CN104862345A - Detoxification method for wood fiber raw material pre-hydrolysis sugar liquid - Google Patents
Detoxification method for wood fiber raw material pre-hydrolysis sugar liquid Download PDFInfo
- Publication number
- CN104862345A CN104862345A CN201510340855.3A CN201510340855A CN104862345A CN 104862345 A CN104862345 A CN 104862345A CN 201510340855 A CN201510340855 A CN 201510340855A CN 104862345 A CN104862345 A CN 104862345A
- Authority
- CN
- China
- Prior art keywords
- concentrated solution
- raw material
- liquid glucose
- prehydrolysis
- liquid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P2201/00—Pretreatment of cellulosic or lignocellulosic material for subsequent enzymatic treatment or hydrolysis
-
- 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
- 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
Landscapes
- Organic Chemistry (AREA)
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Zoology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
- Genetics & Genomics (AREA)
- Saccharide Compounds (AREA)
Abstract
The invention discloses a detoxification method for a wood fiber raw material pre-hydrolysis sugar liquid. According to the detoxification method, a pre-hydrolysis concentrated sugar liquid obtained after dilute sulphuric acid steam explosion pretreatment is taken as a raw material and an ionic liquid is taken as an extraction agent for removing of fermentation inhibitors in the wood fiber raw material pre-hydrolysis concentrated sugar liquid, wherein the ionic liquid is a disubstituted imidazole cationic liquid. The detoxification method has the advantages that the organic ionic liquid is adopted for extraction treatment on a wood fiber raw material pre-hydrolysis concentrated sugar liquid, and the treatment result shows that on the premise that a little fermented sugar is lost, the removing rates of formic acid, acetic acid, levulinic acid, furfuraldehyde, hydroxymethyl furfural and total phenolics in the prehydrolysis concentrated sugar liquid reach 64.54%, 54.88%, 100%, 100%, 87.08% and 70.44% respectively; in the same period, the sugar utilization rate is improved by 74.34%, the ethanol yield is improved by 82.91%, and the fermentation circle is shortened.
Description
Technical field
The invention belongs to the technical field such as lignocellulose raw material biological degradation or bio-transformation production alcohol fuel, chemical industry platform chemicals and other biobased products, be specifically related to a kind of poison-removing method of novel green lignocellulose raw material prehydrolysis liquid glucose.
Background technology
, as a large agricultural country, there is abundant renewable biological source in China, and development lignocellulose raw material is produced alcohol fuel and is considered to most one of biomass energy having application prospect.Mierocrystalline cellulose biorefinery alcohol fuel will to ferment these three key techniques through raw materials pretreatment, cellulase hydrolysis and monose.The supramolecular complex of the compact structure that lignocellulose raw material is mainly made up of Mierocrystalline cellulose, hemicellulose and xylogen, it is very low to the accessibility of cellulase, lignocellulose raw material must carry out pre-treatment before cellulase hydrolysis, and pretreatment process is divided into Physical, chemical method, physico-chemical processes and biological process.But no matter adopt which kind of pretreatment process all inevitably to produce inhibition, the main weak acid of inhibition (formic acid, acetic acid and levulinic acid), furans (furfural, 5 hydroxymethyl furfural) and aldehydes matter etc., these inhibitions have had a strong impact on follow-up yeast-alcohol fermentation, in order to improve subsequent fermentation efficiency, effective elimination fermentation inhibitor i.e. " detoxification " is the required step improving leavening property.
The poison-removing method of lignocellulose raw material is a lot, mainly comprise steam stripped, charcoal absorption, calcium hydroxide crosses neutralisation, electrodialysis, ion-exchange, laccase treatment etc., but these poison-removing method ubiquities in single poison-removing method weak effect, During Detoxification and caused secondary pollution and the shortcoming such as fermentable sugars loss is serious.Therefore find a kind of detoxification efficiency good, environmental protection and operational condition are simple, and can be used for the poison-removing method of the most of inhibition removed in lignocellulose raw material prehydrolysis liquid glucose, the efficiency utilization realizing lignocellulose raw material is very necessary.
Ionic liquid (ionic liquids, ILs), also known as ionic liquid at room temperature, is made up of organic cation and negatively charged ion, and zwitterion has many possible combinations, can design according to particular requirement.Different from organic solvent, there is doping region and nonpolar district in ionic liquid, thus have good solvability to organism, inorganics, biomacromolecule, gas etc. simultaneously.In extracting and separating field, ionic liquid due to its liquid state range wide, non-volatile, structure controllable, has certain selectivity to target compound, is considered to a kind of novel green solvent of alternative conventional solvent, in the extraction research of active skull cap components, by design cationic structural, substituting group, replacement position and composition and negatively charged ion, desirable ionic liquid can be obtained, thus reach the selective extraction of ionic liquid to target product.
Summary of the invention
Goal of the invention: for fermentation inhibitor in lignocellulose raw material prehydrolysis liquid glucose to the high inhibition effect of microorganism growth, there is provided a kind of poison-removing method of lignocellulose raw material prehydrolysis liquid glucose concentrated solution, to most of fermentation inhibitor in lignocellulose raw material prehydrolysis liquid glucose concentrated solution effectively can be removed.Meanwhile, in the process of detoxification, can not lose as far as possible or lose less fermentable sugar.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is as follows:
A kind of poison-removing method of lignocellulose raw material prehydrolysis liquid glucose concentrated solution, it is characterized in that, with the prehydrolysis liquid glucose concentrated solution obtained after the pre-treatment of dilute sulphuric acid steam explosion for raw material, the fermentation inhibitor in lignocellulose raw material prehydrolysis liquid glucose concentrated solution is removed using ionic liquid as extraction agent, extraction agent is 3:1 ~ 3:1 with the ratio (volume ratio, lower same) of prehydrolysis liquid glucose concentrated solution; Wherein, ionic liquid is disubstituted imidazole cationic ion liquid.
The positively charged ion of described disubstituted imidazole cationic ion liquid is selected from 1-butyl-3-Methylimidazole, 1-hexyl-3-Methylimidazole, 1-octyl group-3-Methylimidazole, and negatively charged ion is selected from hexafluorophosphate radical ion, a tetrafluoro borate radical ion.
Described glyoxaline cation type ionic liquid is 1-octyl group-3-methyl imidazolium tetrafluoroborate.
The poison-removing method of described lignocellulose raw material prehydrolysis liquid glucose concentrated solution, the extraction equilibrium time is 10 ~ 60min.
The poison-removing method of described lignocellulose raw material prehydrolysis liquid glucose concentrated solution, extraction temperature is 30 ~ 40 DEG C.
The poison-removing method of described lignocellulose raw material prehydrolysis liquid glucose concentrated solution, extraction rotating speed is 100 ~ 200r/min.
The poison-removing method of described lignocellulose raw material prehydrolysis liquid glucose concentrated solution, ionic liquid and prehydrolysis liquid glucose concentrated solution are than being 1:1 ~ 3:1.
The poison-removing method of described lignocellulose raw material prehydrolysis liquid glucose concentrated solution, the pH of prehydrolysis liquid glucose concentrated solution is 1 ~ 4.
The present invention with the imidazoles of different long alkyl chains for positively charged ion (C
nmim, n=4,6,8), with hexafluorophosphate radical ion (PF
6 -), a tetrafluoro borate radical ion (BF
4 -) be negatively charged ion, design different ionic liquids, be respectively 1-butyl-3-Methylimidazole hexafluorophosphate [C
4mim] [PF
6], 1-hexyl-3-Methylimidazole hexafluorophosphate [C
6mim] [PF
6], 1-octyl group-3-Methylimidazole hexafluorophosphate [C
8mim] [PF
6], 1-hexyl-3-methyl imidazolium tetrafluoroborate [C
6mim] [BF
4], 1-octyl group-3-methyl imidazolium tetrafluoroborate [C
8mim] [BF
4], ionic liquid washing is saturated rear to the detoxification of prehydrolysis liquid glucose concentrated solution.
The method for washing of ionic liquid is, by ionic liquid and distilled water by compared with 1:1 mix and be placed in shaking table, 30 DEG C, react 20min under 150r/min condition.By water and ionic liquid mixed phase 4000r/min, centrifugal 10min after washing terminates, after centrifugal end, collection of ions liquid, using water saturated from liquid as extraction agent.
The poison-removing method of lignocellulose raw material prehydrolysis liquid glucose concentrated solution is specially, water saturated ionic liquid is placed in shaking table in prehydrolysis liquid glucose concentrated solution by comparing 3:1 ~ 1:3 mixing, pH 1 ~ 10 time, 20 ~ 40 DEG C, reaction 10 ~ 80min under 50 ~ 250r/min condition.After reaction terminates, leave standstill, after layering, collect extraction phase and extracting phase respectively.
Lignocellulose raw material prehydrolysis liquid glucose concentrated solution after detoxification adds acid or alkali, is adjusted to proper pH value, adds corresponding nutritive salt, add corresponding strain fermentation and can prepare corresponding chemical, as ethanol or organic acid etc.Described acid, alkali can be sulfuric acid, sodium hydroxide etc.
Beneficial effect: compared with prior art, the present invention adopts novel green solvent to carry out detoxification treatment to lignocellulose raw material prehydrolysis liquid glucose concentrated solution, eliminate most of fermentation inhibitor, thus improve the leavening property of lignocellulose raw material prehydrolysis liquid glucose concentrated solution.Wherein, formic acid clearance is 64.54%, acetic acid clearance 54.88%, the clearance 100% of levulinic acid, furfural, 5 hydroxymethyl furfural 87.08%, total phenol clearance 70.44%.Ethanol fermentation is carried out after adopting charcoal absorption to remove residual ion liquid, compared with the lignocellulose raw material prehydrolysis liquid glucose concentrated solution without detoxification treatment, the utilize speed of microorganism to lignocellulose raw material prehydrolysis liquid glucose concentrated solution increases substantially, fermentation period shortens, in same time, sugar utilization improves 74.34%, ethanol production improves 82.91%, show method that ion liquid abstraction-charcoal absorption is coupled to the excellent properties of prehydrolysis liquid glucose concentrated solution detoxification, for the detoxification of prehydrolysis liquid glucose concentrated solution provides a new way.
Accompanying drawing explanation
Fig. 1 affects result figure to the percentage extraction of inhibition in prehydrolysis liquid glucose concentrated solution the extraction equilibrium time, and its experiment condition is, the pH of prehydrolysis liquid glucose concentrated solution is 2, shaking table temperature 30 DEG C, rotating speed 150r/min, compares 1:1, be respectively 10 sample time, 20,40,60,80min;
Fig. 2 is that the percentage extraction comparing inhibition in prehydrolysis liquid glucose concentrated solution affects result figure, its experiment condition is, the pH of prehydrolysis liquid glucose concentrated solution is 2, shaking table temperature 35 DEG C, rotating speed 150r/min, compare 0.33:1,0.5:1,1:1,1:2,1:3 (ionic liquid: prehydrolysis liquid glucose), extraction time is 60min;
Fig. 3 is that pH affects result figure to the percentage extraction of inhibition in prehydrolysis liquid glucose concentrated solution, its experiment condition is, the pH of prehydrolysis liquid glucose concentrated solution is 1,2,4,6,8, shaking table temperature 35 DEG C, rotating speed 150r/min, comparing 2:1 (ionic liquid: prehydrolysis liquid glucose) extraction time is 60min;
Fig. 4 is through ionic liquid [C
8mim] [BF
4] acid quick-fried maize straw prehydrolysis liquid glucose concentrated solution pichia stipitis (Pichia stipitis) the NLP31 ethanol fermentation situation result figure of detoxification treatment;
Fig. 5 is without ionic liquid [C
8mim] [BF
4] acid quick-fried maize straw prehydrolysis liquid glucose concentrated solution pichia stipitis (Pichia stipitis) the NLP31 ethanol fermentation situation result figure of detoxification treatment.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
The acquisition of lignocellulose raw material prehydrolysis liquid glucose concentrated solution, step is as follows:
(1) dilute acid steam explosion pre-treatment: maize straw, is collected in Inner Mongol Huhehaote City.In maize straw, the massfraction of Mierocrystalline cellulose and hemicellulose is be not 37.17% and 22.84%.Maize straw massfraction is after the sulfuric acid immersion 1 ~ 3h of 0.50% ~ 1.00%, dewaters to solid content 30% ~ 40%, processes 5 ~ 10min, open the blow-off valve of blasting assembly instantaneously, spurted in hopper by material under 1.6 ~ 2.0MPa condition.
(2) water-washing pre-treatment maize straw: divide 3 washing materials with the warm water of solid-to-liquid ratio 1:15, collects filtrate (i.e. acid explosion maize straw prehydrolysis liquid glucose) and filter residue respectively, for subsequent use.
(3) prehydrolysis liquid glucose concentrates: the maize straw prehydrolysis liquid glucose that dilute acid steam explosion pretreatment technology obtains, adopt Rotary Evaporators 70 DEG C, concentrated about 4 times are carried out to acid explosion maize straw prehydrolysis liquid glucose under 170mbar condition.
(4) concentrated front and back main sugar components, fermentation inhibitor adopt high performance liquid chromatography (HPLC) and RPLC (R-HPLC) to analyze, total phenol content in Folin-Ciocalteu colorimetric method for determining prehydrolysis liquid glucose, prehydrolysis liquid glucose concentrated solution is unified dilution 200 times, at 280nm (λ
280) place's employing ultraviolet spectrophotometer mensuration light absorption value.Before and after prehydrolysis liquid glucose vacuum concentration, composition transfer is as shown in table 1.
Composition transfer before and after table 1 prehydrolysis liquid glucose vacuum concentration
As can be seen from Table 1, after concentrated 4 times of prehydrolysis liquid glucose, the content of glucose, wood sugar is respectively 9.31,50.74g/L, wherein have volatile formic acid, acetic acid, furfural content be respectively 0.32,1.60,0.03g//L, clearance reaches 20.00%, 50.30%, 85.00% respectively, and in prehydrolysis liquid glucose concentrated solution, the concentration of cellobiose, pectinose, levulinic acid, hydroxymethylfurfural, aldehydes matter is 4 times before concentrating substantially.
Embodiment 2
The detoxification treatment of lignocellulose raw material prehydrolysis liquid glucose concentrated solution prepared by embodiment 1, process is as follows:
1) washing of ionic liquid: the 1-hexyl-3-methyl imidazolium tetrafluoroborate [C pipetting 5mL respectively
6mim] [BF
4], 1-octyl group-3-methyl imidazolium tetrafluoroborate [C
8mim] [BF
4] ionic liquid and distilled water by compared with 1:1 mix and be placed in shaking table, 30 DEG C, react 20min under 150r/min condition.After washing terminates by water and ionic liquid mixed phase centrifugal 10min under 4000r/min, centrifugal end is standing 20min layering afterwards, and collection of ions liquid, using water saturated ionic liquid as extraction agent.
2) poison-removing method: the 1-butyl-3-Methylimidazole hexafluorophosphate C pipetting 5mL respectively
4mim [PF
6], 1-hexyl-3-Methylimidazole hexafluorophosphate C
6mim [PF
6], 1-octyl group-3-Methylimidazole hexafluorophosphate C
8mim [PF
6], 1-hexyl-3-methyl imidazolium tetrafluoroborate C
6mim [BF
4] and washing saturated after 1-hexyl-3-methyl imidazolium tetrafluoroborate C
6mim [BF
4], 1-octyl group-3-methyl imidazolium tetrafluoroborate C
8mim [BF
4] in the triangle of 5 50mL, adding prehydrolysis liquid glucose concentrated solution (pH regulator is 2) by comparing 1:1, after mixing, being placed in shaking table, 30 DEG C, react 60min under 150r/min condition.After reaction terminates, leave standstill 1h, after layering, collect extraction phase and extracting phase respectively.
Detoxification efficiency is evaluated: carry out composition analysis to the prehydrolysis liquid glucose concentrated solution before and after detoxification, high performance liquid chromatography (HPLC) and RPLC (R-HPLC) is adopted to analyze, total phenol content in Folin-Ciocalteu colorimetric method for determining prehydrolysis liquid glucose concentrated solution, prehydrolysis liquid glucose concentrated solution is unified dilution 200 times, at 280nm (λ
280) place's employing ultraviolet spectrophotometer mensuration light absorption value, calculate the percentage extraction to composition in prehydrolysis liquid glucose concentrated solution.
Percentage extraction E=(C
i-C
f)/C
i* 100%, C
irepresent the concentration of composition in the front prehydrolysis liquid glucose concentrated solution of extraction, C
frepresent the concentration of composition in the rear prehydrolysis liquid glucose concentrated solution of extraction.Result is as shown in table 2.
Table 2 ionic liquid chemical structure is on impact that is sugared and inhibition removal effect
As shown in Table 2, along with three kinds of phosphofluoric acid salt ionic liquid ([C
4mim] [PF
6], [C
6mim] [PF
6] and [C
8mim] [PF
6]) increase of long alkyl chains on positively charged ion imidazoles, the removal effect of inhibition decreases; [C
4mim] [PF
6] best to the removal effect of inhibition, levulinic acid and furfural can 100% to be removed, and the clearance of 5 hydroxymethyl furfural is 76.99%, and formic acid and acetic acid clearance are respectively 25.00% and 13.13%, total phenol clearance is 38.07%, and the rate of loss of sugar is within 5%; Two kinds of tetrafluoroborate ion liquid [C
6mim] [BF
4] and [C
8mim] [BF
4] removal effect of inhibition in prehydrolysis liquid glucose concentrated solution is significantly improved, two kinds of removal effects to inhibition are suitable, but there is [C
6mim] [BF
4] to wood sugar percentage extraction (14.33%) and the higher shortcoming of glucose percentage extraction (11.22%), therefore select [C
8mim] [BF
4] as the extraction agent of sour quick-fried maize straw prehydrolysis liquid glucose concentrated solution, levulinic acid and furfural can 100% to be removed, the clearance of 5 hydroxymethyl furfural is 85.71%, the clearance of formic acid and acetic acid is respectively 56.25% and 36.25%, the clearance of total phenol is 65.05%, and the rate of loss of sugar is within 6%.
Embodiment 3
[C
8mim] [BF
4] determination of extraction equilibrium time
1) [the C of ionic liquid
8mim] [BF
4] washing: the 1-octyl group-3-methyl imidazolium tetrafluoroborate [C pipetting 5mL respectively
8mim] [BF
4] ionic liquid and distilled water by compared with 1:1 mix and be placed in shaking table, 30 DEG C, react 20min under 150r/min condition.After washing terminates by water and ionic liquid mixed phase centrifugal 10min under 4000r/min, centrifugal end is standing 20min layering afterwards, and collection of ions liquid, using water saturated ionic liquid as extraction agent.
2) poison-removing method: pipette respectively the washing of 5mL saturated after 1-octyl group-3-methyl imidazolium tetrafluoroborate [C
8mim] [BF
4] in the triangle of 5 50mL, adding 5mL prehydrolysis liquid glucose concentrated solution (pH regulator is 2) by comparing 1:1, after mixing, being placed in shaking table, 30 DEG C, reaction 10 under 150r/min condition, 20,40,60,80min.After reaction terminates, leave standstill 1h, after layering, collect extraction phase and extracting phase respectively.
Detoxification efficiency is evaluated: carry out composition analysis to the prehydrolysis liquid glucose concentrated solution before and after detoxification, high performance liquid chromatography (HPLC) and RPLC (R-HPLC) is adopted to analyze, total phenol content in Folin-Ciocalteu colorimetric method for determining prehydrolysis liquid glucose concentrated solution, prehydrolysis liquid glucose concentrated solution is unified dilution 200 times, at 280nm (λ
280) place's employing ultraviolet spectrophotometer mensuration light absorption value, calculate the percentage extraction to composition in prehydrolysis liquid glucose concentrated solution.
Percentage extraction E=(C
i-C
f)/C
i* 100%, C
irepresent the concentration of composition in the front prehydrolysis liquid glucose concentrated solution of extraction, C
frepresent the concentration of composition in the rear prehydrolysis liquid glucose concentrated solution of extraction.Result is as shown in table 3.
Composition analysis after the detoxification of prehydrolysis liquid glucose concentrated solution under the different extraction time of table 3
As can be seen from Table 3, [C
8mim] [BF
4] extraction 10min substantially just reaches extraction equilibrium, the composition in extracting phase remains stable substantially, and as shown in Figure 1, along with the increase of extraction time, clearance no longer increases, and in order to extract fully, selects 10 ~ 60min as the detoxification time.
Embodiment 4
[C
8mim] [BF
4] determination of extraction temperature
1) [the C of ionic liquid
8mim] [BF
4] washing: method is with example 3.
2) poison-removing method: pipette respectively the washing of 5mL saturated after 1-octyl group-3-methyl imidazolium tetrafluoroborate [C
8mim] [BF
4] in the triangle of 5 50mL, adding 5mL prehydrolysis liquid glucose concentrated solution (pH regulator is 2) by comparing 1:1, after mixing, being placed in shaking table, respectively at 20,25,30,35,40 DEG C, under 150r/min condition, reacting 60min.After reaction terminates, leave standstill 1h, after layering, collect extraction phase and extracting phase respectively.
Detoxification efficiency is evaluated: with example 3.Percentage extraction E=(C
i-C
f)/C
i* 100%, C
irepresent the concentration of composition in the front prehydrolysis liquid glucose concentrated solution of extraction, C
frepresent the concentration of composition in the rear prehydrolysis liquid glucose concentrated solution of extraction.Result is as shown in table 4.
Composition analysis after the detoxification of prehydrolysis liquid glucose concentrated solution under the different extraction temperature of table 4
As can be seen from Table 4, along with the rising of extraction temperature, the sugared concentration in prehydrolysis liquid glucose concentrated solution has increase slightly, illustrates that raising extraction temperature can reduce the sugar loss in During Detoxification, improve extraction temperature, in prehydrolysis liquid glucose concentrated solution, the concentration of inhibition also reduces to some extent simultaneously.As shown in Figure 3, when temperature rises to 35 DEG C, the clearance of formic acid, total phenol improves 10.59%, 4.04% respectively, in general, extraction temperature can affect partition ratio and the solubleness of ionic liquid in water of extraction system, this is that temperature raises zwitterion motion in quickening ionic liquid, causes viscosity drop, is conducive to mass transfer; Secondly, temperature can affect the binding ability of extraction agent and extract.But temperature raises, the wetting ability of ionic liquid increases thus the solubleness causing ionic liquid in water increases, and not easily select higher temperature as extraction temperature, therefore selecting 30 ~ 40 DEG C is best extraction temperature.
Embodiment 5
[C
8mim] [BF
4] extraction rotating speed determination
1) [the C of ionic liquid
8mim] [BF
4] washing: method is with example 3.
2) poison-removing method: pipette respectively the washing of 5mL saturated after 1-octyl group-3-methyl imidazolium tetrafluoroborate [C
8mim] [BF
4] in the triangle of 5 50mL, add 5mL prehydrolysis liquid glucose concentrated solution (pH regulator is 2) by comparing 1:1, after mixing, be placed in 50,100,150,200, in the shaking table of 250r/min rotating speed, under 35 DEG C of parts, react 60min.After reaction terminates, leave standstill 1h, after layering, collect extraction phase and extracting phase respectively.
Detoxification efficiency is evaluated: with example 3.Percentage extraction E=(C
i-C
f)/C
i* 100%, C
irepresent the concentration of composition in the front prehydrolysis liquid glucose concentrated solution of extraction, C
frepresent the concentration of composition in the rear prehydrolysis liquid glucose concentrated solution of extraction.Result is as shown in table 5.
Composition analysis after the detoxification of prehydrolysis liquid glucose concentrated solution under table 5 different rotating speeds
As can be seen from Table 5, when to extract rotating speed be 50r/min, the concentration of glucose and xylose is respectively 9.08,48.96g/L, and along with the raising of rotating speed, in aqueous phase, the concentration of glucose and xylose does not change substantially.When to extract rotating speed be 50r/min, in aqueous phase the concentration of 5 hydroxymethyl furfural and total phenol be respectively 0.27,1.47g/L; When extraction rotating speed is 150r/min, in aqueous phase the concentration of 5 hydroxymethyl furfural and acetic acid be respectively 0.10,1.33g/L, percentage extraction improves 42.29% and 3.17% respectively.Improve the percentage extraction that rotating speed contributes to improving 5 hydroxymethyl furfural, other inhibition is not had a significant effect, so select 100 ~ 200r/min as extraction optimum revolution.
Embodiment 6
[C
8mim] [BF
4] determination of extraction phase ratio
1) [the C of ionic liquid
8mim] [BF
4] washing: method is with example 3.
2) poison-removing method: pipette 10mL prehydrolysis liquid glucose concentrated solution (pH regulator is 2) respectively in the triangle of 5 50mL, by compare 0.33:1,0.5:1,1:1,2:1,3:1 (ionic liquid: prehydrolysis liquid glucose concentrated solution) add the washing of different volumes saturated after 1-octyl group-3-methyl imidazolium tetrafluoroborate [C
8mim] [BF
4], after mixing, be placed in shaking table, 35 DEG C, react 60min under 150r/min condition.After reaction terminates, leave standstill 1h, after layering, collect extraction phase and extracting phase respectively.
Detoxification efficiency is evaluated: with example 3.Percentage extraction E=(C
i-C
f)/C
i* 100%, C
irepresent the concentration of composition in the front prehydrolysis liquid glucose concentrated solution of extraction, C
frepresent the concentration of composition in the rear prehydrolysis liquid glucose concentrated solution of extraction.Result is as shown in table 6.
Table 6 difference compares composition analysis after the detoxification of lower prehydrolysis liquid glucose concentrated solution
As can be seen from Table 6, the not significant impact of glucose in pre-hydrolyzed solution concentrated solution, wood sugar is compared in extraction process, and along with the increase of ionic liquid add-on, the concentration of the inhibition in prehydrolysis liquid glucose concentrated solution reduces gradually, as can be seen from Figure 2, when profit compare be greater than 2:1 time, percentage extraction increases slowly and tends towards stability gradually, when ionic liquid consumption reaches certain value, in system no longer there is obvious change in inhibition percentage extraction, therefore, economically consider, select optimum oil water to be in a ratio of 1:1 ~ 3:1.
Embodiment 7
[C
8mim] [BF
4] extraction pH determination
1) C of ionic liquid
8mim [BF
4] washing: method is with example 3.
2) poison-removing method: with NaOH or H of 50%
2sO
4the pH value regulating prehydrolysis liquid glucose concentrated solution is 1,2,4,6,8,10.Pipette respectively the washing of 10mL saturated after 1-octyl group-3-methyl imidazolium tetrafluoroborate [C
8mim] [BF
4] in the triangle of 5 50mL, adding 5mL prehydrolysis liquid glucose concentrated solution (pH regulator is 1,2,4,6,8,10) by comparing 2:1, after mixing, being placed in shaking table, 30 DEG C, react 60min under 150r/min condition.After reaction terminates, leave standstill 1h, after layering, collect extraction phase and extracting phase respectively.
Detoxification efficiency is evaluated: with example 3.Percentage extraction E=(C
i-C
f)/C
i* 100%, C
irepresent the concentration of composition in the front prehydrolysis liquid glucose concentrated solution of extraction, C
frepresent the concentration of composition in the rear prehydrolysis liquid glucose concentrated solution of extraction.Result is as shown in table 7.
Composition analysis after the detoxification of prehydrolysis liquid glucose concentrated solution under the different pH of table 7
As can be seen from table 7 and Fig. 3, the percentage extraction of pH value on ionic liquid of solution has important impact, and when pH is greater than 4 and 6, the percentage extraction of formic acid and acetic acid starts obvious decline, and the percentage extraction of 5 hydroxymethyl furfural does not then have considerable change.When pH value is 2, the percentage extraction of formic acid, acetic acid and 5 hydroxymethyl furfural is respectively 64.54%, 54.88%, 87.08%, and total phenol clearance is 70.44%, can draw in acid condition, and effect of extracting is better, is more conducive to the removal of inhibition.Therefore, Optimal pH is selected to be 1 ~ 4.
Embodiment 8
Through ionic liquid [C
8mim] [BF
4] acid quick-fried maize straw prehydrolysis liquid glucose concentrated solution pichia stipitis (Pichia stipitis) the NLP31 ethanol fermentation of detoxification treatment
1) ionic liquid C
8mim [BF
4] detoxification: pipette 200mL and wash saturated rear ionic liquid [C
8mim] [BF
4] in the triangular flask of 1000mL, pipette the acid quick-fried maize straw prehydrolysis liquid glucose concentrated solution 100mL that pH value is adjusted to 2 again, be placed in 35 DEG C, 150r/min shaking table interior extraction 60min, after extraction terminates, after ionic liquid and aqueous phase layering, collect extraction phase (ionic liquid) and extracting phase (aqueous phase) respectively.After detoxification in prehydrolysis liquid glucose concentrated solution sugar and inhibition component concentration as shown in table 8.
2) fermention medium (L composed as follows
-1): (NH
4)
2sO
45g, KH
2pO
43g, MgSO
47H
2o 0.5g, EDTA 30mg, ZnSO
47H
2o 9mg, MnCl
22H
2o 2mg, CoCl
26H
2o 0.6mg, CuSO
45H
2o0.6mg, Na
2moO
4h
2o 0.8mg, CaCl
22H
2o 9mg, FeSO
47H
2o 6mg, H
3bO
32mg, KI 0.2mg; Measure above-mentioned extraction phase 100mL in 250mL triangular flask, the NaOH with 50% regulates ionic liquid [C
8mim] [BF
4] extracting phase pH value to 6.0 after, after adding the charcoal absorption removal residual ion liquid of 10 ~ 20g, add Citric acid monohydrate Food grade again and sodium hydroxide makes its pH maintain about 6.0, add nutritive salt and trace element simultaneously, access OD (600nm, lower same) reaches the P.stipitis NLP31 of 10.Fermentation condition is 30 DEG C, 150r/min, and fermentation course as shown in Figure 4.
With without ionic liquid [C
8mim] [BF
4] detoxification treatment acid quick-fried maize straw prehydrolysis liquid glucose concentrated solution pichia stipitis (Pichia stipitis) NLP31 ethanol fermentation as a comparison, specific as follows:
In direct use embodiment 1, sour quick-fried maize straw prehydrolysis liquid glucose concentrated solution carries out ethanol fermentation.Each inhibition component concentration of prehydrolysis liquid glucose concentrated solution is as shown in table 1.Experimental technique is as follows:
Fermention medium (L composed as follows
-1): (NH
4)
2sO
45g, KH
2pO
43g, MgSO
47H
2o 0.5g, EDTA30mg, ZnSO
47H
2o 9mg, MnCl
22H
2o 2mg, CoCl
26H
2o 0.6mg, CuSO
45H
2o 0.6mg, Na
2moO
4h
2o 0.8mg, CaCl
22H
2o 9mg, FeSO
47H
2o 6mg, H
3bO
32mg, KI 0.2mg; Measure the acid quick-fried maize straw prehydrolysis liquid glucose concentrated solution 100mL of embodiment 1 in 250mL triangular flask, NaOH with 50% regulates the pH of sour quick-fried maize straw prehydrolysis liquid glucose concentrated solution to be about 6.0, add Citric acid monohydrate Food grade again and sodium hydroxide makes its pH maintain about 6.0, add nutritive salt and trace element, access OD reaches the P.stipitis NLP31 of 10 simultaneously.Fermentation condition is 30 DEG C, 150r/min, and fermentation course as shown in Figure 5.
Each inhibition component concentration and clearance in before and after the detoxification of table 8 sour quick-fried maize straw prehydrolysis liquid glucose concentrated solution
| Composition | Prehydrolysis liquid glucose concentrated solution | [C 8mim][BF 4] extracting phase | Clearance % |
| Cellobiose (g/L) | 4.27±0.04 | 4.13±0.01 | 3.19±0.63 |
| Glucose (g/L) | 9.18±0.10 | 9.01±0.03 | 1.88±0.65 |
| Wood sugar (g/L) | 50.16±0.58 | 48.04±0.09 | 4.22±0.94 |
| Pectinose (g/L) | 8.73±0.09 | 7.74±0.01 | 11.26±0.88 |
| Formic acid (g/L) | 0.31±0.00 | 0.11±0.00 | 64.54±0.83 |
| Acetic acid (g/L) | 1.60±0.01 | 0.72±0.02 | 54.88±1.35 |
| Levulinic acid (g/L) | 0.07±0.01 | 0.00±0.00 | 100±0.00 |
| 5 hydroxymethyl furfural (g/L) | 0.42±0.01 | 0.05±0.00 | 87.08±0.52 |
| Furfural (g/L) | 0.04±0.01 | 0.00±0.00 | 100±0.00 |
| Total phenol (g/L) | 3.72±0.04 | 1.10±0.03 | 70.44±0.45 |
| 9 kinds of single phenol (mg/L) | 840.86±43.23 | 1.08±0.78 | 99.87±0.09 |
Result shows: through ionic liquid [C
8mim] [BF
4] and charcoal absorption residual ion liquid detoxification treatment after, the leavening property of lignocellulose raw material prehydrolysis liquid glucose concentrated solution significantly improves, and fermentation period obviously shortens.Compared with the lignocellulose raw material prehydrolysis liquid glucose concentrated solution of non-detoxification, fermentation 48h, Yeast sugar utilization ratio brings up to 95.31% from 20.97% before, and sugar utilization improves 74.34%, ethanol production brings up to 17.32g/L from 2.96g/L before, and ethanol production improves 82.91%.
Claims (10)
1. the poison-removing method of a lignocellulose raw material prehydrolysis liquid glucose concentrated solution, it is characterized in that, with the prehydrolysis liquid glucose concentrated solution obtained after the pre-treatment of dilute sulphuric acid steam explosion for raw material, remove the fermentation inhibitor in lignocellulose raw material prehydrolysis liquid glucose concentrated solution using ionic liquid as extraction agent, extraction agent is 3:1 ~ 3:1 with the ratio of prehydrolysis liquid glucose concentrated solution volume; Wherein, ionic liquid is disubstituted imidazole cationic ion liquid.
2. the poison-removing method of lignocellulose raw material prehydrolysis liquid glucose concentrated solution according to claim 1, it is characterized in that, by water saturated ionic liquid and prehydrolysis liquid glucose concentrated solution by compared with 3:1 ~ 1:3 mix and be placed in shaking table, pH 1 ~ 10 time, 20 ~ 40 DEG C, reaction 10 ~ 80 min under 50 ~ 250 r/min conditions; After reaction terminates, leave standstill, after layering, collect extraction phase and extracting phase respectively.
3. the poison-removing method of lignocellulose raw material prehydrolysis liquid glucose concentrated solution according to claim 1 and 2, it is characterized in that, the method for washing of ionic liquid is: by ionic liquid and distilled water by compared with 1:1 mix and be placed in shaking table, 30 DEG C, react 20 min under 150 r/min conditions; By water and ionic liquid mixed phase 4000 r/min after washing terminates, centrifugal 10 min, after centrifugal end, collection of ions liquid, using water saturated from liquid as extraction agent.
4. the poison-removing method of lignocellulose raw material prehydrolysis liquid glucose concentrated solution according to claim 1 and 2, it is characterized in that, the positively charged ion of described disubstituted imidazole cationic ion liquid is selected from 1-butyl-3-Methylimidazole, 1-hexyl-3-Methylimidazole, 1-octyl group-3-Methylimidazole, and negatively charged ion selects hexafluorophosphate radical ion, a tetrafluoro borate radical ion.
5. the poison-removing method of lignocellulose raw material prehydrolysis liquid glucose concentrated solution according to claim 1 and 2, is characterized in that, described glyoxaline cation type ionic liquid is 1-octyl group-3-methyl imidazolium tetrafluoroborate.
6. the poison-removing method of lignocellulose raw material prehydrolysis liquid glucose concentrated solution according to claim 1 and 2, it is characterized in that, the extraction equilibrium time is 10 ~ 60 min.
7. the poison-removing method of lignocellulose raw material prehydrolysis liquid glucose concentrated solution according to claim 1 and 2, it is characterized in that, extraction temperature is 30 ~ 40 DEG C.
8. the poison-removing method of lignocellulose raw material prehydrolysis liquid glucose concentrated solution according to claim 1 and 2, is characterized in that, extraction rotating speed is 100 ~ 200 r/min.
9. the poison-removing method of lignocellulose raw material prehydrolysis liquid glucose concentrated solution according to claim 1 and 2, is characterized in that, ionic liquid and prehydrolysis liquid glucose concentrated solution volume ratio are 1:1 ~ 3:1.
10. the poison-removing method of lignocellulose raw material prehydrolysis liquid glucose concentrated solution according to claim 1 and 2, is characterized in that, the pH of prehydrolysis liquid glucose concentrated solution is 1 ~ 4.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510340855.3A CN104862345B (en) | 2015-06-18 | 2015-06-18 | A kind of poison-removing method of lignocellulose raw material prehydrolysis liquid glucose |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510340855.3A CN104862345B (en) | 2015-06-18 | 2015-06-18 | A kind of poison-removing method of lignocellulose raw material prehydrolysis liquid glucose |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104862345A true CN104862345A (en) | 2015-08-26 |
| CN104862345B CN104862345B (en) | 2018-10-19 |
Family
ID=53908519
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510340855.3A Active CN104862345B (en) | 2015-06-18 | 2015-06-18 | A kind of poison-removing method of lignocellulose raw material prehydrolysis liquid glucose |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104862345B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110353233A (en) * | 2019-07-26 | 2019-10-22 | 东台捷尔银杏科技有限公司 | A kind of detoxification process of ginkgo powder |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| SE2050722A1 (en) * | 2020-06-16 | 2021-12-17 | Stora Enso Oyj | Recycling of formic acid |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807515A (en) * | 2005-01-20 | 2006-07-26 | 中国科学院过程工程研究所 | Method for preparing degradable material using stalk |
| CN102154412A (en) * | 2011-01-17 | 2011-08-17 | 同济大学 | Method for increasing sugar yield of cellulase enzymolysis through pretreatment by using ion liquid |
| CN103409566A (en) * | 2013-08-26 | 2013-11-27 | 重庆大学 | Method for degrading lignocellulose to generate reducing sugar |
| CN103635582A (en) * | 2011-06-10 | 2014-03-12 | 先正达参股股份有限公司 | Methods for treating lignocellulosic material |
| CN104673858A (en) * | 2015-02-15 | 2015-06-03 | 浙江大学 | Water body remediation wood fiber raw material pretreatment method and corresponding hydrogen production method |
-
2015
- 2015-06-18 CN CN201510340855.3A patent/CN104862345B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1807515A (en) * | 2005-01-20 | 2006-07-26 | 中国科学院过程工程研究所 | Method for preparing degradable material using stalk |
| CN102154412A (en) * | 2011-01-17 | 2011-08-17 | 同济大学 | Method for increasing sugar yield of cellulase enzymolysis through pretreatment by using ion liquid |
| CN103635582A (en) * | 2011-06-10 | 2014-03-12 | 先正达参股股份有限公司 | Methods for treating lignocellulosic material |
| CN103409566A (en) * | 2013-08-26 | 2013-11-27 | 重庆大学 | Method for degrading lignocellulose to generate reducing sugar |
| CN104673858A (en) * | 2015-02-15 | 2015-06-03 | 浙江大学 | Water body remediation wood fiber raw material pretreatment method and corresponding hydrogen production method |
Non-Patent Citations (3)
| Title |
|---|
| 曾国明 等: "离子液体［BMIM］ Cl 处理汽爆活化玉米秸秆及酶解", 《精细化工》 * |
| 梁世中: "《生物反应工程与设备》", 31 August 2011, 华南理工大学出版社 * |
| 陈洪章: "《纤维素生物技术》", 31 March 2011, 化学工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110353233A (en) * | 2019-07-26 | 2019-10-22 | 东台捷尔银杏科技有限公司 | A kind of detoxification process of ginkgo powder |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104862345B (en) | 2018-10-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Varga et al. | Optimization of steam pretreatment of corn stover to enhance enzymatic digestibility | |
| Öhgren et al. | Optimization of steam pretreatment of SO 2-impregnated corn stover for fuel ethanol production | |
| Schwartz et al. | Removal of acid-soluble lignin from biomass extracts using Amberlite XAD-4 resin | |
| Cara et al. | Liquid hot water pretreatment of olive tree pruning residues | |
| WO2012061939A8 (en) | Continuous process for the production of ethanol from lignocellulosic biomass | |
| CN102533907B (en) | Method for increasing enzymolysis efficiency of rice straws through choline and amino acid ionic liquid pretreatment | |
| CN105385724A (en) | Method for improving conversion efficiency of lignocellulose through combined treatment and method for efficiently preparing ethyl alcohol | |
| US20170321231A1 (en) | Surfactant-Improved Simultaneous Saccharification and Co-Fermentation Method for Lignocellulose | |
| CN106732673A (en) | A kind of construction method of the solid acid catalyst with montmorillonite as carrier | |
| CN102766703B (en) | Hydrolysis method for hemicelluloses of lignocelluloses | |
| CN110846345A (en) | Production process of cotton straw fulvic acid and cellulosic ethanol | |
| CN106191135A (en) | Lignocellulose is the biorefinery method of raw material coproduction multi-product | |
| CN105330869A (en) | Hydrolysis method of wood fiber raw material | |
| Romero et al. | Ethanol production from rape straw by a two-stage pretreatment under mild conditions | |
| CN104862345A (en) | Detoxification method for wood fiber raw material pre-hydrolysis sugar liquid | |
| CN113603899B (en) | Method for pretreating lignocellulose by using Lewis base to assist neutral eutectic solvent | |
| Lehto et al. | Purification of hardwood-derived autohydrolysates | |
| Ao et al. | Process optimization for acidic deep eutectic solvent pretreatment of corn stover to enhance enzymatic saccharification | |
| CN101691587A (en) | Detoxification method of wood fibre hydrolysis sugar liquid | |
| CN105039460A (en) | Bamboo wood preprocessing method and application of bamboo wood in enzymatic saccharification | |
| CN101705254B (en) | Method for performing enzyme hydrolysis on wood fiber raw material | |
| CN105255966A (en) | Method for raising hydrolysis yield of microcrystalline cellulose through ionic liquid pretreatment | |
| CN105384665B (en) | Cholinium ion liquid and its application in wheat stalk pretreatment | |
| CN109180617B (en) | Two-phase biomass pretreatment co-production chemical method based on furfural compound extractant | |
| CN103755971A (en) | Method for extracting lignin of straws by acidic ionic liquid and organic solvent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |