Efficient conversion of starch and cellulose from co-products of food industry and agriculture to ethanol
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1 Efficient conversion of starch and cellulose from co-products of food industry and agriculture to ethanol Detmold, April 25-26, 2006 Johan van Groenestijn & Doede Binnema
2 3 projects
3 Ethanol from starch containing biomass Second generation bioethanol production Conversion of starch containing biomass into: Fuel ethanol Biogas Flexibel process for the conversion of different kinds of starch containing biomass Using product residues from the food-industry
4 Alternative process for the conversion of food residues into feed and compost Research partners: TechnologieCentrum Noord-Nederland, Energy Valley, TNO Quality of Life, Van Hall Instituut, Noordelijk Hogeschool Leeuwarden, Oosterhof Holman Milieutechniek Coalition partners: Agromiscanthus, Technogrow, E kwadraat, NLTO-Projecten, Borgesius Webro, Borgesius, Veenhuis, Koopmans Meel, Van der Meulen, Lamb Weston Meijer, Hoepman Suikerwerken, RBV-Leaf, Royal Nedalco, Gastec Technology, Duurzaam Energiestation Noord-Nederland
5 Feasibility study Classification of biomass and product residues from the foodindustry. Conversion of biomass and product residues from the foodindustry. Fermentation Scalinguptopilot plant
6 Process scheme of starch containing biomass conversion Biomass (starch) Enzymatic conversion Fermentation Distillation Bio-ethanol Residu Methane fermentation Biogas Generation of electricity Heat
7 Ready available biomass and product residues from the food-industry in the North Netherlands. Cellulose containing biomass (e.g. wheat grits) 9500 tonnes/annum Starch containing biomass (e.g. return bread/potato peels) 7100 tonnes/annum Candy-based biomass (e.g. marshmallows) 100 tonnes/annum
8 Conversion of starch containing biomass 7100 tonnes/annum starch containing biomass 6400 tonnes/annum convertible starch (converting efficiency ~90%) 7000 tonnes/annum glucose hl/annum bio-ethanol Conversion of return bread
9 Results Conversion of tonnes/annum of biomass from food companies yields: hl/annum bio-ethanol 6 million m 3 /annum of biogas tonnes/annum of total CO 2 emission reduction 1400 kw electricity yield by conversion of biogas
10 A1 kader (840 mm. x 594 mm.) Formaat tekenvlak: 822 mm. x 576 mm. Technologiecentrum Noord-Nederland (TCNN) Bio-Energie in Noord-Nederland Productieproces BioEthanol 8202-FA-1-A n.v.t. A1 1 1 Concept A.T FILENAAM Follow up projects (next step) Pilot plant: tonnes/annum of biomass Full scale plant: tonnes/annum of biomass Deze tekening is gemaakt met AutoCAD 2000
11 Ethanol from lignocellulosic biomass Second generation bioethanol production E.g. using co-products from agriculture Pretreatment and hydrolysis required Fermentation with Saccharomyces cerevisiae Two processes: 1. Thermozym process (TNO, WUR, ECN, companies) 2. Biosulfurol process (TNO, WUR, Techno Invent, companies)
12 Thermozym process Wheat straw Pretreatment at 190 C, 15 bar and a ph between 2 and 4 (dilute sulfuric acid) 10% dry weight slurry After temperature and ph adjustment: enzymes added 1. to reduce viscosity 2. to hydrolyse cellulose and hemicellulose
13 Enzymatic pretreatment Effect of different doses of cellulase on viscosity (GC220, 4h, 50 C) viscosity (cp) ph 4.0 ph 4.5 ph blanco enzyme dose (mg/g dry matter)
14 Result Hydrolysate containing Glucose 32 g/l Xylose 15 g/l Furfural 1.8 g/l Acetic acid 2 g/l
15 Inhibitors Effect of 10 by-products of the pretreatment process on ethanol fermentation tested Concentrations measured in wheat straw hydrolysates CONCLUSION: Furfural and acetic acid most important inhibitors 50% inhibition (fermentation rate as CO2 production) at 4.5 g furfural/l 5.5 g acetic acid/l (ph 4.5) Furfural is converted into less toxic furfurylalcohol during fermentation
16 0,8 0,7 0,6 controle 100% + gluc 50% + gluc. 100% 50% CO2 (mmol/min) 0,5 0,4 0,3 0,2 0,1 0, tijd (min) Fig: CO2 production in ethanol fermentations on wheat straw hydrolysates and glucose medium Control: glucose medium (120 g/l) Hydrolysate (100%) with suppleted glucose (up to 120 g/l) 50% diluted hydrolysate with suppleted glucose (up to 120 g/l) Hydolysate (100%) only (32 g glucose/l) 50% diluted hydrolysate only (16 g glucose/l)
17 Compound Concentration at start (g/l) Glucose 32 0 Concentration at end of fermentation (g/l) Conversions in a wheat straw hydrolysate fermentation Xylose Furfural HMF 0 0 Acetic acid Lactic acid Formic acid Furfuryl alcohol Glycerol Ethanol
18 Fermentations of wheat straw hydrolysate are slower than those of glucose media. Comparable with fermentation of mollasses.
19 Biosulfurol process Wood, grass Pretreatment in 70% sulfuric acid Moderate temperature, ambient pressure Hydrolysis by adding more water Recovery of sulfuric acid Via anion selective membranes Via two stage anaerobic wastewater treatment plant: conversion of sulfate into sulfide, vacuum stripping of H2S, burning of H2S and conversion into SO2, SO3 and eventually H2SO4
20 heat sulfuric acid SO3 H2S oxidator membrane H2S gas sulfuric acid ethanol impreg nation reactor hydrolysis neutralisation bioethanol factory anaerobic wastewater treatment waste water lignocellulosic lignin membrane sulfate biomass recycle water
21 Experiments Experiments with willow wood and switchgrass Conversion of cellulose and hemi-cellulose in monomeric sugars with efficiencies near 80%. Biomass hydrolysates appeared to be acceptable for use in ethanol fermentation. Two stage anaerobic wastewater treatment with H2S stripping proven on full scale Vacuum steam stripping proven on lab scale
22 Advantages over other pre-treatment processes No enzymes are required (cost development uncertain) Broad range of biomass types can be used. The method can be used for various types of wood, straw, grass and organic waste, in contrast with methods that use enzymes. Relatively large and hard pieces of wood can be used. Pretreatment at room temperature allows the use of plastic construction materials The difference with other concentrated sulphuric acid pretreatment processes is the application of novel sulfate recovery processes, made available through developments in other technology areas. Lower overall costs: /l ethanol
23 Acknowledgements The authors gratefully acknowledges Alle van Wijk (TNO) for his work in the starch project and Thermozym project, Jan Zeevalkink, Gijs Bos, Hugo van Buijsen, Jan de Bont, Gert Klip and Marc van der Maarel (TNO) for their work in the Thermozym project, and Rob Bakker, Ronald Maas (WUR), Obbo Hazewinkel (Techno Invent), Koen Meesters and Raymond Creusen (TNO) for their work in the Biosulfurol project. The Thermozym and Biosulfurol projects are supported with a grant of the Dutch Programme EET (Economy, Ecology, Technology) a joint initiative of the Ministries of Economic Affairs, Education, Culture and Sciences and of Housing, Spatial Planning and the Environment. The programme is run by the EET Programme Office, SenterNovem.
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