CN102220385A - Method for removing fermentation inhibitor and pigments of sugar solution - Google Patents

Method for removing fermentation inhibitor and pigments of sugar solution Download PDF

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Publication number
CN102220385A
CN102220385A CN2011101096826A CN201110109682A CN102220385A CN 102220385 A CN102220385 A CN 102220385A CN 2011101096826 A CN2011101096826 A CN 2011101096826A CN 201110109682 A CN201110109682 A CN 201110109682A CN 102220385 A CN102220385 A CN 102220385A
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sugar solution
fermentation
gac
liquid glucose
fermentation inhibitor
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CN2011101096826A
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CN102220385B (en
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吴健
戴桂馥
刘孝臣
刘絮
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Zhai Kunzhang
Zhengzhou Operation And Maintenance Biotechnology Co ltd
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Zhengzhou University
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    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00Technologies for the production of fuel of non-fossil origin
    • Y02E50/10Biofuels, e.g. bio-diesel

Abstract

The invention discloses a method for removing a fermentation inhibitor and pigments of a sugar solution by using oxidative degradation and adsorption, which belongs to the field of fermentation industries. Aiming at the defects that the detoxification cost is high, impurities are incompletely removed, and the fermentation is affected by new matters which are most likely to be introduced, and the like in the traditional sugar solution, the method disclosed by the invention is used for carrying out oxidative degradation and adsorption through the combined effect of activated carbon/hydrogen peroxide/ozone so as to remove the fermentation inhibitor and the pigments of the sugar solution; the method has the advantages that reaction conditions are mild, the processing effect is good, the removal rate of heterocyclic ring and benzene ring matters such as furaldehyde, hydroxymethylfurfural, and the like in the processed sugar solution reaches more than 90%, the removal rate of other inhibitors reaches more than 80%, pigment matters can be completely removed, the reduction rate of nutritional compositions is not higher than 15%, the numerous loss of the nutritional compositions in the sugar solution is reduced, and the method does not cause pollution to environments and is suitable for industrial popularization and application.

Description

A kind of method of removing fermentation inhibitor and pigment in the liquid glucose
Technical field
The present invention relates to a kind of method of removing fermentation inhibitor and pigment in the liquid glucose, relate in particular to a kind of method of utilizing oxidative degradation and absorption to remove fermentation inhibitor and pigment in the liquid glucose, belong to the fermentation industry field.
Background technology
The starting material source of fermentation industry is abundant, mainly utilizes food crop such as corn, wheat, has developed new proferment material again at present, as maize straw, and cellulose substances such as rice straw, xylose residue.The starting material of these fermentations are handled through diverse ways, finally become the fermentation liquid glucose that contains nutritive substance and use for fermentation, comprising treatment processs such as acidolysis, highly pressured hydrolysis, enzymolysis.But in more violent treatment process such as acidolysis, highly pressured hydrolysis, the material of various influence fermentation be can produce, furfural, hydroxymethylfurfural, acetate, phenolic compound, syringic acid, hydroxy-benzoic acid, Vanillin and other toxic compounds and pigment mainly contained.These materials are present in the liquid glucose, have a strong impact on the growth of fermentation thalline, and then have influence on the extraction of whole fermentation process, product and the quality of product etc.
Removal to these materials in the liquid glucose mainly is to carry out detoxification treatment at present, and method has the pH of adjusting, negative pressure evaporation, ion exchange resin, charcoal absorption and enzymolysis process etc.Wherein charcoal absorption is commonplace.The gac wide material sources, the gac after the processing can also be recycled.But activated carbon adsorptive capacity is limited, and is saturated easily, needs frequent regeneration.The relevant report that the certain methods coupling is also arranged as before with charcoal absorption, is adjusted to 7.0 with the pH value from 0.5 with CaO earlier, uses H again 3PO 4Solution is transferred to 5.5 with the pH value, with this understanding, can effectively reduce the inhibition in the liquid glucose, obtains higher ethanol production.But there are various drawbacks in these methods, and are many as processing cost height, nutrition leak, increased many extra materials in the solution after the processing and have been difficult to remove, and what have also can produce a large amount of precipitations, and the influence fermentation is carried out, and environment is caused certain influence.
Summary of the invention
, Impurity removal higher at the not enough cost that existing liquid glucose treatment process exists do not brought new material influence fermentation thoroughly, easily into and defective such as carried out, and the invention provides the novel method of fermentation inhibitor and pigment in the removal liquid glucose that a kind of cost is lower, Impurity removal thoroughly, is not introduced novel substance.
For realizing the object of the invention, the present invention is with gac/hydrogen peroxide/ozone combined action, fermentation inhibitor and pigment in the liquid glucose removed in oxidative degradation and absorption, specifically realize as follows: regulate liquid glucose pH=1-8, gac and hydrogen peroxide or gac and ozone or gac, hydrogen peroxide are added or feed with ozone and contain in the liquid glucose of fermentation inhibitor and pigment, the add-on of gac is 1-100g/L, the final concentration of hydrogen peroxide in solution is 0.1-16.7g/L, and the final concentration of ozone in solution is 0.1-9g/m 3, under 0-40 ℃ of condition, react.Described liquid glucose is for handling the liquid glucose that is generated through methods such as acidolysis, high-pressure liquid hydrolysis or high pressure steam explosions.Described gac is powdered carbon, granulated active carbon, carbonizedfibres or coking resin.Reaction times is 5 minutes-48 hours, with the clearance of inhibition as reaction end.Reacted gac can remove by filter, and residual hydrogen peroxide can use thermal degradation or add the hydrogen peroxide enzyme process and remove, and catalase is a protein matter, stays the carrying out that can not influence fermentation in the fermented liquid.Residual ozone can very fast effusion after by heating, does not heat by stirring to place and also can separate out very soon, no longer includes residually, can not influence the carrying out of fermentation.
The inventive method is applicable to that the processing of method such as acidolysis, highly pressured hydrolysis is the liquid glucose that starting material were obtained with corn, wheat, maize straw, rice straw, xylose residue etc. in the fermentation industry.After reaction is finished, extract reaction solution various inhibition levels of body measurement and nutritive substance level, with the contrast of reaction previous crops, as the index evaluation reaction effect.Heterocycle benzene ring substance such as furfural, hydroxymethylfurfural can be removed more than 90% in the liquid glucose of employing the inventive method processing back, other inhibition clearance reaches more than 80%, the pigment material is removed fully, and the decrement of nutritive substance is lower than 15%, does not introduce new impurity.Advantage of the present invention is: (1) reaction conditions gentleness, and treatment effect is good; (2) cost is low, but large-scale application is in actual production; (3) handle back liquid glucose purity height, fermentation quality and superior product quality; (4) can not cause a large amount of losses of nutritive substance in the treating processes; (5) treating processes can not pollute environment, cleaning, green, environmental protection.
Embodiment
For the present invention is illustrated better, be exemplified below:
Embodiment 1
The mixing solutions 100ml of Sodium Benzoate, furfural and glucose, wherein the mass concentration of three kinds of materials is 1%, regulate its pH=2, to wherein adding gac 5g, mass percent is 30% hydrogen peroxide 0.5ml, under 25 ℃ of reaction conditionss, thorough mixing is even, middle slowly stirring, measure the wherein concentration of each material when being reflected at 1h, 2h, 4h, 8h, 16h, 24h respectively, the Sodium Benzoate clearance reaches 100% behind reaction 2h after testing, furfural clearance when 4h can arrive 100%, and when 8h, the total reduction of glucose only is 10%.The solution that has reacted removes by filter gac, and residual hydrogen peroxide detects after removing with catalase again, and composition is single, only remains glucose.Solution colour becomes near colourless good decolorizing effect by faint yellow.
Embodiment 2
The mixing solutions 100ml of Sodium Benzoate, furfural and glucose, wherein the mass concentration of three kinds of materials is 1%, regulates its pH=4, to wherein add gac 5g, feeding ozone, to make its final concentration in solution be 3g/m 3Under 15 ℃ of reaction conditionss, thorough mixing is even, middle slowly stirring, measure the wherein concentration of each material when being reflected at 1h, 2h, 4h, 8h, 16h, 24h respectively, the Sodium Benzoate clearance reaches 80% behind reaction 2h after testing, and furfural clearance when 4h reaches 100%, and when 8h, the total reduction of glucose only is 10%.The solution that has reacted removes by filter gac, and residue ozone leaves standstill 1h by stirring to be removed, and detects again, and composition is single, only remains glucose.Solution colour becomes near colourless good decolorizing effect by faint yellow.
Embodiment 3
The mixing solutions 100ml of Sodium Benzoate, furfural and glucose, wherein the mass concentration of three kinds of materials is 1%, regulating its pH=1, is 30% hydrogen peroxide 0.5ml to wherein adding gac 2g, mass percent, and feeding ozone, to make its final concentration in solution be 1g/m 3Under 35 ℃ of reaction conditionss, thorough mixing is even, middle slowly stirring, measure the wherein concentration of each material when being reflected at 1h, 2h, 4h, 8h, 16h, 24h respectively, the Sodium Benzoate clearance reaches 100% behind reaction 1h after testing, and furfural clearance when 2h reaches 100%, and the reduction of glucose only is 10% when being reflected at 5h.The solution that has reacted removes by filter gac, and residual hydrogen peroxide is removed with catalase, and residue ozone leaves standstill 1h by stirring to be removed, and detects again, and composition is single, only remains glucose.Solution colour becomes near colourless good decolorizing effect by faint yellow.
Embodiment 4
The maize straw hydrolyzed solution 100ml of vitriol oil hydrolysis, regulate its pH=2, to wherein adding gac 10g, mass percent is 30% hydrogen peroxide 0.5ml, under 5 ℃ of reaction conditionss, thorough mixing is even, and slowly stir the centre, carry out the mensuration of fermentation inhibitor furfural, acetate, phenolic compound when being reflected at 1h, 2h, 4h, 8h, 16h, 24h respectively, when reaction proceeded to 4h after testing, furfural and acetic acid content reduced more than 80%, and phenolic compound can not detect.Its clearance such as nutritive substance in the fermented liquid such as glucose, wood sugar etc. after testing all do not surpass 10%.The solution that has reacted removes by filter gac, and residual hydrogen peroxide is removed with catalase.Solution colour is become faint yellow by dark-brown, good decolorizing effect.
Embodiment 5
The xylose residue hydrolyzed solution 100ml of high-pressure liquid hydrolysis regulates its pH=5, and to wherein adding gac 3g, mass percent is 30% hydrogen peroxide 0.5ml, and it is 6g/m that feeding ozone makes its final concentration in solution 3Under 25 ℃ of reaction conditionss, thorough mixing is even, middle slowly stirring, carry out the mensuration of fermentation inhibitor furfural, hydroxymethylfurfural, acetate when being reflected at 1h, 2h, 4h, 8h, 16h, 24h respectively, measurement result is presented at reacts when proceeding to 2h, and furfural and hydroxymethylfurfural can not detect in the highly pressured hydrolysis liquid, and clearance reaches 100%.Detect when 8h, the acetate clearance has reached more than 90%.Redeterminate component in the liquid glucose, wherein do not had heterocycle phenyl ring class fermentation inhibitor after testing.Its clearance such as nutritive substance in the fermented liquid such as glucose, wood sugar etc. after testing all do not surpass 10%.The solution that has reacted removes by filter gac, and residual hydrogen peroxide is removed with catalase, and residue ozone leaves standstill 1h by stirring to be removed.Solution colour is become faint yellow by dark-brown, good decolorizing effect.
Embodiment 6
The maize straw hydrolyzed solution 100ml of high pressure steam explosion hydrolysis regulates its pH=5, and to wherein adding gac 3g, it is 5g/m that feeding ozone makes its final concentration in solution 3Under 25 ℃ of reaction conditionss, thorough mixing is even, middle slow the stirring carried out the mensuration of fermentation inhibitor furfural, acetate respectively when being reflected at 1h, 2h, 4h, 8h, 16h, 24h, 48h, measurement result is presented at reacts when proceeding to 2h, furfural can not detect in the highly pressured hydrolysis liquid, clearance can reach 100%, and when detecting when 8h, the acetate clearance has reached more than 90%.Redeterminate component in the fermented liquid, wherein do not had heterocycle phenyl ring class fermentation inhibitor after testing.Nutritive substance in the fermented liquid such as glucose, the detection of wood sugar etc. show that clearance does not all surpass 5%.The solution that has reacted removes by filter gac, and residue ozone leaves standstill 1h by stirring to be removed.Solution colour is become faint yellow by dark-brown, good decolorizing effect.
More than each material detection method as follows:
1, the detection of glucose adopts SBA-40E bio-sensing analyser to measure.
2, the detection of Sodium Benzoate adopts ultraviolet spectrophotometry to measure.
3, the permanganate titration that U.S. textile chemist and printing and dyeing teacher association criterion are formulated is adopted in the detection of hydrogen peroxide [1]Measure (AATCC testing method .102-2002).
4, the detection method of ozone adopts the sodium indigotindisulfonate spectrophotometry in the GB [2]Measure (the .GB/T 15437-1995 of State Bueau of Environmental Protection).
5, dual wavelength visible light spectrometry is adopted in the detection of wood sugar [3]Measure (with the content of sugar in the dual wavelength visible light spectrometry rapid determination hemicellulose extract. spectroscopy and spectroscopic analysis, 2010 (4): 1084-1087).
6, vapor-phase chromatography is adopted in the detection of furfural, hydroxymethylfurfural and acetate [4]Measure (furfural and acetic acid content in the gas chromatography determination stalk hydrolyzed solution. brewing science and technology, 2008 (5): 108-110).
7, solid-phase microextraction-vapor-phase chromatography is adopted in the detection of phenolic compound [5]Measure (phenolic compound in solid-phase microextraction-gas chromatography determination water. Henan chemical industry, 2007 (6): 43-44).

Claims (3)

1. method of removing fermentation inhibitor and pigment in the liquid glucose, it is characterized in that, regulate liquid glucose pH=1-8, gac and hydrogen peroxide or gac and ozone or gac, hydrogen peroxide are added or feed with ozone and contain in the liquid glucose of fermentation inhibitor and pigment, the add-on of gac is 1-100g/L, the final concentration of hydrogen peroxide in solution is 1-16.7g/L, and the final concentration of ozone in solution is 0.1-9g/m 3, under 0-40 ℃ of condition, react.
2. the method for fermentation inhibitor and pigment is characterized in that in the removal liquid glucose as claimed in claim 1, the liquid glucose of liquid glucose for being generated through acidolysis, high-pressure liquid hydrolysis or high pressure steam explosion treatment.
3. the method for fermentation inhibitor and pigment is characterized in that in the removal liquid glucose as claimed in claim 1 or 2, and gac is powdered carbon, granulated active carbon, carbonizedfibres or coking resin.
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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103555774A (en) * 2013-11-06 2014-02-05 四川农业大学 Method for pre-treating lignocelluloses raw material for enzyme hydrolysis in combination of strong phosphoric acid and hydrogen peroxide
CN103773904A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 Method used for removing lignocelluloses enzymatic hydrolysate inhibitors
CN104313060A (en) * 2014-09-19 2015-01-28 北京利晟新能生物科技中心(有限合伙) Preparation method of biomass ABE fermentation sugar solution
CN109071583A (en) * 2016-02-25 2018-12-21 格勒诺布尔理工学院 The method for preparing the mixture of monosaccharide and/or oligosaccharide and/or polysaccharide by purifying ligno-cellulosic materials hydrolysate
CN113502301A (en) * 2021-08-26 2021-10-15 泸州老窖股份有限公司 Method for increasing yield of ethanol prepared from distilled spirit distiller grains
CN116493055A (en) * 2023-06-29 2023-07-28 高密同利制糖有限公司 Device and method for adjusting Ph value of sugar solution

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103773904A (en) * 2012-10-24 2014-05-07 中国石油化工股份有限公司 Method used for removing lignocelluloses enzymatic hydrolysate inhibitors
CN103773904B (en) * 2012-10-24 2015-05-13 中国石油化工股份有限公司 Method used for removing lignocelluloses enzymatic hydrolysate inhibitors
CN103555774A (en) * 2013-11-06 2014-02-05 四川农业大学 Method for pre-treating lignocelluloses raw material for enzyme hydrolysis in combination of strong phosphoric acid and hydrogen peroxide
CN103555774B (en) * 2013-11-06 2016-04-13 四川农业大学 A kind of strong phosphoric acid associating hydrogen peroxide preprocessing lignocellulose class raw material is used for the method for enzymic hydrolysis
CN104313060A (en) * 2014-09-19 2015-01-28 北京利晟新能生物科技中心(有限合伙) Preparation method of biomass ABE fermentation sugar solution
CN109071583A (en) * 2016-02-25 2018-12-21 格勒诺布尔理工学院 The method for preparing the mixture of monosaccharide and/or oligosaccharide and/or polysaccharide by purifying ligno-cellulosic materials hydrolysate
CN113502301A (en) * 2021-08-26 2021-10-15 泸州老窖股份有限公司 Method for increasing yield of ethanol prepared from distilled spirit distiller grains
CN116493055A (en) * 2023-06-29 2023-07-28 高密同利制糖有限公司 Device and method for adjusting Ph value of sugar solution
CN116493055B (en) * 2023-06-29 2023-09-12 高密同利制糖有限公司 Device and method for adjusting pH value of sugar solution

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