CN101676394B - Method for preparing alcohol by utilizing potato materials - Google Patents
Method for preparing alcohol by utilizing potato materials Download PDFInfo
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- CN101676394B CN101676394B CN200810222820XA CN200810222820A CN101676394B CN 101676394 B CN101676394 B CN 101676394B CN 200810222820X A CN200810222820X A CN 200810222820XA CN 200810222820 A CN200810222820 A CN 200810222820A CN 101676394 B CN101676394 B CN 101676394B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E50/00—Technologies for the production of fuel of non-fossil origin
- Y02E50/10—Biofuels, e.g. bio-diesel
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P60/00—Technologies relating to agriculture, livestock or agroalimentary industries
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- Y02P60/87—Re-use of by-products of food processing for fodder production
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Abstract
A method for preparing alcohol by utilizing potato materials comprises the following steps: grinding the potato materials, mixing the products after grinding with enzyme and carrying out enzymolysis to obtain enzymolysis products; fermenting the enzymolysis products, separating alcohol from the fermentation products, and then carrying out solid-liquid separation on the liquid waste. The method is characterized by adding water-soluble alginate esters and/or water-soluble alginates into the liquid waste before carrying out solid-liquid separation on the liquid waste. Compared with the prior art, the method of the invention obviously shortens the solid-liquid separation time and increases the treatment capacity of the liquid waste in unit time under the condition of dispensing with new equipment.
Description
Technical field
The invention relates to the alcoholic acid preparation method, more specifically is about adopting potato raw material to prepare the alcoholic acid method.
Background technology
The potato class, for example Ipomoea batatas, yam, 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 types: bitter manioc (poisonous cassava) and sweet taste cassava (nontoxic cassava).The main chemical compositions of fresh tapioca root is a water, secondly is glucide, also has less protein, fat and the pectin of some content.The fresh cassava starch content reaches 25-30 weight %, and dried tapioca(flour) content is about 70 weight %.
Because the waste liquid of potato raw material alcohol prepared by fermenting contains the organism of high density; The waste liquid of the potato raw material alcohol prepared by fermenting of present most ethanol factory discharging is through effectively handling directly outwards discharging, the water surrounding in local and downstream caused have a strong impact on.
At present, the treatment process of the waste liquid of potato raw material alcohol prepared by fermenting has: 1, burning method, and soon the waste liquid of potato raw material alcohol prepared by fermenting burns after concentrating, and the shortcoming of this method causes secondary pollution easily after burning; 2, with the waste liquid ferment preparation of sludge gas of potato raw material alcohol prepared by fermenting, the shortcoming of this method is big and control techniques requirement height for investment.
Therefore, the method that adopts the solid residue in the waste liquid that reclaims preparation of ethanol by fermentation of cassava to dispose waste liquid usually at present as feed, this method comprises carries out solid-liquid separation with waste liquid, obtains solid product; Afterwards solid product is dried.This method is a kind of less investment, the treatment process of operation and the waste liquid of environment amenable preparation of ethanol by fermentation of cassava easily.In this case, the processing power of solid-liquid separation just becomes the key factor of decision liquid waste disposal ability size.
The problem that the method for at present waste liquid of preparation of ethanol by fermentation of cassava being handled exists is; The excessive cycle of solid-liquid separation; Cause the treatment capacity of waste liquid little, and cause the operating load of device of preparation of ethanol by fermentation of cassava lower, throughput can not reach requirement.
Summary of the invention
The objective of the invention is to overcome existing employing potato raw material and prepare the shortcoming that there is the excessive cycle of solid-liquid separation in the alcoholic acid method, provide a kind of short employing potato raw material of cycle of solid-liquid separation to prepare the alcoholic acid method.
The invention provides a kind of employing potato raw material and prepare the alcoholic acid method, this method comprises pulverizes potato raw material, with the product after pulverizing mix with enzyme, enzymolysis, obtain enzymolysis product; This enzymolysis product that ferments, separating alcohol from tunning carries out solid-liquid separation to waste liquid then, wherein, before waste liquid being carried out solid-liquid separation, in waste liquid, adds water soluble algae acid esters and/or water soluble algae hydrochlorate.
Among the present invention; Through in the waste liquid of preparation of ethanol by fermentation of cassava, adding water soluble algae acid esters and/or water soluble algae hydrochlorate; Shortened solid-liquid separation time significantly; Improve the treatment capacity of liquid waste in unit time significantly need not to increase under the situation of new installation, thereby solved the lower bottleneck of operating load of the device that causes preparation of ethanol by fermentation of cassava, improved the throughput of the device of preparation of ethanol by fermentation of cassava.
Embodiment
The invention provides a kind of employing potato raw material and prepare the alcoholic acid method, this method comprises pulverizes potato raw material, with the product after pulverizing mix with enzyme, enzymolysis, obtain enzymolysis product; This enzymolysis product that ferments, separating alcohol from tunning carries out solid-liquid separation to waste liquid then, wherein, before waste liquid being carried out solid-liquid separation, in waste liquid, adds water soluble algae acid esters and/or water soluble algae hydrochlorate.
According to the present invention; The consumption of water soluble algae acid esters and/or water soluble algae hydrochlorate can in very large range change; As long as can shorten solid-liquid separation time; Under the preferable case, with respect to the waste liquid of 1000 weight parts, the consumption of water soluble algae acid esters and/or water soluble algae hydrochlorate is the 0.05-1 weight part; Further be preferably, with respect to the waste liquid of 1000 weight parts, the consumption of water soluble algae acid esters and/or water soluble algae hydrochlorate is the 0.1-0.5 weight part.
The kind of said water soluble algae hydrochlorate can in very large range change; As long as can make collision of molecules aggravation in the waste liquid; Make and be difficult for sedimentary small molecules and be combined into macromole and form bigger throw out and get final product; Under the preferable case, the relative molecular weight of said water soluble algae hydrochlorate is 30000-200000, and relative molecular weight is the molecule of material or the average quality and the nucleic of discrete cell
121/12 ratio of C atomic mass.For example, said water soluble algae hydrochlorate can be selected from one or more in sodium-alginate, potassium alginate and the ammonium alginate.The water soluble algae hydrochlorate that meets above-mentioned requirements can be commercially available; For example, the ammonium alginate of the medicinal varek combinations of potassium alginate and ocean, the Handan City ltd production of the sodium-alginate of Nan Yang, Qingdao seaweed industry ltd production, Qingdao Mingyue Marine Alga Group Corp., Ltd.'s production.
The kind of said water soluble algae acid esters can in very large range change; As long as can make collision of molecules aggravation in the waste liquid; Make and be difficult for sedimentary small molecules and be combined into macromole and form bigger throw out and get final product; Under the preferable case, the relative molecular weight of said water soluble algae acid esters is 30000-200000, and relative molecular weight is the molecule of material or the average quality and the nucleic of discrete cell
121/12 ratio of C atomic mass.For example, said water soluble algae acid esters can be selected from one or more in propylene glycol alginate, ethylene glycol alginate and the Lalgine butanediol ester, is preferably propylene glycol alginate.Known method is synthetic by one of skill in the art obtains for the water soluble algae acid esters that meets above-mentioned requirements, also can be commercially available, for example, the propylene glycol alginate that Qingdao Mingyue Marine Alga Group Corp., Ltd. produces.
Under the preferable case; Before waste liquid being carried out solid-liquid separation, in waste liquid, add water soluble algae acid esters and water soluble algae hydrochlorate; When adding water soluble algae acid esters and water soluble algae hydrochlorate at the same time; Can further shorten solid-liquid separation time, thereby further improve the treatment capacity of liquid waste in unit time.In this case, the consumption of water soluble algae acid esters and water soluble algae hydrochlorate can in very large range change, and under the preferable case, with respect to the water soluble algae acid esters of 100 weight parts, the add-on of said water soluble algae hydrochlorate is the 10-1000 weight part.Further be preferably, with respect to the water soluble algae acid esters of 100 weight parts, the add-on of said water soluble algae hydrochlorate is the 40-300 weight part.
According to the present invention, the method that potato raw material is pulverized can be pulverized the whole bag of tricks that potato raw material is pulverized for can be used in, for example; The breaking method of said cassava can comprise with cassava with pulverize after water mixes; But the particle diameter of the potato raw material of the pulverizing that this method obtains is bigger and inhomogeneous, thereby causes follow-up alcohol yied lower and the residual sugar rate is higher, therefore; Under the preferable case; The method of said pulverizing comprises once to be pulverized potato raw material earlier, obtains crushed products one time, crushed products of part is carried out secondary pulverize; Obtain the secondary crushed products, a crushed products of remainder is mixed then with the potato raw material of not pulverizing once pulverize; Before waste liquid being carried out solid-liquid separation, in waste liquid, add water soluble algae acid esters and/or water soluble algae hydrochlorate.
According to the present invention, the 5-20 weight % that a crushed products of said remainder is whole crushed products weight; A crushed products of remainder accounts for the 5-20 weight % of crushed products of remainder and the gross weight of the potato raw material of not pulverizing.Under the preferable case, the 5-10 weight % that a crushed products of said remainder is whole crushed products weight; A crushed products of remainder accounts for the 5-10 weight % of crushed products of remainder and the gross weight of the potato raw material of not pulverizing.Pulverize in the final crushed products that obtains potato raw material particulate granularity according to method of the present invention little and particle size distribution is more even; The average particulate diameter of this potato raw material can reach 1.8 to less than 2.5 millimeters; Even littler, as be preferably 1.6 to less than 1.8 millimeters.
According to method provided by the invention, before potato raw material is once pulverized, need not potato raw material is mixed with water, perhaps only add a spot of water, for example, the consumption of said water can be 0.5-2 times of potato raw material dry weight, is preferably 1-1.5 doubly.Under the preferable case, before pulverizing potato raw material, need not especially potato raw material to be mixed with water, but crushed products of the part after will once pulverizing is returned and is not mixed again through the potato raw material of pulverizing; Once pulverize then; Crushed products of this part of returning is a potato raw material particulate farinaceous size, and a crushed products of this returning part can either play the effect of dilution, therefore when initial the pulverizing, can potato raw material not mixed with water; In addition; A crushed products of this returning part can be pulverized with the fresh cassava raw material again once more, and not only the amount of consume water is few, and the energy of consumption is less; Usage ratio of equipment is high; Crushing effect is high, and the method pulverized of secondary of the present invention can be good at controlling potato raw material particle grain size in the crushed products that obtains after the pulverizing, makes the potato raw material particle grain size that finally obtains little and even.According to the present invention; For make in the crushed products that finally obtains potato raw material particulate diameter 1.8 to less than 2.5 millimeters; Be preferably 1.6 to less than 1.8 millimeters; After potato raw material was once pulverized, the average particulate diameter of potato raw material was preferably the 2.5-5 millimeter generally at the 2.5-10 millimeter in the crushed products that obtains.
According to an embodiment of the present invention; When said feeding manner is continuously feeding; Can with crushed products of remainder mixes with the potato raw material of not pulverizing and once pulverize after a crushed products in the part taking-up; Continuation and does not mix through the potato raw material of pulverizing and once pulverize, and pulverizes according to such method circulation, successive.
According to another embodiment of the present invention; When said feeding manner is intermittent feeding; Can with crushed products of remainder with does not mix through the potato raw material of pulverizing and once pulverize after a crushed products obtaining directly carry out secondary and pulverize and obtain the secondary crushed products, carry out the secondary pulverizing after also can the crushed products that obtain of this crushed products after first pulverizing being mixed.
Can use conventional various disintegrating apparatus, for example SFSP series beater disintegrating machine.
Said potato raw material can be various potato raw materials, and like Ipomoea batatas, yam, cassava etc., the potato raw material that adopts in the specific embodiments of the present invention is a cassava.Said cassava can be fresh cassava or dried cassava, also can be the mixture of fresh cassava and dried cassava.The weight of said dried cassava and fresh cassava is not special to be limited, and generally, the weight ratio of said dried cassava and fresh cassava is 1:1.5-2.5, is preferably 1:1.5-2.
The general thick 4-8 of sophisticated cassava centimetre, long 20-30 centimetre, potato shape tubbiness is the short cylindrical shape, and cassava mechanism from inside to outside is a potato meat, and entocuticle and exterior skin, exterior skin are Vandyke brown, an adularescent circular fringes, endothelium and meat white.Owing to may contain earth, sandstone impurity and iron contamination in the potato raw material; Can cause damage to disintegrating apparatus; Therefore; According to method of the present invention, can also comprise and potato raw material carried out pretreated routine operation before broken that said 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 said cleaning is conventionally known to one of skill in the art, here repeats no more.
Said enzymolysis step can be accomplished through this area method commonly used, and such as in crushed products, adding microbes producing cellulase and/or enzyme, insulation is accomplished under the growth temperature of microbes producing cellulase and/or the great-hearted temperature of enzyme.Said microbes producing cellulase be can secreting amylase microbes producing cellulase.Said enzyme comprises glycase.
Because microorganism growth can produce by product, the therefore preferred enzyme that directly adds.The consumption of said enzyme is The more the better; From cost consideration, the dry weight basis of the product after preferably pulverizing with every gram, said diastatic consumption is the 4-50 enzyme activity unit; The dry weight basis of the product after more preferably pulverizing with every gram, said diastatic consumption is the 10-30 enzyme activity unit.
Being defined as of the enzyme activity unit of enzyme according to the invention: be 6.0 in the pH value, 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 said enzymolysis can be diastatic any optimum temperature, is generally 50-90 ℃, more preferably 60-70 ℃.The longer the better on the time theory of said enzymolysis, considers plant factor, and the time of preferred said enzymolysis is 20-240 minute, more preferably 30-120 minute.The pH value of said enzymolysis can be generally 3-7 for diastatic the righttest any action pH, and more preferably the pH value is 5-6.Because the fluctuation of pH value is little in the enzymolysis process; Therefore the pH value of said enzymolysis can be regulated before adding enzyme according to this area method commonly used, for example earlier crushed products and water or substratum (enzyme-addedly generally mixing the general substratum with this mikrobe of adding microbes producing cellulase with water) was mixed; In addition; In order to guarantee to distill the concentration of ethanol that obtains, the solid content that generally makes the gained mixture is 20-40 weight %, according to the pH value of 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 5-6 to 3-7.
Glycase is the general name of class of enzymes that can the starch-splitting glycosidic link, and said glycase generally comprises AMS, beta-amylase, saccharifying enzyme and isoamylase.Enzyme according to the invention comprises glycase.
AMS is claimed starch 1 again, the 4-dextrinase, and it can cut the inner α-1 of starch chain at random, brokenly, and the 4-glycosidic link is hydrolyzed to starch SANMALT-S, contains the oligosaccharides of 6 glucose units and has the oligosaccharides of side chain.The mikrobe that produces this enzyme mainly has Bacillus subtilus, black mold, aspergillus oryzae and head mold.
Beta-amylase is claimed starch 1 again, and 4-maltoside enzyme can cut 1 from the starch molecule non reducing end, and the 4-glycosidic link generates SANMALT-S.The product that this enzyme acts on starch is SANMALT-S and limit dextrin.This enzyme is mainly produced by aspergillus, head mold and endomyces.
Saccharifying enzyme is claimed 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 pulullan 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 black mold (left U.S. aspergillus, Aspergillus awamori), head mold (snow-white enzyme, De Shi head mold), to intend endomyces, monascus.
Isoamylase is claimed 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 said 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.
The mikrobe 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 mikrobe 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 said fermentation is a yeast saccharomyces cerevisiae.
In every gram enzymolysis product, the employed zymic inoculum size of said fermentation is 10
3-10
8Colony-forming unit, more preferably 10
4-10
6Colony-forming unit.
The method of a certain amount of bacterium liquid through cast or coating after will diluting that be defined as of said colony-forming unit lets unicellular being dispersed in one by one on the culture medium flat plate of mikrobe 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).Said 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 following:
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.
Said yeast can adopt conventional method inoculation, for example in enzymolysis product, adds the seed liquor of 5-15 volume %.Said 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 said 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 said 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 50-75 hour, more preferably 60-70 hour.Tunning ethanol can be used 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.
According to the present invention, said water cut can obtain through variety of way less than the solid product of 60 weight %, for example can obtain through said waste liquid filtered and squeeze.
Contriver of the present invention has carried out careful research to the existing method that from the waste liquid of potato raw material alcohol prepared by fermenting, reclaims solid residue, finds to use usually in the prior art common pressure filter that the waste liquid of potato raw material alcohol prepared by fermenting is filtered, and waste liquid gets between the common filter plate of pressure filter when filtering; Solid particulate is trapped in the space between the filter plate by the filtration medium of filter plate; Liquid is discharged outside the pressure filter, along with the continuity of filtration procedure by portalling then through filtration medium; The thickness of solid product increases gradually; The resistance of dehydration increases exponentially thereupon, thereby causes the rapid decline of treatment capacity, and because the restriction of the character of common filter plate own; Filter pressure can't further improve (generally below 1MPa), thereby can't further reduce the water cut that obtains solid product.
According to the present invention, can use various device that said waste liquid is filtered and squeezes, under the preferable case; Can use diaphragm filter press to realize, diaphragm filter press has the filtering function identical with the common diaphragm pressure filter, also has solid product is squeezed and function that it is dewatered once more; In diaphragm filter press, common filter plate and membrane filter plate are spaced, and the middle central layer of said membrane filter plate and both sides barrier film compress and form two Sealed sandwiches; The filtering function of said membrane filter plate is identical with common filter plate, but has increased pressing function, promptly; After filtering end, extrusion medium is injected into the sealing ply from middle central layer hand-hole; Because membranous elastic contribution can carry out the blow-up squeezing to the solid product after filtering, and solid product is dewatered once more.
According to the present invention; The consumption of water soluble algae acid esters and/or water soluble algae hydrochlorate can in very large range change; As long as can shorten solid-liquid separation time; Under the preferable case, with respect to the waste liquid of 1000 weight parts, the consumption of water soluble algae acid esters and/or water soluble algae hydrochlorate is the 0.05-1 weight part; Further be preferably, with respect to the waste liquid of 1000 weight parts, the consumption of water soluble algae acid esters and/or water soluble algae hydrochlorate is the 0.1-0.5 weight part.
The kind of said water soluble algae hydrochlorate can in very large range change; As long as can make collision of molecules aggravation in the waste liquid; Make and be difficult for sedimentary small molecules and be combined into macromole and form bigger throw out and get final product; Under the preferable case, the relative molecular weight of said water soluble algae hydrochlorate is 30000-200000, and relative molecular weight is the molecule of material or the average quality and the nucleic of discrete cell
121/12 ratio of C atomic mass.For example, said water soluble algae hydrochlorate can be selected from one or more in sodium-alginate, potassium alginate and the ammonium alginate.The water soluble algae hydrochlorate that meets above-mentioned requirements can be commercially available; For example, the ammonium alginate of the medicinal varek combinations of potassium alginate and ocean, the Handan City ltd production of the sodium-alginate of Nan Yang, Qingdao seaweed industry ltd production, Qingdao Mingyue Marine Alga Group Corp., Ltd.'s production.
The kind of said water soluble algae acid esters can in very large range change; As long as can make collision of molecules aggravation in the waste liquid; Make and be difficult for sedimentary small molecules and be combined into macromole and form bigger throw out and get final product; Under the preferable case, the relative molecular weight of said water soluble algae acid esters is 30000-200000, and relative molecular weight is the molecule of material or the average quality and the nucleic of discrete cell
121/12 ratio of C atomic mass.For example, said water soluble algae acid esters can be selected from one or more in propylene glycol alginate, ethylene glycol alginate and the Lalgine butanediol ester, is preferably propylene glycol alginate.Known method is synthetic by one of skill in the art obtains for the water soluble algae acid esters that meets above-mentioned requirements, also can be commercially available, for example, the propylene glycol alginate that Qingdao Mingyue Marine Alga Group Corp., Ltd. produces.
Under the preferable case; Before waste liquid being carried out solid-liquid separation, in waste liquid, add water soluble algae acid esters and water soluble algae hydrochlorate; When adding water soluble algae acid esters and water soluble algae hydrochlorate at the same time; Can further shorten solid-liquid separation time, thereby further improve the treatment capacity of liquid waste in unit time.In this case, the consumption of water soluble algae acid esters and water soluble algae hydrochlorate can in very large range change, and under the preferable case, with respect to the water soluble algae acid esters of 100 weight parts, the add-on of said water soluble algae hydrochlorate is the 10-1000 weight part.Further be preferably, with respect to the water soluble algae acid esters of 100 weight parts, the add-on of said water soluble algae hydrochlorate is the 40-300 weight part.
According to the present invention, said solid-liquid separation can be the various solid-liquid separating methods of routine, as filtering, for example, can filter through pressure filter, for example, the chamber-type press filter that Jingjin Filter Press Group Co.,Ltd produces.Said filtering condition can in very large range change, and under the preferable case, said filtering condition comprises that filtering pressure is 0.4-1MPa, and filter time is 1-3 hour.
But contriver of the present invention finds, when using common chamber-type press filter that the waste liquid of preparation of ethanol by fermentation of cassava is filtered; Waste liquid gets between the chamber filter plate of pressure filter, and solid particulate is trapped in the space between the filter plate by the filtration medium of filter plate, and liquid then passes through filtration medium; Discharge outside the pressure filter by portalling, along with the continuity of filtration procedure, the thickness of solid product increases gradually; The resistance of dehydration increases exponentially thereupon; Thereby cause the rapid decline of treatment capacity, and because the restriction of the character of chamber filter plate own, filter pressure can't further improve (generally below 1MPa); Thereby can't further reduce the water cut of solid product, the required energy consumption of follow-up oven dry solid product is higher.
Therefore, under the preferable case, said solid-liquid separation is through filtering and squeeze realization to said waste liquid.
According to the present invention, can use various device that said waste liquid is filtered and squeezes, under the preferable case, can use diaphragm filter press to filter and squeeze.
Said diaphragm filter press promptly has the filtering function identical with common chamber-type press filter, has again solid product is squeezed and makes its function of dewatering once more, in diaphragm filter press; Common chamber filter plate and membrane filter plate are spaced, and the middle central layer of said membrane filter plate and both sides barrier film compress and form two Sealed sandwiches, and the filtering function of said membrane filter plate is identical with common chamber filter plate; But increased pressing function; That is, after filtering end, extrusion medium is injected into the sealing ply from middle central layer hand-hole, because membranous elastic contribution; Can carry out the blow-up squeezing to the solid product after filtering, solid product is dewatered once more.
The common chamber filter plate and the quantity of membrane filter plate can be adjusted according to the concentration of waste liquid in the said diaphragm filter press; Under the preferable case; The quantity of common chamber filter plate is 50-60; Said common chamber filter plate can be commercially available, for example the chamber filter plate of Jingjin Filter Press Group Co.,Ltd's production; The quantity of membrane filter plate is 50-60, and said membrane filter plate can be commercially available, for example 1250 type membrane filter plates of Jingjin Filter Press Group Co.,Ltd's production; Common chamber filter plate is spaced with membrane filter plate and the ratio of the quantity of different chamber filter plate and the quantity of membrane filter plate is 1:1; The diaphragm filter press that meets above-mentioned requirements can be commercially available, for example, and the X that Jingjin Filter Press Group Co.,Ltd produces
M AZG600/1500 * 2000U
B KThe diaphragm filter press of model.
The inventor finds, uses diaphragm filter press not only can reduce the water cut of squeezing the solid product that obtains significantly, can also significantly reduce the content that squeezes impurity in the water of removing, and has reduced the wearing and tearing of impurity to equipment, has reduced maintenance cost; And the COD value is also lower in the water of removing, and has alleviated environmental stress.
Among the present invention, the waste liquid of said preparation of ethanol by fermentation of cassava is meant through cassava and ferments when preparing ethanol, distills out after the ethanol that obtains residual solidliquid mixture.
Among the present invention; The condition of said filtration and squeezing can in very large range change, and the condition of said filtration and squeezing makes the water cut of the solid product that obtains less than 60 weight %, under the preferable case; Said filtering condition comprises that filtering pressure is 0.4-1MPa, and filter time is 1-2 hour; The condition of said squeezing comprises that the pressure of squeezing is 10-25MPa, and the time of squeezing is 0.2-1 hour.
Among the present invention, said squeeze pressure can realize that said extrusion medium can be diaphragm filter press various extrusion medium commonly used through in diaphragm filter press, charging into extrusion medium, and for example, said extrusion medium can be pressurized air and/or water.
Also comprise according to the method for the invention the solid product that obtains after the solid-liquid separation is dried; Obtain solid residue; The equipment of said oven dry can be the drying plant of various routines; For example, the WJI-900B boiling drier and the combined dryer of XLS-100 type flash dryer of the HZG series dryer of the long-range company in Shenyang production and the production of Beijing benefit civilian worker trade ltd.Among the present invention, the condition of said oven dry can be the drying condition of routine, and for example, the condition of said oven dry comprises that bake out temperature is 100-200 ℃, and drying time is 0.2-2 hour; Further be preferably, bake out temperature is 120-150 ℃, and drying time is 0.5-1 hour.
To do further specific descriptions to the present invention through embodiment below.
Embodiment 1
Present embodiment is used to explain employing cassava feedstock production alcoholic acid method of the present invention.
(1) pulverizing of cassava raw material
With (thick 4-8 centimetre of 95 kilograms of fresh cassava raw material; Long 20-30 centimetre; Water cut 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; The method of said pulverizing comprises once to be pulverized 60 kilograms of these cassava slices 20 minutes earlier; Obtain average particulate diameter and be 60 kilograms of the crushed products of 4.5 millimeters (adopting the Accu Sizer TM780 optics particle diameter detector of U.S. PPS company to measure), then 60 kilograms of this crushed products of 10 weight % were once pulverized 15 minutes through the fresh cassava raw materials mix of pulverizing with remaining 35 kilograms once more, obtain average particulate diameter and be a crushed products of 3 millimeters; And above-mentioned whole crushed products are carried out secondary pulverized 5 minutes, obtain 95 kilograms of crushed products (average particulate diameter of cassava raw material is 2 millimeters in this crushed products).
Get the above-mentioned crushed products of 10 grams and filter and under 45 ℃, dry 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.In said Erlenmeyer flask, adding 3.00 ml concns is the sulphuric acid soln of 72 weight %, stirs 1 minute.Then Erlenmeyer flask was placed 60 minutes in 30 ℃ water-bath, whenever stirred once to guarantee even hydrolysis at a distance from 5 minutes.Hydrolysis makes the vitriolic concentration dilution to 4 weight % with deionized water after finishing, and filters with B then, obtains altogether filtrating 84 milliliters.20 milliliters of filtratings 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 filtrating is analyzed with Biorad AminexHPX-87P 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 said 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 can the starch in the crushed products all 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 said crushed products of 1 gram is 0.280 gram, then is total to starch-containing 26.6 kilograms in 95 kilograms of crushed products.
(2) enzymolysis
Remaining crushed products behind step (1) sampling and testing is mixed with 21 kg water; Regulate pH value to 5; After being heated to 70 ℃; With the dry weight basis of every gram crushed products, add the AMS (Novozymes Company buys) of 20 enzyme activity units, and the insulation enzymolysis obtained enzymolysis product after 60 minutes under 70 ℃.
(3) fermentation
Make the temperature of enzymolysis product reduce to 33 ℃, in the weight of every gram enzymolysis product, 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.According to the computes alcohol yied, calculation result is seen table 1.
The weight of starch contained therein in alcohol yied=100% * ethanol weight/cassava raw material
The beer of getting behind the 100 gram distillation ethanol filters with B, 20 milliliters of filtratings 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 said performance liquid condition of above-mentioned steps (1), the glucose of measuring and calculating in the beer 372 restrains totally.And according to computes residual sugar rate, calculation result is seen table 1.
The weight of starch contained therein in residual sugar amount/cassava raw material in residual sugar rate=100% * beer
(4) liquid waste disposal
The waste liquid of the potato raw material alcohol prepared by fermenting in the fermentor tank is taken out from fermentor tank, and water flushing fermentor tank mixes the water after waste liquid that takes out and the flushing.
The waste liquid of 15 batches of above-mentioned fermentations is mixed, and (Shanghai Precision Scientific Apparatus Co., Ltd, the water cut that SH-10A) detects in this mixed waste liquor is 95 weight % through moisture determination instrument.The propylene glycol alginate (Qingdao Mingyue Marine Alga Group Corp., Ltd., relative molecular weight is 40000) that in 100 tons of above-mentioned mixed waste liquors, adds 10 kilograms joins waste liquid in the chamber-type press filter (Jingjin Filter Press Group Co.,Ltd) afterwards; After being filled, filters by pressure filter; In the said chamber-type press filter, the quantity of common chamber filter plate (Jingjin Filter Press Group Co.,Ltd, chamber filter plate) is 100; Said filtering condition comprises that filtering pressure is 0.8MPa; Filter time is 2 hours, and obtaining water cut is the solid product A1 of 75 weight %, and the liquid waste disposal amount (separate unit) in time that solid-liquid separation is required and unit time is as shown in table 2.
Comparative Examples 1
The explanation of this Comparative Examples adopts cassava to prepare alcoholic acid reference method.
Method according to embodiment 1 prepares ethanol; Different is; Once pulverized 35 minutes 95 kilograms of fresh cassava raw materials are mixed (weight ratio of cassava raw material fresh weight and water is 1:1) with 95 kg water after; Then a crushed products is directly carried out secondary and pulverized 5 minutes, obtain 190 kilograms of crushed products (average particulate diameter of cassava raw material is 5 millimeters in this crushed products) altogether.According to the said performance liquid condition of embodiment 1 step (1), measure and calculate in these 190 kilograms of crushed products starch-containing 26.5 kilograms altogether.
Remaining crushed products is carried out enzymolysis after adopting the condition identical with embodiment 1 to sampling and testing, and enzymolysis product is fermented, and obtains 13.38 kilograms of ethanol.
Remaining beer filters with B after getting 100 gram distillation ethanol, 20 milliliters of filtratings 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 said performance liquid condition of above-mentioned steps (1), the glucose of measuring and calculating in the beer 583 restrains totally.And calculate alcohol yied and residual sugar rate according to the formula of embodiment 1, calculation result is seen table 1.
In addition; Filter according to the waste liquid of the method identical preparation of ethanol by fermentation of cassava with embodiment 1; Different is not add propylene glycol alginate; Obtaining water cut is the reference solid product CA1 of 75 weight %, and the liquid waste disposal amount (separate unit) in time that solid-liquid separation is required and unit time is as shown in table 2.
Embodiment 2
Present embodiment is used to explain employing cassava feedstock production alcoholic acid method of the present invention.
Method according to embodiment 1 prepares ethanol; Different is; The method of said pulverizing comprises uses SFSP series beater disintegrating machine earlier 30 kilograms of fresh cassava raw materials once to be pulverized 12 minutes; Obtain average particulate diameter and be 5 millimeters 30 kilograms of crushed products; Then with 1.5 kilograms of this crushed products of 5 weight % with remaining 25 kilograms through the fresh cassava raw materials mix pulverized and once pulverized once more 10 minutes; Obtain average particulate diameter and be 4 millimeters 55 kilograms of crushed products, this crushed products of 5 weight % was once pulverized 15 minutes through the cassavas of pulverizing with remaining 40 kilograms for 2.75 kilograms again, obtain 95 kilograms of crushed products altogether; And an above-mentioned crushed products is carried out secondary pulverized 3 minutes, obtain 95 kilograms of crushed products (average particulate diameter of cassava raw material is 2 millimeters in this crushed products).According to the said performance liquid condition of embodiment 1 step (1), measure and calculate in these 95 kilograms of cassava slurries starch-containing 26.8 kilograms altogether.
Remaining crushed products is carried out enzymolysis after adopting the condition identical with embodiment 1 to sampling and testing, and enzymolysis product is fermented, and obtains 14.07 kilograms of ethanol.
Remaining beer filters with B after getting 100 gram distillation ethanol, 20 milliliters of filtratings 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 said performance liquid condition of above-mentioned steps (1), the glucose of measuring and calculating in the beer 348 restrains totally.And calculate alcohol yied and residual sugar rate according to the formula of embodiment 1, calculation result is seen table 1.
Liquid waste disposal
In step (4): the waste liquid of the potato raw material alcohol prepared by fermenting in the fermentor tank is taken out from fermentor tank, and water flushing fermentor tank mixes the water after waste liquid that takes out and the flushing.
The waste liquid of 15 batches of above-mentioned fermentations is mixed, and (Shanghai Precision Scientific Apparatus Co., Ltd, the water cut that SH-10A) detects in this mixed waste liquor is 95 weight % through moisture determination instrument.The sodium-alginate (Nan Yang, Qingdao seaweed industry ltd, relative molecular weight is 80000) that in 100 tons of above-mentioned mixed waste liquors, adds 20 kilograms joins waste liquid in the chamber-type press filter (Jingjin Filter Press Group Co.,Ltd) afterwards; After being filled, filters by pressure filter; In the said chamber-type press filter, the quantity of common chamber filter plate (Jingjin Filter Press Group Co.,Ltd, chamber filter plate) is 100; Said filtering condition comprises that filtering pressure is 0.8MPa; Filter time is 1.8 hours, and obtaining water cut is the solid product A2 of 75 weight %, and the liquid waste disposal amount (separate unit) in time that solid-liquid separation is required and unit time is as shown in table 1.
Embodiment 3
Present embodiment is used to explain employing cassava feedstock production alcoholic acid method of the present invention.
Method according to embodiment 1 prepares ethanol; Different is; The method of said pulverizing comprises uses SFSP series beater disintegrating machine earlier 50 kilograms of fresh cassavas once to be pulverized 15 minutes; Obtain average particulate diameter and be 5.5 millimeters 50 kilograms of crushed products; Then with 4 kilograms of this crushed products of 8 weight % with remaining 45 kilograms of fresh cassava raw materials mix of not pulverizing and once pulverized once more 15 minutes; With this crushed products and the crushed products after pulverizing for the first time mixes that to obtain average particulate diameter altogether be 4 millimeters 95 kilograms of crushed products, and an above-mentioned crushed products is carried out secondary pulverizing 3 minutes, obtain 95 kilograms of crushed products cassava slurries (cassava raw material average particulate diameter is 2 millimeters).According to the said performance liquid condition of embodiment 1 step (1), measure and calculate in these 95 kilograms of crushed products starch-containing 26.6 kilograms altogether.
Remaining crushed products is carried out enzymolysis after adopting the condition identical with embodiment 1 to sampling and testing, and enzymolysis product is fermented, and obtains 13.81 kilograms of ethanol.
Remaining beer filters with B after getting 100 gram distillation ethanol, 20 milliliters of filtratings 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 said performance liquid condition of above-mentioned steps (1), the glucose of measuring and calculating in the beer 372 restrains totally.And calculate alcohol yied and residual sugar rate according to the formula of embodiment 1, calculation result is seen table 1.
Liquid waste disposal
The waste liquid of the potato raw material alcohol prepared by fermenting in the fermentor tank is taken out from fermentor tank, and water flushing fermentor tank mixes the water after waste liquid that takes out and the flushing.
The waste liquid of 15 batches of above-mentioned fermentations is mixed, and (Shanghai Precision Scientific Apparatus Co., Ltd, the water cut that SH-10A) detects in this mixed waste liquor is 95 weight % through moisture determination instrument.In 100 tons of above-mentioned mixed waste liquors, add 10 kilograms ammonium alginate (the medicinal varek combinations in ocean, Handan City ltd, relative molecular weight is 100000) and 10 kilograms propylene glycol alginate (Qingdao Mingyue Marine Alga Group Corp., Ltd., relative molecular weight is 50000); Afterwards waste liquid is joined in the chamber-type press filter (Jingjin Filter Press Group Co.,Ltd); After being filled, filters by pressure filter, in the said chamber-type press filter, and common chamber filter plate (Jingjin Filter Press Group Co.,Ltd; Chamber filter plate) quantity is 100; Said filtering condition comprises that filtering pressure is 0.8MPa, and filter time is 1.8 hours, obtains solid product A3.
(result is as shown in table 3 for Shanghai Precision Scientific Apparatus Co., Ltd, the SH-10A) water cut of detection solid product A3 through moisture determination instrument.
The solid product A3 that obtains is put into (Zhengzhou Wangu Machinery Co., Ltd. in the air-flow tumble-type dryers; JB/T10279-2001) dry; The temperature of oven dry is 180 ℃, obtains solid residue, through moisture determination instrument (Shanghai Precision Scientific Apparatus Co., Ltd; SH-10A) water cut of detection solid residue, the water cut of solid residue and the energy consumption of oven dry are as shown in table 3.
Said energy consumption is meant to dry removes 1 kilogram the coal that water consumed, and unit is a kg/kg.
Embodiment 4
Present embodiment is used to explain employing cassava feedstock production alcoholic acid method of the present invention.
Method according to embodiment 1 prepares ethanol; Different is; 61 kilograms of fresh cassava raw materials section back is pulverized with 166 kilograms of mixtures that obtain after 40 kilograms of dried cassava slices (water cut is 13 weight %) and 65 kg water are mixed; The method of pulverizing comprises uses SFSP series beater disintegrating machine earlier 40 kilograms of cassava raw mixs once to be pulverized 20 minutes; Obtain the cassava average particulate diameter and be 5.5 millimeters 40 kilograms of crushed products; Then 30 kilograms in 3.2 kilograms of this crushed products of 8 weight % and the remaining cassava raw mix are mixed and once pulverized again 10 minutes; Obtain the cassava average particulate diameter and be 5 millimeters totally 70 kilograms of crushed products; With 7 kilograms of this crushed products of 10 weight % of this crushed products again with remaining cassava raw mix in 40 kilograms of mixtures once pulverized 10 minutes; Obtain average particulate diameter and be 4 millimeters totally 110 kilograms of crushed products, with 6.6 kilograms of this crushed products of 6 weight % of this crushed products again with remaining cassava raw mix in 56 kilograms of mixtures once pulverized 10 minutes, obtain average particulate diameter and be 2.5 millimeters 166 kilograms of crushed products; And above-mentioned whole crushed products are carried out secondary pulverized 5 minutes, obtain 166 kilograms of crushed products (average particulate diameter of cassava raw material is 1.6 millimeters in this crushed products).According to the said performance liquid condition of embodiment 1 step (1), record and calculate in 166 kilograms of crushed products starch-containing 43.65 kilograms altogether.
Crushed products after adopting the condition identical with embodiment 1 to sampling and testing is carried out enzymolysis, and different is that amount of water is 30 kilograms during enzymolysis, and enzymolysis product is fermented, and obtains 23.09 kilograms of ethanol.
Remaining beer filters with B after getting 100 gram distillation ethanol, 20 milliliters of filtratings 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 said performance liquid condition of above-mentioned steps (1), the glucose of measuring and calculating in the beer 592 restrains totally.And calculate alcohol yied and residual sugar rate according to the formula of embodiment 1, calculation result is seen table 1.
Liquid waste disposal
Filter according to the waste liquid of the method identical with embodiment 3 to preparation of ethanol by fermentation of cassava, different is that waste liquid is joined diaphragm filter press (Jingjin Filter Press Group Co.,Ltd, X
M AZG600/1500 * 2000U
B K) in carry out solid-liquid separation; In the said diaphragm filter press, with 50 common chamber filter plate (Jingjin Filter Press Group Co.,Ltd of 50 membrane filter plates (Jingjin Filter Press Group Co.,Ltd, 1250 types) replacement; Chamber filter plate), and common chamber filter plate and membrane filter plate be spaced; Said filtering condition comprises that filtering pressure is 0.8MPa, and filter time is 1 hour; In membrane filter plate, charge into the extrusion medium air afterwards, the solid product after filtering is squeezed, the pressure of said squeezing is 10MPa, and the time of squeezing is 0.8 hour, obtains solid product A4.
(result is as shown in table 2 for Shanghai Precision Scientific Apparatus Co., Ltd, the SH-10A) water cut of detection solid product A4 through moisture determination instrument.
The solid product A4 that obtains is put into (Zhengzhou Wangu Machinery Co., Ltd. in the air-flow tumble-type dryers; JB/T10279-2001) dry; The temperature of oven dry is 120 ℃, obtains solid residue, through moisture determination instrument (Shanghai Precision Scientific Apparatus Co., Ltd; SH-10A) water cut of detection solid residue, the water cut of solid residue and the energy consumption of oven dry are as shown in table 2.
Said energy consumption is meant to dry removes 1 kilogram the coal that water consumed, and unit is a kg/kg.
Table 1
| Embodiment or Comparative Examples | Embodiment 1 | Comparative Examples 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 |
| Alcohol yied (%) | 51.6 | 50.5 | 52.5 | 51.9 | 52.9 |
| Residual sugar rate (%) | 1.4 | 2.2 | 1.3 | 1.4 | 1.35 |
The method of the present invention not only amount of consume water is few; Can accomplish pulverizing at short notice; The energy that consumes is less, and usage ratio of equipment is higher, and crush efficiency is higher; The method that adopts secondary of the present invention to pulverize simultaneously can be good at controlling potato raw material particle grain size in the crushed products that obtains after the pulverizing, makes the potato raw material particle grain size that finally obtains little and even.
Data from last table 1 can be found out; Adopt potato raw material provided by the invention to prepare alcoholic acid starch ethanol yield that the alcoholic acid method obtains apparently higher than starch ethanol productive rate by the reference method; And compare with prior art, the residual sugar rate of preparation alcoholic acid method of the present invention reduces greatly.
Table 2
| The embodiment numbering | The solid product numbering | The solid product water cut | Solid-liquid separation is consuming time | Treatment capacity (ton/hour) |
| Embodiment 1 | A1 | 75 weight % | 2 hours | 42 |
| Comparative Examples 1 | CA1 | 75 weight % | 4.5 hour | 18.7 |
| Embodiment 2 | A2 | 75 weight % | 1.8 hour | 46.7 |
Can find out from last table 2; The method that from the waste liquid of preparation of ethanol by fermentation of cassava, reclaims solid residue of the present invention; Shortened solid-liquid separation time significantly; Improve the treatment capacity of liquid waste in unit time significantly need not to increase under the situation of new installation, thereby solved the lower bottleneck of operating load of the device that causes preparation of ethanol by fermentation of cassava, improved the throughput of the device of preparation of ethanol by fermentation of cassava.
Table 3
| The embodiment numbering | Solid product water cut (weight %) | Solid residue water cut (weight %) | Energy consumption (kg/kg) |
| Embodiment 3 | 74 weight % | 10 weight % | 0.31 |
| Embodiment 4 | 55 weight % | 10 weight % | 0.12 |
Can find out from last table 3; The water cut of the solid product A4 that the embodiment of the invention 4 obtains is 55 weight %; The water cut of the solid product A3 that embodiment 3 obtains is then up to 74 weight %; Explanation filters and squeezes the water cut that can reduce the solid product that obtains significantly through using diaphragm filter press to waste liquid; And embodiment 4 compares with embodiment 3, and the energy consumption of baking needed significantly reduces, and explanation can significantly reduce the required energy consumption of recovery solid residue through using diaphragm filter press that waste liquid is filtered and squeezes.
Claims (14)
1. one kind is adopted potato raw material to prepare the alcoholic acid method, and this method comprises pulverizes potato raw material, with the product after pulverizing mix with enzyme, enzymolysis, obtain enzymolysis product; This enzymolysis product ferments; Separating alcohol from tunning; Then waste liquid is carried out solid-liquid separation, it is characterized in that, before waste liquid being carried out solid-liquid separation, in waste liquid, add water soluble algae acid esters and water soluble algae hydrochlorate; With respect to the water soluble algae acid esters of 100 weight parts, the add-on of said water soluble algae hydrochlorate is the 10-1000 weight part; The method of said pulverizing comprises once to be pulverized potato raw material earlier; Obtain crushed products one time; Crushed products of part is carried out secondary pulverize, obtain the secondary crushed products, a crushed products of remainder is mixed then with the potato raw material of not pulverizing once pulverize; The 5-20 weight % that a crushed products of remainder is whole crushed products weight; A crushed products of remainder accounts for the 5-20 weight % of crushed products of remainder and the gross weight of the potato raw material of not pulverizing.
2. method according to claim 1, wherein, with respect to the waste liquid of 1000 weight parts, the consumption of said water soluble algae acid esters and water soluble algae hydrochlorate is the 0.05-1 weight part.
3. method according to claim 2, wherein, with respect to the waste liquid of 1000 weight parts, the consumption of said water soluble algae acid esters and water soluble algae hydrochlorate is the 0.1-0.5 weight part.
4. method according to claim 1, wherein, with respect to the water soluble algae acid esters of 100 weight parts, the add-on of said water soluble algae hydrochlorate is the 40-300 weight part.
5. according to any described method among the claim 1-4; Wherein, The relative molecular weight of said water soluble algae hydrochlorate is 30000-200000; Said water soluble algae hydrochlorate is selected from one or more in sodium-alginate, potassium alginate and the ammonium alginate, and the relative molecular weight of said water soluble algae acid esters is 30000-200000, and said water soluble algae acid esters is a propylene glycol alginate.
6. method according to claim 1, wherein, the 5-10 weight % that a crushed products of remainder is whole crushed products weight; A crushed products of remainder accounts for the 5-10 weight % of crushed products of remainder and the gross weight of the potato raw material of not pulverizing.
7. method according to claim 1, wherein, in the crushed products, the average particulate diameter of potato raw material is the 2-10 millimeter; In the secondary crushed products, the average particulate diameter of potato raw material be 1.6 millimeters to less than 2 millimeters.
8. method according to claim 1, wherein, said solid-liquid separation is through filtering and squeeze realization to said waste liquid.
9. method according to claim 8, wherein, said filtration and squeezing realize that through diaphragm filter press the condition of said filtering condition and said squeezing makes the water cut of the solid product that obtains less than 60 weight %.
10. method according to claim 9, wherein, said filtering condition comprises that filtering pressure is 0.4-1MPa, filter time is 1-2 hour; The condition of said squeezing comprises that the pressure of squeezing is 10-25MPa, and the time of squeezing is 0.2-1 hour.
11. method according to claim 1, wherein, said potato raw material is the mixture of fresh cassava and dried cassava, and the weight ratio of said dried cassava and fresh cassava is 1: 1.5-2.5.
12. method according to claim 1, wherein, the enzyme that said enzymolysis uses comprises glycase, and with the dry weight basis of every gram potato raw material, said diastatic consumption is the 3.8-4.2 enzyme activity unit; The temperature of said enzymolysis is 50-90 ℃, and the time of said enzymolysis is 20-70 minute, and the pH value of said enzymolysis is 5-6.
13. method according to claim 12, wherein, said glycase is one or more in AMS, beta-amylase, saccharifying enzyme and the isoamylase.
14. method according to claim 1, wherein, in every gram enzymolysis product, the employed zymic inoculum size of said fermentation is 10
3-10
8Colony-forming unit, the temperature of said fermentation are 30-33 ℃, and the time of fermentation is 50-75 hour.
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| CN101195836A (en) * | 2008-01-04 | 2008-06-11 | 广西明阳生化科技股份有限公司 | Novel technique for producing manioc waste ethanol |
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| CN101195836A (en) * | 2008-01-04 | 2008-06-11 | 广西明阳生化科技股份有限公司 | Novel technique for producing manioc waste ethanol |
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| Title |
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| 姚文娟等.絮凝法处理酒精废液的研究.《酿酒科技》.2001,全文. * |
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