CN103045700B - Method for pretreating lignocellulose by using renewable ionic liquid aqueous solution - Google Patents
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Abstract
The invention discloses a method for pretreating lignocellulose by using a renewable ionic liquid aqueous solution, including the steps of: (1) taking a choline and amino acid ionic liquid aqueous solution as a pretreatment solvent, mixing lignocellulose and the pretreatment solvent under the protection of nitrogen, stirring at 50-120 DEG C, cooling to room temperature, filtering, washing residue, and drying to obtain the pretreated lignocellulose; and (2) weighing the pretreated lignocelluloses, adding a citrate buffer, adding cellulase, reacting for 3-12 h with 150-250 r/min at 40-60 DEG C to obtain sugar liquid mainly including glucose and xylose. The pretreatment process not only can effectively enhance the efficiency of enzymatic hydrolysis of lignocelluloses, and improve the yield of fermentable reducing sugar, but also has the advantages of environmental protection, renewability, low viscosity, easy operation, low cost, and low power consumption.
Description
Technical field
The invention belongs to lignocellulose utilization and chemical industry application field, be specifically related to the method that the pre-treatment of a kind of utilization [choline] [amino acid] ionic liquid aqueous solution strengthens lignocellulose enzymolysis.
Background technology
Along with rising steadily and the outburst of energy dilemma of day by day deficient, the fuel price of petroleum resources in recent years, the development and utilization of the renewable resourcess such as biomass comes into one's own gradually.Compare with fossil resource, biomass resource has many advantages: its annual production is huge, and take biomass and also can effectively reduce CO as raw material production fuel and industrial chemicals
2discharge and environmental pollution.Lignocellulose enjoys people's concern as distributing the widest and the abundantest renewable biomass resource of content on the earth.Lignocellulose is mainly comprised of xylogen, Mierocrystalline cellulose and hemicellulose.Mierocrystalline cellulose and hemicellulose can be used for fermentation to produce biological fuel (as alcohol fuel and for the preparation of grease of biofuel etc.) and various hardware and software platform compound through the reducing sugar of enzymolysis gained as glucose, wood sugar etc.Yet, due to lignocellulose complex structure, Mierocrystalline cellulose is not only wrapped up by hemicellulose and xylogen, and its molecule is interior and a large amount of hydrogen bonds of intermolecular existence, cause its highly crystalline, therefore being difficult to directly utilize chemical method or biological process is the available energy or hardware and software platform compound by its Efficient Conversion, this has seriously hindered the exploitation of lignocellulose.Therefore, conventionally need to carry out pre-treatment to lignocellulose, remove portion xylogen, destroy its three-dimensional structure, thereby increase reaction site, improve polysaccharide hydrolysis rate.
Ionic liquid is owing to having superpower dissolving power and designability, in recent years by successfully for the pre-treatment (Biotechnol Bioeng, 2011,108,1229) of lignocellulosic material.But for the pretreated ionic liquid of lignocellulose, be mainly traditional imidazoles and miazines ionic liquid (CN102154412) at present.The toxicity of this class ionic liquid is strong, biodegradability is poor, environment unfriendly (Chem Soc Rev, 2011,40,1383); In addition, this class ionic liquid comes from fossil resource, has non-renewable.And this class ionic liquid pretreatment technique is the poor water resistance to moisture conventionally, the existence of micro-moisture can greatly reduce this class ionic liquid to cellulosic solubleness and pre-treatment efficiency (J Am Chem Soc, 2002,124,4974; Green Chem, 2010,12,1967), therefore conventionally need to and treat to ionic liquid that pretreated lignocellulosic material is dried, and causes energy consumption high.It is raw material that reproducible choline and amino acid be take in this seminar, by the reaction of simple acid-base neutralisation, make a class and take the novel ion liquid ([choline] [amino acid] ionic liquid) that choline is negatively charged ion as positively charged ion, amino acid, there is low toxicity, environmental protection, the feature such as renewable, biodegradable, meet Green Chemistry development strategy (Green Chem, 2012,14,304).Already proved, these ionic liquids are a class efficient lignocellulose pre-treatment solvent (Biotechnol Bioeng, 2012,109,2484; Patent 201210004741.8).
Yet the viscosity of ionic liquid is far above conventional molecule-type solvent, therefore cause in preprocessing process stirring, filtration, the operational anomaly difficulty such as centrifugal.In addition, hemicellulose is a kind of acid, alkali, heat sensitive polymkeric substance, and in preprocessing process, easily loss, reduces reducing sugar yield.Simultaneously, utilize pure ionic liquid as pre-treatment solvent, need to and treat that to ionic liquid pretreated lignocellulosic material is dried, and causes energy consumption too high, thereby significantly reduce the economic feasibility of pretreatment technology, therefore in the urgent need to developing the ionic liquid pretreatment technique of height water tolerance.At present, ionic liquid price is still higher, uses in a large number this kind solvent preprocessing lignocellulose also to have the problem that cost is relatively high.
Summary of the invention
The problem existing for prior art, the object of the present invention is to provide the pre-treatment of a kind of utilization [choline] [amino acid] ionic liquid aqueous solution to strengthen lignocellulose enzymolysis, improves the method for fermentable reducing sugar (glucose and wood sugar) yield.
Object of the present invention is achieved through the following technical solutions:
A method of utilizing renewable ionic liquid aqueous solution preprocessing lignocellulose, concrete steps are as follows:
(1) aqueous solution of [choline] [amino acid] ionic liquid of take is pre-treatment solvent, under nitrogen protection, according to lignocellulose, be 1:5 ~ 1:25 mixing lignocellulose and pre-treatment solvent with pre-treatment solvent quality ratio, under 50 ~ 120 ° of C, stir 0.5 ~ 24 hour, be cooled to subsequently room temperature, filter, wash filter residue, the dry rear pretreated lignocellulose that obtains;
(2) take pretreated lignocellulose, according to solid-to-liquid ratio, be that 1 ~ 6mg/mL adds citrate buffer, according to the ratio of lignocellulose after 5 ~ 30U/mg pre-treatment, add cellulase again, at 150 ~ 250r/min, under 40 ~ 60 ° of C, react after 3 ~ 12h, obtain and take the liquid glucose that glucose and xylose is main component.
Preferably, [choline] [amino acid] ionic liquid described in step (1) be take choline as positively charged ion, natural amino acid be anion ion liquid, its structure is as follows:
Preferably, described natural amino acid is a kind of in L-glycine, ALANINE, Serine, L-threonine, Valine, L-Leu, ILE, L-Methionine, L-Phe, L-PROLINE, L-Trp, L-Aspartic acid, altheine, Pidolidone, L-glutaminate, 1B, L-arginine and L-Histidine.
Preferably, the content of [choline] [amino acid] ionic liquid aqueous solution intermediate ion liquid described in step (1) is 5 ~ 95wt%.
Preferably, in step (1), when the content >=50wt% of [choline] [amino acid] ionic liquid aqueous solution intermediate ion liquid, before filtering, add deionized water to dilute.
Preferably, the volume of described deionized water is 1 ~ 3 times of pre-treatment solvent volume.
Preferably, described lignocellulose is a kind of in rice straw, maize straw, corn cob, wheat stalk and bagasse.
Preferably, the concentration of the citrate buffer described in step (2) is 50mmol/L, and pH is 4.8.
Preferably, the cellulase described in step (2) adopts the commercialization cellulase that derives from Trichodermareesei (Trichoderma reesei).
The present invention compared with prior art, has advantages of as follows:
1) the present invention's [choline] [amino acid] ionic liquid aqueous solution used has low toxicity, environmental protection, the feature such as renewable, biodegradable, therefore take the pre-treatment solvent that this solvent is lignocellulose, pretreatment technology environmental friendliness, meet Green Chemistry development strategy.
2) in the present invention's pre-treatment solvent used, contain a large amount of moisture, therefore this pretreatment technology has superpower water tolerance, therefore before pre-treatment, without ionic liquid and lignocellulose are dried, simplified technological process, and greatly reduced energy consumption.
3) in the ionic liquid that the present invention is relatively high in price, viscosity is larger, add a certain amount of, cheap, low viscous water, can not only effectively reduce system viscosity, handled easily, and will greatly reduce the consumption of ionic liquid, thus reduce costs.Meanwhile, add a certain amount of water can effectively regulate the pre-treatment intensity (ionic liquid alkalescence) of ionic liquid, the loss of lowering hemicellulose, improves reducing sugar yield.
4) utilization of the present invention [choline] [amino acid] ionic liquid aqueous solution, as lignocellulose pre-treatment solvent, has significantly strengthened the enzymolysis of lignocellulose, has improved fermentable reducing sugar (glucose and wood sugar) yield.
Accompanying drawing explanation
Fig. 1 is liquid chromatogram after the pretreated raw material enzymolysis of embodiment 1 12h (glucose and wood sugar retention time are respectively 12.0 and 12.9min).
Embodiment
By embodiment, further illustrate the present invention, but be not limited only to embodiment, the amino acid in following examples [choline] [amino acid] used is L-type.
Embodiment 1
50wt%[choline] [glycine] aqueous solution pretreated water rice straw
A) pre-treatment: accurate weighing 150mg rice straw powder (150 ~ 350 μ m) and 3g[choline] (ionic liquid content is 50wt% to [glycine] ionic liquid aqueous solution; Ionic liquid is synthetic according to the described method of document [Green Chem, 2012,14,304]), be jointly placed in 15mL triangular flask, under nitrogen protection, under 90 ° of C, stir 12 hours; Be cooled to subsequently room temperature, add 1 times of pre-treatment solvent volume deionized water dilution, filter, then use the deionized water wash filter residue 5 times of 3 times of volumes, filter residue obtains pretreated rice straw after drying.
B) enzymolysis: the above-mentioned pretreated rice straw 20mg of accurate weighing, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 245U derive from the cellulase (being purchased from Sigma-Aldrich China Branch) of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration (color atlas is shown in accompanying drawing 1).According to the theoretical yield of glucose in rice straw before pre-treatment and wood sugar and document (Biotechnol Bioeng, 2012, the correlation formula in 109:2484), calculates final glucose and xylose yield and is respectively 82% and 49%.
Embodiment 2
50wt%[choline] [tryptophane] aqueous solution pretreated water rice straw
A) pre-treatment: accurate weighing 150mg rice straw powder (150 ~ 350 μ m) and 3g[choline] [tryptophane] ionic liquid aqueous solution (ionic liquid content is 50wt%), jointly be placed in 15mL triangular flask, under nitrogen protection, under 90 ° of C, stir 12 hours; Be cooled to subsequently room temperature, add 2 times of pre-treatment solvent volume deionized water dilution, filter, then use the deionized water wash filter residue 5 times of 3 times of volumes, filter residue obtains pretreated rice straw after drying.
B) enzymolysis: the above-mentioned pretreated rice straw 20mg of accurate weighing, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 245U derive from the cellulase of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in rice straw before pre-treatment and wood sugar, calculate final glucose and xylose yield and be respectively 81% and 45%.
Embodiment 3
50wt%[choline] [phenylalanine] aqueous solution pretreated water rice straw
A) pre-treatment: accurate weighing 150mg rice straw powder (150 ~ 350 μ m) and 3g[choline] [phenylalanine] ionic liquid aqueous solution (ionic liquid content is 50wt%), jointly be placed in 15mL triangular flask, under nitrogen protection, under 90 ° of C, stir 12 hours; Be cooled to subsequently room temperature, add 1 times of pre-treatment solvent volume deionized water dilution, filter, then use the deionized water wash filter residue 5 times of 3 times of volumes, filter residue obtains pretreated rice straw after drying.
B) enzymolysis: the above-mentioned pretreated rice straw 20mg of accurate weighing, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 245U derive from the cellulase of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in rice straw before pre-treatment and wood sugar, calculate final glucose and xylose yield and be respectively 82% and 48%.
Embodiment 4
50wt%[choline] [Methionin] aqueous solution pretreated water rice straw
A) pre-treatment: accurate weighing 150mg rice straw powder (150 ~ 350 μ m) and 3g[choline] [Methionin] ionic liquid aqueous solution (ionic liquid content is 50wt%), jointly be placed in 15mL triangular flask, under nitrogen protection, under 90 ° of C, stir 12 hours; Be cooled to subsequently room temperature, add 1 times of pre-treatment solvent volume deionized water dilution, filter, then use the deionized water wash filter residue 5 times of 3 times of volumes, filter residue obtains pretreated rice straw after drying.
B) enzymolysis: the above-mentioned pretreated rice straw 20mg of accurate weighing, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 245U derive from the cellulase of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in rice straw before pre-treatment and wood sugar, calculate final glucose and xylose yield and be respectively 86% and 48%.
Embodiment 5
5wt%[choline] [Methionin] aqueous solution pretreated water rice straw
A) pre-treatment: accurate weighing 150mg rice straw powder (150 ~ 350 μ m) and 3g[choline] [Methionin] ionic liquid aqueous solution (ionic liquid content 5wt%), be jointly placed in 15mL triangular flask, under nitrogen protection, under 90 ° of C, stir 12 hours; Be cooled to subsequently room temperature, filter, then use the deionized water wash filter residue 5 times of 3 times of pre-treatment solvent volume, filter residue obtains pretreated rice straw after drying.
B) enzymolysis: the above-mentioned pretreated rice straw 20mg of accurate weighing, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 245U derive from the cellulase of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in rice straw before pre-treatment and wood sugar, calculate final glucose and xylose yield and be respectively 82% and 48%.
Embodiment 6
20wt%[choline] [Methionin] aqueous solution pretreated water rice straw
A) pre-treatment: accurate weighing 150mg rice straw powder (150 ~ 350 μ m) and 3g[choline] [Methionin] ionic liquid aqueous solution (ionic liquid content is 20wt%), jointly be placed in 15mL triangular flask, under nitrogen protection, under 60 ° of C, stir 12 hours; Be cooled to subsequently room temperature, filter, then use the deionized water wash filter residue 5 times of 3 times of pre-treatment solvent volume, filter residue obtains pretreated rice straw after drying.
B) enzymolysis: the above-mentioned pretreated rice straw 20mg of accurate weighing, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 245U derive from the cellulase of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in rice straw before pre-treatment and wood sugar, calculate final glucose and xylose yield and be respectively 82% and 50%.
Embodiment 7
20wt%[choline] [Methionin] aqueous solution pretreated water rice straw
A) pre-treatment: accurate weighing 150mg rice straw powder (150 ~ 350 μ m) and 3g[choline] [Methionin] ionic liquid aqueous solution (ionic liquid content is 20wt%), jointly be placed in 15mL triangular flask, under nitrogen protection, under 90 ° of C, stir 1 hour; Be cooled to subsequently room temperature, filter, then use the deionized water wash filter residue 5 times of 3 times of pre-treatment solvent volume, filter residue obtains pretreated rice straw after drying.
B) enzymolysis: the above-mentioned pretreated rice straw 20mg of accurate weighing, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 245U derive from the cellulase of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in rice straw before pre-treatment and wood sugar, calculate final glucose and xylose yield and be respectively 81% and 48%.
80wt%[choline] [Methionin] aqueous solution pre-treatment bagasse
A) pre-treatment: accurate weighing 400mg bagasse and 8g[choline] [Methionin] ionic liquid aqueous solution (ionic liquid content is 80wt%), be jointly placed in 50mL triangular flask, under nitrogen protection, under 90 ° of C, stir 6 hours; Be cooled to subsequently room temperature, add 2 times of pre-treatment solvent volume deionized water dilution, filter, then use the deionized water wash filter residue 5 times of 3 times of volumes, filter residue obtains pretreated rice straw after drying.
B) enzymolysis: the above-mentioned pretreated bagasse 20mg of accurate weighing, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 122.5U derive from the cellulase of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in bagasse before pre-treatment and wood sugar, calculate final glucose and xylose yield and be respectively 84% and 56%.
Embodiment 9
20wt%[choline] [Methionin] aqueous solution pre-treatment bagasse
A) pre-treatment: accurate weighing 1.2g bagasse and 12g[choline] [Methionin] ionic liquid aqueous solution (ionic liquid content is 20wt%), be jointly placed in 50mL triangular flask, under nitrogen protection, under 90 ° of C, stir 6 hours; Be cooled to subsequently room temperature, filter, then use the deionized water wash filter residue 5 times of 3 times of volumes, filter residue obtains pretreated rice straw after drying.
B) enzymolysis: the above-mentioned pretreated bagasse 20mg of accurate weighing, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 122.5U derive from the cellulase of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in bagasse before pre-treatment and wood sugar, calculate final glucose and xylose yield and be respectively 74% and 54%.
Embodiment 10
50wt%[choline] [Methionin] aqueous solution pre-treatment bagasse
A) pre-treatment: accurate weighing 2.5g bagasse and 50g[choline] [Methionin] ionic liquid aqueous solution (ionic liquid content is 50wt%), be jointly placed in 125mL triangular flask, under nitrogen protection, under 90 ° of C, stir 6 hours; Be cooled to subsequently room temperature, add 1 times of pre-treatment solvent volume deionized water dilution, filter, then use the deionized water wash filter residue 5 times of 3 times of volumes, filter residue obtains pretreated rice straw after drying.
B) enzymolysis: the above-mentioned pretreated bagasse 20mg of accurate weighing, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 122.5U derive from the cellulase of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in bagasse before pre-treatment and wood sugar, calculate final glucose and xylose yield and be respectively 80% and 84%.
Embodiment 11
50wt%[choline] [glycine] aqueous solution pre-treatment maize straw
A) pre-treatment: accurate weighing 150mg maize straw powder (150 ~ 350 μ m) and 3g[choline] [glycine] ionic liquid aqueous solution (ionic liquid content is 50wt%), jointly be placed in 15mL triangular flask, under nitrogen protection, under 90 ° of C, stir 12 hours; Be cooled to subsequently room temperature, add 1 times of pre-treatment solvent volume deionized water dilution, filter, then use the deionized water wash filter residue 5 times of 3 times of volumes, filter residue obtains pretreated rice straw after drying.
B) enzymolysis: the above-mentioned pretreated maize straw 20mg of accurate weighing, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 245U derive from the cellulase of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in maize straw before pre-treatment and wood sugar, calculate final glucose and xylose yield and be respectively 80% and 50%.
Embodiment 12
50wt%[choline] [Methionin] aqueous solution pre-treatment corn cob
A) pre-treatment: accurate weighing 150mg corn cob powder (150 ~ 350 μ m) and 3g[choline] [Methionin] ionic liquid aqueous solution (ionic liquid content is 50wt%), jointly be placed in 15mL triangular flask, under nitrogen protection, under 80 ° of C, stir 12 hours; Be cooled to subsequently room temperature, add 1 times of pre-treatment solvent volume deionized water dilution, filter, then use the deionized water wash filter residue 5 times of 3 times of volumes, filter residue obtains pretreated rice straw after drying.
B) enzymolysis: the above-mentioned pretreated corn cob 20mg of accurate weighing, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 122.5U derive from the cellulase of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in corn cob before pre-treatment and wood sugar, calculate final glucose and xylose yield and be respectively 83% and 56%.
Comparative example 1
Not pretreated rice straw enzymolysis
The not pretreated rice straw of accurate weighing 20mg (150 ~ 350 μ m), be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 245U derive from the cellulase of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in rice straw and wood sugar, calculate final glucose and xylose yield and be respectively 20% and 7%.
Comparative example 2
Not pretreated bagasse enzymolysis
The not pretreated bagasse of accurate weighing 20mg, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 122.5U to derive from the cellulase of Trichodermareesei, seal in the constant temperature oscillator that is placed on 200r/min, 50 ° of C and react.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in bagasse and wood sugar, calculate final glucose and xylose yield and be respectively 26% and 6%.
Comparative example 3
[choline] [Methionin] ionic liquid pretreatment bagasse
A) pre-treatment: the bagasse that accurate weighing 400mg is dry and 8g[choline] [Methionin] ionic liquid (water-content is lower than 1%), be jointly placed in 50mL triangular flask, under nitrogen protection, under 90 ° of C, stir 6 hours; Be cooled to subsequently room temperature, add 3 times of pre-treatment solvent volume deionized water dilution, filter, then use the deionized water wash filter residue 5 times of 3 times of pre-treatment solvent volume, filter residue obtains pretreated rice straw after drying.
B) enzymolysis: the above-mentioned pretreated bagasse 20mg of accurate weighing, be placed in the triangular flask of 50mL, add 7mL citrate buffer (50mmol/L, pH4.8) and 122.5U derive from the cellulase of Trichodermareesei, sealing is placed in the constant temperature oscillator of 200r/min, 50 ° of C reacts.After 12h, sampling 200 μ L process 5 minutes with cancellation enzyme reaction under 100 ° of C; After centrifugal (10000g), utilize high-performance liquid chromatogram determination glucose and xylose concentration.According to the theoretical yield of glucose in rice straw before pre-treatment and wood sugar, calculate final glucose and xylose yield and be respectively 82% and 48%.
Claims (9)
1. a method of utilizing renewable ionic liquid aqueous solution preprocessing lignocellulose, is characterized in that, comprises the steps:
(1) aqueous solution of [choline] [amino acid] ionic liquid of take is pre-treatment solvent, under nitrogen protection, according to lignocellulose, be 1:5 ~ 1:25 mixing lignocellulose and pre-treatment solvent with pre-treatment solvent quality ratio, at 50 ~ 120 ℃, stir 0.5 ~ 24 hour, be cooled to subsequently room temperature, filter, wash filter residue, the dry rear pretreated lignocellulose that obtains;
(2) take pretreated lignocellulose, according to solid-to-liquid ratio, be that 1 ~ 6mg/mL adds citrate buffer, according to the ratio of lignocellulose after 5 ~ 30U/mg pre-treatment, add cellulase again, at 150 ~ 250r/min, at 40 ~ 60 ℃, react after 3 ~ 12h, obtain and take the liquid glucose that glucose and xylose is main component.
2. method according to claim 1, is characterized in that: [choline] [amino acid] ionic liquid described in step (1) be take choline as positively charged ion, natural amino acid be anion ion liquid.
3. method according to claim 2, is characterized in that: described natural amino acid is a kind of in L-glycine, ALANINE, Serine, L-threonine, Valine, L-Leu, ILE, L-Methionine, L-Phe, L-PROLINE, L-Trp, L-Aspartic acid, altheine, Pidolidone, L-glutaminate, 1B, L-arginine and L-Histidine.
4. according to the method described in claim 1 or 2 or 3, it is characterized in that: the content of [choline] [amino acid] ionic liquid aqueous solution intermediate ion liquid described in step (1) is 5 ~ 95wt%.
5. according to the method described in claim 1 or 2 or 3, it is characterized in that: in step (1), when the content >=50wt% of [choline] [amino acid] ionic liquid aqueous solution intermediate ion liquid, before filtering, add deionized water to dilute.
6. method according to claim 5, is characterized in that: the volume of described deionized water is 1 ~ 3 times of pre-treatment solvent volume.
7. according to the method described in claim 1 or 2 or 3, it is characterized in that: described lignocellulose is a kind of in rice straw, maize straw, corn cob, wheat stalk and bagasse.
8. according to the method described in claim 1 or 2 or 3, it is characterized in that: the concentration of the citrate buffer described in step (2) is 50mmol/L, pH is 4.8.
9. according to the method described in claim 1 or 2 or 3, it is characterized in that: the cellulase described in step (2) adopts the cellulase that derives from Trichodermareesei (Trichoderma reesei).
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| CN104437633B (en) * | 2014-12-12 | 2016-08-24 | 江苏科技大学 | A kind of preparation method of mimic cellulose enzyme |
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| US20130252285A1 (en) * | 2010-09-22 | 2013-09-26 | The Regents Of The University Of California | Ionic liquid pretreatment of cellulosic biomass: enzymatic hydrolysis and ionic liquid recycle |
| CN102533907B (en) * | 2012-01-10 | 2014-07-16 | 华南理工大学 | Method for increasing enzymolysis efficiency of rice straws through choline and amino acid ionic liquid pretreatment |
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