CN105755883A - Method for improving lignocellulose raw material enzymolysis efficiency and lignose recovery rate - Google Patents
Method for improving lignocellulose raw material enzymolysis efficiency and lignose recovery rate Download PDFInfo
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- CN105755883A CN105755883A CN201610096432.6A CN201610096432A CN105755883A CN 105755883 A CN105755883 A CN 105755883A CN 201610096432 A CN201610096432 A CN 201610096432A CN 105755883 A CN105755883 A CN 105755883A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21C—PRODUCTION OF CELLULOSE BY REMOVING NON-CELLULOSE SUBSTANCES FROM CELLULOSE-CONTAINING MATERIALS; REGENERATION OF PULPING LIQUORS; APPARATUS THEREFOR
- D21C5/00—Other processes for obtaining cellulose, e.g. cooking cotton linters ; Processes characterised by the choice of cellulose-containing starting materials
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Abstract
The invention provides a method for improving lignocellulose raw material (especially bamboo reed fiber raw material) enzymolysis efficiency and lignose recovery rate. According to the method provided by the invention, through methods of ionic liquid dissolving, solid acid catalyzing and raw material regenerating by an acetone water solvent, compact cell wall structures of bamboo reeds are broken, and regenerative raw materials with rough fiber surface and II crystal form cellulose are obtained, so that the problem that liquid acid catalytic-ion liquid is difficult to recycle is solved, and the bamboo reeds can be utilized for high value; lignose powder is recycled with higher yield through heating, decompressing and distilling, so that the problem that ionic liquid lignose is difficult to recycle is solved, and the time for lignose recycle is shortened; a pre-processing and seperation method is simple and convenient to operate; the used reagents can be recycled and reused so as to be green and environmentally friendly; the recycle of acetone is favorable to environment protection and health of operators; the economic feasibility of ionic liquid pre-processing is improved.
Description
Technical field
The invention belongs to lignocellulosic material pretreatment and separation technology field, particularly relate to a kind of method improving Arundo donax fibrous raw material enzymolysis efficiency and lignin recovery rate.
Background technology
Along with the appearance of the worsening shortages of fossil energy and the brought devastating disaster of greenhouse effect, adopt saccharide crops continuable, reproducible or lignocellulose raw material or algal biomass to produce thing alcohol fuel substitute fossil fuels next life and be increasingly subject to people's attention.Alcohol fuel can pass through multiple the lignocellulose raw material such as agriculture and forestry organic waste material such as corn straw, energy-source plant, bagasse or the crops such as Semen Maydis, Caulis Sacchari sinensis or algae fermentation obtains, and plays an important role in alleviating petroleum resources shortage, improving ecological and environmental quality etc..
Secondary alcohol fuel is with wood fibre for raw material, and raw material sources are extensive, technology maturation, have broad application prospects.Lignocellulose raw material is mainly made up of cellulose, lignin and hemicellulose.This three big component structure is complicated, and three is interweaved, and defines the anti-degraded barrier of natural plant.And effective pretreatment can the natural anti-degraded barrier of broken biological matter, improve enzymolysis, saccharification efficiency.Therefore, the production of alcohol fuel generally goes through two steps: one is, by pretreatment, renewable biomass is hydrolyzed to form saccharide；Two is that saccharide produces bio-ethanol through yeast fermentation.
Conventional biomass pretreatment chemical method has acid treatment, alkali process, ozone decomposed, ammonia fiber explosion, ammonia circulation infiltration pretreatment, ion liquid dissolving etc..Wherein, ionic liquid pretreatment is a kind of relatively new preconditioning technique, and it has important advantages in that reagent low toxicity, and adaptability to raw material is extensive, it is believed that be one of the most promising preprocess method.Ionic liquid is a kind of at room temperature melted salt, and 100% by anion and cation composition, has the premium properties such as good solvent, highly polar, non-volatile, difficult oxidized, water and air is stable and composition designability.In many ionic liquids, 1-butyl-3-Methylimidazole. acetate [Emim] [OAc] is considered as the best ionic liquid of pretreating effect.But, [Emim] [OAc] fancy price (90RMB/g) prevents its further industrialized utilization.
Reducing one of ionic liquid pretreatment cost way is industrialization ionic liquid such as 1-butyl-3-Methylimidazole. villaumite [Bmim] Cl adopting price relatively low as far as possible, and by adding the enzymolysis efficiency of [Bmim] Cl that acid catalysis improves.Liquid acid is HCl such as, H2SO4Deng catalytic ionic liquid pretreated feedstock, there is good effect.Another approach reducing ionic liquid pretreatment cost is to reclaim xylogen by-product.Ionic liquid physical ability is partly dissolved lignin, if number of patent application is the published method such as CN201410586525.8, CN201410551903.9, CN201110059319.8.Current ionic liquid lignin recovery method has solvent separation, two-phase extraction, membrane filtration etc..For acetone separation method, it is generally adopted acetone after obtaining acetone lignin liquor and volatilizees in natural environment the method promoting lignin to precipitate out.
But above-mentioned prior art is when at least having the disadvantage in that existing acid catalysis ionic liquid pretreatment for improving fibrous raw material enzymolysis efficiency, strong acid danger is high, the rotproofness of reactor is required higher, and after pretreatment, acid hydrolysis solution needs to neutralize with substantial amounts of alkali, there is the difficult problems such as recovery difficulty.It is high that two-phase extraction and membrane filtration reclaim lignin cost, and the hydrogen bond that under normal temperature condition, ionic liquid and lignin are formed not easily is destroyed, and causes that acetone separation efficiency is low, and acetone is volatilize under natural environment, and the volatilization time is long, and acetone cannot reclaim use substantially.Acetone evaporates in air, and serious harm staff's is healthy.Therefore a kind of new method improving cellulose material enzymolysis efficiency and lignin recovery rate of exploitation it is badly in need of.
Summary of the invention
In order to solve problem of the prior art, according to an aspect of the present invention, the invention provides a kind of method improving lignocellulosic material enzymolysis efficiency and lignin recovery rate, described method includes:
(1) lignocellulosic material is pulverized, form the feed particulate material that granularity is 80～100 orders；
(2) being dissolved in ionic liquid by described feed particulate material, the mass ratio obtaining the ionic liquid serosity of lignocellulosic material, described raw material and ionic liquid is 1:10～30, and dissolution time is 2～4h, and solution temperature is 90～150 DEG C；
(3) adding particle diameter is that 14 orders solid acid to 35 orders carries out catalytic reaction in the ionic liquid serosity of described lignocellulosic material, obtain lignocellulosic material ionic liquid mixed serum, in described mixed serum, the mass percent mark of solid acid is 1% to 3%, catalytic temperature is 90～150 DEG C, and catalysis time is 0.5～1.5h；
(4) by step 3) in the mixed serum that is obtained by reacting pour 1 to 5 times into, it is preferred to the anti-phase reagent regeneration of 3 times of volumes, centrifugal, it is thus achieved that thick reconstituted wood cellulosic material and ionic liquid lignin liquor；
(5) by described thick reconstituted wood cellulosic material hot wash 4-6 time, dry, obtain reconstituted wood cellulosic material and solid acid, then adopt the sieve of 60 order～80 orders to sieve, to reclaim solid acid；
(6) described ionic liquid lignin liquor after heated and stirred a period of time, is reduced pressure and distills, reclaim anti-phase solvent at 50 to 70 DEG C, centrifugal, obtain lignin crude extract, continue to reduce pressure Distillation recovery ionic liquid to the centrifugal liquid obtained again；
(7) by step 6) in the described lignin crude extract that obtains through 1 to 5 deionized water wash, precipitation, filter, dry, obtain lignin powder.
Preferably, in described step (1), described lignocellulosic material is selected from corn straw, wheat straw waste, rice straw, switchgrass, Miscanthus and bagasse, wood chip, wood sawdust and bark, bamboo, waste paper, litter decoration or Arundo donax, it is preferred to Arundo donax.
Preferably, in described step (2), the mass ratio of described lignocellulosic material and ionic liquid is 1:19 to 1:20, and solution temperature is 120 DEG C, and dissolution time is 3h.
Preferably, in described step (3), in described mixed serum, the mass percent mark of solid acid is 1%, and catalytic temperature is 120 DEG C, and catalysis time is 1.5h.
Preferably, in described step (4), described anti-phase solvent is one or more in water, acetone, ethanol and methanol, it is preferred to the mixture of water and acetone.When the mixture of employing water and acetone is as anti-phase solvent, wherein the percent by volume of acetone is preferably 25%-75%, it is preferred to 50%.
Preferably, in described step (5), described solid acid is selected from Amberlyst35DRY, Amberlyst15DRY, Amberlyst35, Amberlyst70, Nafion, γ-Al2O3In one or more, it is preferred to Amberlyst35DRY.
Preferably, in described step (6), heated and stirred temperature is 60 DEG C；When reclaiming anti-phase solvent, the relative vacuum degree of decompression distillation is-0.095～-0.098MPa, and temperature is 50 DEG C；Reclaiming the relative vacuum degree of decompression distillation during ionic liquid is-1.005～-1.012MPa, and temperature is 85 DEG C.
Preferably, in described step (7), described lignin crude extract is through 4 deionized water wash.
Preferably, described ionic liquid is the most cheap technical grade glyoxaline ion liquid, more preferably 1-butyl-3-methyl villaumite ([Bmim] Cl).
Preferably, method according to the present invention does not adopt alkali, liquid acid etc. as catalyst, does not adopt organic solvent as environmentally harmful in acetonitrile, dimethyl sulfoxide or the like.
Beneficial effect
The method according to the invention passes through the method for ion liquid dissolving, solid acid catalysis, acetone aqueous solvent regenerative raw materials, break the cell wall structure that Arundo donax is fine and close, obtain fiber surface coarse, the regenerative raw materials of crystal form of cellulose II, solve the problem that liquid acid catalytic ionic liquids recovery is difficult, make Arundo donax obtain higher value application；Heating decompression is distilled relatively high yield pulp1 recovery and is obtained lignin powder, solves the problem that ionic liquid lignin recovery is difficult, shortens the time of lignin recovery；Pretreatment and separation method are simple to operation；The all recyclable recycling of agents useful for same, environmental protection；The recovery of acetone is conducive to the health of environmental protection and operator；Improve the economic feasibility of ionic liquid pretreatment.
Detailed description of the invention
Arundo donax is perennial energy-source plant, and yield is big, distribution is wide, strong adaptability, it is easy to plantation, and content of cellulose is high, but owing to cell wall structure is fine and close, it is more difficult to utilize to break.The method according to the invention is particularly suitable for Arundo donax as raw material, because have employed ionic liquid and solid acid, it is possible to effectively breaks the fibre wall structure of Arundo donax, and is used.
In method according to the present invention, the particle diameter of described lignocellulosic material is more little, and it is more big with the contact area of extracting solution, is conducive to improving dissolved efficiency；But when described raw material particle size little to a certain extent after easily reunite, be unfavorable on the contrary being fully contacted with ionic liquid.The particle diameter of described raw material is unsuitable excessive, it is to avoid the generation of the problems such as solid acid and regenerative raw materials separation difficulty.Consider that swollen can occur raw material after pretreatment, it is experimentally confirmed, when the granularity of feed particulate material described in the method according to the invention is 80～100 order, both can guarantee that described feed particulate material and extracting solution were fully contacted, agglomeration is avoided to occur, it is easy to again in subsequent treatment and utilizes screening, separate solid acid and regenerative raw materials, be conducive to improving reaction efficiency.
In method according to the present invention, described ionic liquid is the most cheap technical grade glyoxaline ion liquid, more preferably 1-butyl-3-methyl villaumite ([Bmim] Cl), is solvent and the reaction medium of lignocellulose raw material.[Bmim] Cl dissolves cellulosic best solvent.Therefore, adopting ion liquid dissolving fibrous raw material to form serosity is conducive to the site, acid site of solid acid to contact with Arundo donax cellulose.Preferably, described lignocellulose raw material is 1:10～30 with the mass ratio of ionic liquid, it is preferable that 1:19 to 1:20；Dissolution time is 2～4h, it is preferable that 3h；Solution temperature is 90～150 DEG C.When the mass ratio of lignocellulose raw material and ionic liquid is less than 1:10, owing to lignocellulose raw material is excessive, lignocellulose raw material can not form serosity with ionic liquid well, causes the catalytic reaction that the later stage contacts with solid acid not ideal enough；When the mass ratio of lignocellulose raw material and ionic liquid is more than 1:30, ionic liquid is excessive, cost increase, is unfavorable for that heavy industrialization utilizes.
In method according to the present invention, described solid acid can be commercially available solid acid, can be such as the solid acid of purchased from American DOW Chemical, such as Amberlyst35DRY, Amberlyst15DRY, Amberlyst35, Amberlyst70, Nafion, γ-Al2O3In one or more, it is preferred to Amberlyst35DRY.Described solid acid Amberlyst35DRY is a kind of Bronsted acid resin, and spherical in solid, particle diameter is between 0.3～1.18mm, and acid site concentration is more than 5eq/kg, and maximum allowable operating temperature (M.A.O.T.) is 150 DEG C, is widely used in water purification process, is conveniently easy to get.Adopt the solid acid particles of 60 to 80 mesh sieve screenings for catalysis, be beneficial to separating of solid acid and raw material.Based on the gross weight of described mixed serum, the mass fraction of described solid acid is 1%～3%, it is preferable that 1%；Catalysis time is 0.5～1.5h；Catalytic temperature is 90～150 DEG C, it is possible to keep consistent with solution temperature.
Anti-phase solvent, for instance water, acetone, ethanol and methanol etc., can promote the cellulosic material that ion liquid system dissolves to regenerate, precipitate, it is thus achieved that regenerative component, wherein the regeneration effect of water and acetone is best.In method according to the present invention, described anti-phase solvent is one or more in water, acetone, ethanol and methanol, it is preferred to the mixture of water and acetone.When the mixture of employing water and acetone is as anti-phase solvent, wherein the percent by volume of acetone is preferably 25%-75%, it is preferred to 50%.Further, in method according to the present invention, adopt the anti-phase solvent of relative 1 to 5 times of volume of mixed serum because so can recycled fiber sources preferably, the waste of resource can be avoided again.
Step 5 in method according to the present invention) in, thick regeneration Arundo donax fibrous raw material contains ionic liquid residue, and subsequent fiber element enzyme can be suppressed the enzyme hydrolysis of fibrous raw material and last sweat.Owing to described ionic liquid fusing point is between 70～80 DEG C, hot wash is adopted to be easier to remove ionic liquid.Adopt the clear liquid after UV spectrophotometer measuring washing subsequently, when the clear liquid light absorption value at 280nm absworption peak place less than 1 namely it is believed that washes clean.It is said that in general, wash 4～6 times, it is preferable that 5 times.Possibly together with solid acid in thick regeneration Arundo donax fibrous raw material, after lyophilization is complete, solid acid is widely distributed in the feed.Adopting the mode of screening, the sieve taking 60 orders screens, i.e. separable solid acid and regenerative raw materials.Solid acid still can be recycled repeatedly, can effectively reduce cost and environmental protection after reclaiming.Fibrous raw material is after effectively dissolving regeneration, and cellulose crystal formation changes, cellulose I become cellulose II, and occur swollen, surface to become coarse, be conducive to follow-up enzymolysis.
Step 6 in method according to the present invention) in, by described ionic liquid lignin liquor at 50 to 70 DEG C, heated and stirred 10～60 minutes at being preferably 60 DEG C, preferably after 20 minutes, decompression distillation, reclaims anti-phase solvent, centrifugal, obtaining lignin crude extract, continue to reduce pressure Distillation recovery ionic liquid to the centrifugal liquid obtained again.Wherein, the hydrogen bond that under normal temperature condition, ionic liquid and lignin are formed not easily is destroyed, and causes the difficult life of lignin, and the response rate is low.In order to destroy the hydrogen bond between ionic liquid and lignin as much as possible, being heated ionic liquid lignin liquor processing, heating-up temperature is 50～70 DEG C, after stirring 10～60min, carries out decompression distillation.Preferably 60 DEG C, stir 20min.After being distilled out of along with the solvent acetone in lignin liquor, lignin is precipitated gradually.After centrifugation goes out lignin deposit, ionic liquid-aqueous solution is carried out decompression distillation, with the moisture in deionizing liquid, finally reclaims ionic liquid.Owing to being bonded between ionic liquid with water is sufficiently stable, therefore relatively low vacuum can be adopted.After ionic liquid reclaims, performance is basically unchanged, and can be recycled.Preferably, when reclaiming anti-phase solvent, the relative vacuum degree of decompression distillation is-0.095～-0.098MPa, and temperature is 50 DEG C；Reclaiming the relative vacuum degree of decompression distillation during ionic liquid is-1.005～-1.012MPa, and temperature is 85 DEG C.
Hereinafter, will be described in detail the present invention.Before doing so, should be understood that, the term used in this description and in the appended claims should not be construed as and is limited to general sense and dictionary meanings, and should allow inventor suitably define term with carry out the principle of best interpretations basis on, make an explanation according to implication corresponding with the technical elements of the present invention and concept.Therefore, description presented herein, merely for the sake of the preferred embodiment illustrating purpose, is not meant to limit the scope of the present disclosure, thus should be understood that, when without departing from the spirit and scope of the present invention, it is possible to obtained other equivalents or improved procedure by it.
Following example are enumerated only as the example of embodiment of the present invention, and the present invention does not constitute any restriction, and the amendment that it will be appreciated by those skilled in the art that in the scope of the essence and design that not necessarily depart from the present invention each falls within protection scope of the present invention.
In following embodiment, agents useful for same is commercial products if no special instructions.
Embodiment 1
20g Arundo donax is pulverized, forms the feed particulate material of 80-100 order, standby.
Weighing ionic liquid 1-butyl-3-methyl imidazolium villaumite ([Bmim] Cl) 190g, put in round-bottomed flask, 150rpm is heated with stirring to 80 DEG C.Weigh graininess Arundo donax raw material 10g, put into gradually (graininess Arundo donax raw material and ionic liquid mass ratio are 1:19) in above-mentioned round-bottomed flask, after being warming up to 120 DEG C, be slowly stirred 3h.Subsequently, weigh 2g solid acid Amberlyst35DRY and join in above-mentioned round-bottomed flask, continue reaction 1.5h, obtain Arundo donax ionic liquid mixed serum.After reaction terminates into, described Arundo donax ionic liquid mixed serum is poured regeneration in the acetone-water solution that percent by volume is 50% that triploid is long-pending, centrifugal, it is thus achieved that thick regeneration Arundo donax fibrous raw material and ionic liquid lignin liquor.
With the hot deionized waters of about 80 DEG C, described thick regeneration Arundo donax fibrous raw material is washed 5 times, lyophilization, then screen with the sieve of 60 orders, reclaim solid acid, obtain regeneration Arundo donax fibrous raw material.The solid acid reclaimed can recycle further.When 20FPU cellulase/g substrate so that the regeneration Arundo donax fibrous raw material enzymolysis 48h arrived, monosaccharide yield reaches 87.5% (glucose relative to raw material), improves 7 times (12.5%) compared to untreated raw material.
Described ionic liquid lignin liquor is heated to 60 DEG C, stirs 20min, it is thus achieved that ionic liquid lignin hot solution.Being distilled in receiving bottle by described 50 DEG C of decompressions of ionic liquid lignin hot solution basic no liquid oozes.Centrifugal residue, it is thus achieved that lignin crude extract.Described lignin crude extract is washed 4 times, it is thus achieved that lignin powder 0.1030g.The ionic liquid aqueous solution reclaimed being carried out decompression moisture is distilled off, relative vacuum degree is-0.995MPa, and temperature is 90 DEG C, steams to not having moisture to steam always, and the ionic liquid response rate is 98.7%.
Embodiment 2
20g Arundo donax is pulverized, forms the feed particulate material of 80-100 order, standby.
Weighing ionic liquid 1-butyl-3-methyl imidazolium villaumite ([Bmim] Cl) 190g, put in round-bottomed flask, 150rpm is heated with stirring to 80 DEG C.Weigh graininess Arundo donax raw material 10g, put into gradually (graininess Arundo donax raw material and ionic liquid mass ratio are 1:19) in above-mentioned round-bottomed flask, after being warming up to 120 DEG C, be slowly stirred 3h.Subsequently, weigh 2g solid acid Amberlyst35DRY and join in above-mentioned round-bottomed flask, continue reaction 0.5h, obtain Arundo donax ionic liquid mixed serum.After reaction terminates into, described Arundo donax ionic liquid mixed serum is poured regeneration in the acetone-water solution that percent by volume is 50% that triploid is long-pending, centrifugal, it is thus achieved that thick regeneration Arundo donax fibrous raw material and ionic liquid lignin liquor.
With the hot deionized waters of about 80 DEG C, described thick regeneration Arundo donax fibrous raw material is washed 5 times, lyophilization, then screen with the sieve of 60 orders, reclaim solid acid, obtain regeneration Arundo donax fibrous raw material.The solid acid reclaimed can recycle further.When 20FPU cellulase/g substrate so that the regeneration Arundo donax fibrous raw material enzymolysis 48h arrived, monosaccharide yield reaches 73.0% (glucose relative to raw material), improves 5.84 times (12.5%) compared to untreated raw material.
Described ionic liquid lignin liquor is heated to 60 DEG C, stirs 20min, it is thus achieved that ionic liquid lignin hot solution.Being distilled in receiving bottle by described 50 DEG C of decompressions of ionic liquid lignin hot solution basic no liquid oozes.Centrifugal residue, it is thus achieved that lignin crude extract.Described lignin crude extract is washed 4 times, it is thus achieved that lignin powder 0.0863g.The ionic liquid aqueous solution reclaimed being carried out decompression moisture is distilled off, relative vacuum degree is-1.005MPa, and temperature is 85 DEG C, steams to not having moisture to steam always, and the ionic liquid response rate is 99.5%.
Embodiment 3
20g Arundo donax is pulverized, forms the feed particulate material of 80-100 order, standby.
Weighing ionic liquid 1-butyl-3-methyl imidazolium villaumite ([Bmim] Cl) 190g, put in round-bottomed flask, 150rpm is heated with stirring to 80 DEG C.Weigh graininess Arundo donax raw material 10g, put into gradually (graininess Arundo donax raw material and ionic liquid mass ratio are 1:19) in above-mentioned round-bottomed flask, after being warming up to 110 DEG C, be slowly stirred 3h.Subsequently, weigh 2g solid acid Amberlyst35DRY and join in above-mentioned round-bottomed flask, continue reaction 1h, obtain Arundo donax ionic liquid mixed serum.After reaction terminates into, described Arundo donax ionic liquid mixed serum is poured regeneration in the acetone-water solution that percent by volume is 50% that triploid is long-pending, centrifugal, it is thus achieved that thick regeneration Arundo donax fibrous raw material and ionic liquid lignin liquor.
With the hot deionized waters of about 80 DEG C, described thick regeneration Arundo donax fibrous raw material is washed 5 times, lyophilization, then screen with the sieve of 60 orders, reclaim solid acid, obtain regeneration Arundo donax fibrous raw material.The solid acid reclaimed can recycle further.When 20FPU cellulase/g substrate so that the regeneration Arundo donax fibrous raw material enzymolysis 48h arrived, monosaccharide yield reaches 66.1% (glucose relative to raw material), improves 5.29 times (12.5%) compared to untreated raw material.
Described ionic liquid lignin liquor is heated to 70 DEG C, stirs 30min, it is thus achieved that ionic liquid lignin hot solution.Being distilled in receiving bottle by described 50 DEG C of decompressions of ionic liquid lignin hot solution basic no liquid oozes.Centrifugal residue, it is thus achieved that lignin crude extract.Described lignin crude extract is washed 4 times, it is thus achieved that lignin powder 0.0947g.The ionic liquid aqueous solution reclaimed being carried out decompression moisture is distilled off, relative vacuum degree is-1.009MPa, and temperature is 80 DEG C, steams to not having moisture to steam always, and the ionic liquid response rate is 98.9%.
Embodiment 4
20g Arundo donax is pulverized, forms the feed particulate material of 80-100 order, standby.
Weighing ionic liquid 1-butyl-3-methyl imidazolium villaumite ([Bmim] Cl) 190g, put in round-bottomed flask, 150rpm is heated with stirring to 80 DEG C.Weigh graininess Arundo donax raw material 10g, put into gradually (graininess Arundo donax raw material and ionic liquid mass ratio are 1:19) in above-mentioned round-bottomed flask, after being warming up to 150 DEG C, be slowly stirred 3h.Subsequently, weigh 2g solid acid Amberlyst35DRY and join in above-mentioned round-bottomed flask, continue reaction 0.5h, obtain Arundo donax ionic liquid mixed serum.After reaction terminates into, described Arundo donax ionic liquid mixed serum is poured regeneration in the acetone-water solution that percent by volume is 50% that triploid is long-pending, centrifugal, it is thus achieved that thick regeneration Arundo donax fibrous raw material and ionic liquid lignin liquor.
With the hot deionized waters of about 80 DEG C, described thick regeneration Arundo donax fibrous raw material is washed 5 times, lyophilization, then screen with the sieve of 60 orders, reclaim solid acid, obtain regeneration Arundo donax fibrous raw material.The solid acid reclaimed can recycle further.When 20FPU cellulase/g substrate so that the regeneration Arundo donax fibrous raw material enzymolysis 48h arrived, monosaccharide yield reaches 40.0% (glucose relative to raw material), improves 3.20 times (12.5%) compared to untreated raw material.
Described ionic liquid lignin liquor is heated to 60 DEG C, stirs 40min, it is thus achieved that ionic liquid lignin hot solution.Being distilled in receiving bottle by described 50 DEG C of decompressions of ionic liquid lignin hot solution basic no liquid oozes.Centrifugal residue, it is thus achieved that lignin crude extract.Described lignin crude extract is washed 4 times, it is thus achieved that lignin powder 0.1586g.The ionic liquid aqueous solution reclaimed being carried out decompression moisture is distilled off, relative vacuum degree is-1.012MPa, and temperature is 90 DEG C, steams to not having moisture to steam always, and the ionic liquid response rate is 99.6%.
Embodiment 5
20g Arundo donax is pulverized, forms the feed particulate material of 80-100 order, standby.
Weighing ionic liquid 1-butyl-3-methyl imidazolium villaumite ([Bmim] Cl) 190g, put in round-bottomed flask, 150rpm is heated with stirring to 80 DEG C.Weigh graininess Arundo donax raw material 10g, put into gradually (graininess Arundo donax raw material and ionic liquid mass ratio are 1:19) in above-mentioned round-bottomed flask, after being warming up to 140 DEG C, be slowly stirred 3h.Subsequently, weigh 2g solid acid Amberlyst35DRY and join in above-mentioned round-bottomed flask, continue reaction 0.5h, obtain Arundo donax ionic liquid mixed serum.After reaction terminates into, described Arundo donax ionic liquid mixed serum is poured regeneration in the acetone-water solution that percent by volume is 50% that triploid is long-pending, centrifugal, it is thus achieved that thick regeneration Arundo donax fibrous raw material and ionic liquid lignin liquor.
With the hot deionized waters of about 80 DEG C, described thick regeneration Arundo donax fibrous raw material is washed 5 times, lyophilization, then screen with the sieve of 60 orders, reclaim solid acid, obtain regeneration Arundo donax fibrous raw material.The solid acid reclaimed can recycle further.When 20FPU cellulase/g substrate so that the regeneration Arundo donax fibrous raw material enzymolysis 48h arrived, monosaccharide yield reaches 68.5% (glucose relative to raw material), improves 5.48 times (12.5%) compared to untreated raw material.
Described ionic liquid lignin liquor is heated to 60 DEG C, stirs 30min, it is thus achieved that ionic liquid lignin hot solution.Being distilled in receiving bottle by described 50 DEG C of decompressions of ionic liquid lignin hot solution basic no liquid oozes.Centrifugal residue, it is thus achieved that lignin crude extract.Described lignin crude extract is washed 4 times, it is thus achieved that lignin powder 0.1003g.The ionic liquid aqueous solution reclaimed being carried out decompression moisture is distilled off, relative vacuum degree is-1.012MPa, and temperature is 85 DEG C, steams to not having moisture to steam always, and the ionic liquid response rate is 99.7%.
Claims (10)
1. improve lignocellulosic material enzymolysis efficiency and a method for lignin recovery rate, said method comprising the steps of:
(1) lignocellulosic material is pulverized, form the feed particulate material that granularity is 80～100 orders；
(2) being dissolved in ionic liquid by described feed particulate material, the mass ratio obtaining the ionic liquid serosity of lignocellulosic material, described raw material and ionic liquid is 1:10～30, and dissolution time is 2～4h, and solution temperature is 90～150 DEG C；
(3) adding particle diameter is that 14 orders solid acid to 35 orders carries out catalytic reaction in the ionic liquid serosity of described lignocellulosic material, obtain lignocellulosic material ionic liquid mixed serum, in described mixed serum, the mass percent mark of solid acid is 1% to 3%, catalytic temperature is 90～150 DEG C, and catalysis time is 0.5～1.5h；
(4) by step 3) in the mixed serum that is obtained by reacting pour 1 to 5 times into, it is preferred to the anti-phase reagent regeneration of 3 times of volumes, centrifugal, it is thus achieved that thick reconstituted wood cellulosic material and ionic liquid lignin liquor；
(5) by described thick reconstituted wood cellulosic material hot wash 4-6 time, dry, obtain reconstituted wood cellulosic material and solid acid, then adopt the sieve of 60 order～80 orders to sieve, to reclaim solid acid；
(6) described ionic liquid lignin liquor after heated and stirred a period of time, is reduced pressure and distills, reclaim anti-phase solvent at 50 to 70 DEG C, centrifugal, obtain lignin crude extract, continue to reduce pressure Distillation recovery ionic liquid to the centrifugal liquid obtained again；
(7) by step 6) in the described lignin crude extract that obtains through 1 to 5 deionized water wash, it is preferred to through 4 deionized water wash, then precipitate, filter, dry, obtain lignin powder.
2. method according to claim 1, it is characterized in that, in described step (1), described lignocellulosic material is selected from corn straw, wheat straw waste, rice straw, switchgrass, Miscanthus and bagasse, wood chip, wood sawdust and bark, bamboo, waste paper, litter decoration or Arundo donax, it is preferred to Arundo donax.
3. the mass ratio of method according to claim 1, it is characterised in that in described step (2), described lignocellulosic material and ionic liquid is 1:19 to 1:20, and solution temperature is 120 DEG C, and dissolution time is 3h.
4. method according to claim 1, it is characterised in that in described step (3), in described mixed serum, the mass percent mark of solid acid is 1%, and catalytic temperature is 120 DEG C, and catalysis time is 1.5h.
5. method according to claim 1, it is characterised in that in described step (4), described anti-phase solvent is one or more in water, acetone, ethanol and methanol, it is preferred to the mixture of water and acetone.
6. method according to claim 5, it is characterised in that when the mixture of employing water and acetone is as anti-phase solvent, wherein the percent by volume of acetone is 25%-75%, it is preferred to 50%.
7. method according to claim 1, it is characterised in that in described step (5), described solid acid is selected from Amberlyst35DRY, Amberlyst15DRY, Amberlyst35, Amberlyst70, Nafion, γ-Al2O3In one or more, it is preferred to Amberlyst35DRY.
8. method according to claim 1, it is characterised in that in described step (6), heated and stirred temperature is 60 DEG C；When reclaiming anti-phase solvent, the relative vacuum degree of decompression distillation is-0.095～-0.098MPa, and temperature is 50 DEG C；Reclaiming the relative vacuum degree of decompression distillation during ionic liquid is-1.005～-1.012MPa, and temperature is 85 DEG C.
9. method according to claim 1, it is characterised in that described ionic liquid is technical grade glyoxaline ion liquid, it is preferred to 1-butyl-3-methyl villaumite ([Bmim] Cl).
10. method according to claim 1, it is characterised in that described method does not adopt alkali, liquid acid etc. as catalyst, does not adopt the organic solvent such as acetonitrile or dimethyl sulfoxide etc..
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