Conversion of agricultural biomass to fuels and value- -added added Conversion of agricultural biomass to fuels and value products: Thermochemical approach products: Thermochemical approach Navadol Laosiripojana Navadol Laosiripojana The Joint Graduate School of Energy and Environment The Joint Graduate School of Energy and Environment King Mongkut’ ’s University of Technology Thonburi s University of Technology Thonburi King Mongkut
Background Background C onversion of plant lignocellulosic biomass is a key process on recycling of organic carbon in the global biogeochemical cycle. R&D aim to convert lignocellulosic biomass to useful and/or high value- added products (i.e. fuels, chemicals, biomaterials). The concept that integrates the lignocellulosic biomass conversion to fuels, materials, chemicals is called B iorefinery.
Lignocellulosic biomass Lignocellulosic biomass Biomass consists of three polymeric components: ● Cellulose ● Hemicellulose ● lignin Lignocellulosic Composition (%dry basis) Cellulose Hemicellulose Lignin Rice straw 35 25 12 Corn cop 45 35 15 Corn stover 40 25 17 Bagasse 40 24 25 Switchgrass 45 30 12 Wheat straw 30 50 20
Biorefinery A biorefinery is the technology that integrates biomass conversion process to produce fuels, power and chemicals.
I. Syngas conversion pathway I. Syngas conversion pathway Gas Pure purification hydrogen Electricity generation by fuel cells Syngas Biomass or gas turbine Ammonia Methanol Olefins DME Alkane fuel
Syngas conversion: Dimethyl Ether (DME) Syngas conversion: Dimethyl Ether (DME) What is Dimethyl Ether ? What is Dimethyl Ether ? � DME (CH DME (CH 3 OCH 3 ) , the simplest ether , colorless and 3 OCH 3 ) , the simplest ether , colorless and � odorless, contains no sulfurs or aromatics. odorless, contains no sulfurs or aromatics. � Alternative fuel for diesel or liquefied petroleum gas (LPG) Alternative fuel for diesel or liquefied petroleum gas (LPG) � � high cetane number (55 high cetane number (55- -60) 60) � � no SO no SO x , low NO x emission and low pollution for x , low NO x emission and low pollution for � environmental after combustion. environmental after combustion.
Syngas conversion: Dimethyl Ether (DME) Syngas conversion: Dimethyl Ether (DME) � Expect to become a fundamental chemical feedstock Expect to become a fundamental chemical feedstock � in the near future. in the near future. � Easily liquefied and can be used as a transportation Easily liquefied and can be used as a transportation � fuel. fuel. � Can be produced in large quantity through natural gas Can be produced in large quantity through natural gas � or coal. or coal.
Syngas conversion: Dimethyl Ether (DME) Syngas conversion: Dimethyl Ether (DME) A) Gasification A) Gasification � + oxidants � C x H y CO + H 2 C x H y + oxidants CO + H 2 B) Methanol Synthesis (Syngas to Methanol) B) Methanol Synthesis (Syngas to Methanol) � � CO + 2H 2 CH 3 OH CO + 2H CH 3 OH 2 C) Methanol Dehydration (Methanol to DME) C) Methanol Dehydration (Methanol to DME) � � 2CH 3 2CH 3 OH OH CH CH 3 3 OCH OCH 3 3 + H + H 2 2 O O
Syngas conversion: liquid alkanes Syngas conversion: liquid alkanes Fischer– –Tropsch (F Tropsch (F– –T) is regarded as technological schemes T) is regarded as technological schemes Fischer for converting synthesis gas to transportation liquid fuels. for converting synthesis gas to transportation liquid fuels. The proposed and future facilities will be substantially less The proposed and future facilities will be substantially less costly than their very expensive predecessors. Cost reductions costly than their very expensive predecessors. Cost reductions will be attributable to improvements in catalyst/reactor design. will be attributable to improvements in catalyst/reactor design.
Syngas conversion: Fuel Cells Syngas conversion: Fuel Cells A fuel cell is an electrochemical device that produces electricity and heat directly from a gaseous fuel by electrochemical combination of the fuel fuel with an oxidant oxidant. Anode Reaction : H 2 O + 2e - (Oxidation) H 2 + O 2- � (SOFC) CO 2 + 2e - (Oxidation) CO + O 2- � Electrolyte Cathode Reaction : O 2 + 4e - � O 2- + O 2- (Reduction) � H � Overall Reaction : 1/2O : 1/2O 2 + H 2 H 2 O Overall Reaction 2 + H 2 O 2 � CO + CO � 1/2O 2 CO 2 1/2O 2 + CO 2
Syngas conversion: Fuel Cells Syngas conversion: Fuel Cells Seal-less tubular Segmented cell in series design
Syngas conversion: Fuel Cells Syngas conversion: Fuel Cells (a) (b) Monolithic - Co-flow - Cross-flow Flat plate
II. Sugar conversion pathway II. Sugar conversion pathway Ethanol, Purification Purification Chemicals Sugarcane bagasse Rice straw Fermentation Fermentation Pretreatment Pretreatment Hydrolysis Hydrolysis Corn cob & Palm empty Fractionation stover fruit bunch Furans Dehydration Dehydration & Acids Pulp waste Cassava pulp Liquid Aldol-condensation / Aldol-condensation / alkane Hydrogenation Hydrogenation
Pretreatment of lignocellulosic biomass Pretreatment of lignocellulosic biomass Alkaline Alkaline Area Hemicel •%NaOH, T Agricultural Lignin @fixed t, %S by-products Inhibitor Area Alkaline/Oxidation Alkaline/Oxidation Hemicel •%NaOH, T •%PAA, T Lignin @fixed t, %S Inhibitor Cutting mill Diluted acid/Alkaline Diluted acid/Alkaline Area Hemicel •%H 2 SO 4 , T •%NaOH, T Lignin @fixed t, %S Inhibitor Hot compressed water Hot compressed water Area •T, t Hemicel @fixed %S Lignin •Noncatalytic/catalytic Inhibitor
Fractionation of lignocellulosic biomass Fractionation of lignocellulosic biomass General Concept of Fractionation General Concept of Fractionation Lignocellulosic Lignin Cellulose - Epoxy - Bio ethanol - Phenol - Paper - Carbon fiber Hemicellulose - Cellophane - Binders - Carboxymethyl - Xylitol - Activated Cellulose - 2,3 butanediol carbon - Etc. - Lactic acid - Dispersants - Ferulic acid - Etc. - Hydrogel - Etc.
Fractionation process for local lignocellulosic biomass Fractionation process for local lignocellulosic biomass Ternary mixture of methyl isobutyl ketone Ternary mixture of methyl isobutyl ketone (MIBK), ethanol and water. (MIBK), ethanol and water.
Fractionation process for local lignocellulosic biomass Fractionation process for local lignocellulosic biomass Phase separation at various temperatures Phase separation at various temperatures 1 st phase 2 nd phase 3 rd phase 180°C 170°C 200°C 190°C 160°C
Lignocellulosic- -ethanol ethanol production production Lignocellulosic Wood Rice straw Bagasse Lignin removal by: Pretreatment & - Pressurized water Fractionation - Alkaline/PAA - Multi-solvent process Enzymatic hydrolysis Enzyme selection -Commercial enzymes Optimization of time, - BIOTEC enzymes temperature, pH Fermentation process: Yeast screening SSF (Simultaneous - Utilize glucose/C 5 Saccharification and Fermentation - Thermotolerant Fermentation) - Glucose tolerant - Ethanol tolerant Bio-ethanol
Production of furans and organic acids Production of furans and organic acids Lignocellulosic biomass Pretreatment Thermocatalytic hydrolysis: HCW Enzymatic Enable to maximize the hydrolysis sugar yield with rapid production rate without pretreatment required Sugar: glucose + C 5 dehydration Furans and organic acids
50 45 100 HMF Furfural AHG Fructose %Conv. 90 HMF Furfural AHG Glucose 45 90 40 Fructose Xylose %Conv. Xylose 80 Glucose 40 80 35 70 Xylan Cellulose 35 70 30 Conversion (%) Conversion (%) 60 30 60 Yield (%) Yield (%) 25 50 25 50 20 40 20 40 15 30 15 30 10 20 10 20 5 10 5 10 0 0 0 0 Without TiZr Ti Zr Without TiZr Ti Zr Without TiZr Ti Zr Without TiZr Ti Zr catalyst catalyst catalyst catalyst A. Chareonlimkun, V. Champreda, A. Shotipruk, N. Laosiripojana, Fuel 89 (2010) 2873-2880. 30 HMF Furfural AHG Glucose 25 Fructose Xylose 20 Enhance furan yield of Yield (%) 15 12-18% from biomass 10 A. Chareonlimkun, V. Champreda, A. Shotipruk, N. Laosiripojana, Bioresource Technology 101 5 (2010) 4179-4186 0 No Cat. TiZr Ti Zr No Cat. TiZr Ti Zr No Cat. TiZr Ti Zr Bagasse Rice husk corncob
Biomass- -to to- -liquid (BTL) Production liquid (BTL) Production Biomass HMF HMTHFA Alkane C 6 -Sugar Aqueous phase reforming Hydrogen G.W. Huber et al, Science, 308 (2005) 1446 G.W. Huber et al, Science, 308 (2005) 1446 Catalyst A Catalyst B Cellulose Furans C 5,6 -Sugar Hemicellulose Catalyst D Biomass Lignin Phenol Catalyst C Integrative system for converting Integrative system for converting HMTHFA biomass to liquid alkane biomass to liquid alkane Hydrogen Catalyst D Synthesis of novel catalyst Synthesis of novel catalyst for this integrative reaction for this integrative reaction Alkane
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