CN101586124B - Method for preparing ethanol by adopting yam materials - Google Patents
Method for preparing ethanol by adopting yam materials Download PDFInfo
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- CN101586124B CN101586124B CN2008101122706A CN200810112270A CN101586124B CN 101586124 B CN101586124 B CN 101586124B CN 2008101122706 A CN2008101122706 A CN 2008101122706A CN 200810112270 A CN200810112270 A CN 200810112270A CN 101586124 B CN101586124 B CN 101586124B
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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
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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 provides a method for preparing ethanol by adopting yam materials. The starch ethanol yield of the ethanol obtained by adopting the method for preparing the ethanol by the yam materials is obviously higher than that of the ethanol obtained by a reference method, and compared with the prior art, the residual sugar ratio of the method for preparing the ethanol is greatly reduced; and simultaneously, the method provided by the invention can obviously reduce the pressure of wastewater treatment, and wastewater after treatment can meet the requirements of the environment.
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 piece root of cassava is bigger, before adopting cassava raw material enzymolysis, alcohol prepared by fermenting, need pulverize the cassava raw material usually, with the weave construction of destruction cassava, thereby make small starch granules can from tapioca root, disintegrate, separate.In order to improve the extract content of sugar, the disintegration that need make the cassava tissue more fully, more tiny, make the separation of starch granules more thorough.The employing cassava of prior art prepares in the alcoholic acid method, and the breaking method of said cassava generally includes cassava is obtained crushed products with pulverizing after water mixes.Adopt the amount of existing breaking method consume water bigger, in the crushed products that guarantees to obtain to cassava particulate granularity requirements, the energy that adopts existing breaking method to consume is bigger, usage ratio of equipment is low.
Because the waste liquid of preparation of ethanol by fermentation of cassava contains the organism of high density, the waste liquid of the preparation of ethanol by fermentation of cassava 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 preparation of ethanol by fermentation of cassava has: 1, burning method, and soon the waste liquid of preparation of ethanol by fermentation of cassava 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 preparation of ethanol by fermentation of cassava, the shortcoming of this method is big and control techniques requirement height for investment.
Therefore, at present usually the waste liquid of preparation of ethanol by fermentation of cassava is filtered and carry out solid-liquid separation, the solid residue that solid-liquid separation is obtained is as feed; The waste water that solid-liquid separation is obtained carries out wastewater treatment; Though this method has reclaimed the solid residue of the part in the waste liquid, the chemical oxygen demand value (COD) in the waste water after the solid-liquid separation is still very high, usually more than 45000mg/L; Pressure to subsequent wastewater treatment is bigger, and the waste water after handling still can not satisfy environment requirement.
Summary of the invention
The objective of the invention is to overcome existing employing potato raw material, to prepare the amount of the method consume water of pulverizing potato raw material in the alcoholic acid method bigger; The energy that consumes is bigger; The defective that usage ratio of equipment is low and overcome wastewater treatment pressure that the treatment process of the waste liquid of existing preparation of ethanol by fermentation of cassava exists big with handle after waste water can not satisfy the shortcoming of environment requirement; Provide a kind of amount of the consume water of pulverizing potato raw material less; The energy that consumes is less, usage ratio of equipment high and for the processing of the waste liquid of preparation of ethanol by fermentation of cassava can significantly reduce waste water pressure and handle after the waste water employing potato raw material that can satisfy environmental requirement prepare the alcoholic acid method.
Contriver of the present invention finds; The employing potato raw material of prior art prepares in the method for alcohol fuel for the method for pulverizing potato raw material, and no matter potato raw material is fresh cassava or dried cassava, pulverizes after all needing before pulverizing, the cassava raw material is mixed (fresh weight of cassava raw material and the weight ratio of water are generally 1: 1) with water; The amount of consume water is bigger in the crushing process; Thereby the amount of crushed products is also corresponding more, and the storage problem of crushed products also is difficult to resolve determines.In addition, the method for the pulverizing of prior art is generally secondary and pulverizes, that is, with potato raw material with once pulverize earlier after water mixes, a crushed products that obtains is carried out the secondary pulverizing once more, and obtains final crushed products.Potato raw material particle grain size size is inhomogeneous in the crushed products that adopts existing secondary breaking method pulverizing to obtain, and grain graininess is bigger; If in the crushed products that guarantees to obtain cassava particulate granularity can reach certain requirement, then adopt the pulverizing time of existing breaking method to prolong, thereby the energy that consumes is bigger, usage ratio of equipment is low.
In addition; Contriver of the present invention has also carried out careful research to the treatment process of existing preparation of ethanol by fermentation of cassava waste liquid; Discovery is carried out solid-liquid separation through existing method makes the chemical oxygen demand value of the waste water that obtains higher (usually more than 45000mg/L); Very big to follow-up pressure of wastewater treatment, and through the very difficult chemical oxygen demand value that further falls the waste water that obtains after the solid-liquid separation of existing solid-liquid separating method, environmental stress is bigger.
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, and the waste liquid of potato raw material alcohol prepared by fermenting carried out solid-liquid separation; Obtain filter cake and waste water, the waste water that obtains is carried out wastewater treatment, wherein; 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 once with the potato raw material of not pulverizing pulverize; It is the 30000-35000 mg/litre that solid-liquid separation makes the chemical oxygen demand value of the waste water that obtains.
Employing potato raw material provided by the invention prepares in the alcoholic acid method; The method that potato raw material is pulverized is the method that secondary is pulverized, and different with prior art is before pulverizing potato raw material, need potato raw material not mixed with water; Perhaps only add a spot of water; Crushed products of part after then will once pulverizing is returned and is not mixed again through the potato raw material of pulverizing, and once pulverizes once more, and crushed products of this part of returning is a potato raw material particulate farinaceous size; This part crushed products promptly can play the effect of dilution, again can be with not pulverized once more through the potato raw material of pulverizing.The method of the present invention not only amount of consume water is few; The energy that consumes is less; Usage ratio of equipment is high, and crush efficiency is high, and 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; Make the potato raw material particle grain size that finally obtains little and even, also solved the storage problem of crushed products simultaneously.In addition; Contriver of the present invention finds unexpectedly; Adopting potato raw material of the present invention to prepare the starch ethanol productive rate that the alcoholic acid method obtains is significantly improved; Infer that reason possibly be because breaking method 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, thereby the starch in the crushed products is fully discharged; Small starch granules in the potato raw material particle in the crushed products that finally obtains can be fully utilized; Can fully contact with enzyme, enzymolysis, improved the utilization ratio of starch greatly, thereby improved the starch ethanol productive rate greatly.For example; Under all identical situation of other condition, the starch ethanol productive rate that the method for employing embodiment 2 obtains reaches 52.5%, and the residual sugar rate is 1.5%; And the starch ethanol productive rate that the method that adopts Comparative Examples 1 obtains is merely 51.0%; The residual sugar rate is 2.0%, and the increase rate of alcohol yied is up to 2.9%, and the residual sugar rate has reduced by 25%.
Method of the present invention has alleviated the pressure of subsequent wastewater treatment through reducing the chemical oxygen demand value of the waste water that obtains after the solid-liquid separation.For example; The COD value of the waste water A 2 that obtains after embodiment 2 solid-liquid separation is 34500 mg/litre; And the COD value of the waste water CA1 that obtains after Comparative Examples 1 solid-liquid separation is up to 50000 mg/litre, and after carrying out wastewater treatment under the identical condition, the COD value of the waste water D2 that embodiment 2 obtains is 89 mg/litre; And the COD value of the waste water CD1 that Comparative Examples 1 carries out obtaining after the wastewater treatment is still up to 350 mg/litre; Explain that method provided by the invention through reducing the chemical oxygen demand value of the waste water that obtains after the solid-liquid separation, can reduce pressure of wastewater treatment significantly, and the waste water after handling can satisfy environment requirement.
Embodiment
According to the present invention, adopt potato raw material to prepare the alcoholic acid method and comprise potato raw material is pulverized, with the product after pulverizing mix with enzyme, enzymolysis, obtain enzymolysis product; This enzymolysis product that ferments, separating alcohol from tunning, and the waste liquid of potato raw material alcohol prepared by fermenting carried out solid-liquid separation; Obtain filter cake and waste water, the waste water that obtains is carried out anaerobism+aerobic treatment, wherein; 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 once with the potato raw material of not pulverizing pulverize; It is the 30000-35000 mg/litre that solid-liquid separation makes the chemical oxygen demand value of the waste water that obtains.
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; 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 not will to the potato raw material of pulverizing mix 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.Dried cassava is meant that generally water cut is the cassava below the 15 weight %, and fresh cassava is meant that generally water cut is the above cassavas of 60 weight %.
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 be to going fragmentation to cause damage fully; 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, based on requirement (requiring the purity of ethanol 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, the method for said solid-liquid separation is had no particular limits, for example can be for said waste liquid is filtered and squeezing.
Contriver of the present invention has carried out careful research to the method that existing waste liquid from preparation of ethanol by fermentation of cassava carries out solid-liquid separation, finds to use usually in the prior art common pressure filter that the waste liquid of preparation of ethanol by fermentation of cassava 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 filter cake 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 improve the solid content that obtains filter cake, thereby cause the chemical oxygen demand value of the waste water after the solid-liquid separation higher, increase the pressure of subsequent wastewater treatment.
Among the present invention, filter and squeeze, reduced the COD value of the waste water that obtains after the solid-liquid separation significantly, reduced the pressure of subsequent wastewater treatment through waste liquid to preparation of ethanol by fermentation of cassava; Under the preferable case, said filtration and squeezing can realize that diaphragm filter press has the filtering function identical with the common diaphragm pressure filter through using diaphragm filter press; Also have filter cake is squeezed and makes its function of dewatering once more, in diaphragm filter press, common filter plate and membrane filter plate are spaced; 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 filter plate, but has increased pressing function; Promptly; Membranous elastic contribution after filtering end, extrusion medium is injected into the sealing ply from middle central layer hand-hole, owing to can carry out the blow-up squeezing to the filter cake after filtering; Improve the solid content of filter cake, thereby reduced the COD value of the waste water that obtains after the solid-liquid separation.
The quantity of common filter plate and 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 filter plate is 50-60; The quantity of membrane filter plate is 50-60, and common filter plate is spaced with membrane filter plate and the ratio of the quantity of common 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 COD value of the waste water that obtains after the solid-liquid separation 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.
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, said filtering condition has no particular limits, and under the preferable case, said filtering condition comprises that filtering pressure is 0.4-1MPa, and filter time is 2-8 hour; Further be preferably, said filtering condition comprises that filtering pressure is 0.5-0.8MPa, and filtration time is 4-6 hour.
According to the present invention, the condition of said squeezing has no particular limits, and under the preferable case, the condition of said squeezing comprises that the pressure of squeezing is 10-25MPa, and the time of squeezing is 0.2-2 hour; Further be preferably, the condition of said squeezing comprises that the pressure of squeezing is 15-20MPa, and the time of squeezing is 0.5-1 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.
According to the present invention, the method for said wastewater treatment is had no particular limits, for example, can carry out wastewater treatment through disclosed method among the CN1202032C.For example, the waste water that solid-liquid separation is obtained feeds anaerobic reactor and aerobic reactor, leaves standstill, with the supernatant oxidation and remove the suspended substance in the supernatant.
Among the present invention; Said anaerobic reactor is conventionally known to one of skill in the art; In the said anaerobic reactor anaerobic grain sludge is housed; Contain anaerobion in the said anaerobic grain sludge; The kind of this anaerobion is conventionally known to one of skill in the art, for example, and Bacteroides succinogenes (Bacteriodessuccinogenes), Butyrivibrio fibrisolvens (Butyribibrio fibrisolve), ruminococcus flavefaciens (Ruminococcus flavfaciens), Ruminococcus albus (Ruminococcus albus) etc.; When waste water passed through anaerobic reactor, the organism in the waste water was degraded; The kind of said anaerobic grain sludge is conventionally known to one of skill in the art, can be commercially available, for example the anaerobic grain sludge of Paques Environmental Technology's production.
The residence time of said waste water in anaerobic reactor can be selected according to the kind of waste water, and under the preferable case, the time of stop is 25-35 hour.
Reaction conditions in the said anaerobic reactor can in very large range change, and for example, the reaction conditions in the said anaerobic reactor comprises that volumetric loading is 20-25kgCOD/m
3.d, temperature is 30-40 ℃, and the pH value is 6.5-7.5.
Said aerobic reactor is conventionally known to one of skill in the art, for example, can waste water be fed A/O reactor drum (anoxic/Aerobic Pond) and carry out aerobic treatment; In the said A/O reactor drum aerobic particle mud is housed, when waste water is flowed through, organism in the aerobic flora water of decomposition; Be converted into the idiotrophic material; The kind of said aerobic particle mud is conventionally known to one of skill in the art, can be commercially available, for example the aerobic particle mud of the green source of Beijing Feng Ze Environmental Technology AS production.The residence time of said waste water in aerobic reactor can be selected according to the kind of waste water, and under the preferable case, the time of stop is 40-60 hour.
Reaction conditions in the said aerobic reactor can in very large range change, and for example, the reaction conditions in the said aerobic reactor comprises that volumetric loading is 0.1-0.2kgBOD/m
3.d, temperature is 20-40 ℃, and the pH value is 7-8, and dissolved oxygen is 1-3mg/l, and said dissolved oxygen is meant when waste water is carried out aeration, the content of oxygen in water.
According to the present invention, will leave standstill through the waste water of anaerobic reactor and aerobic reactor, with the supernatant oxidation and remove the suspended substance in the supernatant.
Said method with the supernatant oxidation is conventionally known to one of skill in the art; For example use oxygenant that supernatant is carried out oxidation; The kind of said oxygenant is conventionally known to one of skill in the art; For example can be in Youxiaolin, Losantin, iron trichloride and the Na2Fe04 one or more, the time of said oxide treatment is 0.5-1.5 hour.
According to the present invention; Can the suspended substance removal in the supernatant be fallen through various known methods, for example, can supernatant be fed air flotation pool and carry out the air supporting processing; The flocculation agent that said air flotation pool adopts is conventionally known to one of skill in the art; For example can be in aluminium based flocculating agent, iron-based flocculating agent and the composite flocculation agent one or more, above-mentioned flocculation agent can be commercially available, for example; Bodied ferric sulfate (PFS), poly-ferric chloride (PFC), polymeric biacid iron aluminium (PFSIC) and polymerized ferric-aluminum chloride (PFAS) that Huizhou 3R Environmental Chemical Co., Ltd. produces, the surfaceloadingrate of said air flotation pool is 36-72m
3/ m
2.h, the residence time of said supernatant in air flotation pool is 3-5 minute.
To do further specific descriptions to the present invention through specific 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 the disk after being cut into about 1 centimetre after these 95 kilograms of fresh cassava raw materials (water cut 65 weight %) cleaning; Use SFSP series beater disintegrating machine that cassava slice is pulverized then; The method of said pulverizing comprises once to be pulverized 60 kilograms of cassavas 20 minutes earlier; Obtain average particulate diameter and be 4.5 millimeters 60 kilograms of crushed products; 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; Obtaining average particulate diameter is a crushed products of 3 millimeters, and above-mentioned whole crushed products is carried out secondary pulverized 5 minutes, obtains 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 14.05 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 342 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=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 30 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 93.5 weight % through moisture determination instrument.Get 5 tons of these mixed waste liquors and join diaphragm filter press (Jingjin Filter Press Group Co.,Ltd, X
M AZG600/1500 * 2000U
B K) in filter, the quantity of common filter plate is 50 in the said diaphragm filter press, the quantity of membrane filter plate is 50, and common filter plate and membrane filter plate are spaced; Said filtering condition comprises that filtering pressure is 0.8MPa, and filter time is 2 hours, obtains filter cake; In membrane filter plate, charge into the extrusion medium air afterwards, the filter cake after filtering is squeezed, the pressure of said squeezing is 10MPa, and the time of squeezing is 2 hours, obtains the waste water A 1 after the solid-liquid separation.
Through the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate process detection waste water A 1, the result is as shown in table 2.
Waste water A 1 is stirred, form suspension-s; Get suspension-s 1000 grams then, left standstill 24 hours, remove supernatant solution, and take by weighing sedimentary weight, the content of impurity in the waste water A 1 that obtains obtaining after the solid-liquid separation, the result is as shown in table 2.
Waste Water Treatment through biomass energy ltd of Guangxi China Oil and Food Import and Export Corporation carries out wastewater treatment to the waste water A 1 that obtains, and this Waste Water Treatment mainly comprises preparatory acidification, anaerobic reactor, A/O system, settling tank, oxidizing reaction pond, air flotation pool and the sludge thickener in the preparatory acidulated pool.Said anaerobic reactor bottom is provided with the waste water water distributor, interior dress anaerobic grain sludge (Paques Environmental Technology's production); Bottom, said aeration tank is provided with aeration tube, and aerobic particle mud (the green source of Beijing Feng Ze Environmental Technology AS) is housed in the pond; Said oxidizing reaction pond adopts Youxiaolin to carry out oxidation; Said air flotation pool adopts Poly aluminum Chloride (PAC) (Huizhou 3R Environmental Chemical Co., Ltd.) and negatively charged ion PAM
-(SEPIGEL 305) decolours to waste water; Said sludge thickener plays the effect of thickened sludge.
The residence time of said waste water in anaerobic reactor is 25 hours, and the reaction conditions in the said anaerobic reactor comprises that volumetric loading is 21.5kgCOD/m
3.d, temperature is 35 ℃, and the pH value is 6.8, gets into the A/O system from the effusive waste water of anaerobic reactor and carries out aerobic treatment, and the residence time of said waste water in the A/O system is 50 hours, and the reaction conditions in the said A/O system comprises that volumetric loading is 0.1kgCOD/m
3.d, temperature is 20 ℃, and the pH value is 7, and dissolved oxygen is 1mg/l; Water after handle the aeration tank gets into the settling tank sedimentation, and supernatant gets into oxidizing reaction pond oxidation, and the time of said oxidation is 0.5 hour, gets into to discharge after air-flotation system is handled again, and the surfaceloadingrate of said air flotation pool is 40m
3/ m
2.h, said supernatant in air flotation pool, stop time be 3 minutes.
Waste water D1 after obtaining handling, through the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate process detection waste water D1, the result 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 is pulverized the fresh cassava raw material, obtains 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 crushed products starch-containing 26.5 kilograms altogether.According to the condition of embodiment 1 to sampling and testing after remaining crushed products carry out enzymolysis, enzymolysis product is fermented, obtain 13.91 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 embodiment 1 step (1), the glucose of measuring and calculating in the beer 395 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 30 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 93.5 weight % through moisture determination instrument.Get 5 tons of these mixed waste liquors and join diaphragm filter press (Jingjin Filter Press Group Co.,Ltd, X
M AZG600/1500 * 2000U
B K) in filter; The quantity of common filter plate in the said diaphragm filter press (Jingjin Filter Press Group Co.,Ltd, chamber filter plate) is 60, membrane filter plate (Jingjin Filter Press Group Co.,Ltd; 1250 types) quantity is 60, and common filter plate and membrane filter plate are spaced; Said filtering condition comprises that filtering pressure is 0.4MPa, and filter time is 8 hours, obtains filter cake; In membrane filter plate, charge into the extrusion medium air afterwards, the filter cake after filtering is squeezed, the pressure of said squeezing is 25MPa, and the time of squeezing is 0.2 hour, obtains the waste water A 2 after the solid-liquid separation.
Through the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate process detection waste water A 2, the result is as shown in table 2.
Waste water A 2 is stirred, form suspension-s; Get suspension-s 1000 grams then, left standstill 24 hours, remove supernatant solution, and take by weighing sedimentary weight, the content of impurity in the waste water A 2 that obtains obtaining after the solid-liquid separation, the result is as shown in table 1.
Waste Water Treatment through biomass energy ltd of Guangxi China Oil and Food Import and Export Corporation carries out wastewater treatment to the waste water A 2 that obtains, and this Waste Water Treatment mainly comprises preparatory acidification, anaerobic reactor, A/O system, settling tank, oxidizing reaction pond, air flotation pool and the sludge thickener in the preparatory acidulated pool.Said anaerobic reactor bottom is provided with the waste water water distributor, interior dress anaerobic grain sludge (Paques Environmental Technology's production); Bottom, said aeration tank is provided with aeration tube, and aerobic particle mud (the green source of Beijing Feng Ze Environmental Technology AS) is housed in the pond; Said oxidizing reaction pond adopts Youxiaolin to carry out oxidation; Said air flotation pool adopts Poly aluminum Chloride (PAC) (Huizhou 3R Environmental Chemical Co., Ltd.) and negatively charged ion PAM
-(SEPIGEL 305) decolours to waste water; Said sludge thickener plays the effect of thickened sludge.
The residence time of said waste water in anaerobic reactor is 35 hours, and the reaction conditions in the said anaerobic reactor comprises that volumetric loading is 21.5kgCOD/m
3.d, temperature is 38 ℃, and the pH of institute value is 7.2, gets into the A/O system from the effusive waste water of anaerobic reactor and carries out aerobic treatment, and the residence time of said waste water in the A/O system is 55 hours, and the reaction conditions in the said A/O system comprises that volumetric loading is 0.2kgCOD/m
3.d, temperature is 40 ℃, and the pH value is 8, and dissolved oxygen is 3mg/l; Water after handle the aeration tank gets into the settling tank sedimentation, and supernatant gets into oxidizing reaction pond oxidation, and the time of said oxidation is 1.5 hours, after air supporting is handled, discharges again, and the surfaceloadingrate of said air flotation pool is 65m
3/ m
2.h, the residence time of said supernatant in air flotation pool is 5 minutes.Waste water D2 after obtaining handling, through the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate process detection waste water D2, the result 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 2 prepares ethanol; Different is; Once pulverized 35 minutes 95 kilograms of fresh cassava raw materials (water cut 65 weight %) 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 6 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 13.51 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 530 restrains totally.And calculate alcohol yied and residual sugar rate according to the formula of embodiment 1, calculation result is seen table 1.
Filter according to the waste liquid of the method identical preparation of ethanol by fermentation of cassava with embodiment 2; Different is that membrane filter plate is replaced with common filter plate; Said filtering condition comprises that filtering pressure is 0.4MPa, and filter time is 8 hours, obtains reference waste water CA1.
Through the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate process detection reference waste water CA1, the result is as shown in table 2.
CA1 stirs with reference waste water, forms suspension-s; Get suspension-s 1000 grams then, left standstill 24 hours, remove supernatant solution, and take by weighing sedimentary weight, the content of impurity among the reference waste water CA1 that obtains obtaining after the solid-liquid separation, the result is as shown in table 2.
According to reference waste water CA1 being carried out wastewater treatment with embodiment 2 identical methods; Obtain the reference waste water CD1 after the wastewater treatment; Through the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate process detection reference waste water CD1, the result is as shown in table 2.
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 30 kilograms of fresh cassava raw materials (water cut 65 weight %) once to be pulverized 12 minutes; Obtain average particulate diameter and be 5.5 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 3 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 14.28 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 292 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 30 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 93.5 weight % through moisture determination instrument.Get 5 tons of these mixed waste liquors and join diaphragm filter press (Jingjin Filter Press Group Co.,Ltd, X
M AZG600/1500 * 2000U
B K) in filter, the quantity of common filter plate is 55 in the said diaphragm filter press, the quantity of membrane filter plate is 55, and common filter plate and membrane filter plate are spaced; Said filtering condition comprises that filtering pressure is 0.5MPa, and filter time is 6 hours, obtains filter cake; In membrane filter plate, charge into the extrusion medium air afterwards, the filter cake after filtering is squeezed, the pressure of said squeezing is 20MPa, and the time of squeezing is 0.5 hour, obtains waste water A 3.
Through the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate process detection waste water A 3, the result is as shown in table 2.
Waste water A 3 is stirred, form suspension-s; Get suspension-s 1000 grams then, left standstill 24 hours, remove supernatant solution, and take by weighing sedimentary weight, the content of impurity in the waste water A 3 that obtains obtaining after the solid-liquid separation, the result is as shown in table 2.
Waste Water Treatment through biomass energy ltd of Guangxi China Oil and Food Import and Export Corporation carries out wastewater treatment to the waste water A 3 that obtains, and this Waste Water Treatment mainly comprises preparatory acidification, anaerobic reactor, A/O system, settling tank, oxidizing reaction pond, air flotation pool and the sludge thickener in the preparatory acidulated pool.Said anaerobic reactor bottom is provided with the waste water water distributor, interior dress anaerobic grain sludge (Paques Environmental Technology's production); Bottom, said aeration tank is provided with aeration tube, and aerobic particle mud (the green source of Beijing Feng Ze Environmental Technology AS) is housed in the pond; Said oxidizing reaction pond adopts Youxiaolin to carry out oxidation; Said air flotation pool adopts Poly aluminum Chloride (PAC) (Huizhou 3R Environmental Chemical Co., Ltd.) and negatively charged ion PAM
-(SEPIGEL 305) decolours to waste water; Said sludge thickener plays the effect of thickened sludge.
The residence time of said waste water in anaerobic reactor is 30 hours, and the reaction conditions in the said anaerobic reactor comprises that volumetric loading is 21.5kgCOD/m
3.d, temperature is 36 ℃, and the pH value is 7.0, gets into the A/O system from the effusive waste water of anaerobic reactor and carries out aerobic treatment, and the residence time of said waste water in the A/O system is 45 hours, and the reaction conditions in the said A/O system comprises that volumetric loading is 0.12kgCOD/m
3.d, temperature is 30 ℃, and the pH value is 7.5, and dissolved oxygen is 2mg/l; Water after handle the aeration tank gets into the settling tank sedimentation, and supernatant gets into oxidizing reaction pond oxidation, and the time of said oxidation is 1 hour, after air supporting is handled, discharges again, and the surfaceloadingrate of said air flotation pool is 50m
3/ m
2.h, the residence time of supernatant in air flotation pool is 5 minutes.Waste water D3 after obtaining handling, through the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate process detection waste water D3, the result is as shown in table 2.
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 (water cut 65 weight %) and 40 kilograms of dried cassava slices (water cut is 13 weight %) are pulverized with 166 kilograms of mixtures that obtain after 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; The average particulate diameter that obtains cassava is 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; The average particulate diameter that obtains cassava is 4 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 3 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 1.8 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 23.48 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 566 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 30 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 93.5 weight % through moisture determination instrument.Get 5 tons of these mixed waste liquors and join diaphragm filter press (Jingjin Filter Press Group Co.,Ltd, X
M AZG600/1500 * 2000U
B K) in filter, the quantity of common filter plate is 55 in the said diaphragm filter press, the quantity of membrane filter plate is 55, and common filter plate and membrane filter plate are spaced; Said filtering condition comprises that filtering pressure is 0.5MPa, and filter time is 6 hours, obtains filter cake; In membrane filter plate, charge into the extrusion medium air afterwards, the filter cake after filtering is squeezed, the pressure of said squeezing is 20MPa, and the time of squeezing is 0.5 hour, obtains waste water A 4.
Through the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate process detection waste water A 4, the result is as shown in table 2.
Waste water A 4 is stirred, form suspension-s; Get suspension-s 1000 grams then, left standstill 24 hours, remove supernatant solution, and take by weighing sedimentary weight, the content of impurity in the waste water A 4 that obtains obtaining after the solid-liquid separation, the result is as shown in table 2.
Waste Water Treatment through biomass energy ltd of Guangxi China Oil and Food Import and Export Corporation carries out wastewater treatment to the waste water A 4 that obtains, and this Waste Water Treatment mainly comprises preparatory acidification, anaerobic reactor, A/O system, settling tank, oxidizing reaction pond, air flotation pool and the sludge thickener in the preparatory acidulated pool.Said anaerobic reactor bottom is provided with the waste water water distributor, interior dress anaerobic grain sludge (Paques Environmental Technology's production); Bottom, said aeration tank is provided with aeration tube, and aerobic particle mud (the green source of Beijing Feng Ze Environmental Technology AS) is housed in the pond; Said oxidizing reaction pond adopts Youxiaolin to carry out oxidation; Said air flotation pool adopts Poly aluminum Chloride (PAC) (Huizhou 3R Environmental Chemical Co., Ltd.) and negatively charged ion PAM
-(SEPIGEL 305) decolours to waste water; Said sludge thickener plays the effect of thickened sludge.
The residence time of said waste water in anaerobic reactor is 28 hours, and the reaction conditions in the said anaerobic reactor comprises that volumetric loading is 22kgCOD/m
3.d, temperature is 37 ℃, and the pH value is 7.0, gets into the A/O system from the effusive waste water of anaerobic reactor and carries out aerobic treatment, and the residence time of said waste water in the A/O system is 45 hours, and the reaction conditions in the said A/O system comprises that volumetric loading is 0.12kgCOD/m
3.d, temperature is 35 ℃, and the pH value is 7.5, and dissolved oxygen is 2.5mg/l; Water after handle the aeration tank gets into the settling tank sedimentation, and supernatant gets into oxidizing reaction pond oxidation, and the time of said oxidation is 1 hour, after air supporting is handled, discharges again, and the surfaceloadingrate of said air flotation pool is 50m
3/ m
2.h, the residence time of supernatant in air flotation pool is 4 minutes.Waste water D4 after obtaining handling, through the COD value of standard GB 11914-89 water quality-COD determination-potassium dichromate process detection waste water D4, the result is as shown in table 2.
Table 1
| Embodiment or Comparative Examples | Embodiment 1 | Embodiment 2 | Comparative Examples 1 | Embodiment 3 | Embodiment 4 |
| Alcohol yied (%) | 52.8 | 52.5 | 51.0 | 53.3 | 53.8 |
| Residual sugar rate (%) | 1.3 | 1.5 | 2.0 | 1.1 | 1.3 |
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 high, and crushing effect is high; 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 the alcoholic acid starch ethanol yield that obtains 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
Can find out from last table 2; The COD value of the waste water A 2 that obtains after embodiment 2 solid-liquid separation is 34500 mg/litre; And the COD value of the waste water CA1 that obtains after Comparative Examples 1 solid-liquid separation is up to 50000 mg/litre, and after carrying out wastewater treatment under the identical condition, the COD value of the waste water D2 that embodiment 2 obtains is 89 mg/litre; And the COD value of the waste water CD1 that Comparative Examples 1 carries out obtaining after the wastewater treatment is still up to 350 mg/litre; Explain that method provided by the invention through reducing the chemical oxygen demand value of the waste water that obtains after the solid-liquid separation, can reduce pressure of wastewater treatment significantly, and the waste water after handling can satisfy environment requirement.
Claims (12)
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 that ferments, separating alcohol from tunning, and the waste liquid of potato raw material alcohol prepared by fermenting carried out solid-liquid separation; Obtain filter cake and waste water, the waste water that obtains is carried out wastewater treatment, it is characterized in that; 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 once more with the potato raw material of not pulverizing 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; In the crushed products, the average particulate diameter of potato raw material is the 2.5-10 millimeter; In the secondary crushed products, the average particulate diameter of potato raw material be 1.6 millimeters to less than 2.5 millimeters; It is the 30000-35000 mg/litre that solid-liquid separation makes the chemical oxygen demand value of the waste water that obtains.
2. 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.
3. method according to claim 1, wherein, the method for said solid-liquid separation is that said waste liquid is filtered and squeezing.
4. method according to claim 3, wherein, said filtration and squeezing are carried out in diaphragm filter press.
5. method according to claim 4, wherein, said filtering condition comprises that filtering pressure is 0.4-1MPa, filter time is 2-8 hour.
6. method according to claim 5, wherein, said filtering condition comprises that filtering pressure is 0.5-0.8MPa, filtration time is 4-6 hour.
7. method according to claim 4, wherein, the condition of said squeezing comprises that the pressure of squeezing is 10-25MPa, the time of squeezing is 0.2-2 hour.
8. method according to claim 7, wherein, the condition of said squeezing comprises that the pressure of squeezing is 15-20MPa, the time of squeezing is 0.5-1 hour.
9. method according to claim 1, wherein, said potato raw material is the mixture of fresh cassava and dried cassava, the weight ratio of said dried cassava and fresh cassava is 1: 1.5-2.5.
10. method according to claim 1, wherein, the enzyme that said enzymolysis uses is glycase, 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.
11. method according to claim 10, wherein, said glycase is one or more in AMS, beta-amylase, saccharifying enzyme and the isoamylase.
12. 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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| CN101041849A (en) * | 2007-04-26 | 2007-09-26 | 湖南南方马铃薯产业化工程技术有限公司 | Method for producing fuel ethanol by using potato as raw material |
| CN101165189A (en) * | 2007-10-15 | 2008-04-23 | 四川循环科技有限公司 | Meso one-step method ethanol production method for potato raw starch |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101041849A (en) * | 2007-04-26 | 2007-09-26 | 湖南南方马铃薯产业化工程技术有限公司 | Method for producing fuel ethanol by using potato as raw material |
| CN101165189A (en) * | 2007-10-15 | 2008-04-23 | 四川循环科技有限公司 | Meso one-step method ethanol production method for potato raw starch |
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| Title |
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| 陈云芬.薯类作物：绿色能源开发新亮点.《云南日报》.2006, * |
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