CN101497894B - Method for preparing ethanol from wood fiber raw material - Google Patents
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- CN101497894B CN101497894B CN2008100331066A CN200810033106A CN101497894B CN 101497894 B CN101497894 B CN 101497894B CN 2008100331066 A CN2008100331066 A CN 2008100331066A CN 200810033106 A CN200810033106 A CN 200810033106A CN 101497894 B CN101497894 B CN 101497894B
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Abstract
The invention relates to a method for preparing ethanol by wood fibre raw materials, which mainly solves the problem that the ethanol synthesized by the existing wood fibre raw materials has high energy consumption, high requirements for equipment material and severe environmental pollution, is incapable of processing continuously, and does not use pentose. The wood fibre raw materials are pressed by a screw rod and expanded with instant decompression so as to obtain porous fluffy materials; diluted acid is added into the porous fluffy materials for washing and realizing the first separation of pentose, thus obtaining pentose solution and then obtaining ethanol solution by fermentation; the pentose-separated materials are hydrolyzed by cellulase so as to obtain hexose containing solution; the xylogen of the hexose containing solution is removed and the hexose containing solution is fermented by hexose zymogens so as to obtain ethanol solution; and the ethanol solution obtained by fermenting the pentose and the ethanol solution obtained by fermenting the hexose are purified to obtain the ethanol with the purity of 95 percent. The method can be applied to the industrial production of preparing ethanol by wood fibre raw materials.
Description
Technical field
The present invention relates to a kind of method of preparing ethanol from wood fiber raw material.
Background technology
Crises such as the energy that 21 century faced, resource, environment have become the major obstacle of Development of Human Civilization.People are striving to find the new forms of energy that substitute fossil oil, to reduce dependence, control emission of carbon-dioxide to Nonrenewable energy resources, to preserve the ecological environment.Lignocellulose raw material is the renewable resources of output maximum on the earth, comprises forest, agricultural crop straw, agricultural byproducts processing tankage etc.In these resources, be used for except that minority the industries such as paper pulp papermaking, building, weaving, feed at present, major part is slatterned in vain.Therefore, the exploitation lignocellulosic material prepares the developing direction that alcoholic acid technology is following alcohol production.
The technology of lignocellulosic material ethanol production mainly comprises four steps: pre-treatment, enzymic hydrolysis, microbial fermentation and ethanol separate.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 the wooden Biological resources of cellulase hydrolysis to prepare ethanol, cellulase must contact to be adsorbed onto reaction is carried out, therefore, Mierocrystalline cellulose is the key factor of decision hydrolysis rate to the accessibility of cellulase.The condition of surface of cellulosic crystallizing field, wooden Biological resources, the multiple component structure of wooden Biological resources, xylogen are caused wooden Biological resources to be difficult to degraded to cellulosic provide protection and Mierocrystalline cellulose by the factor of structure such as hemicellulose covering and chemical ingredients.Generally, without the enzymatic hydrolyzation of the wooden Biological resources of pretreated native state less than 20%.Therefore, must carry out pre-treatment, Mierocrystalline cellulose, hemicellulose and xylogen are separated, break cellulosic crystalline texture, improve the accessibility of Mierocrystalline cellulose, make cellulase penetrate into Mierocrystalline cellulose enzyme to raw material, thus enzymolysis Mierocrystalline cellulose effectively.The pre-treatment of lignocellulose raw material has several different methods, and commonly used is acidic treatment.Document CN1629321A discloses a kind of method of utilizing stalk plant extract system ethanol with glucose and/or wood sugar, at room temperature, according to the stalk plant: the weight ratio of dilute acid soln is that 1: 4.5～8.5 ratio is mixed stalk with dilute acid soln, be warmed up to 90～100 ℃ of constant temperature then, hemicellulose in the quick hydrolyzing straw, extract sugar soln, the sugar soln alcohol prepared by fermenting.Document CN1070233C discloses a kind of method by fermentative production of ethanol, comprising under 90～130 ℃ temperature, utilizes 0.5～1.0% sulfuric acid or phosphoric acid to the lignocellulosic material processing that is hydrolyzed.Though acid treatment can hydrolyzed hemicellulose, need to consume sulfuric acid, hydrochloric acid or phosphoric acid, require high to the equipment material, strengthened cost of investment, and had problem of environmental pollution to some extent, wastewater treatment capacity increases, whole device running cost height is difficult to use in large-scale industrial production.It is said that at present what prospects for commercial application was arranged most is physico-chemical processes-steam explosion.Steam explosion mainly is to utilize high-temperature high-pressure steam to handle fibrous material, and separates and structural changes by the component of moment pressure leak process realization raw material.It is raw material that document CN1786340A discloses with the stalk, after rough lumber, carry out steam explosion, press 0.5～2% adding caustic soda of the oven dry weight of stalk, handled 12～18 minutes under 145～180 ℃ of vapor phase pulping temperature, 0.9～2.0MPa pressure, instant decompression discharges and obtains steam puffed stalk.Steam explosion has the treatment time weak point, reduces pharmaceutical chemicals consumption, free of contamination advantage, but but has the shortcoming that lignin separation is incomplete, the part wood sugar is destroyed, loss solubility hemicellulose component makes the reduction of total reducing sugar utilization ratio; Simultaneously because steam explosion is that raw material is contained in the steam-explosion jar, can only one jar one jar ground batch process, can not continuous operation, production efficiency is low.
Lignocellulosic material is after pre-treatment, and hemicellulose wherein is converted into pentose, and pentose does not all utilize at present, pollutes.The material that removes hemicellulose is converted into hexose behind cellulase hydrolysis, can make ethanol behind the zymohexose.In the prior art, the hexose that obtains behind the cellulase hydrolysis generally is to be directly used in fermentation, because hexose concentration is low, the alcohol concn that causes the fermentation back to generate is lower, thereby has increased the dense energy consumption of putting forward of postorder.
Summary of the invention
Technical problem to be solved by this invention is to have the energy consumption height in the existing preparing ethanol from wood fiber raw material process, the equipment material is required height, and environmental pollution is serious, can not serialization handle, the problem that pentose does not utilize provides a kind of method of new preparing ethanol from wood fiber raw material.It is low, pollution-free that this method has energy consumption, but continuous operation, the characteristics that the total reducing sugar utilization ratio is high.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows: a kind of method of preparing ethanol from wood fiber raw material may further comprise the steps:
A) lignocellulose raw material is made pressure through screw rod, the expanded porous fluffy materials that obtains of instant decompression under 80～200 ℃, 1～10MPa condition;
B) porous fluffy materials that obtains of step a) is washed with diluted acid under 55～100 ℃, pH＜7 conditions, obtains the material of pentose solution and cellulose after the washing;
C) material of the cellulose of step b) through cellulase hydrolysis, obtains containing the solution of hexose under 30～70 ℃, pH=1～7 conditions;
D) solution separating that contains hexose that step c) obtains obtains hexose solution after removing xylogen;
E) the hexose solution that obtains of step d) obtains ethanolic soln A after the fermentation of zymohexose bacterium under 20～45 ℃, anaerobic condition;
F) pentose solution that obtains of step b) at 20～45 ℃, ventilation than being after the pentose fermentation bacterium is fermented, to obtain ethanolic soln B under 0.1～1 the aerobic condition;
G) the ethanolic soln B that obtains of the ethanolic soln A that obtains of step e) and step f) mixes after the dense purity that obtains is put forward in rectifying is 95% ethanol.
In the technique scheme, the temperature preferable range that the step a) screw rod is made pressure is 100～150 ℃, and the pressure preferable range is 2～7MPa; Step b) weak acid scrubbing temperature preferable range is 70～95 ℃; Step c) enzymic hydrolysis temperature preferable range is 40～60 ℃, and the pH preferable range is 3～6; Step e) zymohexose temperature preferable range is 25～40 ℃; Step f) pentose fermentation temperature preferable range is 25～40 ℃, and ventilation is 0.3～0.5 than preferable range.The preferred version of diluted acid described in the step b) is to be selected from least a in sulfuric acid, hydrochloric acid or the phosphoric acid, and its weight percent concentration preferable range is 0.5～3%; The preferred version of cellulase described in the step c) is to be selected from least a in Trichodermareesei or the aspergillus niger, more preferably scheme is for being selected from Trichodermareesei, its consumption preferable range is 5～30FPIU/ gram Mierocrystalline cellulose, wherein FPIU is a filter paper enzyme activity international unit, equals to generate in the enzymatic reaction enzyme amount of 1.0 μ mol glucose; The hexose solution preferred version that obtains behind the step d) separation removal xylogen is dense to containing fermentation again after the hexose 10～20% by weight percentage for carrying earlier; The bacterium of zymohexose described in step e) preferred version is to be selected from least a in motion fermentation sporangium or the yeast saccharomyces cerevisiae, more preferably scheme is for being selected from yeast saccharomyces cerevisiae, its consumption preferable range is 2～20 grams per liters, and the alcohol concn preferable range is 60～110 grams per liters in the ethanolic soln that obtains behind the zymohexose; The step f) preferred version is to carry the dense pentose 6～10% that extremely preferably contains by weight percentage before the pentose solution fermentation earlier, described pentose fermentation bacterium preferred version is to be selected from least a in pichia stipitis or the candiyeast, more preferably scheme finishes red trunk yeast for being selected from, its consumption preferable range is 2～20 grams per liters, and the alcohol concn preferable range is 30～50 grams per liters in the ethanolic soln that obtains after the pentose fermentation.It is dense for carrying through nanofiltration membrane that the solution that step d) contains hexose is preferably put forward dense mode, and going into the film pressure preferable range is 1～5MPa; The solution that step f) contains pentose is preferably put forward dense mode and is carried densely through nanofiltration membrane, and going into the film pressure preferable range is 1～5MPa.The lignocellulose raw material preferred version is for being selected from maize straw, rice straw, wheat straw stalk, reed or beanstalk.
In the inventive method, the isolated xylogen preferred version of step d) is modulated pitch, burnt fuel or cracking system aromatic hydrocarbons for being used to, and makes solid waste almost nil.Wherein transfer the bituminous method to be, pitch is at first handled under hot conditions with mineral acid, generates acid treatment pitch, and under stirring condition, the black liquor that will contain xylogen joins in the acid treatment pitch lentamente then, and dehydration forms stable xylogen mediation pitch.
In the inventive method, because the mode that adopts screw rod to make pressure, moment pressure release is handled lignocellulose raw material, forms countless porous fluffy bodies, make the refinement that is broken of the form of lignocellulose raw material, the intrinsic crystalline structure is destroyed, reduce the cellulosic polymerization degree, degree of crystallinity, destroyed the key coat of xylogen, hemicellulose, sloughed xylogen, increased effective ratio area, increased cellulosic accessibility, made cellulase penetrate into Mierocrystalline cellulose, effectively the enzymolysis Mierocrystalline cellulose; Simultaneously owing to need not adopt steam and chemical substance, so energy consumption is low, pollution-free, but continuous operation.Raw material with screw rod make press pre-treatment after owing to improved specific surface area greatly, thus only need get final product hydrolyzed hemicellulose with a spot of acid elution, so corrosion-resistant less demanding to equipment, the also corresponding minimizing of the treatment capacity of waste water.Behind the acid elution, realize that pentose separates in advance, obtain the pentose liquid glucose, obtain ethanol after the fermentation again, improved utilization ratio of raw materials, thereby improved the total reducing sugar utilization ratio.In addition pentose liquid glucose and hexose liquid glucose preferably through carry dense after again the fermentation, especially preferably carry dense with film, improved the alcohol concn after the fermentation, reduce postorder ethanol and put forward the energy consumption of dense operation, the ethanol yield reaches 19%, improve 11 percentage points than prior art with a large amount of acid hydrolysis lignocellulose raw materials, obtained better technical effect.
Description of drawings
Fig. 1 is the process flow diagram of prior art.
Fig. 2 is the inventive method process flow diagram.
Among Fig. 1,1 is lignocellulose raw material, and 2 for acid hydrolysis, and 3 are converted into pentose for hemicellulose, 4 are not utilized for pentose, and 5 is cellulase, and 6 is cellulose hydrolysis, 7 for cellulose conversion be hexose, 8 is zymohexose, and 9 carry densely for ethanol, and 10 is 95% ethanol, and 11 is xylogen.
Among Fig. 2,1 is lignocellulose raw material, and 5 is cellulase, and 6 is cellulose hydrolysis, and 8 is zymohexose, 9 carry densely for ethanol, and 10 is 95% ethanol, and 12 make the pressure explosion for screw rod, and 13 is acid elution, 14 for pentose separates, and 15 is pentose fermentation, and 16 is the xylogen deep processing, and 17 are the hexose separation.
Among Fig. 1, lignocellulose raw material is at first through dilute acid hydrolysis, and hemicellulose wherein is converted into pentose and separates; The material that has removed hemicellulose is behind cellulase hydrolysis, and cellulose conversion is a hexose; Hexose generates ethanol after fermenting; To obtain purity be 95% ethanol to cat head after the last ethanolic soln rectifying, and the tower still obtains xylogen.
Among Fig. 2, lignocellulose raw material is made pressure through screw rod, the expanded porous fluffy materials that obtains of instant decompression; This porous fluffy materials adds weak acid scrubbing, realizes that pentose separates in advance, obtains pentose solution, obtains ethanolic soln after the fermentation.The material that has separated pentose in addition obtains containing the solution of hexose through cellulase hydrolysis; The solution separating that contains hexose removes xylogen after obtain ethanolic soln after the fermentation of zymohexose bacterium.To obtain purity after dense be 95% ethanol to the ethanolic soln that ethanolic soln that last pentose fermentation obtains and zymohexose obtain through carrying.
The present invention is further elaborated below by embodiment.
Embodiment
[embodiment 1]
400 gram maize straws are made pressure through screw rod, the expanded porous fluffy materials that obtains of instant decompression under 100 ℃, 2.5MPa condition; Is that 1.5% dilute sulphuric acid wash with weight percent concentration with above-mentioned porous fluffy materials under 75 ℃, pH＜7 conditions, obtains the pentose weight percent concentration after the washing and be 2.5% the pentose solution and the material of cellulose; The material of cellulose through the hydrolysis of 10FPIU/ gram Mierocrystalline cellulose Trichodermareesei, obtains containing the solution of hexose under 43 ℃, pH=5 condition, its weight percent concentration is 4%; After the above-mentioned solution separating that contains hexose removes xylogen, obtain ethanolic soln behind 8 grams per liter fermentation by saccharomyces cerevisiae under 35 ℃, anaerobic condition, its concentration is 60 grams per liters; Than being to obtain ethanolic soln under 0.4 the aerobic condition behind the complete red trunk yeast fermentation of 8 grams per liters, its concentration is 30 grams per liters to above-mentioned pentose solution behind weak acid scrubbing at 35 ℃, ventilation; At last, to carry and obtain purity after dense be 95% ethanol to the ethanolic soln rectifying that obtains of the ethanolic soln that obtains of zymohexose and pentose fermentation.
Wherein the yield of each step is: pentose yield 80.7%, pentose fermentation pentose utilization ratio 81.2%, pentose ethanol yield 80.5%, cellulose hydrolysis yield 81.5%, zymohexose hexose utilization ratio 84.3%, hexose ethanol yield 81.6%, total reducing sugar utilization ratio are 80.5%, and the ethanol yield is 16.8%.
[embodiment 2]
400 gram wheat straw stalks are made pressure through screw rod, the expanded porous fluffy materials that obtains of instant decompression under 120 ℃, 5MPa condition; Is that 1.5% dilute sulphuric acid wash with weight percent concentration with above-mentioned porous fluffy materials under 80 ℃, pH＜7 conditions, obtains the pentose weight percent concentration after the washing and be 3% the pentose solution and the material of cellulose; The material of cellulose through the hydrolysis of 20FPIU/ gram Mierocrystalline cellulose Trichodermareesei, obtains containing the solution of hexose under 53 ℃, pH=4.5 condition, its weight percent concentration is 5%; After the above-mentioned solution separating that contains hexose removes xylogen, be that evaporation and concentrating obtains the hexose concentrated solution to containing hexose 10% under 100 ℃ of conditions in temperature; Above-mentioned hexose concentrated solution is obtained ethanolic soln behind 10 grams per liter fermentation by saccharomyces cerevisiae under 35 ℃, anaerobic condition, its concentration is 70 grams per liters; Above-mentioned pentose solution behind weak acid scrubbing evaporation and concentrating under 100 ℃ of conditions obtains the pentose concentrated solution to containing pentose 7%; With this pentose concentrated solution at 35 ℃, ventilation than being behind the complete red trunk yeast fermentation of 9 grams per liters, to obtain ethanolic soln under 0.45 the aerobic condition, its concentration is 35 grams per liters; At last, to carry and obtain purity after dense be 95% ethanol to the ethanolic soln rectifying that obtains of the ethanolic soln that obtains of zymohexose and pentose fermentation.
Wherein the yield of each step is: pentose yield 82.8%, pentose fermentation pentose utilization ratio 83.7%, pentose ethanol yield 81.6%, cellulose hydrolysis yield 83.8%, zymohexose hexose utilization ratio 85.3%, hexose ethanol yield 82.8%, total reducing sugar utilization ratio are 81.5%, and the ethanol yield is 18.1%.
[embodiment 3]
400 gram rice straw bars are made pressure through screw rod, the expanded porous fluffy materials that obtains of instant decompression under 120 ℃, 5MPa condition; Is that 1.5% dilute hydrochloric acid wash with weight percent concentration with above-mentioned porous fluffy materials under 90 ℃, pH＜7 conditions, obtains the pentose weight percent concentration after the washing and be 3.5% the pentose solution and the material of cellulose; The material of cellulose through the hydrolysis of 20FPIU/ gram Mierocrystalline cellulose Trichodermareesei, obtains containing the solution of hexose under 43 ℃, pH=4.2 condition, its weight percent concentration is 5.5%; After the above-mentioned solution separating that contains hexose removes xylogen, in room temperature, to go into film pressure be to concentrate through nanofiltration membrane under the 1.8MPa condition, carry densely, obtain the hexose concentrated solution to containing hexose 10%; Above-mentioned hexose concentrated solution is obtained ethanolic soln behind 9 grams per liter fermentation by saccharomyces cerevisiae under 35 ℃, anaerobic condition, its concentration is 80 grams per liters; Above-mentioned pentose solution behind the salt acid elution in room temperature, to go into film pressure be to concentrate through nanofiltration membrane under the 2.0MPa condition, carries densely to containing pentose 7%, obtains the pentose concentrated solution; With this pentose concentrated solution at 35 ℃, ventilation than being behind the complete red trunk yeast fermentation of 9 grams per liters, to obtain ethanolic soln under 0.5 the aerobic condition, its concentration is 39 grams per liters; At last, to carry and obtain purity after dense be 95% ethanol to the ethanolic soln rectifying that obtains of the ethanolic soln that obtains of zymohexose and pentose fermentation.
Wherein the yield of each step is: pentose yield 85.8%, pentose fermentation pentose utilization ratio 85.5%, pentose ethanol yield 83.8%, cellulose hydrolysis yield 84.2%, zymohexose hexose utilization ratio 87.2%, hexose ethanol yield 85.9%, total reducing sugar utilization ratio are 81.8%, and the ethanol yield is 18.6%.
Carry with nanofiltration membrane dense, as long as the film both sides exist concentration difference and just can realize.Obviously, it is dense to 7% equally weight percent concentration to be that 3.5% pentose solution is carried, and it is dense to 10% that weight percent concentration is that 5.5% hexose solution is carried, and carries dense ratio with nanofiltration membrane and carry dense consuming little energy with evaporation mode.
[embodiment 4]
400 gram reeds are made pressure through screw rod, the expanded porous fluffy materials that obtains of instant decompression under 140 ℃, 5MPa condition; Is that 1.5% dilute hydrochloric acid wash with weight percent concentration with above-mentioned porous fluffy materials under 95 ℃, pH＜7 conditions, obtains the pentose weight percent concentration after the washing and be 4% the pentose solution and the material of cellulose; The material of cellulose through the hydrolysis of 20FPIU/ gram Mierocrystalline cellulose Trichodermareesei, obtains containing the solution of hexose under 53 ℃, pH=4 condition, its weight percent concentration is 6.5%; After the above-mentioned solution separating that contains hexose removes xylogen, in room temperature, to go into film pressure be to concentrate through nanofiltration membrane under the 2.2MPa condition, carry densely, obtain the hexose concentrated solution to containing hexose 20%; Above-mentioned hexose concentrated solution is obtained ethanolic soln behind 10 grams per liter fermentation by saccharomyces cerevisiae under 35 ℃, anaerobic condition, its concentration is 110 grams per liters; Above-mentioned pentose solution behind weak acid scrubbing in room temperature, to go into film pressure be to concentrate through nanofiltration membrane under the 2.2MPa condition, carries densely to containing pentose 10%, obtains the pentose concentrated solution; With this pentose concentrated solution at 35 ℃, ventilation than being behind the complete red trunk yeast fermentation of 10 grams per liters, to obtain ethanolic soln under 0.5 the aerobic condition, its concentration is 50 grams per liters; At last, to carry and obtain purity after dense be 95% ethanol to the ethanolic soln rectifying that obtains of the ethanolic soln that obtains of zymohexose and pentose fermentation.
Wherein the yield of each step is: pentose yield 89.6%, pentose fermentation pentose utilization ratio 89.5%, pentose ethanol yield 84.2%, cellulose hydrolysis yield 85%, zymohexose hexose utilization ratio 90%, hexose ethanol yield 90%, the total reducing sugar utilization ratio is 84%, and the ethanol yield is 19.3%.
[comparative example 1]
400 gram maize straws under 120 ℃ of conditions are 2% dilute sulphuric acid hydrolysis through 1900 gram weight percentage concentrations, isolated material is after the hydrolysis of 15FPIU/ gram Mierocrystalline cellulose Trichodermareesei, obtain weight percent concentration and be 2% sugary soln, this sugary soln obtains ethanolic soln behind 10 grams per liter fermentation by saccharomyces cerevisiae under 35 ℃, anaerobic condition, its concentration is 35 grams per liters; At last above-mentioned ethanolic soln rectifying being carried and being obtained purity after dense is 95% ethanol.
Wherein the yield of each step is: cellulose hydrolysis yield 75%, and the sugared utilization ratio 78% of sugar-fermenting, ethanol yield 74%, total reducing sugar utilization ratio are 41%, the ethanol yield is 8%.
Use the dilute acid hydrolysis lignocellulose raw material, can produce resolvents such as aldehydes, unfavorable to follow-up fermentation, so the total reducing sugar utilization ratio is low, the alcohol concn that obtains after the fermentation is low, carries dense many to 95% consumed energy.In addition, use acid hydrolysis, used acid amount is big, and the subsequent wastewater treatment amount is big.
[comparative example 2]
Adding 400 gram weight percentage concentrations are 2% NaOH solution in 400 gram maize straws, handle 20 minutes under 150 ℃ of temperature, 1.5MPa pressure, and instant decompression discharges and obtains steam puffed stalk.Isolated material is after the hydrolysis of 15FPIU/ gram Mierocrystalline cellulose Trichodermareesei, obtain weight percent concentration and be 2.6% sugary soln, this sugary soln obtains ethanolic soln behind 10 grams per liter fermentation by saccharomyces cerevisiae under 35 ℃, anaerobic condition, its concentration is 30 grams per liters; At last above-mentioned ethanolic soln rectifying being carried and being obtained purity after dense is 95% ethanol.
Wherein the yield of each step is: cellulose hydrolysis yield 75%, and the sugared utilization ratio 75% of sugar-fermenting, ethanol yield 70%, total reducing sugar utilization ratio are 38%, the ethanol yield is 6.7%.
Though it is short that steam explosion is handled the lignocellulose raw material treatment time, but the consumption of pharmaceutical chemicals reduced, but require the expenditure of energy, and the part wood sugar is destroyed, loss solubility hemicellulose component and the total reducing sugar utilization ratio is reduced; Simultaneously because steam explosion is that raw material is contained in the steam-explosion jar, can only one jar one jar ground batch process, can not continuous operation, production efficiency is low.In addition, because the total reducing sugar utilization ratio is low, the alcohol concn that obtains after the fermentation is low, and alcohol concn is carried dense many to 95% consumed energy.
[comparative example 3]
Adding 400 gram weight percentage concentrations are 2% NaOH solution in 400 gram maize straws, handle 20 minutes under 150 ℃ of temperature, 1.5MPa pressure, and instant decompression discharges and obtains steam puffed stalk.Isolated material is after the hydrolysis of 15FPIU/ gram Mierocrystalline cellulose Trichodermareesei, obtain weight percent concentration and be 2.6% sugary soln, this sugary soln room temperature, go into film pressure be under the 2.2MPa condition through nanofiltration membrane carry dense to contain sugar 12%, obtain ethanolic soln behind 12 grams per liter fermentation by saccharomyces cerevisiae then under 35 ℃, anaerobic condition, its concentration is 40 grams per liters; At last above-mentioned ethanolic soln rectifying being carried and being obtained purity after dense is 95% ethanol.
Wherein the yield of each step is: cellulose hydrolysis yield 75%, and the sugared utilization ratio 75% of sugar-fermenting, ethanol yield 70%, total reducing sugar utilization ratio are 38%, the ethanol yield is 6.7%.
Carry with nanofiltration membrane dense, as long as the film both sides exist concentration difference and just can realize.Obviously, earlier the sugar amount concentration in the sugary soln is improved, can increase the fermentation concentration of ethanolic soln afterwards, again it is carried densely, can reduce the consumption of energy to 95% ethanol.
Claims (7)
1. the method for a preparing ethanol from wood fiber raw material may further comprise the steps:
A) lignocellulose raw material is made pressure through screw rod, the expanded porous fluffy materials that obtains of instant decompression under 100～200 ℃, 1～10MPa condition;
B) porous fluffy materials that obtains of step a) is washed with diluted acid under 70～95 ℃, pH＜7 conditions, obtains the material of pentose solution and cellulose after the washing;
C) material of the cellulose of step b) through cellulase hydrolysis, obtains containing the solution of hexose under 30～70 ℃, pH=1～7 conditions;
D) solution separating that contains hexose that step c) obtains obtains hexose solution after removing xylogen;
E) the hexose solution that obtains of step d) is carried densely after contain hexose 10～20% by weight percentage earlier, obtains ethanolic soln A under 20～45 ℃, anaerobic condition after the fermentation of zymohexose bacterium;
F) pentose solution that obtains of step b) carry earlier dense after contain pentose 6～10% by weight percentage, at 20～45 ℃, ventilation than being after the pentose fermentation bacterium is fermented, to obtain ethanolic soln B under 0.1～1 the aerobic condition;
G) the ethanolic soln B that obtains of the ethanolic soln A that obtains of step e) and step f) mixes after the dense purity that obtains is put forward in rectifying is 95% ethanol.
2. according to the method for the described preparing ethanol from wood fiber raw material of claim 1, it is characterized in that it is 100～150 ℃ that the step a) screw rod is made the temperature of pressure, pressure is 2～7MPa; Step c) enzymic hydrolysis temperature is 40～60 ℃, pH=3～6; Step e) zymohexose temperature is 25～40 ℃; Step f) pentose fermentation temperature is 25～40 ℃, and ventilation is than being 0.3～0.5.
3. according to the method for the described preparing ethanol from wood fiber raw material of claim 1, it is characterized in that diluted acid described in the step b) is selected from least a in sulfuric acid, hydrochloric acid or the phosphoric acid, its weight percent concentration is 0.5～3%; Cellulase described in the step c) is derived from least a in Trichodermareesei or the aspergillus niger, and its consumption is 5～30FPIU/ gram Mierocrystalline cellulose; The bacterium of zymohexose described in the step e) is selected from least a in motion fermentation sporangium or the yeast saccharomyces cerevisiae, and its consumption is 2～20 grams per liters, and alcohol concn is 60～110 grams per liters in the ethanolic soln that obtains behind the zymohexose; Described pentose fermentation bacterium is selected from finishes at least a in red trunk yeast or the candiyeast, and its consumption is 2～20 grams per liters, and alcohol concn is 30～50 grams per liters in the ethanolic soln that obtains after the pentose fermentation.
4. according to the method for the described preparing ethanol from wood fiber raw material of claim 3, it is characterized in that cellulase is derived from Trichodermareesei, the zymohexose bacterium is selected from yeast saccharomyces cerevisiae, and the pentose fermentation bacterium is selected from finishes red trunk yeast.
5. according to the method for the described preparing ethanol from wood fiber raw material of claim 1, it is characterized in that step e) hexose solution to put forward dense mode dense for carrying through nanofiltration membrane, going into film pressure is 1～5MPa; The step f) pentose solution put forward dense mode for carry densely through nanofiltration membrane, going into film pressure is 1～5MPa.
6. according to the method for the described preparing ethanol from wood fiber raw material of claim 1, it is characterized in that lignocellulose raw material is selected from maize straw, rice straw, wheat straw stalk, reed or beanstalk.
7. according to the method for the described preparing ethanol from wood fiber raw material of claim 1, it is characterized in that the isolated xylogen of step d) is used to modulate pitch, fuel combustion or cracking system aromatic hydrocarbons.
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|---|---|---|---|---|
| CN103031339B (en) * | 2011-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing ethanol by wood fiber raw material |
| CN103031340B (en) * | 2011-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing ethanol by using wood fiber raw material |
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| CN101736039B (en) * | 2010-01-07 | 2012-07-25 | 南京林业大学 | Method for preparing ethanol through cellulase hydrolysis and fermentation of plant fibrous material |
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| CN103031342B (en) * | 2011-10-09 | 2015-01-07 | 中国石油化工股份有限公司 | Method for producing ethanol by wood fiber raw material |
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| CN109852638A (en) * | 2017-12-15 | 2019-06-07 | 凌受明 | A method of using cotton stalk core biorefinery ethyl alcohol |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103031339B (en) * | 2011-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing ethanol by wood fiber raw material |
| CN103031340B (en) * | 2011-10-09 | 2015-04-29 | 中国石油化工股份有限公司 | Method for producing ethanol by using wood fiber raw material |
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| CN101497894A (en) | 2009-08-05 |
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Address after: 100029 Beijing City, Chaoyang District Hui Street No. 6 Patentee after: China Petrochemical Group Corp. Patentee after: SINOPEC Shanghai Engineering Company Limited Address before: 100029 Beijing City, Chaoyang District Hui Street No. 6 Patentee before: China Petrochemical Group Corp. Patentee before: Sinopec Shanghai Engineering Co., Ltd. |