrs 3 000 per tonne of tyres for a plant with a capacity
of 2 000 tonnes per annum.
The profitability study for this project was carried out by ACKERMANS
and VAN HAAREN - N.V. (Antwerp) . This concluded that small units for
treating used tyres by means of pyrolysis with simultaneous post-cracking
Tyre circuit —
Gas circuit _
Nitrogen circuit
Water c i r c u i t *.

Extractor ¡
pump
j Light aromatics
ι (200 1 barrel)
Production

Heavy o i l s
(200 1 barrel)

to
Ln
i»Water reject)
jWater
­ Water entry c i r c u i t
point )

Carbon Metal
con­ con­
tainer tainer
Fig. 9. Operating diagram
Industrial unit for the pyrolysis of used tyres with Production Production
simultaneous post­cracking. Capacity: 2000 t / a 780 t/a 140 t / a
226

(2 000 tonnes per annum capacity) would not only prove to be a profitable
investment, but would also solve a serious environmental problem.
If the hypotheses on which the operation of an industrial unit are
based can be shown to be realistic by the pilot plant, it could reasonably
be assumed that a considerable number of plants of this type might be
marketed both in Belgium and abroad.

6. GENERAL CONCLUSIONS

The following conclusions can be drawn from this study into the
pyrolysis of tyres with simultaneous post-cracking:

1. Originality of both the process and the prototype

The process is original because it enables the depolymerization of


rubber by thermal cracking and the aromatization of olefins thus produced to
take place in one stage and within the same plant. This produces high yields
of benzene, toluene and xylene (BTX), which have a higher market value than
heating fuel. The prototype as designed is also original, and the plant
could be built by companies from the Wallonia region: this is amply
demonstrated by the fact that EUROFOORS (Liège), after carrying out a
detailed technical study, drew up a cost estimate for a demonstration unit
with a capacity of 2 000 tonnes per annum.

2. Tyre pyrolysis: location strategy

The study into the cost of collecting used tyres shows that
expenditure increases rapidly in proportion to distance, and that a large
number of lorries and containers is needed if they are to be used solely for
this purpose. This is why the authors of the study believe that the
processing of used tyres must be carried out within existing structures for
the collection and treatment of urban waste.
The current collection capacity for the Charleroi region has been
estimated at 2 000 tonnes per annum. The tonnage of tyre waste that can be
treated by any one pyrolysis plant will depend on the size of the urban
centre which supplies it. Treatment capacity has been estimated at between 4
and 5 000 tonnes per year per million inhabitants.
We recommend that the idea of a single, large-capacity plant serving
an entire country or region, as has been proposed in the past, be abandoned.
A pyrolysis plant with a capacity of 40 to 50 000 tonnes per annum
creates a number of problems. Quite apart from the fact that the distances
to be covered within such a large region would drastically increase
collection and transport costs, there is also the danger that suppliers
might begin to speculate by stockpiling available tyres.
A large plant must be guaranteed regular supplies and would thus be
highly vulnerable to any manipulations in this supply. Furthermore, a large
plant requires a much greater level of investment and thus constitutes a
much higher financial risk for developers.
A large plant also needs the appropriate infrastructure, and since
this would have to be created from scratch, investment and running costs
would again be pushed up. We thus propose that the treatment of tyres be
integrated into existing regional and local centres (this solution could
also be adopted for other types of waste). This will effectively constitute
an extension of existing activities, and will mean that advantage can be
taken of the infrastructure and experience already to hand. It should be
emphasized that, under this scheme, the collection of tyres would be carried
out by bodies which are already highly experienced in the field of household
227

refuse collection. This does not, however, mean that this type of
installation would always have to be limited to small units. Indeed, these
could be of a considerable size where large centres of population are
concerned. It is clear that large urban centres such as Paris, London,
Tokyo, etc., represent a potential of tens of thousands of tonnes per annum.

3. Profitability

The difference between the price of crude and refined products is


between 80 and 100% in the case of benzols. For carbon, the difference
between the fuel price and the price of either carbon black or active carbon
varies by a factor of 1 to 10. Pyrolysis thus has enormous development
potential and will have a great impact on job creation within the treatment
plants themselves and within industrial undertakings wishing to develop
their activities or specialize. Initially, however, it would seem advisable
to stick to the collection of raw products separated into fractions which
are sufficiently differentiated to enable exploitation to take place. The
demand for, and price of, these raw products will help determine which
strategy should be adopted in order to optimize the exploitation of these
by-products.
A profitability study carried out by Ackermans and Van Haaren S.A.
(Antwerp) came to the following conclusions :

"Results of the profitability analysis show that small units for


treating used tyres by means of pyrolysis with simultaneous post-
cracking and having a capacity of 2 000 tonnes per annum would
represent a profitable investment and would also solve a serious
environmental problem."
"If the hypotheses on which the operation of an industrial unit are
based can be shown to be realistic by the pilot plant, it could
reasonably be assumed that a considerable number of plants of this
type might be marketed both in Belgium and abroad."

The report does, however, draw attention to the sensitivity of benzol


and oil prices to fluctuations in the price of oil.

4. Market

Two aspects must be considered here: firstly, the market for pyrolysis
products, and secondly, the market for the sale of pyrolysis plants. As far
as pyrolysis products are concerned, i.e. BTX and residual carbon, the
market is favourable. It has been estimated that the demand for benzene both
in Belgium and worldwide will continue to increase steadily. The price of
BTX varies according to the price of oil, because light aromatics are
obtained by the steam cracking of oil fractions. Marketable quantities of
BTX produced by tyre pyrolysis are small in comparison with those produced
by the petrochemical industry, and would therefore have little or no effect
on prices.
Carbon can fetch prices of up to 10 times its minimum value (based on
calorific value) when it is used as a reinforcing medium in the production
of tyres, or as active carbon used in water purification (high-quality
utilization). However, since there are currently insufficient quantities of
this type of carbon to enable industrial tests and demonstrations to be
carried out, it is not yet possible to say that it will sell on the market
without additional and specific processing being carried out for each
individual application.
228

As far as the sale of pyrolysis plants is concerned, it should be


possible to build four or five units in Wallonia and an equal number in the
north of the country and in Brussels. The export potential is considerable,
and the technology could be sold if it were shown that the chosen formula
(plants constructed on a decentralized basis and integrated into existing
waste treatment centres) were economically viable.

5. Economic and social benefits

One obvious advantage is that this process converts waste into


valuable raw materials. In doing so, it produces fuel and combustibles and
so results in an overall energy saving. This in turn means that less money
m u s t be spent on importing energy from abroad.
Integration of this process into existing waste treatment centres will
create new jobs within these centres and within those branches of industry
involved in exploiting the by-products obtained.

6. Ecological implications

One of the roles of waste treatment centres is to protect the


environment by eliminating waste. If used tyres can be disposed of in a
profitable way, numerous ecological benefits can be reaped at no extra cost.
The treatment of used tyres is receiving priority attention from the
Commission of the European Communities in the context of environmental
protection. This project is thus entirely appropriate in the light of the
Commission's current concerns.

7. usefulness of a semi-industrial pilot plant

The process as a whole must be tested at pilot level in order to


ensure that all component parts work at optimum efficiency. A pilot plant
will also serve to establish yields and will ensure that products are
generated in sufficient quantity to be of use to industrial operators.
The pilot plant could provide a number of useful services once the
development phase comes to an end: it could be used for training personnel
from other treatment centres wishing to acquire a similar unit, or for
carrying out research into the pyrolysis of wastes other than tyres (plastic
material, wood, etc.). The existence of a training unit for personnel
employed in businesses who wanted to purchase such a plant would be
extremely useful for promoting the method on a commercial basis .

REFERENCES

(1) WILLIAMS, Philos. Trans. Roy. Soc. London. Ser. A 1 5 0 , 241 (1860).
(2) STANDINGER and FRITSCHI, Helv. Chim. Acta, 5, 758 (1922).
(3) STANDINGER and GEIGER, Helv. Chim. Acta, 9, 549 (1946).
(4) MIDGLEY and HENNE, J. Amer. Chem. S o c , 26, 1215 (1929).
(5) KATO and SOMESHIMA, J. Soc. Chem. Ind. Japan, 3 8 , 596 (1935).
(6) O R O , HAN and ZLATKIS, Anal. Chemist., 39, 27 (1967).
(7) TANATA and GOMYO, Japan, Kokai 7438, 895 (CI. 14 E 331, 13(9) F2) 11
Apr. 1 9 7 4 , Appli. 7281, 419, 16 Aug. 1972.
(8) JO and YODA (Nippon Zeon C o , L t d ) . Japan Kokai 7 4 , 102, 595 (Cl. 14 E
331, I, 12(9)F2, 91 C 9 1 ) , 17 Sep. 1974, Appli. 73 1 4 , 588, 05 Feb.
1973.
(9) SONGA, G e r . Offen., 2, 3 2 8 , 400 (Cl. c 01b) 20 Jan. 1974.
(10) ISHIBASHI, NODA and TERADA, Japan Kokai 7545, 799 (Cl. C O I B , B O I D ) , 24
Apr. 1975, Appli. 7396, 413, 27 Aug. 1973.
229

(11) KUDO, Japan Kokai 7575, 593 (CI. COIB, BOID), 20 Jan. 1975, Appli. 73
126, 013, 09 Nov. 1973.
(12) R. CYPRES and B. BETTENS, "Traitement pyrolytique des déchets de
caoutchouc". Ann. des Mines de Belgique, 10, 873-890, 1981.
(13) Convention Region Wallonne-Association Momentanée ICDI-TSIRA, "Faisa-
bilité de petites unités de pyrolyse de pneus usagés avec postcraquage
simultané", 171 pp, 1984.
(14) R. CYPRES and C. BRAEKMAN-DANHEUX, "Processus d'aromatisation dans la
formation des goudrons de haute température". Ann. des Mines de
Belgique, 11, 1109-1115, 1974.
(15) R. CYPRES, C. BRAEKMAN-DANHEUX, R. DERIE and M. BERKOL, "Aromatisation
of a C 4 alkane/alkene/hydrogen mixture obtained by catalytic dehydro-
genation of isobutane". J. Anal. Appi. Pyrol., 1, 339-246, 1980.
(16) R. CYPRES, "Aromatic hydrocarbons formation during coal pyrolysis",
Fuel Process. Technol., 15, 1-15, 1987.
(17) MADORSKY, "Thermal Degradation of Organic Polymers", p. 219, Inter-
science (1969) .
(18) WEIZMANN, BERGMANN, HIGGETT, STEINER and SALZBACHER, Ind. Eng. Chem.
43, 2312-18 (1951).
(19) BREDAEL P., Ann. Mines Belgique, 12, 1045, 1975.
(20) BENSON and HAUGEN, J. of Phys. Chem., 71, 6, 1967.

ACKNOWLEDGEMENTS

We should like to thank Miss GILLET and Mr PILATI, engineers at the


ICDI and TSIRA respectively, for their contribution in drawing up the
feasibility study.
We should also like to thank the Wallonia region and Minister BUSQUIN
for the financial support which was granted to TSIRA and ICDI for the
purpose of carrying out this feasibility study.
230

CHEMICALS FROM ALMOND SHELLS BY PYROLYSIS IN FLUIDIZED BED

R. Font, A. Marcilla, E. Verdú and J. Devesa


División de Ingeniería Química. Universidad de Alicante. Spain

Summary

Flash pyrolysis of almond shells at moderate and high temperatures


in a fluidized bed reactor and an Analytical Flash Pyrolysis A pparatus
(Pyroprobe 100) have been studied, with almond shells non­impregnated
and impregnated with inorganic chemicals. The A nalytical Flash Pyro­
lysis A pparatus was used for screening of catalysts and selecting
operation conditions. A t moderate temperatures, the yields of the
following fractions and chemicals have been obtained: solid, liquids
(water, methanol, formaldehyde, acetone, 2­propanol, acetic acid,
hydroxyacetone, propionic acid, 3­methyl­l­butanol, 2­furaldehyde,
dry residue at 120 sc, gases ( CO , CO, CH , H ). At high temperatures
the gases analyzed have been the following: H , CO, CO , CH ,
C H , C H , C H , C H , C ­hydrocarbons. The greatest yields (,Λ.%
basis) obtained in the different operating conditions in the fluidized
bed reactor have been the following: A ) A t temperature range 440­
610 ­C, pyrolyzing almond shells (without impregnation): 1056 acetic
acid; 1.8% hydroxyacetone; 1.0% l­hydroxy­2­butanone; 0.7% 2­furalde­
hyde; 1.0% methanol+formadehyde. B) A t temperature range 470­610
-C, pyrolyzing almond shells impregnated with CoCl (14.1% g
CoCl /total g ) : 7.0% acetic acid, 7.0% 2­furaldehyde, 0.6% methanol +
formaldehyde. C) At high temperature (820­900 2 C) pyrolysis of almond
shells (without impregnation): 30% CO, 16% CO, 5.7 % CH, 2.8%
C 0.8% H , 1.0% C Η , 0.7% C H . Recovery ofXoCl from the char ­
2H4'
as also Been studied. Kinetic expressions for the pyroly­
coal formed
sis of almond shells non­impregnated and impregnated with CoCl, have
also been deduced.

1. INTRODUCTION
Pyrolysis is one of the alternatives to be considered for conversion
of biomass to activated carbon, fuels and chemicals. Pyrolysis processes
of biomass at moderate temperatures (380­600 a C) yield a pyrolytic oil
which is a mixture of organic chemicals with water, a low BTU gas and char­
coal. Flash pyrolysis of lignocellulosic materials leads to an increase
in the amount of liquids produced.
High temperature (>700 9 C) flash pyrolysis of biomass yields a mixture
of gases: carbon oxides, hydrogen and light hydrocarbons. Flash pyrolysis
can be achieved discharging the biomass on a hot sand fluidized bed
reactor.
The process of biomass decomposition occurs via both primary and se­
condary reactions. By selecting the operating conditions (temperature,
heat transfer and residence time of volatiles), it is possible either to
accelerate or to slow down the different reactions involved in the process,
according to their apparent activation energy. Using catalysts is another
way to change the most favourable reaction paths.
Catalysts may be classified as primary or secondary. Primary catalysts
231

act on the primary reactions (directly from biomass). Secondary catalysts


have their effect on the products of the primary reactions (carbon, vola­
tiles).
A research of the pyrolysis of almond shells (an abundant and readily
available agricultural byproduct in the area) is being carried out at the
Chemical Engineering Division of the A licante University. The scope of
this investigation is to study the chemical products which can be produced
at moderate and high temperatures from the almond shells,non­impregnated
and impregnated with chemical compounds.

2. EXPERIMENTAL SECTION
Almond shells were washed, dried, crushed and sieved to obtain a uni­
form material. The almond shells composition (wt%) is the following: 29%
cellulose, 19% hemicellulose, 51% lignin, 0.2% ash (d : 0.297­0.500 mm).
Calcinated sand, at 900 2 C was used as an inert bed in the fluidized
bed reactor (see references 1, 2, 3 ) . Pyrolysis in the experimental system
was run as follows: First, a dried almond shells sample of the selected
particle size was placed in the feed hopper. The inert gas flow (from an
industrial Ν source) was set and the oven switched on. Once the reactor
reached the selected temperature, the feeding valve was opened and the
sample fell into the sand bed fluidized reactor.
In order to carry out the experiments at moderate temperature with
almond shells impregnated with CoCl , the samples were prepared as follows:
Five batches of 60 g of almond shells mixed with catalysts solutions of
known concentrations were prepared in a "rotavapor" Buchi, providing agita­
tion and a 60 mmHg vacumm for 2 hours. Afterwards, the samples were dried
at 110 9 C for 20 hours. Once the five samples were prepared, they were
mixed well.
In addition, an A nalytical Flash Pyrolysis A pparatus (Pyroprobe 100)
was used for catalyst screening (nominal heating rate 20 s C/ms).
Analytical methods and more details of the equipment and procedure
used can be found elsewhere (1, 2, 3 ) .

3. EXPERIMENTAL RESULTS AND CONCLUSIONS


A. MODERATE TEMPERATURE. NON­IMPREGNATED A LMOND SHELLS
Table I shows the overall yields obtained in the experiments carried
out between 365 and 710 a C. The residence time of the vapours inside the
fluidized bed is considered lower than 0.5 s, and the residence time of
the vapours inside the reactor on the sand bed is around 3 s. The heating
rate, according to Scott and Piskorz (4) is about 500 s C/s.
Liquid fractions present a maximum within the 420­610 S C temperature
range, decreasing from 610 S C due to their cracking and reforming. The
high yields in liquids obtained (about 65% dry basis) are similar to those
obtained by other researchers (5, 6 ,7).
The acetic acid yield is around 10% (dry basis) within the 440­610
a
C temperature range. This yield is significantly higher than those report­
ed by other authors working with other biomasses, typically around 7% from
hardwood and 7.84% from beechwood (5 ,8).
A kinetic study has also been carried out (3). Two schemes of reac­
tions have been considered:

Scheme I (biomass, Β) » a(gases, G)+b(liquids, L)+c(solids, S)


1
w gases, G
Scheme II (biomass, Β)^­2­^liquids, L (g)
^"^ solids, S
232

Assuming first-order reactions, it has been tested that similar expre-


ssions can be obtained from both schemes.
On considering the expresions deduced, the correlation of the yields
of the total of the gases, the total of the liquids and the solid residue
to the schemes suggested is good. The expressions obtained for the kinetic
constants in the 400-460 *C temperature range are the following:

k = 7.11.107exp(-32.0/RT) s _ 1
k = 1.49.108exp(-35.1/RT) s" 1
k = 14.73exp(-10.8/RT) s-1 (R in Kcal/molsK)

B. MODERATE TEMPERATURE. ALMOND SHELLS IMPREGNATED WITH CoCl


Samples of almond shells impregnated with different catalysts have
been pyrolyzed in an Analytical Flash Pyrolysis Apparatus (AFPA) at 440
a
C. From previous results (1), it was concluded that AFPA was a suitable
device for experiments to select catalysts and operating conditions. Diffe-
rent catalysts have been tested: KCl, NaCl, BaCl , CaCl , CdCl , MnCl ,
CoCl , CuCl , NiCl , CrCl and NaOH, NiSO , CoSO . An increase in 2-furalcfe
hyde yield can be observed when increasing the acidity of the cation. A re^
markable increase was obtained for the cations of intermediate acidity Cd ,
Mn and Co . An increase of hydroxyacetone yield with respect to non-ca-
talytic pyrolysis of almond shells was observed with NaOH (basic catalyst).
From the screening carried out, three catalysts (NaOH, MnCl and
CoCl ) were selected for study the influence of the catalyst to almond
shells ratio, using the AFPA. An increase of some yields has been observed
when increasing the amount of catalyst impregnated at 440 2 C. With NaOH
(3.7 g of NaOH/100 total g of almond shells+NaOH), the yield of hydroxyace-
tone is 1.3%. With MnCl (14 g MnCl /100 total g) and with CoCl (13.5
g/100 total g ) , the yields of acetic acid and 2-furaldehyde are about 7-
8%.
CoCl was selected for the study of the pyrolysis in the fluidized bed
reactor, Because this catalyst allowed a better control of the homogeneity
of the impregnation step due to the blue color acquired by the dried almond
shells impregnated previously with CoCl .
Table II shows the results obtainea in a series of experiments carried
out at 500 2 C in a fluidized bed reactor and with different catalyst to
almond shells ratios, including the results corresponding to almond shells
without catalyst.
A similar variation of the composition of the liquids obtained, compa-
red to that obtained in the test of catalyst selection can be noted. Acetic
acid yield was around 7% when using CoCl , as compared with 9.8% when pyro-
lyzing without catalyst. On the other hand, 2-furaldehyde yields increased
up to 7.5% (at 14.1% of CoCl ) when increasing the catalyst to almond
shells ratio, as compared to 0.57% when no CoCl was used. Due to this,
the amount of organic liquids analyzed increased up to 16.9% when almond
shells were impregnated with 14.1% of CoCl .
A slight increase in the water yield due to the presence of CoCl
can also be noticed, although this yield remains almost constant when in-
creasing the catalyst/almond shells ratio. With respect to the rest of
the components analyzed, the absence of compounds such as acetaldehyde,
hydroxyacetone, isoamyl alcohol and l-hydroxy-2-butanone, and an increase
in the yields of methanol+formaldehyde, acetone, 2-propanol and propionic
acid, are notable when pyrolyzing with 14.1% of CoCl .
This liquid distribution is typical of the acidic catalysts, since
the latter favour the dehydration reaction versus the fission reactions
233

(10). Furthermore, we observed a decrease in tar yields (dry residue at


120 ? C ) , which is also typical of this type of catalysts (11, 12).
With regard to the gases, no significant variation in the composition
of the gas obatined was observed. Nevertheless, a decrease in the yield
of gases as well as an increase in the solid residue yield can be noted.
In order to study the influence of the temperature a series of experi­
ments at 410, 425, 445, 470, 500 and 610 = c was carried out with almond
shells impregnated with 14.1% of CoCl . Table III shows the operating con­
ditions and the results obtained in this series of experiments. The follow­
ing can be observed:
­ A decrease in solid residue occurs when the temperature is
increased, but the drop is not as marked as that observed when pyrolyzing
without catalyst (1). This fact may be due to two opposing effects. On
one hand, the solid decomposition occurs to a greater extent when the tem­
perature is increased but the presence of CoCl favours the reactions of
condensation leading to the formation of carbon flO).
The liquid fraction remains almost constant within the 425­610 S C
temperature range, probably due to the fact that the primary reactions
are almost completed, and to the small residence time which produces almost
no decomposition of the condensable volatiles.
With respect to the liquids analyzed, it can be observed that the
yield of acetic acid decreases by 30% at 500 sc when using CoCl , whereas
the yield of 2­furaldehyde increases up to 1000% within the 425­610 S C
temperature range, when using CoCl . Thus, when pyrolyzing almond shells
impregnated with CoCl at 500 *C it is possible to obtain a yield of acetic
acid around 7.2%. This is similar to values obtained by other researchers
working with other biomass without catalyst. Goldstein (8) reported around
7% from hard wood while Beaumont and Schwob (5) obtained around 7.84% from
beech hardwood. In addition, a yield of 7.5% of 2­furaldehyde, which is
very high for a pyrolytic process and similar to that obtained by the con­
ventional methods used for obtaining this compound by acid hydrolysis of
lignocellulosic materials can be obtained by using CoCl as catalyst.
Total recovery of the CoCl , from the charcoal formed at 445 sc, is
achieved by extraction with a solution of HCl under the following condi­
tions: concentration of HCl lmol/L, extraction time 17 h, ratio g extrac­
tant solution/g charcoal 33 and temperature 46 sc.
From the kinetic study carried out in the 410­500 ? C temperature ran­
ge, with almond shells impregnated with CoCl (14.1%), the following ex­
pressions for the first­order reactions of tne scheme II previously pre­
sented have been obtained:
k =8.93exp(­13.29/RT) s _ 1
k2=0.097exp(­4.28/RT) s ­ 1
k3=0.0055 s­1 (R in kcal/molSK)

C. HIGH TEMPERATURE. ALMOND SHELLS NO IMPREGNA TED


By high temperature pyrolysis around 820­900 =C the following yields
(% weight) have been obtained (2): 0.7­ 1.6%H , 25­46% CO , 15­28% CO ,
5­8.6% C H , 0.7­0.8% C H , 2.3­4.2%C Η , 0.06­0.09% C H , 0.9­1.2% C­H^,
6
0.3­0.5% C ^ 2 , 0.44­0.60% ^­hydrocarbons* 47. 5­88.0% Tolal gas.
Most of the gas produced is formed by secondary reactions correspond­
ing to the cracking of tars in the hot zone of the reactor on the fluidized
sand bed (residence time of volatiles around 1­2 s ) .
On the other hand, by pyrolysis of the dry residue at 890 sc (obtained
from the tar produced in the pyrolysis of almond shells at 610 sc, by dis­
tillation up to 120 sc), the following yields in gaseous products are ob­
Table I.
Constant temperature pyrolysis results

Temperature 365 400 420 425 440 440 460 495 495 495 610 710
Solids 69.2 54.2 47.0 46.8 29.4 30.6 27.5 26.4 26.3 26.4 11.3 6.7
Liquids 21.1 36.3 41.4 41.6 57.0 52.0 56.0 58.5 57.2 59.3 65.1 43.2
acetic acid 0.42 3.2 3.5 4.0 10.3 9.0 9.0 10.0 9.6 9.9 10.4 7.7
2-furaldehyde 0.77 0.045 0.46 0.5b 0.91 0.64 0.67 0.75 0.57 0.40 0.85 0.67
water 10.6 16.6 16.4 16.7 18.7 16.4 17.7 16.7 17.7 16.7 16.5 14.2

methanol+formaldehyde 0.33 1.4 1.0 1.5 0.92 1.3 1.1 0.56 1.1 1.2 0.70 0.58
acetone 0.04 0.06* 0.14* 0.16* 0.12 0.26 0.25 0.08 0.07 0.06 0.25 0.17
2-propanol 0.01 - - - 0.06 0.18 0.33 0.05 0.06 0.04 _ 0.04
hydroxyacetone 0.79 0.88 0.92 0.85 2.1 1.4 1.5 1.9 1.9 1.7 1.8 1.4
l-hydroxy-2-butanone 0.59 0.40 0.52 0.50 1.1 1.1 1.2 1.4 1.3 1.2 1.3 0.66
3-methyl-l-butanol 0.67 0.26 0.33 0.41 0.44 0.77 0.81 0.41 0.90 0.78 0.46 0.22
propionic acid - 0.10 0.13 0.15 0.49 0.28 0.33 0.10 0.17 0.15 0.18 0.26
acetaldehyde - - - - 0.06 - 0.01 0.10 0.21 0.24 0.10 0.16
dry residue at 120 2C 7.9 13.0 18.0 16.4 24.1 20.6 22.3 27.0 23.0 26.1 34.5 18.1
Gases 5.3 8.1 8.3 8.6 13.1 13.3 14.2 14.4 15.7 14.3 22.9 53.2
CO 4.4 6.0 4.8 4.9 9.0 9.0 9.9 10.2 10.3 10.0 10.6 13.3
CO 0.90 1.9 2.9 3.1 3.8 3.7 3.6 3.6 4.7 3.8 10.7 34.5
CH
4 0.04 0.13 0.36 0.44 0.37 0.47 0.61 0.61 0.70 0.50 1.6 5.4
H
2 - 0.09 0.15 0.15 - 0.09 0.10 - - - - 0.23
Total
95.6 97.3 96.7 95.1 99.6 95.9 97.7 99.2 99.2 100 99.2 103

*acetone+2-propanol
Tables IIII
Influence of the CoCl to almond shells ratio. Yields (wt%) on moisture free almond shell

Catalyst - CoCl (3.0%) CoCl 2 (6.4%) CoCl, (14.1%)


C

temperature 495 500 500 500


Solids 26.4 28.1 37.9 41.3
Liquids 58.3 54.6 45.9 46.1
Major compounds
acetic acid 9.8 7.4 6.5 7.2
2-furaldenyde 0.57 3.3 5.2 7.5
water 17.0 23.6 21.1 23.2
Minor compounds
methanol+formaldehyde 0.95 0.50 0.70 1.4
acetone 0.07 0.36 0.15 0.19 to
2-propanol 0.05 0.78 0.37 0.17
hydroxyacetone 1.8 - - -
l-hydroxy-2-butanone 1.3 - - -
3-methyl-1-butanol 0.69 0.04 - -
propionic acid 0.14 0.13 0.13 0.42
acetaldehyde 0.18 - - -
dry residue at 120°C 25.4 15.4 11.7 5.7
2-furaldehyde yield/added cation mol - 143 106 69.2
Gases 14.8 13.9 12.7 12.4
CO- 10.2 9.1 8.1 9.3
CO2 4.0 4.0 4.1 2.4
CH4 0.60 0.80 0.54 0.60

Total 99.5 96.6 96.5 99.8


Table III
Influence of the temperature on the pyrolysis of almond shells impregnated with 14.1% of CoCl . Yields
(wt%) on moisture free almond shells. Fluidized bed reactor.

Temperature (aC) 410 425 445 470 500 610


Solids 57.0 46.3 45.2 44.7 41.3 24.8
Liquids 34.6 42.8 42.3 42.1 46.1 42.8
Major compounds
acetic acid 3.7 5.8 5.5 5.5 7.2 6.4
2-furaldenyde 6.1 7.7 6.9 6.9 7.5 7.2
water 19.4 22.7 23.2 24.2 23.2 21.5
Minor compounds
methanol+formaidenyde 0.61 1.3 1.0 0.69 1.4 0.34
acetone - 0.13 0.14* 0.18 0.19 0.24
2-propanol - 0.07 - 0.08 0.17 0.35 to
hydroxyacetone - - - - - - σ\
l-hydroxy-2-butanone - - - - - -
3-methyl-l-butanol - - 0.09 - - -
propionic acid - - - 0.07 0.42 0.44
acetaldehyde - - - - - -
dry residue at 120SC 4.8 5.1 4.2 4.5 5.7 6.3
Gases 4.4 6.7 7.5 7.7 12.4 26.7
CO 4.1 5.3 5.0 4.8 9.3 17.5
CO 0.23 1.1 2.0 2.3 2.4 7.8
0.05 0.33 0.41 0.45 0.60 0.86
H 0.03 0.02 0.09 0.14 0.16 0.55
2
Total 96.0 95.8 95.0 04.5 99.8 94.3

*acetone+2-propanol
237

tained: 0.88% Η , 20.9% CO, 22.8% CO , 6.1% CH , 0.37% C H , 3.0% C H ,


0.02% C H , 0.37% C H , 0.18% C Η and 0.1% C ­hydrocarbons. These yields
are expressed in wt% on a dry residue basis.
In order to study the influence of different catalysts on the hydro­
carbon yields from high temperature pyrolysis, a set of experiments with
almond shells impregnated with different organic chemicals (NaOH, NaCl,
KCl, CaCl , BaCl , MnCl , ZnCl , CuCl , NiCl , CoCl , CrCl , NiS0 4 ) were
carried out using the A TPA '(Pyroprobe 100) at 850 ?C (2). A general de­
crease can be observed in hydrocarbon yields with respect to the pyrolysis
of almond shells without catalysts. On the other hand, no significant chan­
ge has been observed in the composition of the hydrocarbons.

REFERENCES

(1) Font, R., Marcilla, Α., Verdú, E. and Devesa, J. (1986) Fluidized­
Bed Flash Pyrolysis of Almond Shells. Temperature Influence and Cata­
lyst Screening. Ind. Eng. Chem. Prod. Res. Dev., 25, 491.
(2) Font, R., Marcilla, Α., Devesa, J and Verdú, E. (1988) Gaseous Hydro­
carbons from Flash Pyrolysis of A lmond Shells. Ind. Eng. Chem. Res.
27, 1143.
(3) Verdú, E. (1988) Thesis Dissertation. Pirólisis de Cascara de Almendra.
Universidad de Alicante.
(4) Scott, D.S. and Piskorz, J. (1984)The Continuous Flash Pyrolysis of Bio
mass. Can. J. Chem. Eng., 62, 404.
(5) Beaumont, 0. and Schwob, Y. (1984) Influence of Physical and Chemical Pa
rameters on Wood Pyrolysis. Ind. Eng. Chem. Process Des. Dev. 23, 6377
(6) Finney, C S . and Garret D.E. (1974) Flash Pyrolysis of Solid Wastes. E
nergy Sources, 1, 295.
(7) Sass, A. (1974) Garret's Coal Pyrolysis Process. Chem. Eng. Prog., 70,
72.
(8) Goldstein, I.S. (1981) Organic Chemicals from Biomass. CRC. Boca Raton
Fl., Chapter 5.
(9) Thurner, F. and Mann, U. (1981) Kinetics Investigation of Wood Pyroly­
sis, Ind. Eng. Chem. Process Des. Dev., 20, 482.
(10) Shafizadeh, F. (1975) Industrial Pyrolysis of Cellulosic Materials, Ap
plied Polymer Symposium, John Wiley & Sons, 28, 153.
(11) Smicek, S. and Cerny, C.T. (1970) Active Carbon, Elsevier Pubi. Co.,
Amsterdam.
(12) Gray, M.R., Corcoran W.H. and Gavalas, G.R. (1985) Pyrolysis of a Wood
Derived Material. Effects of Moisture and Ash Content, Ind. Eng. Chem.
Process Des. Dev., 24, 646.
238

BIOMASS PYROLYSIS IN MOLTEN SALTS FOR FUEL


PRODUCTION

J.K.Maund and D.M.Earp


Department of Chemical Engineering & Applied Chemistry,
Aston University, Birmingham, B4 7ET, United Kingdom.

SUMMARY
Molten alkali metal salts are recognised as having considerable potential as
high temperature liquid phase media lor the pyrolysis, gasification,
combustion and catalytic conversion of organic chemicals. A two litre
capacity molten salt system for the pyrolysis of biomass is described. The
heating rate of wood, in both air and molten salt, has been studied and
compared, and has been found to be between four and ten times faster in
molten salt. The pyrolysis of wood in both molten Li/Na/K carbonate and
Na/K hydroxide eutectics has been studied and the results of these studies
are presented. The hydroxide melt system is favoured as it produces good
purity hydrogen. However, the melt system becomes contaminated with
carbonate and organic residues and the hydroxide, being consumed,
requires regeneration; preliminary studies indicate this to be feasible.

1. INTRODUCTION
Molten salt processes are already well established, particularly in the
metallurgical industry, where they are used for thermochemical and heat
treatment and for cleaning (1). More recently, molten alkali metal salts, in
particular, have been recognised as having considerable potential as high
temperature, liquid phase media for the pyrolysis, gasification, combustion, or
catalytic conversion of organic materials such as biomass, coal and a variety of
waste products. A number of examples, from laboratory scale to demonstration
plants, have been developed throughout the world for coal gasification (2)(3)(4);
biomass and waste gasification (5) and combustion (6); and plastics pyrolysis (7).
Fused metal salts as reaction media for the thermal conversion of biomass
have a number of advantages over conventional gas phase processes:
(i) Chemical stability in the liquid phase at temperatures up to 1000°C;
(ii) Appropriate physical properties of high thermal conductivity, low
viscosity, low volatility, and appropriate melting point temperature;
(iii)The ability to dissolve biomass into the liquid phase, so that heat and
mass transfer become homogeneous and, therefore, very rapid;
(iv)The possibility of homogeneous catalysis or chemical reaction to control
the chemical composition of the products.
The Department of Chemical Engineering and Applied Chemistry at Aston
University has been carrying out a 2-year contract with the European Community
continuing its research into thermal processing of biomass in molten salts (8)(9).
This paper summarises the experimental work performed to date within the
contract . Molten salt processing has been studied for some ten years in the
Department, and biomass conversion for almost as long, with the thermochemical
processing of biomass in molten salts first being studied in 1980 (10).
239

2. EXPERIMENTAL EQUIPMENT
The experimental equipment has been described in detail before (11)(12). It
consists of a two litre capacity stirred tank reactor into which the biomass is fed by
a sealed laboratory scale screw feeder. Vapour leaving the reactor is cooled by
water-cooled heat exchangers which condense the liquid products, which are
then collected for analysis. The product gas is burned in a flare. The reactor is
heated by a purpose built 3 kW electric resistance furnace, with a three-term
electronic temperature controller.
The product gas composition is continuously monitored for H2, CO, CO2 and
CH4 using dedicated gas analysers and recorded, at about 10 second intervals,
by a micro-computer based data-logger, developed within the Department for
use with an open-core downdraft gasifier (13). Reactor pressure is measured
using a water manometer, product gas flowrate by rotameter and total volume of
gas produced by gas meter; these variables, along with the temperature of the
salt bath, are recorded manually.
To prevent the ingress of air into the system and to provide a 'carrier' for the
gas analysis system, the rig is operated with a nitrogen purge. This purge is
introduced at three points, the stirrer, the feeder and the reactor, the flow of each
being metered separately.

3. EXPERIMENTAL WORK
The experimental work so far performed has covered three main areas,
particle heating rate tests, pyrolysis in the molten lithium/potassium/sodium
carbonate eutectic and pyrolysis in the potassium/sodium hydroxide eutectic.

3.1 Heating Rate


Before the experimental rig was finally piped up and closed, a number of
experiments were carried out, firstly to commission the furnace and its
temperature controller, and secondly to investigate the heating rate of wooden
dowels of different sizes in molten salts at different temperatures and to compare
these with rates in air at the same temperatures. These experiments were to
enable the relative heat transfer characteristics of the two media to be evaluated.
In order to obtain a reasonable range of temperatures for this work, the
sodium/potassium hydroxide eutectic (51 mole % KOH/49 mole % NaOH, melting
point 193°C) was used, allowing a temperature range of 250 to 500°C. However,
because of the risk of combustion the runs in air were only performed at 250°C.
Dowels of 6, 9,12,15 and 22 mm diameter were used, each cut to a length equal
to its diameter. The temperature at the centre of the dowel was monitored by
drilling a small hole into the centre and fitting it with a chromel/alumel type
thermocouple. The temperature history was recorded using the data logging
system at frequencies of up to two readings per second. When the dowel
temperature had reached the furnace control temperature, it was removed from
the furnace.

3.2 Pyrolysis In Molten Alkali Carbonate Eutectic


For the initial pyrolysis runs, it was decided to employ the Li/Na/K carbonate
eutectic (43.5 mole % IJ2CO3/31.5 mole % Na2CO3/25.0 mole % K2CO3, melting
point 397°C) as this was both non-corrosive and had been used successfully in
tyre and plastics pyrolysis at Aston (14)(15). A salt temperature of 500 °C was
chosen,as this was the midpoint for the proposed experimental programme range
(12). To prevent "overloading" of the melt, a low feed rate was selected. This was
initially about 8.4 g/min continuous feeding, although due to operational
240

difficulties (see Section 4), was later reduced to a rate of 4.9 g/min in one minute
cycles (1 minute on/1 minute off). The feed material used consisted of in-house
manufactured pine 'chips' (without bark) sieved to the size range 0 to 4.75 mm.

3.3 Pyrolysis In Hydroxide Eutectic


As a result of difficulties encountered with the carbonate eutectic (see
Section 4), it was decided to employ an alternative salt system. Previous
experience at Aston (15) and simple solubility tests indicated that the K/NaOH
eutectic, as used in the heating rate experiments (see Section 3.1 above), was a
solvent for wood, so it was decided to employ this salt. The bath temperature was
set at 300°C. This temperature was chosen as it was about the midpoint of the
solubility range for wood, this range of temperatures having been identified in a
series of simple solubility tests. A low feed rate of 4.9 g/min was selected in
order to prevent "overloading" of the salt, with the feeder being operated both
continuously and semi-continuously, as in the carbonate runs. The same feed
material as for the carbonate runs was employed.

4. RESULTS AND DISCUSSION

4.1 Heating Rate


A summary of the results of the heating rate work is presented in Figure 1.
These show that the particle heating rate in the molten salt was, as anticipated,
more rapid than in a gaseous environment. The heating rates measured in
molten salt were between four and ten times faster than those measured in air.
This is in close agreement with the results of Tada and Yasunishi (16)(17) of
Tottori University. It was also observed that in the alkaline melt the cellulose core
of the wood was dissolved leaving a honeycomb-like structure of lignin.

4.2 Pyrolysis in Molten Alkali Carbonate Eutectic


Each run performed with this system had to be terminated after
approximately 20 minutes due to a 'back-up' of feed in the feed inlet pipe up to
the feeder. On each occasion when the rig was stripped down after a run, it was
found that the surface of the melt was covered in a layer of char. On top of this
char layer there were layers of progressively less pyrolysed feed, until in the
feeder tube itself, fresh unreacted feed was found. Initially, it was felt that either
the feed rate was too high for the salt system and was therefore 'overloading' the
melt or there was insufficient agitation to provide adequate mixing of the salt and
feed. However, when these problems persisted at high agitation rates and low
feed rates, it was concluded that the molten salt was merely acting as a heat sink
causing the biomass to undergo conventional pyrolysis without any solution. This
theory was supported by simple solubility tests. Calculations based on previous
pyrolysis work at Aston (19) indicated that both the rate of pyrolysis and particle
heating rate were rapid at the conditions prevailing in the reactor.
It was decided that the carbonate salt system was unsuitable for the present
reactor arrangement when operating in the pyrolysis mode. However, it was
concluded that it could be operated as a gasifier, but such a study does not lie
within the scope of this project.
241

10°

15 mm Air
• 15 mm Salt
A 12 mm Salt

10 u
20 40 60 80 100
% Ultimate Temperature

Figure 1 Dowel Heating Times in Air and Molten Salt


The products formed in the runs using the carbonate melt system were
typical of conventional pyrolysis and, as well as the char consisted of:
a thick smoke of fine tar particles. This was difficult to condense and to
disentrain from the gas stream. However, some was disengaged from the
gas, both in the condensers and the gas rotameter, and proved to be
reasonably fluid and readily soluble in acetone.
gas, at very low yields, this consisting primarily of CO and C0 2 (up to 95 %),
the balance being CH 4 and H2.
As some of the feed material added to the reactor was only partially
pyrolysed the mass balances and product yields could not be calculated.

4.4 Pyrolysis in Hydroxide Eutectic


A number of successful runs, of up to one hour in duration, have so far been
performed using a hydroxide melt system. In this case the wood fed to the reactor
dissolves in the melt to yield gaseous, liquid and solid products.
The gaseous product formed, consists of approximately 98% hydrogen, the
balance being mainly methane. The gas evolution was vigorous and resulted in
the melt foaming, with a volume increase of approximately 25%. This foaming
caused a blockage in the gas outlet line, due to frozen melt, which required minor
redesign (11) to prevent its recurrence.
The liquid product formed, consists of 97-99% water, the balance being an
organic product, which, due to its low yield and concentration, has not yet been
identified. This liquid is also alkaline, probably due to droplets of hydroxide
entrained in the product gas which dissolve in the condensate. The gas and
liquid products formed are very similar to those found in previous work at Aston
on small scale batch pyrolysis and solution of wood in molten hydroxides (10).
242

The work of I rédale and Hatt (10) also showed that the composition of the product
gas and the yield of gas were strongly dependent on the melt temperature. This
is currently under investigation to determine the optimum operating temperature.
The majority of the carbon in the feed is not liberated as part of the gaseous
or liquid products, but is retained in the melt either as an organic residue, which
may consist of formate or ethanoate ions (10), or by reaction with the hydroxide to
form carbonate. Melt with these 'impurities' is known as 'fouled'. Figure 2
illustrates the effect of the amount of wood pyrolysed on the hydroxide and
carbonate levels in the melt. The colour of the melt and of its aqueous solution,
also vary with the quantity of wood pyrolysed. Colours vary from that of the fresh
melt (which is white when solid and colourless when liquid) with a colourless
solution, via a pale yellow, of melt and solution, to a dark brown coloured melt
and solution. The light absorption, of the solution is directly proportional to the
quantity of wood pyrolysed, with a characteristic absorption at 260 nm. The
colouring of the melt is probably due to the organic residue, although the fraction
of this residue in the melt has not, as yet, been reliably quantified.

40

30-
SP

20

ε
o
υ3 10

100 200 300 400


Wood Added (gramme)

Figure 2 Hydroxide and Carbonate Content of Melt


Against Weight of Wood Pyrolysed
High levels of carbonate and organic residue in the melt lower its
effectiveness as a reaction medium. The hydrogen yield drops as more wood is
pyrolysed (see Figure 3) and the melt becomes more fouled. There is also
evidence to suggest that the wood solution becomes saturated, this being shown
by filtration of an aqueous solution of the melt. When small quantities of wood
have been pyrolysed (less than 50 g wood/ kg of melt) little or no solid filtrate is
produced. However, as the quantity of wood pyrolysed increases, a filtrate of fine
char particles is obtained, the number and size of these increasing with the
quantity of wood pyrolysed.
243

350

4>
ε
ε
300

■e
■3
¡5
s 250­
MD
ε
■β
>>
s
200
100 200 300 400

Wood Added (gramme)

Figure 3 Hydrogen Yield A gainst Weight of Wood Pyrolysed


This phenomenon indicates that the solution of the wood is being inhibited, so it
pyrolyses, with little or no solution, leaving a char residue.
In order to utilise the same melt in a continuous process, it would be
necessary to regenerate the melt, for instance, by reaction with steam (20):
CO3" (I) + H 2 0 (g) ^ OH" (I) + C0 2 (g)
Attempts to carry out this reaction in the molten salt at up to 750°C with a
water partial pressure of 0.3 bar showed it to be very slow. There is, however,
evidence that it takes place in the presence of live steam at a somewhat higher
temperature. This is an area for further investigation.
It has already been shown that the melt may be partially regenerated simply
by heating. Fouled melt was heated to a temperature of 400°C and yielded a gas
containing hydrogen and methane. This gas production was considered to be
due to the breakdown of the organic residue in the melt.
Hatt and Iredale (10) suggested the following overall reaction for wood in the
molten hydroxide eutectic:
C 6 H 9 0 4 (wood) + 12 OH" + 2 H 2 0 6 C o f * 12.5 H 2
However, this is a simplification of the process and the range of products
indicates that the actual process is more complicated. A more realistic appraisal
of the reactions occurring may be represented by the routes they proposed for the
molten salt pyrolysis of cellulose (see Figure 4). A gain, however, this is a
simplification, as it does not consider the other main constituents of the wood (that
is lignin and hemi­cellulose). The range of products formed could be explained
by considering the breakdown of these other components and, in particular.lignin.
244

Cellulose
i
S ace hari η ic Acids-
I
1,2 - epoxides
'poxioes 1

6 CO + 6 H 2 5 CO +κ C H 4 + 3 H 2 < 6C
6 C FF lragments
shift I shift 11pyrolysisJ

12 H 2 + 6 CO§~ 5 C0|"+ C H 4 + 8 H 2 H 2 / CO§"

Figure 4 Proposed Routes for the Pyrolysis of Cellulose in


Molten Sodium/Potassium Hydroxide (10)

5. CONCLUSIONS
There is considerable evidence that molten salts are potentially valuable
media for the conversion of biomass into useful fuels and chemicals. The work
performed in this project and by other groups has demonstrated the technical
feasibility of this type of process.
The salt employed has been demonstrated to have an important influence
on the process and hence the products. The salt type determines whether it acts
simply as a heat source or as a chemical reagent. Previous work at Aston (21 )
has demonstrated the use of molten salts as liquid phase catalytic reaction
media. It should, therefore, be feasible to select a suitable salt and catalyst
system to produce specific products.
The sodium carbonate melt acts as a heat source causing the wood to
undergo 'normal' pyrolysis, although at higher heating rates than conventional
pyrolysis systems which employ a gaseous heating medium. The suitability of
this system for gasification and combustion has already been demonstrated, its
particular advantage being its ability to absorb contaminants, such as sulphur.
The hydroxide melt system produces hydrogen of high purity and, therefore,
has considerable potential to provide hydrogen either as a fuel gas or as a
chemical reagent, for instance for the upgrading of pyrolytic oils. A potential
problem of this salt system is the fouling of the melt, with carbonate and an
organic residue, requiring the melt to be regenerated. However, there is
evidence to suggest that this may be feasible by reaction of the fouled melt with
steam. Partial regeneration of the melt to recover hydrogen and methane by heat
treatment has already been demonstrated. This heat treatment is believed to
drive off the organic residue remaining in the melt.
245

REFERENCES
(1) Anon., "Guidelines for Safety in Heat Treatment - Part 1 Use of Molten Salt
Baths", The Wolfson Heat Treatment Centre, Aston University B'ham, (1981)
(2) Chong V M, "Coal Gasification Process", US Patent 3 770 399, (Nov. 1983)
(3) Susie M et al., "Coal Gasification in Molten Salt", Glas Sriska Akademija
Naukai Odelene Prirodus Matematickih 48 (1981) 27.
(4) Cover A E & Schreiner W.C., "The Kellogg Molten Salt Process", Energy
Communications 1/2, (1975) 135.
(5) Yosim S J & Barclay Κ M, "The Gasification of Wastes Using Molten Salts",
Preprint, ACS Division of Fuel Chemistry 21/1 (1976), 73.
(6) Moffat J M & Kohl A L, "Gasification of Wood in a Bath of Molten Alkali
Carbonates", in "5th Canadian Bioenergy R&D Seminar", ed. Hasnain S,
Elsevier Applied Science (1984).
(7) Bertolini G E & Fontaine J, "Value Recovery from Plastics Waste by Pyrolysis
in Molten Salts", Conservation & Recovery 10/4 (1981) 27.
(8) Maund J K, Bridgwater A V & Smith E L,"Thermal Conversion of Biomass in
Molten Salt Media",'Energy from Biomass 1', G Grassi & H Zibetta (eds),
Elsevier Applied Science, London (1987)
(9) Maund J K, Bridgwater A V & Smith E L.'Thermal Conversion of Biomass in
Molten Salts", '4th EC Conference - Biomass for Energy & Industry', Orléans,
France, (May 1987)
(10) Iredale PJ and Hatt BW, "The Pyrolysis and Gasification of Wood in Molten
Hydroxide Eutectics", in, "Fundamentals of Thermochemical Biomass
Conversion", Overend RP, Milne TA an<-" iVludge LK (eds), Elsevier Applied
Science, London (1985).
(11) Earp D M and Maund JK, "Thermal Conversion of Biomass in Molten Salt
Media", Third EEC Progress Report - January to September 1988.
(12) Earp D M and Maund JK, "Thermal Conversion of Biomass in Molten Salt
Media", paper presented at, "Energy from Biomass - EEC Contractors
Meeting", Paestum, Italy (1988)
(13) Earp DM, "The Gasification of Biomass in a Downdraft Reactor", PhD Thesis,
Aston University (1988)
(14) Venning NJ, "Fuels from Tyres by Pyrolysis in Molten Salts", PhD Thesis,
Aston University, (1981)
(15) Pitt MJ, "Pyrolysis of Plastics in Molten Salts", MPhil Thesis, Aston University,
(1979)
(16) Maund JK and Earp D M, "Fuels from Biomass by Conversion in Molten
Salts", pp. 542-556 "Research in Thermochemical Biomass Conversion",
eds. A V Bridgwater & J L Kuester, Elsevier Applied Science, (1988)
(17) Yasunishi A & Tada Y, 'Wood Pyrolysis in Molten Salt', Kagaku Kogaku
Ronbunshu, 11/3, (1985) 346.
(18) Tada Y & Yasunishi A, 'Wood Pyrolysis with Molten Salt as Heating
Medium', Kagaku Kogaku Ronbunshu, 13/3, (1987) 376.
(19) Smith EL, Private Communication
(20) Maund JK, "Thermal Conversion of Biomass in Molten Salt Media", paper
presented at Institute of Energy Conference: "Gasification - Status and
Prospects", Harrogate, UK, (May 1988)
(21) Al-Muslih E F, "Oxidation of Organic Compounds in Molten Salts", PhD .
Thesis, Aston University, (1984)
246

FLASH-PYROLYSIS OF SULCIS COAL

L. Conti and G. Scano


Dipartimento di Chimica, Universita1 di Sassari

Summary
F l a s h - p y r o l y s i s of an i t a l i a n c o a l ( S u l c i s c o a l ) has been
i n v e s t i g a t e d in f l u i d i z e d bed p y r o l i s e r in n i t r o g e n or
methane a t m o s p h e r e and between 600 and 900 °C. The
maximum t a r y i e l d s i s o b t a i n e d a t 600-620 °C. The
p y r o l y s i s o i l can be upgraded a f t e r w a r d s . Experiments i n
methane a t m o s p h e r e s u p p o r t a p o s s i b l e r a d i c a l i c mechanism
for t h e r e a c t i o n .

1. INTRODUCTION
Continued reduction of crude oil and natural-gas reserves
stimulates the interest of many research groups in coal
conversion to gaseous or liquid products, which can represent
new raw material for the chemical industry.
In our laboratory, research on the utilization of Sulcis
coal as an alternative to direct combustion was started a few
years ago 1 - 2 ; in this connection, we began to study fluidized
bed flash-pyrolysis of this coal.
In the present communication, we report some of the
results obtained in this research.
2. RESULTS AND DISCUSSION
Pyrolysis experiments were conducted in a fluidized bed
stainless steel pyrolyser able to heat coal powder at 10^
C/sec with short residence time (0.3 sec)3. in this way, the
tars undergo only a partial decomposition and can be quickly
removed.
Table 1 reports the approximate and ultimate analysis of
Sulcis coal :
Tab. 1 Analysis of Sulcis coal
Proximate analysis Ultimate analysis
Moisture (wt%) 7.4 C (wt% maf) 68.2
Ash (wt% mf) 10.9 H (wt% maf) 4.8
Volatile matter (wt% mf) 45.3 Ν (wt% maf) 1.7
Fixed carbon (wt% mf) 43.8 S (wt% maf) 8.7
Fig. 1 reports the yields of total volatile matter, tar,
gas and hydrogen sulphide against temperature in nitrogen
atmosphere; Fig. 2 reports the tar-component yields (A STM
247

A Hydrogen sulfide
O C1-C3 hydrocarbons
Π Tars
• Volatile matters

Τ — ι — ι — ι — Γ
soo 6βο τοβ eoe 9oa IDOO

F i g . 1. Trends of product y i e l d s versus p y r o l y s i s temperatures

m —

τ—ι—ι—Γ
BOO eoo TOO eoo 900 1000
F i g . 2. Yields of l i g h t o i l s and c a r b o i d s v e r s u s temperature
248

2700­75), relative to the original coal, plotted against


temperature.
As can be noted, a maximum tar yield is obtained at
600­620 °C; the pyrolysis oil presents a satisfactory H/C
ratio and sulphur content and can be upgraded afterwards''.
The characteristics of the tar obtained at 600 °C and the
composition of gaseous hydrocarbons are listed in Tables 2 and
3.

Tab. Characteristcs of tar Tab. 3 Hydrocarbons C­|­Cz,

C (wt%) 75.2 CH4 (wt%) 30.5


H (wt%) 7.7 C2H4 (wt%) 26.7
Ν (wt%) 1 .0 C2H6 (wt%) 9.5
S (wt%) 3.6 C3H6 (wt%) 22.8
Asphalt. (wt%) 41.2 (wt%) 10.5
C4H8 (wt%)
Preasphalt.. (wt%) 32.3 traces
H/C 1 .2 C2H2
The trends ob served in Fig. 2 suggest the following
mechanism : 3

ils «««^^
primary light oils
^ ^ ^ second ary gas
sem icoke ^~
^ residue
carboids ^
Coal
secondary light oils
primary gas

chars
The coal decomposes essentially with a radical mechanism.
The volatiles formed include unreactive substances as well as
reactive ones (carboids). Especially in the intial stages of
decomposition, when free radicals are likely to exist, the
unreactive volatiles (primary light oils and gases) escape
into the atmosphere. Only a part of the reactive volatiles
escape, while the most of them polymerize giving a semicoke;
or decompose into secondary light oils.
In turn the semicoke reacts to gives gas and a solid
residue. The breakdown of the primary light oils, and of the
secondary ones perhaps, is noticed at higher pyrolysis
temperatures (600­750 * C ) , as well as an increase in carboids.
The decrease of carboids in the oil produced at 900 °C can be
explained by quick decomposition.
A further check of the validity of such mechanism was
provided by some tests carried out in methane atmosphere. In
our experimental temperature range, methane cracking gives a
high concentration of free radicals5. These react with the
radicals deriving from coal pyrolysis, particularly with the
carboids that are thus quenched, hindering their decomposition
into semicoke and secondary light oils.
Infact, we observed a greater tar production but
especially a variation in composition (light oils/carboids
ratio) in methane than nitrogen atmosphere, as we can be see
249

in Tab. 4.

Tab. 4 Tar yields at different temperatures (wt % on coal


m.a. f. )

Temp . 450 600 750 880

N2 CH4 N2 CHz, N2 CH4 N2 CHz,

Tar 13.5 8.7 19.521.0 15.2 20.2 10.8 11.9


Light oil 6.8 3.6 5.0 4.1 2.0 1.8 4.6 1.5
Carboid 6.7 5.1 14.5 16.9 13.2 18.4 6.2 10.4
Light oil/carboid 1.01 0.70 0.3 0.24 0.15 0.10 0.74 0.14

References
(1) C. Botteghi, L.Conti and R. Mansani, Boll. Soc. Sarda
Sci. Nat.; 19, 27 (1980)
(2) L. Conti, C. Botteghi and R. Rausa, Tecnologie Chimiche,
4, 38 (1981)
(3) L. Conti and R. Rausa , Fuel Processing Technology,
17, 107 (1987)
(4) S.C. Che, S.A. Quader and E.W. Knell, in "Refining of
Syntetic Crudes". M.L. Gorbaty and B.M. Harney, Editors,
Am. Chem. Soc. Washington, D.C. (1979)
(5) D.B. Anthony and J.B. Howard, AICHE Journal; 22, 625
(1976)
250

RAPPORTEURS REPORT ON SESSION IV


PYROLYSIS CASE STUDIES

D J O'Neil
Georgia Tech Research Institute
Georgia Institute of Technology
Atlanta
Georgia 30332
USA

Session 4 (Pyrolysis Case Studies) consisted of five papers, with two papers
withdrawn. The Session was chaired by Dr G Grassi assisted by Dr A V
Bridgwater.

1. Sugars from Cellulosics by the Waterloo Fast Pyrolysis Process


Dr Piskorz
Dr Piskorz of the University of Waterloo (Canada) reported the experimental
results achieved for the production of anhydrosugars and other sugars via
atmospheric flash pyrolysis in a fluidised bed reactor. Pretreatment of the
lignocellulosic feedstocks was a preferred method prior to pyrolysis in order to
maximise the conversion of the cellulose fraction to fermentable sugars.
Conversion efficiency of cellulose to fermentable sugar of 72% was reported.
Sugars were isolated in a water-soluble extract of pyrolyzate with the non-water-
soluble fraction producing a "pyrolytic lignin" fraction. Pretreatment with dilute
sulphuric acid had yielded hemicellulose derivatives. Success was claimed in
fermenting the sugar solution to ethanol but no details were provided on
conversion efficiency, ratio, or the need to acclimatise fermenting agents (e.g.
baker's yeast).
A question addressed the method of analysis/characterisation which was
used to identify laevo-glucosan which had been cited as a key pyrolysis product. It
was understood that, while l-glucosan had often been cited as a precursor to
formation of cellulose, it had often escaped detection, at least in earlier studies on
the structure of cellulose. Dr Piskorz explained that, while GCMS and FTIR were
methods of analysis that could be used, he had used standard samples of glucose
(and other sugars) and had used HPLC to correlate the elution times of the
standards with the pyrolysis components. Some of the sugar standards were also
synthesised in his laboratory and were used for HPLC correlation. Additionally, the
l-glucosan was isolated, converted to glucose via hydrolysis and the glucose
product was fermented to ethanol.
The question was raised of the cost of production of sugars via the flash
pyrolysis process in relation to the citation that Brazilian studies had been
unsuccessful in producing sugars from lignocellulosics at competitive rates. Dr
Piskorz replied that they had estimated the cost of sugar production via the
pyrolysis process to be $0.10-$0.15/kg. It was noted that current costs of raffinate
sugars were $0.06-$0.08/kg and that his results were not attractive. Dr Piskorz
cited the fact that he was reporting experimental results and that his costs were
preliminary.
It would appear that the production of fermentable sugars would be at a
disadvantage vis-a-vis the well-established prehydrolysis and dilute hydrolysis
processes which have been developed in the 1980's which retain a higher yield of
fermentable sugars and low levels of toxifying compounds and for which hexose
251

production costs have been reported at $0.07-$0.08/kg. The Waterloo researchers


claim only an advantage over enzymatic hydrolysis which has the greater potential
for maximal production of fermentable sugars from both the hemicellulose and
cellulose fractions assuming further reductions in conversion times. Several
questions remain to be answered before a cost-effective biomass conversion
process could be economic: cost of acid, disposal of acid solutions, degradation ol
hemicellulose and loss of volatile derivatives (furfural-based), fermentation
inhibition (furural, hydroxymethyl furfural, phenols, etc), mass market for "pyrolytic
lignin" residues etc.

2. Production of Benzols and Active Carbon by Pyrolysls with


Simultaneous Post-cracking of Waste Rubber and Plastic
Material
Dr B Bettens
Dr Bettens reported on a "dual pyrolysis" process for the conversion of waste
tires (rubber) and plastics, with emphasis on the former - a whole tire pyrolysis
process involving two pyrolytic stages, viz (i) depolymerisation (actually
decomposition since a monomer is not the primary product) at a temperature range
of 400-500°C, and (ii) a higher temperature cracking process at 700-800°C. Olefin
production is characteristic of the first stage and "aromatisation" to BTX (benzene,
toluene xylene) production is characteristic of the second stage. Bettens reported
mass balance and temperature dependence for the principal product groups, i.e.
solid (char), liquids and gases. The liquid phase composition could include 60-
70% of BTX compounds (naphthalene and higher fused aromatics could be
observed). A simple depolymerisation and aromatisation reaction mechanism was
presented. The effects of temperature and process conditions (including flow rate)
were examined on depolymerisation and BTX formation.
A feasibility study for a 2000 t/d plant (c.1984) was described and a plant
investment of BF 30.4 million was reported (22 million for capital equipment, 0.8
million for assembly, 0.6 million for electricity and 7.0 million for miscellaneous
costs). Raw material (waste tire) costs were reported as 1550 BF/ton (if collected -
and delivered?) or 600 BF if tires were "turned in" to the plant for payment by
individual delivery. Dr Bettens described a manufacturing process for a 2000 t/d
plant, critical elements of which were a "feed delivery" system for whole autombile
tires (no shredding required), a large first stage direct heating zone (major gaseous
volume expansion allowed), and a smaller adjacent cracking reactor zone.
Activation of carbon residue was cited as a saleable product.
Considerable questioning arose with regard to the practical operation of the
proposed plant. In particular, there was a question on the efficiency and the
method of direct heating and the problem of fouling of heating elements. A
situation was cited from the experience of one of the audience relative to an acute
fouling problem, due to rapid coking of electrical radiant heating elements in a
rubber pyrolyzer with loss of heat transfer and failure of the electrical system due to
overheating. Dr Bettens recapped the process with emphasis on the conveyor
transport system into and through the kiln which was claimed to allow adjustment of
the contact (residence) time, facilitating rapid reactions. They do not stress heat
transfer as being a problem in the first stage - "not a problem". Dr Bettens noted
that a scraping system was included in the design to remove scale (foulants). Pilot
tests had not been run which established the optimum "contact" time for the tires in
the kiln. A condenser system was described for both the first and second stages.
Further work was necessary to balance the take-off (two points) of light fractions
and heavy fractions. This was recognised as a problem. No information had been
252

produced to support the claim of activated carbon production. It was speculated


that a steam activation process would be used but that a subcontractor would be
needed to implement that operation. In summary, basic technical issues remain
before a reliable process is established and before reliable process economics can
be generated.

3. Low Temperature Conversion of Biomass to Oil


Professor Bayer
Professor Bayer argues from both an experimental and theorectical
standpoint that, in contrast to conventional .widsom on biomass pyrolysis
technology, high carbon-hydrogen organic compounds of low oxygen content need
not only be achievable by high-temperature pyrolysis. Evidence was presented
that fatty acids and a series of aliphatic hydrocarbons (often associated with olefin
analogues) can be produced from biomass which is rich in lipids and proteins.
Sewage sludge, because of the high microbial content, was proposed as a
productive source of pyrolysis products in which C-C bonds would be retained
while heteroatoms (S, Ν, O) may be readily eliminated. Reaction temperatures
were in a low range of 280-400°C, with a precaution that temperatures in excess of
380°C should be avoided, normally because of the potential conversion of organic
amides (RCONH2) to organic nitrites (or cyanide products) via dehydration.
A principal reaction pathway for formation of hydrocarbons was postulated
as involving conversion of glycerol at 280-330°C to fatty acids, followed by
conversion of the factty acids to hydrocarbons via decarboxylation at 300-380°C.
The limitation of boiling points of the pyrolysis products was such as to indicate
their practical use as diesel fuel replacements. Sewage sludge was a source of
raw "oil" at yields of 27%. The solid residue was usable as a fuel source for
dewatering. Of considerable interest was the observation that not only
heteroatoms, but also halogen atoms (CI,F), could be removed under non-oxidative
conditions in the presence of inorganic catalysts such as silicates.
One observer noted that the presence of water in the feedstock could modify
the catalyst. Bayer speculated on the role of catalysis and noted that over 200
catalysts had been assessed with the goal of maximising the yield of the higher
value-added olefins. Lipid-rich plants were desirable and easily manipulated. It
was apparent that the aliphatic-to-olefin ratio could be preferentially manipulated to
favour olefin production
To the suggestion that the low-temperature pyrolysis may be more
significantly applied to destruction of organic components, specifically hazardous
waste compounds, Professor Bayer emphasised that it is better, in any event, to
maintain the C-C linkage in the organic compounds, making the point that it was
very costly to build-up/synthesise higher molecular weight organic compounds,
from C-|- compounds, such as methane. He had not addressed the question of the
treatment of PCB compounds, only chlorinated dioxins.
When asked to explain how low oxygen content (3-5%) products were
realised at low and high temperatures, Professor Bayer postulated that his products
(with 85-95% the HHV of petroleum products) were a result of a different chemistry.
At higher temperatures he postulated the formation of stable intermediate products,
such as ketones, which could only be destroyed under the more extreme
conditions. At lower temperatures, the decomposition of carboxylic acids, on the
other hand, could be readily achieved via decarboxylation (-C02). Moreover, the
formation of methane (CH4), depleted the available hydrogen which would be
needed for extensive deoxygenation at higher temperatures.
253

Issues which remain on the practical implementation of the process include


process efficiency (dewatering energy requirements?), rate of reaction (20 minutes
preferred at small-scale), mass and heat transfer requirements, nature and
availability of uniform raw material (process design), cost and efficiency of
catalysts, cost of separation processes and refining to extract narrow fuel fractions,
etc.

4. Chemicals from Almond Shells by Pyrolvsis in a F luidised Bed


Dr R F ort
The University of Alicante paper focussed on the results of pyrolysis in a
laboratory-scale fluidised bed reactor of impregnated almond shells, a biomass
waste product. The FBR was equipped with a comprehensive sampling train and,
assisted by chemical analysis, product yields and compositional data on oils and
gaseous products could be determined. The investigators report oil yields of 46-
58% with preferred particle sizes of 0.2-0.3mm.
Several variations on conversion approaches were investigated.
Post-pyrolysis of the dried oil residue, arising from pyrolysis at 610°C and
subsequent distillation at 120°C, when conducted at 890°C yielded a "producer
gas" with high CO/C0 2 content (43%), 1% hydrogen, 6% methane and C 2 - C4.
The balance was not reported. The results correspond to the results of other
investigators.
In perhaps the most interesting aspect of the research the almond shells
were impregnated with acidic compounds yielding substantial quantities of furfural.
Since furfural is produced commercially from oat residues it would be informative to
compare yields under comparable conditions with almond shells to determine the
potential for economic production of furfural from the locally available biomass
resource. Is there a potential for development of an integrated multiple product
(furfural, pyrolysis oil) process which could use the oil, the product gases, or char
as a process fuel? A remaining technical problem, to be investigated, will be the
efficiency of acid impregnation since pore closure has been reported by other
investigators (Roy, Canada).

5. Biomass Pyrolysis in Molten Salts for F uel Production


Dr J Κ Maund
The application of molten salts as a heating mechanism for the pyrolysis of
wood was reported. A small bench-scale CSTR reactor and condensation train
with gas metering was described. The dissolution of wood in the molten salt was
considered to have been observed though there was scepticism on the part of one
of the audience that wood could be dissolved under non acidic conditions. No firm
evidence was presented to support the solubility claim.
The investigator's preference for a thermal regeneration of hydroxide salts
due to carbonate formation, rather than by the conventional "wet method", was a
judgement based on the avoidance of evaporation costs (high Hv) required by the
latter method, principally. The products were reported to be high in hydrogen in the
gases (potentially the process has produced more hydrogen than was available in
the ligno-cellulosic precursor?), and the condensed phase was mostly water. The
latter result was considered to be significant. However, it would appear that the
researchers might have overlooked quite serious losses of the organic
condensation which, in fact, were observed as aerosols, as smoke and as liquid
products in their gas rotameter Their observations of the latter species very
pointedly express the serious difficulties in oil collection which face any reliable
pyrolysis process. While the problem is solvable, the more significant problem
254

which has not been addressed, and which was raised from the audience, is the
effect of build-up of adventitious impurities (e.g. metals in the wood) which can
radically and rapidly change the rheology of the molten salt system as well as
change the eutectic point or stability of the eutectic mixture. The latter, in turn, will
affect the reaction temperature stability and, hence, the process. The investigators
reported that their runs were not of such a duration that these problems had been
observed.
On a positive note it was suggested to the researcher that he might explore
the use of processes for decarboxylation of waste terephthalate compounds
(polymer production by-products). D r Maund reported that they had used the
process elsewhere for monomer recovery from waste polymers and were currently
investigating the decomposition of glass-reinforced plastic with a goal of recovering
the resin decomposition products (possibly monomer derivation) after dissolution of
the glass in the molten salt. (NOTE: It appears unlikely that Ε-glass and possibly A-
glass would dissolve completely without radically altering the composition, reaction
temperature, and rheology of the salt medium).
In summary, a much greater experimental base with the lab-system appears
to be required and it would seem that each process application would have to be
tailored for each feedstock.
SESSION V

GASIFICATION CASE STUDIES


257

PERFORMANCE OF A PILOT SCALE FLUIDIZED BED GASIFIER FUELED BY RICE H

Hartiniati, A. Soemardjo, and M. Youvial


LSDE-BPP Teknologi, Indonesian Energy Research Laboratory
Puspiptek - Serpong, Indonesia.

Sumnary

The performance of a 16 inch fluidized bed rice husks gasifier was


determined for the bed temperatures ranging from 1330 -1600°F. The
fuel flow rate was varied from 75 -105 kg/hr. No operational
problems were observed during 36 hours of continuous operation. The
whole study was completed for about 250 hours, and it was found that
the gas quality varied between 650 - 1050 Kcal/Kg (4100 - 6300
KJ/Nm3), depending on the bed operating temperature and/or air to
fuel ratio.
The maximum energy produced was 2920 Kcal-gas/Kg-fuel at the fuel
flow rate of 93 Kg/hr and the bed temperature of 1445°F. The lower
heating value of the gas in this condition was 975 Kcal/Kg. Fuel to
gas energy efficiency was found to be 63-67%.

1. INTRODUCTION.
To reduce our great dependence on oil and gas, the biggest commodity
export of Indonesia, since the last decade the government has adopted a
policy to conserve its petroleum reserves and prolong the availability of
an exportable surplus by promoting the development of alternative energy
resources where these can provide an economic substitute for oil. The
development for alternative energy resources then raised our interest in
biomass gasification.
Gasification is a thermochemical process in which the purpose is to
transfer the chemical energy contained in the solid fuel into a gasesous
energy carrier, preferably with a minimum " loss " into thermal energy.
This process creates many possibilities to generate low, medium or high
Btu of gases, depends on the reactor type and the gasifying medium
(3).
In Indonesia, agriculture wastes are abundant in many areas and not
utilized well. It is estimated that about 29 millions ton wastes per year
are produced and as by products, they have a negative value due to the
high cost involved in disposing of them. They should be properly handled
and several concepts for handling and converting these wastes into a
valuable gas fuel have been developed.
To utilize and increase the value of agriculture wastes, the
Fluidized Bed Gasification is one of the most promising conversion
process because of its ability to use a wide variety of fuels.
Since the gas quality produced by a gasifier depends on the nature
of the fuel used and gasifier operating conditions, these conditions need
to be optimized in order to be able to provide data for application
studies.
258

Gasification of rice husks is comparatively difficult due to the


high ash content and the particularly high silica content of the ash.
Major problem of utilizing rice husks is the nature of this feed
stock, i.e.the high ash content ( see table I ), the low bulk density
(100 Kg/m3) and the poor flow characteristics. Morover, processing of
rice husks above 900°C is problematic due to ash sintering( 3 ). Table I
presents the characteristic of rice husk used inthe experiment.

2. EXPERIMENTAL
A schematic diagram of 16 inch diameter pilot plant fluidized bed
rice husks gasifier is given in figure 1. A s shown in this figure, a
rotron cyclonair blower supplied fluidizing air to the plenum of the
reactor through an LPG start - up burner which was used to preheat the
bed before commencement of solids feeding. A fter the bed temperature
reached 950 - 1000°F the starting burner was then shut off and the feeder
was simultaneously started. The bed material within the reactor is an
aluminum oxide refractory sand having a particle size as shown in
table II. The air passed from the plenum through the distributor into the
bed to react with the rice husks which have been introduced into the bed
via the feeding system.
The rice husks were stored in a surge hopper ι metered through a
three-screw feeder, directed through a pressure sealing rotary lock
hopper to an injector conveyor, and then injected into the lower part of
the bed, just above the distributor. Upon entering the reactor,
sufficient amounts of rice husks burn to bring the bed temperature up to
the desired set point temperature. During operation the Barber - Colman
temperature controller automatically set the gasifier air flow rate.
After some initial oscillations in the range of 30°F about the set point,
the bed temperature settled down and remain within 8-10°F of the set
point. The gas leaving the reactor bed was passed through a double
cyclones in which most of particles were separated from the gas stream.
Subsequently the gas was burned in a dual fuel burner having an array of
LPG/or natural gas and low Btu gas heads. Table II shows the operating
variables used in the experiment.

3. MEASUREMENT. SAMPLING AND ANALYSIS.


Bed operating temperature and rice husks flow rate were the
variables in these experiments, while the air flow rate and the gas
composition were measured. A ir flow rates were measured by means of an
orifice, the solid fuel flow rate was set at the desired set point by
means of switch. The metering feeder was calibrated first before the
experiment began. The flow rate of the product gas was derived from the
known flow rate of nitrogen entering the gasifier with the air and the
nitrogen content of the product gas.
The bed temperature was monitored by a thermocouple penetrating the
fluidized bed. The thermocouple temperature was displayed on a Barber -
Colman microprocessor based temperature controller having a resolution
of plus or minus 1°F.
The train for sampling product gas is illustrated in Figure 2. A
sample of hot gas was extracted from the main gas stream exiting the
gasifier. The gas was passed through a hot filter packed with silica wool
to separate particulates, then is cooled to an ice condensor to remove
condensibles. Subsequently the gas is dried in a dryrite co1umn prior
directing to a GLC unit for its composition analysis.
259

Gas Duct ITc

Cyclones / Exriauşt
Hoppe­ /

rluidi'zed Bed Ash O


Orurrs ner <-
Feeder "χ


Injector
TempXpjTţroller

VΦ Ι v älart Up
Burner P i
>i1ice
^Ftow Control Valve
\d^^er
Figure 1. Schematic Diagram of BPPT gasiti«­ during test at the Puspiptek
Energy Research Laboratory( Serpong.

Hot Filter
(glass wool)

to GLC

\Condensate Flask

Figure 2. Schematic Drawing o1 Gas Sampling System.


260

Table I. Fuel Characteristics

Proximate Analysis Ultimate Analysis!


( % weight ) ( %'weight ) ¡

¡ Moisture content 9,96


¡ Ash content 20,61
¡ Volatile matter 54,68
¡ Fixed carbon 15,02
¡ Sulphur 0,02 !
¡ Carbon total 34,94 !
! Hydrogen Total 5,46 !
¡ Nitrogen 0,11 !
¡ Oxygen 38,86 !
! Heating value 3220
! [ = kcal/kg ]
¡ Specific gravity 1,44

Table II. Operating Conditions

Fuel rice husk


Moisture content 0,14 kg water per kg
dry ash free material
Operating temperatures 1330 - 1600 ° F
Fuel flow rate 75 - 105 kg/hr
Air flow rate 100 - 250 kg/hr
Bed material 0,3 - 0,4 mm = 26 %
0,4 - 0,6 mm = 45 %
0,6 - 0,8 mm = 29 %
Reactor diameter 16 inch ( 40 cm )
Static bed height 24 inch ( 60 cm )

Table III. The average gas composition of the


product gas (Vol % dry)

! Temp. H2 CO C02 N2 CH4 C2H4 LHV !


(KJ/NM3)!

! 1330 3.67 8.28 13.88 68.73 3.63 1.81 4093 !


¡ 1400 4.74 12.23 15.04 58.84 6.73 2.42 6340 ¡
! 1450 5.46 12.31 13.62 61.19 5.99 1.43 5528 ¡
! 1500 5.18 10.43 14.05 62.34 6.17 1.84 5585 I
! 1540 5.04 10.14 12.18 66.54 5.04 1.06 4590 ¡
¡ 1600 3.74 8.87 13.99 67.83 3.72 1.85 4398 i
261

4. RESULTS AND DISCUSSION.


The test