Biofuel production using total sugars from lignocellulosic materials. Diego Alonso Zarrin Fatima Szczepan Bielatowicz Oda Kamilla Eide

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1 Biofuel production using total sugars from lignocellulosic materials Diego Alonso Zarrin Fatima Szczepan Bielatowicz Oda Kamilla Eide

2 scope of the presentation 1. Available lignocellulosic materials 2. Production of biofuels Design of a Biofuel factory. 3.

3 1. Available lignocellulosic materials Finland Norway Poland Spain Europe

4 a) Finland Land area: km2 - Forest area: 70 % 60 % privately owned, 25% state owned, 9% by companies, 5 % by other 20 % of the energy needs derived from wood logging residues and stumps

5 Haga clic para modificar el estilo de texto del patrón Segundo nivel Tercer nivel Cuarto nivel Quinto nivel

6 Haga clic para modificar el estilo de texto del patrón Segundo nivel Tercer nivel Cuarto nivel Quinto nivel

7 B) Norway Forestry residues: 4-5 Twh Pine Spruce Composition: % cellulose, % hemicellulose, % lignin Straw : tons dry material Wheat Composition: % cellulose, % hemicellulose, % lignin

8 Haga clic para modificar el estilo de texto del Largest production insegundo the nivel Tercer nivel south-eastern part, good nivel infrastructurecuarto Quinto nivel Forestry residues generated all throughout the year Wheat straw produced during the summer and autumn in relations with the harvesting, large storage space needed Maps and tables generated from statistisk sentralbyrå (Stat bank Norway):

9 3. Poland Straw 10 mill. tons Wood 0,56 mill. m3 Potatoes 0,9 mill. tons According to researches from Polish Institute of Soil Science and Plant Cultivation, 0.6 mill. ha can be used to produce bioethanol.

10 4. Spain - Quantity & Distribution Quantity: 87 Mt/year.

11 Spain - Seasons, storage &transportation 1. Seasonal distribution. Summer: hemp and sunflower Winter: oat, pea, rapeseed and triticale. 2. Storage. - Prefabricated storage. - Outer container and hopper. - Underground tank. 3. Transportation. Bags, tipper trailer, truck, rail.

12 Best raw material in Spain Current best raw material Glycerin, a major waste from the manufacture of biodiesel --- first 2nd generation biofuel of Spain Future: Lignocellulosic materials (made of wood of fast growing trees, urban wastes ) are about to be the future. 2nd generation biofuels

13 Europe Haga clic para modificar el estilo de texto del patrón Segundo nivel Tercer nivel Cuarto nivel Quinto nivel

14 Europe Europe in general: availability of lignocellulosic materials is largest in the South Western parts Norway: low to moderate amounts of both agricultural and forestry residues Finland: low in agricultural residues, much forestry residues Poland: much agricultural residues and relatively much forestry residues as well Of our regions, Spain has the largest amount of available lignocellulosic material with 87 Mt.

15 2.Production of biofuels Pretreatments Bioethanol Bio butanol Bio methane

16 a) Pretreatment Mechanical pretreatment to break down the biomass into smaller pieces Thermal, chemical or biological pretreatment Solubilise hemicellulose and lignin Reduce crystallinity, increase porosity and increase surface area of cellulose -> better hydrolysis yield Forming of inhibitory compounds, degradational products, precipitation of solubilised lignin

17 B) Ethanol - Fermentation Simultaneous saccharification and fermentation (SSF) Separate hydrolysis and fermentation (SHF) Consolidated Bioprocessing (CBP) Purification: distillation & pervaporation

18 Ideal microorganism? Ethanol yield and productivity Cellulolytic activity Ability to withstand high concentration of ethanol and high temperature Tolerance to inhibitors Saccharomyces cerevisae Escherichia coli Hansenula polymorpha Kluyveromyces marxianus

19 C) Methane- Anaerobic Digestion Enzymatic hydrolysis Amino-acids Glucose Acidogenesis Fatty-acids Hydrogen Acetic acid Methanogenesis CO2 CH4

20 D) Butanol - Fermentation Microorganism: Clostridium acetobutylicum. (P262 or ATCC 824). Industrial application & subproducts: ABE process. 2 different stages (different products): 1. Butyric and acetic acids (acidogenesis). 2. Butanol, acetone and etanol (solventogenesis). Inhibitory compounds: above all, syringaldehyde, ferulic and pcoumaric acids. Yields: normal clostridial processes produce concentration of 13 g l-1 (regarded as the natural limit). 0,411 g g-1 is the maximum

21 Butanol - upconcentration Usual methods: adsorption, liquid-liquid extraction, gas striping and pervaporation. Selected one: pervaporation: transport through the membrane of one compound, which is also desorbed to the permeate side as vapour

22 Butanol current and future sources Sources of butanol (1st generation). Agricultural byproducts (straw, corn stalks). Energy crops: sugar beets, sugar cane, wheat cassava and corn grain. Future: 2nd generation (forest biomass, urban wastes, etc.). HIGHER PROFITS!

23 3. Design of a Biofuel factory Alternatives Final selection

24 A) General Description Size reduction, to decrease the size of the particles in order to increase the surface area. Pre-treatment, to reduce the crystallinity of the cellulose, disrupting both lignin and hemicellulose. Enzymatic hydrolysis, in order to obtain monomeric sugars from the polymeric ones. Fermentation, to obtain ethanol or butanol from the monomeric sugars produced. Ethanol recovery, usually by distillation.

25 B) Detailed Description 1. Feed stream: The feed stream is straw, with a flow of kg/h and a composition (% dry weight) : cellulose, as glucose, 32.4 %; hemicellulose, as xylose, 19.1%; acid lignin, 21.3%; ash, 6.4 %; moisture, 6.9 %. 2. Size reduction: After this stage, the particles are 20 mm long. 3. Pretreatment: - Steam explosion (cheap process and does not use chemicals). - Specific characteristics of this process are 19 bar and 210ºC for 10 minutes. 4. Enzymatic hydrolysis : An enzymatic hydrolysis is also done, with a % of dry matter of 30%.

26 C) Prices of the different products Prices of the chemical products are always changing depending on the demand; current prices of the chemicals produced are: Butanol: 1,25 /L!! Ethanol & Acetone: 0,35 /L Methane: 0,1 0,3 /m3 = 0,2 m3 According to these prices, it is highly recommended to produce butanol above other products, as more benefit could be achieved.

27 Biofuel Production H2O 15 % loss Solid Feed: Straw Mechanical pretreatment Enzymes Enzymes Steam explosion Solid Hydrolysis Liquid Methane production Fermentation Ethanol, buthanol production

28 Ethanol production H2O kg/h C6 = kg/h ; 32,4 % C5 = kg/h ; 19,1 % Others = ; 48,5 % Mechanical pretreatment kg/h 15 % loss Steam explosion kg/h Enzymes Enzymes cellulase (NS50013) β-glucosidase (NS50010) Solid Hydrolysis Fermentation C6 Saccharomyces cerevisae Υ = 0,99 C6 = 4992 kg/h Fermentation C5 + C6 Liquid Pichia stipitis Ethanol = 3450 kg/h Υ = 0,82 C6 = 4992 kg/h C5 = 1319 kg/h C6 = 1893 kg/h C5 = 2740 kg/h C6H12O6 3 CH4 + 3 CO2 C5H10O5 2.5 CH CO2 CH4 = 1235,2 kg/h CH4 = 1729,67 m3/h Price, /m3 Income, /h Ethanol = 3294 kg/h Methane 0,2 346 S. cerevisae P. stipitis Price, /m3 0,35 0,35 Income, /h Total income, /h

29 Butanol production kg/h 15 % loss H2O kg/h C6 = kg/h ; 32,4 % C5 = kg/h ; 19,1 % Others = ; 48,5 % Mechanical pretreatment Steam explosion kg/h Enzymes cellulase (NS50013) β-glucosidase (NS50010) Solid Clostridium acetobutylicum Υ = 0,4 C6 = 4992 kg/h C5 = 1319 kg/h Fermentation Hydrolysis Acetone = 757 kg/h Butanol = 1515 kg/h Ethanol = 252 kg/h Liquid C6 = 1893 kg/h C5 = 2740 kg/h C6H12O6 3 CH4 + 3 CO2 C5H10O5 2.5 CH CO2 CH4 = 1235,2 kg/h CH4 = 1729,67 m3/h Price, /m3 Income, /h Methane 0,2 346 Acetone Butanol Ethanol Price, /m3 0,35 1,2 0,35 Income, /h Total income, /h 2691 Total income Price, /h 3037

30 Results Total income /h: EtOH (C6) + CH4 EtOH (C6+C5) + CH4 ButOH (C6+C5) + CH * Direct methane from raw material: 962 /h

31 Biofuel Production H2O 15 % loss Enzymes Feed: Straw Mechanical pretreatment Steam explosion Hydrolysis Enzymes Fermentation Buthanol production Methane production

32 Design Final Considerations Of all the processes, a combination of butanol and methane production is most cost effective. However: Inhibition compounds Cost of waste management Cost of enzymes Cost of wear on the equipment Purification cost will cause the total income to probably be around 50 % lower.

33 Thank you!

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