Wednesday, August 13: Seminar on Biosystems Engineering Mar del Plata, Argentina Biotechnology research for biomass-based products other than bioethanol Telma Teixeira Franco - FEQ/ Unicamp, Brazil franco@feq.unicamp.br UNICAMP
STATE UNIVERSITY OF CAMPINAS, UNICAMP created October 1966 Unicamp concentrates almost 20% of the post-graduation (Msc +PhD) of the coutry. 14,000 undergraduate students, � 14,000 post-graduate students (MsC+PhD), � 2,100 lecturers and professors. � 10,000 students on continuous education (evening /week-end courses) � Chemical Engineering School � 570 bachelor and 450 PhD +MsC students �
Outline •Sugarcane & Conventional use of sugarcane •Sugarcane bagasse – bioethanol •Potential for biorefinery of sugar cane •Non-bioethanol research from sugarcane •Feasibility of acrylic acid production from sugars •Sugar acrylates by biocatalysis •Photobioreactors and microalgae UNICAMP
Evolution of sugarcane in Brazil Aver. Cane productivity (Tons cane per hectare) 80 75 70 +80% 65 60 55 50 45 40 35 30 1961 1963 1965 1967 1969 1971 1973 1975 1977 1979 1981 1983 1985 1987 1989 1991 1993 1995 1997 1999 2001 2003 2005 2007 Fao Stat database
World Bioethanol Production 42.2 million kl (2004) 54.0 million kl (2007) 9.8% 11% 5% Others 9% India Brazil 2.7% China EU 6% 36% USA 2.5% 39% 33% 45% Source: FO Licht 4
Brazil: main crops 2004 Brazil: 851 10 6 Brazil: 851 10 6 ha ha Ceará á: 14,6 10 : 14,6 10 6 6 ha Cear ha ● ● ● ● Surface Surface Paraí íba: 5,7 10 ba: 5,7 10 6 6 ha Para ha 6 [10 6 ha] [10 ha] Pasture 150- -200 200 Pasture 150 Soya 21.5 Soya 21.5 Corn 12.3 Corn 12.3 Sugarcane 5.6 Sugarcane 5.6 ● ● Agric. land 58.0 Agric. land 58.0 Paraná á: 20,0 10 : 20,0 10 6 6 ha Paran ha Bioethanol, 2007
Present Location of Sugar-Etanol Mills in Brazil 7 Fingueruti, 2007
Existing Sugar and Ethanol Production Technology SUGAR AND ETHANOL PRODUCTION RECEPTION, CANE PREPARING, JUICE SUGAR SUGAR EXTRACTION PROCESSING BAGASSE MOLASSES JUICE STEAM AND POWER ETHANOL ETHANOL GENERATION PROCESSING STILLAGE
Conventional sugar and ethanol chain - Brazil Sugar cane 425 million tons 50% 50% Sugar Ethanol 29 millions tons 23 billions cubic meters Exportation Exportation Internal Market Internal Market (2/3) (15%) (1/3) (85%) Fuel Others Fuel Others (50%) uses (90%) uses (50%) (10%) Etanol, Alcoolqu í mica e Biorrefinarias BNDES Setorial, Rio de Janeiro, n. 25, p. 5-38, mar. 2007
Technology for Ethanol Production Present performance Cane at unused Trash Distillery Bagasse excess: 33 Kg/TC (16,5 Kg biomass( Dry ) basis Ethanol from juice: 85 l/TC Future benchmark Cane at Biomass ( Dry basis ):70 Kg/TC Trash Distillery Bagasse excess:140 Kg/TC (70 Kg biomass ( Dry basis ) Ethanol from juice: 92,5 l/TC Ethanol (Hydrolysis) Biomass Electrical energy production
Sugarcane process to bioethanol and power introducing Hydrolysis Sugarcane stalks Trash (a) Lignin Electricity Bagasse Juice extraction unit Steam &Energy Unit Steam and Power Water Total reducing sugar juice Bagasse Sugar Liquor Ethanol production Unit Hydrolysis Unit Stillage Lignin Bio-ethanol (a) from juice and biomass
Hydrolysis Steps Bagasse (I) Bagasse screening and cleaning (I) Rind, pith and sand removed from fiber (II) Delignifying and Pretreatment and (II) hemicellulose hydrolysis hemicellulose hydrolysis step Pentoses (III) Cellulose conversion by Water enzyme catalysis Cellulose hydrolysis (III) (IV) Liquor separation from hexoses lignin and washing Lignin to power plant (V) Removal of inhibitors and Liquor separation (IV) concentration of liquor, recover of condensed water for reuse in process (V) Purifying and concentration Water Liquor to fermentation
Biorefinery for chemicals/biochemicals Fermentors ( yeast, bacteria, e + downstream processing with/out cell recycling Sugar-cane crushed Sugar-cane (juice+ trash and bagasse) Sucrose Glucose Pentoses Lignin Acrylic acid, ethanol, organic acids, polymers, … UNICAMP
Biobased product flow-chain from biomass feedstock Secondary Intermediary Biomass Building blocks Precurssors Plattaform Products chemicals chemicals industry starch transport food environment comunication housing leisure health Kamm & Kamm, 2006
Products from sugar-cane - Brazil Secondary chemicals and products Renewable Biomass feedstock Chemicals & products Fermented Intermediate chemicals • Fuels Platform • Hydrolysed bagasse C 2 • Bagasse fibers for • Lysine, glutamate Sugars paper industry • Citric acid C 3 Glucose • Hemicellulos • Lactic acid • Acetylated fibers e Fructose + • Fumaric acid • Furfural Xylose C 4 • Acetic acid • Cellulose Arabinos • Fructose/glucose • 2,3 butanediol e • Xylose C 5 • Acetone/butanol Sucrose • Sorbitol • Bioethanol • Glycerol • Xylitol C 6 • Ethyl acetate • Polyhydroxybutyrate • Xanthane • Liquid fertilizers polymer • Yeasts s • Polyethylene • Polypropylene (in preparation From: INDUSTRIAL PERSPECTIVES FOR BIOETHANOL. ed. Telma Teixeira Franco, Editora Uniemp, Sao Paulo, ISBN 85- UNICAMP 98951-06-4, 2006.
Present situation - first generation products vinasse Environment fertilizer yeast distillates Infrastruture Sugar cane and bioethanol Logistics sugar • electrical bagasse Product energy quality • fuel energy Bonomi, 2006
UNICAMP LEBBPOR - non bioethanol activities Material application Succinic acid Cellulose & hemicellulose hydrolisate L- and D-lactic acid Microbial acrylic acid from sugar (2005) Sugar acrylates (sucrose, frutose, etc, from 2003.) Energy application [1] Photobioreactor Light + CO2 � Biomass Biomass � Carbohydrates rich /Oil rich (algae) [2] Conventional fermentation � microbial oils from hydrolizates (cells) Chemical Engineering of Unicamp
Acrylic acid case, started in 2002 FEQ O CH C H 2 C OH • Polymerized as acid or as methyl, ethyl or butyl ester • Polymer for flocculants, coatings, paints, adhesives, and binders for leather and textile.
Why acrylic acid? • Production capacity = 4.2 million tons (2003) • Price = 0.85-0.90 $/lb = 1.95 $/kg (Chemical Market Reporter, 11 April 2005) • Market size = $ 8 billion Straathof, 2005
Alternative routes Sugar Alcohol Fermentation Fermentation Esterification Dehydration Lactic Acrylic acid acid H 2 O Lactic acid ester Alcohol Esterification Acrylic acid ester Dehydration H 2 O
Directly to acrylic acid is attractive Sugar Alcohol Fermentation Fermentation Esterification Dehydration Lactic Acrylic acid acid H 2 O Lactic acid ester Alcohol Esterification Acrylic acid ester Dehydration H 2 O
Direct fermentation of sugars to acrylate • Desired stoichiometry C 6 H 12 O 6 ==> 2 CH 2 =CH-COOH + 2 H 2 O (0.8 kg/kg glucose) • ATP formation by this reaction to support growth and maintenance • Cell retention/recycling to minimize growth requirements • No aeration
Fermentation titers obtained for products related to acrylic acid Acid Final Ferment- Strain Reference conc. ation pH (g/ L) Acetic 180-200 ? Acetobacter (Maselli and Horwarth, 1984) Propanoic 65 6.5 P. acidipropionici (Huang et al., 2002) Butanoic 42 6.0 C. tyrobutyricum (Huang et al., 2002) Lactic 210 6.2 (Bai et al., 2003) Lactobacillus lactis Pyruvic 135 5.0 S. cerevisiae (van Maris et al., 2004a) Fumaric 64 5.5 Rhizopus arrhizus (Riscaldati et al., 2002) Itaconic 75 2.0 Aspergillus (Yahiro et al., 1997) terreus
Microbial tolerance to acrylate In general, a high toxicity is to be expected BUT: • The C=C-COOH sub-structure is present in fumarate and itaconate • Some cell types survive 35 g/L acrylate Using selective pressure, genome shuffling, etc. it is expected that 50 g/L acrylate is a realistic maximum concentration
Hypothetical metabolic pathways to acrylate sugars sugars methionine methionine acetyl-CoA acetyl-CoA methylcitrate pyruvate oxaloacetate glycerol methylcitrate pyruvate oxaloacetate glycerol DMSP DMSP α -alanine aspartate α -alanine aspartate methylmal.CoA lactate β -alanine methylmal.CoA lactate β -alanine propanoyl-CoA lactoyl-CoA β -alanyl-CoA mal. semiald. propanoyl-CoA lactoyl-CoA β -alanyl-CoA mal. semiald. malonyl-CoA malonyl-CoA propanoate propanoate acrylyl-CoA 3-HP-CoA 3-HP 3-hydroxypropanal acrylyl-CoA 3-HP-CoA 3-HP 3-hydroxypropanal acrylate acrylate Which might give a high yield?
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