CN103031339B - Method for producing ethanol by wood fiber raw material - Google Patents
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Abstract
The invention relates to a method for producing ethanol by a wood fiber raw material, which mainly solves the problem of low total sugar yield rate in the prior art. Aiming at well solving the problem, the method adopts the technical scheme that the method comprises the following steps of (1) crushing the wood fiber raw material, and effectively and continuously impregnating the wood fiber raw material with dilute acid at the temperature of 20 to 80 DEG C, maintaining for 1 to 15 minutes, and dehydrating; (2) treating the dehydrated material for 1 to 35 minutes at the temperature of 80 to 200 DEG C and the pressure of 0.4 to 10 MPa; (3) carrying out instantaneous depressurizing and blasting on the material treated in step (2), so as to obtain a porous fluffy wet material containing pentose; (4) washing the porous fluffy wet material containing the pentose to obtain a pentose solution, and a material containing cellulose and lignin; (5) adding water into the material containing the cellulose and the lignin, so as to prepare into the required concentration of a dry matter, and hydrolyzing by a cellulase to obtain an enzymatic hydrolyzate containing hexose; (6) fermenting the enzymatic hydrolyzate containing the hexose to obtain a fermented liquor A containing ethanol; (7) fermenting the pentose solution to obtain a fermented liquor B containing ethanol; and (8) mixing the fermented liquor A and the fermented liquor B, and concentrating to obtain the ethanol with the purity of 95%. The method can be used for the industrial production of the ethanol produced by the wood fiber raw material.
Description
Technical field
The present invention relates to a kind of method by preparing ethanol from wood fiber raw material.
Background technology
The crises such as the energy that 21 century faces, resource, environment, have become the major obstacle of Development of Human Civilization.People are striving to find the new forms of energy of substitute fossil fuels, to reduce dependence to Nonrenewable energy resources, control the discharge of carbonic acid gas, to preserve the ecological environment.Lignocellulose raw material is the renewable resources that on the earth, output is maximum, comprises forest, agricultural crop straw, agricultural byproducts processing tankage etc.At present in these resources, be used for except the industries such as paper pulp papermaking, building, weaving, feed except minority, major part is slatterned in vain.Therefore, exploitation lignocellulosic material prepares the developing direction that the technique of ethanol is following alcohol production.
The technique that lignocellulosic material prepares ethanol mainly comprises four steps: pre-treatment, enzymic hydrolysis, fermentable and separation of ethanol.Wherein, preconditioning technique is converted into the committed step of the energy as lignocellulose, has become the focus that researcher is paid close attention to.Lignocellulosic material contains Mierocrystalline cellulose, hemicellulose and xylogen, when adopting cellulase hydrolysis Woody Biomass to prepare ethanol, cellulase must Contact-sorption to cellulosic substrate just can make reaction carry out, therefore, the accessibility of Mierocrystalline cellulose to cellulase is the key factor determining hydrolysis rate.The condition of surface of cellulosic crystallizing field, Woody Biomass, the multiple component structure of Woody Biomass, xylogen are caused Woody Biomass to be difficult to degrade to cellulosic provide protection and Mierocrystalline cellulose by the factor of the structures such as hemicellulose covering and chemical composition.Generally, the enzymatic hydrolyzation of the Woody Biomass of not pretreated native state is less than 20%.Therefore, pre-treatment must be carried out to raw material, Mierocrystalline cellulose, hemicellulose are separated with xylogen, break cellulosic crystalline texture, improve Mierocrystalline cellulose to the accessibility of enzyme, make cellulase penetrate into Mierocrystalline cellulose, thus enzymolysis Mierocrystalline cellulose effectively.
The pre-treatment of lignocellulose raw material has multiple method, and comparatively conventional is acidic treatment.CN101705255A discloses a kind of method utilizing crop material fermentative production of ethanol, at 120 ~ 150 DEG C, absolute pressure is under the condition of 0.2 ~ 0.6MPa, with 0.5% ~ 1% diluted acid, pretreatment reaction is carried out 1 ~ 3 hour to stalk, then by obtaining ethanol through enzymatic hydrolysis and fermentation after the warm water washing of 60 DEG C.Plant or plant refuse are carried out immersion treatment with the acid solution of 0.1 ~ 3% by CN101696419A at the temperature of 160 ~ 300 DEG C, decompose and obtain xylogen, and isolate Mierocrystalline cellulose, D-wood sugar and L-arabinose; Apply constructed saccharomyces cerevisiae engineered yeast again and carry out fermentative production of ethanol in 28 ~ 30 DEG C.Although this acid treatment method can hydrolyzed hemicellulose, the by product produced is many, and the loss of total reducing sugar is large, and part by product produces restraining effect to fermentation, causes follow-up total sugar utilization lower.
Current bibliographical information what have prospects for commercial application most is physico-chemical processes-steam explosion.Steam explosion mainly under neutral or basic conditions, utilizes the fibrous material of high-temperature high-pressure steam process, and realizes Component seperation and the structural changes of raw material by moment pressure leak process.Document CN101693905A discloses the maize straw segment of maturation, then temperature be 220 ~ 240 DEG C, pressure be the condition of 1.6 ~ 1.8MPa under steam explosion pre-treatment 4 ~ 6 minutes, obtain steam puffed stalk.It is raw material that document CN1786340A discloses with stalk, steam explosion is carried out after rough lumber, by stalk oven dry weight 0.5 ~ 2% add caustic soda, under 145 ~ 180 DEG C of vapor phase pulping temperature, 0.9 ~ 2.0MPa pressure, process 12 ~ 18 minutes, instant decompression release obtains steam puffed stalk.Although steam explosion has treatment time short, few, the free of contamination advantage of pharmaceutical chemicals consumption under neutral or alkaline condition, but on the one hand because hemicellulose, Mierocrystalline cellulose and xylogen three winding arrangement are not fully opened, the accessibility of Mierocrystalline cellulose to cellulase is low, causes subsequent fiber element hydrolysis efficiency lower; On the other hand, due under neutrallty condition, hemicellulose effectively cannot be degraded into pentose, and pentose fails to make full use of; This all makes total reducing sugar yield lower.In addition, owing to being that raw material is contained in steam-explosion jar, can only a tank one tank ground batch process, can not continuous operation, production efficiency is low.
Acid treatment of the prior art is only at high temperature process raw material, obtain for the purpose of pentose by direct degradation of hemicellulose, can not make remaining hemicellulose, between Mierocrystalline cellulose and xylogen combine closely loose, follow-up enzymolysis process cellulase cannot be improved to cellulosic accessibility, thus make total reducing sugar yield lower.And the inventive method, first adopt diluted acid to flood lignocellulose raw material at low temperatures.In this process, although lignocellulose raw material is by acid dipping, Yin Wendu is lower, hemicellulose is not yet degraded, hemicellulose, Mierocrystalline cellulose, xylogen three still exist with solid form, just allow acid penetrate in stalk structure, are then used by extruding, dehydration separating acid solution circulated.Raw material after low temperature dipping, again by High Temperature High Pressure boiling, and maintain the suitable residence time, remaining acid is allowed thoroughly to penetrate in lignocellulose raw material structure, the most of hemicelluloses in hemicellulose, Mierocrystalline cellulose and xylogen three winding arrangement are made to take the lead in acid condition deviating from from winding arrangement, generate pentose, the most important thing is to make remaining hemicellulose, combining closely between Mierocrystalline cellulose and xylogen obtain preliminary breaking.
Material after diluted acid low temperature dipping, high temperature steaming, then through instant decompression explosion.With moment pressure release mode process lignocellulose raw material, countless porous fluffy body can be formed, the form of lignocellulose raw material is broken refinement, inherent crystalline structure is destroyed, make hemicellulose, the winding arrangement of Mierocrystalline cellulose and xylogen three is fully opened, reduce the cellulosic polymerization degree, degree of crystallinity, destroy xylogen, the key coat of hemicellulose, separate xylogen, add effective ratio area, add cellulosic accessibility, cellulase is made to penetrate into Mierocrystalline cellulose enzymolysis Mierocrystalline cellulose effectively, thus further increase total sugar utilization.Compared with acid treatment of the prior art, final total reducing sugar yield can improve more than 15%, achieves good technique effect.
In addition, the inventive method can realize pulverizing in three-stage screw extrusion equipment, diluted acid dipping, extruding, tentatively expanded, High Temperature High Pressure boiling, moment pressure release, because material is ejected instantaneously, the residence time is short, so can realize continuous operation.Pentose liquid glucose first ferments after concentrate again, particularly preferably uses film concentrate, improves the alcohol concn after pentose fermentation, alleviates the energy consumption burden of postorder ethanol concentrate operation.
Below by embodiment, the present invention is further elaborated.
Summary of the invention
Technical problem to be solved by this invention is that prior art exists the low problem of total reducing sugar yield, provide a kind of newly by the method for preparing ethanol from wood fiber raw material.The method has the high feature of total reducing sugar yield.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method by preparing ethanol from wood fiber raw material, comprises the following steps:
1) lignocellulose raw material is pulverized, with the effective continuous impregnating of diluted acid under 20 ~ 80 DEG C of conditions, 1 ~ 15 minute residence time, then dewater;
2) material after dehydration processes 1 ~ 35 minute under temperature 80 ~ 200 DEG C, pressure 0.4 ~ 10MPa condition;
3) step 2) material after process through instant decompression explosion, obtain containing the porous fluffy wet stock of pentose;
4) the porous fluffy wet stock containing pentose obtains pentose solution at 10 ~ 100 DEG C through washing, and the material of cellulose and xylogen;
5) step 4) cellulose that obtains and xylogen material in add water, be made into required dry concentration, 30 ~ 70 DEG C, under the condition of pH=1 ~ 7 through cellulase hydrolysis 8 ~ 120 hours, obtain the enzymolysis solution containing hexose;
6) step 5) obtain containing hexose enzymolysis solution 20 ~ 45 DEG C, carry out zymophyte fermentation 12 ~ 144 hours under the anaerobic condition of pH=3 ~ 8, obtain the fermentation liquid A containing ethanol;
7) step 4) pentose solution that obtains 20 ~ 45 DEG C, pH=3 ~ 8, ventilation ratio carry out zymophyte fermentation 12 ~ 144 hours under being the aerobic condition of 0.1 ~ 1, obtain the fermentation liquid B containing ethanol;
8) fermentation liquid A and fermentation liquid B obtains through concentrate the ethanol that purity is 95% after mixing.
In technique scheme, step 1) diluted acid dipping temperature preferable range is 30 DEG C ~ 70 DEG C, dipping residence time preferable range is 3 ~ 11 minutes.Step 2) treatment temp preferable range is 120 ~ 190 DEG C, processing pressure preferable range is 0.5 ~ 2MPa, and treatment time preferable range is 8 ~ 30 minutes.Step 4) washing temperature preferable range is 20 ~ 80 DEG C.Step 5) hydrolysis temperature preferable range is 40 ~ 60 DEG C, pH value preferable range is 3 ~ 6, and enzymolysis time preferable range is 12 ~ 96 hours.Step 6) zymohexose temperature preferable range is 25 ~ 40 DEG C, pH value preferable range is 4 ~ 7, and fermentation time preferable range is 24 ~ 120 hours.Step 7) pentose fermentation temperature preferable range is 25 ~ 40 DEG C, pH value preferable range is 4 ~ 7, and ventilation ratio preferable range is 0.3 ~ 0.5, and fermentation time preferable range is 24 ~ 120 hours.Step 1) described in diluted acid be selected from least one in sulfuric acid, oxalic acid or phosphoric acid, its weight percent concentration is 0.3 ~ 3%.Step 1) lignocellulose raw material is after diluted acid dipping, and dry matter content is 10 ~ 80%, and preferable range is 20 ~ 75%.Step 3) described in containing pentose porous fluffy wet stock in dry matter content be 20 ~ 45%, wherein pentose content accounts for 8 ~ 20% of dry total amount.Step 4) described in washing liquid-solid ratio be (1: 1) ~ (20: 1).Step 5) described in required dry concentration be 10 ~ 35%.The bacterial classification of production of cellulose enzyme is selected from least one in Trichodermareesei or aspergillus niger, and preferred version is for being selected from Trichodermareesei; The consumption of cellulase is 0.02 ~ 0.20 gram of/gram of Mierocrystalline cellulose.Described zymohexose bacterium is selected from least one in zymomonas mobilis or yeast saccharomyces cerevisiae, and preferred version is for being selected from yeast saccharomyces cerevisiae, and its consumption is 0.1 ~ 10 grams per liter.Described pentose fermentation bacterium is selected from least one in pichia stipitis or candiyeast, and preferred version is for being selected from pichia stipitis, and its consumption is 0.2 ~ 20 grams per liter.Step 7) described in before pentose solution fermentation first concentrate to containing pentose 40 ~ 120 grams per liter.Lignocellulose raw material preferred version is for being selected from maize straw, rice straw, Wheat Straw, plant plait or beanstalk.
In the inventive method, step 1) in the acid-containing solution that removes can recycle.Step 5) cellulase hydrolysis, step 6) containing hexose enzymolysis solution fermentation and step 7) pentose solution ferment time, can add microbiotic, microbiotic is selected from least one in penicillin or penbritin, and its consumption is 1 × 10
-4~ 10 × 10
-4grams per liter.Step 6) containing hexose enzymolysis solution fermentation and step 7) pentose solution ferment time, fermentable nitrogenous source can also be added, fermentable nitrogenous source is selected from least one in ammonium chloride, ammonium nitrate, ammonium sulfate, Secondary ammonium phosphate, primary ammonium phosphate, urea, corn steep liquor or soybean-cake flour, and its consumption is 0.02 ~ 1 grams per liter.Through rectifying concentrate after fermentation liquid A and B mixes, tower top obtains the ethanol that purity is 95%, is separated and obtains xylogen at the bottom of tower.Xylogen can fully utilize, and for the preparation of cement water reducing agent, without aldehyde wood-based plate, wood plastic composite and modulation pitch, cracking aromatic hydrocarbons or fuel combustion modulation pitch, the fuel of burning or cracking aromatic hydrocarbons, makes solid waste almost nil.Wherein preparation without aldehyde wood-based plate method is: xylogen can synthesize not containing the environment friendly composite material of formaldehyde as sizing agent.
In the inventive method, step 6) in before fermentation, described hexose content is 40 ~ 120 grams per liters.In the ethanolic soln obtained after fermentation, alcohol concn is 20 ~ 100 grams per liters.In the fermentation liquid A that zymohexose obtains, alcohol concn is 20 ~ 60 grams per liters.In the fermentation liquid B that pentose fermentation obtains, alcohol concn is 20 ~ 60 grams per liters.
In the inventive method, step 1), step 2) and step 3), these three are carried out pretreated step to lignocellulose raw material and can carry out in three-stage screw extrusion machine.Namely three-stage screw extrusion machine is used to carry out pre-treatment to lignocellulose raw material, wherein, a) in the first paragraph of three-stage screw extrusion machine, lignocellulose raw material is pulverized, and through the effective continuous impregnating of diluted acid under 20 ~ 80 DEG C of conditions, 1 ~ 15 minute residence time, extruding, dehydration and tentatively expanded; B) in the second segment of three-stage screw extrusion machine, the boiling 1 ~ 20 minute under temperature 80 ~ 200 DEG C, pressure 0.4 ~ 10MPa condition of the material after dehydration; C) in the 3rd section of three-stage screw extrusion machine, the material instant decompression explosion after boiling obtains the porous fluffy wet stock containing pentose.The porous fluffy wet stock obtained after this pre-treatment, again through enzymolysis, fermentation, concentrate, obtains the ethanol that purity is 95%.
Embodiment
[embodiment 1]
In the first paragraph of three-stage screw extrusion machine, 500 grams of maize straws are pulverized, then 60 DEG C through 1.5% dilute sulphuric acid continuous impregnating, 7 minutes residence time, extruding, dehydration and tentatively expanded.In the second segment of three-stage screw extrusion machine, the maize straw after dehydration 160 DEG C, maintain 20 minutes under 0.7MPa condition.In the 3rd section of three-stage screw extrusion machine, the material after boiling steams quick-fried through screw extruding, and instant decompression is expanded obtains porous fluffy wet stock.The porous fluffy wet stock obtained is under the condition of 60 DEG C, and liquid-solid ratio is through washing obtain the material of pentose solution and cellulose and xylogen at 5: 1, and it is 40.69 grams per liters that pentose solution concentrate obtains pentose sugar concentration; Concentrated pentose solution proceeds in fermentor tank, and adding urea concentration is 0.3 grams per liter, and penicillin concn is 3 × 10
-4grams per liter; Zymophyte is selected from pichia stipitis, and its consumption is 12 grams per liters; In fermenting process, temperature is 55 DEG C, pH=6.0; In the karusen B obtained after the most final pentose fermentation, alcohol concn is 15.59 grams per liters.Be separated the material of cellulose and xylogen after pentose, be 18% by dry concentration proportioning after adding the water, the concentration adding penicillin is 3 × 10
-4grams per liter, temperature controls at 55 DEG C, adds cellulase under pH=4.5 condition by 0.10 gram of/gram cellulosic consumption, and enzymolysis obtains the enzymolysis solution containing hexose.To obtain enzymolysis solution proceeds in fermentor tank, adds microbiotic and fermentation nitrogen source; Before inoculation, each component content is respectively: hexose sugar concentration is 86.43 grams per liters; Urea concentration is 0.3 grams per liter, and penicillin concn is 3 × 10
-4grams per liter; Zymophyte is selected from yeast saccharomyces cerevisiae, and its consumption is 12 grams per liters; In fermenting process, temperature is 55 DEG C, pH=6.0; In the karusen A obtained after the most final zymohexose, alcohol concn is 39.31 grams per liters.Finally ferment after the ethanolic soln A and B rectifying concentrate that obtain and obtain the ethanol that purity is 95%.
Result is: total reducing sugar yield 77.01%, sugar alcohol transformation efficiency 43.19%.
[embodiment 2]
In the first paragraph of three-stage screw extrusion machine, 500 grams of Wheat Straws are pulverized, then 60 DEG C through 1.5% dilute sulphuric acid continuous impregnating, after 9 minutes residence time, extruding, dehydration and tentatively expanded.In the second segment of three-stage screw extrusion machine, the Wheat Straw after dehydration 170 DEG C, maintain 18 minutes under 0.8MPa condition.In the 3rd section of three-stage screw extrusion machine, the material after boiling steams quick-fried through screw extruding, and instant decompression is expanded obtains porous fluffy wet stock.The porous fluffy wet stock obtained is under the condition of 60 DEG C, and liquid-solid ratio is through washing obtain the material of pentose solution and cellulose and xylogen at 5: 1; It is 37.57 grams per liters that pentose solution concentrate obtains pentose sugar concentration; Concentrated pentose solution proceeds in fermentor tank, and adding urea concentration is 0.3 grams per liter, and penicillin concn is 3 × 10
-4grams per liter; Zymophyte is selected from pichia stipitis, and its consumption is 12 grams per liters; In fermenting process, temperature is 55 DEG C, pH=6.0; In the karusen B obtained after the most final pentose fermentation, alcohol concn is 14.21 grams per liters.Be separated the material of cellulose and xylogen after pentose, be 15% by dry concentration proportioning after adding the water, the concentration adding penicillin is 3 × 10
-4grams per liter, temperature controls at 55 DEG C, adds cellulase under pH=4.5 condition by 0.12 gram of/gram cellulosic consumption, and enzymolysis obtains the enzymolysis solution containing hexose.To obtain enzymolysis solution proceeds in fermentor tank, adds microbiotic and fermentation nitrogen source; Before inoculation, each component content is respectively: hexose sugar concentration is 84.25 grams per liters; Urea concentration is 0.3 grams per liter, and penicillin concn is 3 × 10
-4grams per liter; Zymophyte is selected from yeast saccharomyces cerevisiae, and its consumption is 12 grams per liters; In fermenting process, temperature is 55 DEG C, pH=6.0; In the karusen A obtained after the most final zymohexose, alcohol concn is 37.9 grams per liters.Finally ferment after the ethanolic soln A and B rectifying concentrate that obtain and obtain the ethanol that purity is 95%.
Result is: total reducing sugar yield 76.68%, sugar alcohol transformation efficiency 42.77%.
[embodiment 3]
In the first paragraph of three-stage screw extrusion machine, 500 grams of rice straws are pulverized, then 60 DEG C through 1.5% dilute sulphuric acid continuous impregnating, after 8 minutes residence time, extruding, dehydration and tentatively expanded.Rice straw in the second segment of three-stage screw extrusion machine after dehydration 170 DEG C, maintain 25 minutes under 0.8MPa condition.In the 3rd section of three-stage screw extrusion machine, the material after boiling steams quick-fried through screw extruding, and instant decompression is expanded obtains porous fluffy wet stock.The porous fluffy wet stock obtained is under the condition of 60 DEG C, and liquid-solid ratio is through washing obtain the material of pentose solution and cellulose and xylogen at 5: 1; It is 34.91 grams per liters that pentose solution concentrate obtains pentose sugar concentration; Concentrated pentose solution proceeds in fermentor tank, and adding urea concentration is 0.3 grams per liter, and penicillin concn is 3 × 10
-4grams per liter; Zymophyte is selected from pichia stipitis, and its consumption is 12 grams per liters; In fermenting process, temperature is 55 DEG C, pH=6.0; In the karusen B obtained after the most final pentose fermentation, alcohol concn is 12.67 grams per liters.Be separated the material of cellulose and xylogen after pentose, be 19% by dry concentration proportioning after adding the water, the concentration adding penicillin is 3 × 10
-4grams per liter, temperature controls at 55 DEG C, adds cellulase under pH=4.5 condition by 0.12 gram of/gram cellulosic consumption, and enzymolysis obtains the enzymolysis solution containing hexose.To obtain enzymolysis solution proceeds in fermentor tank, adds microbiotic and fermentation nitrogen source; Before inoculation, each component content is respectively: hexose sugar concentration is 79.27 grams per liters; Urea concentration is 0.3 grams per liter, and penicillin concn is 3 × 10
-4grams per liter; Zymophyte is selected from yeast saccharomyces cerevisiae, and its consumption is 12 grams per liters; In fermenting process, temperature is 55 DEG C, pH=6.0; In the karusen A obtained after the most final zymohexose, alcohol concn is 35.24 grams per liters.Finally ferment after the ethanolic soln A and B rectifying concentrate that obtain and obtain the ethanol that purity is 95%.
Result is: total reducing sugar yield 75.55%, sugar alcohol transformation efficiency 41.97%.
[embodiment 4]
In the first paragraph of three-stage screw extrusion machine, 500 grams of plant plaits are pulverized, then 65 DEG C through 1.5% dilute sulphuric acid continuous impregnating, after 6 minutes residence time, extruding, dehydration and tentatively expanded.In the second segment of three-stage screw extrusion machine, the reed after dehydration 180 DEG C, maintain 20 minutes under 1.1MPa condition.In the 3rd section of three-stage screw extrusion machine, the material after boiling steams quick-fried through screw extruding, and instant decompression is expanded obtains porous fluffy wet stock.The porous fluffy wet stock obtained is under the condition of 60 DEG C, and liquid-solid ratio is through washing obtain the material of pentose solution and cellulose and xylogen at 5: 1, and it is 14.71 grams per liters that pentose solution concentrate obtains pentose sugar concentration; Concentrated pentose solution proceeds in fermentor tank, and adding urea concentration is 0.3 grams per liter, and penicillin concn is 3 × 10
-4grams per liter; Zymophyte is selected from pichia stipitis, and its consumption is 12 grams per liters; In fermenting process, temperature is 55 DEG C, pH=6.0; In the karusen B obtained after the most final pentose fermentation, alcohol concn is 5.56 grams per liters.Be separated the material of cellulose and xylogen after pentose, be 17% by dry concentration proportioning after adding the water, the concentration adding penicillin is 3 × 10
-4grams per liter, temperature controls at 55 DEG C, adds cellulase under pH=4.5 condition by 0.14 gram of/gram cellulosic consumption, and enzymolysis obtains the enzymolysis solution containing hexose.To obtain enzymolysis solution proceeds in fermentor tank, adds microbiotic and fermentation nitrogen source; Before inoculation, each component content is respectively: hexose sugar concentration is 94.89/ liter; Urea concentration is 0.3 grams per liter, and penicillin concn is 3 × 10
-4grams per liter; Zymophyte is selected from yeast saccharomyces cerevisiae, and its consumption is 12 grams per liters; In fermenting process, temperature is 55 DEG C, pH=6.0; In the karusen A obtained after the most final zymohexose, alcohol concn is 43.16 grams per liters.Finally ferment after the ethanolic soln A and B rectifying concentrate that obtain and obtain the ethanol that purity is 95%.
Result is: total reducing sugar yield 78.35%, sugar alcohol transformation efficiency 44.45%.
[comparative example 1]
500 grams of maize straws 160 DEG C, being directly 1.3% through concentration under 0.7MPa condition, dilute sulphuric acid is hydrolyzed 20 minutes, the concentration that isolated material adds penicillin is 3 × 10
-4grams per liter, temperature controls at 55 DEG C, adds cellulase under pH=5.0 condition by 0.12 gram of/gram cellulosic consumption, and enzymolysis obtains the enzymolysis solution containing pentose and hexose.The enzymolysis solution obtained containing pentose and hexose is proceeded in fermentor tank, adds microbiotic and fermentation nitrogen source; Before inoculation, each component content is respectively: pentose sugar concentration is 31.23 grams per liters, and hexose sugar concentration is 15.02 grams per liters; Urea concentration is 0.3 grams per liter, and penicillin concn is 3 × 10
-4grams per liter; After 10 grams per liter fermentation by saccharomyces cerevisiae, obtain ethanolic soln under anaerobic condition, its concentration is 18.81 grams per liters.The ethanol that purity is 95% is obtained after the ethanolic soln rectifying concentrate that obtains of finally fermenting.
Result is: total reducing sugar yield 36.91%, sugar alcohol transformation efficiency 33.19%.
[comparative example 2]
In 500 grams of maize straws, add the NaOH solution that concentration is 2%, under 150 DEG C of temperature, 1.5MPa pressure, process 20 minutes, instant decompression release obtains steam puffed stalk.The concentration that isolated material adds penicillin is 3 × 10
-4grams per liter, temperature controls at 55 DEG C, adds cellulase under pH=4.5 condition by 0.12 gram of/gram cellulosic consumption, and enzymolysis obtains the enzymolysis solution containing pentose and hexose.The enzymolysis solution obtained containing pentose and hexose is proceeded in fermentor tank, adds microbiotic and fermentation nitrogen source; Before inoculation, each component content is respectively: pentose sugar concentration is 2.57 grams per liters, and hexose sugar concentration is 10.84 grams per liters; Urea concentration is 0.3 grams per liter, and penicillin concn is 3 × 10
-4grams per liter; After 10 grams per liter fermentation by saccharomyces cerevisiae, obtain ethanolic soln under anaerobic condition, its concentration is 5.19 grams per liters.The ethanol that purity is 95% is obtained after the ethanolic soln rectifying concentrate that obtains of finally fermenting.
Result is: total reducing sugar yield 14.67%, sugar alcohol transformation efficiency 38.72%.
Calculation formula:
The total reducing sugar (gram) of the total reducing sugar (gram) that total reducing sugar yield=actual obtains/should obtain in theory
Sugar alcohol transformation efficiency=actual ethanol (gram)/actual total reducing sugar (gram) obtained obtained.
Claims (8)
1., by a method for preparing ethanol from wood fiber raw material, comprise the following steps:
1) lignocellulose raw material is pulverized, with the effective continuous impregnating of diluted acid under 20 ~ 80 DEG C of conditions, 1 ~ 15 minute residence time, then dewater;
2) material after dehydration processes 1 ~ 35 minute under temperature 80 ~ 200 DEG C, pressure 0.4 ~ 10MPa condition;
3) step 2) material after process through instant decompression explosion, obtain containing the porous fluffy wet stock of pentose;
4) the porous fluffy wet stock containing pentose obtains pentose solution at 10 ~ 100 DEG C through washing, and the material of cellulose and xylogen;
5) step 4) cellulose that obtains and xylogen material in add water, be made into required dry concentration, 30 ~ 70 DEG C, under the condition of pH=1 ~ 7 through cellulase hydrolysis 8 ~ 120 hours, obtain the enzymolysis solution containing hexose;
6) step 5) obtain containing hexose enzymolysis solution 20 ~ 45 DEG C, carry out zymophyte fermentation 12 ~ 144 hours under the anaerobic condition of pH=3 ~ 8, obtain the fermentation liquid A containing ethanol;
7) step 4) pentose solution that obtains 20 ~ 45 DEG C, pH=3 ~ 8, ventilation ratio carry out zymophyte fermentation 12 ~ 144 hours under being the aerobic condition of 0.1 ~ 1, obtain the fermentation liquid B containing ethanol;
8) fermentation liquid A and fermentation liquid B obtains through concentrate the ethanol that purity is 95% after mixing;
Step 1), step 2) and step 3), these three are carried out pretreated step to lignocellulose raw material and carry out in three-stage screw extrusion machine; Wherein, a) in the first paragraph of three-stage screw extrusion machine, lignocellulose raw material is pulverized, and through the effective continuous impregnating of diluted acid under 20 ~ 80 DEG C of conditions, 1 ~ 15 minute residence time, extruding, dehydration and tentatively expanded; B) in the second segment of three-stage screw extrusion machine, the boiling 1 ~ 20 minute under temperature 80 ~ 200 DEG C, pressure 0.4 ~ 10MPa condition of the material after dehydration; C) in the 3rd section of three-stage screw extrusion machine, the material instant decompression explosion after boiling obtains the porous fluffy wet stock containing pentose.
2., according to claim 1 by the method for preparing ethanol from wood fiber raw material, it is characterized in that step 1) diluted acid dipping temperature is 30 ~ 70 DEG C, continuous impregnating, 3 ~ 11 minutes residence time; Step 2) treatment temp is 120 ~ 190 DEG C, processing pressure is 0.5 ~ 2MPa, and the treatment time is 8 ~ 30 minutes.
3., according to claim 1 by the method for preparing ethanol from wood fiber raw material, it is characterized in that step 4) washing temperature is 20 ~ 80 DEG C; Step 5) hydrolysis temperature is 40 ~ 60 DEG C, pH=3 ~ 6, enzymolysis time is 12 ~ 96 hours; Step 6) zymohexose temperature is 25 ~ 40 DEG C, pH=4 ~ 7, fermentation time is 24 ~ 120 hours; Step 7) pentose fermentation temperature is 25 ~ 40 DEG C, pH=4 ~ 7, ventilation ratio is 0.3 ~ 0.5, and fermentation time is 24 ~ 120 hours.
4., according to claim 1 by the method for preparing ethanol from wood fiber raw material, it is characterized in that step 1) described in diluted acid be selected from least one in sulfuric acid, oxalic acid or phosphoric acid, its weight percent concentration is 0.3 ~ 3%.
5., according to claim 1 by the method for preparing ethanol from wood fiber raw material, it is characterized in that step 1) lignocellulose raw material is after diluted acid dipping, and dry matter content is 10 ~ 80%; Step 3) described in containing pentose porous fluffy wet stock in dry matter content be 20 ~ 45%, wherein pentose content accounts for 8 ~ 20% of dry total amount; Step 4) described in washing liquid-solid ratio be (1: 1) ~ (20: 1); Step 5) described in required dry concentration be 10 ~ 35%.
6. according to claim 1 by the method for preparing ethanol from wood fiber raw material, it is characterized in that the bacterial classification of production of cellulose enzyme is selected from least one in Trichodermareesei or aspergillus niger, the consumption of cellulase is 0.02 ~ 0.20 gram of/gram of Mierocrystalline cellulose; Zymohexose bacterium is selected from least one in zymomonas mobilis or yeast saccharomyces cerevisiae, and its consumption is 0.1 ~ 10 grams per liter; Described pentose fermentation bacterium is selected from least one in pichia stipitis or candiyeast, and its consumption is 0.2 ~ 20 grams per liter.
7., according to claim 1 by the method for preparing ethanol from wood fiber raw material, it is characterized in that step 7) described in before pentose solution fermentation first concentrate to containing pentose 40 ~ 120 grams per liter.
8., according to claim 1 by the method for preparing ethanol from wood fiber raw material, it is characterized in that lignocellulose raw material is selected from maize straw, rice straw, Wheat Straw, plant plait or beanstalk.
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