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Advances in gasification/pyrolysisof biomass wastes for 2nd

generation biofuel production

Presented by Presented by

Dr Rong YANDr Rong YANCentre Director, Senior ScientistCentre Director, Senior Scientist

(Email: (Email: ryan@ntu.edu.sgryan@ntu.edu.sg))

Institute of Environmental Science and Engineering Institute of Environmental Science and Engineering (IESE)(IESE)

NanyangNanyang Technological University, SingaporeTechnological University, Singapore

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

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Outline of Presentation

1. Background introduction- Biomass energy- Palm oil wastes – a representative for SE Asia

2. IESE’s 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 CO2sequestration

4. Summary

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Biomass EnergyCO2 + 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 Singapore sits in a region teeming with Biomass Energy SourcesEnergy Sources……..

05

1015202530354045

Indonesia

Malaysia

Philippin

es

Thailand

Vietnam

Energy Potential of AgroEnergy Potential of Agro--processing Residues as processing Residues as Percentage of Total Primary Energy Production, %Percentage of Total Primary Energy Production, %

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 Yield (Million tons) Commanding

(Mt)Malaysia Indonesia Others World World

1990 6.1 2.4 2.5 12.0 12.51995 7.8 4.7 3.1 15.6 16.62000 9.4 7.0 4.0 20.4 22.12005 11.0 10.4 4.5 25.9 28.42010 12.0 12.6 5.2 29.8 35.5

High yield, 5 times of peanut oil

Utilization: edible oil, butter, food industry, Soap, stearic acid, glycerine, etc.

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Waste:Waste:600-700 kg POME ~ 20 m3 biogas

210 kg fibers + shells ~ 45 kWh

230 kg empty fruit bunches (EFB) ~ ) ~ ~ 35 kWh

Energy consumption:Energy consumption:2020--25 kWh/t25 kWh/t0.73 ton steam0.73 ton steam

1 1 tonnetonne fresh fruitfresh fruit 200 kg200 kgPalm oilPalm oil

Wastes from Palm Oil Plant Wastes from Palm Oil Plant

~ 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 volatile matters (~75%) and have high calorific value (~ 20 MJ/kg).

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Biomass Conversion Technologies

DirectCombustion

Gasification

Anaerobic Digestion

PyrolysisCharcoal Production

DirectCombustion

Gasification

Anaerobic Digestion

PyrolysisCharcoal Production

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Keys:

- Biomass Wastes

- Alternative Feedstock

- 2nd and 3rd Generation Biofuel Technologies

- Sustainability

- Net GHGs Reduction

Issues in Sustainable BioenergyDevelopment

- Food or fuel?

- Truly renewable?

- Negative environmental and social impact?

- Sustainable?

- etc.

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IESE’s work in advanced wastes gasification/pyrolysis for 2nd gen.

biofuel production

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0.1 1 10 100 10000

1

2

3

4

5

6

Vol

ume

cont

ent (

%)

Particle size (µm)

shell fiber EFB

Proximate analysis (wt.%) Ultimate analysis (wt.%, d) LHV (MJ/kg)

Molecular formula

Mad Vad Ad FCad C H N S O

Shell 5.73 73.74 2.21 18.37 53.78 7.20 0.00 0.51 36.30 22.14 CH1.61O0.51

Fiber 6.56 75.99 5.33 12.39 50.27 7.07 0.42 0.63 36.28 20.64 CH1.69O0.54

EFB 8.75 79.67 3.02 8.65 48.79 7.33 0.00 0.68 40.18 18.96 CH1.80O0.62

Palm oil wastes Brought from Malaysia

Shell

EFB

Fiber

Ground

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Fixed Bed and Fluidized Bed Reactors in IESE

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Kinetics and Reactivity of Palm oil Wastes Pyrolysis

Yan R., Yang H.P., Chin T., Liang D.T., Chen H.P., Zheng C.G. "Influence of temperature on the distribution of gaseous productsfrom 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).

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

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Fundamentals and Mechanisms of Palm oil Wastes Pyrolysis

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).

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.

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Crude Oil from Palm oil Wastes Pyrolysis

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).

Main findings:

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

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Catalytic Biomass Gasification for Tar Removal

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).

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 NiOnanoparticles on the surface of γ-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.

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

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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.

Biosyngas – an ideal intermediate between biomass and existing refineries !

Catalytic biomass gasification for

syngas

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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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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 %.

Main Findings from Torrefaction of Palm oil wastes

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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 hydrocarbonsSide chainsAromatic hydrocarbonsPolynuclear aromaticsResins and asphaltenes: super stacked structure

Benefits:Carried out at ambient temperature and pressureRequires lower capital and operational costsVersatility: multiple functions in one reactor -biodesulfurization, biodenitrogenation, and demetallizationUpgrade oil qualityReducing carbon emission by increased H/C ratio of fuel

MPA funded project PI – Dr Rong Yan, Oct. 2009 – Sept. 2011

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

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Advanced Chemical Looping Combustion (CLC) for CO2 Capture

Chemical looping gasification with hydrogen production and CO2 capture

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.

2. Advantages: Flexibility to produce H2 or electricity; better energy conversion efficiency and lower cost.

3. A*star funded project (2009-2011).

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

• Fundamental understanding to the relationship between performance and properties of the developed carriers.

• Advanced CLC process development.

200 400 600 800 1000 1200 14000

10

20

30

40

50

60

70

80

90

100

FR temperature (oC)

Various Calcium species

CaSO4CaO

CaSCaCO3

Perc

enta

ges

of v

ario

us c

acliu

m s

peci

es

Thermodynamic simulation result

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

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MSW/Sludge Gasification/Pyrolysis for BioenergyProdcution

NEA funded project PI – Dr Rong Yan, Feb. 2010 – Jan. 2012

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.

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 bioenergyproducts.

(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

∆OOOO≥ 47≥ 478. Cetane number8. Cetane number

OOOOx≤ 1Undefined9. Content of FAME 9. Content of FAME with with ≥ 4 double4 doublebonds (%mol/mol)bonds (%mol/mol)

xxxOx≥ 6(Vehicle use)

≥ 37. Oxidative stability 7. Oxidative stability (hours)(hours)

O

O

-1

163

0.875

4.4

JatrophaJatropha SoybeanSoybeanRapeseedRapeseedPalmPalmAlgaeAlgae(1)(1)EuropeanEuropeanASTMASTM

OOOO≤ 0.5≤ 0.55. Acid value 5. Acid value ((mgKOH/gmgKOH/g))

0.8850.8830.8780.8640.86-0.9Undefined2. Density (kg/m2. Density (kg/m33))

Undefined

Undefined

≥ 130

1.9-6

Biodiesel StandardBiodiesel Standard

160150160115≥ 1203. Flash point (3. Flash point (°°C)C)

-2-57-11Listed4. Cold filter4. Cold filterplugging point (plugging point (°°C)C)

OOO41≥ 35(Heating use)

6. Heating value6. Heating value(MJ/kg)(MJ/kg)

4.4 4.04.55.23.5-51. Viscosity1. Viscosity(mm(mm22/s @ 40/s @ 40°°C) C)

BiodieselBiodieselPropertiesProperties

O – Good ∆ – Fair x – Poor(1) Miao and Wu (2006), Biodiesel production from heterotropic microalgal oil, Bioresource Technology, V. 97, pp 841-846.

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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.

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

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Thank you!!Thank you!!