CN102757982A - Novel method for producing fermentable sugars by hydrolyzing biomass under synergistic effect of acid and salt - Google Patents

Novel method for producing fermentable sugars by hydrolyzing biomass under synergistic effect of acid and salt Download PDF

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Publication number
CN102757982A
CN102757982A CN2011101132574A CN201110113257A CN102757982A CN 102757982 A CN102757982 A CN 102757982A CN 2011101132574 A CN2011101132574 A CN 2011101132574A CN 201110113257 A CN201110113257 A CN 201110113257A CN 102757982 A CN102757982 A CN 102757982A
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acid
method described
biomass
hydrolysis
fermentable sugars
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王钦宏
周娜
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Tianjin Institute of Industrial Biotechnology of CAS
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Tianjin Institute of Industrial Biotechnology of CAS
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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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel

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Abstract

The invention relates to a novel method for producing fermentable sugars by hydrolyzing biomass under the synergistic effect of acid and magnesium salt. Particularly, the biomass which is taken as the raw materials and the acid and magnesium salt which are taken as mixed catalysts are hydrolyzed at the temperature of 120 to 230 DEGC; and the hydrolysate stays in a reactor for 1 to 60 min. The total yield of the sugars can reach above 70% and is higher than the sum of the yields of the sugars obtained by using the acid and magnesium salt separately.

Description

The novel method that a kind of hydrochlorate synergy hydrolyzing biomass is produced fermentable sugars
Technical field
The invention belongs to renewable biomass resources development and utilization field, particularly a kind of high efficiency method that utilizes acid and inorganic magnesium salt synergy 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 staple comprises Mierocrystalline cellulose, semicellulose and xylogen etc., and wherein the content of Mierocrystalline cellulose and semicellulose accounts for 70%-80%.Mierocrystalline cellulose and semicellulose under certain conditions can hydrolysis generate the malt sugar of solubilities such as glucose, wood sugar; These saccharide compounds can comprise alcohol fuel and hydrogen through the method production of chemistry or bio-transformation; And various carbon group compounds, like high value such as glycerine, lactic acid, amino acid, polyvalent alcohol, diprotic acid bio-based product.Like this, not only can substitute existing is the technology of feedstock production alcohol fuel with grain and glucide, reduces the production cost of the energy, solves the shortage of energy sources problem; For effective minimizing environmental pollution, protection ecology and environment also benefit 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 of lignocellulosic materials for ethanol production:a review.Bioresource Technology 2002; 83:1-11).
Directly the concentrated acid hydrolysis method at first be with the sulfuric acid about 70-77% water cut 10% biomass crystalline structure destruction.The acid in this step and the ratio of substrate were at 1.25: 1, and temperature is controlled at about 50 ℃.Adding water then is diluted to 20-30% to acid and is heated to 100 ℃ of sugar that make biomass degradation discharge solubility.Concentrated acid technology is very early by Industry Promotion, particularly in states such as the FSU and Japan.But specific period and environment that the successful use of these technologies just is confined to.For example when energy dilemma, under the situation of not considering economic competitiveness such as biofuel production.Mainly contain 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 in the U.S. at present; Utilize it to handle the various biomass wastes that come from industrial and agricultural production and life; Produce comprise biofuel and other high value added products in, solve environmental pollution problems.
Directly the dilute acid hydrolysis method is coordinated semicellulose and cellulosic property difference in the biomass resource through two one-step hydrolysis, reduces in the technological process discharging the destruction of sugar, raising candy output and efficient.The first step is under relatively mild condition, to carry out, from the semicellulose that is prone to degraded, to discharge sugar (Lee Y, Iyer P to greatest extent; 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 with the Mierocrystalline cellulose part of fierce relatively reaction conditions hydrolysis difficult degradation.The NREL report points out that the dilute acid hydrolysis process of cork is: elder generation acts on 3min with 0.7% dilute sulphuric acid at 190 ℃; 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 technology are set up in Germany, Japan and in the past 50 years of Russia.But these diluted acids soak into technology still is difficult in market with keen competition, be able to existence.Utilize the enterprise of this technical matters to remain processing now as relating to the waste treatment of environmental problem and in some paper industries, using.
What extensively paid close attention at present is the enzyme hydrolysis process that is based upon on the biomass pre-treatment basis.Biomass resource is through pre-treatment (the Mosier N of different thermochemical process; Wyman C; Dale B, et al.Features of promising technologies for pretreatment of lignocellulosic biomass.BioresourceTechnology 2005; 96:673-686) back uses cellulase to carry out enzymic hydrolysis as the compound enzymic preparation of core to make the biomass resource of being made up of polymkeric substance be degraded into monose and liquid glucose or the malt sugar formed of the oligosaccharides of solubility on a small quantity.These liquid glucoses or malt sugar can be used to the bio-based compound of fermentative prodn Mierocrystalline cellulose alcohol or other high added value.The thermochemistry pre-treatment of biomass resource has multiple diverse ways, comprises the hot water pre-treatment, sour pre-treatment; The alkali pre-treatment, ammonia is swollen quick-fried, and lime pile buries processing etc.; It mainly acts on is to be coated on Mierocrystalline cellulose peripheral xylogen and semicellulose in removal or the degradation biological matter resource; Destroy tough and tensile stubborn Mierocrystalline cellulose crystalline structure, make zymin act on crystalline structure effectively and be destroyed Mierocrystalline cellulose, quicken sugar (the Zhu JY that enzyme liberating discharges solubility; Pan X; Zalesny RS Jr.Pretreatment of woody biomass for biofuel production:energy efficiency, technologies, and recalcitrance.Appl Microbiol Biotechnol.201087 (3): 847-57.).
Though it is the most promising at present technology that the thermochemistry pre-treatment of biomass resource adds enzymic hydrolysis, it is the process of a complicacy relatively.Different thermochemistry pre-treatment meetings influence enzymolysis process subsequently significantly, and different biomass resources also has different influences in different thermochemical process, thereby influences enzymolysis.Also have the cost of zymin and the development that efficient influences whole technology especially.Its technology cost also fails to reach people's re-set target at present; When particularly linking with production of fuel ethanol; Need especially further to improve technology, comprise the exploration and the combination use of the pretreated process of thermochemistry, improve the efficient of zymin; (Lin Y, Tanaka S.Ethanol fermentation from biomass resources:current state and prospects.Applied Microbiology and Biotechnology 2006 such as reduce cost; 69:627-642).
At present; An other potential technology that is used to utilize 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 has unique solvability between gas, liquid; 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 is lacked (being lower than 10s); Reaction preference is high, and environment is not polluted.But utilize overcritical hydrolysis technology to carry out Wood Adhesives from Biomass, its staple is an oligose, needs other supporting technologies and is converted into oligose the monose that can be used for microbial fermentation production.Therefore should certain limitation still be arranged technology, need be further perfect, improve the productive rate of monose.
In sum, the biomass resource effectively hydrolyzing, improve the output of sugar and the great challenge property 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 the important prerequisite (DOE Biomass Multi-year Program Plan.2008) that realizes the renewable biomass resources effective utilization cheaply.
Summary of the invention
[the object of the invention]
The object of the present invention is to provide a kind of efficient novel method of utilizing acid and magnesium salts synergy hydrolyzing biomass resource to produce mikrobe sugar capable of using.The fermentable sugars productive rate that after the synergy hydrolysis, generates 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.By contrast cheap inorganic mineral magnesium salts is added corresponding acid, during the two synergy hydrolyzing biomass, cost is low, and efficient is high.The fermentable sugars that generates also can be utilized by mikrobes such as yeast saccharomyces cerevisiaes.The magnesium salts that adds can reuse after separating.
[thinking of the present invention]
The inorganic mineral magnesium salts is a kind of weak Lewis acid, and it has the effect of destroying cellulosic crystalline network and hydrolyzation catalysis simultaneously.At normal temperatures,, surpass about 160 ℃ in temperature and can discharge proton, the pH value is dropped between the 4-5 though be neutral.And after cooling, can recover neutral.With after acid mixes, the character of the salt of acidity and the magnesium salts of acid makes the structure destructible more of biomass with it, makes wherein Mierocrystalline cellulose, the semicellulose generation fermentable sugars of degrading.
[technological line of the present invention]
Technological line of the present invention is following:
(1) biomass material of selecting for use is crushed to the 4-200 order;
(2) preparation is by the mixed catalyst of acid and corresponding salt formation thereof;
(3) biomass material that crushes and a certain amount of hydrochlorate mixed catalyst are put into reactor drum;
(4) reactor drum is heated 1-60min down at 120-230 ℃, the total reducing sugar recovery can reach more than 70%;
(5) with reactor drum as in the cooling bath, its internal temperature is reduced to below 105 ℃, in order to avoid the sugar that generates is degraded rapidly.
(6) with behind the hydrolyzed solution adjusting pH to 5.0 that generates, at 30 ℃, 200rpm cultivates down 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) total sugar yield is high, and acid and the two synergy of magnesium salts can make sugar generation more than 70%, the summation of the total reducing sugar recovery that obtains when being higher than independent use acid or salt.
(2) cost is low, and magnesium chloride is cheap, and can reuse after the cooling.
(3) the two synergy can make Mierocrystalline cellulose and semicellulose direct hydrolysis generate malt sugar, and need not use the enzyme bacterium.
(4) magnesium salts does not have the effect that obviously suppresses for most of microbe cell growth etc.
Practical implementation
Embodiment 1
Get 1g and be crushed to 40 purpose biomass materials, add 5mL (1) 2%HCl respectively; Perhaps (2) 2%HCl and 2.5%MgCl 2Mixed catalyst.Reactor drum behind heating 10min under 180 ℃, is put into cooling bath rapidly, the temperature in the reactor drum is reduced to rapidly below 105 ℃.Do not add MgCl 2The time, the total reducing sugar recovery has only 42.59%, and is added with MgCl 2The hydrochlorate mixed catalyst then can make the total reducing sugar recovery be increased to 83%.
Embodiment 2
Get 1g and be crushed to 10 purpose biomass materials, add 5mL (1) 4%HCl respectively; Perhaps (2) 4%HCl and 2.5%MgCl 2Mixed catalyst.Reactor drum behind heating 10min under 180 ℃, is put into cooling bath rapidly, the temperature in the reactor drum is reduced to rapidly below 105 ℃.Do not add MgCl 2The time, the total reducing sugar recovery is 72%, and is added with MgCl 2The hydrochlorate mixed catalyst then can make the total reducing sugar recovery be increased to 80%.
Embodiment 3
Get 1g and be crushed to 10 purpose biomass materials, add 5mL (1) 0.5%HCl respectively; Perhaps (2) 0.5%HCl and 2.5%MgCl 2Mixed catalyst.Reactor drum behind heating 10min under 180 ℃, is put into cooling bath rapidly, the temperature in the reactor drum is reduced to rapidly below 105 ℃.Do not add MgCl 2The time, the total reducing sugar recovery is 6.7%, and is added with MgCl 2The hydrochlorate mixed catalyst then can make the total reducing sugar recovery be increased to 7.5%.
Embodiment 4
Get said hydrolyzed liquid 5mL, regulate about pH to 5.0, the yeast saccharomyces cerevisiae that activation is good (Angel dry yeast 1-3%) is inoculated in the hydrolyzed solution, and in 30 ℃, 200rpm cultivates down.Behind the 36h, the glucose in the hydrolyzed solution can transform generation ethanol fully.

Claims (9)

1. one kind is utilized efficient novel method sour and that magnesium salts synergy hydrolyzing biomass resource is produced the mikrobe fermentable sugars, and step is following:
(1) biomass material is added in a certain amount of acid and the magnesium salts mixed catalyst the higher fermentable sugars of productive rate in the time of can making Mierocrystalline cellulose and hydrolysis of hemicellulose in the biomass generate than utilize separately pure diluted acid catalyzer;
(2) with the sufficiently long time of heating under the reactor drum certain temperature, the recovery of total reducing sugar is reached more than 70%;
(3) glucose of hydrolysis generation can generate ethanol fully by the yeast saccharomyces cerevisiae utilization.
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 acid comprises H 2SO 4, HCl and HNO 3Deng strong acid; Described salt comprises MgSO 4, MgCl 2And MgNO 3Deng.
5. by the method described in the claim 3, it is characterized in that: described acid concentration is at 0.5-6%; Described salt concn is at 0.5-7.5%.
6. by the method described in the claim 1, it is characterized in that: described reactor drum is a batch reactor.
7. by the method described in the claim 1, it is characterized in that: required Heating temperature is between 120-230 ℃, and the reaction times is at 1-60min.
8. by the method described in the claim 1, it is characterized in that: after reflection finished, reactor drum needed in cold water, to be cooled to below 50 ℃, in order to avoid the sugar that generates is degraded.
9. 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.
CN2011101132574A 2011-04-27 2011-04-27 Novel method for producing fermentable sugars by hydrolyzing biomass under synergistic effect of acid and salt Pending CN102757982A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104229805A (en) * 2014-09-03 2014-12-24 华南理工大学 Method for preparing fermentable sugar and nanometer silicon dioxide by utilizing rice hulls

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002018610A1 (en) * 2000-08-09 2002-03-07 Midwest Research Institute Ethanol production with dilute acid hydrolysis using partially dried lignocellulosics
US20100268000A1 (en) * 2009-04-20 2010-10-21 Qteros, Inc. Compositions and Methods for Fermentation of Biomass

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002018610A1 (en) * 2000-08-09 2002-03-07 Midwest Research Institute Ethanol production with dilute acid hydrolysis using partially dried lignocellulosics
US20100268000A1 (en) * 2009-04-20 2010-10-21 Qteros, Inc. Compositions and Methods for Fermentation of Biomass

Non-Patent Citations (1)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104229805A (en) * 2014-09-03 2014-12-24 华南理工大学 Method for preparing fermentable sugar and nanometer silicon dioxide by utilizing rice hulls
CN104229805B (en) * 2014-09-03 2016-06-29 华南理工大学 A kind of method utilizing rice husk to prepare fermentable sugars and nano silicon

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Application publication date: 20121031