The 8th Asian Petroleum Technology Symposium, February 23-24, 2010 in Tokyo, Japan.

Advances in gasification/pyrolysis of biomass wastes for 2nd generation biofuel production

Presented by Dr Rong YAN Centre Director, Senior Scientist (Email: ryan@ntu.edu.sg) Institute of Environmental Science and Engineering (IESE) Nanyang Technological University, Singapore

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Outline of Presentation
1. Background introduction - Biomass energy - Palm oil wastes a representative for SE Asia 2. IESEs work in advanced biomass gasification/pyrolysis - Palm oil wastes pyrolysis for efficient bio-syngas production - Catalytic biomass gasification for tar removal and H2 yield - Modeling and simulation development - Fundamental understanding of palm oil waste gasification - Industrial consultancy on palm oil waste torrefaction 3. Other on-going projects related to clean fuel and CO2 sequestration 4. Summary

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Biomass Energy
CO2 + H2O + Biomass + O2

Advantage of biomass energy: Zero CO2 emission Low pollutant emission (N, S and ash) Energy plant, environmental friendly Renewable and huge amount Compatibility with fossil fuel utilization

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Singapore sits in a region teeming with Biomass Energy Sources.

Energy Potential of Agro-processing Residues as Percentage of Total Primary Energy Production, %
45 40 35 30 25 20 15 10 5 0
s d ia ia n e s am s n a n y e l i la ai et on pp i a i h d l i V T M In Ph

Traditional biomass: Open burning, small domestic/industrial burners/boilers lead to Low efficiency High emissions Haze episodes Advanced bioenergy technology

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The Yield and Commanding of Palm Oil

Year Malaysia 1990 1995 2000 2005 2010 6.1 7.8 9.4 11.0 12.0 Yield (Million tons) Indonesia 2.4 4.7 7.0 10.4 12.6 Others 2.5 3.1 4.0 4.5 5.2 World 12.0 15.6 20.4 25.9 29.8 Commanding (Mt) World 12.5 16.6 22.1 28.4 35.5

High yield, 5 times of peanut oil Utilization: edible oil, butter, food industry, Soap, stearic acid, glycerine, etc.

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Wastes from Palm Oil Plant

Energy consumption: 20-25 kWh/t 0.73 ton steam

1 tonne fresh fruit

200 kg Palm oil

Waste:
600-700 kg POME ~ 20 m3 biogas 210 kg fibers + shells ~ 45 kWh 230 kg empty fruit bunches (EFB) ~ ~ 35 kWh

~ 30 Mt/year in Malaysia and 8.8 Mt/year in Indonesia of palm oil wastes (fruit shell, empty fruit bunch, and fiber) are generated. These wastes contain high iESE volatile matters (~75%) and have high calorific value (~ 20 MJ/kg).

Biomass Conversion Technologies

Direct Combustion Anaerobic Digestion

Gasification

Charcoal Production

Pyrolysis

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Issues in Sustainable Bioenergy Development

- Food or fuel? - Truly renewable? - Negative environmental and social impact? - Sustainable? - etc. Keys: - Biomass Wastes - Alternative Feedstock - 2nd and 3rd Generation Biofuel Technologies - Sustainability - Net GHGs Reduction

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IESEs work in advanced wastes gasification/pyrolysis for 2nd gen. biofuel production

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Palm oil wastes

Shell
Volume content (%) 6 5 4 3 2 1 0 0.1

Brought from Malaysia

shell fiber EFB

EFB

Ground

Fiber

10 100 Particle size (m)

1000

Proximate analysis (wt.%) Mad Shell Fiber 5.73 6.56 8.75 Vad 73.74 75.99 79.67 Ad 2.21 5.33 3.02 FCad

Ultimate analysis (wt.%, d) C H 7.20 7.07 7.33 N 0.00 S O

LHV (MJ/kg) 22.14 20.64 18.96

Molecular formula CH1.61O0.51 CH1.69O0.54 CH1.80O0.62

18.37 53.78 12.39 50.27 8.65 48.79

0.51 36.30

0.42 0.63 36.28 0.00 0.68 40.18

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EFB

Fixed Bed and Fluidized Bed Reactors in IESE

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Kinetics and Reactivity of Palm oil Wastes Pyrolysis

Main findings: 1. Pyrolysis of palm oil wastes can be divided into 4 stages at different temperatures; 2. Kinetic parameters of biomass degradation were explored; 3. Reaction rate was controlled by kinetics at low temperature (< 355C) 4. Gaseous products composition was highly dependent of pyrolysis temperature
Yan R., Yang H.P., Chin T., Liang D.T., Chen H.P., Zheng C.G. "Influence of temperature on the distribution of gaseous products from pyrolyzing palm oil wastes", Combustion and Flame, 142: 24-32 (2005). Yang H.P. Yan R., Chin T., Liang D.T., Chen H.P., Zheng C.G. Thermogravimetric analysis Fourier transform infrared analysis of palm oil wastes pyrolysis, Energy & Fuels, 18(6): 1814-1821 (2004).

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Fundamentals and Mechanisms of Palm oil Wastes Pyrolysis

Main findings: 1. Model biomass samples were synthesized based on three major components (cellulous, hemi-cellulous, lignin) to explore in-depth the mechanisms of biomass; 2. No significant interaction of the major components was observed in pyrolysis and prediction equations were established; 3. In the course of biomass pyrolysis, the evolution of gas, oil and solid products occurred at various forms in tendency.
Yang H.P., Yan R., Chen H.P., Lee D.H., Liang D.T., Zheng C.G. Mechanism of palm oil wastes pyrolysis in a packed bed, Energy & Fuels, 20(3): 1321-1328 (2006). Yang H.P., Yan R., Chen H.P., Zheng C.G., Lee D.H., Liang D.T. An in-depth investigation of biomass pyrolysis based on three major components: xylan, cellulose and lignin, Energy & Fuels, 20(1): 388-393 (2006).

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Crude Oil from Palm oil Wastes Pyrolysis

Main findings:
Li J.F., Yan R.*, Xiao B., Wang X.L., Yang H.P., Liang D.T. Influence of temperature on the formation of oil from pyrolyzing palm oil wastes in a fixed bed reactor, Energy & Fuels, 21 (4): 2398-2407 (2007).

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Temperature played a critical role, and oil components demonstrated a close link with gas releasing from pyrolyzing palm oil wastes.

Catalytic Biomass Gasification for Tar Removal

Development of Nano- NiO/Al2O3 Catalyst for tar removal and increasing H2 yield

Nanocatalyst size: 12 and 18 nm

Catalyst was eggshell structure which coated NiO nanoparticles on the surface of -Al2O3 sphere

Main findings:
1. Catalyst improved significantly the yield of H2 and ration of H2/CO for downstream FT process. 2. Cost of catalyst was reduced largely by coating active elements on supports, as applied in synthesis procedure.

Li J.F., Yan R.*, Xiao B., Liang T.D., Du L.J. Development of nano-NiO/Al2O3 catalyst to be used for tar removal in biomass gasification, Environmental Science and Technology, 42(16) 6224-6229 (2008). Li J.F., Yan R.*, Xiao B., Liang D.T., Lee D.H. Preparation of nano-NiO particles and evaluation of their catalytic activity in pyrolyzing biomass components, Energy & Fuels, 22(1), 16-23 (2008).

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3. Highly potential of industrial application of the developed catalysts for biomass gaisifcation

Catalytic Biomass Gasification to Generate Syngas for Biofuel Production

Home - grown technology:
Development of the new and novel nano-catalysts that enhance biomass gasification process with significantly increased yields of hydrogen and minimized air pollution.

Advantages: (1) gas cleaning

is easier, (2) the yield of H2 or syngas is the highest, (3) environmental impacts are the minimum even negligible, (4) power cycles are more efficient, and (5) carbon credit is awarded.

Catalytic biomass gasification for syngas

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Biosyngas an ideal intermediate between biomass and existing refineries !

Modeling and Simulation of Biomass Gasification/Pyrolysis

Non-homogeneous characteristics of biomass constituent difficult to apply simulation works to the pyrolysis of biomass to gaseous products. Two computation codes: HSC Chemistry and Sandia PSR to consider thermodynamic and kinetic phenomena. The principle of simulations: (1) Ultimate analysis of biomass, (2) HSC calculations for gas phase compositions, (3) Sandia PSR code for kinetics involving in the pyrolysis. Palm oil wastes were studied as sample biomass. The gaseous products obtained from HSC calculations: H2, CO2, CO, CH4 and negligible C2+ hydrocarbons. After PSR program: the final products :H2, CO2, CO, CH4, C2H2, C2H4, C2H6 and C3H8 which are more realistic products in the modern fast pyrolysis.

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HSC calculation for Fiber pyrolysis PSR input values calculated from HSC (moles)
Normalized PSR results for each point species concentration application

Details of newly evolved species taken from normalized PSR results Lee D.H., Yang H.P., Yan R.*, Liang D.T. Prediction of gaseous products from biomass pyrolysis through combined kinetic and thermodynamic simulations, Fuel, 86(3): 410-417 (2007).

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Torrefaction of Palm oil wastes

Torrefaction is a mild pyrolysis process that improves the fuel properties of wood. Final product of torrefied biomass is pellet which has 1.3 more energy density.

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Main Findings from Torrefaction of Palm oil wastes

The major parameters of torrefaction are temperature and residence time (RT). Higher temperature (300 C) affects more than longer RT (27 min) for energy density increase. The Energy density increase at 300 C and 27 min RT was 70 %.

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Other On-going Projects at IESE (NTU) Related to Clean Energy and Carbon Sequestration

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Biocrakcing and BDS of Heavy Fuel Oil into Marine Distillates

Biocracking: breaking of complex molecules by biological catalyst, e.g. bacteria, fungi. Target compounds of biocracking: Long chain saturated and unsaturated hydrocarbons Side chains Aromatic hydrocarbons Polynuclear aromatics Resins and asphaltenes: super stacked structure

MPA funded project

PI Dr Rong Yan, Oct. 2009 Sept. 2011

Benefits: Carried out at ambient temperature and pressure Requires lower capital and operational costs Versatility: multiple functions in one reactor biodesulfurization, biodenitrogenation, and demetallization Upgrade oil quality Reducing carbon emission by increased H/C ratio of fuel

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Bunker oil (residue) contains mostly heavy molecules of organo-S with aromatic rings

Advanced Chemical Looping Combustion (CLC) for CO2 Capture

A*star funded project
PI Dr Rong Yan, May 2009 April 2012

Introduction:
1. Chemical-looping combustion (CLC) is a combustion technology with inherent separation of CO2 from flue gas. CO2 steam is ready for sequestration and utilization. Advantages: Flexibility to produce H2 or electricity; better energy conversion efficiency and lower cost. A*star funded project (2009-2011).
Various Calcium species CaS CaCO3

2. 3.

Chemical looping gasification with hydrogen production and CO2 capture

Percentages of various caclium species

100 90 80 70 60 50 40 30 20 10 0

Objective and Scope:

Developing novel oxygen carrier with sufficient robustness to resist attrition during CLC in a fluidized bed (FB) reactor.

CaSO4
200 400 600 800 1000
o

CaO

1200

1400

FR temperature ( C)

Fundamental understanding to the relationship between performance and properties of the developed carriers. Advanced CLC process development.

iESEThermodynamic simulation result

MSW/Sludge Gasification/Pyrolysis for Bioenergy Prodcution

Objectives: The project targets at the development and commercialization of a sustainable waste management technology to convert sludge/ MSW in Singapore and other cities into bioenergy, through advanced gasification/pyrolysis including (1) sludge/MSW fast pyrolysis to generate bio-oil, and (2) sludge /MSW gasification to produce bio-syngas.

NEA funded project

PI Dr Rong Yan, Feb. 2010 Jan. 2012

Work Scope:
(1) A new reactor will be designed and established to teat efficiently the wastes in a cost-effective way. (2) Catalytic gasification/pyrolysis will be performed to obtain quality bioenergy products. (3) A conceptual design of the pilot plant of waste gasification/pyrolysis will be delivered at the end of project, and a demonstration pilot plant will be built in a facility designated by industrial partner. (4) A practical and sustainable option of treating sludge/MSW in cities could be provided with the success of proposed study.

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Quality of Biodiesel ERIA WG Standardization for East Asia

Properties
1. Viscosity (mm2/s @ 40 40C) 2. Density (kg/m3) 3. Flash point ( (C) 4. Cold filter plugging point ( (C) 5. Acid value (mgKOH/g) mgKOH/g) 6. Heating value (MJ/kg) 7. Oxidative stability (hours) 8. Cetane number 9. Content of FAME with 4 double bonds (%mol/mol) Biodiesel Standard ASTM
1.9-6

Biodiesel Algae(1)
5.2

European
3.5-5

Palm
4.5

Rapeseed
4.4

Jatropha
4.4

Soybean
4.0

Undefined

0.86-0.9

0.864 115 -11

0.878 160 7

0.883 150 -5

0.875 163 -1

0.885 160 -2

130
Undefined

120
Listed

0.5
Undefined

0.5 35
(Heating use)

O
41

O O O O O

O O x O O

O O x O O

O O x O

3 47
Undefined

6
(Vehicle use)

x O x

47 1

O Good

Fair

x Poor

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(1) Miao and Wu (2006), Biodiesel production from heterotropic microalgal oil, Bioresource Technology, V. 97, pp 841-846.

Summary
1. A large amount of biomass wastes (eg. palm oil wastes) are available in SE Asia as resources for bioenergy 2. Biomass gasification/pyrolysis/torrefaction technology is a promising solution for bioenergy production from biomass wastes. 3. IESE at Nanyang Technological University (Singapore) has accumulated strong experiences on wastes thermal conversion for 2nd generation biofuel development. 4. Since 2001, four PhD students graduated from this area, over 30 SCI papers published, and two patents filed. 5. IESE has been providing industrial consultancies on biomass wastes thermal conversion.

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6. We are keen to work together with international collaborators for further developments.

Thank you!!

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