Development of Hydrolysis Route for Cellulosic Ethanol from Sugarcane Biomass

Catalytic Processes Laboratories Biomass Conversion Group UFPEDevelopment of hydrolysis route for cellulosic ethanol from sugarcane biomass Henrique M. Baudel

ACKNOWLEDGEMENTS- MCT, CNPq, CAPES, FINEP, FACEPE (Brazil) STINT (Sweden), EULA-ALFA (European community), MES (Cuba)- Cesar Abreu, Mario T. Kato, A.M.Souto-Maior (UFPE)- Guido Zacchi, Gunnar Lidén, Bärbel Hahn-Hagerdal, Mats Galbe Marie Linde; P. Sassner; C. Roslander (Lund University, Sweden)- Silvia Nebra (NIPE/UNICAMP; FINEP-BIOETANOL)- Claudio Z.Zaror, Oscar Parra (Univ. de Concepción, Chile)- Carlos Martín (UMCC, Cuba)- George J.M. Rocha, Adilson Gonçalves (EEL/USP)- Aldo J.P. Dillon; M.Camassola (UCS); Alexandra Salgueiro (UNICAP)- C. E. Vaz Rossel (CTBE), Luiz P. Ramos (UFPR), E.M.P. Bon (UFRJ)- CTC colleagues and associates- Students: J. Augusto Tomé, Isaías B. Soares, M.R. Tavares (UFPE) Khalil Bensalem, Benjamin Bois (Univ. Lyon, France) J. Sendelius, Cristhian Carrasco (Lund University, Sweden)- Benjamin Knudsen, E.M. Bordin, Frank Haagensen (Novozymes)- Carlos F. Chagas (Bioenzima); Antenor Dvorak (REGMED)

Frequently Asked Questions (FAQ)• Why to produce Ethanol from Cane Biomass ?• Fuel or Chemical Ethanol ?• Holocellulosic or Cellulosic Ethanol ?• Chemical or Enzymatic Processes ?

Why to produce Ethanol from Cane Biomass ?• Cellulosic Ethanol Claimed by the Market• Urged Profitable Eco-Friendly Depletion of Surplus Biomass Ethanol from Surplus Cane Biomass = OpportunityPossibilities- more product (ethanol) using the same feedstock (sugarcane)- complimentary with current plant activities- getting best using (as much as possible) AMAP conventional technologies- simpler process configuration- easy and fast to implement (turn key)- no major environmental issues No competition- profitable, low investment with food!- self-sufficiency on energy

Bagasse or Straw?Preliminary Issues• Bagasse more suitable to burn ?• Straw less recalcitrant to hydrolysis ?• Bagasse available in-house• Straw to be collected and transported ?• Bagasse naturally comminuted• Straw to be milled ?

Holocellulosic or Cellulosic Ethanol ?1985 2000 2005 2015 ?ChemicalCellulosic ??????Bagasse Straw Chemical or Enzymatic Enzymatic Bagasse Straw Processes ? Cellulosic HolocellulosicOnce made feasible, Thermo-Chemical enzymatic will be Thermo-Biochemical ?????? unrivalled in themedium-long term! Fuel or Chemical Ethanol ? BOTH!

Cellulosic Ethanol from Sugarcane Biomass Enzymatic Hydrolysis of Bagasse

Feedstock Sugar Ethanol Production Production ProductionPreparation Saccharification Fermentation and Pretreatment Hydrolysis Purification Residue Processing

Industrial R&D approach Pretreatment Feedstock Hydrolysis Economic Assessment Residue Processing Fermentation per ton dry biomassLitres of Ethanol per ton cane per hectare

A Practical and Pragmatic ApproachIntegration with existing 1st Generation Ethanol plants- Capital cost, energy efficiency, emissions, transportation costsMolasses boosting / Mixing with dilute hydrolysates- No concentration required = energy savings / lower degradation- Moderate cellulose conversions = cheaper enzyme cocktails- Simpler fermentationCombustion of the residual cellulignin / mixing with bagasse- Use of existing boilers / steam generators- Deliver of additional bagasse for ethanol production- No recovery systems or conditioning required Separate Hydrolysis and Fermentation (SHF) - Simpler equipments and configurations = lower capital costs - Use of existing fermentation equipments - Processable solid LC residue = eco-efficiency - Easy yeast recovery

Process Development Concept Biomass Pretreatment Cellulosic Slurry Ethanol Separation Prehydrolysate LC Pulp Enzymes Enzymatic cane juice / Hydrolysis molasses Slurry Yeast Hydrolysate C6 Recovery and Separation Fermentation Distillation LC Solid Stillage SurplusSurplus Biomass Yeast Burning Treatment and Disposal Heat / Power

Process Development Concept Biomass Pretreatment Cellulosic Slurry Ethanol Separation Prehydrolysate LC Pulp Enzymes Enzymatic cane juice / Hydrolysis molasses Slurry Attractive in the short-term. Separation Hydrolysate C6 Yeast Recovery and Fermentation Distillation Competitive in the medium-term. LC Solid Best for the long-term ?Surplus Biomass Stillage Surplus Yeast Burning Treatment and Disposal Heat / Power

Pretreatment• Do minor differences among feedstocks result in significant differences performance?• Washed or unwashed incoming biomass?• Mill or Diffuser ?• Single-step or two steps? Over 1200 pretreatment runs performed at Lab/Bench, PDU and Industrial scales during 2002-08!

Pretreatment LAB / Bench Scale PARR Batch Stirred 1-L Reactor POP Batch 1.5 L-ReactorAcidic and Alkaline Pretreatments Acidic and Alkaline Pretreatments(without explosion): (with/without explosion):- Dilute Acid, (C)LHW - (C)WEX, Dilute acid,(C)LHW- Lime / Soda ; (C)WAO, WPO - (L)AFEX, Lime / Soda ; WPO

Pretreatment PDU ScaleSteam Explosion. Process Development Unit (PDU) Lund University, Sweden.

Pretreatment PDU Scale HB-21 polyvalent batch rotary 23-L reactor. REGMED, Brazil - Dual-Chamber (1L and 20 L) - Electrically Heated - Gas Inlet (O2, CO2, NH3) - Rapid Discharge Valve - Adaptable to Cyclone / Flash TankAcidic and Alkaline Pretreatments- Dilute Acid, (C)LHW, (C) WEX, (C)STEX- Lime / Soda ; (C)WAO, WPO, AFEX

Pretreatment Industrial Scale 2000 L batch reactor Feeding system (O2, catalysts, NH3) Controllable biomass loading Controllable heating profile Controllable pressure profile Controllable discharge valve Steam flow meter Cyclone / flash tankPolyvalent Steam Treatment Unit. CTC associate mills. Brazil.

PretreatmentSimilar bagasse compositions result in different PT performances. 100 86 82 80 75 74 Xylan 60 Glucan 43 43 Lignin 38 39 40 Others Fiber reactivity 20 0 A B C D E F Unwashed bagasse. 200ºC, 5 min, no catalyst. 24-h enzymatic hydrolysis, 2% WIS, pH 4.8, 15 FPU/g. (The use of catalysts on STEX tends to reduce such differences)

PretreatmentBagasse originated from diffusers tends to be less recalcitrant than the ones proceeding from mill/crushers, notably with uncatalysed STEX (Steam Explosion) processes and rigid cane varieties. Soft 100 Rigid Holocelulose removal 90 80 70 C: Catalysed C NC C NC C NC C NC C NC C NC C NC C NC C NC NC: Uncatalysed(normalized) M MD D M MD D M MD D M: Mill D: Diffuser 180ºC 190ºC 200ºC MD: Mixed Soft cane varieties are well processed in simpler equipments, under milder operational conditions.

Pretreatment Pre-washed bagasse tend to pretreat better, notably with uncatalysed STEX (Steam Explosion) processes. Pre-washed Fiber Reactivity HC Removal Unwashed100 10085 8570 7055 5540 40 180ºC 190ºC 200ºC 180ºC 190ºC 200ºC 180ºC 190ºC 200ºC 180ºC 190ºC 200ºC Uncatalysed Catalysed Uncatalysed Catalysed (normalized) Fiber reactivity may be influenced, although not exclusively related to hemicellulose removal.

PretreatmentGlobal efficiency tends to be more favoured by hemicellulose removal than by delignification 100 90 Higher Xylan Removal Glucan recovery 80 De 70 lign ific 60 atio De n 50 sac 40 et y lati 30 on 20 Higher Lignin 10 Removal 0 0,4 0,5 0,6 0,7 0,8 0,9 1,0 (xylan+lignin) / glucan glucan / (xylan + lignin) Delignification of ST bagasse does NOT necessarily improve process efficiency

PretreatmentTwo-step pretreatment tends to render more reactive fibers for uncatalysed STEX (Steam Explosion) processes. Unwashed bagasse 100 Single step Fiber reactivity 80 Two steps 60 40 20 0 180ºC 190ºC 200ºC 180ºC 190ºC 200ºC Catalysed Uncatalysed (normalized)(The use of catalysts on STEX tends to reduce such differences)

Small differences among PT bagasses result in significantly different fiber reactivity levels and cellulose conversions crystallization EHHC/HHHC Crystallinity Converted cellulose EHHC: Easy to Hydrolyse Hemicelluloses HHHC: Hard to Hydrolyse Hemicelluloses Washed uncatalysed ST bagasse. 180-200ºC , 5-10 min. 8-10%Hemicelluloses; 58-62%Cellulose; 25-28% Lignin. 24-h enzymatic hydrolysis; 2% WIS; 15 FPU/g. HC ratio (EHHC/HHHC) defines pretreatment severity levels for optimal HC removal from a given biomass

Still to Investigate 100 Fiber reactivity 80 60 40 ?????? Uncatalysed Catalysed 20 0 PCS1 PCS2 PCS3 PCS1 PCS2 PCS3 PSC: Physico-Chemical Severity PSC = f (T, t, P, H2O, additives) Pore Size CrystallinityHow to address the influence of the lignin removal on fiber reactivity ?How do catalysts alter LCC structure while removing HC and/or lignin ?How do HC and lignin behave after fragmentation and removal ?Is delignification really necessary ?

" The challenges we face are real. They are serious and they are many. They will not be met easily... ... or in a short span of time But know this: - They WILL be met!" Barack Houssein Obama

Development of Hydrolysis Route for Cellulosic Ethanol from Sugarcane Biomass

by CTBE - Brazilian Bioethanol Sci&Tech Laboratory on Apr 28, 2011

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Development of Hydrolysis Route for Cellulosic Ethanol from Sugarcane Biomass Presentation Transcript