BIOETHANOL AND BIOHYDROGEN INTEGRATION: PERSPECTIVES AND CHALLENGES

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1 BIOETHANOL AND BIOHYDROGEN INTEGRATION: PERSPECTIVES AND CHALLENGES Viridiana Ferreira-Leitão Av. Venezuela, 82 /302, , Rio de Janeiro, RJ, Brazil +55 (21)

2 NATIONAL INSTITUTE OF TECHNOLOGY (INT) The National Institute of Technology (INT) is a research unit of the Ministry of Science, Technology and Innovation founded in INT Rio de Janeiro (RJ)

3 INOVATION WITH HUMAN CAPITAL 700 Employees and Collaborators 196 DSc and MSc

4 NATIONAL INSTITUTE OF TECHNOLOGY (INT) Our mission is to participate in the sustainable development of our country through technological research, knowlegde transfer and innovation.

5 DIVISION OF CATALYSIS AND CHEMICAL PROCESS Biohydrogen Ethanol 2G

6 BIOCATALYSIS LABORATORY Cell wall Biogas Microfibril Effluent Plant cell Hemicellulose Elementary fibril Lignin BIOETHANOL Cellulose Substrate BIOHYDROGEN

7 BIOETHANOL PROJECT BAGASSE AND STRAW PROCESSING Cell wall Microfibril Plant cell Hemicellulose Elementary fibril Lignin Cellulose

8 BIOMASS PRETREATMENT STEAM EXPLOSION ACID PRETREATMENT IONIC LIQUIDS HYDROTHERMAL

9 ETHANOL 2G INT Enzyme production Yeast Ethanol Biomass Pretreatment Hydrolysis Fermentation Distilation Lignin Residues Pretreatment; Hydrolysis; Chemical and structural characterization of biomass. SSF: saccarification and fermentation simultaneous

10 ETHANOL 2G - OPPORTUNITIES C6 sugars: conventional fermentation by yeasts 4-8 h C5 sugars: non conventional fermentation for the Brazilian ethanol sector

Chemical Industry based on renewable sources.

11 ETHANOL 2G - OPPORTUNITIES ABIQUIM in 2010 Brazilian Chemistry Association: In the next 20 years Brazil should start and implement actions to promote a Chemical Industry based on renewable sources. C6 sugars: conventional fermentation by yeasts 4-8 h C5 sugars: non conventional fermentation for the Brazilian ethanol sector

12 PRODUCTS FROM CELLULOSE FURANIC POLYMERS REGENERATED CELLULOSE ETHERS POLYESTERS ENZYMES LEVULINIC ACID DMF HMF VITAMIN C SYNTETIC RUBBER BUTADIENE SORBITOL (BIO)POLYMERS ETHYLENE Alcohol-chemistry ETHANOL POLY-HYDROXY-ALCANOATES ESTERS ACETIC ACID BIOPOLYMERS SCP BUTANOL ACETONE GLYCEROL CITRIC ACID BUTIRIC ACID GLUTAMIC ACID LACTIC ACID GLUCONIC ACID SUCCINIC ACID ESTERS GLUCOSE CELLULOSE BIOMASS Pereira Jr., 2010.

13 NYLON TETRA HYDRO FURAN PRODUCTS FROM HEMICELLULOSE FURAN LYSINA RESINS and PLASTICS GLUTAMIC ACID ORGANIC ACIDS PHA s DMF FURFURAL ACETONE ENZYMES BUTANOL XYLITOL SORBITOL MANITOL GALACTOL ARABITOL SCP ETHANOL ACETIC ACID URONIC ACID MONOSSACHARIDES (SUGARS) XYLOSE; GLUCOSE; ARABINOSE; GALACTOSE; MANNOSE HEMICELLULOSE CELLULOSE BIOMASS Pereira Jr., 2010.

14 PRODUCTS FROM LIGNIN ENERGY SOLID FUEL LIQUID HYDROCARBONS SIMILAR TO THOSE OF PETROLEUM CRUDE OIL CHEMICAL PRODUCTS LIQUID FUELS PHENOL, BIO-OILS VANILLIN, OXIDIZED LIGNIN PHENOLIC RESINS METHANOL PYROLYSIS OXIDIZING PROCESSES SYNGAS GASIFICATION HEMICELLULOSE CELLULOSE BIOMASS LIGNIN Pereira Jr., 2010.

16 ETHANOL PATENTS X CRUDE OIL PRICES 800 C12P706: Ethanol, i.e non beverage Number of patents 100 Number of patents Crude oil (US$/Barrel) Year Waste and Biomass Valor, : Crude oil (US$/Barrel)

17 TOP 5 PLAYERS PATENTS APPLICANTS Waste and Biomass Valor, :17-32.

19 BIOMASS AVAILABILITY IN BRAZIL Crop World Production % Brazilian Residual biomass production in Brazil production production (1000 ton) (1000 ton) (1000 ton) Sugar cane , Cassava , Citrus , Corn , Wheat , Coconut ,6 481 Over 500 million ton of agricultural residues/year Ferreira-Leitão et al., Waste and Biomass Valorization, 1:65-76

21 Yield (%) PRETREATMENT STUDIES SO 2 AND CO , ,8 glucose (%) ,6 xylose (%) severity 30 3, , C 210C 220C 190C 190C 200C 210C 220C Without impregnating agent SO2 CO2 3

23 SO 2 CO 2

29 HYDROTHERMAL X ACID

30 HYDROTHERMAL X ACID SOLID FRACTION ACID PRETREATMENT HYDROTHRMAL HEMICELULOSE SOLUBILIZATION ~ 90% ~ 90% LIGNIN SOLUBILIZATION ~ 20% ~ 7% CELLULOSE SOLUBILIZATION < 4% < 1% LIQUID FRACTION (g L -1 ) ACID PRETREATMENT HYDROTHRMAL GLUCOSE 1,5 0,4 XILO-OLIGOSACCHARIDES - 18,2 XYLOSE 58,4 5,5 ARABINOSE 5,2 0,7 ACETIC ACID 2,8 2,6 FURFURAL 0,74 0,50 HMF 0,16 0,15 ph 0,9 3 LIQUID FRACTION (g L -1 ) ACID HYDROLYSIS HYDROTHRMAL GLUCOSE

31 BIOHYDROGEN FERMENTATIVE PROCESS Biogas Effluent Substrate

32 HYDROGEN CLEAN ENERGY Direct combustion: 2H 2(g) + O 2(g) 2H 2 0 (l) + energy High energy density H 2 : directly as fuel or in fuel cells Production from renewables or non-renewable sources

33 H 2 PRODUCTION Current production: FOSSIL FUELS Gas reforming Hydrocarbon oxidation Coal gasification H 2 O Eletrolysis H 2 O Photochemical process Processos termoquímicos Alternative technology: BIOMASSA Biomass gasification Ethanol reforming (steam) Liquid phase reforming Biological process

34 H 2 PRODUCTION BY ANAEROBIC FERMENTATION ORGANIC MATTER Hydrolytic bacteria HYDROLYSIS Hydrolysis products Acidogenic bacteria ACIDOGENESIS Organic acids, alcohols, H 2, etc Acetogenic bacteria ACETOGENESIS SO4-2 /NO 3- H 2 + CO 2 Homoacetogenic bacteria Acetate Nitrate and sulfatereducing bacteria Methanogenic hydrogenotrophic Methanogenic acetoclastic METHANOGENESIS HS - /NH 3 CH 4 + CO 2

35 WIDE UTILIZATION OF RENEWABLE RESIDUES Brazilian agroindustrial residues (sisal juice, POME, etc) for BioH 2 production Residual glycerin from biodiesel for BioH 2 production Residues from 1G and 2G ethanol for BioH 2 production

36 DIFFERENT RESIDUES NEW OPPORTUNITIES Palm oil mill effluent (POME) Glycerin Cashew juice BIOH2 Glycerin Residues from 1G and 2G ethanol Sisal juice coconut residues

38 ANALYTICAL METHODOLOGY Analytes Refractive index detector UV detector (210 nm) Carbohydrates Sucrose, glucose, fructose, xylose, raminose, galactose, arabinose, manose and maltose ---- Alcohols Ethanol, butanol and glycerin ---- Volatile fatty acids Acetic, propionic, isobutyric, butyric, glyceric, tartronic, lactic, formic, pyruvic, caprylic, caproic and valeric acids Acetic, propionic, isobutyric, butyric, lactic, formic, pyruvic, caprylic, caproic and valeric acids Validation parameters Selectivity Precision Limite of detection (LOD) Robustness Linearity Accuracy Limite of quantification (LOQ) De Sá et al., 2011, International Journal of Hydrogen Energy

$HPX-87H and deashing Reservoir Temperature: 55ºC Data system Detector Refractive index$

39 SIMULTANEOUS ANALYSIS OF CARBOHYDRTES AND VFAs BY HPLC Flow: 1,0 ml/min Pump Injector Injection volume: 20μL Column and precolumn: Mobile phase: H 2 SO 4 5 mmol/l Column Aminex HPX-87H and deashing Reservoir Temperature: 55ºC Data system Detector Refractive index detector: sucrose, glucose and fructose UV detector (210 nm): acetic, propionic, isobutyric and butyric acids

X acid, alkaline and heat pretratment of bacterial communities 70 49x 64x 3.

41 Level of hydrogenase gene expression Level of hydrogenase gene expression of Clostridium sp. X acid, alkaline and heat pretratment of bacterial communities 70 49x 64x 3.78 mol H 2 /mol sucrose 4.62 mol H 2 /mol sucrose mol H 2 /mol sucrose 15x mol H 2 /mol sucrose Untreated Acid Alkaline Heat

Maximum yield of H 2 (mol H 2 /mol substrate) EVALUATION OF DIFFERENT SUBSTRATES FOR H 2 PRODUCTION Maximum yields of H 2 obtained from different substrates 4.17 mol H 2 /mol sucrose 5 4.

43 Maximum yield of H 2 (mol H 2 /mol substrate) EVALUATION OF DIFFERENT SUBSTRATES FOR H 2 PRODUCTION Maximum yields of H 2 obtained from different substrates 4.17 mol H 2 /mol sucrose mol H 2 /mol sucrose mol H 2 /mol glucose mol H 2 /mol fructose 1.88 mol H 2 /mol xylose mol H 2 /mol glycerin 1 0 Sucrose 1: heat pretreated inoculum recycled Sucrose 2: fresh heat pretreated inoculum

44 EVALUATION OF DIFFERENT SUBSTRATES FOR H 2 PRODUCTION Inocula Substrate Reactor mode Maximum yield of H 2 References Sludge from UASB for treatment of swine waste Sucrose Batch 1.6 mol H 2 /mol sucrose MAINTINGUER, 2009 Sludge from a skyway wastewater treatment plant Sucrose Batch 6.12 mol H 2 /mol sucrose ZHU AND BÉLAND, 2006 Sludge from a full-scale anaerobic reactor treating citrateproducing wastewater Sucrose Continuos 1.61 mol H 2 /mol sucrose ZHAO AND YU, 2008 Sludge from local wastewater treatment plant Sucrose Continuos 3.88 mol H 2 /mol sucrose LEE et al., 2006 Anaerobic sludge from a municipal sewage treatment plant Sucrose Batch 4.24 mol H 2 /mol sucrose THIS WORK Sludge from a UASB reactor treating wastewater from a candy factory Glucose Batch 1.46 mol H 2 /mol glucose DAVILA-VAZQUEZ et al., 2008 Anaerobic sludge from a municipal sewage treatment plant Glucose Continuous 1.63 mol H 2 /mol glucose WU et al., 2008 Digested sludge from a sewage treatment plant Glucose Batch 1.8 mol H 2 /mol glucose WANG AND WAN, 2008 Anaerobic sludge from a municipal sewage treatment plant Glucose Batch 2.19 mol H 2 /mol glucose THIS WORK Sludge from a municipal sewage treatment plant Fructose Continuous 1.68 mol H 2 /mol fructose LEE et al., 2007 Anaerobic sludge from a municipal sewage treatment plant Fructose Batch 2.09 mol H 2 /mol fructose THIS WORK Sludge from a municipal sewage treatment plant Xylose Batch 2 mol H 2 /mol xylose LIN AND CHENG, 2006 Sludge from UASB for treatment of swine waste Xylose Batch 0.8 mol H 2 /mol xylose MAINTINGUER, 2009 Anaerobic sludge from a municipal sewage treatment plant Xylose Batch 1.88 mol H 2 /mol xylose THIS WORK Wheat soil from the Pennsylvania State University Farms Glycerin Batch 0.28 mol H 2 /mol glycerin SELEMBO et al., 2009 Anaerobic sludge from a municipal sewage treatment plant Glycerin Batch 0.80 mol H 2 /mol glycerin THIS WORK

$fraction hydrothermal pretreatment Sisal$

45 DIFFERENT BRAZILIAN AGROINDUSTRIAL RESIDUES FOR H 2 PRODUCTION Vinasse 1G C5 fraction hydrothermal pretreatment Sisal Juice Glycerin mmol H 2 /g COD

46 PRODUÇÃO DE BIOH 2 UTILIZAÇÃO DE RESÍDUOS AGROINDUSTRIAIS BRASILEIROS

47 Ethanol 1G and 2G CANA-DE-AÇÚCAR Moagem Fermentação Destilação Vinhoto Bagaço ETANOL 1G Pré-tratamento Xilose Hidrólise BioH 2 Fermentação Destilação Vinhoto enriquecido com xilose ETANOL 2G

48 BIODIESEL Óleo vegetal ou gordura animal Etanol/Metanol Catalisador NaOH/KOH Transesterificação Glicerina BIODIESEL

R O T A M E T A B Ó L I C A 20 3-hydroxy-propionaldehyde 21 GLYCEROL 18 NAD + NADH

GLUCOSE 2 ATP ADP Glucose-6-phosphate Fructose-6-phosphate SUCROSE 4 ATP ADP

1,3-bisphosphoglycerate-bisphosphate 7 ADP ATP 3-phosphoglycerate-phosphate 13

Fd red 2H + P i HSCoA 3 5 8 CO 2 Acetyl-CoA 14 2H + NADH + H + NAD + Acetyl-phosphate

49 R O T A M E T A B Ó L I C A 20 3-hydroxy-propionaldehyde 21 GLYCEROL 18 NAD + NADH Dihydroxyacetone ATP 19 ADP Dihydroxyacetone-phosphate NADH NAD + 1,3-PROPANEDIOL NADH NAD + GLUCOSE 2 ATP ADP Glucose-6-phosphate Fructose-6-phosphate SUCROSE 4 ATP ADP Fructose-1,6-bisphosphate Glyceraldehyde-3-phosphate NAD 6 + NADH 1,3-bisphosphoglycerate-bisphosphate 7 ADP ATP 3-phosphoglycerate-phosphate 13 Phosphoenolpyruvate-phosphate 9 ADP ATP Pyruvate H 2 CoA H Fd ox Fd ox 12 Fd red Fd red 2H + P i HSCoA CO 2 Acetyl-CoA 14 2H + NADH + H + NAD + Acetyl-phosphate Butyryl-CoA ADP P i ATP HSCoA ACETATE Butyryl-phosphate 17 ADP ATP BUTYRATE 1 FRUCTOSE ATP AD P NADH NAD + XYLOSE 22 Xylulose 23 ATP ADP Xylulose-5-phosphate

50 Costa Pinto - Piracicaba (SP) 2014/2015. PROMISING TECHNOLOGIES

51 PROMISING TECHNOLOGIES 2G ethanol in 2014; São Miguel dos Campos, Alagoas; 82 milion liter/year; 2020 intend to produce 1 billion de liters/year.

52 PROMISING TECHNOLOGIES TAKAKI BAKERY KITAHIROSHIMA, JAPAN JANUARY, 2010

53 Bioreactor 1- Hydrogen production for fuel cell 2- Methane production for co-generation 3- Gasification of fermentation residues

54 Prof. Dr. Naomichi Nishio (Hiroshima University) and Lívian de Sá (INT)

55 COUNTRIES REPRESENTED AT THE TASK 21 MEETING IN BRAZIL Norway Sweden Canada Mexico United Kingdom 12 countries 9 Task 21 members USA 3 observer countries Netherlands Japan Taiwan Brazil Chile Australia

56 PRESENTATIONS IN THE TASK 21 IN BRAZIL 3 Number of presentations Presentations 0 USA Canada Mexico Chile Brazil Netherlands Norway Sweden U. K. Australia Japan Taiwan

57 COMPANIES IN THE TASK 21 IN BRAZIL

58 ORGANIZERS AND LATIN-AMERICA OBSERVERS

59 BIOCATALYSIS LAB - SCOPE AND EXPERIENCE Enzymatic conversion of renewable substrates into chemicals; Lignocelluloses processing for ethanol or chemicals production; The use of microorganisms and enzymes as catalysts in hydrolytic or oxidative reactions.

60 MAIN PARTNERS Federal University of Rio de Janeiro (UFRJ) Federal University of Juiz de Fora (UFJF) EMBRAPA (Brazilian Agricultural Research Corporation) INMETRO Lund University (Sweden)

61 FINANCIAL SUPPORT

62 INT/MCTI - BIOCATALYSIS GROUP

63 National Institute of Technology Division of Catalysis and Chemical Processes Biocatalysis Laboratory Viridiana Santana Ferreira-Leitão THANK YOU FOR YOUR ATTENTION

Recent Developments and Current Situation of Cellulosic Ethanol R&D in Brazil

Recent Developments and Current Situation of Cellulosic Ethanol R&D in Brazil Research Center in Applied Chemistry Department of Chemistry Federal University of Paraná (UFPR), Brazil www.quimica.ufpr.br/paginas/luiz-ramos