CN101988077A - Method for preparing ethanol from potato raw material - Google Patents
Method for preparing ethanol from potato raw material Download PDFInfo
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- CN101988077A CN101988077A CN2009100902122A CN200910090212A CN101988077A CN 101988077 A CN101988077 A CN 101988077A CN 2009100902122 A CN2009100902122 A CN 2009100902122A CN 200910090212 A CN200910090212 A CN 200910090212A CN 101988077 A CN101988077 A CN 101988077A
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- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/02—Preparation of oxygen-containing organic compounds containing a hydroxy group
- C12P7/04—Preparation of oxygen-containing organic compounds containing a hydroxy group acyclic
- C12P7/06—Ethanol, i.e. non-beverage
- C12P7/08—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate
- C12P7/10—Ethanol, i.e. non-beverage produced as by-product or from waste or cellulosic material substrate substrate containing cellulosic material
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- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M21/00—Bioreactors or fermenters specially adapted for specific uses
- C12M21/18—Apparatus specially designed for the use of free, immobilized or carrier-bound enzymes
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- C12M—APPARATUS FOR ENZYMOLOGY OR MICROBIOLOGY; APPARATUS FOR CULTURING MICROORGANISMS FOR PRODUCING BIOMASS, FOR GROWING CELLS OR FOR OBTAINING FERMENTATION OR METABOLIC PRODUCTS, i.e. BIOREACTORS OR FERMENTERS
- C12M41/00—Means for regulation, monitoring, measurement or control, e.g. flow regulation
- C12M41/12—Means for regulation, monitoring, measurement or control, e.g. flow regulation of temperature
- C12M41/18—Heat exchange systems, e.g. heat jackets or outer envelopes
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention relates to a method for preparing ethanol from a potato raw material. The method comprises the following steps of: grinding the potato raw material, mixing a ground product and enzyme and performing enzymolysis in an enzymolysis device so as to obtain an enzymolysis product; and fermenting the enzymolysis product. The enzymolysis device comprises a flash tower, a heat source, an enzymolysis tank, a material source and a vacuum pump, wherein the flash tower comprises a first interface, a second interface, a third interface and a discharge hole; the material source is communicated with the flash tower through the first interface; the enzymolysis tank is communicated with the discharge hole through the flash tower; the vacuum pump is communicated with the second interface of the flash tower; and the heat source is communicated with the third interface of the flash tower. The method for mixing the ground product and the enzyme and performing enzymolysis in the enzymolysis device comprises the following steps of: conveying the ground product from the material source to the flash tower through the first interface; starting the vacuum pump so as to form negative pressure in the flash tower; absorbing a heat medium in the heat source into the flash tower; contacting the ground product with the heat medium in the flash tower; heating the ground product; and conveying the heated ground product to the enzymolysis tank through the discharge hole and mixing the ground product and the enzyme for enzymolysis.
Description
Technical field
The present invention relates to a kind of preparation alcoholic acid method, more specifically, the present invention relates to a kind of employing potato raw material and prepare the alcoholic acid method.
Background technology
The potato class, for example Ipomoea batatas, potato, cassava etc., therefore rich in starch being widely used in fields such as fermentation sugaring, system starch.
Cassava is tropical and the subtropics is perennial, the annual potato in temperate zone belongs to shrub, originates in South America, and suiting in medial temperature is 25-29 ℃, the low latitudes growth of quantity of precipitation 1000-1500 millimeter every year.Before 1820, cassava is passed to southern china greatly, mainly in Guangdong, the plantation of Guangxi and Hainan, expand provinces such as Yunnan, Fujian, Guizhou now gradually to.Cassava is divided into two classes: bitter manioc (poisonous cassava) and sweet taste cassava (nontoxic cassava).The main chemical compositions of fresh tapioca root is a water, secondly is carbohydrate, also has less protein, fat and the pectin of some content.The fresh cassava starch content reaches 25-30 weight %.
Existing utilize potato raw material particularly cassava prepare the alcoholic acid method and generally comprise earlier potato raw material is pulverized, crushed products is mixed with enzyme carries out enzymolysis, the enzymolysis product that obtains is fermented.The enzymolysis of crushed products generally carries out in enzymatic vessel, for example, crushed products is mixed in enzymatic vessel with microbes producing cellulase and/or enzyme, the condition of enzymolysis comprises hydrolysis temperature, time and pH value, wherein, hydrolysis temperature is generally temperature and/or the great-hearted temperature of enzyme that makes the microbes producing cellulase growth, therefore, in enzymolysis process, need heat to reach hydrolysis temperature enzymatic vessel usually.Modal enzymatic vessel bottom is provided with muff heater, starts muff heater earlier before enzymolysis enzymatic vessel is carried out preheating, reach hydrolysis temperature after, crushed products and microbes producing cellulase and/or enzyme joined carry out enzymolysis in the enzymatic vessel.When adopting existing enzymolysis device to carry out enzymolysis, enzymatic vessel heated need expend a large amount of electric energy, cost is higher, is unfavorable for save energy.
Summary of the invention
The objective of the invention is to overcome adopting existing employing potato raw material to prepare the defective that the power consumption of alcoholic acid method is higher, cost is higher, a kind of save energy is provided, adopts potato raw material to prepare the alcoholic acid method cheaply.
Appearance along with increasingly serious energy shortage problem, for save energy, minimizing are polluted, are reduced cost, the thermal medium that the present inventor utilizes other workshop section to produce, be used for enzymolysis step as the exhaust steam of from rectifying workshop section, discharging, hot water etc. as thermal source, and replaced the device that when enzymolysis, heats to enzymatic vessel.
The invention provides a kind of employing potato raw material and prepare the alcoholic acid method, this method comprises pulverizes potato raw material, and crushed products and mixed being incorporated in a kind of enzymolysis device of enzyme are carried out enzymolysis, obtains enzymolysis product; This enzymolysis product ferments, wherein, described enzymolysis device comprises flashing tower, thermal source, enzymatic vessel, material source and vacuum pump, described flashing tower comprises first interface, second interface, the 3rd interface and discharge port, the material source is communicated with flashing tower by first interface, enzymatic vessel is communicated with the discharge port of flashing tower, and vacuum pump is communicated with second interface of flashing tower, and thermal source is communicated with the 3rd interface of flashing tower; Crushed products and enzyme mixed be incorporated in the method for carrying out enzymolysis in a kind of enzymolysis device and comprise by first interface crushed products is delivered to the flashing tower from the material source, with crushed products before the material source is delivered to the flashing tower, simultaneously or start vacuum pump afterwards, make and form negative pressure in the flashing tower, thermal medium in the thermal source is inhaled in the flashing tower, and crushed products is contacted in flashing tower with thermal medium, the temperature of crushed products is raise, and the crushed products after then this temperature being raise is delivered in the enzymatic vessel to mix with enzyme by discharge port carries out enzymolysis; Described thermal medium is 100-170 ℃ hot water or a water vapour.
The thermal medium that the present inventor utilizes other workshop section to produce dexterously, be used for mixing at flashing tower as thermal source as the exhaust steam of from rectifying workshop section, discharging, hot water etc. and carry out heat exchange with crushed products, to play is the effect that crushed products is heated, and has replaced the device that heats to enzymatic vessel when enzymolysis.Not only reduce cost, also made the energy can be recycled recycling, saved the energy, also improved enzymolysis efficiency simultaneously greatly.
Description of drawings
Fig. 1 is the structural representation of the enzymolysis device that adopts in the method provided by the invention;
Fig. 2 is the structural representation of the enzymolysis device that adopts in the method provided by the invention.
Embodiment
As shown in Figure 1, employing potato raw material provided by the invention prepares the alcoholic acid method and comprises the potato raw material pulverizing, and crushed products and mixed being incorporated in a kind of enzymolysis device of enzyme are carried out enzymolysis, obtains enzymolysis product; This enzymolysis product ferments, wherein, described enzymolysis device comprises flashing tower 1, thermal source 2, enzymatic vessel 3, material source 10 and vacuum pump 4, described flashing tower 1 comprises first interface 5, second interface 6, the 3rd interface 7 and discharge port 11, material source 10 is communicated with flashing tower 1 by first interface 5, enzymatic vessel 3 is communicated with the discharge port of flashing tower 1, and vacuum pump 4 is communicated with second interface 6 of flashing tower 1, and thermal source 2 is communicated with the 3rd interface 7 of flashing tower 1; Crushed products and enzyme mixed be incorporated in the method for carrying out enzymolysis in a kind of enzymolysis device and comprise by first interface 5 crushed products is delivered to the flashing tower 1 from material source 10, with crushed products before material source 10 is delivered to the flashing tower 1, simultaneously or start vacuum pump 4 afterwards, make and form negative pressure in the flashing tower 1, thermal medium in the thermal source 2 is inhaled in the flashing tower 1, and crushed products is contacted in flashing tower 1 with thermal medium, the temperature of crushed products is raise, and the crushed products after then this temperature being raise is delivered in the enzymatic vessel 3 to mix with enzyme by discharge port 11 carries out enzymolysis; Described thermal medium is 100-170 ℃ hot water or a water vapour.
According to method provided by the invention, described enzymatic vessel 3 is communicated with the discharge port of flashing tower 1, and vacuum pump 4 is communicated with second interface 6 of flashing tower 1, and thermal source 2 is communicated with the 3rd interface 7 of flashing tower 1.The temperature of the thermal medium in the thermal source 2 can reach about 100-170 ℃.To treat the enzymolysis material before material source 10 is delivered to the flashing tower 1, simultaneously or start vacuum pump 4 afterwards, flashing tower 1 is vacuumized, thermal medium can be sucked from thermal source 2 in the flashing tower 1 when reaching certain vacuum in the flashing tower 1 and spend, crushed products is transported in the flashing tower 1 from material source 10 by first interface 5, crushed products is contacted in flashing tower 1 with thermal medium and carry out heat exchange, play the effect that crushed products is heated, when crushed products reached hydrolysis temperature, material is directly fed carried out enzymolysis in the enzymatic vessel 3.Generally speaking, in normal production process, vacuum pump 4 can be opened always, and makes the vacuum tightness in the flashing tower 1 require to satisfy the amount that can suck required thermal medium, and can guarantee crushed products can not extracted out.
Preferred embodiment as shown in Figure 2, can thermal source 2 be communicated with the 3rd interface 7 of flashing tower 1 by communicating vessels 8 according to one of the present invention, the top of described communicating vessels 8 is higher than the liquid level of crushed products in the flashing tower 1.
Since vacuum pump in the course of the work unstable or under the situation of ground lack of standardization operated vacuum pumps, when the vacuum tightness in the flashing tower 1 can not reach the condition that sucks thermal medium, crushed products in the flashing tower 1 has by suck-back goes into trend in the communicating vessels 8, if the top of communicating vessels 8 is lower than or flush with the liquid level of crushed products in the flashing tower 1, then the crushed products in the flashing tower 1 can be gone in the communicating vessels 8 by suck-back, thereby causes line clogging.And according to enzymolysis device provided by the invention, because the top of communicating vessels 8 is higher than the liquid level of crushed products in the flashing tower 1, and the pressure in the flashing tower 1 is less than the pressure in the thermal source 2, make insufficient pressure in the flashing tower 1 the crushed products suck-back is gone in flashing tower 1 and the pipeline that thermal source 2 is communicated with, and because the action of gravity of material self, being gone into the top that crushed products in the communicating vessels 8 also fails to arrive communicating vessels by suck-back will be back in the flashing tower 1 again, thereby avoided material to be gone into pipeline, produced the problem that makes pipeline obstruction by suck-back.
According to the present invention, under the preferable case, for the ease of using, the top of described communicating vessels 8 is higher than the top of flashing tower 1, and the difference of altitude between the top of the top of described communicating vessels 8 and flashing tower 1 can be 1-2.5 rice, more preferably 1.5-2 rice.Because bending pipe communicating vessels is not easy to produce the dead angle, and can make the more smooth and easy of Flow of Goods and Materials, under the preferable case, described communicating vessels 8 is the bending pipe, and for example, the shape of described bending pipe can be inverted U-shaped pipe or serpentine tube.Consider production cost, according to a specific embodiments of the present invention, described communicating vessels 8 is the inverted U-shaped pipe more preferably, and the vertical difference of altitude of the top of described inverted U-shaped pipe and flashing tower 1 can be 1-2.5 rice, is preferably 1.5-2 rice.
The material of described communicating vessels 8 can have certain intensity and heat-stable material is made by various, for example, and materials such as iron, stainless steel.
According to the present invention, in order more to help the heat effect of hot steam to crushed products, preferably make thermal medium and crushed products counter current contact in flashing tower 1 in the thermal source 2, that is, make the position of first interface 5 that feeds crushed products be lower than the position of the 3rd interface 7 that thermal source 2 is communicated with the 3rd interface 7 of flashing tower 1 by communicating vessels 8.
For the ease of the amount of the hot steam that contact with crushed products of control with the temperature of controlling crushed products and be convenient to control the feeding amount of crushed products to control the liquid level of crushed products in the flashing tower, under the preferable case, following any one or several position also are provided with valve: can be provided with valve between the 3rd interface 7 of communicating vessels 8 and flashing tower 1; Can be provided with valve between communicating vessels 8 and the thermal source 2; Can be provided with valve between the material source 10 and first interface 5.
According to the present invention, described flashing tower 1 can be the various flashing towers of this area routine, for example, can be various packing towers commonly used or sieve-tray tower.The stage number of described flashing tower 1 or theoretical plate number depend on the heat exchange degree that hope reaches.Usually, under the identical situation of other condition, stage number or theoretical plate number are high more, and the degree of heat exchange is high more, that is to say that the heat of thermal medium can fully pass to crushed products more.The present inventor discovers, for crushed products is the farinaceous size of 20-40 ℃ potato raw material, when thermal medium is 100-170 ℃ a water vapour, the stage number of flashing tower 1 or theoretical plate number are preferably the 2-6 piece, the temperature that can make the crushed products of discharging from flashing tower 1 under this condition satisfies the enzymolysis requirement at 50-90 ℃.
Described packing tower is filled with one or more in Raschig ring, Pall ring, cascade ring, saddle type ring, arc saddle type, square saddle type, Dixon ring, Cannon ring, Lamb wave line and the net corrugated regular filler.The sieve plate of described sieve-tray tower preferably also has overflow weir, and like this, the sieve aperture that thermal medium passes from the bottom of sieve-tray tower on the sieve plate upwards flows, and crushed products flows downward when stopping to the height that surpasses overflow weir on sieve plate, enters next sieve plate.In order further to improve heat exchanger effectiveness, the position of first interface 5 is arranged on the 0th or the 1st column plate place of packing tower or sieve-tray tower, the position at the bottom of the position of the 3rd interface 7 is arranged on last piece column plate place of packing tower or sieve-tray tower or more leans on tower.
According to the present invention, can also be provided with the temperature test unit on the flashing tower 1, to monitor the temperature of crushed products in flashing tower 1 at any time, when the temperature of crushed products in the flashing tower 1 reaches enzymatic hydrolysis condition, just it can be delivered to and carry out enzymolysis in the enzymatic vessel 3.In addition, can also be provided with the liquid level test cell on the flashing tower 1, dredge the liquid level of delivering to crushed products in the flashing tower 1 to monitor.
According to the present invention, the gauge pressure of described flashing tower 1 can be-0.3 to-0.01 MPa, is preferably-0.1 to-0.05 MPa; The weight ratio for the treatment of enzymolysis material and thermal medium of contact can be 15-30 in flashing tower 1: 1; The time of contact, generally speaking, can be 5-10 minute described duration of contact as long as guarantee to treat that the enzymolysis material can reach hydrolysis temperature.
According to the present invention, described thermal source 2 can provide various thermal mediums such as water vapour, hot water, and for example, described thermal source 2 can be for carrying the pipeline of various thermal mediums, also can be for storing the container of various thermal mediums.
In order to save the energy, to make the energy can be recycled recycling, described thermal source 2 is preferably the thermal medium that other workshop section produces, as the exhaust steam of discharging from rectifying workshop section, hot water etc.
When the thermal medium in the thermal source 2 is contacted in flashing tower 1 with crushed products, in order to guarantee the consumption of thermal medium, described thermal source 2 is preferably the container that can store various thermal mediums, and before contact thermal medium temporarily is kept in the container, the temperature of described thermal medium is generally 100-170 ℃.
Described enzymatic vessel can be the various enzymatic vessels of this area routine, for example the container of the band whipping appts of 250 cubic metres of carbon steel materials.In order to monitor hydrolysis temperature, also can be provided with the temperature test unit on the described enzymatic vessel 3.
The number of described vacuum pump 4 can for one also can be a plurality of for what be connected in parallel, can make flashing tower 1 reach vacuum requirements as long as can satisfy.The position that makes second interface 6 that vacuum pump 4 is communicated with flashing tower 1 also is not particularly limited, can be positioned at any position of flashing tower 1, preferably in the middle part or the middle and upper part of flashing tower 1.
The thermal medium that described thermal source 2 provides carries out heat exchange with the form of water vapour and crushed products in flashing tower 1 after, can directly from flashing tower 1, discharge remaining hot steam outside the tower, in order to reach environmental requirement, this device can also comprise condenser 9, described condenser 9 can be communicated with the top of flashing tower 1, make with flashing tower 1 after crushed products contacts in steam be transported in the condenser 9, be condensed into water, so that in other workshop section, use.Therefore, when the enzymolysis device that provides in the method for the present invention also comprises condenser 9 and used thermal medium for hot water vapour or hot water, can also by-product distilled water when realizing enzymolysis when the enzymolysis device that adopts method of the present invention to provide carries out enzymolysis.Under the preferable case, for the ease of operation, described condenser 9 is communicated with the top of flashing tower 1.Described condenser can be the various condensers of this area routine, for example shell-and tube condenser.
Described crushed products can be the various materials that can carry out enzymolysis, farinaceous size for example, and described farinaceous size is generally amyloid material is carried out pre-treatment, as the slurries that obtain after pulverizing; The viscosity of described crushed products is generally 1200-1500mpa.s.
The present inventor discovers, is 20-40 ℃ farinaceous size for crushed products, is preferably the potato raw material farinaceous size; When thermal medium was 100-170 ℃ a water vapour, the stage number of flashing tower 1 or theoretical plate number were preferably the 2-6 piece, and the temperature that can make the crushed products of discharging from flashing tower 1 under this condition satisfies the enzymolysis requirement at 50-90 ℃.
Described potato raw material can be various potato raw materials, and as Ipomoea batatas, potato, cassava etc., the potato raw material that adopts in the specific embodiments of the present invention is a cassava.Described potato raw material can be fresh cassava or dried cassava, if adopt fresh cassava, fresh cassava can be mixed with water before pulverizing, also can not mix with water and directly pulverizing; If adopt dried cassava, usually need before pulverizing dried cassava be mixed with water, the consumption of described water is as long as guarantee and will can access farinaceous size after the dried cassava pulverizing, generally speaking, the weight ratio of described cassava and water can be 1: 0.2-5 is preferably 1: 0.5-2.Described potato raw material also can be the mixture of fresh cassava and dried cassava.The weight of described dried cassava and fresh cassava is not particularly limited, and generally, the weight ratio of described dried cassava and fresh cassava can be 1: 1.5-2.5 is preferably 1: 1.5-2.
According to the present invention, described breaking method can be the breaking method of this area routine, as long as the weave construction of cassava is destroyed, makes small starch granules can disintegrate from tapioca root, separate and get final product.For example, can adopt dry type to pulverize or case of wet attrition, the difference between two kinds of grinding modes mainly is whether cassava is mixed with water.Case of wet attrition comprises mixes the cassava after the peeling with water, carry out one or many then and pulverize.The consumption of water can be with reference to the consumption of above-mentioned water.The average particulate diameter of the product after the pulverizing is preferably the 1.5-10 millimeter.Can use conventional various pulverizers, for example SFSP series beater disintegrating machine.
Also contain one deck thin skin in the exterior skin of fresh cassava raw material, promptly entocuticle contains prussiate and a kind of cyanogen two---phaseolunatin that can cause food poisoning in this entocuticle.Phaseolunatin is hydrolyzed the back and produces prussic acid.Prussic acid and prussiate all have severe toxicity, and it is very fast to poison.They can enter human body by number of ways, as skin absorption, wound invade, respiratory tract sucks, eats by mistake etc., enter human body after, can make the central nervous system paralysis, make oxyphorase poisoning in respiratory enzyme and the blood, cause expiratory dyspnea, systemic cell can make body death because of anoxia asphyxia.Therefore, under the preferable case, before the fresh cassava raw material is pulverized, need remove the entocuticle of fresh cassava raw material earlier usually.Described method of removing fresh cassava raw material entocuticle has can adopt various barking method of the prior art, for example, adopts artificial method of removing the peel to remove the exterior skin and the entocuticle of fresh cassava raw material, removes the silt on raw material surface simultaneously; Perhaps adopt peeling equipment to remove the peel, described peeling equipment can adopt various peeling equipments, for example the peeling equipment of disclosed potato raw material among the CN101289674A.
Owing to may contain earth, sandstone impurity and iron contamination in the potato raw material, can cause damage to peeling equipment, therefore, according to method of the present invention, before can also comprising peeling potato raw material is carried out pretreated routine operation, described pretreated step generally comprises the step of removing impurity and cleaning.As, after fresh cassava is gathered, remove earth, root, palpus and impurity such as wooden part and sandstone on the cassava.And cassava cleaned, the method and apparatus of described cleaning is conventionally known to one of skill in the art.
Described enzymolysis step can be finished by this area method commonly used, such as adding microbes producing cellulase and/or enzyme in crushed products, is incubated under the growth temperature of microbes producing cellulase and/or the great-hearted temperature of enzyme and finishes.Described microbes producing cellulase be can secreting amylase microbes producing cellulase.Described enzyme is an amylase.
Because microorganism growth can produce by product, the therefore preferred enzyme that directly adds.The consumption of described enzyme is The more the better, for cost consideration, the dry weight basis of the product after preferably pulverizing with every gram, described diastatic consumption is the 4-50 enzyme activity unit, the dry weight basis of the product after more preferably pulverizing with every gram, described diastatic consumption is the 10-30 enzyme activity unit.
The enzyme activity unit of enzyme of the present invention can in the pH value be 6.0, temperature is that 1 minute is converted into the required enzyme amount of glucose with 1 milligram of starch is an enzyme activity unit under 70 ℃ the condition.
The temperature of described enzymolysis can be diastatic any optimum temperature, is generally 50-90 ℃, more preferably 60-70 ℃.The longer the better on the time theory of described enzymolysis, considers plant factor, and the time of preferred described enzymolysis is 20-240 minute, more preferably 30-120 minute.The pH value of described enzymolysis can be generally 3.0-7.0 for diastatic the suitableeest any action pH, and more preferably the pH value is 5.0-6.0.Because the fluctuation of pH value is little in the enzymolysis process, therefore the pH value of described enzymolysis can be regulated before adding enzyme according to this area method commonly used, for example earlier crushed products and water or substratum (are enzyme-addedly generally mixed with water, add microbes producing cellulase generally with the substratum of this microorganism) mix, the solid content that generally makes the gained mixture is 20-40 weight %, pH value according to the gained mixture, the mixture pH regulator that to treat enzymolysis with sulphuric acid soln or sodium hydroxide more preferably is adjusted to the pH value and is 5.0-6.0 to 3.0-7.0.
Enzyme of the present invention is an amylase.Amylase is the general name of class of enzymes that can the starch-splitting glycosidic link, and described amylase generally comprises α-Dian Fenmei, beta-amylase, saccharifying enzyme and isoamylase.
α-Dian Fenmei claims starch 1 again, the 4-dextrinase, and it can cut the α-1 of starch chain inside at random, brokenly, and the 4-glycosidic link is hydrolyzed to starch maltose, contains the oligosaccharides of 6 glucose units and has the oligosaccharides of side chain.The microorganism that produces this enzyme mainly has Bacillus subtilus, aspergillus niger, aspergillus oryzae and head mold.
Beta-amylase claims starch 1 again, and 4-maltoside enzyme can cut 1 from the starch molecule non reducing end, and the 4-glycosidic link generates maltose.The product that this enzyme acts on starch is maltose and limit dextrin.This enzyme is mainly produced by aspergillus, head mold and endomyces.
Saccharifying enzyme claims starch α-1 again, the 4-glucuroide, and this enzyme acts on the non reducing end of starch molecule, is unit with glucose, acts on the α-1 in the starch molecule successively, and the 4-glycosidic link generates glucose.The product that this enzyme acts on behind the amylopectin has glucose and has α-1, the oligosaccharides of 6-glycosidic link; The product that acts on after the amylose starch almost all is a glucose.This enzyme produces bacterium mainly to be aspergillus niger (left U.S. aspergillus, Aspergillus awamori), head mold (snow-white enzyme, De Shi head mold), to intend endomyces, monascus.
Isoamylase claims starch α-1 again, and 6-glucuroide, branching enzyme, this enzyme act on the α-1 at amylopectin molecule branching-point place, and the 6-glycosidic link is with whole side chain cutting-out the becoming amylose starch of amylopectin.It mainly is to dislike bacteriums such as gas bacillus, genus bacillus and some false monospore bacillus that this enzyme produces bacterium.
The enzyme that preferred described enzymolysis uses also comprises phosphoesterase.Because the phosphoric acid dextrin hydrolysis that phosphoesterase can make phosphoric acid and alcoholic hydroxyl be combined into ester becomes glucose, and discharge phosphoric acid, have the power that extremely significantly liquefies, so the enzyme that enzymolysis uses comprises phosphoesterase, hydrolyzed starch more fully is to increase alcohol yied.
Amylase of the present invention can be preferably selected from one or more in α-Dian Fenmei, saccharifying enzyme, transfering grape glycosidase and the phosphoesterase.
The microorganism of monose such as glucose and/or fructose, oligosaccharides such as sucrose and/or semi-lactosi of can fermenting may be used to fermenting process of the present invention, because yeast saccharomyces cerevisiae is the microorganism of the zymohexose that ethanol-tolerant, by product are few, alcohol yied is high of widespread usage on the wine industry, therefore the employed yeast of preferred described fermentation is a yeast saccharomyces cerevisiae.
In every gram enzymolysis product, the employed zymic inoculum size of described fermentation is the 103-108 colony-forming unit, more preferably the 104-106 colony-forming unit.
Described colony-forming unit is defined as the method for a certain amount of bacterium liquid after the dilution by cast or coating, allows unicellular being dispersed in one by one on the culture medium flat plate of microorganism in it, and after waiting to cultivate, each viable cell just forms a bacterium colony.It is the single celled number that contains in every milliliter of bacterium liquid.
Employed yeast is fermented in the present invention can be for being purchased yeast solids preparation (such as dried yeast powder) or barms, such as No. 2 (Rasse II) yeast in Lars, have another name called No. two yeast of Germany, No. 12 (Rasse XII) yeast in Lars, have another name called Germany No. 12 yeast, K word yeast, No. five yeast in Nanyang (1300) and Nanyang mixed yeasts (1308).Described zymic colony-forming unit can be measured by means commonly known in the art, such as the methylene blue staining viable bacteria counting method.The concrete grammar of methylene blue staining viable bacteria counting method is as follows:
1 gram dried yeast powder is dissolved in 10 ml sterile waters, or 1 milliliter of actication of culture liquid is diluted to 10 milliliters with sterilized water, add 0.5 milliliter of 0.1 weight % methylene blue, be incubated 30 minutes down at 35 ℃.Under 10 times of opticmicroscopes,, can get the number of viable bacteria in 1 gram dry yeast or the 1 milliliter of actication of culture liquid, i.e. colony forming single-digit with the number (dead bacterium dyeing, viable bacteria is not dyeed) of viable bacteria in the solution after the blood counting chamber counting insulation.
Described yeast can adopt conventional method inoculation, for example adds the seed liquor of 5-15 volume % in enzymolysis product.Described seed liquor can be the aqueous solution or the culture medium solution of dry yeast, also can or be purchased the activated seed liquid of bacterial classification for dry yeast.
The temperature of described fermentation can be any temperature that is suitable for yeast growth, is preferably 30-36 ℃, more preferably 30-33 ℃.The pH value is 4-6, is preferably 4-4.5.The time of described fermentation can be for beginning from inoculation to occur to the decline phase of yeast growth the time of (being that fermentation time is that lag phase, logarithmic phase add stationary phase), and the time of preferred fermentation is 55-70 hour, more preferably 60-70 hour.Tunning ethanol can be with conventional method, according to requirement (requiring alcoholic acid purity to reach more than 99% such as the fuel alcohol) separation and refining of different Industrial products, such as distilling, concentrate, dewatering.
The present invention will be described in more detail below by embodiment.
Used cassava raw material is the new fresh cassava with a collection of results among the embodiment, and thick 4-8 centimetre, long 20-30 centimetre, water content is about 65 weight %.
To further describe in detail the present invention by embodiment below.
Present embodiment is used to illustrate that employing cassava of the present invention prepares the alcoholic acid method
(1) use enzymolysis device shown in Figure 1 to carry out enzymolysis.
Described enzymolysis device comprises flashing tower 1, thermal source 2, enzymatic vessel 3, material source 10, vacuum pump 4 and condenser 9, described flashing tower 1 comprises first interface 5, second interface 6, the 3rd interface 7 and discharge port 11, material source 10 is communicated with flashing tower 1 by first interface 5, enzymatic vessel 3 is communicated with the discharge port of flashing tower 1, vacuum pump 4 is communicated with second interface 6 of flashing tower 1, thermal source 2 is communicated with the 3rd interface 7 of flashing tower 1, and condenser 9 is communicated with the top of flashing tower 1.The stage number of flashing tower is 6, and from top to bottom, first interface 5 and the 3rd interface 7 lay respectively at the 1st and the 6th column plate place of flashing tower.
(2) pulverizing of cassava raw material
With (thick 4-8 centimetre of 95 kilograms of fresh cassava raw material, long 20-30 centimetre, water content 65 weight %) be cut into 1 centimetre of disk that the left and right sides is thick after the cleaning, use SFSP series beater disintegrating machine that this cassava slice is pulverized then, obtaining average particulate diameter is 95 kilograms of crushed products of 2 millimeters (adopting the Accu SizerTM 780 optics particle diameter detectors of U.S. PPS company to measure).
Get the above-mentioned crushed products of 10 grams and filter and dry under 45 ℃ to constant weight 3.4 grams, 300.0 milligrams of these dried crushed products of weighing are positioned in 100 milliliters of dry Erlenmeyer flasks of heavy 80 grams.Adding 3.00 ml concns in described Erlenmeyer flask is the sulphuric acid soln of 72 weight %, stirs 1 minute.Then Erlenmeyer flask was placed 60 minutes in 30 ℃ water-bath, stirred once to guarantee even hydrolysis every 5 minutes.Hydrolysis makes the vitriolic concentration dilution to 4 weight % with deionized water after finishing, and filters with B then, obtains 84 milliliters of filtrates altogether.20 milliliters of filtrates are transferred in the triangular flask of 50 milliliters of exsiccant.Use 2.5 gram lime carbonate to regulate this pH value of filtrate to 5.5, left standstill 5 hours, collect supernatant liquid.With the supernatant liquid that 0.2 micron membrane filtration is collected, gained filtrate is analyzed with Biorad AminexHPX-87P high performance liquid chromatography (HPLC).HPLC condition: sample size 20 microlitres; Moving phase is the HPLC ultrapure water of the 0.2 micron membrane filtration and the sonic oscillation degassing; Flow velocity is 0.6 ml/min; Column temperature 80-85 ℃; Detector temperature 80-85 ℃; Detector is a refractive index detector; Be 35 minutes working time.With D-(+) glucose of 0.1-4.0 mg/ml concentration range as standard model.HPLC analyzes and to obtain that glucose concn is 3.70 mg/ml in the crushed products acid hydrolysis liquid, calculating can get the described crushed products acid hydrolysis of 1 gram can obtain the glucose that weight is 0.311 gram, because being the sulphuric acid soln of 72 weight %, concentration the starch in the crushed products all can be hydrolyzed into glucose, therefore the weight of gained glucose is 1.11 times of starch weight in the crushed products, promptly the starch content in the described crushed products of 1 gram is 0.280 gram, then is total to starch-containing 26.6 kilograms in 95 kilograms of crushed products.
With above-mentioned crushed products with obtain farinaceous size after 21 kg water are mixed, deliver in the material source 10 and preserve.
(3) enzymolysis
Opening vacuum pump 4 vacuumizes flashing tower 1, make that the gauge pressure of flashing tower 1 is-0.25 MPa, open the valve between thermal source 2 and the flashing tower 1 then, making temperature in the thermal source 2 is that 130 ℃ water vapor is inhaled in the flashing tower 1, open the valve in material source 10 simultaneously, making by first interface 5 is that 30 ℃ above-mentioned farinaceous size is delivered to the flashing tower 1 from material source 10 with temperature, and farinaceous size is contacted in flashing tower 1 with water vapor, the weight ratio of water vapor and this crushed products is 15: 1, the time of contact is 8 minutes, the temperature that monitor farinaceous size by the temperature monitoring apparatus that is provided with on the flashing tower 1 this moment is increased to 65 ℃, farinaceous size is delivered in the enzymatic vessel 3 to mix with amylase by discharge port carries out enzymolysis, the time of enzymolysis is 60 minutes, and the pH value of described enzymolysis is 5; With the dry weight basis of every gram crushed products, add the α-Dian Fenmei (Novozymes Company buys) of 20 enzyme activity units; Remainder water steam in the flashing tower 1 is extracted and be condensed into to the power supply of open cold condenser 9 out water.
(4) fermentation
The enzymolysis product that step (2) is obtained is delivered in the fermentor tank, and temperature reduces to 33 ℃, in the weight of every gram enzymolysis product, and inoculation 10
5The distillery yeast of colony-forming unit (the super highly active dry yeast in Angel, Hubei Angel Yeast stock company), the gained mixture under 33 ℃ in fermentor tank stir culture 65 hours, at 100 ℃ of distillation gained tunnings, the gained distillation fraction can get 13.73 kilograms of ethanol at 78.3 ℃ of following second distillations.Calculate alcohol yied according to following formula, calculation result sees Table 1.
The weight of starch contained therein in alcohol yied=100% * ethanol weight/cassava raw material
The karusen of getting behind the 100 gram distillation ethanol filters with B, 20 milliliters of filtrates is transferred in dry 50 milliliters the triangular flask, leaves standstill 5 hours, collects supernatant liquid.0.2 the supernatant liquid that the micron membrane filtration is collected, according to the described high performance liquid phase condition of above-mentioned steps (1), the glucose of measuring and calculating in the karusen 372 restrains totally.And according to following formula calculating residual sugar rate, calculation result sees Table 1.
The weight of starch contained therein in residual sugar amount/cassava raw material in residual sugar rate=100% * karusen
Comparative Examples 1
This Comparative Examples is used for explanation and adopts cassava to prepare alcoholic acid reference method.
Method according to embodiment 1 prepares ethanol, and different is, does not adopt enzymolysis equipment of the present invention, and adopts after feeding farinaceous size in the enzymatic vessel, adopts electrically heated method that hydrolysis temperature is promoted to 65 ℃, and be heat-up time
0.5Hour.Method fermentation according to embodiment 1 obtains 13.43 kilograms of ethanol.
Remaining karusen filters with B after getting 100 gram distillation ethanol, 20 milliliters of filtrates is transferred in the triangular flask of 50 milliliters of dryings, leaves standstill 5 hours, collects supernatant liquid.0.2 the supernatant liquid that the micron membrane filtration is collected, according to the described high performance liquid phase condition of above-mentioned steps (1), the glucose of measuring and calculating in the karusen 575 restrains totally.And calculate alcohol yied and residual sugar rate according to the formula of embodiment 1, calculation result sees Table 1.
Present embodiment is used to illustrate that employing cassava of the present invention prepares the alcoholic acid method
Method according to embodiment 1 prepares ethanol, and different is to use enzymolysis device shown in Figure 2 to carry out enzymolysis.
Described enzymolysis device comprises flashing tower 1, thermal source 2, enzymatic vessel 3, material source 10, vacuum pump 4 and condenser 9, described flashing tower 1 comprises first interface 5, second interface 6, the 3rd interface 7 and at least one discharge port, material source 10 is communicated with flashing tower 1 by first interface 5, enzymatic vessel 3 is communicated with the discharge port of flashing tower 1, vacuum pump 4 is communicated with second interface 6 of flashing tower 1, condenser 9 is communicated with the top of flashing tower 1, thermal source 2 is communicated with the 3rd interface 7 of flashing tower 1 by the inverted U-shaped pipe, the top of described inverted U-shaped pipe is higher than the top of flashing tower 1, and the vertical difference of altitude of inverted U-shaped pipe and flashing tower 1 is 2.5 meters.Opening vacuum pump 4 vacuumizes flashing tower 1, make that the gauge pressure of flashing tower 1 is-0.1 MPa, open the valve between thermal source 2 and the flashing tower 1 then, making temperature in the thermal source 2 is that 150 ℃ water vapor is inhaled in the flashing tower 1, open the valve in material source 10 simultaneously, making by first interface 5 is that 35 ℃ farinaceous size is delivered to the flashing tower 1 from material source 10 with temperature, and farinaceous size is contacted in flashing tower 1 with water vapor, the weight ratio of water vapor and farinaceous size is 25: 1, the time of contact is 5 minutes, the temperature that monitor farinaceous size by the temperature monitoring apparatus that is provided with on the flashing tower 1 this moment is increased to 55 ℃, farinaceous size is delivered in the enzymatic vessel 3 to mix with amylase by discharge port carries out enzymolysis, the time of enzymolysis is 80 minutes, and the pH value of described enzymolysis is 5; With the dry weight basis of every gram farinaceous size, add the α-Dian Fenmei (Novozymes Company buys) of 30 enzyme activity units; Remainder water steam in the flashing tower 1 is extracted and be condensed into to the power supply of open cold condenser 9 out water.
And according to the method for embodiment 1 enzymolysis product is fermented, obtain 14.07 kilograms of ethanol.
Remaining karusen filters with B after getting 100 gram distillation ethanol, 20 milliliters of filtrates is transferred in the triangular flask of 50 milliliters of dryings, leaves standstill 5 hours, collects supernatant liquid.0.2 the supernatant liquid that the micron membrane filtration is collected, according to the described high performance liquid phase condition of above-mentioned steps (1), the glucose of measuring and calculating in the karusen 348 restrains totally.And calculate alcohol yied and residual sugar rate according to the formula of embodiment 1, calculation result sees Table 1.
Present embodiment is used to illustrate that employing cassava of the present invention prepares the alcoholic acid method
Method according to embodiment 1 prepares ethanol, and different is to use enzymolysis device shown in Figure 2 to carry out enzymolysis.
Described enzymolysis device comprises flashing tower 1, thermal source 2, enzymatic vessel 3, material source 10, vacuum pump 4 and condenser 9, described flashing tower 1 comprises first interface 5, second interface 6, the 3rd interface 7 and at least one discharge port, material source 10 is communicated with flashing tower 1 by first interface 5, enzymatic vessel 3 is communicated with the discharge port of flashing tower 1, vacuum pump 4 is communicated with second interface 6 of flashing tower 1, condenser 9 is communicated with the top of flashing tower 1, thermal source 2 is communicated with the 3rd interface 7 of flashing tower 1 by the inverted U-shaped pipe, the top of described inverted U-shaped pipe is higher than the top of flashing tower 1, and the vertical difference of altitude of inverted U-shaped pipe and flashing tower 1 is 1 meter.Opening vacuum pump 4 vacuumizes flashing tower 1, make that the gauge pressure of flashing tower 1 is-0.02 MPa, open the valve between thermal source 2 and the flashing tower 1 then, making temperature in the thermal source 2 is that 150 ℃ water vapor is inhaled in the flashing tower 1, open the valve in material source 10 simultaneously, making by first interface 5 is that 35 ℃ farinaceous size is delivered to the flashing tower 1 from material source 10 with temperature, and farinaceous size is contacted in flashing tower 1 with water vapor, the weight ratio of water vapor and farinaceous size is 20: 1, the time of contact is 6 minutes, the temperature that monitor farinaceous size by the temperature monitoring apparatus that is provided with on the flashing tower 1 this moment is increased to 60 ℃, farinaceous size is delivered in the enzymatic vessel 3 to mix with amylase by discharge port carries out enzymolysis, the time of enzymolysis is 60 minutes, and the pH value of described enzymolysis is 5; With the dry weight basis of every gram farinaceous size, add the α-Dian Fenmei (Novozymes Company buys) of 30 enzyme activity units; Remainder water steam in the flashing tower 1 is extracted and be condensed into to the power supply of open cold condenser 9 out water.
And according to the method for embodiment 1 enzymolysis product is fermented, obtain 13.81 kilograms of ethanol.
Remaining karusen filters with B after getting 100 gram distillation ethanol, 20 milliliters of filtrates is transferred in the triangular flask of 50 milliliters of dryings, leaves standstill 5 hours, collects supernatant liquid.0.2 the supernatant liquid that the micron membrane filtration is collected, according to the described high performance liquid phase condition of above-mentioned steps (1), the glucose of measuring and calculating in the karusen 372 restrains totally.And calculate alcohol yied and residual sugar rate according to the formula of embodiment 1, calculation result sees Table 1.
Present embodiment is used to illustrate that employing cassava of the present invention prepares the alcoholic acid method
Method according to embodiment 1 prepares ethanol, and different is to prepare the enzymolysis device according to Fig. 2.
Described enzymolysis device comprises flashing tower 1, thermal source 2, enzymatic vessel 3, material source 10, vacuum pump 4 and condenser 9, described flashing tower 1 comprises first interface 5, second interface 6, the 3rd interface 7 and at least one discharge port, material source 10 is communicated with flashing tower 1 by first interface 5, enzymatic vessel 3 is communicated with the discharge port of flashing tower 1, vacuum pump 4 is communicated with second interface 6 of flashing tower 1, condenser 9 is communicated with the top of flashing tower 1, thermal source 2 is communicated with the 3rd interface 7 of flashing tower 1 by the inverted U-shaped pipe, the top of described inverted U-shaped pipe is higher than the top of flashing tower 1, and the vertical difference of altitude of inverted U-shaped pipe and flashing tower 1 is 1.5 meters.Opening vacuum pump 4 vacuumizes flashing tower 1, make that the gauge pressure of flashing tower 1 is-0.3 MPa, open the valve between thermal source 2 and the flashing tower 1 then, making temperature in the thermal source 2 is that 150 ℃ water vapor is inhaled in the flashing tower 1, open the valve in material source 10 simultaneously, making by first interface 5 is that 25 ℃ farinaceous size is delivered to the flashing tower 1 from material source 10 with temperature, and farinaceous size is contacted in flashing tower 1 with water vapor, the weight ratio of water vapor and farinaceous size is 20: 1, the time of contact is 7 minutes, the temperature that monitor farinaceous size by the temperature monitoring apparatus that is provided with on the flashing tower 1 this moment is increased to 65 ℃, farinaceous size is delivered in the enzymatic vessel 3 to mix with amylase by discharge port carries out enzymolysis, the time of enzymolysis is 70 minutes, and the pH value of described enzymolysis is 5; With the dry weight basis of every gram farinaceous size, add the α-Dian Fenmei (Novozymes Company buys) of 25 enzyme activity units; Remainder water steam in the flashing tower 1 is extracted and be condensed into to the power supply of open cold condenser 9 out water.
And according to the method for embodiment 1 enzymolysis product is fermented, obtain 13.95 kilograms of ethanol.
Remaining karusen filters with B after getting 100 gram distillation ethanol, 20 milliliters of filtrates is transferred in the triangular flask of 50 milliliters of dryings, leaves standstill 5 hours, collects supernatant liquid.0.2 the supernatant liquid that the micron membrane filtration is collected, according to the described high performance liquid phase condition of above-mentioned steps (1), the glucose of measuring and calculating in the karusen 359 restrains totally.And calculate alcohol yied and residual sugar rate according to the formula of embodiment 1, calculation result sees Table 1.
Table 1
| Embodiment or | Embodiment | 1 | Comparative Examples 1 | |
|
|
| Alcohol yied (%) | 51.6 | 50.3 | 52.9 | 51.9 | 52.4 | |
| Residual sugar rate (%) | 1.4 | 2.1 | 1.3 | 1.4 | 1.35 |
Data from last table 1 adopt potato raw material provided by the invention to prepare alcoholic acid starch ethanol yield that the alcoholic acid method obtains apparently higher than Comparative Examples 1, and the residual sugar rate also reduce greatly as can be seen than Comparative Examples 1.The more important thing is, adopt enzymolysis equipment of the present invention, not only power consumption is few, and enzymolysis efficiency is higher.
Claims (14)
1. one kind is adopted potato raw material to prepare the alcoholic acid method, and this method comprises pulverizes potato raw material, and crushed products and mixed being incorporated in a kind of enzymolysis device of enzyme are carried out enzymolysis, obtains enzymolysis product; This enzymolysis product ferments, it is characterized in that, described enzymolysis device comprises flashing tower (1), thermal source (2), enzymatic vessel (3), material source (10) and vacuum pump (4), described flashing tower (1) comprises first interface (5), second interface (6), the 3rd interface (7) and discharge port (11), material source (10) is communicated with flashing tower (1) by first interface (5), enzymatic vessel (3) is communicated with the discharge port of flashing tower (1), vacuum pump (4) is communicated with second interface (6) of flashing tower (1), and thermal source (2) is communicated with the 3rd interface (7) of flashing tower (1); Crushed products and enzyme mixed be incorporated in the method for carrying out enzymolysis in a kind of enzymolysis device and comprise by first interface (5) crushed products is delivered to the flashing tower (1) from material source (10), with crushed products before material source (10) are delivered to the flashing tower (1), simultaneously or start vacuum pump (4) afterwards, make and form negative pressure in the flashing tower (1), thermal medium in the thermal source (2) is inhaled in the flashing tower (1), and crushed products is contacted in flashing tower (1) with thermal medium, the temperature of crushed products is raise, and the crushed products after then this temperature being raise is delivered in the enzymatic vessel (3) to mix with enzyme by discharge port (11) carries out enzymolysis; Described thermal medium is 100-170 ℃ hot water or a water vapour.
2. method according to claim 1, wherein, thermal source (2) is communicated with the 3rd interface (7) of flashing tower (1) by communicating vessels (8), and the top of described communicating vessels (8) is higher than the liquid level of crushed products in the flashing tower (1).
3. method according to claim 2, wherein, the top of described communicating vessels (8) is higher than the top of flashing tower (1).
4. method according to claim 3, wherein, the difference of altitude between the top of the top of described communicating vessels (8) and flashing tower (1) is a 1-2.5 rice.
5. according to any described method among the claim 2-4, wherein, described communicating vessels (8) is the bending pipe.
6. method according to claim 5, wherein, described communicating vessels (8) is inverted U-shaped pipe or serpentine tube.
7. method according to claim 1, wherein, described thermal medium and crushed products counter current contact.
8. method according to claim 7 wherein, is 20-40 ℃ a potato raw material farinaceous size from the described crushed products of material source (10), and the time of described contact is 5-10 minute.
9. method according to claim 8, wherein, the crushed products of contact and the part by weight of thermal medium are 15-30 in flashing tower (1): 1.
10. method according to claim 1, wherein, the gauge pressure of described flashing tower (1) is-0.3 to-0.01 MPa.
11. method according to claim 1, wherein, described crushed products is the potato raw material farinaceous size, and the condition of described enzymolysis comprises that the temperature of enzymolysis is 50-90 ℃, and the time of enzymolysis is 20-240 minute, and the pH value of enzymolysis is 3-7; The enzyme that described enzymolysis uses is amylase, and with the dry weight basis of every gram crushed products, described diastatic consumption is the 4-50 enzyme activity unit; Described amylase is selected from one or more in α-Dian Fenmei, saccharifying enzyme, transfering grape glycosidase and the phosphoesterase.
12. method according to claim 1, wherein, described enzymolysis device also comprises condenser (9), and described condenser (9) is communicated with the top of flashing tower (1), and this method also comprises making to enter in the condenser (9) with water vapor after crushed products contacts carries out condensation.
13. method according to claim 1, wherein, the average particulate diameter of described crushed products is the 1.5-10 millimeter.
14. method according to claim 1, wherein, in every gram enzymolysis product, the employed zymic inoculum size of described fermentation is 10
3-10
8Colony-forming unit, the temperature of described fermentation are 30-36 ℃, and the time of fermentation is 50-75 hour.
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