CN101586136B - Method of high-efficiency pretreatment on biomass - Google Patents
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- CN101586136B CN101586136B CN200910040819XA CN200910040819A CN101586136B CN 101586136 B CN101586136 B CN 101586136B CN 200910040819X A CN200910040819X A CN 200910040819XA CN 200910040819 A CN200910040819 A CN 200910040819A CN 101586136 B CN101586136 B CN 101586136B
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Abstract
The invention discloses a method capable of carrying out green high-efficiency hydrolysis pretreatment on lignocellulose biomass. The method in the invention comprises the steps of hydrolyzing the hemicellulose in the cellulose biomass into saccharide products mainly containing xylose and oligose thereof using a two-step temperature-changing segmentation hydrolysis method so as to accomplish the pretreatment, and adding the pretreated solid raw material mainly containing cellulose and lignin to cellulase so as to accomplish enzymatic hydrolysis and recover the saccharide products to the utmostextent. The invention uses high-temperature liquid water as reaction medium, has the advantages that the method has low cost and is environment-friendly and green. The reaction conditions are moderat e, the saccharide products are degraded less, and the recovery rate is high. By adopting the two-step temperature-changing segmentation hydrolysis method, the method not only hydrolyzes the hemicellulose to the utmost extent to obtain the saccharide products, but also further pre-treats the raw material such that the cellulose is made into glucose through enzymatic hydrolysis, reaching the purposeof protecting environment and hydrolyzing the lignocellulose biomass highly effectively. The raw material is capable of realizing waste utilization and promotes the development of green industries.
Description
Technical field
The present invention relates to biological chemistry and chemical technology field, relate in particular to a kind of cellulose series biomass method of high-efficiency pretreatment and realization equipment thereof.
Technical background
But the renewable energy source resource of unique fixed carbon that biomass are world energy sourceses circle generally acknowledges has bright prospects with its production liquid fuel and Chemicals.With producing liquid fuel using biomass and Chemicals two technological lines are arranged: the one, obtain synthetic gas through gasifying biomass and realize through chemistry and biochemical method again; Another study route is to build sugared platform; Promptly through hydrolysis; Polysaccharide fraction-Mierocrystalline cellulose in the biomass and hydrolysis of hemicellulose are obtained carbohydrate, further process, handle acquisition biogasoline, ethanol, butanols, Xylitol, levulinic acid equal energy source Chemicals again.
The development in science and technology of 21 century is called as " sugar is economical " or " glucide economy ", is important foundation and the assurance that promotes to realize " sugar is economic " with the vegetable fibre degraded for sugared midbody, but does not still have method capable of being industrialized at present.Lignocellulose biomass by hydrolyzation is very potential technology.
Lignocellulose biomass by hydrolyzation in general sense; Finger is under certain temperature and catalyst action; Make wherein Mierocrystalline cellulose and semicellulose add the process that water decomposition (saccharification) becomes monose; The hydrolysis of hemicellulose product is for the wood sugar being main five-carbon sugar, and the cellulose hydrolysis product is that glucose is main hexose.Different according to used catalyzer, the method for biomass by hydrolyzation has three kinds: with dilute acid hydrolysis and the concentrated acid hydrolysis of acid as catalyzer, be the enzymic hydrolysis of catalyzer with the cellulase.
The research of concentrated acid hydrolysis starts from 1820s, refers to that concentration becomes biomass by hydrolyzation at sulfuric acid more than 30% or hydrochloric acid the method for monose.Reaction conditions is: in 100 ℃, and normal pressure, 2-10 hour, be homogeneous hydrolysis, generally divide pre-treatment and two steps of hydrolysis to carry out.Advantage is that sugared transformation efficiency is high, and no matter Mierocrystalline cellulose still is a semicellulose can both reach more than 90%; Shortcoming is that speed of response is slow, complex process, and production environment is abominable, and acid must be reclaimed and the expense height.Be mainly used in agricultural wastes such as handling corn cob, wheat straw.
Enzymic hydrolysis starts from the 1950's, is newer biomass by hydrolyzation technology.Refer to utilize cellulase that the solid-state Mierocrystalline cellulose in the biomass is carried out saccharification and then fermentation generation ethanol.Be to carry out under about 4.8 the condition at normal pressure, 45-50 ℃, pH; Can form single carbohydrate product and productive rate can reach more than 90%; Generate sugar the secondary decomposition can not take place, therefore more and more receive various countries and pay attention to, even have the people to predict that enzymic hydrolysis has the acid-hydrolyzed trend of substituting.Shortcoming is a long reaction time, and low, the easy inactivation of existing cellulose enzyme effect, the difficult recovery are less economical, are difficult to the production of realization continuity, and the while production of cellulase will consume the biomass material about 9%.In addition, must carry out pre-treatment before the enzymic hydrolysis, but pretreated purpose be remove delignification, dissolve semicellulose, destroy cellulosic crystalline structure, the surface in contact of the plain enzyme of increased fiber, the enzymic hydrolysate yield will rely on effects of pretreatment to a great extent.So enzymic hydrolysis from the production of cellulase, to be applied to equipment of pretreatment, running cost all very high, process of industrialization is hindered.
Dilute acid hydrolysis is at first proposed in 1856 by the Mei Ersensi of France; Fritzs in 1898 propose the commerce conception of timber ethanol production; The U.S. and Germany once set up fuel ethanol plants with this method during the World War I and the World War II, and the later stage lacks because of timber and the supply of cheap oil stops production.Dilute acid hydrolysis refers generally to use 10% as catalyzer Mierocrystalline cellulose, hydrolysis of hemicellulose to be become the method for monose with mineral acids such as interior sulfuric acid or hydrochloric acid, and temperature 100-240 ℃, pressure generally is higher than 10 normal atmosphere greater than the hold-up vp.Advantage is that reaction process is fast, is fit to continuous production, and acid solution need not reclaim; Shortcoming is temperature required higher with pressure, and by product is more, and reactor material requires high.Two study routes are arranged at present: the one, as the method for biomass by hydrolyzation, the 2nd, as the most economical pretreatment process of enzymic hydrolysis.
Enzymic hydrolysis is current generally acknowledged biomass by hydrolyzation mainstream technology, lacks difficult points such as high-efficiency pretreatment method, cellulase cost be high but be faced with.The high-temperature liquid state water law is the pretreatment process that receives much attention in recent years; The high temperature liquid water hydrolysis (HotLiquid Water) claim automatic hydrolysis (Autohydrolysis) again; Be meant at a certain temperature and under the condition greater than this filament saturation vp, make water keep liquid state to come the semicellulose in the hydrolyzing biomass.Its principle is under HTHP, and water can dissociate H
+And OH
-, possess soda acid autocatalysis function, thereby accomplish the hydrolysis of semicellulose.The advantage of this method is to need not catalyzer, and is with low cost, and the carbohydrate product recovery is high.
In biomass high-temperature liquid water hydrolysis research field, Appell seminar at first 350 ℃ with CO atmosphere under with Na
2CO
3For catalyzer is hydrolyzed into heavy oil with wood chip in the liquid hot water of HTHP, after this people deepen continuously to the research of this method, mainly concentrate on the discussion of selection of catalysts and reaction mechanism.Boocock is catalyzer with Ni, and Tomoaki seminar is that catalyzer is studied timber or cellulose hydrolysis respectively with alkali and Ni.G.Garrote seminar researching high-temperature liquid water is produced xylooligosaccharides in recent years; Be raw material with big wheat husk, corn cob, eucalyptus, rice husk etc. respectively; Find that at 158 ℃ the xylan hydrolyzable more than 90% is an oligose in the product, wherein big wheat husk effect is best, and the xylooligosaccharides yield reaches 27.1% of raw material total amount; Oligose is 4 times of monose in the product, and degraded product such as furfural is few.Sasaki etc. obtain supercritical water with further elevated temperature of high-pressure liquid hot water and pressure, do not add any catalyzer Mierocrystalline cellulose is hydrolyzed.Since 2000; Near-critical water has entered into investigator's visual field; The Masahiro of Japan's forestry and Forest products institute etc. has studied the conduct hydrolysis of 310-320 ℃ of timber powder in near-critical water; The raw material of finding 70-90% can be converted into water-soluble substances, and is main with monose and oligose in the product.
The flourish seminar of the domestic national energy clean utilization Wang Shu of key lab of Zhejiang University is once with this method hydrolysis kahikatea, the livings poplar of speed and corn straw, and contrasts, with this as two go on foot the extremely low acids hydrolysis technologies the first step.The Lv Xiu of Zhejiang University sun seminar produces Chemicals such as levulinic acid with regard to the biomass near-critical water and reaction kinetics is studied.
Biochemical conversion laboratory, Chinese Academy of Sciences Guangzhou energy institute biomass energy center began to carry out the research of this technology from 2006; With the pretreatment process of high-temperature liquid state water law as enzymic hydrolysis; Seek the carbohydrogenic new way of biomass efficient; Two sections alternating temperature pretreatment technology of biomass high-temperature liquid water are proposed, to realize building of efficient sugared platform.
Carry out the patent inquiry through the State Intellectual Property Office of the People's Republic of China website, at present domestic relevant lignocellulose biomass by hydrolyzation aspect related patent U.S. Patent No. is following:
(1) prepare the method for reductive monosaccharide by biomass by hydrolyzation. open (bulletin) number: CN1432574;
(2) process for ordinary-pressure hydrolysis of hemicellulose by preheating with concentrated acid, open (bulletin) number: CN1327972;
(3) a kind of method of acid hydrolysis plant cellulose. open (bulletin) number: CN1109100;
(4) the pretreated method of a kind of biomass, open (bulletin) number: CN1824782;
(5) apparatus for preparing liquid fuel by biological matter ultra-low acid hydrolyzing, open (bulletin) number: CN1624076;
(6) obtain the method for product sugar stream from cellulose biomass, application number/patent No.: 200580031101;
(7) cellulose materials is changed into the alcoholic acid method and apparatus, open (bulletin) number: CN101268121A;
See from above patent situation; Patent (1)-(5) are the acid hydrolysis technology all; Patent (6) focuses on the Separation and Recovery of carbohydrate product, and the have only patent (7) more relevant with this project " changes into the alcoholic acid method and apparatus with cellulose materials ", and this patented claim people is Denmark gloomy Biosys Corp. of Hall nurse Chris rattan; A kind of hydrothermal pretreatment method of enzymatic saccharification is again disclosed; But and the details of not mentioned pretreatment technology, the present invention proposes two step segmentation alternating temperature high temperature liquid water hydrolysis processs, has essence different with it.
Summary of the invention
The object of the present invention is to provide and a kind ofly can implement green high-efficient hydrolysis pretreatment method,, build efficient biomass sugar platform, for the suitability for industrialized production of the biomass-based energy and Chemicals is carried out place mat to improve sugared yield to lignocellulose-like biomass.
For achieving the above object, the technical scheme below the present invention has taked:
It is main carbohydrate product that the present invention adopts two step alternating temperature sectional method for hydrolysis that the hydrolysis of hemicellulose in the cellulose series biomass is become wood sugar and oligose thereof, accomplishes pre-treatment; Be that main solid material adds cellulase with pretreated Mierocrystalline cellulose and xylogen again, it is main product liquid that cellulose hydrolysis is become glucose, accomplishes enzymic hydrolysis, to reclaim the carbohydrate product to greatest extent.
Concrete steps of the present invention are:
1) with the lignocellulose-like biomass raw material of granularity between 0.5-2mm; In mass ratio 1: 5-1: 20 ratio adds entry; In high-pressure reactor (pressure range of high-pressure reactor is 2-10MPa); Under 160-200 ℃ high-temperature liquid state water surrounding, react 10-60min, solid-liquid separation is accomplished the first step hydrolysis; The first step hydrolyzed liquid product is that five-carbon sugars such as wood sugar, xylooligosaccharides are main hydrolyzed solution, and solid product is a main ingredient with Mierocrystalline cellulose and xylogen.
2) product liquid is collected and is finished; In high-pressure reactor (pressure range of high-pressure reactor is 2-10MPa) with the solid product of the first step hydrolysis for the second time in mass ratio 1: 5-1: 20 ratio adds water, is warming up to 200-260 ℃, the reaction 0-30min; Solid-liquid separation; Cooling, the product liquid of this moment is mainly a small amount of glucose, liquid oligomeric glucose and furfural class by product, and solid product is that good Mierocrystalline cellulose of pre-treatment and xylogen are main enzymolysis raw material.
3) with step 2) solid product that obtains adds the cellulase of 8-30FPU according to every gram raw material dry weight, and at pH value 4.0-5.5, temperature is at 37 ℃ to 55 ℃ and stir down, is hydrolyzed into glucose concn and no longer raises, and liquid is taken out the completion enzymolysis; The enzymolysis solution staple is a glucose, and the solid residue main ingredient is an xylogen.
4) with step 1), step 2) enzymolysis product of hydrolyzed liquid product and step 3) merges and obtains the lignocellulose biomass by hydrolyzation product, can be used for the microbial fermentation ethanol production, or produce butanols, hydro carbons equal energy source Chemicals through biochemistry or chemical process; Because of solid residue is the highest xylogen of calorific value in the biomass, can be used for burning as the technology thermal source or be used as the raw material of producing other Chemicals.Through above two step alternating temperature pre-treatment and follow-up enzymolysis, polysaccharide component-semicellulose in the lignocellulose and Mierocrystalline cellulose are hydrolyzed into the product liquid that wood sugar and glucose and corresponding liquid oligomeric sugar thereof are the master respectively.
The equipment of realizing this technology comprises the system and device that is the main body with intermittence, diafiltration and successive high-pressure reactor.
Said lignocellulose-like biomass raw material comprises the plant class material that contains Mierocrystalline cellulose and semicellulose; Comprise forestry waste such as wood chip; Agricultural wastes such as stalk, bagasse etc. sugar (wine) factory processing waste, and cellulose family energy-source plants such as fastgrowing trees, napier grass.
Characteristics of the present invention and technique effect are:
1. adopting high temperature liquid water is reaction medium, has the characteristics of cheapness, environmental protection, green, and reaction conditions is gentle, the less degraded of carbohydrate product, and the recovery is high.
2. adopt the method for two step alternating temperature graded hydrolysiss; Be products such as corresponding monose and oligose and small amount of acetic acid, furfural earlier with lower temperature hydrolyzed hemicellulose; With comparatively high temps raw material is carried out the secondary temperature elevation pre-treatment again, both guaranteed semicellulose to greatest extent hydrolysis obtain sugared product, again further pre-treatment raw material; Make cellulase can its effectively hydrolyzing be generated glucose, reach the purpose of environmental protection, effectively hydrolyzing lignocellulosic biolobic material.
3. the lignocellulose-like biomass raw material of raw material comprises the plant class material that contains Mierocrystalline cellulose and semicellulose; Comprise forestry waste such as wood chip; Agricultural wastes such as stalk, bagasse etc. sugar (wine) factory processing waste, and cellulose family energy-source plants such as fastgrowing trees, napier grass.Can realize utilization of waste material, promote the green agriculture development.
Description of drawings
Fig. 1 is the inventive method schema.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is further described.
As shown in Figure 1, biomass material is pulverized, make its granularity between 0.5-2mm; In mass ratio 1: 5-1: 20 ratio adds deionized water; The pressure range of packing into is in the high-pressure reactor of 2-10MPa, under 160-200 ℃ high-temperature liquid state water surrounding, handles 10-60min, collects product liquid; Accomplish the first step hydrolysis, obtain the first step hydrolyzed liquid product and solid product.With its Rapid Realization solid-liquid separation, product liquid is that five-carbon sugar such as wood sugar is main hydrolyzed solution, and solid product is a main ingredient with Mierocrystalline cellulose and xylogen.With the first step solid product for the second time with mass ratio 1: 5-1: 20 ratio adds entry;, pressure range is warming up to 200-260 ℃ in being the high-pressure reactor of 2-10MPa; Reaction 0-30min takes out the solid product and the second one-step hydrolysis product liquid, solid-liquid separation; Cooling, the solid product of this moment are that good Mierocrystalline cellulose of pre-treatment and xylogen are main enzymolysis raw material.The second one-step hydrolysis solid product adds the cellulase of 8-30FPU according to every gram raw material dry weight, and at pH value 4.0-5.5, temperature is under 37 ℃ to 55 ℃ and the stirring condition; Being hydrolyzed into glucose concn no longer raises; Solid-liquid separation obtains enzymolysis product liquid and solid residue, accomplishes enzymolysis.The enzymolysis solution staple is a glucose, and enzymolysis residue main ingredient is an xylogen.Through above two step alternating temperature pre-treatment and follow-up enzymolysis, polysaccharide component-semicellulose in the lignocellulose and Mierocrystalline cellulose are hydrolyzed into the product liquid that wood sugar and glucose and corresponding liquid oligomeric sugar thereof are the master respectively.The first step, the second one-step hydrolysis product liquid and enzymolysis product are used for the microbial fermentation ethanol production, or produce butanols, hydro carbons equal energy source Chemicals through biochemistry or chemical process; Because of solid residue is the highest xylogen of calorific value in the biomass, can be used for burning as the technology thermal source or be used as the raw material of producing other Chemicals.
Embodiment 1:
With the Eucalyptus is hydrolysis material, it is crushed and screened, and be raw material with 0.5-2mm Eucalyptus bits, add water by 20: 1 mass ratio of liquid-solid ratio; Be fed in the autoclave, the confined reaction system is at mixing speed 500r/min, under the condition of pressure 2Mpa; 160 ℃ the reaction 60min, or pressure 4Mpa, 180 ℃ the reaction 20min, or pressure 4Mpa200 ℃ the reaction 10min; To obtain the mxm. of wood sugar and oligose product thereof, the product liquid cooling is collected, accomplish the first step pre-treatment; In still, squeeze into deionized water at normal temperature rapidly, liquid-solid ratio 20: 1; Be heated under 200 ℃, pressure 4Mpa and product liquid to be incubated 30min to collect or be heated to 240 ℃ and product liquid is incubated 20min collects, or be heated to 260 ℃, product liquid is cooled off collection at once; Add water in the still, treat that solid product is cooled to room temperature, take out, accomplish the second step pre-treatment; Cooled solid product is through the pretreated product of two step alternating temperatures, and it as the enzymic hydrolysis raw material, is carried out cellulase hydrolysis, and enzymatic hydrolysis condition is: pH 4.0,50 ℃ of temperature, and liquid-solid ratio 20: 1, enzyme concentration is 8FPU/g, 72 hours enzymic hydrolysis time.Through above two step pre-treatment, the xylan transformation efficiency in the raw material all can reach 100%, and the wood sugar and the xylooligosaccharides recovery are between 85% to 92% in the first step pre-treatment liquid product; After the second step alternating temperature is handled; VISOSE has 6% to 17% conversion, and the sugared recovery is between 5% to 10%, through the pretreated raw material of two step alternating temperatures; VISOSE enzymolysis rate is 85% to 95%, and total reducing sugar in the Eucalyptus (xylan and the VISOSE) recovery is between 80% to 97%.Select liquid-solid ratio 5: 1 simultaneously and make an experiment at 10: 1, find that the result is close, the carbohydrate production concentration increases in the product.
Embodiment 2:
With the Eucalyptus is hydrolysis material, it is crushed and screened, and be raw material with 0.5-2mm Eucalyptus bits; Add water by 5: 1 mass ratio of liquid-solid ratio, put into the reaction under high pressure system, the confined reaction system; Be heated to 180 ℃, under the condition of pressure 10Mpa, reaction 20min; The product liquid cooling is collected, accomplish the first step pre-treatment; In still, squeeze into deionized water at normal temperature rapidly, liquid-solid ratio 5: 1 is heated to 200 ℃ of reaction 20min, at once the product liquid cooling is emitted, and adds water in the reactor drum, treats that solid product is cooled to room temperature, takes out, and accomplishes the second step pre-treatment; Cooled solid product is through the pretreated product of two step alternating temperatures, and it as the enzymic hydrolysis raw material, is carried out cellulase hydrolysis, and enzymatic hydrolysis condition is: pH 5.5, and temperature is 37 ℃, liquid-solid ratio 5: 1, enzyme concentration 30FPU/g, 72 hours enzymic hydrolysis time.Through above two step pre-treatment, the xylan transformation efficiency in the raw material reaches 100%, and the wood sugar and the xylooligosaccharides recovery reach 91.68% in the first step pre-treatment liquid product; After the second step alternating temperature was handled, VISOSE had 8.46% to transform, the sugared recovery 5.20%, and through the pretreated raw material of two step alternating temperatures, VISOSE enzymolysis rate is 89.94%, total reducing sugar in the Eucalyptus (xylan and the VISOSE) recovery reaches 96.63%.
Above embodiment proves, through the above two steps alternating temperature pre-treatment, can realize semicellulose and cellulosic efficient conversion in the biomass, the cellulose-binding enzymic hydrolysis, and this technology has reclaimed the carbohydrate product preferably.
Claims (1)
1. method of high-efficiency pretreatment on biomass, it is characterized in that being made up of following steps: with the Eucalyptus is hydrolysis material, and it is crushed and screened; With 0.5-2mm Eucalyptus bits is raw material, adds water by 5: 1 mass ratio of liquid-solid ratio, puts into the reaction under high pressure system; The confined reaction system is heated to 180 ℃, under the condition of pressure 10MPa; Reaction 20min collects the product liquid cooling, accomplishes the first step pre-treatment; In still, squeeze into deionized water at normal temperature rapidly, liquid-solid ratio 5: 1 is heated to 200 ℃ of reaction 20min, at once the product liquid cooling is emitted, and adds water in the reactor drum, treats that solid product is cooled to room temperature, takes out, and accomplishes the second step pre-treatment; Cooled solid product is through the pretreated product of two step alternating temperatures, and it as the enzymic hydrolysis raw material, is carried out cellulase hydrolysis, and enzymatic hydrolysis condition is: pH 5.5, and temperature is 37 ℃, liquid-solid ratio 5: 1, enzyme concentration 30FPU/g, 72 hours enzymic hydrolysis time.
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| CN102676706A (en) * | 2011-03-09 | 2012-09-19 | 逢甲大学 | Preparation method and preparation equipment for reducing saccharide |
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