CN104031947A - Method for producing ethanol by synchronous saccharification and fermentation of cellulose industrial waste residue - Google Patents
Method for producing ethanol by synchronous saccharification and fermentation of cellulose industrial waste residue Download PDFInfo
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- CN104031947A CN104031947A CN201310074043.XA CN201310074043A CN104031947A CN 104031947 A CN104031947 A CN 104031947A CN 201310074043 A CN201310074043 A CN 201310074043A CN 104031947 A CN104031947 A CN 104031947A
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Abstract
The invention provides a method for producing ethanol by synchronous saccharification and fermentation of cellulose industrial waste residue. The method comprises the following steps of a, mixing cellulose-containing industrial waste residue and water to obtain a fermentation substrate solution having a bonedry component mass concentration of 6-15%, b, mixing the fermentation substrate solution and a pH value conditioning agent to obtain a mixed solution having a pH value of 5.0-5.5, c, mixing the mixed solution having a pH value of 5.0-5.5, cellulose, yeast and a nutrition salt, and carrying out fermentation to obtain ethanol. Through the method, an industrial waste residue bonedry component mass concentration is in a range of 6-15% and saccharification and fermentation are synchronously carried out at a pH value of 5.0-5.5. The above conditions are conducive to performance of maximum effects of cellulase and yeast so that a fermentation yield is improved. Through the synchronous saccharification and fermentation, a production period is shortened.
Description
Technical field
The invention belongs to technical field of biological fermentation, relate in particular to a kind of method of utilizing cellulose industry waste residue simultaneous saccharification and fermentation to produce ethanol.
Background technology
Along with the exhaustion day by day of fossil resource, the minimizing day by day of prospective oil, energy issue of world is faced with acid test.The continuous increase of simultaneous energy consumption, the impact of fossil energy environmental pollution and global climate is on the rise.Therefore, very urgent to the demand of various new forms of energy especially renewable energy source and clean energy.Biomass energy is a kind of clean energy products of utilizing energy-source plant or organic waste in agricultural and forest industries to produce, and it has received increasing concern as renewable energy source.Alcohol fuel is the first-selected product of Biomass Energy Development, is that the whole world solves one of the most effective approach of energy dilemma at present, and its research and application are mentioned important strategic position by many countries.
In the prior art, the biological process of ethanol is produced and is mainly comprised the following steps: raw materials pretreatment, enzymic hydrolysis, fermentation and rectifying.The raw material that the biological process of ethanol adopts is at present food crop mostly, yet because China has a large population and a few land, grain-production pressure is large, the alcohol fuel development space that the food crop such as corn, wheat of take are raw material is extremely restricted, be difficult to support for a long time China's fuel ethanol industrial sustainable development, so prior art focuses mostly at agriculture and forestry organic waste material and other cellulose residues to the selection of raw material.The Chinese patent that is CN101139533A such as publication number discloses the sweet sorghum stalk slag after solid fermentation and with enzyme hydrolysis method, has produced the method for alcohol fuel, and it selects sweet sorghum stalk is raw material, by the fermentative production of ethanol again of enzymic hydrolysis after its solid fermentation; Publication number is that the Chinese patent of CN102010883A discloses a kind of method of producing alcohol fuel with paper mill sludge, and the raw material of its use is paper mill sludge, first carries out enzymic hydrolysis fermentative production of ethanol again.The raw material that the disclosed method of above-mentioned prior art adopts concentrates on agriculture and forestry organic waste material, and agriculture and forestry organic waste material first enzymolysis secondary fermentation after certain pre-treatment is produced to ethanol, although this method can improve the yield of ethanol, long reaction time, has increased cost.
In order to shorten the reaction times of Biological preparation ethanol, in prior art, studied the method for simultaneous saccharification and fermentation, the Chinese patent that is CN101265485A as publication number discloses a kind of method of utilizing Jerusalem artichoke raw material saccharification and fermentation synchronously to produce ethanol; The Chinese patent that publication number is CN102242158A for another example discloses a kind ofly take lotus skin powder and is that raw material simultaneous saccharification and fermentation produces the method for ethanol, and the raw material adopting in these methods is that starchiness is easy to saccharification, so can select simultaneous saccharification and fermentation method.
Prior art, in order to expand the scope of application of simultaneous saccharification and fermentation method, adopt cellulosic material synchronous fermentation to produce ethanol, yet because Mierocrystalline cellulose is difficult for saccharification, in prior art, the yield of the simultaneous saccharification and fermentation method ethanol of disclosed cellulosic material is lower.
Summary of the invention
The object of the present invention is to provide a kind of method of producing ethanol based on cellulose industrial residue simultaneous saccharification and fermentation, method provided by the invention has higher alcohol getting rate, has shortened the production cycle, and has realized the recycling to industrial residue.
The invention provides a kind of method of producing ethanol based on cellulose industrial residue simultaneous saccharification and fermentation, comprise the following steps:
A) industrial residue of cellulose is mixed with water, obtain fermentation substrate solution, in described fermentation substrate solution, the mass concentration of over dry component is 6%～15%;
B) described fermentation substrate solution is mixed with pH value conditioning agent, obtain pH value and be 5.0～5.5 mixing solutions;
C) mixing solutions that is 5.0～5.5 by described pH value mixes with cellulase, yeast and nutritive salt, ferments, and obtains ethanol.
Preferably, cellulosic mass content > 55% in the industrial residue of described cellulose.
Preferably, the add-on of described cellulase is 10～15FPU/g Mierocrystalline cellulose.
Preferably, to account for the massfraction of described fermentation substrate solution be 0.01%～0.1% to described yeast.
Preferably, described nutritive salt comprises urea and corn starch.
Preferably, to account for the massfraction of described fermentation substrate solution be 0.5%～3% to described nutritive salt.
Preferably, to account for the massfraction of described fermentation substrate solution be 0.01%～0.1% to described urea.
Preferably, to account for the massfraction of described fermentation substrate solution be 0.5%～2% to described corn starch.
The temperature of preferably, fermenting in described step c) is 25 ℃～43 ℃.
The time of preferably, fermenting in described step c) is 68h～96h.
The invention provides a kind of method of producing ethanol based on cellulose industrial residue simultaneous saccharification and fermentation, comprise the following steps: a) industrial residue of cellulose is mixed with water, obtain fermentation substrate solution, in described fermentation substrate solution, the mass concentration of over dry component is 6%～15%; B) described fermentation substrate solution is mixed with pH value conditioning agent, obtain pH value and be 5.0～5.5 mixing solutions; C) mixing solutions that is 5.0～5.5 by described pH value mixes with cellulase, yeast and nutritive salt, ferments, and obtains ethanol.Method provided by the invention be take and contained cellulosic industrial residue as raw material, and in control industrial residue, the mass concentration of over dry component is 6%～15%, adopt under the condition that cellulase and yeast are 5.0～5.5 by industrial residue in pH value and carry out simultaneous saccharification and fermentation, under these conditions, be conducive to cellulase and yeast to cellulosic conversion in industrial residue, and cellulase and yeast can both be brought into play its maximum effect under these conditions, improved the productive rate of fermentation; And because saccharification and fermentation are carried out simultaneously, shortened the production cycle.Therefore, method provided by the invention can obtain larger productive rate within a short period of time.Experimental result shows, method provided by the invention obtains cellulosic the yield of liquor can be up to 89% of theoretical maximum.
Embodiment
The invention provides a kind of method of producing ethanol based on cellulose industrial residue simultaneous saccharification and fermentation, comprise the following steps:
A) industrial residue of cellulose is mixed with water, obtain fermentation substrate solution, in described fermentation substrate solution, the mass concentration of over dry component is 6%～15%;
B) described fermentation substrate solution is mixed with pH value conditioning agent, obtain pH value and be 5.0～5.5 mixing solutions;
C) mixing solutions that is 5.0～5.5 by described pH value mixes with cellulase, yeast and nutritive salt, ferments, and obtains ethanol.
The invention provides a kind of method that industrial residue simultaneous saccharification and fermentation based on cellulose is produced ethanol, method provided by the invention be take and contained cellulosic industrial residue as raw material, and in control industrial residue, the mass concentration of over dry component is 6%～15%, adopt under the condition that cellulase and yeast are 5.0～5.5 by industrial residue in pH value and carry out simultaneous saccharification and fermentation, under these conditions, be conducive to cellulase and yeast to cellulosic conversion in industrial residue, and, cellulase and yeast can both be brought into play its maximum effect under these conditions, improved the productive rate of fermentation, and because saccharification and fermentation are carried out simultaneously, shortened the production cycle.Therefore, method provided by the invention can obtain larger productive rate within a short period of time.
First the present invention mixes the industrial residue of cellulose with water, obtain fermentation substrate solution, and in described fermentation substrate solution, the mass concentration of over dry component is 6%～15%.The industrial residue of the cellulose that the present invention adopts is preferably the industrial residue that contains lignocellulose, the present invention does not have special restriction to the source of the industrial residue of described cellulose, can adopt furfural dregs, also can adopt xylose residue, adopt the cellulosic industrial residue that contains well known to those skilled in the art; The present invention does not have special restriction to producing the raw material of described industrial residue, as adopted the industrial residue after stalk, rice husk, reed or bamboo are produced.The industrial residue of the cellulose that the present invention adopts has preferably been removed wherein most hemicellulose or xylogen, the preferred > 55% of cellulosic mass content in the industrial residue of described cellulose, more preferably > 60%; Water ratio in the industrial residue of described cellulose is preferably 60%～90%, and more preferably 65%～85%;
The present invention mixes the industrial residue of the cellulose obtaining with water, obtain fermentation substrate solution, and in described fermentation substrate solution, the mass concentration of over dry component is 6%～15%.The present invention preferably adds water in the industrial residue of described cellulose, and the present invention does not have special restriction to the kind of described water, adopts water well known to those skilled in the art.In the present invention, described water is preferably deionized water.The mass concentration that the present invention controls over dry component in the fermentation substrate solution obtain is 6%～15%, more preferably 8%～12%, within the scope of this mass concentration, be conducive to cellulase and yeast to cellulosic effect, and can improve cellulosic the yield of liquor.
Obtain after fermentation substrate solution, the present invention mixes described fermentation substrate solution with pH value conditioning agent, obtains pH value and be 5.0～5.5 mixing solutions.The present invention is in order to make cellulase and yeast give play to the effect of its maximum simultaneously, regulating the pH value of fermentation substrate solution is 5.0～5.5, in this pH value condition, met the optimum condition of cellulase and yeast simultaneously, can make cellulase and yeast give play to the effect of its maximum simultaneously, thereby can improve cellulosic the yield of liquor and shorten the production cycle.The present invention does not have special restriction to described pH value conditioning agent, adopts conventional acidic cpd or the basic cpd of those skilled in the art.In the present invention, described pH value is adjusted and is preferably sulfuric acid or sodium hydroxide.
Obtain pH value and be after 5.0～5.5 mixing solutions, the mixing solutions that the present invention is 5.0～5.5 by described pH value mixes with cellulase, yeast and nutritive salt, ferments, and obtains ethanol.In the mixing solutions that the present invention is preferably 5.0～5.5 to described pH value, add cellulase, yeast and nutritive salt.The present invention does not have special restriction to the source of described cellulase, adopt cellulase well known to those skilled in the art, as adopted deposit number, it is the cellulase of CCTCC M2011195, also can adopt the commercial goods of cellulase, as the cellulase of Ningxia Sunson Industrial Group Co., Ltd.'s sale; The add-on of described cellulase is preferably 10～15FPU/g Mierocrystalline cellulose, and every 1g dry weight Mierocrystalline cellulose adds the cellulase of 10～15FPU;
The present invention does not have special restriction to the kind of described yeast yet, adopts yeast well known to those skilled in the art, as adopted Angel highly active dry yeast.The massfraction that described yeast preferably accounts for described fermentation substrate solution is 0.01%～0.1%, more preferably 0.01%～0.05%;
The present invention does not have special restriction to described nutritive salt yet, adopts the nutritive salt adopting in cellulose fermentation process well known to those skilled in the art, and in the present invention, described nutritive salt preferably includes urea and corn starch; The present invention does not have special restriction to described corn starch, adopts well known to those skilled in the art as the corn starch in nutritive salt; The massfraction that described nutritive salt preferably accounts for described fermentation substrate solution is 0.5%～3%, more preferably 0.6%～2.2%; In described nutritive salt, the massfraction that described urea preferably accounts for fermentation substrate solution is 0.01%～0.1%, more preferably 0.03%～0.08%; The massfraction that described corn starch preferably accounts for described fermentation substrate solution is 0.5%～2%, more preferably 1%～1.5%;
The mixing solutions that is 5.0～5.5 by described pH value ferments after mixing with cellulase, yeast and nutritive salt, obtains ethanol.In the present invention, the temperature of described fermentation is preferably 25 ℃～43 ℃, more preferably 30 ℃～40 ℃, most preferably is 35 ℃～40 ℃; The time of described fermentation is preferably 68h～96h, and more preferably 70h～90h, most preferably is 72h～85h.Under above-mentioned leavening temperature and fermentation time, cellulase and yeast can be brought into play its effect preferably, are conducive to cellulosic fermentation, thereby can improve the yield of leavened prod.
The present invention, after the mixing solutions that is 5.0～5.5 by described pH value mixes with cellulase, yeast and nutritive salt, obtains thick mash, in described thick mash, contains ethanol; The present invention preferably carries out rectifying by described thick mash, obtains dehydrated alcohol.The present invention does not have special restriction to the method for described rectifying, adopts the technical scheme of rectifying well known to those skilled in the art.
The present invention weighs the quality of the ethanol obtain, according to the quality of the ethanol obtaining, calculates cellulosic the yield of liquor, and result shows, the cellulosic the yield of liquor that method provided by the invention obtains can, up to 50%, be 89% of theoretical maximum.Method provided by the invention has not only been utilized and has been contained cellulosic industrial residue, and method provided by the invention has higher product yield and shorter production cycle.
The invention provides a kind of method of producing ethanol based on cellulose industrial residue simultaneous saccharification and fermentation, comprise the following steps: a) industrial residue of cellulose is mixed with water, obtain fermentation substrate solution, in described fermentation substrate solution, the mass concentration of over dry component is 6%～15%; B) described fermentation substrate solution is mixed with pH value conditioning agent, obtain pH value and be 5.0～5.5 mixing solutions; C) mixing solutions that is 5.0～5.5 by described pH value mixes with cellulase, yeast and nutritive salt, ferments, and obtains ethanol.Method provided by the invention be take and contained cellulosic industrial residue as raw material, and in control industrial residue, the mass concentration of over dry component is 6%～15%, adopt under the condition that cellulase and yeast are 5.0～5.5 by industrial residue in pH value and carry out simultaneous saccharification and fermentation, under these conditions, be conducive to cellulase and yeast to cellulosic conversion in industrial residue, and cellulase and yeast can both be brought into play its maximum effect under these conditions, improved the productive rate of fermentation; And because saccharification and fermentation are carried out simultaneously, shortened the production cycle.Therefore, method provided by the invention can obtain larger productive rate within a short period of time.Experimental result shows, method provided by the invention obtains cellulosic the yield of liquor can be up to 89% of theoretical maximum.
In order to further illustrate the present invention, below in conjunction with embodiment, the method based on cellulose industrial residue simultaneous saccharification and fermentation production ethanol provided by the invention is described in detail, but they can not be interpreted as to limiting the scope of the present invention.
In following examples, commercially available cellulase is provided by Ningxia Sunson Industrial Group Co., Ltd., is 40,000 unit fiber element enzymes;
Embodiment 1
The industrial residue that derives from maize straw of take is raw material, and its content of cellulose is 58%, and wet slag water ratio is 70%.In the industrial residue of this maize straw of 2.67kg, add 7.33kg deionized water, the reaction system that the massfraction that obtains quality and be 10kg waste residue over dry composition is 8%, and the pH value of this system is adjusted to 5.0; It is in 15L fermentor tank that the reaction system that is 5.0 by the pH obtaining drops into volume, add wherein cellulase solution to ferment, this cellulase is that deposit number is the cellulase of CCTCC M2011195, the add-on of cellulase solution is the Mierocrystalline cellulose of 12FPU/g, also in fermentor tank, add 2g dry yeast, 5g urea and 50g corn steep liquor, at 38 ℃, ferment, 72h secondary fermentation finishes.
The present invention detects the concentration of ethanol after fermentation, and result shows, alcohol concn is 2.34%, and calculating cellulosic the yield of liquor is 50%, is 89% of theoretical maximum.
Embodiment 2
The industrial residue that derives from rice husk of take is raw material, and its content of cellulose is 60%, and wet slag water ratio is 78%.In the industrial residue of this rice husk of 4.54kg, add 5.46kg deionized water, the reaction system that the massfraction that obtains quality and be 10kg waste residue over dry composition is 10%, and the pH value of this reaction system is adjusted to 5.5; It is in 15L fermentor tank that the reaction system that is 5.5 by the pH value obtaining drops into volume, add wherein commercially available cellulase, the add-on of cellulase is 10FPU/g Mierocrystalline cellulose, also in fermentor tank, add 1g dry yeast, 10g urea and 75g corn steep liquor, at 40 ℃, ferment, 72h secondary fermentation finishes;
The present invention detects the concentration of ethanol after fermentation, and result shows, alcohol concn is 2.94%, and calculating Mierocrystalline cellulose the yield of liquor is 49%, is 87.5% of theoretical maximum
Embodiment 3
The industrial residue that derives from corn cob of take is raw material, and its content of cellulose is 70%, wet slag water ratio 75%.In the industrial residue of this corn cob of 4kg, add 6kg deionized water, the reaction system that the massfraction that obtains quality and be 10kg waste residue over dry composition is 10%, and the pH value of this system is adjusted to 5.0; In the fermentor tank of the input volume 15L of the reaction system that is 5.0 by the pH value obtaining, add wherein commercially available cellulase, the add-on of cellulase is 15FPU/g Mierocrystalline cellulose, also adds wherein 1g dry yeast, 7g urea and 50g corn steep liquor, at 42 ℃, ferment, 72h secondary fermentation finishes.
The present invention detects the concentration of the ethanol obtaining after fermentation, and result shows, alcohol concn is 3.22%, and calculating Mierocrystalline cellulose the yield of liquor is 46%, is 82% of theoretical maximum.
As seen from the above embodiment, the invention provides a kind of method of producing ethanol based on cellulose industrial residue simultaneous saccharification and fermentation, comprise the following steps: a) industrial residue of cellulose is mixed with water, obtain fermentation substrate solution, in described fermentation substrate solution, the mass concentration of over dry component is 6%～15%; B) described fermentation substrate solution is mixed with pH value conditioning agent, obtain pH value and be 5.0～5.5 mixing solutions; C) mixing solutions that is 5.0～5.5 by described pH value mixes with cellulase, yeast and nutritive salt, ferments, and obtains ethanol.Method provided by the invention be take and contained cellulosic industrial residue as raw material, and in control industrial residue, the mass concentration of over dry component is 6%～15%, adopt under the condition that cellulase and yeast are 5.0～5.5 by industrial residue in pH value and carry out simultaneous saccharification and fermentation, under these conditions, be conducive to cellulase and yeast to cellulosic conversion in industrial residue, and cellulase and yeast can both be brought into play its maximum effect under these conditions, improved the productive rate of fermentation; And because saccharification and fermentation are carried out simultaneously, shortened the production cycle.Therefore, method provided by the invention can obtain larger productive rate within a short period of time.Experimental result shows, method provided by the invention obtains cellulosic the yield of liquor can be up to 89% of theoretical maximum.
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. based on cellulose industrial residue simultaneous saccharification and fermentation, produce a method for ethanol, comprise the following steps:
A) industrial residue of cellulose is mixed with water, obtain fermentation substrate solution, in described fermentation substrate solution, the mass concentration of over dry component is 6%～15%;
B) described fermentation substrate solution is mixed with pH value conditioning agent, obtain pH value and be 5.0～5.5 mixing solutions;
C) mixing solutions that is 5.0～5.5 by described pH value mixes with cellulase, yeast and nutritive salt, ferments, and obtains ethanol.
2. method according to claim 1, is characterized in that, cellulosic mass content > 55% in the industrial residue of described cellulose.
3. method according to claim 1, is characterized in that, the add-on of described cellulase is 10～15FPU/g Mierocrystalline cellulose.
4. method according to claim 1, is characterized in that, the massfraction that described yeast accounts for described fermentation substrate solution is 0.01%～0.1%.
5. method according to claim 1, is characterized in that, described nutritive salt comprises urea and corn starch.
6. according to the method described in claim 1 or 5 any one, it is characterized in that, the massfraction that described nutritive salt accounts for described fermentation substrate solution is 0.5%～3%.
7. method according to claim 5, is characterized in that, the massfraction that described urea accounts for described fermentation substrate solution is 0.01%～0.1%.
8. method according to claim 5, is characterized in that, the massfraction that described corn starch accounts for described fermentation substrate solution is 0.5%～2%.
9. method according to claim 1, is characterized in that, the temperature of fermenting in described step c) is 25 ℃～43 ℃.
10. method according to claim 1, is characterized in that, the time of fermenting in described step c) is 68h～96h.
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Citations (4)
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| CN1451755A (en) * | 2002-04-12 | 2003-10-29 | 中国农业大学 | Method for producing alcohol by solid fermentation of stalks |
| CN1944658A (en) * | 2006-06-09 | 2007-04-11 | 山东大学 | Method for producing cellulose alcohol using corncob processing leftover by fermenting |
| CN101024847A (en) * | 2007-04-06 | 2007-08-29 | 山东大学 | Method for producing alcohol and feed by utilizing seaweed chemical waste material |
| CN101736038A (en) * | 2010-01-12 | 2010-06-16 | 张功峰 | Method for extracting fuel ethanol through whole-plant pulverizing double-enzyme fermentation |
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- 2013-03-08 CN CN201310074043.XA patent/CN104031947A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1451755A (en) * | 2002-04-12 | 2003-10-29 | 中国农业大学 | Method for producing alcohol by solid fermentation of stalks |
| CN1944658A (en) * | 2006-06-09 | 2007-04-11 | 山东大学 | Method for producing cellulose alcohol using corncob processing leftover by fermenting |
| CN101024847A (en) * | 2007-04-06 | 2007-08-29 | 山东大学 | Method for producing alcohol and feed by utilizing seaweed chemical waste material |
| CN101736038A (en) * | 2010-01-12 | 2010-06-16 | 张功峰 | Method for extracting fuel ethanol through whole-plant pulverizing double-enzyme fermentation |
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Application publication date: 20140910 |