CN106188612A - A kind of fermentation of ligno-cellulose hydrolysate process surfactant recovery technology - Google Patents
A kind of fermentation of ligno-cellulose hydrolysate process surfactant recovery technology Download PDFInfo
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- fermentation
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- cellulose hydrolysate
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- 238000000855 fermentation Methods 0.000 title claims abstract description 76
- 230000004151 fermentation Effects 0.000 title claims abstract description 76
- 239000004094 surface-active agent Substances 0.000 title claims abstract description 54
- 239000001913 cellulose Substances 0.000 title claims abstract description 39
- 229920002678 cellulose Polymers 0.000 title claims abstract description 39
- 239000000413 hydrolysate Substances 0.000 title claims abstract description 33
- 238000011084 recovery Methods 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000005516 engineering process Methods 0.000 title claims abstract description 21
- 230000008569 process Effects 0.000 title claims abstract description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 99
- 239000003112 inhibitor Substances 0.000 claims abstract description 30
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 19
- 239000000872 buffer Substances 0.000 claims abstract description 18
- 240000004808 Saccharomyces cerevisiae Species 0.000 claims abstract description 16
- 235000014680 Saccharomyces cerevisiae Nutrition 0.000 claims abstract description 16
- 210000005253 yeast cell Anatomy 0.000 claims abstract description 12
- 238000001784 detoxification Methods 0.000 claims abstract description 10
- 238000004821 distillation Methods 0.000 claims abstract description 9
- 238000004880 explosion Methods 0.000 claims abstract description 4
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 37
- 239000008103 glucose Substances 0.000 claims description 37
- 239000007788 liquid Substances 0.000 claims description 26
- 235000000346 sugar Nutrition 0.000 claims description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 claims description 10
- LHGVFZTZFXWLCP-UHFFFAOYSA-N guaiacol Chemical compound COC1=CC=CC=C1O LHGVFZTZFXWLCP-UHFFFAOYSA-N 0.000 claims description 8
- 229920001223 polyethylene glycol Polymers 0.000 claims description 8
- 210000004243 sweat Anatomy 0.000 claims description 8
- NOEGNKMFWQHSLB-UHFFFAOYSA-N 5-hydroxymethylfurfural Chemical compound OCC1=CC=C(C=O)O1 NOEGNKMFWQHSLB-UHFFFAOYSA-N 0.000 claims description 7
- RJGBSYZFOCAGQY-UHFFFAOYSA-N hydroxymethylfurfural Natural products COC1=CC=C(C=O)O1 RJGBSYZFOCAGQY-UHFFFAOYSA-N 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 210000004027 cell Anatomy 0.000 claims description 6
- 239000010813 municipal solid waste Substances 0.000 claims description 6
- 239000002023 wood Substances 0.000 claims description 6
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 239000003960 organic solvent Substances 0.000 claims description 5
- -1 polydimethylsiloxane Polymers 0.000 claims description 5
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- JOOXCMJARBKPKM-UHFFFAOYSA-N 4-oxopentanoic acid Chemical compound CC(=O)CCC(O)=O JOOXCMJARBKPKM-UHFFFAOYSA-N 0.000 claims description 4
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 239000002154 agricultural waste Substances 0.000 claims description 4
- 229960001867 guaiacol Drugs 0.000 claims description 4
- 239000010695 polyglycol Substances 0.000 claims description 4
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 4
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 4
- 235000012141 vanillin Nutrition 0.000 claims description 4
- 239000002699 waste material Substances 0.000 claims description 4
- 230000002401 inhibitory effect Effects 0.000 claims description 3
- 229920000151 polyglycol Polymers 0.000 claims description 3
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 239000000758 substrate Substances 0.000 claims description 3
- 150000008163 sugars Chemical class 0.000 claims description 3
- 241000609240 Ambelania acida Species 0.000 claims description 2
- 244000025254 Cannabis sativa Species 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 241000209140 Triticum Species 0.000 claims description 2
- 235000021307 Triticum Nutrition 0.000 claims description 2
- 240000008042 Zea mays Species 0.000 claims description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 2
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 2
- 239000010905 bagasse Substances 0.000 claims description 2
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 2
- 235000005822 corn Nutrition 0.000 claims description 2
- 239000004205 dimethyl polysiloxane Substances 0.000 claims description 2
- 235000013312 flour Nutrition 0.000 claims description 2
- 239000006174 pH buffer Substances 0.000 claims description 2
- 239000010893 paper waste Substances 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920000435 poly(dimethylsiloxane) Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- XPFJYKARVSSRHE-UHFFFAOYSA-K trisodium;2-hydroxypropane-1,2,3-tricarboxylate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].[Na+].[Na+].OC(=O)CC(O)(C(O)=O)CC(O)=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O XPFJYKARVSSRHE-UHFFFAOYSA-K 0.000 claims description 2
- LEAHFJQFYSDGGP-UHFFFAOYSA-K trisodium;dihydrogen phosphate;hydrogen phosphate Chemical compound [Na+].[Na+].[Na+].OP(O)([O-])=O.OP([O-])([O-])=O LEAHFJQFYSDGGP-UHFFFAOYSA-K 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 claims 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 claims 2
- 229940043265 methyl isobutyl ketone Drugs 0.000 claims 2
- DURPTKYDGMDSBL-UHFFFAOYSA-N 1-butoxybutane Chemical compound CCCCOCCCC DURPTKYDGMDSBL-UHFFFAOYSA-N 0.000 claims 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical group COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims 1
- 239000000446 fuel Substances 0.000 abstract description 6
- 239000002028 Biomass Substances 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 2
- 235000019441 ethanol Nutrition 0.000 abstract 5
- 230000015556 catabolic process Effects 0.000 abstract 1
- 230000008878 coupling Effects 0.000 abstract 1
- 238000010168 coupling process Methods 0.000 abstract 1
- 238000005859 coupling reaction Methods 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 230000004087 circulation Effects 0.000 description 12
- 238000004064 recycling Methods 0.000 description 12
- 238000002474 experimental method Methods 0.000 description 9
- 239000000126 substance Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 239000002994 raw material Substances 0.000 description 5
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 229920002582 Polyethylene Glycol 600 Polymers 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 108010059892 Cellulase Proteins 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 239000008118 PEG 6000 Substances 0.000 description 2
- 229920002535 Polyethylene Glycol 1500 Polymers 0.000 description 2
- 229920002593 Polyethylene Glycol 800 Polymers 0.000 description 2
- 235000009392 Vitis Nutrition 0.000 description 2
- 241000219095 Vitis Species 0.000 description 2
- 229940106157 cellulase Drugs 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 235000013305 food Nutrition 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- 230000005764 inhibitory process Effects 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002736 nonionic surfactant Substances 0.000 description 2
- 229920002523 polyethylene Glycol 1000 Polymers 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- VUYXVWGKCKTUMF-UHFFFAOYSA-N tetratriacontaethylene glycol monomethyl ether Chemical group COCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO VUYXVWGKCKTUMF-UHFFFAOYSA-N 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 229920002488 Hemicellulose Polymers 0.000 description 1
- 229920000604 Polyethylene Glycol 200 Polymers 0.000 description 1
- 229920001030 Polyethylene Glycol 4000 Polymers 0.000 description 1
- 229920002584 Polyethylene Glycol 6000 Polymers 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 210000003969 blast cell Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000010261 cell growth Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 150000002240 furans Chemical class 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000007781 pre-processing Methods 0.000 description 1
- 235000019260 propionic acid Nutrition 0.000 description 1
- 238000001448 refractive index detection Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The present invention provides a kind of fermentation of ligno-cellulose hydrolysate process surfactant recovery technology, belongs to biomass degradation producing fuel ethyl alcohol by ferment field.The ligno-cellulose hydrolysate of this heat chemistry pretreatment such as technology acidolysis or steam explosion, it is not necessary to detoxification treatment, directly adjust pH value, add surfactant, access saccharomyces cerevisiae carry out alcohol fermentation after be directly separated recovery yeast cells；The enrichment of surfactant, fermentation inhibitor, buffer agent is realized while distillation ethanol；Realize surfactant by extractive fermentation mortifier, buffer agent reclaims with the integrated separation of fermentation inhibitor.Advantage of the present invention is: not only increase the efficiency that recycles of yeast, and achieve surfactant, buffer agent, the coupling of fermentation inhibitor are reclaimed again；Relative to the process of distillation ethanol, surfactant reclaims the most additionally increases energy expenditure, and recovery process is simple, effectively reduces pollution, reduces cost fall, has been pushed further into the process of industrialization of cellulosic ethanol.
Description
Technical field
The present invention relates to biomass material degraded and produce alcohol fuel field by fermentation technology, be specifically related to one
Plant the surfactant recovery method to ligno-cellulose hydrolysate detoxification.
Background technology
Along with the exhaustion day by day of fossil energy and increasingly sharpening of environmental pollution, renewable and clean energy resource fuel second
The development and utilization of alcohol receives the extensive concern of people.Traditional alcohol fermentation with sugar or starch as raw material,
Both of which is the main source of food, with grain for raw material production alcohol fuel structure safe to world food
Become threat, find other raw material substitution grain imperative.Lignocellulose enriches the most
Biomass resource, with lignocellulose for raw material production alcohol fuel not only can effectively alleviating energy crisis, subtract
Light environmental pollution, and meet the target of sustainable development of the extensive petroleum replacing of future fuel ethanol, have
Great economic worth and social meaning.
Lignocellulose is converted into ethanol it is generally required to four steps: heat-chemistry pretreatment, cellulase hydrolysis,
Fermentable and distillation.Pretreatment needs to complete under severe conditions, the wood of ability destruction height polymerization
The structure of quality, cellulose and hemicellulose so that ensuing cellulase hydrolysis is possibly realized.Acidolysis
Or the conditions such as the high temperature of heat chemistry preprocessing process, high pressure such as steam explosion can make to generate in hydrolyzed solution or discharge
The fermentation inhibitors such as organic acid, furans and phenols, these compounds are to saccharomycetic normal growth and second
Alcohol sweat produces strong inhibition effect, has become as a main barrier of cellulosic ethanol large-scale production
Hinder.
Therefore, the ligno-cellulose hydrolysate to pretreatment carries out detoxification treatment and seems and be even more important.Literary composition at present
Offer the poison-removing method of report mainly include washing detoxification, physics detoxification (air-extraction, membrane separation process are concentrated in vacuo),
Chemical detoxication (Calx neutralization, activated carbon adsorption, ion exchange, solvent extraction), biological detoxication.Such as literary composition
Offer Bioprocess Biosyst Eng (2013) 36:659 666 use active carbon adsorption discuss furfural,
The impact on yeast cell growth speed of the fermentation inhibitor such as HMF, levulic acid；Patent CA102226204B
Disclose the poison-removing method of a kind of lignocellulose ethanol fermentation liquid, solvable by adding in pending sugar liquid
Property electrolytic salt post-heating obtain constant temperature material liquid and carry out Membrane Materials by membrane module and remove in sugar liquid rear supervention
Ferment produces the material of inhibitory action., the mode such as washing, physics, chemical detoxication consume great lot of water resources,
Equipment investment cost height and complex process, and detoxification efficiency is poor, sugar loss is serious.This laboratory passes through
Nonionic surfactant is added, to fermentation strain while alcohol fermentation in ligno-cellulose hydrolysate
Carry out protecting outside chemistry, improve the yeast cells toleration to fermentation inhibitor, thus improve cellulosic ethanol
Fermentation efficiency (CN 201410280800.3 and CN 201410454864.0).
But during separation of ethanol, the discharge of wastewater containing nonionic surfactant and fermentation inhibitor is led
Cause environmental pollution；And surfactant is fine chemicals, toxicity inhibition thing also can pass through chemical conversion system
High level chemicals, reclaims surfactant and fermentation inhibitor is possible not only to reduce pollution, can also effectively drop
Low cost.
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of fermentation of ligno-cellulose hydrolysate process surface to live
Property agent recovery technology.A kind of fermentation of ligno-cellulose hydrolysate process surfactant that the present invention proposes reclaims
Technology, first basic ideas carry out solid-liquid separation and reclaim yeast cells fermentation liquid；Then liquid is being carried out
The enrichment of surfactant and fermentation inhibitor is realized while distillation ethanol；Finally pass through organic solvent extracting again
Take fermentation inhibitor and can realize the integrated separation recovery of surfactant, fermentation inhibitor.
In order to realize the object of the invention, for the support that the thought offer of the present invention is clear and definite, the method comprises the steps of firstly, preparing
A series of ligno-cellulose hydrolysate model things, then add yeast cells, surfactant, adjustment pH
After ferment.Carrying out solid-liquid separation after fermentation, be separately recovered insoluble matter and supernatant, insoluble matter is yeast
Cell is recycling；Supernatant is carried out containing surfactant, fermentation inhibitor, buffer agent.To supernatant
Carry out distilling, extract, redistillation, distillation residue predominantly surfactant, buffer agent can be directly used for
Sweat next time, fermentation inhibitor is extracted collection and can be used for chemical conversion high level chemicals.
A kind of fermentation of ligno-cellulose hydrolysate process surfactant recovery technology, according to following steps
Carry out: the ligno-cellulose hydrolysate of the heat chemistry pretreatment such as acidolysis or steam explosion, be not required to detoxification treatment,
Directly add buffer to adjust pH value, interpolation surfactant, access after Ethanol in Saccharomyces cerevisiae ferments surface
Activating agent and fermentation inhibitor carry out integrated separation recovery.
Described Surfactant and fermentation inhibitor carry out integrated separation recovery, first carry out fermentation liquid
Solid-liquid separation reclaims yeast cells；Then carry out liquid distilling realize while ethanol surfactant,
Fermentation inhibitor, the enrichment of buffer agent；Realize surface by organic solvent extraction fermentation inhibitor the most again to live
Property agent, the integrated separation of buffer agent and fermentation inhibitor reclaim.
The concentration of described surfactant is 0～0.4g/mL hydrolyzed solution, and the cell of described saccharomyces cerevisiae is dense
Degree is: 0.13*108Hundred million-1.4*109Individual/m.
Described fermentation temperature is 30-39 DEG C, and fermentation time is 4～100h；The pH of buffer is 4.0～5.5；
Vapo(u)rizing temperature is 30-100 DEG C, and distillation pressure is-0.01Mpa～-0.1Mpa, and distillation time is 10 minutes-120
Minute.
Described lignocellulose is from agricultural wastes, forestry waste, special energy crop or/and each
Plant the garbage of cellulose；
Described agricultural wastes are that wheat stalk, corn straw are or/and Caulis et Folium Oryzae；
Described forestry waste be lumbering produce branch and leaf, discarded wood is or/and wood flour；
Described special energy crop is sugar grass or/and Ramulus Salicis Babylonicae journey；
The garbage of described various cellulose is that urban solid garbage, waste paper are or/and bagasse.
Described ligno-cellulose hydrolysate contains one or more fermentable sugars such as glucose, xylose, can send out
Ferment sugar concentration is 60-500g/L.
Described ligno-cellulose hydrolysate contains fermentation inhibitor, and fermentation inhibitory substrate concentration is 0～6.0g/L；
Described fermentation inhibitor is phenol, guaiacol, vanillin, 5 hydroxymethyl furfural (HMF), furfural, second
One or more of acyl propanoic acid or acetic acid.
Described described surfactant be Polyethylene Glycol, poly glycol monomethyl ether, NHD,
At least one in polydimethylsiloxane, tween；It is preferably Polyethylene Glycol.
The molecular weight of described surfactant polyethylene is 200-8000；It is preferably 200-2000.
Described organic solvent is:
Described pH buffer agent is: Acetic acid-sodium acetate, citric acid-sodium citrate, phosphoric acid-sodium phosphate, sulphuric acid are molten
Liquid.
Hinge structure, lives in a kind of ligno-cellulose hydrolysate detoxification sweat surface that the present invention proposes
Property agent recovery method is as it is shown in figure 1, the method has the advantage that the present invention is during separating alcohol
Synchronize to achieve the enrichment of surfactant, buffer agent, yeast cells, do not increase any extra energy and disappear
Consumption；Then the surfactant of enrichment is realized surfactant, buffer agent, fermentation inhibitor by extraction
Integrated separation reclaim.Fermentation inhibitor can be used for producing high level chemicals, improves lignocellulose further
The atom utilization of raw material.Sum it up, the recovery technology of surfactant enters one during cellulose production
Step has promoted cellulosic ethanol process of industrialization, is with a wide range of applications.
Accompanying drawing explanation
Fig. 1 surfactant, yeast, buffer agent integration recycle schematic diagram.
The cycling and reutilization schematic diagram of Fig. 2 yeast.
The common loop recycling schematic diagram of Fig. 3 surfactant and yeast.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not subject to
The restriction of embodiment, the content described in following embodiment and description simply illustrates the principle of the present invention,
Without departing from the spirit and scope, the present invention also has various changes and modifications, these changes
Both fall within the range of claimed invention with improvement.Claimed scope is by appended right
Claim and equivalent thereof define.
It addition, what deserves to be explained is, in following embodiment, in fermentation liquid, the assay of each component thing uses
High performance liquid chromatograph (Agilent 1260), calculates its conversion ratio, ethanol yield according to the inventory of substrate, depends on
According to ethanol quality, activated water and pH liquid long-pending calculating concentration of alcohol in fermentation liquid.
Chromatographic condition is: ion exchange column, and column temperature is 65 DEG C, refractive index detection device, and detector is 50 DEG C；
Flowing phase: 5Mm H2SO4, flow velocity 0.6ml/min, sample size 25uL.
Embodiment 1
Ligno-cellulose hydrolysate model thing 20mL, the wherein 71g.L Han concentration of glucose-1, mixing mortifier
(phenol, guaiacol, vanillin, HMF, furfural, levulic acid mixture) (2.0g.L-1), add
0.2g.mL-1PEG-400 (is not added with PEG) in comparative example, add barm cell concentration 0.8*108~
0.96*108Individual/mL, is adjusted to 4.3 by pH value, puts in shaking table and shakes, fermentation 48 under the conditions of 33 DEG C
Hour.Carrying out solid-liquid separation after fermentation, the yeast cells of recovery is directly used in fermentation next time.Glucose converts
Rate, concentration of alcohol are the most as shown in Figure 2.From figure, comparative example data are not it can be seen that fermentation system adds
During PEG, glucose converts hardly, and yeast cells is almost the most dead, it is impossible to recycling.And when sending out
After adding PEG in ferment system, glucose complete 100% converts and obtains 32g.L-1Ethanol；Recovery yeast is used
In sweat next time, the glucose of 90% still can be made to convert and can obtain 25g.L-1Ethanol；Even if ferment
The second time circulation of blast cell still can make the glucose of 40% convert and produce ethanol, the addition of this explanation PEG
Substantially improve the yeast cells toleration to fermentation inhibitor.
Embodiment 2
Ligno-cellulose hydrolysate model thing 20mL, the wherein 71g.L Han concentration of glucose-1, mixing mortifier
(phenol, guaiacol, vanillin, HMF, furfural, levulic acid mixture) (2.0g.L-1), add
0.2g.mL-1PEG-1000, adds barm cell concentration 0.8*108～0.96*108Individual/mL, uses sulfuric acid solution
PH value is adjusted to 4.3, puts in shaking table and shake, ferment 48 hours under the conditions of 33 DEG C.Ferment laggard
Row solid-liquid separation, supernatant liquid carries out distilling, extracts, redistillation, remaining liq be surfactant,
Buffer agent can be directly used for sweat (such as Fig. 1) next time together with the yeast reclaimed, and adds part Yeast.
PEG-1000 circulates 3 results as shown in Figure 3 altogether with the yeast of recovery.It can be seen that PEG-1000
Can be with recycling, inversion rate of glucose and concentration of alcohol remain unchanged substantially.
Embodiment 3
Experimental procedure is identical with embodiment 2, and difference is adding 0.2g.mL-1PEG-200, glucose converts
Rate, ethanol yield and concentration data are shown in Table 1. as can be seen from the table, PEG-200 can with recycling,
After three circulations, glucose converts completely, and concentration of alcohol remains unchanged substantially.
Table 1 inversion rate of glucose, concentration of alcohol data
Embodiment 4
Ligno-cellulose hydrolysate model thing 20mL, the wherein 70g.L Han concentration of glucose-1, phenol, more wound
Wood phenol (2.0g.L-1), 0.2g.mL-1PEG-800, adds barm cell concentration 0.8*108～0.96*108Individual
/ mL, is adjusted to 4.3 with sulfuric acid solution by pH value, puts in shaking table and shakes, fermentation 48 under the conditions of 33 DEG C
Hour.Carrying out solid-liquid separation after fermentation, supernatant liquid carries out distilling, extracts, redistillation, and remaining liq is i.e.
Sweat next time is can be directly used for for surfactant, buffer agent.PEG-800 reclaims circulation 3 times altogether
Result is as shown in table 2.As can be seen from the table, PEG-800 can be with recycling, inversion rate of glucose
And concentration of alcohol remains unchanged substantially.
Table 2 inversion rate of glucose, concentration of alcohol data
Embodiment 5
Ligno-cellulose hydrolysate model thing 20mL, the wherein 400g.L Han concentration of glucose-1, phenol 1.0
g.L-1, add 0.2g.mL-1PEG-600, adds barm cell concentration 5*108Individual/mL, will with sulfuric acid solution
PH value is adjusted to 4.3, puts in shaking table and shakes, and ferments 72 hours under the conditions of 33 DEG C.Carry out after fermentation
Solid-liquid separation, supernatant liquid carries out distilling, extracts, redistillation, and remaining liq is surfactant, slow
Electuary can be directly used for sweat (such as Fig. 1) next time together with the yeast reclaimed, and adds part Yeast.
It is as shown in table 3 that PEG-600 and the yeast of recovery circulate 3 results altogether.As can be seen from the table, PEG-600
Can be with recycling, after three circulations, glucose converts completely, and concentration of alcohol remains unchanged substantially.
Table 3 inversion rate of glucose, concentration of alcohol data
Embodiment 6
Experimental procedure is identical with embodiment 5, and difference is 4.3 adjusting pH with Acetic acid-sodium acetate, glucose
Conversion ratio, ethanol yield and concentration data are shown in Table 4. as can be seen from the table, and PEG-600 can reclaim profit again
With, after three circulations, glucose converts completely, and concentration of alcohol remains unchanged substantially.
Table 4 inversion rate of glucose, concentration of alcohol data
Embodiment 7
Experimental procedure is identical with embodiment 5, difference be fermentation temperature be 39 DEG C, surfactant is
PEG-2000, inversion rate of glucose, ethanol yield and concentration data are shown in Table 5. as can be seen from the table,
PEG-2000 can be with recycling, and after three circulations, glucose converts completely, and concentration of alcohol maintains not substantially
Become.
Table 5 inversion rate of glucose, concentration of alcohol data
Embodiment 8
Experimental procedure is identical with embodiment 5, difference be fermentation temperature be 30 DEG C, surfactant is
PEG-1500, inversion rate of glucose, ethanol yield and concentration data are shown in Table 6. as can be seen from the table,
PEG-1500 can be with recycling, and after three circulations, glucose converts completely, and concentration of alcohol maintains not substantially
Become.
Table 6 inversion rate of glucose, concentration of alcohol data
Embodiment 9
Experimental procedure is identical with embodiment 2, and difference is adding 0.2g.mL-1PEG-4000, glucose turns
Rate, ethanol yield and concentration data are shown in Table 7. as can be seen from the table, and PEG-4000 can reclaim profit again
With, after three circulations, glucose converts completely, and concentration of alcohol remains unchanged substantially.
Table 7 inversion rate of glucose, concentration of alcohol data
Embodiment 10
Experimental procedure is identical with embodiment 2, and difference is adding 0.2g.mL-1PEG-6000, glucose turns
Rate, ethanol yield and concentration data are shown in Table 8. as can be seen from the table, and PEG-6000 can reclaim profit again
With, after three circulations, glucose converts completely, and concentration of alcohol remains unchanged substantially.
Table 8 inversion rate of glucose, concentration of alcohol data
Embodiment 11
Experimental procedure is identical with embodiment 2, and difference is adding 0.2g.mL-1Tween 80, glucose converts
Rate, ethanol yield and concentration data are shown in Table 9. as can be seen from the table, tween 80 can with recycling,
After three circulations, glucose converts completely, and concentration of alcohol remains unchanged substantially.
Table 9 inversion rate of glucose, concentration of alcohol data
Embodiment 12
Experimental procedure is identical with embodiment 2, and difference is adding 0.2g.mL-1Poly glycol monomethyl ether, Fructus Vitis viniferae
Sugar conversion ratio, ethanol yield and concentration data are shown in Table 10. as can be seen from the table, and poly glycol monomethyl ether can
With recycling, after three circulations, glucose converts completely, and concentration of alcohol remains unchanged substantially.
Table 10 inversion rate of glucose, concentration of alcohol data
Embodiment 13
Experimental procedure is identical with embodiment 2, and difference is adding 0.2g.mL-1NHD, Fructus Vitis viniferae
Sugar conversion ratio, ethanol yield and concentration data are shown in Table 11. as can be seen from the table, and NHD can
With recycling, after three circulations, glucose converts completely, and concentration of alcohol remains unchanged substantially.
Table 10 inversion rate of glucose, concentration of alcohol data
Claims (11)
1. a fermentation of ligno-cellulose hydrolysate process surfactant recovery technology, it is characterized in that following the steps below: the ligno-cellulose hydrolysate of the heat chemistry pretreatment such as acidolysis or steam explosion, it is not required to detoxification treatment, directly adds Surfactant after buffer adjusts pH value, interpolation surfactant, access Ethanol in Saccharomyces cerevisiae fermentation and carry out integrated separation recovery with fermentation inhibitor.
2. according to a kind of fermentation of ligno-cellulose hydrolysate process surfactant recovery technology described in claim 1, it is characterized in that: described Surfactant and fermentation inhibitor carry out integrated separation recovery, first fermentation liquid is carried out solid-liquid separation and reclaims yeast cells；Then while carrying out distilling ethanol, realize the enrichment of surfactant, fermentation inhibitor, buffer agent to liquid；The last integrated separation recovery being realized surfactant, buffer agent and fermentation inhibitor again by organic solvent extraction fermentation inhibitor.
3. according to a kind of fermentation of ligno-cellulose hydrolysate process surfactant recovery technology described in claim 1, it is characterised in that the concentration of described surfactant is 0～0.4g/mL hydrolyzed solution, and the cell concentration of described saccharomyces cerevisiae is: 0.13*108Hundred million-1.4*109Individual/mL.
4. according to a kind of fermentation of ligno-cellulose hydrolysate process surfactant recovery technology described in claim 1, it is characterised in that: described fermentation temperature is 30-39 DEG C, and fermentation time is 4～100h；The pH of buffer is 4.0～5.5；Vapo(u)rizing temperature is 30-100 DEG C, and distillation pressure is-0.01Mpa～-0.1Mpa, and distillation time is 10 minutes-120 minutes.
5. according to a kind of fermentation of ligno-cellulose hydrolysate process surfactant recovery technology described in claim 1, it is characterised in that: described lignocellulose is from agricultural wastes, forestry waste, special energy crop or/and the garbage of various cellulose；
Described agricultural wastes are that wheat stalk, corn straw are or/and Caulis et Folium Oryzae；
Described forestry waste be lumbering produce branch and leaf, discarded wood is or/and wood flour；
Described special energy crop is sugar grass or/and Ramulus Salicis Babylonicae journey；
The garbage of described various cellulose is that urban solid garbage, waste paper are or/and bagasse.
6. according to a kind of fermentation of ligno-cellulose hydrolysate process surfactant recovery technology described in claim 1, it is characterized in that: described ligno-cellulose hydrolysate contains one or more fermentable sugars such as glucose, xylose, fermentable sugars concentration is 60-500g/L.
7. according to a kind of fermentation of ligno-cellulose hydrolysate process surfactant recovery technology described in claim 1, it is characterised in that: described ligno-cellulose hydrolysate contains fermentation inhibitor, and fermentation inhibitory substrate concentration is 0～6.0g/L；
Described fermentation inhibitor is one or more of phenol, guaiacol, vanillin, 5 hydroxymethyl furfural (HMF), furfural, levulic acid or acetic acid.
8. according to a kind of fermentation of ligno-cellulose hydrolysate process surfactant recovery technology described in claim 1, it is characterised in that described described surfactant is at least one in Polyethylene Glycol, poly glycol monomethyl ether, NHD, polydimethylsiloxane, tween；It is preferably Polyethylene Glycol.
9. according to the recovery technology of a kind of ligno-cellulose hydrolysate detoxification sweat surfactant described in claim 8, it is characterised in that the molecular weight of described surfactant polyethylene is 200-8000；It is preferably 200-2000.
10. according to a kind of fermentation of ligno-cellulose hydrolysate process surfactant recovery technology described in claim 1, it is characterised in that described organic solvent is: benzene, toluene, ether, ethyl acetate, n-butyl ether, petroleum ether, dimethyl sulfoxide or methyl iso-butyl ketone (MIBK).
11. according to a kind of fermentation of ligno-cellulose hydrolysate process surfactant recovery technology described in claim 1, it is characterised in that: described pH buffer agent is: Acetic acid-sodium acetate, citric acid-sodium citrate, phosphoric acid-sodium phosphate or sulfuric acid solution.
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| CN109706273B (en) * | 2017-10-26 | 2022-09-16 | 中国科学院大连化学物理研究所 | Method for catalyzing hydrolysis fermentation of lignocellulose by phosphorus pentoxide |
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