CN102226204A - Method for detoxifying sugar solution in lignocellulose ethanol fermentation - Google Patents

Method for detoxifying sugar solution in lignocellulose ethanol fermentation Download PDF

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CN102226204A
CN102226204A CN2011101211608A CN201110121160A CN102226204A CN 102226204 A CN102226204 A CN 102226204A CN 2011101211608 A CN2011101211608 A CN 2011101211608A CN 201110121160 A CN201110121160 A CN 201110121160A CN 102226204 A CN102226204 A CN 102226204A
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poison
removing method
membrane
liquid glucose
liquid
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CN102226204B (en
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张�林
王亚飞
陈欢林
周志军
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Zhejiang University ZJU
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    • 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
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • 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
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    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
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Abstract

The invention discloses a method for detoxifying a sugar solution in lignocellulose ethanol fermentation, comprising the steps of: adding soluble electrolyte into the sugar solution to be processed, followed by heating to obtain a constant-temperature raw material liquid; letting the constant-temperature raw material liquid pass through a membrane module for membrane distillation; removing substances which inhibit the subsequent fermentation process from the sugar solution while trying not to minimize effective sugar components. The method provided by the invention requires short operation time and low temperature, and low-quality industrial waste heat and other economical heat sources can be directly used, thus achieving the purpose of saving energy and reducing cost; simultaneously, the coking of sugar in the solution will not happen.

Description

The poison-removing method of liquid glucose in a kind of lignocellulose ethanol fermentation
Technical field
The invention belongs to lignocellulosic material biological degradation and bio-transformation production alcohol fuel and other derivative fields in the biological chemistry, be specifically related to the method for a kind of improved film distillation technology as the detoxification of lignocellulose raw material hydrolysis sugar liquid.
Background technology
Energy dilemma aggravation impels the fast development of biofuel, and wherein bio-ethanol is subjected to people and more and more pays close attention to.And lignocellulose comprises three big steps for raw material production ethanol: pre-treatment, hydrolysis and fermentation.The final purpose of pre-treatment and hydrolysis is a carbohydrate polymer in the degrading plant cell walls, and making it to become can be by the low molecular saccharides of production of ethanol from microbial fermentation.In various preprocessing method of raw materials, dilute acid pretreatment and steam explosion pretreatment process generally are considered to comparatively effective.In various preprocessing process, because degraded takes place in heat or sour effect, part Mierocrystalline cellulose, hemicellulose and xylogen and Decomposition generation formic acid, acetate, levulinic acid, furfural, hydroxymethylfurfural and phenolic compound etc. have inhibiting material to follow-up fermentation.Inhibition raises along with pretreatment temperature and the prolongation in treatment time and increasing, and the produced simultaneously amount also kind with lignin material is relevant, and these materials must detoxification removal before fermenting.
The poison-removing method of hydrolysis sugar liquid mainly contains charcoal absorption, lime neutralization, ion-exchange, vacuum concentration stripping at present, organic solvent extraction etc., but these methods exist that detoxification efficiency is poor, cost height, complex operation or shortcoming such as sugar loss is big when fermentation inhibitor removes.Therefore, the lignocellulose ethanol industry is badly in need of the good poison-removing method of a kind of detoxification efficiency.
Membrane distillation is that a kind of dewatering microporous film that adopts is the membrane sepn process of mass transfer motivating force with film both sides vapor pressure difference.When the solution temperature of film both sides not simultaneously, the water vapor pressure of the hot side aqueous solution and membrane interface is higher than cold side, water vapor will see through fenestra enter cold side and condensation.Also remove for volatile organic inhibition by the method for hot side vaporization, cold side condensation.
Summary of the invention
The invention provides the poison-removing method of liquid glucose in a kind of effective lignocellulose ethanol fermentation, in removing liquid glucose, follow-up fermentation produced inhibiting material in, do not reduce effective sugar component as far as possible.
The poison-removing method of liquid glucose in a kind of lignocellulose ethanol fermentation adds solubility electrolytic salt post-heating and obtains the constant temperature stock liquid in pending liquid glucose, the constant temperature stock liquid is carried out membrane distillation by membrane module.
Because film itself does not have selectivity in the membrane distillation process, just play an effect of separating cold fluid and hot fluid, therefore the present invention adds the vapour pressure that the solubility electrolytic salt optionally changes inhibition in separated system, improve the relative volatility of inhibition, make organic inhibition more see through film and condensation, thereby reach higher inhibition clearance.The trace soluble electrolytic salt that adds is that follow-up fermentation there is not an influence or even a favourable class material, so can not influence the alcoholic acid yield.
Described pending liquid glucose is meant the prehydrolysis liquid glucose of raw material in the lignocellulose fermentative production of ethanol process.
Described solubility electrolytic salt and water have certain binding ability, can change the relative volatility of acetate with respect to water, thereby can improve acetate in the concentration that sees through side, pay the utmost attention to the salt that needs interpolation in the fermention medium of downstream, as preferred CaCl 2, NaCl or (NH 4) 2SO 4
Described solubility electrolytic salt add-on is 0.5%～5% of a liquid glucose quality.At the hydrolysis sugar liquid that different pretreatments obtains, inhibition concentration is slightly different, sets out according to inhibition removal situation and cost-effective angle, and preferred solubility electrolytic salt add-on is 0.5%～2% of a liquid glucose quality.
From preventing sugared coking and considering that from energy-conservation angle the temperature of described constant temperature stock liquid optimum is 50 ℃～70 ℃.
Described membrane module preferably adopts hydrophobic microporous membrane, and the optimum strong microporous membrane of hydrophobicity that adopts is as polyvinylidene fluoride dewatering microporous film, tetrafluoroethylene dewatering microporous film, hydrophobic polypropylene microporous membrane or polyethylene dewatering microporous film.Preferred 0.1～1.0 μ m of described hydrophobic micropore membrane pore size.
Flow through under the effect of feedstock pump valve and under meter of homothermic stock liquid enters the tube side of membrane module, carries out mass transfer, heat transfer on the film surface, oozes surplus sugar soln and carried dense and detoxification, is circulated back in the head tank in the thermostatic bath.Be evacuated to condenser system condensation in per-meate side by vacuum pump and see through water vapor and the volatile organic inhibition that fenestra enters the membrane module shell side, after condenser condenses, be collected in the water tank.The sugar soln of hot side circulates continuously, and its organic inhibition that contains constantly is removed, reach preset requirement after, obtain the sugar soln after the detoxification.
The membrane distillation process is conventional membrane distillation process, and downstream general vacuum type, direct contact type, GAP TYPE or the gas that the adopts formula of sweeping realizes condensation, and the present invention preferably adopts vacuum type to realize.The membrane module feed side is for necessarily being heated to homothermic constant temperature stock liquid, seeing through side is vacuum state, water in the constant temperature stock liquid and volatile components (inhibition) from constant temperature stock liquid main diffusion to contacted frictional belt, dewatering microporous film surface, and the interface in frictional belt and the formation of film surface is vaporizated into steam, steam diffuses to per-meate side by dewatering microporous film and solution can not see through hydrophobic membrane and is trapped, and the steam that sees through film is evacuated to the condenser system condensation by vacuum pump.The impellent of this process is the steam pressure difference that film both sides temperature head causes, water and volatile components constantly are removed by the circulation of hot side, thereby realizes concentrating and the detoxification purpose of liquid glucose.
The present invention have the operating time short, temperature is low, can directly utilize low-grade industrial waste heat and other economic thermals source, realizes save energy, the purpose that reduces cost, coking phenomenon can not take place in the sugar in the solution simultaneously.
Description of drawings
Fig. 1 is the vacuum membrane distillation device of liquid glucose detoxification;
Among the figure: 1 head tank; 2 thermals source; 3 feedstock pumps; 4 valves; 5 spinner-type flowmeters; 61 thermometers; 62 thermometers; 7 membrane modules; 81 condensers; 82 condensers; 9 receiving flasks; 10 circulation ability of swimming vacuum pumps
Fig. 2 is for adding CaCl 2Influence to acetate and furfural clearance;
Fig. 3 is for adding the influence of NaCl to acetate and furfural clearance;
Fig. 4 for Angel wine brewing high-activity yeast to the ethanol fermentation course of detoxification prehydrolysis liquid glucose not;
Fig. 5 is the ethanol fermentation course of wine brewing high-activity yeast in Angel to detoxification prehydrolysis liquid glucose.
Embodiment
The pending liquid glucose that the embodiment of the invention is selected for use adopts the pre-and enzymolysis processing technology acquisition hydrolysis sugar liquid of steam explosion for the raw material maize straw, main sugar component before and after the membrane distillation adopts determined by ultraviolet spectrophotometry, and fermentation inhibitor adopts high performance liquid chromatography (HPLC) analysis.The main component of pending liquid glucose is as shown in table 1.
The pending liquid glucose main component of table 1
Figure BDA0000060523100000041
The membrane module that adopts is single tubular fibre formula assembly, and used film is the hydrophobic polypropylene microporous membrane, and the aperture is 0.15 μ m, and membrane area is about 0.08m 2, the vacuum type operation is adopted in the downstream.Be described in detail the influence situation of different salt concn below in conjunction with technical scheme and accompanying drawing to the liquid glucose detoxification efficiency.
Embodiment 1
Adopt device as shown in Figure 1.Get pending liquid glucose 400ml in head tank 1, add different mass fractional solid CaCl respectively 2Add-on is 0.5% of a liquid glucose quality, 1%, 2% and 5%, be heated to 60 ℃ of constant temperature by thermal source 2, open feedstock pump 3, the constant temperature stock liquid is through valve 4 and spinner-type flowmeter 5, stock liquid enters membrane module 7 with the flow velocity of 0.5～2m/s, and thermometer 61 and 62 are equipped with in membrane module import and exit, can measure the temperature that enters assembly and flow out the assembly liquid glucose.Liquid glucose flows back into behind the mass-and heat-transfer in membrane module in the head tank 1 in the thermal source.(vacuum tightness 0.090～0.095MPa) is collected in the water tank 9 after condenser 8 condensations, and 81 and 82 is respectively the import and the outlet of water coolant and the steam that sees through fenestra is aspirated by vacuum pump 10.After certain hour (60min) was carried out in operation, the HPLC analysis was carried out in sampling in head tank 1.The result as shown in Figure 2.
As can be seen from Figure 2, the rejection of glucose can both remain on more than 99.5%, and effectively the sugar component loss is considerably less; The maximum material removal rate of main inhibition acetate and furfural is respectively 58.3% and 87.4%, and with CaCl 2The rising of concentration slightly raises, and this is because the reactive force between calcium chloride and the water is far longer than the reactive force between calcium chloride and the acetate, has reduced the vapour pressure of water, has always improved the relative volatility of acetate with respect to water.The amount of adding calcium chloride is big more, and the degree that relative volatility improves is also big more, but considers in the fermenting process to the inorganic ion demand CaCl of interpolation 2Add-on is 0.5%～2% of a liquid glucose quality.。
Embodiment 2
Equipment therefor as shown in Figure 1.Water intaking is separated liquid glucose 400ml in head tank 1, add different mass fractional solid NaCl respectively, add-on is 0.5%, 1%, 2% and 5% of a liquid glucose quality, be heated to 60 ℃ of constant temperature by thermal source 2, open feedstock pump 3, the constant temperature stock liquid is through valve 4 and spinner-type flowmeter 5, and stock liquid enters membrane module 7 with the flow velocity of 0.5～2m/s, thermometer 61 and 62 are equipped with in assembly import and exit, can measure the temperature that enters assembly and flow out the assembly liquid glucose.Liquid glucose flows back into the head tank in the thermal source behind the mass-and heat-transfer in membrane module.(vacuum tightness 0.090～0.095MPa) is collected in the water tank 9 after condenser 8 condensations, and 81 and 82 is respectively the import and the outlet of water coolant and the steam that sees through fenestra is aspirated by vacuum pump 10.After certain hour (60min) was carried out in operation, the HPLC analysis was carried out in sampling in head tank.The result as shown in Figure 3.
As can be seen from Figure 3, the rejection of glucose can both remain on more than 99.5%; The maximum material removal rate of main inhibition acetate and furfural is respectively 50.4% and 83.8%, and slightly raises with the rising of NaCl concentration, but compares with interpolation calcium chloride, reach identical clearance, and the NaCl concentration that needs to add is greater than CaCl 2Concentration.This shows, NaCl improve acetate to the relative volatility degree of water on effect not as good as CaCl 2
Compare detoxification efficiency
For detoxification efficiency relatively, with the comparison of fermenting of the hydrolysis sugar liquid before and after the detoxification.Yeast adopts commercial Angel wine brewing high-activity yeast, fermention medium (L) composed as follows: 0.2g MgSO 4, 2g KH 2PO 4, 2g (NH 4) 2SO 4, 0.2g CaCl 2, the 2g yeast powder.Fermentation condition is, 35 ℃, and 150r/min, the fermentation situation is as shown in Figure 4 and Figure 5.
As can be seen from Figure 4, wine brewing high-activity yeast in Angel is to the hydrolysis sugar liquid fermentation of not detoxification, and in 12～24h, alcohol concn maintains between 9.25～18.80g/L, and the utilization ratio of glucose is the highest has only 49%, illustrates that the fermentation efficiency of detoxification hydrolyzed solution is not high.And Fig. 5 (adds 2weight%CaCl for the hydrolysis sugar liquid of wine brewing high-activity yeast in Angel after to detoxification 2) the fermentation course, alcohol concn reaches 41.71g/L when 24h, and sugared utilization ratio and ethanol yield are respectively 97.28% and 90.72%.Contrast two figure as can be seen, pending liquid glucose is after the membrane distillation detoxification, and its ethanol fermentation performance is greatly improved.

Claims (9)

1. the poison-removing method of liquid glucose in the lignocellulose ethanol fermentation is characterized in that: add solubility electrolytic salt post-heating and obtain the constant temperature stock liquid in pending liquid glucose, the constant temperature stock liquid is carried out membrane distillation by membrane module.
2. poison-removing method as claimed in claim 1 is characterized in that: described solubility electrolytic salt is CaCl 2, NaCl or (NH 4) 2SO 4
3. poison-removing method as claimed in claim 1 is characterized in that: described solubility electrolytic salt add-on is 0.5%～5% of a liquid glucose quality.
4. poison-removing method as claimed in claim 3 is characterized in that: described solubility electrolytic salt add-on is 0.5%～2% of a liquid glucose quality.
5. poison-removing method as claimed in claim 1 is characterized in that: described constant temperature stock liquid temperature is 50 ℃～70 ℃.
6. poison-removing method as claimed in claim 1 is characterized in that: described membrane module adopts hydrophobic microporous membrane.
7. poison-removing method as claimed in claim 6 is characterized in that: described hydrophobic microporous membrane is polyvinylidene fluoride dewatering microporous film, tetrafluoroethylene dewatering microporous film, hydrophobic polypropylene microporous membrane or polyethylene dewatering microporous film.
8. poison-removing method as claimed in claim 6 is characterized in that: described hydrophobic micropore membrane pore size is 0.1～1.0 μ m.
9. poison-removing method as claimed in claim 1 is characterized in that: described membrane distillation downstream adopts vacuum type to realize condensation.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10407700B2 (en) 2014-11-20 2019-09-10 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Surfactant-improved simultaneous saccharification and co-fermentation method for lignocellulose

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101270372A (en) * 2008-04-15 2008-09-24 中国石油化工股份有限公司 Concentration method for sugar liquid in cellulose alcoholic fermentation
CN101691587A (en) * 2009-10-15 2010-04-07 南京林业大学 Detoxification method of wood fibre hydrolysis sugar liquid

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101270372A (en) * 2008-04-15 2008-09-24 中国石油化工股份有限公司 Concentration method for sugar liquid in cellulose alcoholic fermentation
CN101691587A (en) * 2009-10-15 2010-04-07 南京林业大学 Detoxification method of wood fibre hydrolysis sugar liquid

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
王许云等: "膜蒸馏技术最新研究现状及进展", 《化工进展》, vol. 26, no. 2, 28 February 2007 (2007-02-28) *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10407700B2 (en) 2014-11-20 2019-09-10 Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences Surfactant-improved simultaneous saccharification and co-fermentation method for lignocellulose

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