CN102925595A - New method for producing fermentable sugar through hydrolyzing biomasses by utilizing ionic liquid - Google Patents
New method for producing fermentable sugar through hydrolyzing biomasses by utilizing ionic liquid Download PDFInfo
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- CN102925595A CN102925595A CN2011102347022A CN201110234702A CN102925595A CN 102925595 A CN102925595 A CN 102925595A CN 2011102347022 A CN2011102347022 A CN 2011102347022A CN 201110234702 A CN201110234702 A CN 201110234702A CN 102925595 A CN102925595 A CN 102925595A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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Abstract
The invention relates to a new method for producing fermentable sugar through hydrolyzing biomasses by utilizing an ionic liquid. The new method is concretely characterized in that the biomasses which are adopted as a raw material are de-crystallized at 90-120DEG C for 1-6h and then are hydrolyzed at 80-130DEG C for 1-6h in the ionic liquid which is adopted as a green solvent, so the total yield of the total sugar can reach above 70%.
Description
Technical field
The invention belongs to renewable biomass resources development and utilization field, particularly a kind of high efficiency method that utilizes ionic liquid effect hydrolyzing biomass resource to produce biological fermentable sugars.
Technical background
Biomass are renewable resourcess the abundantest on the earth, and annual output is approximately 1.5-2.0 * 10
12Ton.Its main component comprises Mierocrystalline cellulose, hemicellulose and xylogen etc., and wherein the content of Mierocrystalline cellulose and hemicellulose accounts for 70%-80%.Mierocrystalline cellulose and hemicellulose can be hydrolyzed the malt sugar of solubilities such as generating glucose, wood sugar under certain conditions, these saccharide compounds can comprise alcohol fuel and hydrogen by the method production of chemistry or bio-transformation, and various carbon group compounds, such as glycerine, lactic acid, amino acid, polyvalent alcohol, the contour value bio-based of diprotic acid product.Like this, not only can substitute the existing technique for preparing alcohol fuel take grain and glucide as raw material, reduce the production cost of the energy, solve the shortage problem of the energy; For effective environmental contamination reduction, the protection ecosystem environment also benefits simultaneously.Yet, at a conservative estimate, in the Wood Adhesives from Biomass process, the generation of malt sugar accounts for 30% (Wyman CE.What is (and is not) vital to advancing cellulosic ethanol.Trends in Biotechnology 2007 of total cost at least; 25:153-157).Biomass resource is converted into the method for the main three kinds of method main flows of sugared platform of malt sugar or liquid glucose at present: directly Concentrated acid hydrolysis method, direct dilute acid hydrolysis method and thermochemistry pre-treatment add enzyme hydrolysis method (Sun Y, Cheng J.Hydrolysis oflignocellulosic materials for ethanol production:a review.Bioresource Technology 2002; 83:1-11).
Directly the Concentrated acid hydrolysis method at first is with the sulfuric acid about 70-77% water content to be destroyed at 10% biomass crystalline structure.The acid in this step and the ratio of substrate were at 1.25: 1, and temperature is controlled at about 50 ℃.Then adding water is diluted to 20-30% to acid and is heated to 100 ℃ of sugar that make biomass degradation discharge solubility.Concentrated acid technique is very early by Industry Promotion, particularly in states such as USSR (Union of Soviet Socialist Republics) and Japan.But specific period and environment that the successful use of these techniques just is confined to.For example when energy dilemma, in the situation that do not consider the economic competitiveness such as biofuel production.In the U.S. two Arkenol of company and Masada Resource Group and USDOE and renewable energy source National Laboratory (NREL) cooperation improvement and this technology of business promotion are arranged at present, utilize it to process the various biomass wastes that come from industrial and agricultural production and life, produce comprise biofuel and other high value added products in, solve the problem of environmental pollution.
Directly the dilute acid hydrolysis method is coordinated hemicellulose and cellulosic property difference in the biomass resource by two one-step hydrolysis, reduces in the technological process discharging the destruction of sugar, raising candy output and efficient.The first step is to carry out under relatively mild condition, from the hemicellulose of easy degraded, to discharge to greatest extent sugar (Lee Y, Iyer P, Torget R.Dilute-Acid Hydrolysis of Lignocellulosic Biomass.In:Tsao G, Brainard A, Bungay H, et al., eds.Recent Progress in Bioconversion of Lignocellulosics:Springer Berlin/Heidelberg, 1999:93-115.).Second step is hydrolyzed the Mierocrystalline cellulose part of difficult degradation with relatively fierce reaction conditions.NREL report points out that the dilute acid hydrolysis process of cork is: act on 3min with 0.7% dilute sulphuric acid at 190 ℃ first; Then with 0.4% diluted acid at 215 ℃ of other 3min of effect.Higher candy output is arranged like this.The diluted acid process has quite more industry experience.Many factories that utilize diluted acid to soak into technique are set up in Germany, Japan and in the past 50 years of Russia.But these diluted acids soak into technique still is difficult to existence in market with keen competition.The refuse that utilizes now the enterprise of this technical matters to remain to process as relate to environmental problem is processed and is used in some paper industries.
At present wide concerned be the enzyme hydrolysis process that is based upon on the biomass pre-treatment basis.Biomass resource is by pre-treatment (the Mosier N of different thermochemical process, Wyman C, Dale B, et al.Features of promising technologies for pretreatment of lignocellulosic biomass.Bioresource Technology 2005; Be that the compound enzymic preparation of core carries out enzymic hydrolysis and makes the biomass resource that is comprised of polymkeric substance be degraded into liquid glucose or malt sugar that monose and a small amount of oligosaccharides of solubility form with cellulase 96:673-686).These liquid glucoses or malt sugar can be used to the bio-based compound of fermentative production cellulose alcohol or other high added value.The thermochemistry pre-treatment of biomass resource has multiple diverse ways, comprise hot-water pretreatment, the acid pre-treatment, the alkali pre-treatment, ammonia is swollen quick-fried, lime heap buried processing etc., its Main Function is xylogen and the hemicellulose that is coated on the Mierocrystalline cellulose periphery in removal or the degradation biological matter resource, destroy tough and tensile stubborn cellulose crystals structure, make zymin can effectively act on the destroyed Mierocrystalline cellulose of crystalline structure, the acceleration enzyme liberating discharges the sugar (ZhuJY of solubility, PanX, Zalesny RS Jr.Pretreatment of woody biomass for biofuel production:energy efficiency, technologies, and recalcitrance.Appl Mcirobial Biotechnol.2010,87 (3): 847-57.).
Although it is the present the most promising technique that the thermochemistry pre-treatment of biomass resource adds enzymic hydrolysis, it is the process of a complexity relatively.Different thermochemistry pre-treatment meetings affects enzymolysis process subsequently significantly, and different biomass resources also has different impacts in different thermochemical process, thereby affects enzymolysis.Also have the cost of zymin and the development that efficient affects whole technique especially.Its process costs also fails to reach people's re-set target at present, when particularly linking with the production of fuel alcohol, require further improvement especially technique, comprise the exploration of the pretreated process of thermochemistry and be used in combination, improve the efficient of zymin, reduce (Lin Y, the Tanaka S.Ethanol fermentation from biomass resources:current state and prospects.Applied Microbiology and Biotechnology 2006 such as cost; 69:627-642).
At present, an other potential technology be used to utilizing biomass to obtain sugar is supercutical fluid (Supercritical fluid, SCF) technology for hydrolyzing (what North Sea, Lin Lu, Sun Runcang, Sun Yong. the lignocellulose chemical hydrolysis produces fermentable sugars research. chemical progress 2007; 19:1141-1146; Yu Q, Wu P, Xu P, Li L, Liu T, Zhao L. Synthesis of cellulose/titanium dioxide hybrids in supercritical carbon dioxide.Green Chemistry 2008; 10:1061-1067).In supercutical fluid, the spread coefficient of molecule is between gas, liquid, has unique solvability, make reaction become homogeneous phase, and then the chemical reaction under the acceleration super critical condition, its distinguishing feature is to react without any need for catalyzer the reaction times shorter (being lower than 10s), reaction preference is high, and environment is not polluted.But utilize supercritical hydrolysis technique to carry out Wood Adhesives from Biomass, its main component is oligose, need to have other supporting technologies that oligose is converted into and can be used for the monose that microbial fermentation is produced.Therefore this technology still has certain limitation, need to be further perfect, improve the productive rate of monose.
In sum, the biomass resource effectively hydrolyzing, improve the output of sugar and the huge challenge task that productive rate remains its trans-utilization.Improve in development on the basis of existing various technology platforms, the biomass resource technology for hydrolyzing of Development of New Generation, set up novel, sugared platform remains extremely important (DOE BiomassMulti-year Program Plan.2008) cheaply.
Summary of the invention
[purpose of the present invention]
The object of the present invention is to provide a kind of ionic liquid effect hydrolyzing biomass resource of utilizing to produce the efficient novel method that microorganism can utilize sugar.The fermentable sugars productive rate that generates after ionic liquid effect hydrolysis can reach between the 70-90%, utilizes traditional direct Concentrated acid hydrolysis method, direct dilute acid hydrolysis method and thermochemistry pre-treatment to add enzyme hydrolysis method, and energy consuming ratio is higher.When utilizing by contrast the green solvent ionic liquid effect hydrolyzing biomass of safety and environmental protection, cost is low, and efficient is high.The fermentable sugars that generates can be utilized by yeast saccharomyces cerevisiae after ion exchange column separates.Employed ionic liquid can reuse after separating.
[thinking of the present invention]
Ionic liquid is a kind of green solvent of safety and environmental protection, and it has the effect of destroying simultaneously cellulosic crystalline network and dissolving cellulos.Mierocrystalline cellulose after the dissolving can generate fermentable sugars through hydrolysis.Ionic liquid in the hydrolyzed solution can reuse after separating; Glucide can be used for producing biofuel as important hardware and software platform compound, chemical preparations, polymer and material etc.
[technological line of the present invention]
Technological line of the present invention is as follows:
(1) biomass material of selecting is crushed to the 4-200 order;
(2) biomass material and a certain amount of ionic-liquid catalyst that crush are put into reactor;
(3) with reactor heating 1-6h under 90-120 ℃, make cellulose dissolution in the biomass material;
(4) add a small amount of acid and a certain amount of water and be hydrolyzed 80-130 ℃ of lower the continuation, the total reducing sugar rate of recovery can reach more than 70%;
(5) with reactor as in the cooling bath, its internal temperature is down to rapidly below 50 ℃, in order to avoid the sugar that generates is degraded;
(6) utilize ion exchange column with hydrolyzed solution intermediate ion liquid with after glucide separates, ionic liquid is reusable;
(7) hydrolyzed solution after will separating is regulated pH to 5.0, at 30 ℃, cultivate under the 200rpm behind the inoculation yeast saccharomyces cerevisiae, but the glucose complete hydrolysis in the hydrolyzed solution generates ethanol.
[advantage of the present invention]
Advantage of the present invention is:
(1) selecting ionic liquid is solvent, and safety and environmental protection can not cause corrosion to plant and instrument, and reacted ionic liquid can reuse after separating, and meets the principle of Green Chemistry;
(2) total sugar yield is high, can reach more than 70%;
(3) can make Mierocrystalline cellulose and hemicellulose direct hydrolysis generate malt sugar through ion liquid dissolving and after adding the water hydrolysis, and need not use the biological enzyme bacterium;
(4) biomass behind ion liquid dissolving, when acid adding and water were hydrolyzed reaction again, the consumption of required acid was compared with using an acidic catalyst, and consumption has reduced by 50 times.
Implementation
Embodiment 1
Getting 0.1g and be crushed to 40 purpose biomass material and 2g[EMIM] Cl is behind 105 ℃ of reacting by heating 3h, add successively 7wt%HCl (HCl accounts for the per-cent of biomass quality) and 5,20,25,33 and 43% water is behind 105 ℃ of lower continuation hydrolysis 3h, rapidly reactor is put into cooling bath, the temperature in the reactor is reduced to rapidly below 50 ℃, the total reducing sugar rate of recovery can reach 90% under this condition.
Embodiment 2
Getting 0.1g and be crushed to 10 purpose biomass material and 2g[EMIM] Cl is behind 90 ℃ of reacting by heating 3h, add successively 7wt%HCl (HCl accounts for the per-cent of biomass quality) and 5,20,25,33 and 43% water is behind 105 ℃ of lower continuation hydrolysis 3h, rapidly reactor is put into cooling bath, the temperature in the reactor is reduced to rapidly below 50 ℃, the total reducing sugar rate of recovery can reach 40% under this condition.
Embodiment 3
Getting 0.1g and be crushed to 40 purpose biomass material and 2g[EMIM] Cl is behind 105 ℃ of reacting by heating 3h, add successively the water of 7wt%HCl (HCl accounts for the per-cent of biomass quality) and 5% behind 105 ℃ of lower continuation hydrolysis 3h, rapidly reactor is put into cooling bath, temperature in the reactor is reduced to rapidly below 50 ℃, and the total reducing sugar rate of recovery can reach 20% under this condition.
Embodiment 4
Get said hydrolyzed liquid 5mL, regulate about pH to 5.0, the yeast saccharomyces cerevisiae (Angel dry yeast 1-3%) that activation is good is inoculated in the hydrolyzed solution, in 30 ℃, cultivates under the 200rpm.Behind the 36h, the glucose in the hydrolyzed solution can transform generation ethanol fully.
Claims (10)
1. efficient novel method of utilizing ionic liquid effect hydrolyzing biomass resource to produce the microorganism fermentable sugars, step is as follows:
(1) biomass material is added in a certain amount of ionic liquid, the cellulosic crystalline texture in the biomass is damaged, and is dissolved in the ionic liquid;
(2) add a certain amount of HCl and the necessarily water continuation hydrolysis of content to reactor, the rate of recovery of total reducing sugar is reached more than 70%;
(3) glucose of hydrolysis generation can be utilized by yeast saccharomyces cerevisiae fully, generates ethanol.
2. press the method described in the claim 1 by claim 1, it is characterized in that: described biomass material comprises cork, hardwood, agricultural wastes, stalk and algae bio matter etc.
3. press the method described in the claim 1 by claim 1, it is characterized in that: described biomass material should be crushed to the 4-200 order before use.
4. by the method described in the claim 1, it is characterized in that: described ionic liquid comprises alkyl imidazole ionic liquid, alkyl pyridine class ionic liquid and quaternary ammonium alkyl class ionic liquid etc.
5. by the method described in the claim 3, it is characterized in that: described acid content is at 0-10%; Described water-content is at 5-50%.
6. by the method described in the claim 1, it is characterized in that: described reactor is batch reactor.
7. by the method described in the claim 1, it is characterized in that: required decrystallizing temperature is between 90-120 ℃, and the reaction times is at 1-6h.
8. by the method described in the claim 1, it is characterized in that: required hydrolysis temperature is between 80-130 ℃, and the reaction times is at 1-6h.
9. by the method described in the claim 1, it is characterized in that: after reflection finished, reactor needed to be cooled in cold water below 50 ℃, in order to avoid the sugar that generates is degraded.
10. by the method described in the claim 1, it is characterized in that: the glucose that hydrolysis generates can be transformed by the yeast saccharomyces cerevisiae utilization fully and generate ethanol under 30 ℃ of condition.
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Cited By (2)
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| CN103740867A (en) * | 2014-01-02 | 2014-04-23 | 上海大学 | Method for preparing glucose by hydrolyzing straw celluloses |
| CN105039424A (en) * | 2015-07-07 | 2015-11-11 | 河南科技大学 | Method for producing ethanol from biomass containing cellulose |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105039424A (en) * | 2015-07-07 | 2015-11-11 | 河南科技大学 | Method for producing ethanol from biomass containing cellulose |
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Application publication date: 20130213 |