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Feedstock Recycling and Pyrolysis of Waste Plastics: Converting Waste Plastics into Diesel and Other Fuels Edited by
J. Scheirs and W. Kaminsky 2006 John Wiley & Sons, Ltd ISBN: 0-470-02152-7
Wiley Series in Polymer Science
Series Editor
John Scheirs
ExcelPlas
PO Box 2080
Edithvale, VIC 3196
Australia
scheirs.john@pacific.net.au
Modern Fluoropolymers
High Performance Polymers for Diverse Applications
Polymer Recycling
Science, Technology and Applications
Metallocene-based polyolefins
Preparations, Properties and Technology
Polymer–Clay Nanocomposites
Modern Polyesters
Chemistry and Technology of Polyesters and Copolymers
Forthcoming Titles
Edited by
JOHN SCHEIRS
ExcelPlas Australia
and
WALTER KAMINSKY
University of Hamburg, Germany
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Contributors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xix
Series Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxiii
Preface . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxv
About the Editors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . xxix
I INTRODUCTION 1
II CATALYTIC CRACKING 43
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 193
2 Operation Modes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
3 Zeolites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
4 Polymer-to-catalyst Ratio . . . . . . . . . . . . . . . . . . . . . . . . . 196
5 Initial Degradation Mechanism . . . . . . . . . . . . . . . . . . . . . 199
6 Product Distribution . . . . . . . . . . . . . . . . . . . . . . . . . . . . 201
6.1 Conversion, Liquid Yield, Coke Content . . . . . . . . . . . 202
6.2 Characterization of Gaseous/Liquid Products . . . . . . . . 203
6.3 Boiling Point Distribution of Liquid Fraction . . . . . . . . 203
7 Concluding Remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . 204
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
2 Catalytic Liquefaction of MWP . . . . . . . . . . . . . . . . . . . . . 210
2.1 Liquid Phase Contact . . . . . . . . . . . . . . . . . . . . . . . 210
2.2 Thermal Cracking plus Catalytic Upgrading . . . . . . . . . 211
2.3 Co-processing of MWP . . . . . . . . . . . . . . . . . . . . . . 216
3 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
2 Reaction Kinetics of Degradation . . . . . . . . . . . . . . . . . . . 226
2.1 Reaction Mechanism . . . . . . . . . . . . . . . . . . . . . . . . 228
3 Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 239
3.1 Monofunctional Catalysts . . . . . . . . . . . . . . . . . . . . . 239
3.2 Bifunctional Catalysts . . . . . . . . . . . . . . . . . . . . . . . 241
3.3 Solid Alkalis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 244
CONTENTS ix
III QUALITY OF FUELS 249
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 435
1.1 Fluidized-bed Technology for Waste Thermal Treatments:
The Key Role of Hydrodynamics . . . . . . . . . . . . . . . 435
1.2 From Plastic Waste to Feedstocks and Energy by Means
of Fluidized-bed Pyrolysis . . . . . . . . . . . . . . . . . . . . 437
2 Different Stages in the Fluidized-bed Pyrolysis of a Plastic Waste 444
2.1 An Overview of Physical and Chemical Phenomena . . . 444
2.2 The Polymer Degradation Process . . . . . . . . . . . . . . . 452
3 Operability Range of Fluidized-bed Pyrolysers . . . . . . . . . . . 453
3.1 The Phenomenology of Bed Defluidization . . . . . . . . . 453
3.2 Predictive Defluidization Models and Operability Maps . 454
4 The Effect of the Main Process Variables on the Yield and
Composition of Pyrolysis Products . . . . . . . . . . . . . . . . . . . 456
CONTENTS xiii
4.1 Fluidized-bed Pyrolysis of Monopolymeric Waste . . . . . 462
4.2 Fluidized-bed Pyrolysis of Multipolymeric Waste . . . . . 464
4.3 Fluidized-bed Pyrolysis of Other Polymeric Wastes . . . . 466
5 Operating Experience with Industrial Fluidized-bed Pyrolysers 467
5.1 The BP Chemicals Polymer Cracking Process . . . . . . . 467
5.2 The Akzo Process . . . . . . . . . . . . . . . . . . . . . . . . . 468
5.3 The Ebara TwinRec Process . . . . . . . . . . . . . . . . . . . 469
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 471
6 Conclusions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 525
1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 709
2 Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 709
2.1 Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 709
2.2 Plastics Suitable for Pyrolysis . . . . . . . . . . . . . . . . . . 710
3 Pyrolysis: Mode of Operation and Apparatus . . . . . . . . . . . . 710
3.1 Batch Pyrolysis . . . . . . . . . . . . . . . . . . . . . . . . . . . 710
3.2 Types of Pyrolyzers . . . . . . . . . . . . . . . . . . . . . . . . 711
4 Pyrolysis: Thermal Cracking/Noncatalytic Cracking . . . . . . . 712
4.1 Operation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 712
4.2 Process Mechanism . . . . . . . . . . . . . . . . . . . . . . . . 713
4.3 Degradation of Polymers . . . . . . . . . . . . . . . . . . . . . 713
5 Pyrolysis Catalyst . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 715
5.1 Role and Effect of Catalyst . . . . . . . . . . . . . . . . . . . 715
5.2 Properties of Catalyst . . . . . . . . . . . . . . . . . . . . . . . 716
6 Pyrolysis: Output Characteristics . . . . . . . . . . . . . . . . . . . . 719
6.1 Effect of Temperature on Pyrolysis Products . . . . . . . . 719
6.2 By-products of Pyrolysis . . . . . . . . . . . . . . . . . . . . . 719
7 Pyrolysis of Heteroatom Polymers . . . . . . . . . . . . . . . . . . . 720
7.1 Pyrolysis of PVC . . . . . . . . . . . . . . . . . . . . . . . . . . 720
7.2 Pyrolysis of ABS . . . . . . . . . . . . . . . . . . . . . . . . . . 721
8 Refinement of Pyrolysis Output Products . . . . . . . . . . . . . . 721
8.1 Removal of Unsaturation and Olefinic Products . . . . . . 721
8.2 Various Examples of Pyrolysis . . . . . . . . . . . . . . . . . 722
8.3 Comparison of Pyrolysis of PE and PP . . . . . . . . . . . . 724
9 Recently Developed Innovative Technologies . . . . . . . . . . . . 724
xviii CONTENTS
Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 757
Contributors
Umberto Arena,
M. Blazsó,
Department of Environmental Sciences,
Institute of Materials and Environmental
University of Naples II,
Chemistry,
Via Vivaldi 43,
Chemical Research Center Hungarian
81100 Caserta, Italy
Academy of Sciences,
Pf. 17, H-1525 Budapest,
Masao Asai, Pusztaszeri ut́ 58–67,
Rekisei Kouyu Co. Ltd, H-1025 Budapest, Hungary
Niigata Plastic Liquefaction Center,
3-1 Heiwa, Alfons Buekens,
Niigata, Japan Vrije Universiteit Brussel (V.U.B.),
Domstraat 7,
Sam Behzadi, 1602 Vlezenbeek, Belgium
Department of Chemical and Materials
Engineering, H.A. Chase,
The University of Auckland, Department of Chemical Engineering,
Private Bag 92019, University of Cambridge,
Auckland, New Zealand New Museums Site,
xx CONTRIBUTORS
Pembroke Street, P.O. Box 3640,
Cambridge CB2 3RA, UK 76021 Karlsruhe, Germany
The Wiley Series in Polymer Science aims to cover topics in polymer science where sig-
nificant advances have been made over the past decade. Key features of the series will be
developing areas and new frontiers in polymer science and technology. Emerging fields
with strong growth potential for the twenty-first century such as nanotechnology, pho-
topolymers, electro-optic polymers will be covered. Additionally, those polymer classes in
which important new members have appeared in recent years will be revisited to provide
a comprehensive update.
Written by foremost experts in the field from industry and academia, these books have
particular emphasis on structure–property relationships of polymers and manufacturing
technologies as well as their practical and novel applications. The aim of each book in
the series is to provide readers with an in-depth treatment of the state-of-the-art in that
field of polymer technology. Collectively, the series will provide a definitive library of
the latest advances in the major polymer families as well as significant new fields of
development in polymer science.
This approach will lead to a better understanding and improve the cross-fertilization of
ideas between scientists and engineers of many disciplines. The series will be of interest
to all polymer scientists and engineers, providing excellent up-to-date coverage of diverse
topics in polymer science, and thus will serve as an invaluable ongoing reference collection
for any technical library.
John Scheirs
June 1997
Preface
This book covers thermal and catalytic pyrolysis processes that produce liquid fuels (or
other useful chemicals) from waste plastics. The book provides a comprehensive overview
of the main commercial plastics pyrolysis processes, the types of plastics that can be
processed, the properties of the respective fuels produced and the key variables influenc-
ing the pyrolysis of plastics such as temperature, residence time, pressure and catalyst
types.
Only some 15–20% of all waste plastics can be effectively recycled by conventional
mechanical recycling technologies (i.e. sort/grind/wash/extrusion). Beyond this level the
plastics become increasingly commingled and contaminated with extraneous materials
such as soil, dirt, aluminium foils, paper labels and food remnants.
Pyrolysis is a tertiary or feedstock recycling technique capable of converting plastic
waste into fuels, monomers, or other valuable materials by thermal and catalytic cracking
processes. This method can be applied to transform both thermoplastics and thermosets in
high-quality fuels and chemicals. Moreover it allows the treatment of mixed, unwashed
plastic wastes.
In its simplest definition pyrolysis is the degradation of polymers at high temperatures
under nonoxidative conditions to yield valuable products (e.g. fuels and oils). Pyrolysis
is also referred to as polymer cracking and its main advantages are that it can deal with
plastic waste which is otherwise difficult to recycle and it creates reusable products with
unlimited market acceptance.
As feedstock recycling and pyrolysis is not incineration there are no toxic or environ-
mentally harmful emissions. Pyrolysis recycling of mixed plastics thus has great potential
for heterogenous plastic waste that cannot be economically separated.
This book provides an overview of the science and technology of pyrolysis of waste
plastics. The book will describe the types of plastics that are suitable for pyrolysis recy-
cling, the mechanism of pyrolytic degradation of various plastics, characterization of the
pyrolysis products and details of commercially mature pyrolysis technologies.
The major advantage of the pyrolysis technology is its ability to handle unsorted,
unwashed plastic. This means that heavily contaminated plastics such as mulch film
(which sometimes contains as much as 20% adherent dirt/soil) can be processed with-
out difficulty. Other normally hard to recycle plastics such as laminates of incompat-
ible polymers, multilayer films or polymer mixtures can also be processed with ease,
xxvi PREFACE
unlike in conventional plastic recycling techniques. In fact, most plastics can be pro-
cessed directly, even if contaminated with dirt, aluminium laminates, printing inks, oil
residues, etc.
The production of gasoline, kerosene and diesel from waste plastics is an emerging
technological solution to the vast amount of plastics that cannot be economically recovered
by conventional mechanical recycling.
Pyrolysis recycling of mixed waste plastics into generator and transportation fuels is
seen by many as the answer for recovering value from unwashed, commingled plastics
and achieving their desired diversion from landfill. Pyrolytic recycling of plastic wastes
has already been achieved on commercial scale albeit to a limited extent. Nevertheless, the
development and improvement of the pyrolysis plastics recycling technologies in recent
years has great commercial potential. The development of bench-scale experiments carried
out in laboratories to full-scale pyrolysis processes have now resulted in a number of
technically mature processes.
Through the use of low-temperature vacuum pyrolysis and cracking catalysts, liquid
fuels yield of up to 80% are possible with the resultant product resembling diesel fuel,
kerosene, gasoline or other useful hydrocarbon liquids. There are now emerging a number
of processes which will take post-consumer plastics and catalytically convert them into
gasoline and low-sulfur diesel fuel. The diesel fuel meets or exceeds both European and
Federal EPA standards for emissions and is designed specifically for the solid waste
disposal industry that has significant investment in diesel-powered equipment. The types
of plastic targeted as feedstock for this project have no commercial value and would
otherwise be sent to landfill.
High-temperature pyrolysis and cracking of waste thermoplastic polymers, such as
polyethylene, polypropylene and polystyrene is an environmentally acceptable method of
recycling. These type of processes embrace both thermal pyrolysis and cracking, catalytic
cracking and hydrocracking in the presence of hydrogen. Mainly polyethylene, polypropy-
lene and polystyrene are used as the feedstock for pyrolysis since they have no heteroatom
content and the liquid products are theoretically free of sulfur.
The principal output products are gaseous and liquid hydrocarbon fractions that are
remarkably similar to the refinery cracking products. Their chemical composition and
properties strongly depend on the input feed composition, (i.e. proportion of polyethylene,
polypropylene and polystyrene in the feedstock) and they can also be unstable due to their
high reactive olefins content (especially from polyethylene and polystyrene cracking).
The book also explores the application of various acidic catalysts, such as silica–
alumina, zeolites (HY, HZSM-5, mordenite) or alkaline compounds such as zinc oxide.
However, the main problem with catalytic cracking is that in the course of the crack-
ing process all catalysts deactivate very quickly. Expensive zeolite catalysts increase the
cost of waste plastics cracking process to the point where it becomes economically unac-
ceptable since the catalyst becomes contained in coke residue and therefore cannot be
recovered and regenerated.
Effective engineering design of the cracking reactor for waste plastic processing is very
important since the carbonaceous solid residue is one of the cracking products (levels up
to 10% or more) and its continuous removal from the reactor is necessary to ensure
profitable running. Stirred vessel reactors which have augers in the bases to facilitate
continuous char removal are presented.
PREFACE xxvii
This book is truely international in scope with contributing authors from Spain, Saudi
Arabia, Italy, New Zealand, Japan, Turkey, Hungary, Poland, Belgium, France, Germany,
Korea, UK, USA, India, China and Australia.
John Scheirs
Walter Kaminsky
8 August, 2005
About the Editors
Dr John Scheirs is a polymer research specialist with an emphasis on plastic recycling and
pyrolysis of waste plastics into fuels. He serves as a consultant for Ozmotech Australia and
has worked on the development of their Thermofuel process which can convert unwashed
mixed plastics into low-sulfur diesel transportation fuel. He has studied the pyrolysis of
HDPE, PP, PET and engineering plastics.
John Scheirs is the author of the leading book on plastics recycling entitled Polymer
Recycling: Science, Technology and Applications published by John Wiley & Sons Ltd,
Chichester in 1998. He is also a member of the editorial board of the international journal
Polymer Degradation and Stabilization, Elsevier Scientific, Netherlands.
John Scheirs is now the principal consultant with ExcelPlas Polymer Technology where
he specializes in polymer recycling, polymer degradation, polymer processing and testing.
Professor Walter Kaminsky was born 1941 in Hamburg and studied chemistry at
the University of Hamburg. His thesis was in the field of metallocene chemistry and his
habilitation in the field of recycling of polymers by pyrolysis. Since 1979, he has occupied
the role of Full Professor of Technical and Macromolecular Chemistry at the University
of Hamburg.
He is currently supervising a group of 15 students and scientists in the field of pyrol-
ysis of plastic waste in a fluidized bed process and a group in the field of metal-
locene/methylaluminoxane chemistry. His past experience includes the development of
pilot plants for the feedstock recycling of plastic wastes and scrap tires, and discovering
highly active metallocene catalysts for the polymerization of olefins. He has published
more than 300 papers and books and holds 20 patents. He has organized several interna-
tional symposia in the field of pyrolysis and olefin polymerization.
In 1987 he received, together with Hansjörg Sinn, the European Research Prize for
the development of the Hamburg process for pyrolysis of polymers. In 1997 he received
the Carothers Award of the American Chemical Society (Delaware Section), and in the
same year the Walter Ahlström Prize in Helsinki, Finland. Since 1998 he has been an
Honorary Member of the Royal Society of Chemistry in London, and Honorary Professor
of the Zhejiang University in China. In 1999 he received the Benjamin Franklin Medal
for Chemistry, Philadelphia and in 2003 the Hermann Staudinger Prize of the German
Chemical Society (GDCh).