CN1880415A - Process for preparing fuel ethanol by using straw fiber materials - Google Patents

Process for preparing fuel ethanol by using straw fiber materials Download PDF

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CN1880415A
CN1880415A CN 200510017683 CN200510017683A CN1880415A CN 1880415 A CN1880415 A CN 1880415A CN 200510017683 CN200510017683 CN 200510017683 CN 200510017683 A CN200510017683 A CN 200510017683A CN 1880415 A CN1880415 A CN 1880415A
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mol
straw
peroxidase
liquid
fermentation
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CN100497551C (en
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张百良
宋安东
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Henan Agricultural University
Henan Tianguan Group Co Ltd
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Henan Agricultural University
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Abstract

This invention discloses a method for producing fuel ethanol from a straw fibre raw material, comprising: (1) raw material selection; (2) disintegration; (3) pre-processing; (4) double-enzyme saccharifying; (5) sterilization; (6) enlargement culture and application of Pachysolen tannophilus P-01; (7) fermentation; (8) distillation; characterizing: the pre-processing employs white-rot fungi solid culture to decompose lignin. The procedures comprise: (1) bacterium: Coridus versicolor; (2) crude laccase production: (1) culture media producing condition,(2) fermentation: inoculate 6 parti-color Coriolus versicolor seed stopper per 1000ml, 28-30Deg C, 150rpm shake culture for 7d, remove the hypha by filtration so as to obtain the crude laccase; (3) crude peroxidase production: i. culture media, ii. fermentation: inoculate 6 rings of Phanerochete chrysosporium spores per 100ml, 37-39Deg C, static culture for 9d, remove hypha by filtration so as to obtain crude peroxidase; (4) conditions of enzyme liquid decomposing straw: add 1ml crude peroxidase and crude laccase respectively to the straw powder and mix homogenously, and then decompose the straw at 45Deg C, pH 4.5 for 72h. This invention can improve the ethanol yield and decease cost.

Description

The technology of preparing fuel ethanol by using straw fiber materials
Technical field
The present invention relates to a kind of production method of liquid fuel, especially a kind of technology that adopts preparing fuel ethanol by using straw fiber materials.
Background technology
Have serious crisis and cause under the background of serious environmental pollution at traditional fossil energy such as coal, oil etc., alcohol fuel is renewable with it, non-environmental-pollution, use technology advantage such as reach a standard enjoys government and society to pay attention in motor vehicle.Yet traditional production of fuel ethanol adopts that mainly starchy material such as wheat, corn, potato are done etc., and perhaps saccharine material such as cane molasses, beet sirup etc. need to consume a large amount of farm crop, and production cost is higher.China is a large agricultural country, and the vegetable fibre resource is very abundant, and only the agricultural crop straw annual output just reaches 700,000,000 tons, present utilization mainly is a countryside kitchen work usefulness, and part is the field also, makes the energy by gasification, curing on a small quantity and uses, utilize level low, serious waste of resources, the environmental pollution that causes is serious.To all will produce good benefit to resource and society if adopt stalk fibrid raw material to produce alcohol fuel.The someone had invented the method for producing alcohol fuel from fiber in recent years, and its main technique is as follows: (1) chooses raw material: agricultural crop straw, mainly comprise wheat stalk, maize straw, straw etc., and after the seasoning, standby.(2) pulverize: 20～40 order straw powder are pulverized, are screened into to the stalk straw through beater grinder.(3) raw material is carried out pre-treatment: mainly be that lignin degradation is handled.(4) double enzymes saccharification: adopting cellulase and zytase is under 15 the condition stalk to be carried out saccharification at 45 ℃, pH4.5,150rpm, liquid-solid ratio, obtains reducing sugar.(5) filter: become clarifying saccharification liquid after the saccharification liquid of stalk is removed insoluble solid matter after filtering.(6) sterilization: will be through adding the adjusted saccharification liquid of nutritive substance through 121 ℃, the 30min sterilising treatment.(7) fermentation: adopt P-01 to initial sugared concentration be 6% saccharification liquid 30 ℃ of fermentations, the cycle is 84h.(8) distillation: originally operate in and adopt tower in the suitability for industrialized production or the pillar distillation, identical with the distillation mode in the present suitability for industrialized production.Though above-mentioned technology can utilize crop straws for producing to go out alcohol fuel, because the pretreatment process of raw material is not in place, influence the output capacity of alcohol fuel, to such an extent as to make production alcoholic acid expense too high.
Summary of the invention
After the purpose of this invention is to provide a kind of pretreatment process and improving to stalk fibrid raw material, the technology of the preparing fuel ethanol by using straw fiber materials that can improve the ethanol output capacity, reduces cost.
Technical scheme of the present invention is: a kind of technology of preparing fuel ethanol by using straw fiber materials may further comprise the steps
(1) raw material: agricultural crop straw, mainly comprise wheat stalk, maize straw, straw etc., after the seasoning, standby;
(2) pulverize: 20～40 order straw powder are pulverized, are screened into to the stalk straw through beater grinder;
(3) pre-treatment: raw material carries out lignin degradation through white-rot fungi under liquid training method handles;
(4) double enzymes saccharification: adopting cellulase and zytase is under 15 the condition stalk to be carried out saccharification at 45 ℃, pH4.5,150rpm, liquid-solid ratio, obtains reducing sugar;
(5) filter: become clarifying saccharification liquid after the saccharification liquid of stalk is removed insoluble solid matter after filtering;
(6) sterilization: will be through adding the adjusted saccharification liquid of nutritive substance through 121 ℃, the 30min sterilising treatment;
(7) enlarged culturing and the application of pachysolen tannophilus (Pachysolen tannophilus) P-01: with minimum medium P-01 is carried out enlarged culturing, insert fermention medium by 10% inoculum size afterwards and ferment;
Minimum medium A (g/100ml): MgSO 47H 2O 0.05, CaCl 2H 2O 0.01, KH 2PO 40.1, (NH 4) 2SO 40.5 NaCl 0.01, agar 2.0, pH5.0;
(8) fermentation: adopt P-01 to initial sugared concentration be 6% saccharification liquid 30 ℃ of fermentations, the cycle is 84h;
(9) distillation: originally operate in and adopt tower in the suitability for industrialized production or the pillar distillation, identical with the distillation mode in the present suitability for industrialized production.
The key of present technique concentrates on the raw materials pretreatment stage, adopt the liquid crude enzyme liquid degradation of rice straw of biological method, utilize the complete of microbial destruction lignocellulose structure and make the part xylogen be decomposed into carbonic acid gas and water fully, thereby lignocellulose is easier to the treatment stage of saccharification by the cellulase effect.
Pretreated concrete steps
(1) bacterial classification: variegated rainbow conk (Coridus versicolor), characteristic: be so kind as to give by the Chinese Academy of Agricultural Sciences Shanghai edible mushrooms, be a kind of fungi, under culture medium condition, can produce the enzyme that decomposes xylogen, comprise lignin peroxidase, manganese-dependent peroxidase and laccase etc.; (2) thick laccase production; 1. substratum formation condition glucose 2g/l, ammonium tartrate 12mmol/L, pH4.5 acetate-sodium acetate buffer 10mmol/L, KH 2PO 41.47 * 10 -2Mol/L, MgSO 47H 2O 2.03 * 10 -3Mol/L, CaCl 22H 2O 6.8 * 10 -4Mol/L, VB 12.97 * 10 -6Mol/L, micro-mixed solution 7ml/L, tween 80 1g/L.Material holds than being 1: 5,121 ℃ of 30min that sterilize; The trace element mixed solution is composed as follows: Padil 7.8 * 10 -3Mol/L, MgSO 47H 2O 1.2 * 10 -2Mol/L, MnSO 4H 2O 2.9 * 10 -3Mol/L, NaCl 1.7 * 10 -2Mol/L, FeSO 47H 2O 3.59 * 10 -4Mol/L, CoCl 27.75 * 10 -4Mol/L, CaCl 22H 2O 9.0 * 10 -4Mol/L, ZnSO 47H 2O3.48 * 10 -4Mol/L, CuSO 45H 2O 4 * 10 -5Mol/L, KAl (SO 4) 212H 2O 2.1 * 10 -5Mol/L, HBO 31.6 * 10 -4Mol/L, NaMnO 44.1 * 10 -5Mol/L; 2. fermentation: connect 6 variegated rainbow conk bacterial classification plugs by every 100ml, 28～30 ℃, 150rpm shaking culture 7d, the elimination mycelia gets thick laccase; (3) thick peroxidase production, 1. substratum glucose 10g/l, ammonium tartrate 2mmol/L, pH 4.5 acetate-sodium acetate buffer 10mmol/L, KH 2PO 42g/L, MgSO 47H 2O0.5g/L, CaCl 22H 2O 0.1g/L, VB 11mg/L, Li Lu alcohol 3mmol/L, micro-mixed solution 7ml/L (it is the same to fill a prescription), tween 80 1g/L; 2. fermentation: connect 6 ring Phanerochaete chrysosporium spores by every 100ml, 37～39 ℃, static cultivation 9d, the elimination mycelia gets thick peroxidase; (4) enzyme liquid degradation of rice straw condition adds thick peroxidase and thick each 1ml of laccase in the straw powder, mixing, 45 ℃, during pH4.5 to stalk effect 72h.
Embodiment
A kind of technology of preparing fuel ethanol by using straw fiber materials may further comprise the steps (1) raw material and chooses: agricultural crop straw, and after the seasoning, standby; (2) pulverize: 20～40 order straw powder are pulverized, are screened into to the stalk straw through beater grinder; (3) pre-treatment; (4) double enzymes saccharification: adopting cellulase and zytase is under 15 the condition stalk to be carried out saccharification at 45 ℃, pH4.5,150rpm, liquid-solid ratio, obtains reducing sugar; (5) filter: become clarifying saccharification liquid after the saccharification liquid of stalk is removed insoluble solid matter after filtering; (6) sterilization: will be through adding the adjusted saccharification liquid of nutritive substance through 121 ℃, the 30min sterilising treatment; (7) enlarged culturing and the application of pachysolen tannophilus (Pachysolen tannophilus) P-01: with minimum medium P-01 is carried out enlarged culturing, insert fermention medium by 10% inoculum size afterwards and ferment; Minimum medium is A (g/100ml): MgSO 47H 2O 0.05, CaCl 2H 2O 0.01, KH 2PO 40.1, (NH 4) 2SO 40.5 NaCl 0.01, agar 2.0, pH5.0.
(8) fermentation: adopt P-01 to initial sugared concentration be 6% saccharification liquid 30 ℃ of fermentations, the cycle is 84h; (9) distillation: originally operate in and adopt tower in the suitability for industrialized production or the pillar distillation, identical with the distillation mode in the present suitability for industrialized production; It is characterized in that: pre-treatment is adopted the method for liquid crude enzyme liquid degradation of rice straw to carry out lignin degradation and is handled, concrete steps (one) bacterial classification: variegated rainbow conk (Coridus versicolor), characteristic: be so kind as to give by the Chinese Academy of Agricultural Sciences Shanghai edible mushrooms, be a kind of fungi, under culture medium condition, can produce the enzyme that decomposes xylogen, comprise lignin peroxidase, manganese-dependent peroxidase and laccase etc.; (2) thick laccase production; 1. substratum formation condition glucose 2g/l, ammonium tartrate 12mmol/L, pH4.5 acetate-sodium acetate buffer 10mmol/L, KH 2PO 41.47 * 10 -2Mol/L, MgSO 47H 2O 2.03 * 10 -3Mol/L, CaCl 22H 2O 6.8 * 10 -4Mol/L, VB 12.97 * 10 -6Mol/L, micro-mixed solution 7ml/L, tween 80 1g/L.Material holds than being 1: 5,121 ℃ of 30min that sterilize; The trace element mixed solution is composed as follows: Padil 7.8 * 10 -3Mol/L, MgSO 47H 2O 1.2 * 10 -2Mol/L, MnSO 4H 2O 2.9 * 10 -3Mol/L, NaCl 1.7 * 10 -2Mol/L, FeSO 47H 2O 3.59 * 10 -4Mol/L, CoCl 27.75 * 10 -4Mol/L, CaCl 22H 2O 9.0 * 10 -4Mol/L, ZnSO 47H 2O3.48 * 10 -4Mol/L, CuSO 45H 2O 4 * 10 -5Mol/L, KAl (SO 4) 212H 2O 2.1 * 10 -5Mol/L, HBO 31.6 * 10 -4Mol/L, NaMnO 44.1 * 10 -5Mol/L; 2. fermentation: connect 6 variegated rainbow conk bacterial classification plugs by every 100ml, 28～30 ℃, 150rpm shaking culture 7d, the elimination mycelia gets thick laccase; (3) thick peroxidase production, 1. substratum glucose 10g/l, ammonium tartrate 2mmol/L, pH 4.5 acetate-sodium acetate buffer 10mmol/L, KH 2PO 42g/L, MgSO 47H 2O0.5g/L, CaCl 22H 2O 0.1g/L, VB 11mg/L, Li Lu alcohol 3mmol/L, micro-mixed solution 7ml/L (it is the same to fill a prescription), tween 80 1g/L; 2. fermentation: connect 6 ring Phanerochaete chrysosporium spores by every 100ml, 37～39 ℃, static cultivation 9d, the elimination mycelia gets thick peroxidase; (4) enzyme liquid degradation of rice straw condition adds thick peroxidase and thick each 1ml of laccase in the straw powder, mixing, 45 ℃, during pH4.5 to stalk effect 72h.
The comparison of present technique and conventional art
1, cost is low
Technology Production cycle (d) The alcohol yied (%) of raw material (dry weight) Product ton cost (unit)
Do not carry out pretreated technology 6.25 3.33 3150
The pretreatment technology of liquid enzyme liquid degraded 9.25 7.31 2540
Traditional starchy material technology 5 42％ 3300
2, environmental pollution is little
Technology Environmental pollution
Use present technique PH between 6-7.5, no a large amount of acid ions and metal ion in the water body, environmental pollution is little, pollutes easily and administers
Adopt acid-hydrolyzed pretreatment technology There are a large amount of acid ions in pH in the water body between 2-3, environmental pollution is serious, pollutes to be difficult to administer
Adopt the pretreatment technology of basic hydrolysis There are a large amount of metal ions in pH in the water body between 10-11, the COD severe overweight, and environmental pollution is serious, pollutes to be difficult to administer
3, mild condition
Technology Condition Equipment requirements
Use present technique Action pH is between 6-7.5 Require lowly, general carbon steel gets final product, and equipment cost is low
Adopt acid-hydrolyzed pretreatment technology Action pH is between 1.5-2 Require height, need stainless steel, the equipment cost height
Adopt the pretreatment technology of basic hydrolysis Action pH is between 11-12 Require height, need stainless steel, the equipment cost height

Claims (2)

1, a kind of technology of preparing fuel ethanol by using straw fiber materials may further comprise the steps (1) raw material and chooses: agricultural crop straw, and after the seasoning, standby; (2) pulverize: 20～40 order straw powder are pulverized, are screened into to the stalk straw through beater grinder; (3) pre-treatment; (4) double enzymes saccharification: adopting cellulase and zytase is under 15 the condition stalk to be carried out saccharification at 45 ℃, pH4.5,150rpm, liquid-solid ratio, obtains reducing sugar; (5) filter: become clarifying saccharification liquid after the saccharification liquid of stalk is removed insoluble solid matter after filtering; (6) sterilization: will be through adding the adjusted saccharification liquid of nutritive substance through 121 ℃, the 30min sterilising treatment; (7) enlarged culturing and the application of pachysolen tannophilus (Pachysolen tannophilus) P-01: with minimum medium P-01 is carried out enlarged culturing, insert fermention medium by 10% inoculum size afterwards and ferment; (8) fermentation: adopt P-01 to initial sugared concentration be 6% saccharification liquid 30 ℃ of fermentations, the cycle is 84h; (9) distillation: originally operate in and adopt tower in the suitability for industrialized production or the pillar distillation, identical with the distillation mode in the present suitability for industrialized production; It is characterized in that: pre-treatment is adopted the method for liquid crude enzyme liquid degradation of rice straw to carry out lignin degradation and is handled, concrete steps (one) bacterial classification: variegated rainbow conk (Coridus versicolor), characteristic: be so kind as to give by the Chinese Academy of Agricultural Sciences Shanghai edible mushrooms, be a kind of fungi, under culture medium condition, can produce the enzyme that decomposes xylogen, comprise lignin peroxidase, manganese-dependent peroxidase and laccase etc.; (2) thick laccase production; 1. substratum formation condition glucose 2g/l, ammonium tartrate 12mmol/L, pH4.5 acetate-sodium acetate buffer 10mmol/L, KH 2PO 41.47 * 10 -2Mol/L, MgSO 47H 2O 2.03 * 10 -3Mol/L, CaCl 22H 2O 6.8 * 10 -4Mol/L, VB 12.97 * 10 -6Mol/L, micro-mixed solution 7ml/L, tween 80 1g/L.Material holds than being 1: 5,121 ℃ of 30min that sterilize; The trace element mixed solution is composed as follows: Padil 7.8 * 10 -3Mol/L, MgSO 47H 2O 1.2 * 10 -2Mol/L, MnSO 4H 2O 2.9 * 10 -3Mol/L, NaCl 1.7 * 10 -2Mol/L, FeSO 47H 2O3.59 * 10 -4Mol/L, CoCl 27.75 * 10 -4Mol/L, CaCl 22H 2O 9.0 * 10 -4Mol/L, ZnSO 47H 2O 3.48 * 10 -4Mol/L, CuSO 45H 2O 4 * 10 -5Mol/L, KAl (SO 4) 212H 2O 2.1 * 10 -5Mol/L, HBO 31.6 * 10 -4Mol/L, NaMnO 44.1 * 10 -5Mol/L; 2. fermentation: connect 6 variegated rainbow conk bacterial classification plugs by every 100ml, 28～30 ℃, 150rpm shaking culture 7d, the elimination mycelia gets thick laccase; (3) thick peroxidase production, 1. substratum glucose 10g/l, ammonium tartrate 2mmol/L, pH 4.5 acetate-sodium acetate buffer 10mmol/L, KH 2PO 42g/L, MgSO 47H 2O 0.5g/L, CaCl 22H 2O 0.1g/L, VB 11mg/L, Li Lu alcohol 3mmol/L, micro-mixed solution 7ml/L (it is the same to fill a prescription), tween 80 1g/L; 2. fermentation: connect 6 ring Phanerochaete chrysosporium spores by every 100ml, 37～39 ℃, static cultivation 9d, the elimination mycelia gets thick peroxidase; (4) enzyme liquid degradation of rice straw condition adds thick peroxidase and thick each 1ml of laccase in the straw powder, mixing, 45 ℃, during pH4.5 to stalk effect 72h.
2, the method for preparing fuel ethanol by using straw fiber materials according to claim 1 is characterized in that: minimum medium is A (g/100ml): MgSO 47H 2O 0.05, CaCl 2H 2O 0.01, KH 2PO 40.1, (NH 4) 2SO 40.5 NaCl 0.01, agar 2.0, pH5.0.
CNB2005100176832A 2005-06-14 2005-06-14 Process for preparing fuel ethanol by using straw fiber materials Expired - Fee Related CN100497551C (en)

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Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7449313B2 (en) 2007-11-03 2008-11-11 Rush Stephen L Systems and processes for cellulosic ethanol production
US7514247B2 (en) 2007-11-03 2009-04-07 Wise Landfill Recycling Mining, Inc. Systems and processes for cellulosic ethanol production
US7662617B2 (en) 2007-11-03 2010-02-16 Rush Stephen L Systems and processes for cellulosic ethanol production
CN102344843A (en) * 2010-08-03 2012-02-08 尚征 Crop straw briquettes fuel production line
CN101289678B (en) * 2007-04-17 2012-03-21 中粮集团有限公司 Process for preparing ethanol by using cellulose-containing raw material
CN102559763A (en) * 2012-01-12 2012-07-11 湖南大学 Method for promoting complex enzyme to catalyze degradation of straws by using active mediator combination
CN101463367B (en) * 2007-12-19 2012-09-26 中国科学院过程工程研究所 Method for improving enzymolysis efficiency of steam exploded straw by laccase and cellulase
CN101831337B (en) * 2009-03-12 2013-03-20 尚征 Process technique for producing crop straw fuel
CN103859579A (en) * 2014-04-01 2014-06-18 吉林烟草工业有限责任公司 Method for degrading lignin in tobacco stems
CN107177637A (en) * 2017-06-15 2017-09-19 沈阳农业大学 The methods and applications pre-processed using microorganism to maize straw hydrolysis and saccharification
CN108497261A (en) * 2018-03-01 2018-09-07 河南农业大学 A method of removing aflatoxin in biological raw material using strain fermentation
CN108728500A (en) * 2018-06-26 2018-11-02 深圳崀途科技有限公司 A kind of technique that alcohol fuel is prepared using stalk

Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101289678B (en) * 2007-04-17 2012-03-21 中粮集团有限公司 Process for preparing ethanol by using cellulose-containing raw material
US7514247B2 (en) 2007-11-03 2009-04-07 Wise Landfill Recycling Mining, Inc. Systems and processes for cellulosic ethanol production
US7662617B2 (en) 2007-11-03 2010-02-16 Rush Stephen L Systems and processes for cellulosic ethanol production
US7449313B2 (en) 2007-11-03 2008-11-11 Rush Stephen L Systems and processes for cellulosic ethanol production
CN101463367B (en) * 2007-12-19 2012-09-26 中国科学院过程工程研究所 Method for improving enzymolysis efficiency of steam exploded straw by laccase and cellulase
CN101831337B (en) * 2009-03-12 2013-03-20 尚征 Process technique for producing crop straw fuel
CN102344843A (en) * 2010-08-03 2012-02-08 尚征 Crop straw briquettes fuel production line
CN102559763A (en) * 2012-01-12 2012-07-11 湖南大学 Method for promoting complex enzyme to catalyze degradation of straws by using active mediator combination
CN102559763B (en) * 2012-01-12 2014-03-19 湖南大学 Method for promoting complex enzyme to catalyze degradation of straws by using active mediator combination
CN103859579A (en) * 2014-04-01 2014-06-18 吉林烟草工业有限责任公司 Method for degrading lignin in tobacco stems
CN107177637A (en) * 2017-06-15 2017-09-19 沈阳农业大学 The methods and applications pre-processed using microorganism to maize straw hydrolysis and saccharification
CN108497261A (en) * 2018-03-01 2018-09-07 河南农业大学 A method of removing aflatoxin in biological raw material using strain fermentation
CN108728500A (en) * 2018-06-26 2018-11-02 深圳崀途科技有限公司 A kind of technique that alcohol fuel is prepared using stalk

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