Shi, Zhongping

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Engineering Conferences International

Butanol extractive fermentation to simultaneously produce “properties improved” biodiesel & butanol in a water Bio-energy III, ECIMay 22-27, 2011, Lanzarote, Spainand energy-saving operation wayZhongping ShiSchool of Biotechnol., Jiangnan Univ., Wuxi, China2011-05-26Scopes of the presentation1) ObjectivesBio-energy III, Lanzarote, Spain 2) Methods3) Updated results4) ConclusionsImportant organic chemicals & intermediateHigh performance fuel & liquid fuel additiveBio-ButanolBio-energy III, Lanzarote, Spain - Objectives Bio-energy III, Lanzarote, Spain - Objectives Traditional ABE fermentation & purification processBtOH 13g/l, ACE 6.5g/l, EtOH 2g/l  Example of Related Palm oil methyl ester Fossil dieselsthe major index Performance (One of bio-diesels) (#2 diesel US)Cetane Number Ignition delay, 49 56(CN) combustion, black smokeGeneral comparison of Fossil Diesels & Bio-diesels Bio-energy III, Lanzarote, Spain - Objectives Combustion Heat Combustion properties 39.8 45.7(MJ/Kg) Output powerBoiling point (°C) Ignition at low temp. +10 °C -7 °CS content (wt, %) Air pollution, environment 0.01 0.07Total gas exhausts Air pollution, environment, 0.421 0.486amount (g/Kwh) global green-house effectAvailable sources Sustainable/renewable features Renewable biomass Fossil sourcesDisadvantagesAdvantagesIncreased CN value of the bio-diesel extracted butanolBio-energy III, Lanzarote, Spain - Objectives CetaneNumber(CN)Original BDBD extractedwith 12 g/l BtOHBD extracted with 12 g/l BtOH but treated with 1.6% Na2SO4 dehydrationBD: Bio-diesel#1 High raw materialscost#2 Low fermentationproductivity by end products inhibition1) Developing an integrated AB fermentation to enhance productivity;2) Direct utilizing butanol extracted bio-diesel as “properties improved” biodiesel, eliminating products recovery process;3) Fully utilizing residual waste water to save fresh water & minimize water pollution;Bio-energy III, Lanzarote, Spain - Objectives #3 Low products concentration, hugeenergy requirementfor purification4) Recovering BtOH in the waste to increase “aimed” yield.High quality’sproductsEnergy saving,low operation costHighproductivityIntegrationCreating novel Biofuels system,products diversityTechnological flow-chartBio-energy III, Lanzarote, Spain - Methods  Original BiodieseltankFermentorMedium preparation tankComplement of starch, fresh waster, etc.Full waste supernatant recycling & repeated utilizationn-octanoltank 1Adhering operation unit using activated carbonProperties improved biodiesel“properties improved”biodiesel production system coupled with butanol extractive fermentationStirred tank for recovering butanolin supernatantn-octanoltank 2 concentrated with butanolPure butanol fuelDirect utilizationDistillation unitn-octanol recoveryWaste supernatant,Solid/liquid separationStrain: Clostridium acetobutylicum ATCC824Fermentation medium: corn flour & cassava powders (15%∼30%)Fermentation volume: 2.0∼2.5 LFermentation conditionsBio-energy III, Lanzarote, Spain - Methods Fermentation extractants: bio-diesels/olyel alcohol, volume ratio 1:1Fermentation condition: 37°C, strictly anaerobic, static Initial urea amount: 1% (w/w) of the total sugarYeast extracts addition amount: 2.5 g/L-brothBio-energy III, Lanzarote, Spain - Methods Fermentor and instrumentsUsing n-octanol to extract BtOH in residual wastes before pretreatment51015202530Butanol conc. (g/l)20406080100Butanol recovery ratio (%)BtOH conc. in n-octanolBtOH conc. in supernatantBio-energy III, Lanzarote, Spain - Results 00.00 0.20 0.40 0.60 0.80 1.00Volume ratio of n-octanol vs waste supernatant0Butanol recovery ratio (%)Aimed BuOH yield =consumedStarchBtOHBtOH olocndieselBio tan−− +Ease distillation load& save purification energy0.150.200.250.00 0.20 0.40 0.60 0.80 1.00Volume ratio of n-octanol vs waste supernatantAimed butanol yield (-)Bio-energy III, Lanzarote, Spain - Results Color changes of waste supernatant after adding activated carbonWithout activated C treatment With activated C treatmentBio-energy III, Lanzarote, Spain - Results 3040Gas production (L/L-broth)Pretreatment (residual BtOH extraction + activated C adhere)& full (100%) utilization of supernatant - gas production3% (w/v) activated carbonMedium preparation with fresh water Removal of melanoidin010200 20 40 60Fermentation time (h)Gas production (L/L-broth)Medium preparation with pretreated supernatantMedium preparation with non-pretreated supernatantToxic melanoidin formedBio-energy III, Lanzarote, Spain - Results AB fermentation when using fresh water for medium preparation 510Solvents conc. (g/l)4.55.5pH (-)-450-400ORP (mv)ORP(A) (A)BtOH in BDACE in brothACE in BDBtOH in brothAgitationA: without neutral red addition; B: with 0.1% (w/v) neutral red addition00 20 40 60 80 100Solvents conc. (g/l)05100 20 40 60 80 100Fermentation time (h)Solvents conc.（g/L）3.50 20 40 60 80 100-500pH3.54.55.50 20 40 60 80 100Fermentation time (h)pH (-)-500-400-300ORP (mV)pHORP(B) (B)Bio-energy III, Lanzarote, Spain - Results AB fermentation using 100% pretreated waste supernatant for medium preparation 510Solvents conc. (g/L)(A)4.55.5pH (-)-500-450-400ORP (mv)pHORPA: without neutral red addition; B: with 0.1% (w/v) neutral red addition00 20 40 60 80 1003.50 20 40 60 80 100-55005100 20 40 60 80 100Fermentation time (h)Solvents conc. (g/L)(B)3.54.55.50 20 40 60 80 100Fermentation time (h)pH (-)-600-550-500-450-400ORPpHBtOH in BDBtOH in brothACE in brothACE in BDAgitationBio-energy III, Lanzarote, Spain - Results 101520Butanol conc. (g/L)6080100Supernatant recycle rate (%),residual starch conc. (g/L)Repeated utilization of pretreated waste supernatant△: residual starch conc.; ○: BtOH in aqueous broth; ●: BtOH in bio-diesel; □: waste recycle ratio051 2 3 4 5 6 7 8 9 10 11 12 13 14 15Fermentation run (-)Butanol conc. (g/L)02040Supernatant recycle rate (%),residual starch conc. (g/L)Yields of total solvents (T), total butanol (B), and aimed butanol (A)Bio-energy III, Lanzarote, Spain - Results Yields of total solvents, total butanol and “aimed” butanol in different fermentation runs 3040Yields (-)TBA1) Traditional AB fer.; 2) Extractive AB fer. using fresh water without recovering residual butanol and using supernatant for the next run; 3) Extractive AB fer. with fresh water, recovering residual butanol and using waste supernatant; 4) Extractive AB fer. using 100% pre-treated waste supernatant; 5) Extractive AB fer. using fresh water for medium preparation with addition of 0.1% neutral red; 6) Extractive AB fer. using 100% pre-treated waste supernatant with addition of 0.1% neutral red.10201 2 3 4 5 6Fermentation runs (-)Yields (-)Bio-energy III, Lanzarote, Spain - Results "Propertiesimproved"biodieselStarchconsumedAimedBtOH Total aimed BtOH BtOH/(BtOH+ACE)Total BtOHproductivityrun #  amount  (L/L- biodiesel broth n-octanol supernatant* (g/L) Yields (-)** amount (g/L-broth)  (in n-octanol, %) (g/h/L-broth)BtOH concentration (g/L), inThe performance and comparison of the integrated AB extractive fermentation processbroth)1 0.00 0.00 11.63 0.00 0.00 46.12 0.00 0.00 0.00 0.182 0.97 9.57 8.80 27.20 3.36 74.15 19.86 14.72 80.98 0.213 0.96 10.09 7.00 23.50 2.30 72.00 19.98 14.39 88.68 0.224 0.97 11.44 10.07 31.10 3.86 66.38 26.09 17.32 92.97 0.275 0.97 9.95 7.88 27.30 2.42 61.87 24.42 15.11 91.21 0.25Run #1: Traditional AB fermentation; Run #2: AB extractive fermentation using fresh water; Run #3: AB extractive fermentation using 100% waste supernatant; Run #4: AB extractive fermentation using fresh water and with 0.1% (w/v) neutral red addition; Run #5: AB extractive fermentation using 100% supernatant and with 0.1% (w/v) neutral red addition.Bio-energy III, Lanzarote, Spain - Results Exploring the possibility of using cassava as fermenting source for bio-butanol productionCorn based sources•competition with foods for arable landCassava•high productivity in in-arable lands even mountain areas•non-competition with foods for arable land•high starch content, but low protein content, cheapBio-energy III, Lanzarote, Spain - Results Very low solvents production rates510BtOH, ACE conc.(g/L)Open symbols: cornClosed symbols: cassavaBtOH BtOHACE1015202530BtOH, ACE conc.(g/L)203040Total BtOH conc.(g/L)BtOHACETotal BtOH Total BtOHOpen symbols: cornClosed symbols: cassavaTraditional AB fermentation Extractive AB fermentation using oleyl alcohol05101520250 20 40 60 80Time (h)Gas production (L/L-broth)0204060800 25 50 75 100Time (h)Gas production (L/L-broth)Broken lines: cornSolid lines: cassava00 20 40 60 80Time (h)BtOH, ACE conc.(g/L)ACE0520 40 60 80 100Time (h)BtOH, ACE conc.(g/L)010 Total BtOH conc.(g/L)BtOHACEBio-energy III, Lanzarote, Spain - Results 4.44.95.4pH(-)-550-450-350-250-150ORP(mv)4.555.5pH(-)-500-400-300-200-1000ORP(mv)Broken lines: cornSolid lines: cassavaBlack: pH; Red: ORPBroken lines: cornSolid lines: cassavaBlack: pH; Red: ORP18h40hLong time delay in shifting from acidogenic to solventogenic phase Traditional AB fermentation Extractive AB fermentation using oleyl alcohol012340 20 40 60 80Time(h)Acids conc.(g/L)012340 20 40 60 80 100Time(h)Acids conc.(g/L)3.90 20 40 60 80Time(h)-650 40 20 40 60 80 100Time(h)-600Broken lines: cornSolid lines: cassavaCircle: butyrateTriangle: AcetateFast-dropSlow-dropFast-dropSlow-dropBio-energy III, Lanzarote, Spain - Results 4.44.95.4pH(-)-450-350-250-150ORP(mv)YE additionBroken: cornSolid: cassavaBlack: pH; Red: ORP4.555.5pH(-)-400-300-200-1000ORP(mv)YE additionBroken: cornSolid: cassavaBlack: pH; Red: ORPYeast extract stimulates bio-butanol production from cassavaTraditional AB fermentation Extractive AB fermentation using oleyl alcohol01020300 20 40 60Time (h)Gas production (L/L-broth)Broken lines: cornSolid lines: cassava0204060800 25 50 75 100Time (h)Gas production (L/L-broth)YE addition YE addition3.90 20 40 60 80Time(h)-650-5503.540 20 40 60 80 100Time(h)-600-500Bio-energy III, Lanzarote, Spain - Results Yeast extract stimulates bio-butanol production from cassavaTraditional AB fermentation Extractive AB fermentation using oleyl alcohol10BtOH, ACE conc.(g/L)202530BtOH, ACE conc.(g/L) 3040Total BtOH conc.(g/L)Open symbols: cornClosed symbols: cassavaOpen symbols: cornClosed symbols: cassavaBtOHBtOH050 10 20 30 40 50 60Time (h)BtOH, ACE conc.(g/L)05101520 40 60 80 100Time (h)BtOH, ACE conc.(g/L)01020Total BtOH conc.(g/L)ACEACEBtOHBtOHACEACETotal BtOHTotal BtOHBio-energy III, ECI, Lanzarote, Spain - Results Yeast extract stimulates bio-butanol production from cassavaCoAT:CoA-transferaseCoAT be activated when adding yeast extract ??GlucoseStarchPyruvateNADNADHH+H2HydrogenaseEMPNADNADH + H H2CO2Acetyl-CoAAcetoacetyl-CoACO2AcetoneButyryl-CoAHydrogenaseH2NADHNADButanolNADHNADH2HydrogenaseButyrateAcetateCoATCoATCoAT1) A novel, integrated fermentation process in production of both “properties improved” bio-diesel for direct use and pure butanol, was proposed.2) Using a small amount n-octanol to recover BtOH in residual wastes before medium preparation, aimed butanol yield increased from 13% to 21%, easing purification load.Bio-energy III, Lanzarote, Spain - Conclusions 3) The fermentation residual waste could be 100% re-utilized for medium preparation by pre-treating with 3% activated carbon to remove melanoidin.4) Fully recycling of fermentation residual waste for AB extractive fermentation could be continued for at least 15 runs without performance deterioration.5) Yeast extract stimulates bio-butanol production from cassava.○Thanks for sponsorships from Major State Basic Research Development Program (#2007CB714303) & National Natural Science Foundation Program (#20976072), of China.Bio-energy III, Lanzarote, Spain - Acknowledgement ○ Thanks for the hard experimental works & contribution from following students: Mr. ZG Li, Mr. X Li, Ms. JP Zheng, Ms. L Li.Bio-energy III, Lanzarote, SpainNanjingWuxiYangtze River DeltaYellow SeaThe Yangtze RiverOur location – welcome to visit us for communication/consultationShanghaiHangzhouSuzhouTaihu LakeEastern China SeaBio-energy III, Lanzarote, SpainThank you!

Butanol Extractive Fermentation to Simultaneously Produce Properties Improved Bio-diesel and Butanol in a Water and Energy-Saving Operation Way

https://dc.engconfintl.org/cgi/viewcontent.cgi?article=1039&amp;context=bioenergy_iii

Butanol Extractive Fermentation to Simultaneously Produce Properties Improved Bio-diesel and Butanol in a Water and Energy-Saving Operation Way

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