Upgrading of by-products from biodiesel and sugar industry by bioconversion and chemical catalysis
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1 Upgrading of by-products from biodiesel and sugar industry by bioconversion and chemical catalysis Exo59, Golden, USA 25 April 27 Thomas Willke Federal Agricultural Research entre Institute of Technology and Biosystems Engineering Bundesallee 5, D Braunschweig - telephone: ++49 () WN-2117 Biorefinery hain links Transport Market Added value? onversion Separation, Purification Products, Energy Separation Storage, onservation? Pretreatment Transport Biomass Storage, onservation, Availability? Energy Demand, Biomass/Energy Losses
2 Some Important Steps in Biorefineries The whole process combines physical, chemical and biotechnological steps Pretreatment, onservation, Separation Physical, mechanical (destructure, milling, sieving) (Thermo)chemical (heat, acid, base, ) Biological (enzymes, microorganisms) ombination of all onversion Biotechnological (bacteria, fungi, enzymes) hemical-catalytic (e.g. noble-metal-catalysis) (Thermo)chemical (pressure, heat, ) ombination of all Biorefineries in Germany Existing Sugar Ethanol, Products Starch il Biodiesel, Glycerol Residues waste streams Biogas Ethanol, Products Lignocellulose Just starting with biogas (energy maize)
3 Biorefinery in Germany The main problem: costs ost reduction in Biorefinery Transportation efficiency Energy-density of feedstock and products Infrastructure, distances More efficient processes Biocatalysts, chemical catalysts Productivity Product concentration heaper and more efficient feedstocks Agricultural/industrial residues Lignocellulose Additional use of wase water/-air Processes Starch, Sugar Sugar-Refinery (for example: Südzucker, crop energies) Starch-/ Sugar Plants Sucrose Ethanol Residues Glucose Products Biogas Electricity, eat Glucose/Fructose Fructose Products Products Palatinit Fertiliser, Animal feed
4 Top 12 Platform hemicals From Biomass 1,4-Succinic, fumaric and malic acids 2,5-Furan dicarboxylic acid 3-ydroxypropionic acid Aspartic acid Glucaric acid Glutamic acid Itaconic acid Levulinic acid 3-ydroxybutyrolactone Glycerol (1,3-propanediol) Sorbitol Xylitol/arabinitol Ethanol? Source: Top Value Added hemicals From Biomass, PNNL & NREL, 24 Immobilisation in Biotechnology Example: ethanol-production with immobilised yeasts bead surface biofuel, chemical feedstock wheat yeast-cells inside x 1 sugarbeet starch, sucrose immobilised yeasts or bacteria (biokatalyst) ethanol
5 Bead Production with Jetutter Scheme and operation pressure cutting tool motor nozzle D or M cutting wire n u wire u fluid liquid jet cut cylinder bead u fluid u wire = fluid velocity = wire velocity m = motor n = rotations D = diameter of the nozzle Animation of the utting Process
6 Jetutter optimisation of settings for low spray losses suited adjustments almost no losses unsuited adjustments high losses Bioethanol Production Advantage of immobilisation free cells immobilised cells microorganism activity [kg Et/(kg BDM h)] activity [kg Et/(m 3 cat h)] productivity [kg Et/(m 3 h)] yeast Saccharomyces cerevisiae bacterium Zymomonas mobilis
7 Ethanol Fermentation: Production Plant onventional or with immobilised cells conventional fermentation separator biomass recycling nutrients molasses 6 x 2 m 3 ethanol buffer process design with immobilised cells BMA Braunschweig, capacity: 6, litres Et / 24 h Separator (smaller) nutrients buffer molasses 3 x 6 m 3 ethanol Ethanol-Fermentation: Pilot Plant Immobilised yeast, continuously, 3-step BMA-Braunschweig
8 Palatinose-Production Example for immobilisation on an industrial scale immobilised cells of Protaminobacter rubrum saccharose palatinose Palatinose-Production Bioconversion
9 Industrial Production of Palatinose with Immobilised Microorganisms 8, tons per year Itaconic Acid Production The process Sugar Itaconic acid or? glycerol 1% (byproduct of biodiesel production) Fungi, aerobic Yeast, aerobic chemical feedstock
10 Itaconic Acid Production Fermentation from glucose Glucose [g/l] itaconic acid glucose time course[d] Itaconic acid [g/l] conditions batch (without pcontroll) mineral-salt medium, P-limitation p 1,7 33 result final concentration > 8 g/l IA max. productivity > 1 g/(l h) Yield:,6 g/g = 83% of Theory Itaconic Acid Production other substrates? Itaconic acid [g/l] 8 7 Glucose Saccharose Glycerol Lactose time [d] conditions batch (without pcontroll) mineral-salt medium, P-limitation p 1,7 33 Result (for Glucose) final concentration > 8 g/l IA max. productivity > 1 g/(l h) Yield:,6 g/g = 83% of Theory
11 Innovative Technologies hemical catalysis with gold catalysts milk sugar T = 4-6 p = 7-9 wood 2 2 starch Galactose 2 Lactose Glucose oxygen 2 supported gold catalyst 2 Galactonsäure 2 Lactobionsäure 2 Gluconsäure Sugar acids omplexing agents Ingredients for cosmetics, food, pharmaceuticals Functional Food 2 xidation of Monosaccharides Selectivity of the gold catalyst (PL-data) 2, Peakfläche im UV-Detektor , Gluconic Signal im UV-Detektor Galactonic Zeit, min Zeit, min Signal im UV-Detektor Xylonic 2 Signal im UV-Detektor Ribonic Zeit, min Zeit, min
12 Processes il mill, biodiesel plant Me Et Rapeseed Residues Biogas Electricity, eat RME (REE), Biodiesel Glycerol Fatty acids, Fats Sugar biological chemical? 1,3-Propanediol Acroleine 1,2-PD + 1,3-PD Biotensides Rapeseed Rapeseed meal Proteins, Animal Feed Fertiliser Sunflower Biodiesel from Rapeseed Production Rapeseed RME-production seed oil ( %) 9 % biodiesel oil 1 % glycerol by-products oil mill ( %) rapeseed cake ( % oil) rapeseed meal (1...2 % oil) about 4 % protein
13 Biodiesel Production capacity in Germany Tons per year * Data: UFP, *estimated Price of Raw Glycerol 1 8 glycerine 8% crude price in bulk FR Rotterdam [ /t] ? 27: < 1 /t
14 1,3-Propandiol from Glycerol 1,3-propanediol glycerol 1% (byproduct of biodiesel production) bacteria, anaerobic chemical feedstock (polymers) 1,3-Propanediol Fermentation Strain NRRL124 (from culture collection) concentration [g/l] 1 8 1,3-propanediol 6 glycerol 4 n-butyrate 2 acetate time course [h] conditions fed-batch (p-controlled) mineral-salt medium + YE p results final concentration > 72 g/l 1,3-PD productivity: > 1.7 g PD /(L h)
15 1,3-Propanediol Fermentation Strain IK123 (from screening) concentration [g/l] glycerol 1,3-propanediol n-butyrate acetate time course[h] conditions fed-batch (p-controlled) mineral-salt medium + YE p result final concentration > 1 g/l 1.3-PD productivity: > 2 g PD /(L h) 1,3-Propandiol-Fermentation: ost Reduction Influence of glycerol and nutrients price per t 1,3-PD salts, Na yeast extract RI (2 %) depreciation allocated fixed costs direkt fixed costs energy feedstock/media 5 glycerol glycerolwater pharmaglycerol salts, Na yeast extract glycerol salts, Na glycerol substitution of yeast extract
16 Processes in Future Lignocellulose Lignocellulose Pretreatment? Glucose Products Xylose Products Lignin Products? Biogas Residues Wastewater Electricity, eat Energy from Renewable Resources Biogas feedstock gas boiler crops heat biogas sulfur removal motor-p manure reforming electricity, heat fuel cell biogas plant residues by-products food- and agro-industry, e.g. fats reforming compression liquid storage electricity, heat fuel
17 Biogas Plants in Germany number PJ = 2,3 GWh Gaspower =,85 GWh electric power + heat + auxiliary power + losses * year 26 * estimated Source: German Biogas Association and own Data Electricity from Biogas fuel-cell pilot plant located at thefal
18 Biorefineries Manifold interactions Locality limate, Soil, Water Infrastructure, Logistic Industry Technology Methods Processes Transport Auxilaries Energy, Seed, Fertilizer Pest Management Market onsumer, Products eat & Power Biorefinery Products eat, power Fuels Materials Feed & Food? Biomass Yield, Quality, Price Seasonal Availability Policy Directions, Rules Subsidies, Tax Benefits Economy EnergySituation Prices, Globalisation Foreign Trade Feedstocks Man Needs Population development Social aspects Thank you for your attention!
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