d4 universiti teknologi mara

8/6/2019 D4 Universiti Teknologi MARA

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Cost-Effective Technologies for ThermochemicalConversion of Biomass to Produce Fuels,

Chemicals, Materials and Power

Mohammad Asadullah

Professor (Dr)

Universiti Teknologi MARA

Faculty of Chemical EngineeringUniversiti Teknologi MARA
http://www.joomlaworks.gr/


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Content Introduction to R & D Projects Based on BiomassBackgroundProblem Statement ObjectivesMalaysian Government Policy of Utilizing BiomassBiomass Potentiality in MalaysiaTechnologies for Thermochemical Conversion of Biomass

Gasification of Biomass and Model of Commercial Plant Pyrolysis of Biomass and Model of Commercial Plant Summary and Conclusion


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R&D/Commercialization Projects

First R&DProject:BiomassGasification

Heat

Power

Liquid

Fuels

Power

ChemicalsSecond R&DProject: BiomassPyrolysis &Biorefinery

Materials


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What is Biomass

Biomasses are organic materials derived fromliving organisms, i.e. from plants or animals.

Depending on the source of biomass, it can be

classified as primary and secondary biomasses.

Background


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Formation of Biomass

C6 H12 O6 6H 2 O + 6CO 2

+ 6 O 2

Cellulose +Hemicellulose +Lignin

PrimaryBiom ass

Secondary Biomass
http://www.google.com/imgres?imgurl=http://www.vitabiogroup.com/imagens/biomass/biomass1.jpg&imgrefurl=http://www.vitabiogroup.com/interna.php?pg=biomass&usg=__uZsJgVO69sMbbTc3eBIS8jkrqa4=&h=240&w=335&sz=25&hl=en&start=103&sig2=9B5wUxnJX8mL3XlyXf9gjA&zoom=1&tbnid=5HWkNKGcb4-PUM:&tbnh=85&tbnw=119&ei=sKyQTd3nFIvfccGBjYQK&prev=/images?q=Picture+of+agricultural+biomass&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://newsimg.bbc.co.uk/media/images/42472000/jpg/_42472473_cowdung_patties203.jpg&imgrefurl=http://news.bbc.co.uk/2/hi/programmes/from_our_own_correspondent/6279929.stm&usg=__MSkmt5GX3yu40dfGXiGQIxwV8e8=&h=152&w=203&sz=18&hl=en&start=3&sig2=R_oP2zZhfaSQbZ_93OJotw&zoom=1&tbnid=qf-2aavYOAiNRM:&tbnh=79&tbnw=105&ei=m6uQTZesOdS8cdD98a0I&prev=/images?q=Cow+dung&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://www.arunaelectricalworks.com/biomass/img/BiomassIntro/biomass_fuel.jpg&imgrefurl=http://www.arunaelectricalworks.com/biomass/BiomassIntro.aspx&usg=__sYvLdrOJ3TJaTm2cD1qWM1ikI08=&h=191&w=219&sz=16&hl=en&start=99&sig2=AhJe5L6fPv8DCOpuWCPglw&zoom=1&tbnid=p63kjLHMAfHyHM:&tbnh=93&tbnw=107&ei=sKyQTd3nFIvfccGBjYQK&prev=/images?q=Picture+of+agricultural+biomass&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://www.vitabiogroup.com/imagens/biomass/biomass1.jpg&imgrefurl=http://www.vitabiogroup.com/interna.php?pg=biomass&usg=__uZsJgVO69sMbbTc3eBIS8jkrqa4=&h=240&w=335&sz=25&hl=en&start=103&sig2=9B5wUxnJX8mL3XlyXf9gjA&zoom=1&tbnid=5HWkNKGcb4-PUM:&tbnh=85&tbnw=119&ei=sKyQTd3nFIvfccGBjYQK&prev=/images?q=Picture+of+agricultural+biomass&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://cache2.asset-cache.net/xc/81551738.jpg?v=1&c=IWSAsset&k=2&d=77BFBA49EF8789215ABF3343C02EA548AC5671C2A1AA514DC4B88A942F0BE7F2379A24E075764100E30A760B0D811297&imgrefurl=http://www.life.com/image/81551738&usg=__oKvYOIcoHzYCmPL4hXeXyMa0aQ4=&h=371&w=594&sz=51&hl=en&start=106&sig2=bfMXUhk3f1jo3XxchjR2pg&zoom=1&tbnid=G26CSkNOyO4ThM:&tbnh=84&tbnw=135&ei=sKyQTd3nFIvfccGBjYQK&prev=/images?q=Picture+of+agricultural+biomass&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://c1.cleantechnica.com/files/2008/03/wood1.jpg&imgrefurl=http://cleantechnica.com/2008/03/09/interview-biomass-gas-and-electric-produces-energy-from-waste-products/&usg=__Dl7gAJADOg-zjHF3CBABOyDK_6g=&h=331&w=461&sz=57&hl=en&start=110&sig2=Vqn1uslOh8hZV7EyrDT1tQ&zoom=1&tbnid=seWgRfzE6PoEnM:&tbnh=92&tbnw=128&ei=sKyQTd3nFIvfccGBjYQK&prev=/images?q=Picture+of+agricultural+biomass&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://www.instablogsimages.com/images/2009/05/01/brick_dUxFh_23302.jpg&imgrefurl=http://www.greendiary.com/entry/cow-dung-ecofaebrick-bags-first-prize/&usg=__dzuIM0jCi4097kDC5m-stkz021c=&h=991&w=550&sz=578&hl=en&start=24&sig2=0idnwrPMxXS7QCq9MFvfJg&zoom=1&tbnid=rjQy6LFr3ezxWM:&tbnh=149&tbnw=83&ei=mquQTc6JFseGcaLQ_fcJ&prev=/images?q=Cow+dung&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://www.autoblog.com/media/2006/03/Cow-Dung-resized.jpg&imgrefurl=http://www.autoblog.com/2006/03/06/m/&usg=__RroO7P2HpPBR6fEhiPDSnIQuV4Q=&h=298&w=450&sz=28&hl=en&start=14&sig2=5CT4Tbtzvfl7NjVYv20gog&zoom=1&tbnid=E4JNZ1vp_5z7kM:&tbnh=84&tbnw=127&ei=m6uQTZesOdS8cdD98a0I&prev=/images?q=Cow+dung&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://tyler.blogware.com/cowdung.jpg&imgrefurl=http://tyler.blogware.com/2006/4/11/&usg=__RgHACWxBEkhelPQz4zNCVhRqv-M=&h=220&w=220&sz=16&hl=en&start=6&sig2=b2ycePBel3xhCTCPhzy62w&zoom=1&tbnid=Ckdb2BJWMytx4M:&tbnh=107&tbnw=107&ei=m6uQTZesOdS8cdD98a0I&prev=/images?q=Cow+dung&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://newsimg.bbc.co.uk/media/images/42472000/jpg/_42472473_cowdung_patties203.jpg&imgrefurl=http://news.bbc.co.uk/2/hi/programmes/from_our_own_correspondent/6279929.stm&usg=__MSkmt5GX3yu40dfGXiGQIxwV8e8=&h=152&w=203&sz=18&hl=en&start=3&sig2=R_oP2zZhfaSQbZ_93OJotw&zoom=1&tbnid=qf-2aavYOAiNRM:&tbnh=79&tbnw=105&ei=m6uQTZesOdS8cdD98a0I&prev=/images?q=Cow+dung&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://en.delaval.ca/NR/rdonlyres/8334143D-7458-45B0-B2A0-19F059FC716A/0/Cows.jpg&imgrefurl=http://en.delaval.ca/About_DeLaval/PressCentre/Image_gallery_genaral.htm&usg=__32XNkJ7yd0Owj59aSVQKCg9Qa40=&h=1312&w=2000&sz=2843&hl=en&start=154&sig2=HnCuTLTFFqh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Biomass is the Source of Fuels,Chemicals, Materials & Power

Every singlecarbon usedfrom fossilresources wouldbe excess into

the atmosphere. Millionsof years

Chemicals Materials PowerFuels
http://www2.wwnorton.com/college/geo/animations/oil_formation_trapping.htmhttp://www.google.com/imgres?imgurl=http://www.arunaelectricalworks.com/biomass/img/BiomassIntro/biomass_fuel.jpg&imgrefurl=http://www.arunaelectricalworks.com/biomass/BiomassIntro.aspx&usg=__sYvLdrOJ3TJaTm2cD1qWM1ikI08=&h=191&w=219&sz=16&hl=en&start=99&sig2=AhJe5L6fPv8DCOpuWCPglw&zoom=1&tbnid=p63kjLHMAfHyHM:&tbnh=93&tbnw=107&ei=sKyQTd3nFIvfccGBjYQK&prev=/images?q=Picture+of+agricultural+biomass&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://cache2.asset-cache.net/xc/81551738.jpg?v=1&c=IWSAsset&k=2&d=77BFBA49EF8789215ABF3343C02EA548AC5671C2A1AA514DC4B88A942F0BE7F2379A24E075764100E30A760B0D811297&imgrefurl=http://www.life.com/image/81551738&usg=__oKvYOIcoHzYCmPL4hXeXyMa0aQ4=&h=371&w=594&sz=51&hl=en&start=106&sig2=bfMXUhk3f1jo3XxchjR2pg&zoom=1&tbnid=G26CSkNOyO4ThM:&tbnh=84&tbnw=135&ei=sKyQTd3nFIvfccGBjYQK&prev=/images?q=Picture+of+agricultural+biomass&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://www.autoblog.com/media/2006/03/Cow-Dung-resized.jpg&imgrefurl=http://www.autoblog.com/2006/03/06/m/&usg=__RroO7P2HpPBR6fEhiPDSnIQuV4Q=&h=298&w=450&sz=28&hl=en&start=14&sig2=5CT4Tbtzvfl7NjVYv20gog&zoom=1&tbnid=E4JNZ1vp_5z7kM:&tbnh=84&tbnw=127&ei=m6uQTZesOdS8cdD98a0I&prev=/images?q=Cow+dung&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://newsimg.bbc.co.uk/media/images/42472000/jpg/_42472473_cowdung_patties203.jpg&imgrefurl=http://news.bbc.co.uk/2/hi/programmes/from_our_own_correspondent/6279929.stm&usg=__MSkmt5GX3yu40dfGXiGQIxwV8e8=&h=152&w=203&sz=18&hl=en&start=3&sig2=R_oP2zZhfaSQbZ_93OJotw&zoom=1&tbnid=qf-2aavYOAiNRM:&tbnh=79&tbnw=105&ei=m6uQTZesOdS8cdD98a0I&prev=/images?q=Cow+dung&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1


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Global Carbon Cycle

Burning of fossil fuel

Burning of biomass

4.5

1.5

1

95

103

101

50

53

53

48

2

100

5


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Mass Balance of the GlobalCarbon Cycle

Mass Balance

NET EMISSION = OUTPUT - INPUT= (100 + 4.5 + 1.5 + 1.0) - (100.0 +2.0)= 5.0 Bt/y

CO 2 Consumption

CO 2 Release Plant and soil respiration = 100.0 Bt/yLand use = 1.0 Bt/y

Fossil fuels burning = 4.5 Bt/yBiomass burning = 1.5 Bt/y

Ocean uptake (Sedimentation)

= 2.0 Bt/yPhotosynthesis = 100.0 Bt/y


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Global Mean Temperature Profile

The global temperature is supposed toincrease by 5 oC within 2050.

These are theoverall problemsrelated to the fossilresources.


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Overall Objective of this Technology

Fuels

Millionsof years

ChemicalsMaterialsPower

Fuels

Moderntechnology

Chemicals

Materials

Power

0 yearOverall objective

is to reducemillions of years

to zero year.
http://www.google.com/imgres?imgurl=http://www.arunaelectricalworks.com/biomass/img/BiomassIntro/biomass_fuel.jpg&imgrefurl=http://www.arunaelectricalworks.com/biomass/BiomassIntro.aspx&usg=__sYvLdrOJ3TJaTm2cD1qWM1ikI08=&h=191&w=219&sz=16&hl=en&start=99&sig2=AhJe5L6fPv8DCOpuWCPglw&zoom=1&tbnid=p63kjLHMAfHyHM:&tbnh=93&tbnw=107&ei=sKyQTd3nFIvfccGBjYQK&prev=/images?q=Picture+of+agricultural+biomass&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://cache2.asset-cache.net/xc/81551738.jpg?v=1&c=IWSAsset&k=2&d=77BFBA49EF8789215ABF3343C02EA548AC5671C2A1AA514DC4B88A942F0BE7F2379A24E075764100E30A760B0D811297&imgrefurl=http://www.life.com/image/81551738&usg=__oKvYOIcoHzYCmPL4hXeXyMa0aQ4=&h=371&w=594&sz=51&hl=en&start=106&sig2=bfMXUhk3f1jo3XxchjR2pg&zoom=1&tbnid=G26CSkNOyO4ThM:&tbnh=84&tbnw=135&ei=sKyQTd3nFIvfccGBjYQK&prev=/images?q=Picture+of+agricultural+biomass&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://www.autoblog.com/media/2006/03/Cow-Dung-resized.jpg&imgrefurl=http://www.autoblog.com/2006/03/06/m/&usg=__RroO7P2HpPBR6fEhiPDSnIQuV4Q=&h=298&w=450&sz=28&hl=en&start=14&sig2=5CT4Tbtzvfl7NjVYv20gog&zoom=1&tbnid=E4JNZ1vp_5z7kM:&tbnh=84&tbnw=127&ei=m6uQTZesOdS8cdD98a0I&prev=/images?q=Cow+dung&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://newsimg.bbc.co.uk/media/images/42472000/jpg/_42472473_cowdung_patties203.jpg&imgrefurl=http://news.bbc.co.uk/2/hi/programmes/from_our_own_correspondent/6279929.stm&usg=__MSkmt5GX3yu40dfGXiGQIxwV8e8=&h=152&w=203&sz=18&hl=en&start=3&sig2=R_oP2zZhfaSQbZ_93OJotw&zoom=1&tbnid=qf-2aavYOAiNRM:&tbnh=79&tbnw=105&ei=m6uQTZesOdS8cdD98a0I&prev=/images?q=Cow+dung&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www2.wwnorton.com/college/geo/animations/oil_formation_trapping.htmhttp://www.google.com/imgres?imgurl=http://www.arunaelectricalworks.com/biomass/img/BiomassIntro/biomass_fuel.jpg&imgrefurl=http://www.arunaelectricalworks.com/biomass/BiomassIntro.aspx&usg=__sYvLdrOJ3TJaTm2cD1qWM1ikI08=&h=191&w=219&sz=16&hl=en&start=99&sig2=AhJe5L6fPv8DCOpuWCPglw&zoom=1&tbnid=p63kjLHMAfHyHM:&tbnh=93&tbnw=107&ei=sKyQTd3nFIvfccGBjYQK&prev=/images?q=Picture+of+agricultural+biomass&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://cache2.asset-cache.net/xc/81551738.jpg?v=1&c=IWSAsset&k=2&d=77BFBA49EF8789215ABF3343C02EA548AC5671C2A1AA514DC4B88A942F0BE7F2379A24E075764100E30A760B0D811297&imgrefurl=http://www.life.com/image/81551738&usg=__oKvYOIcoHzYCmPL4hXeXyMa0aQ4=&h=371&w=594&sz=51&hl=en&start=106&sig2=bfMXUhk3f1jo3XxchjR2pg&zoom=1&tbnid=G26CSkNOyO4ThM:&tbnh=84&tbnw=135&ei=sKyQTd3nFIvfccGBjYQK&prev=/images?q=Picture+of+agricultural+biomass&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://www.autoblog.com/media/2006/03/Cow-Dung-resized.jpg&imgrefurl=http://www.autoblog.com/2006/03/06/m/&usg=__RroO7P2HpPBR6fEhiPDSnIQuV4Q=&h=298&w=450&sz=28&hl=en&start=14&sig2=5CT4Tbtzvfl7NjVYv20gog&zoom=1&tbnid=E4JNZ1vp_5z7kM:&tbnh=84&tbnw=127&ei=m6uQTZesOdS8cdD98a0I&prev=/images?q=Cow+dung&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://newsimg.bbc.co.uk/media/images/42472000/jpg/_42472473_cowdung_patties203.jpg&imgrefurl=http://news.bbc.co.uk/2/hi/programmes/from_our_own_correspondent/6279929.stm&usg=__MSkmt5GX3yu40dfGXiGQIxwV8e8=&h=152&w=203&sz=18&hl=en&start=3&sig2=R_oP2zZhfaSQbZ_93OJotw&zoom=1&tbnid=qf-2aavYOAiNRM:&tbnh=79&tbnw=105&ei=m6uQTZesOdS8cdD98a0I&prev=/images?q=Cow+dung&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1


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Why Biomass is a CarbonNeutral Fuel

Heat or

6CO 2 + 6H 2O

Bacterialaction

NaturalCycleC6H12 O6

XGasificationGas orLiquid

6H 2O + 6CO 2

Pyrolysis

Artificial Cycle

Energy

Biomass
http://www.google.com/imgres?imgurl=http://www.arunaelectricalworks.com/biomass/img/BiomassIntro/biomass_fuel.jpg&imgrefurl=http://www.arunaelectricalworks.com/biomass/BiomassIntro.aspx&usg=__sYvLdrOJ3TJaTm2cD1qWM1ikI08=&h=191&w=219&sz=16&hl=en&start=99&sig2=AhJe5L6fPv8DCOpuWCPglw&zoom=1&tbnid=p63kjLHMAfHyHM:&tbnh=93&tbnw=107&ei=sKyQTd3nFIvfccGBjYQK&prev=/images?q=Picture+of+agricultural+biomass&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1http://www.google.com/imgres?imgurl=http://www.arunaelectricalworks.com/biomass/img/BiomassIntro/biomass_fuel.jpg&imgrefurl=http://www.arunaelectricalworks.com/biomass/BiomassIntro.aspx&usg=__sYvLdrOJ3TJaTm2cD1qWM1ikI08=&h=191&w=219&sz=16&hl=en&start=99&sig2=AhJe5L6fPv8DCOpuWCPglw&zoom=1&tbnid=p63kjLHMAfHyHM:&tbnh=93&tbnw=107&ei=sKyQTd3nFIvfccGBjYQK&prev=/images?q=Picture+of+agricultural+biomass&um=1&hl=en&safe=off&sa=X&rls=com.microsoft:en-us&biw=1259&bih=588&tbs=isch:1&um=1&itbs=1


12/60

Malaysian Governmental Policy of Utilizing Renewable Resources, 2011

On June 10, 2010, the government announced the NationalRenewable Energy Policy and Action Plan with a goal of increasing renewable energy from 1% to 5.5% of electricity

supply by 2015.The program is going to be launched by the secondquarter of 2011.

Source: Renewable energy world.com, August 16, 2010

The current proposal limits the program to 219 MW in

2011, increasing to nearly 1,000 MW in 2015. The bulk of the new generating capacity to be installed under theprogram is set aside for biomass and minihydro.


13/60

Quota of Biomass Energy out of TotalRenewable Energy Generation


14/60

Comparison of Tariffs for PV andBiomass Energy


15/60


16/60

Problems with Existing GasificationTechnology

High temperature method > 1000 oC

Tar yield > 5%Tar deposits in the down stream applicationof syngas and makes problems

Tar separation by physical filtration isnot technically viable


17/60

Fundamental Concept of Gasification ina Down Draft Gasifier

Biomass

Zone I

Zone IIOxidation

ReductionZone III

Pyrolysis

Char Volatiles (Liquid vapour + CO, H 2 ,H2O, CO 2 , CH 4 , C 2 H2 )

C + CO 2 2COC + H 2O CO + H 2CO + H 2O CO2 + H 2

CO, H 2 , H 2O, CO 2 , CH 4 , C 2H2 , N 2, tar Char + Ash

Char + Ash Volatiles

AirO2H2 OCO2

C + O 2 COC + O 2 CO2H2+ O2 H2O

(CO, H 2 , H 2 O, CO 2 ,CH4 , C 2 H2 , N 2 )


18/60

Asadullah et al ., Catalysis Communication , 2, 2001, 63-68.

Catalytic Gasification of Cellulose

Asadullah et al., Industrial and Engineering Chemistry Research , 40, 2001 , 5894 .


19/60

Result of Catalyst Screaming


20/60

Feeder

Air

Vibrator

Productgas

Furnace

Thermocouple Distributor

Catalyst particles

Asadullah et al., Applied Catalysis A: General, Volume 255,Issue 2, 8 December 2003, Pages 169-180

Asadullah et al. , Industrial and Engineering Chemistry Research ,41, 2002, 4567-4575

Catalytic Gasification of Cellulose


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TEM Images of Rh/CeO 2 Catalyst

30 nm 30 nm

Asadullah et al. , Industrial and Engineering Chemistry Research ,41, 2002, 4567-4575

Rh/CeO 2sintered anddeactivated


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TEM Images of Rh/CeO 2/SiO 2 Catalyst

TEM images of Rh/CeO 2/SiO 2; (a) fresh catalyst, (b) after reaction

Asadullah et al., Journal of Catalysis, 208, 2002 , 255-259

Rh/CeO 2 /SiO 2No sintering

at all afterreaction


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Asadullah et al., Applied Catalysis A: General 255 (2003) 169 180.

Rh/CeO 2/SiO 2 Catalyst for RealBiomass Gasification

No problemsat all even at650 oC

Ashproblems


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T (oC) Formation rate

(mmol/min) H2/CO C-

conv Charyield

Cokeyield

Taryield

CO H2 CO 2 CH4 (%-C) (%-C) (%-C) (%-C)

Cedar 550 2152 2686 1841 517 1.3 78 20.8 1.2 0

600 2599 3232 1752 269 1.2 80 19.1 0.8 0

650 2902 3541 1605 148 1.2 81 18.5 0.5 0

Jute stick 550 2032 2634 1729 323 1.3 71 24.0 3.0 2.0

600 2362 3036 1818 306 1.3 78 17.0 1.0 0.0

650 3057 3255 1577 218 1.1 84 14.5 0.5 0.0

Bagasse 550 1850 2057 1645 416 1.1 68 21.0 4.0 7.0

600 2050 2357 1739 516 1.2 75 21.0 2.0 2.0

650 2965 3264 1587 205 1.1 82 17.0 1.0 0.0

Ricestraw 550 1797 2057 1569 366 1.2 65 21.0 4.0 10.0

600 2102 2162 1677 452 1 74 19.0 4.0 3.0

650 2878 3167 1524 172 1.1 80 16.0 2.0 2.0 Conditions: Catalyst 3 g, ER = 0.24, feeding rate 150 mg/min (moisture: 5 10%), N 2 flow 100 ml/min, O 2 flow 35 ml/min through the catalyst bed.

Effect of Temperature on the Gasification ofVarious Biomass on Rh/CeO 2 /SiO 2 Catalyst


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0

20

40

60

80

100

450 550 650 750 850 950 1050

W e i g

h t r a t

i o / %

Temperature/K

Rice straw

Bagasse

Cedar

Jute stick

Properties of Various Biomasses


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Mechanism of Rh/CeO 2/SiO 2 Catalytic Reaction

CO 2 + H 2OCH 4

H2O O2

CharCO + H 2

H2O

Tar

Oxidizedcatalyst

Reducedcatalyst

CeO 2

SiO 2

O2 Mobility

high

Highsurface

area

Very

active

RhCeO 2SiO2


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Problem Statement and Objectivesfor Further Development of Catalysts

Problem:

Rh catalyst is expensive

Objectives:

To develop cheap catalysts with high activity

To produce highly dispersed catalyst on highsurface area cheap materials


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Asadullah, et al., Fuel, doi:10.1016/j.fuel.2010.12.039.

Asadullah et al. , Fuel (In Press, 2011)

Cheap Catalyst for Tar Reforming

Charsupportedcatalyst

P f f Ch S d


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0

5

10

15

20

25

30

35

400 500 600 700 800 900Temperature ( oC)

T a r y i e l

d ( w t %

o f b i o m a s s ,

d b ) Pyrolysis

Reforming no catalystReforming with H-charReforming with Fe-charReforming with Ni-char

0

5

10

15

20

25

30

35

400 500 600 700 800 900Temperature ( oC)

T a r y i e l

d ( w t %

o f b i o m a s s ,

d b )

Pyrolysis

Reforming no catalyst

Reforming with ilmenite

Performance of Char SupportedCatalyst

Ilmenite CatalystChar supportedcatalyst

P f f Ch S t d


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0

500

1000

1500

2000

2500

260 300 340 380 420 460 500Wavelength (nm)

(a)

I n t e n s i t y ( a

. u . ,

p e r g o f b i o m a s s ( d b )

PyrolysisReforming no catalystReforming with H-charReforming with Fe-charReforming with Ni-char

0

500

1000

1500

2000

2500

260 300 340 380 420 460 500Wavelength (nm)

(b)

I n t e n s

i t y ( a

. u . ,

p e r g o

f b i o m a s s

( d b )

PyrolysisReforming no catalys tReforming with H-charReforming with Fe-charReforming with Ni-char

0

500

1000

1500

2000

2500

260 300 340 380 420 460 500Wavelength (nm)

(c)

I n t e n s

i t y ( a

. u . ,

p e r g o

f b i o m a s s

( d b ) )


0

500

1000

1500

2000

2500

260 300 340 380 420 460 500

Wavelength (nm)(d)

I n t e n s i

t y ( a

. u . ,

p e r g o

f b i o m a s s

( d b )


0

500

1000

1500

2000

2500

260 300 340 380 420 460 500Wavelength (nm)

(e)

I n t e n s i

t y ( a

. u . ,

p e r g o f

b i o m a s s

( d b )


Constant energy ( = -2800 cm -1) synchronous spectra of mallee wood tar solution (4ppm) after the steam reforming of its volatiles with/without the char-supported

catalysts at the temperatures of (a), 500 C; (b), 600 C; (c), 700 C; (d), 800 C and(e), 850 C.

Performance of Char SupportedCatalyst


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Asadullah et al., Bioresource Technology ,doi:10.1016/j.biortech.2010.05.048

Asadullah et al ., Industrial and Engineering Chemistry Research, 48, 2 009, 9858-9863.

Asadullah et al., Fuel ProcessingTechnology In Press, Corrected Proof , Available online 3 September 2009.

A schematic diagram of the fluidised-bedreactor used for the fast heating pyrolysis.

Char Characteristics Studies

L b S l D t ti Pl t f


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Product gasoutlet

Air inlet

Water

Steam Thermocouple

Thermocouple

Lab Scale Demonstration Plant forBiomass Gasification

Lab Scale Demonstration Plant for


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Solidsamplingport

399mm

340mm

1-100 rpm

400mm

Solid samplingport

Solid samplingport

Solid samplingport

Lookingglass

Lookingglass

Lookingglass

1500mm

150mm

Gas samplingport

Gas samplingport

Gas samplingport

Gas samplingport

Thermocouple

Thermoco

uple

Lab Scale Demonstration Plant forBiomass Gasification

Looking

glass

Solidsampling

port

Rotatingshaft


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Water in

Water out

300 mm

120mm

Moving

Moving

Moving

Moving

Hot gas

out

1350 mm

150 mm

350 mm

350 mm

350 mm

80 mm

360mm

20 o

20 o

20 o

Inner Design

RotatingArms


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1500mm

120

mm

150mm

Air

Water

Out View of the Gasifier Main Body

BiomassHopper

CatalystHopper

Gas outlet


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1500mm

120mm

150mm

Air Water

Volatiles inletinto thecatalystchamber

Inner Design


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Picture of Complete Gasifier


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f l f


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Pi f C l G ifi


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Product Gas Quality from Non-


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Gasification temperature, oC 850 50 850 50 850 50 850 50 850 50

Biomass feeding rate, kg/h 4 4 4 4 4

Air fuel ratio 0.09 0.18 0.27 0.36 0.53 Steam flow rate, kg/h 0.6 0.6 0.6 0.6 0.6

Gas composition

H2 26.62 17.54 19.77 15.11 16.11

CO 30.42 33.59 27.27 31.34 24.76

CH4 11.55 12.50 10.55 10.55 9.73 C2H6 0.32 0.43 0.38 0.39 0.39

C2H4 1.74 2.42 2.17 2.59 2.45

CO 2 12.87 11.12 12.94 13.55 13.36

N2 10.38 14.73 21.73 24.94 30.67

O2 0.24 0.85 1.29 0.08 1.00

LHV, MJ/kg 13.43 12.60 10.75 10.14 9.21

LHV, MJ/Nm 3 11.76 12.10 10.36 10.35 9.34

Tar yield, mg/Nm 3 5100 9900 8600 8400 10900

Tar yield, mg/MJ 929 725 866 1027 589

Product Gas Quality from Non-Catalytic Experiment

Product Gas Quality from


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Gasification temperature, oC 850 50 850 50 850 50

Biomass feeding rate, kg/h 4 4 4 Air fuel ratio 0.09 0.27 0.53

Steam flow rate, kg/h 0.6 0.6 0.6

Gas composition

H2 50.50 35.98 31.37

CO 32.15 35.89 33.30 CH4 4.14 6.14 7.22

C2H6 0.08 0.07 0.05

C2H4 0.24 0.36 0.37

CO 2 5.05 6.72 9.54

N2 6.58 10.01 13.97 O2 0.02 0.03 0.01

LHV, MJ/kg 13.74 12.03 9.18

LHV, MJ/Nm 3 10.44 9.95 8.31

Tar yield, mg/Nm 3 2400 4900 2200

Tar yield, mg/MJ 929 866 589

Product Gas Quality fromCatalytic Experiment


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Empty Fruit Bunches 19.00 million tones/y

Mesocarp Fiber 13.00 million tones/yShell 5.20 million tones/y

Palm Kernel Expeller 2.11 million tones/y

Total 47.61 million tones/y

Approximate energycontent

8.09 x 10 11 MJ2.24 x 10 5 GWh

Total price 6.27 x 10 4 BRM

Biomass Potentiality in Malaysia


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Input and Output of a 20 MWPower Plant

Raw Materials Wood chips 176 t/day 64,689 t/y

Power

Generation

Gasification New type

Efficiency >50%

Electricity tobe sold

636 x 10 6 kWh 231 x 10 9 kWh

Total sell

price- RM

177 MRM/day 64 BRM/y

EnvironmentalEffects

CO2 reduction 91,000 t/y

Energy saving 60,944 t heavyoil/y

Model of Commercial Power Generation


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Gasifier

Gas Scrubbing

Water

Fly Ash

Catalytic

Reformer

GasEngine

Steampowergeneration

To Stack

Ashcollector

Conveyer

Gas Cooler

Gas BufferTank

Steam +Air

Gas Filter

Model of Commercial Power Generationfrom Biomass (Wood Log)


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N l f h P


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Novelty of the Process

Moisture content 0-50% in biomass can be used

Biomass particle size 3-5 cm 3, real size from the large scalechipper, can be used

Almost all kinds of cellulosic biomass can be used

Pyrolyser is a compact and high throughput design

Catalyst is char supported and thus very cheap

Biorefinery Concept to Produce Fuels,


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Dryer

Pyrolyzer

H2O

Char

Bi-oil

W e t B i o

m a s s

W e t B i o

m a s s

Resin

Electricity

Gas (H 2)

Gas (H 2) GasEnginesor FuelCellsGasifier

SteamReformer

Route 1b

R o u t e1

R o u t e2

Route 1a

Route 1c

O p t i on1

O p t i on

3

Option 2

Option 2a

Option 2bWater

Light Olefine, CO 2

Oxidizer EsterifierH2O2 Ethanol

D i s t i l l er y

Low Temperature

Hydrogenation

High TemperatureHydrogenation

H2

H2

H2

ZSM-5400-500 oC

SteamActivator

AdsorbentActivated Carbon

Fertilizerabsorber

Slow ReleaseFertilizer

O

OH

OH

O

OH

OH

OH

OH

OH

OHOH

OH

OH

CH 3

OH

OH

OH

OH

CH 3

OH

OH

OH

OH

OH

OH

OH

OH

O

O

H

O

O

O

O

H

O

O

O

O

O

OH OH

OO

O

OH

O

O

OH

OH

O

OH

O

OOOH

OH

O OH

OH Polymerizer

(to Steam Reformeror Furnace)

Light Alkane

y pChemicals, Materials and Power

Rotating Cone Reactor for


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Rotating Cone Reactor forFast Pyrolysis

Controlpanel

BinCombustor

Reactor Condenser

Pump

Compressor

Liquidcollector

CoolingWater

Screw feeder

Flue gas

Productgas


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120mm


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120mm

Product Distribution from Jute


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Product Distribution from JuteStick Pyrolysis

Pyrolysis conditionsJute stick feeding rate, kg/h 0.50

Temperature, oC 500

Nitrogen gas flow rate, ml/min 300

Pyrolysis products

Bio-oil

First condenser, kg/h (wt%) 0.14 (28)

Second condenser, kg/h (wt%) 0.16 (32)Total, kg/h (wt%) 0.30 (60)

Char, kg/h (wt%) 0.12 (24)

Gas, kg/h (wt%) 0.08 (16)

Effect of Temperature on Product


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Effect of Temperature on Product Distribution

0

20

40

60

80

100

0 200 400 600 800

Temperature, oC

Y i e l d o f b i o - o i l a n d c h a r , w t %

0

4

8

12

16

20

Y i e l d o f g a s , w t %

Gas

Bio-oil

Char


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What is Bio-oil?

Bio-oil is a dark brown liquid. It contains about 200 types of chemicals mainly phenols, aromatic hydrocarbons, carboxylicacids and other highly oxygenated materials.

Bio-oil

Physical Properties of


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Physical Properties of Bio-oil

PropertiesDensity, g/cc 1.07 - 1.09

pH 3.20 - 3.35

Water content, wt% 15 - 20Char/Solid content, wt% 0.07 - 0.10

Pyrolytic lignin 3.83 - 4.91

Acid Value 122.5 - 134.2 Ash content, wt% 0.03

Viscosity, Centipoise 2.59


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Next Step Pilot Plant

Condenser

Char Collector

Pyrolyser10 kg/h

Conveyer Dryer

Pyrolyzer

H2O

Char

Bi-oil

W e t

B i o m

a s s

W e t

B i o m

a s s

Resin

ElectricityGas(H2)

Gas(H2)

GasEngine

s orFuelCells

Gasifier

SteamReformer

Route1b

R o u t

e1

R o u t

e2

Route1a

Route1c

O p t i o

n1

O p t i o

n 3

Option 2

Option2a

Option 2b

Water

LightOlefine, CO 2

Oxidizer

EsterifierH2O2 Ethanol

D i s t i l l er

y

LowTemperatureHydrogenation

HighTemperatureHydrogenationH

2

H2

H2 ZSM-5

400-500 oC

SteamActivato

rAdsorbentActivated

CarbonFertilize

rabsorb

er

Slow ReleaseFertilizer

O

OH

OH

O

OH

OH

OH

OH

OH

OHOH

OH

OH

CH 3

OH

OH

OH

OH

CH 3

OH

OH

OH

OH

OH

OH

OH

OH

O

O

H

O

O

O

O

H

O

O

O

O

O

OH OH

OO

O

OH

O

O

OH

OH

O

OH

O

OO

OH

OHO OH

OH Polymerizer

(to SteamReformer

orFurnace)

Light Alkane

Bio-oil Tank

Bio-oil forRefining

Novelty of this Process


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Novelty of this Process

Compact and high throughput pyrolyser has been designed.

A novel catalyst has been developed for bio-oil reforming.

Bio-oil has been separated in high volatile fraction and highmolecular organic fraction.Novolac resin has been synthesized from organic fraction.

Big particles of biomass can be pyrolysed as a fast heatingpyrolysis.

High surface area activated carbon has been produced fromchar.

Summary and Conclusion


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Summary and Conclusion

Gasification technology is almost ready for large scalepilot plant testing.

For pilot plant, approximate costing may be RM 1,000,000 to5,000,000 depending on the plant size from 50 kg to 1 ton/h.

Pyrolysis technology is ready for lab scale pilot plant withthe capacity of 20 kg/h 50 kg/h. Approximate costing maybe RM 2,000,000 for pyrolysis and refining setup.

From bio-oil, liquid fuels, chemicals, materials includingbioplastic and resin and power can be produced.

d4 universiti teknologi mara

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