CN101285106A - Process for preparing multicomponent liquid glucose and lignose while effectively hydrolyzing lignocellulosic biomass - Google Patents
Process for preparing multicomponent liquid glucose and lignose while effectively hydrolyzing lignocellulosic biomass Download PDFInfo
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Abstract
The invention discloses a method for efficiently hydrolyzing lignocellulosic biomass and synchronously preparing multi-component liquid glucose and lignin. The method comprises the steps that: the lignocellulosic biomass through physical crushing is added with phosphoric acid to perform acid hydrolysis; then organic solvent is added to extract the lignin, the layering and the phase separation are performed, then the lignin is extracted out while the organic solvent is reclaimed under the condition of pressure reduction and distillation; phosphoric acid can be reclaimed through steps such as neutralization, filtration, acidification and so on, hemicellulose hydrolyzed liquid glucose is obtained at the same time; and the remained cellulose undergoes the zymohydrolysis to prepare cellulosic hydrolyzed liquid glucose. The method can separate lignin, hemicellulose and cellulose, remarkably decreases the degree of crystallinity of the cellulose hydrolyzed by phosphoric acid, and remarkably improves the zymohydrolysis efficiency; and the prepared hydrolyzed liquid glucose does not contain fermentation inhibitors. The method has mild treatment conditions, simple process and less side reactions; the phosphoric acid and the organic solvent can both be reclaimed and circularly used; and the method is environment-friendly, and has broad social and economic benefits.
Description
Technical field
The invention belongs to technical field of bioengineering, relate to a kind of method of effectively hydrolyzing lignocellulosic biolobic material, can obtain cellulosic hydrolysate, hemicellulose hydrolysate and xylogen simultaneously.
Background technology
Lignocellulose-like biomass comprises waste and residuum (as agricultural crop straw, husk, corn cob, wheat bran, bagasse etc.), forest (cork and hardwood) and forestry processing waste, the careless class etc. of agriculture production, is renewable resources abundant, the most cheap on the earth.The main organic composition of lignocellulosic material comprises Mierocrystalline cellulose, hemicellulose and xylogen three parts, and wherein the polymer substance of the complexity that mainly is formed by connecting with β-1,4 glycosidic link by glucose molecule of Mierocrystalline cellulose can generate glucose through hydrolysis; Hemicellulose is made up of poly-pentose, hexosan and polyuronide, can generate wood sugar, pectinose, semi-lactosi etc. through hydrolysis; The natural high moleculer eompound that xylogen is made up of the phenyl-propane unit can be used for preparing Biodegradable material, also can be used as fuel.Deficient gradually along with global fossil resource, biorefinery becomes the important development direction, but present large biorefinery product for example ethanol, organic acid, amino acid, microbiotic etc. directly with foodstuff starch after liquefaction, saccharification are handled as fermentation raw material.Along with the production-scale continuous expansion of biorefinery, the demand of grain is increased sharply, and global staple food supply is nervous gradually, is unfavorable for the development of biorefinery industry.The annual agricultural wastes that form of China are up to 700,000,000 tons, wherein the overwhelming majority goes out of use or burns, if can be hydrolyzed into reducing sugar to a large amount of agriculture lignocellulosic materials and the Mierocrystalline cellulose in the industrial fiber waste material, hemicellulose cost-effectively, be used for the production of large biorefinery product, to help improving the situation of present resource anxiety, environmental degradation, China is set up recycling economy, realize that Sustainable development has important economy and social effect.
Present lignocellulose is hydrolyzed into reducing sugar and can be divided into acid hydrolysis and enzymic hydrolysis two class methods.Hemicellulose is combined between Mierocrystalline cellulose and the xylogen as the molecule tamanori in the lignocellulosic material; And the reticulated structure that xylogen has surrounds and adds set Mierocrystalline cellulose and hemicellulose as support frame, is unfavorable for cellulosic hydrolysis; Hemicellulose, xylogen and derivative thereof also have the obvious suppression effect to the activity of cellulase simultaneously; And cellulosic crystalline texture demonstrates rigidity and the cellulosic degraded of the serious obstruction of height water-insoluble.Therefore in utilizing the process of lignocellulose, must change the structure of natural cellulose, destroy the connection between Mierocrystalline cellulose-xylogen-hemicellulose, remove delignification and hemicellulose, reduce cellulosic degree of crystallinity, increase the sponginess of raw material.Wherein destroying cellulosic crystalline texture, make cellulosic structure loose, is the key that improves hydrolysis efficiency.
The lignocellulose acid hydrolysis process of patent report is divided into concentrated acid hydrolysis, dilute acid hydrolysis and organic acid hydrolysis method at present.(1) concentrated acid hydrolysis, the general vitriol oil and the concentrated hydrochloric acid of adopting, under lower temperature, carry out (as U.S. Pat 5562777), can destroy xylogen, hemicellulose and cellulosic key coat, hydrocellulose and hemicellulose, the sugar yield height, the fermentation inhibitor of by-product is less, in addition Chinese patent 01113751.7 adopt 8～20% the vitriol oil soak for a long time raw material (10～18 hours) carry out pyrohydrolysis again can single-minded ground degradation of hemicellulose.But the corrodibility of the vitriol oil, concentrated hydrochloric acid is strong, and is very high to the equipment material requirement, and seriously poison environment, and Separation and Recovery and reconcentration have then increased the complicacy and the cost of technology greatly.(2) dilute acid hydrolysis method, general dilute sulphuric acid, dilute hydrochloric acid, the rare nitric acid (as Chinese patent 200710029054.0,02145150.8) of adopting, at high temperature (100-220 ℃) carries out long-time hydrolysis, and dilute acid hydrolysis often only acts on hemicellulose, can not hydrocellulose, can not remove xylogen, the hydrolysis sugar productive rate generally is lower than 50%, and with the degraded of monose, by product is many, harmful to fermenting, need to adopt multiple poison-removing method, complex process.(3) organic acid hydrolysis, general lower boiling organic acid of employing such as trifluoroacetic acid, trifluoromethanesulfonic acid (as Chinese patent 200710037882.9), the degradable hemicellulose is oligose and monose, and by distillation recovery organic acid, but hydrolysis time is grown (1-12 hour), fluorine-containing organic acid toxicity is big, and trifluoroacetic acid, trifluoromethanesulfonic acid are residual big to fermentation harm.
Enzymic hydrolysis is to utilize the cellulase effectively hydrolyzing lignocellulosic, generates monose.The advantage of enzyme hydrolysis process is: can react at normal temperatures, hydrolysising by-product is few, and saccharification yield height does not produce harmful fermented material.But must Mierocrystalline cellulose be separated with xylogen, hemicellulose by pre-treatment, the inner hydrogen bond of crystal form Mierocrystalline cellulose is opened, become unformed Mierocrystalline cellulose, could improve the catalytic efficiency of cellulase.The preprocessing means of patent report comprises following method at present: (1) steam explosion, handle biomass material with high-pressure saturated steam (as U.S. Pat 4070232), suddenly decompression then, make raw material explosion degraded, cause the hemicellulose degraded, make the cellulose dissolution increase, but this method xylogen stripping is less, relate to the high pressure equipment, cost of investment is higher.(2) dilute acid pretreatment method, but diluted acid direct hydrolysis hemicellulose makes the raw material porous that becomes, the contact area that helps increased fiber element and cellulase, but because the cellulosic xylogen of parcel is failed effective elimination in the diluted acid treating processes, make matrix structure still tight, enzymolysis efficiency is still not high, still has a large amount of inhibition by products to produce in the preprocessing process, need to adopt multiple poison-removing method, complex process.(4) alkali method for pretreating can be dissolved in the characteristics of basic solution (as sodium hydroxide, ammonia soln) according to xylogen, utilizes OH
-Hydrogen bond between weakening Mierocrystalline cellulose and the hemicellulose and the ester bond between saponification hemicellulose and the lignin molecule, cause cellulosic degree of polymerization to reduce, degree of crystallinity descends, destroy the wherein structure of xylogen (as Chinese patent 200710175743.2), but need long-time high temperature steaming in the alkaline purification process, the sugar loss is more, and alkali can not reclaim, and also has problems such as neutralization, washing simultaneously.(5) organic solvent method, utilize xylogen to be soluble in organic solvent, after other method of employing has been destroyed xylogen and hemicellulose and cellulosic key coat, with an organic solvent extract xylogen, and by distillation recovery organic solvent, organic solvent commonly used comprises ethanol, methyl alcohol, acetone, acetate (as Chinese patent 200710029054.0,200710037882.9), but these solvents and water are miscible, the phase-splitting difficulty, solvent recovering rate is low, and xylogen purity is low, also has patent to adopt organic solvent high temperature steaming extraction xylogen (as Chinese patent 200710175743.2), time is long, the temperature height, energy consumption higher (100-200 ℃, 0.5-6 hour).(6) other pretreatment process, as ozonize, oxide treatment, biological treatment etc., but these methods are all immature because of technology, cost is too high or efficient is too low, lack competitiveness.
This shows, develop a kind of simple, eco-friendly high-efficient treatment method, with three kinds of main component Mierocrystalline celluloses, hemicellulose and lignin separation in the lignocellulose-like biomass and be used, the various reagents and the extraction agent that use can be recycled, reduce the processing cost of biomass material, to help the development of biorefinery industry, have great social significance and huge economic benefit.
Summary of the invention
Technical problem to be solved by this invention provides a kind of method of effectively hydrolyzing lignocellulosic biolobic material, can obtain cellulose hydrolysis liquid glucose, hydrolysis of hemicellulose liquid glucose and xylogen simultaneously.
For solving the problems of the technologies described above, thinking of the present invention is: pass through phosphoric acid hydrolysis, effectively destroy xylogen, hemicellulose and cellulosic key coat, reduce cellulosic degree of crystallinity, improve cellulosic hydrolysis efficiency, prepare high-quality cellulose hydrolysis liquid glucose, simultaneously separating lignin, hydrolysis of hemicellulose liquid glucose be as byproduct, and realize phosphoric acid and Recovery of Organic Solvent and recycle.Cellulose hydrolysis liquid glucose by this law preparation can be used as carbon source and is used for fermentation, and xylogen can be used for preparing material, and the hydrolysis of hemicellulose liquid glucose can be used for extracting wood sugar and prepares Xylitol, or is used for fermentation as carbon source.
Concrete technical scheme of the present invention is as follows:
A kind of effectively hydrolyzing lignocellulosic biolobic material prepares the method for polycomponent liquid glucose and xylogen simultaneously, it is characterized in that this method comprises the steps:
1, lignocellulose-like biomass being carried out physical pulverization handles;
2, adopt phosphoric acid that lignocellulose-like biomass is hydrolyzed;
3, in the reaction system of step 2, add organic solvent extraction;
4, the reaction system of step 3 gets cellulose solids after solid-liquid separation, and Mierocrystalline cellulose promptly obtains the cellulose hydrolysis liquid glucose through enzymic hydrolysis; The clear liquid part that the reaction system of step 3 obtains after solid-liquid separation is through standing demix, and organic phase reclaims organic solvent through distillation, promptly separates out xylogen, remaining water, and the phosphoric acid recovery with wherein promptly gets the hydrolysis of hemicellulose liquid glucose.
Wherein, described lignocellulose-like biomass is agroforestry wastes such as maize straw, corn cob, straw, wheat straw, bagasse or sawdust.
In the step 1, described physical pulverization is treated to mechanical disintegration or grinding, with raw material pulverizing to 10～150 orders.
In the step 2, the content of phosphoric acid is 50～90%, can be the preparation of 85～119% phosphoric acid by concentration, the solid-liquid ratio of lignocellulose and phosphoric acid is 10～30% (w/v) (solid-liquid ratio that is lignocellulose and phosphoric acid is/100 milliliters of 10～30 grams), hydrolysis temperature is 30～70 ℃, and hydrolysis time is 30～120 minutes.Can thoroughly destroy xylogen, hemicellulose and cellulosic key coat with the phosphoric acid hydrolysis lignocellulose-like biomass, and significantly reduce cellulosic degree of crystallinity, be monose with hydrolysis of hemicellulose simultaneously, and side reaction is few.
In the step 3, described organic solvent is alcohols, ketone or ester compound, the ester compound that character such as ethyl acetate, propyl acetate, butylacetate or ethyl formate are comparatively stable, water solubility is little, consumption of organic solvent is 5～30% (w/v) (being that consumption of organic solvent is/100 milliliters of 5～30 grams), extraction temperature is 10～30 ℃, 5～60 minutes extraction time, extraction process will stir.After extraction finishes, most of xylogen organic solvent mutually in, hydrolysis of hemicellulose sugar is at aqueous phase, and that Mierocrystalline cellulose both had been insoluble to organic solvent was also water insoluble, then existed with solid phase form.
In the step 4, described solid-liquid separating method is centrifugal or filters.After the solid-liquid separation, available organic solvent repetitive scrubbing solid part 1～4 time further extracts xylogen residual in the cellulose solids, and the liquid portion that obtains after washings and the solid-liquid separation merges.
In the step 4, the solid cellulose that obtains, its degree of crystallinity significantly reduces, and does not contain cellulase inhibitions such as xylogen, hemicellulose substantially.Can adopt the hot wash cellulose solids before the enzymic hydrolysis, reclaim by the sugar and the residual phosphoric acid of cellulose adsorption, the water after washings and water are separating of oil merges.Cellulosic lytic enzyme is that cellulase (contains inscribe β-1,4-dextranase, circumscribed β-1,4-dextranase and beta-glucosidase, be also referred to as cellobiase), the substrate massfraction is 5～30% (w/v) (being that concentration of substrate is/100 milliliters of 5～30 grams), and the cellulase addition is 1～5% (w/w), and the enzymic hydrolysis temperature is 35～60 ℃, pH is 4.0～6.0, and hydrolysis time is 24～72 hours.The cellulose hydrolysis liquid glucose that enzymatic hydrolysis reaction obtains mainly contains glucose, does not contain fermentation inhibitors such as furfural class, organic acid and phenols, can be used as carbon source and is used for fermentation.
In the step 4, Recovery of Organic Solvent adopts distillation under vacuum to reclaim organic solvent, and xylogen precipitates gradually separates out, and can obtain the xylogen solid through centrifugal or filtration, and dry back is as industrial chemicals or preparation novel material.
In the step 4, the method that reclaims phosphoric acid is, add calcium hydroxide or lime carbonate at aqueous phase, the formation calcium phosphate precipitation is realized the detoxification to hydrolysis sugar liquid simultaneously, after filtration calcium phosphate precipitation is separated with the hydrolysis of hemicellulose liquid glucose, the vitriol oil of calcium phosphate precipitation adding 50～98% carries out acidifying, separates recyclable phosphoric acid after filtration and obtains byproduct calcium sulfate.The hydrolysis of hemicellulose liquid glucose that obtains mainly contains wood sugar, pectinose, does not contain inhibitions such as furfural, organic acid and phenols, can be used for extracting wood sugar and prepares Xylitol or be used for fermentation as carbon source.The calcium sulfate that obtains can be used as the raw material of making building materials or directly as industrial chemicals.
In the step 4, the phosphoric acid of recovery returns step 2, and the organic solvent of recovery returns step 3.
Beneficial effect of the present invention: the mode that the present invention adopts phosphoric acid hydrolysis, organic solvent extraction to combine with enzymic hydrolysis is handled lignocellulose-like biomass, strong phosphoric acid belongs to middle strong acid, and is not volatile, is difficult for decomposing, do not belong to oxidizing acid, have hydrolysis ability preferably, corrodibility is little, mild condition, hydrolytic side reactions is few, can effectively destroy xylogen, hemicellulose and cellulosic key coat, be monose with hydrolysis of hemicellulose, and cellulosic degree of crystallinity significantly reduces; The esters extractant stable in properties in sour environment that adopts, the solvent recovering rate height, the xylogen purity height of extraction can be used as byproduct; It is simple that phosphoric acid reclaims technology, and can finish the separation and the detoxification treatment of double Mierocrystalline cellulose liquid glucose simultaneously, and byproduct calcium sulfate can be used as material of construction; Can realize cellulosic efficient enzymolysis on this basis, the cellulose hydrolysis rate reaches more than 80%; The various hydrolysis sugar liquid quality height of this law preparation do not contain fermentation inhibitor, are suitable for as fermenting carbon source.The present invention not only can promote the comprehensive utilization of agroforestry waste by the multiple-stage treatment to lignocellulose-like biomass, reduces environmental pollution, and help reducing raw materials cost, promote the development of biorefinery industry, promote sustainable development, have economic and social benefit widely.
Description of drawings
Fig. 1 prepares the method flow diagram of polycomponent liquid glucose and xylogen simultaneously for the effectively hydrolyzing lignocellulosic biolobic material.
Embodiment:
The following examples elaborate to the present invention, but to the present invention without limits.Quantitative detecting method in following examples: xylogen adopts improved Klason method, and Mierocrystalline cellulose adopts the nitric acid Ethanol Method, and hemicellulose adopts the Phloroglucinol weighting method, furfural, phenols, acetate all adopt the HPLC method, phosphorus acid content adopts GB-T 2091-2003 volumetry, and total reducing sugars adopts the DNS colorimetry, and cellulose crystallity is measured (Cu target by X-ray diffraction, automatically monochromator filtering, wavelength 1.54056A, pipe is pressed 40kV, pipe stream 200mA, scan at 10～50 °, the Segal method is calculated).
Embodiment 1:
Get the exsiccant maize straw, through mechanical disintegration to 40 order, get 5g corn stalk powder (content of cellulose 24.7%, hemicellulose 20.1%, xylogen 15.6%), add 85% phosphoric acid, solid-liquid content is 12.5% (w/v), and reaction solution stirs hydrolysis 60 minutes in 50 ℃ of following constant temperature, be cooled to 30 ℃, add 50mL propyl acetate (10%w/v) and stir extraction 10min, filter, filter cake propyl acetate (10%w/v) washing 3 times, washings and filtrate are merged, layering, the underpressure distillation organic phase reclaims extraction agent, and the propyl acetate rate of recovery is 92%, separate out the xylogen solid, through centrifugal drying, obtain xylogen 0.73g (purity 96%), lignin removing rate 89.8%.
Adopt the hot wash cellulose solids, water after washings and the oily water separation is merged, adding lime carbonate in solution reacts, calcium phosphate precipitation is separated with the hydrolysis of hemicellulose filtering sugar solution by using, total reducing sugars content is 16g/L in the isolating hydrolysis sugar liquid, add up to 0.8g, it is 79.6% that hydrolysis of hemicellulose gets sugared rate, does not detect inhibitions such as furfural, phenols, acetate.Add 98% sulfuric acid acidation in the calcium phosphate, reclaiming phosphorus acid content is 81%, and the phosphoric acid rate of recovery is 94%.
Cellulose crystallity after the separation reduces to 26% by 61%, and the substrate massfraction is 10% (w/v), adds cellulase 5% (w/w), and the enzymic hydrolysis temperature is 50 ℃, pH4.8, hydrolysis 48h.Solid-liquid separation obtains the cellulase hydrolysis liquid glucose, and total reducing sugars content is 20g/L, adds up to 1.07g, and the cellulose hydrolysis rate is 87%, does not detect fermentation inhibitor furfural, phenols, acetate.And under the same terms, undressed cellulose hydrolysis rate only is 42%.
As adopting acetone extract, the acetone rate of recovery only is 55% under identical pretreatment condition, lignin removing rate 67.7%, and xylogen purity is 83%, and the phosphoric acid rate of recovery is 85%, and cellulose crystallity only reduces to 41%, and the cellulose hydrolysis rate is 74%.
Embodiment 2:
Get the exsiccant corn cob, be crushed to 60 orders, get 5g corn cob meal (content of cellulose 29.8% through mechanical mill, hemicellulose 32.4%, xylogen 18.3%), add 80% phosphoric acid, solid-liquid content is 20% (w/v), and reaction solution stirs hydrolysis 30 minutes in 60 ℃ of following constant temperature, is cooled to 20 ℃, add ethyl acetate (20%w/v) and stir extraction 30min, filter, filter cake washs 3 times with ethyl acetate, merging filtrate, layering, underpressure distillation organic phase, the ethyl acetate rate of recovery are 95%.The xylogen solid that separates out, dry after filtration, obtain xylogen 0.94g (purity 95%), lignin removing rate 97.4%.
Adopt the hot wash cellulose solids, water with washings and water after separating of oil merges, adding lime carbonate in solution reacts, calcium phosphate precipitation is separated with the hydrolysis of hemicellulose filtering sugar solution by using, total reducing sugars content is 44g/L in the isolating hydrolysis sugar liquid, add up to 1.45g, it is 89.6% that hydrolysis of hemicellulose gets sugared rate, does not detect inhibitions such as furfural, phenols, acetate.Add 98% sulfuric acid acidation in the calcium phosphate, reclaiming phosphorus acid content is 78%, and the phosphoric acid rate of recovery is 96%.
Cellulose crystallity after the separation reduces to 35% by 66%, and the substrate massfraction is 25% (w/v), adds cellulase 3% (w/w), and the enzymic hydrolysis temperature is 45 ℃, pH5.0, hydrolysis 24h.Solid-liquid separation obtains the cellulase hydrolysis liquid glucose, and total reducing sugars content is 66g/L, adds up to 1.32g, and the cellulose hydrolysis rate is 88.3%, does not detect fermentation inhibitor furfural, phenols, acetate.And under the same terms, undressed cellulose hydrolysis rate only is 36%.
As adopting methanol extraction, the Methanol Recovery rate only is 73% under identical pretreatment condition, lignin removing rate 87%, and xylogen purity is 90%, and the phosphoric acid rate of recovery is 75%, and cellulose crystallity only reduces to 54%, and the cellulose hydrolysis rate is 81%.
Embodiment 3:
Get exsiccant bagasse,, get 5g bagasse particle (content of cellulose 38.2% through mechanical disintegration to 20 order, hemicellulose 22.5%, xylogen 19.8%), add 50% phosphoric acid, solid-liquid content is 25% (w/v), and reaction solution stirs hydrolysis 40 minutes in 40 ℃ of following constant temperature, is cooled to 30 ℃, add ethyl formate (30%w/v) and stir extraction 20 minutes, filter, filter cake washs 2 times with ethyl formate, merging filtrate, layering, underpressure distillation organic phase, the ethyl formate rate of recovery are 85%.The xylogen solid that separates out through centrifugal drying, obtains xylogen 1.02g (purity 93%), lignin removing rate 96%.
Adopt the hot wash cellulose solids, water with washings and water after separating of oil merges, adding calcium hydroxide in solution reacts, calcium phosphate precipitation is separated with the hydrolysis of hemicellulose filtering sugar solution by using, total reducing sugars content is 19g/L in the isolating hydrolysis sugar liquid, add up to 0.74g, it is 65.8% that hydrolysis of hemicellulose gets sugared rate, does not detect inhibitions such as furfural, phenols, acetate.Add 98% sulfuric acid acidation in the calcium phosphate, reclaiming phosphorus acid content is 80%, and the phosphoric acid rate of recovery is 92%.
Cellulose crystallity after the separation reduces to 46% by 67%, and the substrate massfraction is 20% (w/v), adds cellulase 2% (w/w), and the enzymic hydrolysis temperature is 40 ℃, pH4.5, hydrolysis 42h.Solid-liquid separation obtains the cellulase hydrolysis liquid glucose, and total reducing sugars content is 60.5g/L, adds up to 1.57g, and the cellulose hydrolysis rate is 82.2%, does not detect fermentation inhibitor furfural, phenols, acetate.And under the same enzyme hydrolysising condition, the plain percent hydrolysis of undressed bagasse fibre only is 39%.
As adopting alcohol extraction, the ethanol rate of recovery only is 75% under identical pretreatment condition, lignin removing rate 82%, and xylogen purity is 69%, and the phosphoric acid rate of recovery is 85%, and cellulose crystallity reduces to 51%, and the cellulose hydrolysis rate is 69%.
Embodiment 4:
Get the exsiccant straw,, get 5g straw powder (content of cellulose 33.5% through mechanical disintegration to 80 order, hemicellulose 23.0%, xylogen 11.6%), add 75% phosphoric acid, solid-liquid content is 10% (w/v), and reaction solution stirs hydrolysis 120 minutes in 30 ℃ of following constant temperature, adds ethyl acetate (25%w/v) and stirs extraction 40 minutes, filter, filter cake washs 2 times with ethyl acetate, merging filtrate, layering, underpressure distillation organic phase, the ethyl acetate rate of recovery are 93%.The xylogen solid that separates out gradually in the rest solution, dry after filtration, obtain xylogen 0.5g (purity 97%), lignin removing rate 84%.
Adopt the hot wash cellulose solids, water with washings and water after separating of oil merges, adding lime carbonate in solution reacts, calcium phosphate precipitation is separated with the hydrolysis of hemicellulose filtering sugar solution by using, total reducing sugars content is 14.3g/L in the isolating hydrolysis sugar liquid, add up to 0.86g, it is 74.8% that hydrolysis of hemicellulose gets sugared rate, does not detect inhibitions such as furfural, phenols, acetate.Add 98% sulfuric acid acidation in the calcium phosphate, reclaiming phosphorus acid content is 78%, and the phosphoric acid rate of recovery is 90%.
Cellulose crystallity after the separation reduces to 37% by 60%, and the substrate massfraction is 5% (w/v), adds cellulase 1% (w/w), and the enzymic hydrolysis temperature is 50 ℃, pH4.8, hydrolysis 36h.Solid-liquid separation obtains the cellulase hydrolysis liquid glucose, and total reducing sugars content is 16g/L, adds up to 1.60g, and the cellulose hydrolysis rate is 95.5%, does not detect fermentation inhibitor phenols, acetate, furfural.And under the same enzyme hydrolysising condition, undressed straw cellulose percent hydrolysis only is 37%.
Embodiment 5:
Get the exsiccant wheat straw, through mechanical disintegration to 10 order, get 5g wheat straw particle (content of cellulose 37.0%, hemicellulose 25.0%, xylogen 23.1%), add 85% phosphoric acid, solid-liquid content is 30% (w/v), and reaction solution stirs hydrolysis 30 minutes in 70 ℃ of following constant temperature, is cooled to 20 ℃, add butylacetate (15%w/v) and stir extraction 15 minutes, centrifugal layering is washed solid residue 3 times with butylacetate, and filtrate and organic phase merge, organic solvent is reclaimed in underpressure distillation, and the butylacetate rate of recovery is 97%.The xylogen solid that separates out through centrifugal drying, obtains xylogen 1.14g (purity 93%), lignin removing rate 94%.
Adopt the hot wash cellulose solids, recovery is by the sugar and the residual phosphoric acid of cellulose adsorption, with washings with separate organic phase after feed liquid merge, adding calcium hydroxide in solution reacts, calcium phosphate precipitation is separated with the hydrolysis of hemicellulose filtering sugar solution by using, and total reducing sugars content is 37.9g/L in the isolating hydrolysis sugar liquid, adds up to 1.138g, it is 91.0% that hydrolysis of hemicellulose gets sugared rate, does not detect inhibitions such as furfural, phenols, acetate.Add 90% sulfuric acid acidation in the calcium phosphate, reclaiming phosphorus acid content is 79%, and the phosphoric acid rate of recovery is 88%.
Cellulose crystallity after the separation reduces to 40% by 62%, and the substrate massfraction is 10% (w/v), adds cellulase 4% (w/w), and the enzymic hydrolysis temperature is 50 ℃, pH5.5, hydrolysis 32h.Solid-liquid separation obtains the cellulase hydrolysis liquid glucose, and total reducing sugars content is 30.2g/L, adds up to 1.49g, and the cellulose hydrolysis rate is 80.3%, does not detect fermentation inhibitor furfural, phenols, acetate.And under the same enzyme hydrolysising condition, undressed wheatgrass cellulose percent hydrolysis only is 35%.
Embodiment 6:
Get the exsiccant sawdust, through mechanical disintegration to 150 order, get 5g sawdust (content of cellulose 44.2%, hemicellulose 10.3%, xylogen 26.0%), add 90% phosphoric acid, solid-liquid content is 10% (w/v), and reaction solution stirs hydrolysis 30 minutes in 70 ℃ of following constant temperature, is cooled to 10 ℃, add ethyl acetate (30%w/v) and stir extraction 60 minutes, centrifugal layering is washed solid residue 4 times with ethyl acetate, and filtrate and organic phase merge, organic solvent is reclaimed in underpressure distillation, and the ethyl acetate rate of recovery is 97%.The xylogen solid that separates out through centrifugal drying, obtains xylogen 1.34g (purity 89%), lignin removing rate 92%.
Adopt the hot wash cellulose solids, recovery is by the sugar and the residual phosphoric acid of cellulose adsorption, water with washings and water after separating of oil merges, adding calcium hydroxide in solution reacts, calcium phosphate precipitation is separated with the hydrolysis of hemicellulose filtering sugar solution by using, and total reducing sugars content is 18.5g/L in the isolating hydrolysis sugar liquid, adds up to 0.51g, it is 99.0% that hydrolysis of hemicellulose gets sugared rate, does not detect inhibitions such as furfural, phenols, acetate.Add 50% sulfuric acid acidation in the calcium phosphate, reclaiming phosphorus acid content is 85%, and the phosphoric acid rate of recovery is 89%.
Cellulose crystallity after the separation reduces to 37% by 69%, and the substrate massfraction is 10% (w/v), adds cellulase 4% (w/w), and the enzymic hydrolysis temperature is 50 ℃, pH4.8, hydrolysis 72h.Solid-liquid separation obtains the cellulase hydrolysis liquid glucose, and total reducing sugars content is 35.5g/L, adds up to 2.05g, and the cellulose hydrolysis rate is 93.0%, does not detect fermentation inhibitor furfural, phenols, acetate.And under the same enzyme hydrolysising condition, undressed sawdust cellulose hydrolysis rate only is 45%.
Embodiment 7:
Adopt raw material, pre-treatment and the enzymatic hydrolysis condition identical with embodiment 2, but adopt phosphoric acid and ethyl acetate all from the recovery article in the sepn process, the corn cob result is: lignin removing rate 95.3%, it is 91.4% that hydrolysis of hemicellulose gets sugared rate, the cellulose hydrolysis rate is 87.0%, all do not detect inhibition in the hydrolysis sugar liquid, do not have significant difference with the effect that adopts fresh phosphoric and ethyl acetate to handle.
Claims (10)
1, a kind of effectively hydrolyzing lignocellulosic biolobic material prepares the method for polycomponent liquid glucose and xylogen simultaneously, it is characterized in that this method comprises the steps:
(1) lignocellulose-like biomass being carried out physical pulverization handles;
(2) adopt phosphoric acid that lignocellulose-like biomass is hydrolyzed;
(3) in the reaction system of step (2), add organic solvent extraction;
(4) reaction system of step (3) gets cellulose solids after solid-liquid separation, and Mierocrystalline cellulose promptly obtains the cellulose hydrolysis liquid glucose through enzymic hydrolysis; The clear liquid part that the reaction system of step (3) obtains after solid-liquid separation is through standing demix, and organic phase reclaims organic solvent through distillation, promptly separates out xylogen, remaining water, and the phosphoric acid recovery with wherein promptly gets the hydrolysis of hemicellulose liquid glucose.
2, effectively hydrolyzing lignocellulosic biolobic material according to claim 1 prepares the method for polycomponent liquid glucose and xylogen simultaneously, it is characterized in that described lignocellulose-like biomass is maize straw, corn cob, straw, wheat straw, bagasse or sawdust.
3, effectively hydrolyzing lignocellulosic biolobic material according to claim 1 prepares the method for polycomponent liquid glucose and xylogen simultaneously, it is characterized in that the physical pulverization described in the step (1) is treated to mechanical disintegration or grinding, with raw material pulverizing to 10～150 orders.
4, effectively hydrolyzing lignocellulosic biolobic material according to claim 1 prepares the method for polycomponent liquid glucose and xylogen simultaneously, it is characterized in that in the step (2), the content of phosphoric acid is 50～90%, the solid-liquid ratio of lignocellulose and phosphoric acid is 10～30% (w/v), hydrolysis temperature is 30～70 ℃, and hydrolysis time is 30～120 minutes.
5, effectively hydrolyzing lignocellulosic biolobic material according to claim 1 prepares the method for polycomponent liquid glucose and xylogen simultaneously, it is characterized in that in the step (3), described organic solvent is an ester compound, consumption of organic solvent is 5～30% (w/v), extraction temperature is 10～30 ℃, 5～60 minutes extraction time, extraction process will stir.
6, effectively hydrolyzing lignocellulosic biolobic material according to claim 5 prepares the method for polycomponent liquid glucose and xylogen simultaneously, it is characterized in that in the step (3), described organic solvent is ethyl acetate, propyl acetate, butylacetate or ethyl formate.
7, effectively hydrolyzing lignocellulosic biolobic material according to claim 1 prepares the method for polycomponent liquid glucose and xylogen simultaneously, it is characterized in that in the step (4), and described solid-liquid separating method is centrifugal or filters.
8, effectively hydrolyzing lignocellulosic biolobic material according to claim 1 prepares the method for polycomponent liquid glucose and xylogen simultaneously, it is characterized in that in the step (4), cellulosic lytic enzyme is a cellulase, the substrate massfraction is 5～30% (w/v), the cellulase addition is 1～5% (w/w), the enzymic hydrolysis temperature is 35～60 ℃, and pH is 4.0～6.0, and hydrolysis time is 24～72 hours.
9, effectively hydrolyzing lignocellulosic biolobic material according to claim 1 prepares the method for polycomponent liquid glucose and xylogen simultaneously, it is characterized in that in the step (4), the method that reclaims phosphoric acid is, add calcium hydroxide or lime carbonate at aqueous phase, form calcium phosphate precipitation, after filtration calcium phosphate precipitation is separated with the hydrolysis of hemicellulose liquid glucose, the vitriol oil of calcium phosphate precipitation adding 50～98% carries out acidifying, separates recyclable phosphoric acid after filtration and obtains byproduct calcium sulfate.
10, effectively hydrolyzing lignocellulosic biolobic material according to claim 1 prepares the method for polycomponent liquid glucose and xylogen simultaneously, it is characterized in that in the step (4), the phosphoric acid of recovery returns step (2), and the organic solvent of recovery returns step (3).
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