Valorization of Olive Mill Solid Waste to Ethanol by Microwave Pretreatment and Enzymatic Saccharification
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1 Valorization of Olive Mill Solid Waste to Ethanol by Microwave Pretreatment and Enzymatic Saccharification Yoram Gerchman; Hiba Abu Tayeh; Hassan Azaizeha 6 th International Conference on Sustainable Solid Waste Management
2 Why biofuels? >
3 Bioethanol as fuel an old idea The fuel of the future is going to come from fruit like that sumach out by the road, or from apples, weeds, sawdust almost anything. There is fuel in every bit of vegetable matter that can be fermented. There s enough alcohol in one year s yield of an acre of potatoes to drive the machinery necessary to cultivate the fields for a hundred years. Henry ford in the New York Times 1925 gerchman.yoram@gmail.com
4 Ethanol as fuels São Paulo, Brazil Nebraska, USA Biodiesel Ethanol
5 What to make ethanol from? 2 nd generation Sugarcane Corn OECD FAO Agricultural Outlook 2017 gerchman.yoram@gmail.com
6 2 nd generation Ethanol agricultural waste as feedstock
7 2 nd generation 2 nd generation ethanol to increase cellulosicethanol production in 2020 at least 16 5 billion gallons.html
8 Not all countries agricultural waste are equal explained/index.php/agricultural_production_ _crops#cereals
9 In the Mediterranean olives are a major agricultural crop 50 years or over ~2,100,000 tons olive oil in Europe only (~12,000,000 ton olives) Eurostat 2014
10 Composition of olive fruit After extraction of oil much biomass is left Amount and composition depending on the extraction process usedy
11 Olive oil extraction methods Olive Mill Solid Waste (OMSW) I II III II I I I II
12 Olive oil extraction wastes Traditional (press) 3 Phase 2 phase Comments Modern (centrifugal) 2,700,000 ton of olive oil produced WW (2015/16) Oil 200 L 200 L 200 L Cultivar dependent Wash water Other water m m m 2 270, ,000 m m 2 OMWW 0.6 m 2 (~10% solids) m m 2 With 60% solids ( metric COD: 67, ,000 mg/l BOD: 34,000 50,000 mg/l Polyphenols: 6 12 g/l ton)
13 Olive oil extraction wastes cont. Traditional (press) 3 Phase 2 phase Comments Modern (centrifugal) 2,700,000 ton of olive oil produced WW (2015/16) Oil 200 L 200 L 200 L Cultivar dependent Wash water Other water m m m 2 270, ,000 m m 2 OMWW 0.6 m 2 (~10% solids) OMSW 0.4 ton (~20% water) m m m 2 (50% water) With 60% solids ( metric ton)
14 Olive Mill Solid Waste vallorization Soil amendment w/ or w/o pre composting ress.com/tag/composting/ Enemansa, Vilarta de SJ, near Ciudad Real, Spain ~1,350,000 tons/y from olive oil industrycausing health.html
15 Olive Mill Solid Waste composition w/w 2 phase 3 phase (modern) 3 phase (pressing) Moisture (w/fw) 55 75% 40 55% 20 25% Volatiles (w/dw) 65 82% Cellulose (w/dw) 18 37% Hemicellulose (w/dw) 14 36% Lignin (w/dw) 20 43% Protein % Sugars ~1.5% Ash (K>Ca>Mg> ) ~2%, ~0.3%,0.07%, Considered phytotoxic waste due to low ph (~5) and abundance of tannins
16 Experimental setting Biomass (OMSW) Dried 3P OMSW High lignin content lignin inhibit cellulase enzymes Pretreatment cab also result in sugar loss and enzyme/ fermentation inhibitors Grinding/Milling Pretreatment Saccharification Sugars released Heating vs microwave: Dupont Accelrase 1500 vs Novozyme Ctec2 Cellobiose, Glucose, Arabinose, Xylose quantification HPLC DAD RI Fermentation Ethanol in water Ethanol quantification
17 Experimental structure Waste Solids: Amount 1. Suspend in water 2. Add None/FA/SA 3. Treat by MW/Au Add Enzymes: 1. Cellulase (Accelrase 1500/Cellic CTec2 2. Accelerase BG 3. Incubate 24h Hydro lisate Analyze: Free sugars, Furfural, HMF Add Waste Liquid Analyze: Sugars, Furfural, HMF Solids: Amount Ethanol! Analyze: Growth Sugar consumption
18 Formation of fermentation inhibitors Results Pretreatment waste liquid Microwave (140⁰C,10 min) Lost sugars Autoclave (120⁰C,10 min)
19 Hydro lysate Ferr. Inh. released by enzymatic saccharifi cation Microwave Autoclave
20 Hydro lysate Glucose released by enzyme saccharif ication
21 Hydro lysate Other Sugars released by enzymatic saccharific ation Microwave Autoclave
22 Ethanol produced (Ethanol Red yeast) Pretreatment Enzyme Additive None (DW) FA SA Microwave Cellic CTec2 10 g/l 67% (of theoretical) Accellerase 5 33% % 12 80% 2.5 g/l 16.6% % Autoclave Cellic CTec % Accellerase % % % % % % teoretical EtOH : 18.4% w/w cellulose content in the OMSW; 160 g/l pretreated solid content in the enzymatic hydrolysis; 0.51 g/g theoretical ethanol yield from glucose.
23 Hydro lysate Fermentation kinetics MW 13.5g/L ~78 mg/g raw Accellerase Cellic CTec2 FA No Add. SA
24 Fermentation kinetics Autoclave ~6 g/l ~32 mg/g raw Accellerase Cellic CTec2 FA No Add. SA
25 Factor analysis EtOH concentration (g/l) EtOH yield (mg/g) Experimental Parameter Degree of freedom F Sig. F Sig. Pretreatment (1 st ) Additive (2 nd ) Enzyme (4 th ) Pretreatment * Additive (3 rd ) Pretreatment * Enzyme Additive * Enzyme Pretreatment * Additive * Enzyme Corrected total degrees of freedom = 31; in italics statistically significant correlations
26 What about the remnants? 100 Cd Cu Ni Pb Se Zn 50 ppm starting conc. each 80 Removal (%) Control DW ACC DW NOV FA ACC FA NOV SA ACC SA NOV Incubation time (min)/ additive/ enzyme
27 Summary OMSW can be efficiently used as feed stock for ethanol production Choice of pretreatment (and additives) is the most crucial factor affecting ethanol yields (for other pretreatments see Yan Rosen s posters) Using yeast that can utilize pentose sugars can help (not tested here) Using the leftover solids could results in better economics
28 Decentralized pretreatment? Today The future? DuPont Iowa Ethanol Plant (For sale 2017) Pretreatment on a truck? Local fermentation and distillation?
29 Thanks Collaborators: Heba Abu Tayeh M.Sc. (Ph.D. student) Prof. Hassan Azaizeh (Tel Hai college and Galilee Soc. R&D) Funding: Israeli Ministry of Environmental Protection Israeli Ministry of Energy and Water Israeli Ministry of Science and Technology Questions?
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