CN101676396B - Method for preparing alcohol by utilizing potato materials - Google Patents

Method for preparing alcohol by utilizing potato materials Download PDF

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Publication number
CN101676396B
CN101676396B CN2008102228229A CN200810222822A CN101676396B CN 101676396 B CN101676396 B CN 101676396B CN 2008102228229 A CN2008102228229 A CN 2008102228229A CN 200810222822 A CN200810222822 A CN 200810222822A CN 101676396 B CN101676396 B CN 101676396B
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raw material
weight
crushed products
water soluble
cylinder
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CN101676396A (en
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黄加军
姜勇
柳树海
贾成国
王利
于天杨
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Cofco Corp
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Cofco Corp
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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
    • 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
    • Y02P60/80—Food processing, e.g. use of renewable energies or variable speed drives in handling, conveying or stacking
    • Y02P60/87—Re-use of by-products of food processing for fodder production

Abstract

The invention provides a method for preparing alcohol by utilizing potato materials. The productivity of the starch-alcohol of the alcohol obtained by the method is obviously higher than that of the starch-alcohol of the alcohol obtained by the current methods, and compared with the prior art, the residual sugar rate in the method of the invention is greatly reduced. In addition, the method provided by 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, thus overcoming the bottleneck that the device used for preparing the alcohol by fermenting cassava has relatively low operation load and increasing the production capacity of the device.

Description

A kind of method that adopts potato raw material to prepare ethanol
Technical field
The invention relates to the preparation method of ethanol, more specifically about adopting potato raw material to prepare the method for ethanol.
Background technology
The potato class, such as Ipomoea batatas, potato, cassava etc., therefore rich in starch is widely used in the fields such as fermentation sugaring, starch processed.
Cassava is that Perenniporia martius is perennial, the annual potato in temperate zone belongs to shrub, originates in South America, and suiting in medial temperature is 25-29 ℃, the growth of the low latitudes of average annual precipitation 1000-1500 millimeter.Before 1820, cassava is passed to southern china greatly, mainly in Guangdong, the plantation of Guangxi and Hainan, expand gradually now the provinces such as Yunnan, Fujian, Guizhou to.Cassava is divided into two classes: bitter manioc (poisonous cassava) and sweet taste cassava (nontoxic cassava).The main chemical compositions of fresh tapioca root is water, secondly is carbohydrate, also has less protein, fat and the pectin of some content.The fresh cassava starch content reaches the 25-30 % by weight, and dried tapioca (flour) content is about 70 % by weight.
Because the piece root of cassava is larger, before adopting cassava raw material enzymolysis, alcohol prepared by fermenting, usually need to pulverize the cassava raw material, 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, need to make the disintegration of cassava tissue more abundant, more tiny, make the separation of starch granules more thorough.The employing cassava of prior art prepares in the method for ethanol, and the breaking method of described cassava generally includes cassava is obtained crushed products with pulverizing after water mixes.Adopt existing breaking method to consume the amount of water larger, in the crushed products that guarantees to obtain to the granularity requirements of cassava particle, the energy that adopts existing breaking method to consume is larger, the utilization ratio of equipment is low.
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 processing 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 the method easily causes secondary pollution after burning; 2, with the waste liquid ferment preparation of sludge gas of potato raw material alcohol prepared by fermenting, the shortcoming of the method is that investment is large and the control techniques requirement is high.
Therefore, the method that usually adopts the solid residue in the waste liquid that reclaims preparation of ethanol by fermentation of cassava to dispose waste liquid as feed at present, the method comprises carries out solid-liquid separation with waste liquid, obtains solid product; Afterwards solid product is dried.The method is a kind of less investment, the easy treatment process of operation and the waste liquid of environment amenable preparation of ethanol by fermentation of cassava.In this case, the processing power of solid-liquid separation just becomes the key factor that determines the liquid waste disposal capacity of water.
The problem that the method for at present waste liquid of preparation of ethanol by fermentation of cassava being processed 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 the method for pulverizing potato raw material in the method that existing employing potato raw material prepares ethanol, to consume the amount of water larger, the energy that consumes is larger, the defective that the utilization ratio of equipment is low and overcome the shortcoming that there is the excessive cycle of solid-liquid separation in the existing method that reclaims solid residue from the waste liquid of potato raw material alcohol prepared by fermenting, provide a kind of amount of the consumption water of pulverizing potato raw material less, the energy that consumes is less, and the utilization ratio of the equipment cycle high and solid-liquid separation, shorter employing potato raw material prepared the method for ethanol.
The present inventor finds, the employing potato raw material of prior art prepares in the method for alcohol fuel for the method for pulverizing potato raw material, no matter potato raw material is fresh cassava or dried cassava, pulverize after all needing before pulverizing, the cassava raw material to be mixed (fresh weight of cassava raw material and the weight ratio of water are generally 1:1) with water, the amount that consumes water in the crushing process is larger, 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 separating twice, that is, with potato raw material with once pulverize first after water mixes, a crushed products that obtains is carried out separating twice again, and obtains final crushed products.The size of potato raw material particle is inhomogeneous in the crushed products that adopts existing separating twice method pulverizing to obtain, and grain graininess is larger; If in the crushed products that guarantees to obtain the granularity of cassava particle can reach certain requirement, then adopt the grinding time of existing breaking method to prolong, thereby the energy that consumes is larger, the utilization ratio of equipment is low.
The invention provides a kind of method that adopts potato raw material to prepare ethanol, the method comprises: with potato raw material peeling, the potato raw material after the peeling is pulverized, 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, wherein, the method of described pulverizing comprises that the potato raw material after will removing the peel first once pulverizes, and obtains crushed products one time, and crushed products of part is carried out separating twice, obtain the separating twice product, then the potato raw material of not pulverizing after crushed products of remainder and the peeling is mixed once pulverize; Before being carried out solid-liquid separation, waste liquid in waste liquid, adds water soluble algae acid esters and/or water soluble algae hydrochlorate.
Employing potato raw material provided by the invention prepares in the method for ethanol, the method that potato raw material after the peeling is pulverized is the method for separating twice, unlike the prior art be, before pulverizing potato raw material, do not need potato raw material is mixed with water, perhaps only add a small amount of water, crushed products of part after then will once pulverizing is returned and again not mixing through the potato raw material of pulverizing through peeling, and then once pulverize, the farinaceous size that crushed products of this part of returning is the potato raw material particle, this part crushed products namely can play the effect of dilution, again can be with again not pulverized through the potato raw material of pulverizing through peeling.The amount that method of the present invention not only consumes water is few, the energy that consumes is less, the utilization ratio of equipment is high, crush efficiency is high, adopt simultaneously the particle diameter of potato raw material particle in the crushed products that obtains after the method for separating twice of the present invention can be good at controlling pulverizing, make the particle diameter of the potato raw material particle that finally obtains little and even, also solved simultaneously the storage problem of crushed products.In addition, the present inventor finds unexpectedly, the starch ethanol productive rate that the method that adopts potato raw material of the present invention to prepare ethanol obtains is significantly improved, infer that reason may be because breaking method of the present invention can be good at controlling the particle diameter of potato raw material particle in the crushed products that obtains after the pulverizing, make the particle diameter of the potato raw material particle 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, greatly improve the utilization ratio of starch, thereby greatly improved the starch ethanol productive rate.For example, in the situation that other condition is all identical, the starch ethanol productive rate that the method for employing embodiment 2 obtains reaches 52.5%, the residual sugar rate is 1.5%, and the starch ethanol productive rate that the method that adopts Comparative Examples 1 obtains only is 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%.
Among the present invention, by 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 significantly the time of solid-liquid separation, in the situation that need not to increase the treatment capacity that new installation has improved liquid waste in unit time significantly, thereby the bottleneck that the operating load that has solved the device that causes preparation of ethanol by fermentation of cassava is lower has improved the throughput of the device of preparation of ethanol by fermentation of cassava.
Description of drawings
Fig. 1 is the front view of the employed potato class of barking method of the present invention peeling equipment;
Fig. 2 is the vertical profile schematic diagram of the employed potato class of barking method of the present invention peeling equipment;
Fig. 3 is the cross-sectional schematic diagram of the annexation of expression sprocket wheel and cylinder.
Embodiment
According to the present invention, the method that adopts potato raw material to prepare ethanol comprises: with the potato raw material peeling, the potato raw material after the peeling is pulverized, 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, wherein, the method of described pulverizing comprises that the potato raw material after will removing the peel first once pulverizes, and obtains crushed products one time, and crushed products of part is carried out separating twice, obtain the separating twice product, then the potato raw material of not pulverizing after crushed products of remainder and the peeling is mixed once pulverize; Before being carried out solid-liquid separation, waste liquid in waste liquid, adds water soluble algae acid esters and/or water soluble algae hydrochlorate.
According to the present invention, the 5-20 % by weight that a crushed products of described remainder is whole crushed products weight; The 5-20 % by weight of the gross weight of the potato raw material of not pulverizing after crushed products that a crushed products of remainder accounts for remainder and the peeling.Under the preferable case, the 5-10 % by weight that a crushed products of described remainder is whole crushed products weight; The 5-10 % by weight of the gross weight of the potato raw material of not pulverizing after crushed products that a crushed products of remainder accounts for remainder and the peeling.Pulverize according to method of the present invention that the granularity of potato raw material particle in the final crushed products that obtains is 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 less, as be preferably 1.6 to less than 1.8 millimeters.
According to method provided by the invention, before the potato raw material after will removing the peel is once pulverized, need not potato raw material is mixed with water, perhaps only add a small amount of water, for example, the consumption of described 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 again not mixing through the potato raw material of pulverizing through peeling, then once pulverize, the farinaceous size that crushed products of this part of returning is the potato raw material particle, 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 again with fresh cassava raw material again, the amount that not only consumes water is few, the energy that consumes is less, the utilization ratio of equipment is high, crushing effect is high, and the method for separating twice of the present invention can be good at controlling the particle diameter of potato raw material particle in the crushed products that obtains after the pulverizing, and makes the particle diameter of the potato raw material particle that finally obtains little and even.According to the present invention, for the diameter that makes potato raw material particle in the crushed products that finally obtains 1.8 to less than 2.5 millimeters, be preferably 1.6 to less than 1.8 millimeters, after potato raw material is once pulverized, the average particulate diameter of potato raw material is preferably the 2.5-5 millimeter generally at the 2.5-10 millimeter in the crushed products that obtains.
According to a specific embodiment of the present invention, when described feeding manner is continuously feeding, part taking-up in the crushed products after crushed products of remainder can being mixed with the potato raw material of not pulverizing after the peeling and once pulverize, continue with peeling after do not mix through the potato raw material of pulverizing and once pulverize, and according to such method circulate, continuous pulverizing.
According to another embodiment of the present invention, when described feeding manner is intermittent feeding, can with after crushed products of remainder and the peeling mix will for the potato raw material of pulverizing and once pulverize after a crushed products obtaining directly carry out separating twice and obtain the separating twice product, also can carry out separating twice after the crushed products mixing that obtains of this crushed products after first pulverizing.
Can use conventional various disintegrating apparatus, for example SFSP series beater disintegrating machine.
Described potato raw material can be various potato raw materials, and such as Ipomoea batatas, potato, cassava etc., the potato raw material that adopts in the specific embodiments of the present invention is cassava.Described potato raw material can be fresh cassava or dried cassava, if adopt dried cassava, usually need to before once pulverizing dried cassava be mixed with water, and can determine according to amount of water described in the preceding method of the present invention the consumption of water; Also can be the mixture of fresh cassava and dried cassava.The weight of described dried cassava and fresh cassava is not particularly limited, and generally, the weight ratio of described dried cassava and fresh cassava is 1:1.5-2.5, is preferably 1:1.5-2.
Ripe the general thick 4-8 of cassava centimetre, long 20-30 centimetre, potato shape tubbiness is the short cylindrical shape, and cassava mechanism from inside to outside is potato meat, and entocuticle and exterior skin, exterior skin are Vandyke brown, an adularescent circular fringes, and endothelium and meat are white.Also contain one deck thin skin in the exterior skin of cassava raw material, namely entocuticle contains prussiate and a kind of cyanogen two---phaseolunatin that can cause food poisoning in this entocuticle.Phaseolunatin is hydrolyzed rear generation prussic acid.Prussic acid and prussiate have severe toxicity, and it is very fast to poison.They can enter human body by number of ways, as skin absorb, wound is invaded, respiratory tract sucks, eats by mistake etc., enter human body after, can make the central nervous system paralysis, make oxyphorase poisoning in respiratory enzyme and the blood, cause expiratory dyspnea, systemic cell can make body dead because of anoxia asphyxia.Therefore, usually before the cassava raw material is pulverized, need to remove first the entocuticle of fresh cassava raw material.
The method of removing the fresh cassava raw material entocuticle has a lot, usually adopts artificial method of removing the peel to remove exterior skin and the entocuticle of fresh cassava raw material in the prior art, removes simultaneously the silt on raw material surface.If do not remove this layer internal surface or remove thoroughly can not cause the residual larger of prussiate in the cassava raw material, in enzymolysis and fermenting process, the more meeting of cyanide content makes enzyme deactivation, yeast is poisoned, so that yeast is dead; And cause fermentation residual sugar amount to raise, and ripe raw spirit degree descends, and namely alcohol yied reduces, and production efficiency is low, and labor strength is large.
Therefore, according to the present invention, the method also preferably includes uses a potato seed class peeling equipment that fresh cassava raw material is removed the peel.As depicted in figs. 1 and 2, this peeling equipment comprises support 1, cylinder 2, spiral feeder 3 and drive unit (not shown), cylinder 2 rotationally, be mounted obliquely within on the support 1, cylinder 2 has opening for feed 4 and discharge port 5, described screwfeed device 3 is arranged in cylinder 2 and is fixedly connected with the inwall of cylinder, and described drive unit is used for head roll 2 and screwfeed device 3 rotates together.The method of potato raw material (that is, fresh cassava raw material) peeling is comprised that potato raw material puts in the described cylinder 2 by described opening for feed 4, utilize described drive unit head roll 2 and screwfeed device 3 to rotate together.The velocity of rotation of head roll 2 and screwfeed device 3 can be 2-50 rev/min, is preferably 5-25 rev/min.Under the pushing effect of screwfeed device 3, potato raw material constantly moves forward; Potato raw material is along with cylinder 2 and screwfeed device 3 rotate simultaneously, in rotation process, rub between the potato raw material, also rub between potato raw material and cylinder wall and the screwfeed device, thereby the epidermis of potato class is got rid of, and the potato class after the peeling is discharged from discharge port 5.
Described cylinder 2 can be made by various anti-abrasive materials, for example, and steel, rubber or rigid plastics.Can also be provided with spray equipment in the described cylinder 2, spray equipment can be fixedly mounted on the inwall of cylinder, and is positioned at the position near the opening for feed of cylinder.Described spray equipment can be the various spray equipments of routine.According to the present invention, the method can also be included in the peeling process water sprayed on the potato raw material by spray equipment the dirt on the potato raw material (such as earth, impurity etc.) is got rid of.Described injection flow rate is not particularly limited, as long as guarantee the dirt on the potato raw material is removed.
Under the preferable case, as shown in Figure 1, described cylinder 2 comprises first paragraph cylinder 2a and second segment cylinder 2b from the entrance end to the exit end, and first paragraph cylinder 2a and second segment cylinder 2b are communicated with, and are provided with spray equipment among the second segment cylinder 2b.Spray equipment can be fixedly mounted on the inwall of second segment cylinder 2b, and is positioned at the position near the opening for feed of second segment cylinder.
According to method of the present invention, in order to reach better decortication effect, also has friction structure on the inwall of described cylinder 2.Described friction structure can for various shaggy structures, be preferably one or more Ribbed Bar, more preferably the multi-ribbon rib reinforcement.Ribbed Bar has cross rib, can use hot rolled ribbed steel bar and the cold rolled reinforcing steel bar with ribs of conventional all size, as meets the Ribbed Bar of GB1499-1998 regulation.The nominal diameter of Ribbed Bar can be the 6-25 millimeter, is preferably the 8-20 millimeter; The cross rib spacing can be the 3-16 millimeter, is preferably the 4-12 millimeter.The trade mark of Ribbed Bar includes but not limited to HRB335, HRB400 and HRB500.Described Ribbed Bar is fixedly connected with the inwall of cylinder 2, and in the cylinder rotation process, Ribbed Bar can play rubbing effect to potato raw material.Be fixedly connected with Ribbed Bar for the ease of the inwall at cylinder 2, Ribbed Bar is preferably parallel with the central axis of cylinder 2.
Described cylinder 2 can flatly or be mounted obliquely within on the support 1.When described cylinder was flatly installed, potato raw material moved forward under the pushing effect of screwfeed device 3, finally discharged from the discharge port of cylinder.When described drum-inclined ground was installed, the position of opening for feed was higher than discharge port, and potato raw material can also move down by the action of gravity of self (namely moving forward).The angle of inclination of cylinder 2 can be the 0-15 degree, is preferably the 5-10 degree; The length of cylinder 2 can be 2-10 rice, is preferably 3.5-7 rice.When cylinder comprised described first paragraph cylinder and second segment cylinder, length herein referred to the length sum of first paragraph cylinder and second segment cylinder.Described angle of inclination refers to central shaft and the horizontal angle of cylinder.There is no particular limitation to the interior diameter of cylinder, can remove the peel as required the amount of the potato raw material of processing and select suitable cylinder interior diameter, and generally speaking, the cylinder interior diameter can be 1-2 rice.
Described screwfeed device 3 can be the various screwfeed devices of mechanical field routine.Described screwfeed device 3 can be fixedly connected with on the inwall that mode is connected to cylinder 2 by routine various, and for example, as shown in Figure 2, screwfeed device 3 is fixedly connected on the inwall of cylinder 2 by fastening piece 8.In order to reach better decortication effect, the pitch of described screwfeed device 3 is preferably 0.3-0.8 rice, and thread depth is preferably 0.1-0.4 rice.The screwfeed device can be made by various anti-abrasive materials, for example, and steel, rubber, nylon.
The present invention is not particularly limited described drive unit, as long as energy head roll 2 and screwfeed device 3 rotate together.For example, described drive unit can comprise drive source, transmission chain and sprocket 6.As shown in Figure 3, sprocket wheel 6 is fixed on the cylinder 2.When cylinder 2 comprises first paragraph cylinder 2a and second segment cylinder 2b, preferably sprocket wheel 6 is installed between first paragraph cylinder 2a and the second segment cylinder 2b.Because cylinder 2 is installed in rotation on the support 1, so transmission chain is with the transmission of power of drive source during to sprocket wheel, and sprocket wheel can drive cylinder and rotate.Rotating mounting means can be the whole bag of tricks of routine, for example, can use supporting roll or bracing frame that roller shelves is located on the support, and cylinder can be rotated around central shaft.Drive source can be for the various devices that can produce power, such as electric motor.
For the ease of charging, this peeling equipment can also comprise windmill feeder 7.Shown in Fig. 1 or 2, windmill feeder 7 is installed on the opening for feed 4 of cylinder.Windmill feeder 7 can be the various windmill feeders of mechanical field routine.
To adopt potato class peeling equipment of the present invention be between the potato raw material that utilizes in cylinder and the effect of the frictional force between potato raw material and the barrel and potato raw material is removed the peel.According to the preferred barking method of the present invention the cassava raw material is removed the peel, the clearance of prussiate can reach more than 75%, and loss rate of raw materials can remain on below 5 % by weight, thereby is conducive to further improve the productive rate of ethanol.
Owing to may contain earth, sandstone impurity and iron contamination in the potato raw material, can cause damage to peeling equipment, therefore, according to method of the present invention, before can also comprising peeling potato raw material is carried out pretreated routine operation, described pretreated step generally comprises the step of removing impurity and cleaning.As, after fresh cassava is gathered, remove earth, root, palpus and the impurity such as wooden part and sandstone on the cassava.And cassava cleaned, the method and apparatus of described cleaning is conventionally known to one of skill in the art, here repeats no more.
Described enzymolysis step can be finished by this area method commonly used, such as adding microbes producing cellulase and/or enzyme in crushed products, is incubated under the growth temperature of microbes producing cellulase and/or the great-hearted temperature of enzyme and finishes.Described microbes producing cellulase be can secreting amylase microbes producing cellulase.Described enzyme comprises amylase.
Because microorganism growth can produce by product, therefore preferably directly add enzyme.The consumption of described enzyme is The more the better, for cost consideration, the dry weight basis of the product after preferably pulverizing with every gram, described diastatic consumption is the 4-50 enzyme activity unit, the dry weight basis of the product after more preferably pulverizing with every gram, described diastatic consumption is the 10-30 enzyme activity unit.
The enzyme activity unit of enzyme of the present invention is defined as: 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 described enzymolysis can be diastatic any optimum temperature, is generally 50-90 ℃, more preferably 60-70 ℃.The longer the better on the time theory of described enzymolysis, considers plant factor, and the time of preferred described enzymolysis is 20-240 minute, more preferably 30-120 minute.The pH value of described enzymolysis can be generally 3-7 for diastatic the suitableeest 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 described enzymolysis can be regulated before adding enzyme according to this area method commonly used, for example first crushed products and water or substratum (are enzyme-addedly generally mixed with water, add microbes producing cellulase generally with the substratum of this microorganism) mix, in addition, in order to guarantee to distill the concentration of the ethanol that obtains, the solid content that generally makes the gained mixture is the 20-40 % by weight, pH value according to the gained mixture, the mixture pH regulator that to treat enzymolysis with sulphuric acid soln or sodium hydroxide more preferably is adjusted to the pH value and is 5-6 to 3-7.
Amylase is the general name of class of enzymes that can the starch-splitting glycosidic link, and described amylase generally comprises α-amylase, beta-amylase, saccharifying enzyme and isoamylase.Enzyme of the present invention comprises amylase.
α-amylase claims again starch Isosorbide-5-Nitrae-dextrinase, and it can cut the α-Isosorbide-5-Nitrae of starch chain inside-glycosidic link at random, brokenly, and Starch Hydrolysis is maltose, contains the oligosaccharides of 6 glucose units and with the oligosaccharides of side chain.The microorganism that produces this enzyme mainly has Bacillus subtilus, aspergillus niger, aspergillus oryzae and head mold.
Beta-amylase claims again starch Isosorbide-5-Nitrae-maltoside enzyme, can cut Isosorbide-5-Nitrae-glycosidic link from the starch molecule non reducing end, generates maltose.The product that this enzyme acts on starch is maltose and limit dextrin.This enzyme is mainly produced by aspergillus, head mold and endomyces.
Saccharifying enzyme claims again starch α-Isosorbide-5-Nitrae-glucuroide, and this enzyme acts on the non reducing end of starch molecule, take glucose as unit, acts on successively α-Isosorbide-5-Nitrae in the starch molecule-glycosidic link, generates glucose.This enzyme acts on that product behind the amylopectin has glucose and with α-1, the oligosaccharides of 6-glycosidic link; The product that acts on after the amylose starch almost all is glucose.It mainly is aspergillus niger (left U.S. aspergillus, Aspergillus awamori), head mold (snow-white enzyme, De Shi head mold), endomycopsi.sp, monascus that this enzyme produces bacterium.
Isoamylase claims again starch α-1, and 6-glucuroide, branching enzyme, this enzyme act on the α-1 at amylopectin molecule branching-point place, and the 6-glycosidic link downcuts the whole side chain of amylopectin and becomes amylose starch.It mainly is to dislike the bacteriums such as gas bacillus, genus bacillus and some Pseudomonas that this enzyme produces bacterium.
The enzyme that preferred described enzymolysis uses also comprises phosphoesterase.Because the phosphoric acid dextrin that phosphoesterase can make phosphoric acid and alcoholic hydroxyl be combined into ester is hydrolyzed into 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 microorganism of monose such as glucose and/or fructose, oligosaccharides such as sucrose and/or semi-lactosi of can fermenting may be used to fermenting process of the present invention, because yeast saccharomyces cerevisiae is the microorganism of the zymohexose that ethanol-tolerant, by product are few, alcohol yied is high generally used on the wine industry, therefore the employed yeast of preferred described fermentation is yeast saccharomyces cerevisiae.
In every gram enzymolysis product, the inoculum size of the employed yeast of described fermentation is 10 3-10 8Colony-forming unit, more preferably 10 4-10 6Colony-forming unit.
Described colony-forming unit is defined as the method for a certain amount of bacterium liquid after the dilution by cast or coating, allows unicellular being dispersed in one by one on the culture medium flat plate of microorganism in it, and after cultivating, 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).The colony-forming unit of described yeast can be measured by means commonly known in the art, such as the methylene blue staining viable bacteria counting method.The concrete grammar of methylene blue staining viable bacteria counting method is as follows:
1 gram dried yeast powder is dissolved in 10 ml sterile waters, or 1 milliliter of actication of culture liquid is diluted to 10 milliliters with sterilized water, add 0.5 milliliter of 0.1 % by weight methylene blue, 35 ℃ of lower insulations 30 minutes.Under 10 times of opticmicroscopes, with the number (dead bacterium dyeing, viable bacteria is not dyeed) of viable bacteria in the solution after the blood counting chamber counting insulation, 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.
Described yeast can adopt conventional method inoculation, for example adds the seed liquor of 5-15 volume % in the enzymolysis product.Described seed liquor can be the aqueous solution or the culture medium solution of dry yeast, also can or be purchased the activated seed liquid of bacterial classification for dry yeast.
The temperature of described fermentation can be any temperature that is suitable for yeast growth, is preferably 30-36 ℃, more preferably 30-33 ℃.The pH value is 4-6, is preferably 4-4.5.The time of described fermentation can be for beginning from inoculation to occur to the decline phase of yeast growth the time of (being that fermentation time is that lag phase, logarithmic phase add stationary phase), and the time of preferred fermentation is 50-75 hour, more preferably 60-70 hour.Tunning ethanol can be with conventional method, according to 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 consumption of water soluble algae acid esters and/or water soluble algae hydrochlorate can in very large range change, as long as can shorten the time of solid-liquid separation, 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; More 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 described water soluble algae hydrochlorate can in very large range change, as long as can make intermolecular collision aggravation in the waste liquid, making the small molecules that is difficult for precipitation be combined into the larger throw out of macromole formation gets final product, under the preferable case, the relative molecular weight of described water soluble algae hydrochlorate is 30000-200000, and relative molecular weight is the molecule of material or average quality and the nucleic of discrete cell 121/12 ratio of C atomic mass.For example, described 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 potassium alginate of the sodium alginate of Nan Yang, Qingdao seaweed industry company limited production, Qingdao Mingyue Marine Alga Group Corp., Ltd.'s production and the production of Handan City Ocean Medicinal varek combinations company limited.
The kind of described water soluble algae acid esters can in very large range change, as long as can make intermolecular collision aggravation in the waste liquid, making the small molecules that is difficult for precipitation be combined into the larger throw out of macromole formation gets final product, under the preferable case, the relative molecular weight of described water soluble algae acid esters is 30000-200000, and relative molecular weight is the molecule of material or average quality and the nucleic of discrete cell 121/12 ratio of C atomic mass.For example, described 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.The water soluble algae acid esters that meets above-mentioned requirements can obtain by well known to a person skilled in the art that method is synthetic, 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 being carried out solid-liquid separation, waste liquid in waste liquid, adds water soluble algae acid esters and water soluble algae hydrochlorate, when adding at the same time water soluble algae acid esters and water soluble algae hydrochlorate, can further shorten the time of solid-liquid separation, 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 described water soluble algae hydrochlorate is the 10-1000 weight part.More preferably, with respect to the water soluble algae acid esters of 100 weight parts, the add-on of described water soluble algae hydrochlorate is the 40-300 weight part.
According to the present invention, described solid-liquid separation can be the various solid-liquid separating methods of routine, as filtering, for example, can filter by pressure filter, for example, the chamber-type press filter that Jingjin Filter Press Group Co.,Ltd produces.The condition of described filtration can in very large range change, and under the preferable case, the condition of described filtration comprises that the pressure of filtration is 0.4-1MPa, and the time of filtration is 1-3 hour.
But, the present inventor finds, when using common chamber-type press filter that the waste liquid of preparation of ethanol by fermentation of cassava is filtered, waste liquid enters between the chamber filter plate of pressure filter, solid particulate is trapped in the space between the filter plate by the filtration medium of filter plate, liquid then passes through filtration medium, discharge outside the pressure filter by portalling, continuity along with filtration procedure, the thickness of solid product increases gradually, the resistance of dehydration increases exponentially thereupon, thereby cause the rapid decline for the treatment of capacity, and because the restriction of chamber filter plate nature, filter pressure can't further improve (generally below 1MPa), thereby can't further reduce the water content of solid product, the required energy consumption of follow-up oven dry solid product is higher.
Therefore, under the preferable case, described solid-liquid separation is by filtering and squeeze realization to described waste liquid.
According to the present invention, can use various device that described waste liquid is filtered and squeezes, under the preferable case, can filter and squeeze with diaphragm filter press.
Described diaphragm filter press namely has the filtering function identical with common chamber-type press filter, have again solid product is squeezed and function that it is dewatered again, in diaphragm filter press, common chamber filter plate and membrane filter plate are spaced, the middle central layer of described membrane filter plate and both sides barrier film compress and form two Sealed sandwiches, the filtering function of described membrane filter plate is identical with common chamber filter plate, but increased pressing function, namely, after filtering end, extrusion medium is injected into the sealing ply from middle central layer hand-hole, because the elastic contribution of barrier film can carry out to the solid product after filtering the blow-up squeezing, and solid product is dewatered again.
Common chamber filter plate and the quantity of membrane filter plate can be adjusted according to the concentration of waste liquid in the described diaphragm filter press, under the preferable case, the quantity of common chamber filter plate is 50-60, described 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 described 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 from 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 significantly the water content of squeezing the solid product that obtains, and 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, when the waste liquid of described preparation of ethanol by fermentation of cassava refers to ferment to prepare ethanol by cassava, distill out after the ethanol that obtains residual solidliquid mixture.
Among the present invention, the condition of described filtration and squeezing can in very large range change, and the condition of described filtration and squeezing makes the water content of the solid product that obtains less than 60 % by weight, under the preferable case, the condition of described filtration comprises that the pressure of filtration is 0.4-1MPa, and the time of filtration is 1-2 hour; The condition of described squeezing comprises that the pressure of squeezing is 10-25MPa, and the time of squeezing is 0.2-1 hour.
Among the present invention, described squeeze pressure can realize by be filled with extrusion medium in diaphragm filter press, and described extrusion medium can be diaphragm filter press various extrusion medium commonly used, and for example, described extrusion medium can be pressurized air and/or water.
The method according to this invention comprises that also the solid product that solid-liquid separation is obtained dries, obtain solid residue, the equipment of described oven dry can be the drying plant of various routines, for example, 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 company limited.Among the present invention, the condition of described oven dry can be the drying condition of routine, and for example, the condition of described oven dry comprises that bake out temperature is 100-200 ℃, and drying time is 0.2-2 hour; More preferably, bake out temperature is 120-150 ℃, and drying time is 0.5-1 hour.
The below will do further specific descriptions to the present invention by embodiment.
Embodiment 1
The present embodiment is used for illustrating that employing cassava raw material of the present invention prepares the method for ethanol.
(1) peeling of cassava raw material and pulverizing
Be prepared as follows the peeling equipment shown in Fig. 1,2 and 3.
Cylinder 2 comprises first paragraph cylinder 2a and second segment cylinder 2b from top to bottom, and first paragraph cylinder 2a and second segment cylinder 2b are communicated with, and the length of first paragraph cylinder 2a and second segment cylinder 2b is respectively 1.8 meters and 1.6 meters; Described cylinder 2 is formed from steel, and interior diameter is 1.6 meters; (trade mark is HRB335 to fix the hot rolled ribbed steel bar that 40 length are 1.5 meters on the inwall of first paragraph cylinder 2a, nominal diameter is 12 millimeters), each bar hot rolled ribbed steel bar is parallel with the central axis of cylinder, each bar hot rolled ribbed steel bar distributes equally spacedly along the circumference of inner wall of rotary drum, and the circumferential distance between adjacent two hot rolled ribbed steel bars is 0.125 meter; (trade mark is HRB500 to fix the hot rolled ribbed steel bar that 50 length are 1.2 meters on the inwall of second segment cylinder 2b, nominal diameter is 16 millimeters), each bar hot rolled ribbed steel bar is parallel with the central axis of cylinder, each bar hot rolled ribbed steel bar distributes equally spacedly along the circumference of inner wall of rotary drum, and the circumferential distance between adjacent two hot rolled ribbed steel bars is 0.1 meter; Cylinder 2 is mounted obliquely within on the support 1, and the angle of inclination is 5 degree.Screwfeed device 3 is made by rubber, and pitch is 0.5 meter, and thread depth is 0.2 meter; Screwfeed device 3 is fixedly connected on the inwall of cylinder 2 by fastening piece 8.Drive unit comprises electric motor, transmission chain and sprocket 6; Sprocket wheel 6 is fixed on the cylinder 2, and to sprocket wheel, the power of electric motor is 5.5 kilowatts to transmission chain with the transmission of power of electric motor.
Actuating motor makes cylinder 2 and screwfeed device 3 rotate (rotating speed is 7 rev/mins) around the central shaft of cylinder; With (thick 4-8 centimetre of the new fresh cassava of the double centner surface clean of results, long 20-30 centimetre, water content 65 % by weight) join in the cylinder 2 by opening for feed 4 continuously, the cassava after the peeling is discharged from discharge port 5, collects and obtains 95 kilograms of cassava raw materials after the peeling.
To be cut into 1 centimetre of disk that the left and right sides is thick after these 95 kilograms of cassava raw materials cleanings, then the cassava slice after using SFSP series beater disintegrating machine to peeling is pulverized, the method of described pulverizing comprises first once to be pulverized 60 kilograms of cassavas through peeling 20 minutes, 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 the fresh cassava raw materials of 60 kilograms of not processes of removing the peel with remaining 35 kilograms of processes of this crushed products of 10 % by weight being pulverized mix once to be pulverized 15 minutes again, obtain average particulate diameter and be a crushed products of 3 millimeters, and above-mentioned whole crushed products were carried out separating twice 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 dry under 45 ℃ to constant weight 3.4 grams, 300.0 milligrams of these dried crushed products of weighing are positioned in 100 milliliters of dry Erlenmeyer flasks of heavy 80 grams.Adding 3.00 ml concns in the described Erlenmeyer flask is the sulphuric acid soln of 72 % by weight, stirs 1 minute.Then Erlenmeyer flask was placed 60 minutes in 30 ℃ water-bath, stirred once to guarantee even hydrolysis every 5 minutes.Hydrolysis makes the concentration dilution of sulfuric acid to 4 % by weight after finishing with deionized water, then filter with Büchner funnel, obtains altogether 84 milliliters of filtrates.20 milliliters of filtrates are transferred in the 50 milliliters dry triangular flask.Use 2.5 gram calcium carbonate to regulate the pH value to 5.5 of this filtrate, left standstill 5 hours, collect supernatant liquid.With the supernatant liquid that 0.2 micron membrane filtration is collected, gained filtrate is analyzed with Biorad AminexHPX-87P high performance liquid chromatography (HPLC).HPLC condition: sample size 20 microlitres; Moving phase is 0.2 micron membrane filtration and the degassed HPLC ultrapure water of sonic oscillation; Flow velocity is 0.6 ml/min; Column temperature 80-85 ℃; Detector temperature 80-85 ℃; Detector is 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, can be calculated the described crushed products acid hydrolysis of 1 gram and can obtain the glucose that weight is 0.311 gram, because being the sulphuric acid soln of 72 % by weight, concentration the starch in the crushed products all can be hydrolyzed into glucose, therefore the weight of gained glucose is 1.11 times of starch weight in the crushed products, namely the starch content in the described crushed products of 1 gram is 0.280 gram, then is total to starch-containing 26.6 kilograms in 95 kilograms of crushed products.
(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 ℃, dry weight basis with every gram crushed products, the α-amylase (Novozymes Company buys) that adds 20 enzyme activity units, and the insulation enzymolysis obtained enzymolysis product after 60 minutes under 70 ℃.
(3) fermentation
Make the temperature of enzymolysis product be down to 33 ℃, with the weighing scale 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 lower second distillations.Be calculated according to the following formula alcohol yied, calculation result sees Table 1.
The weight of starch contained therein in alcohol yied=100% * ethanol weight/cassava raw material
The karusen of getting behind the 100 gram distillation ethanol filters with Büchner funnel, 20 milliliters of filtrates is transferred in dry 50 milliliters the triangular flask, leaves standstill 5 hours, collects supernatant liquid.0.2 the supernatant liquid that the micron membrane filtration is collected, according to the described high performance liquid phase condition of above-mentioned steps (1), the glucose of measuring and calculating in the karusen 342 restrains totally.And being calculated according to the following formula the residual sugar rate, calculation result sees Table 1.
The weight of starch contained therein in residual sugar amount/cassava raw material in residual sugar rate=karusen
(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 waste liquid of taking-up and the water after the flushing.
The waste liquid of 15 batches of above-mentioned fermentations is mixed, and (Shanghai Precision Scientific Apparatus Co., Ltd, the water content that SH-10A) detects in this mixed waste liquor is 95 % by weight by moisture determination instrument.Propylene glycol alginate (the Qingdao Mingyue Marine Alga Group Corp., Ltd. that in 100 tons of above-mentioned mixed waste liquors, adds 10 kilograms, relative molecular weight is 40000), 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 described chamber-type press filter, common chamber filter plate (Jingjin Filter Press Group Co.,Ltd, chamber filter plate) quantity is 100, the condition of described filtration comprises that the pressure of filtration is 0.8MPa, the time of filtering is 2 hours, obtaining water content is the solid product A1 of 75 % by weight, and the liquid waste disposal amount (separate unit) in the time that solid-liquid separation is required and unit time is as shown in table 2.
Embodiment 2
The present embodiment is used for illustrating that employing cassava raw material of the present invention prepares the method for ethanol.
Method according to embodiment 1 prepares ethanol, and different is that the method for the artificial peeling of employing scrapes off with the entocuticle of cutter with the cassava raw material in step (1), collects and obtains 95 kilograms of cassava raw materials after the peeling.Method according to embodiment 1 is pulverized the 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 described high performance liquid phase 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 karusen filters with Büchner funnel after getting 100 gram distillation ethanol, 20 milliliters of filtrates is transferred in the triangular flask of 50 milliliters of dryings, leaves standstill 5 hours, collects supernatant liquid.0.2 the supernatant liquid that the micron membrane filtration is collected, according to the described high performance liquid phase condition of embodiment 1 step (1), the glucose of measuring and calculating in the karusen 395 restrains totally.And calculate alcohol yied and residual sugar rate according to the formula of embodiment 1, calculation result sees 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 waste liquid of taking-up and the water after the flushing.
The waste liquid of 15 batches of above-mentioned fermentations is mixed, and (Shanghai Precision Scientific Apparatus Co., Ltd, the water content that SH-10A) detects in this mixed waste liquor is 95 % by weight by moisture determination instrument.Sodium alginate (Nan Yang, the Qingdao seaweed industry company limited that in 100 tons of above-mentioned mixed waste liquors, adds 20 kilograms, relative molecular weight is 80000), 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 described chamber-type press filter, common chamber filter plate (Jingjin Filter Press Group Co.,Ltd, chamber filter plate) quantity is 100, the condition of described filtration comprises that the pressure of filtration is 0.8MPa, the time of filtering is 1.8 hours, obtaining water content is the solid product A2 of 75 % by weight, and the liquid waste disposal amount (separate unit) in the 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 the reference method of ethanol.
Method according to embodiment 2 prepares ethanol, different is, once pulverized 35 minutes cassava raw material after 95 kilograms of peelings 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 separating twice 5 minutes, obtain altogether 190 kilograms of crushed products (average particulate diameter of cassava raw material is 5 millimeters in this crushed products).According to the described high performance liquid phase 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 karusen filters with Büchner funnel after getting 100 gram distillation ethanol, 20 milliliters of filtrates is transferred in the triangular flask of 50 milliliters of dryings, leaves standstill 5 hours, collects supernatant liquid.0.2 the supernatant liquid that the micron membrane filtration is collected, according to the described high performance liquid phase condition of above-mentioned steps (1), the glucose of measuring and calculating in the karusen 530 restrains totally.And calculate alcohol yied and residual sugar rate according to the formula of embodiment 1, calculation result sees Table 1.
Filter according to the waste liquid of the method identical with embodiment 2 to preparation of ethanol by fermentation of cassava, different is not add propylene glycol alginate, obtaining water content is the reference solid product CA1 of 75 % by weight, and the liquid waste disposal amount (separate unit) in the time that solid-liquid separation is required and unit time is as shown in table 2.
Embodiment 3
The present embodiment is used for illustrating that employing cassava raw material of the present invention prepares the method for ethanol.
Method according to embodiment 1 prepares ethanol, different is, the method of described pulverizing comprises uses SFSP series beater disintegrating machine first the fresh cassava raw material after 30 kilograms of peelings once to be pulverized 12 minutes, obtain average particulate diameter and be 5.5 millimeters 30 kilograms of crushed products, then the fresh cassava raw materials of 1.5 kilograms of processes of removing the peel with remaining 25 kilograms of processes of this crushed products of 5 % by weight being pulverized do not mix and again once pulverized 10 minutes, obtain average particulate diameter and be 3 millimeters 55 kilograms of crushed products, with 2.75 kilograms of this crushed products of 5 % by weight again with remaining 40 kilograms of once not pulverizing 15 minutes through the cassavas of pulverizing through peeling, obtain altogether 95 kilograms of crushed products, and an above-mentioned crushed products carried out separating twice 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 described high performance liquid phase 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 karusen filters with Büchner funnel after getting 100 gram distillation ethanol, 20 milliliters of filtrates is transferred in the triangular flask of 50 milliliters of dryings, leaves standstill 5 hours, collects supernatant liquid.0.2 the supernatant liquid that the micron membrane filtration is collected, according to the described high performance liquid phase condition of above-mentioned steps (1), the glucose of measuring and calculating in the karusen 292 restrains totally.And calculate alcohol yied and residual sugar rate according to the formula of embodiment 1, calculation result sees 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 waste liquid of taking-up and the water after the flushing.
The waste liquid of 15 batches of above-mentioned fermentations is mixed, and (Shanghai Precision Scientific Apparatus Co., Ltd, the water content that SH-10A) detects in this mixed waste liquor is 95 % by weight by moisture determination instrument.Ammonium alginate (the Handan City Ocean Medicinal varek combinations company limited that in 100 tons of above-mentioned mixed waste liquors, adds 10 kilograms, relative molecular weight is 100000) and propylene glycol alginate (Qingdao Mingyue Marine Alga Group Corp., Ltd. of 10 kilograms, 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 described chamber-type press filter, common chamber filter plate (Jingjin Filter Press Group Co.,Ltd, chamber filter plate) quantity is 100, the condition of described filtration comprises that the pressure of filtration is 0.8MPa, the time of filtering 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 content of detection solid product A3 by 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 ℃, obtain solid residue, by moisture determination instrument (Shanghai Precision Scientific Apparatus Co., Ltd, SH-10A) water content of detection solid residue, the water content of solid residue and the energy consumption of oven dry are as shown in table 3.
Described energy consumption refers to dry the coal that the water of removing 1 kilogram consumes, and unit is kg/kg.
Embodiment 4
The present embodiment is used for illustrating that employing cassava raw material of the present invention prepares the method for ethanol.
Method according to embodiment 1 prepares ethanol, different is, 64 kilograms of fresh cassavas are removed the peel according to the method for embodiment 1 obtain 61 kilograms of cassava raw materials, and section, then the fresh cassava raw material after 61 kilograms of peelings and 40 kilograms of dried cassava slices (water content is 13 % by 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 first 40 kilograms of cassava raw mixs through peeling 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 % by weight and the remaining cassava raw mix are mixed and re-start and once pulverize 10 minutes, obtain the cassava average particulate diameter and be 4.5 millimeters totally 70 kilograms of crushed products, with 7 kilograms of this crushed products of 10 % by 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 3.5 millimeters totally 110 kilograms of crushed products, with 6.6 kilograms of this crushed products of 6 % by 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 millimeters 166 kilograms of crushed products, and above-mentioned whole crushed products were carried out separating twice 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 described high performance liquid phase 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 karusen filters with Büchner funnel after getting 100 gram distillation ethanol, 20 milliliters of filtrates is transferred in the triangular flask of 50 milliliters of dryings, leaves standstill 5 hours, collects supernatant liquid.0.2 the supernatant liquid that the micron membrane filtration is collected, according to the described high performance liquid phase condition of above-mentioned steps (1), the glucose of measuring and calculating in the karusen 566 restrains totally.And calculate alcohol yied and residual sugar rate according to the formula of embodiment 1, calculation result sees 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 described diaphragm filter press, with 50 membrane filter plate (Jingjin Filter Press Group Co.,Ltd, 1250 types) replace 50 common chamber filter plate (Jingjin Filter Press Group Co.,Ltd, chamber filter plate), and common chamber filter plate and membrane filter plate be spaced; The condition of described filtration comprises that the pressure of filtration is 0.8MPa, and the time of filtration is 1 hour; Be filled with afterwards the extrusion medium air in membrane filter plate, the solid product after filtering is squeezed, the pressure of described squeezing is 10MPa, and the time of squeezing is 0.8 hour, obtains solid product A4.
(result is as shown in table 3 for Shanghai Precision Scientific Apparatus Co., Ltd, the SH-10A) water content of detection solid product A4 by 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 ℃, obtain solid residue, by moisture determination instrument (Shanghai Precision Scientific Apparatus Co., Ltd, SH-10A) water content of detection solid residue, the water content of solid residue and the energy consumption of oven dry are as shown in table 3.
Described energy consumption refers to dry the coal that the water of removing 1 kilogram consumes, and unit is kg/kg.
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 amount that method of the present invention not only consumes water is few, can finish at short notice pulverizing, the energy that consumes is less, the utilization ratio of equipment is high, crushing effect is high, adopt simultaneously the particle diameter of potato raw material particle in the crushed products that obtains after the method for separating twice of the present invention can be good at controlling pulverizing, make the particle diameter of the potato raw material particle that finally obtains little and even.
Data from upper table 1 can be found out, the productive rate of the starch ethanol of the ethanol that the method that adopts potato raw material provided by the invention to prepare ethanol obtains is apparently higher than the productive rate of the starch ethanol of the ethanol that is obtained by reference method, and compared with the prior art, the residual sugar rate for preparing the method for ethanol of the present invention reduces greatly.
Table 2
The embodiment numbering The solid product numbering The solid product water content Solid-liquid separation is consuming time Treatment capacity (ton/hour)
Embodiment 1 A1 75 % by weight 2 hours 42
Comparative Examples 1 CA1 75 % by weight 4.5 hour 18.7
Embodiment 2 A2 75 % by weight 1.8 hour 46.7
As can be seen from Table 2, the method that from the waste liquid of preparation of ethanol by fermentation of cassava, reclaims solid residue provided by the invention, shortened significantly the time of solid-liquid separation, in the situation that need not to increase the treatment capacity that new installation has improved liquid waste in unit time significantly, thereby the bottleneck that the operating load that has solved the device that causes preparation of ethanol by fermentation of cassava is lower has improved the throughput of the device of preparation of ethanol by fermentation of cassava.
Table 3
The embodiment numbering Solid product water content (% by weight) Solid residue water content (% by weight) Energy consumption (kg/kg)
Embodiment 3 74 % by weight 10 % by weight 0.31
Embodiment 4 55 % by weight 10 % by weight 0.12
As can be seen from Table 3, the water content of the solid product A4 that the embodiment of the invention 4 obtains is 55 % by weight, the water content of the solid product A3 that embodiment 3 obtains is then up to 74 % by weight, explanation is by using diaphragm filter press waste liquid to be filtered and squeezes the water content that can reduce significantly the solid product that obtains, and embodiment 4 compares with embodiment 3, the energy consumption of baking needed significantly reduces, and explanation can significantly reduce the required energy consumption of recovery solid residue by using diaphragm filter press that waste liquid is filtered and squeezes.

Claims (22)

1. method that adopts potato raw material to prepare ethanol, the method comprises: with the potato raw material peeling, the potato raw material after the peeling is pulverized, 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, the method for described pulverizing comprises that the potato raw material after will removing the peel first once pulverizes, and obtains crushed products one time, crushed products of part is carried out separating twice, obtain the separating twice product, then the potato raw material of not pulverizing after crushed products of remainder and the peeling is mixed once pulverize, carry out afterwards separating twice; Before being carried out solid-liquid separation, waste liquid in waste liquid, adds water soluble algae acid esters and/or water soluble algae hydrochlorate, wherein, the 5-20 % by weight of the gross weight of the potato raw material of not pulverizing after crushed products that the 5-20 % by weight that a crushed products of remainder is whole crushed products weight, a crushed products of remainder account for remainder and the peeling; Described potato raw material is dried cassava, and the method also comprises the dried cassava after the peeling is added entry before once pulverizing, the consumption of water be the potato raw material dry weight 0.5-2 doubly; Perhaps described potato raw material be fresh cassava or for weight ratio be the dried cassava of 1:1.5-2.5 and the mixture of fresh cassava.
2. method according to claim 1, wherein, the 5-10 % by weight that a crushed products of remainder is whole crushed products weight; The 5-10 % by weight of the gross weight of the potato raw material of not pulverizing after crushed products that a crushed products of remainder accounts for remainder and the peeling.
3. method according to claim 1, wherein, in the crushed products, the average particulate diameter of potato raw material is the 2.5-10 millimeter; In the separating twice product, the average particulate diameter of potato raw material is 1.6 millimeters to 2.5 millimeters.
4. method according to claim 1, wherein, with respect to the waste liquid of 1000 weight parts, the consumption of described water soluble algae acid esters and/or water soluble algae hydrochlorate is the 0.05-1 weight part.
5. method according to claim 4, wherein, with respect to the waste liquid of 1000 weight parts, the consumption of described water soluble algae acid esters and/or water soluble algae hydrochlorate is the 0.1-0.5 weight part.
6. method according to claim 1, wherein, added water soluble algae acid esters and water soluble algae hydrochlorate before waste liquid is carried out solid-liquid separation in waste liquid, with respect to the water soluble algae acid esters of 100 weight parts, the add-on of described water soluble algae hydrochlorate is the 10-1000 weight part.
7. method according to claim 6, wherein, with respect to the water soluble algae acid esters of 100 weight parts, the add-on of described water soluble algae hydrochlorate is the 40-300 weight part.
8. according to claim 1,4,5,6 or 7 described methods, wherein, the relative molecular weight of described water soluble algae hydrochlorate is 30000-200000, described water soluble algae hydrochlorate is selected from one or more in sodium alginate, potassium alginate and the ammonium alginate, the relative molecular weight of described water soluble algae acid esters is 30000-200000, and described water soluble algae acid esters is propylene glycol alginate.
9. method according to claim 1, wherein, described solid-liquid separation is by filtering and squeeze realization to described waste liquid.
10. method according to claim 9, wherein, described filtration and squeezing realize by diaphragm filter press, the condition of described filtration and the condition of described squeezing make the water content of the solid product that obtains less than 60 % by weight.
11. method according to claim 10, wherein, the condition of described filtration comprises that the pressure of filtration is 0.4-1MPa, and the time of filtration is 1-2 hour; The condition of described squeezing comprises that the pressure of squeezing is 10-25MPa, and the time of squeezing is 0.2-1 hour.
12. method according to claim 1, wherein, the method comprises that also the product that described solid-liquid separation is obtained dries, and the condition of described oven dry comprises that bake out temperature is 100-200 ℃, and drying time is 0.2-2 hour.
13. method according to claim 1, wherein, described potato raw material is fresh cassava, fresh cassava is by using a potato seed class peeling equipment to remove the peel, this potato class peeling equipment comprises support (1), cylinder (2), spiral feeder (3) and drive unit, cylinder (2) is installed in rotation on the support (1), cylinder (2) has opening for feed (4) and discharge port (5), described screwfeed device (3) is arranged in cylinder (2) and is fixedly connected with the inwall of cylinder, and described drive unit is used for head roll (2) and screwfeed device (3) rotates together; The method of fresh cassava peeling comprises that fresh cassava passes through described opening for feed (4) and puts in the described cylinder (2), utilizes described drive unit head roll (2) and screwfeed device (3) to rotate together.
14. method according to claim 13 wherein, has friction structure on the inwall of described cylinder (2).
15. method according to claim 14, wherein, described friction structure is one or more Ribbed Bar.
16. method according to claim 15, wherein, described Ribbed Bar is parallel with the central axis of cylinder (2).
17. method according to claim 13, wherein, the angle of inclination of described cylinder (2) is the 0-15 degree, and length is 2-10 rice; The velocity of rotation of cylinder (2) and screwfeed device (3) is 2-50 rev/min.
18. method according to claim 13, wherein, the pitch of described screwfeed device (3) is 0.3-0.8 rice, and thread depth is 0.1-0.4 rice.
19. method according to claim 13, wherein, described drive unit comprises drive source, transmission chain and sprocket (6), and sprocket wheel (6) is fixed on the cylinder (2), transmission chain with the transmission of power of drive source to sprocket wheel.
20. method according to claim 1, wherein, the enzyme that described enzymolysis uses comprises amylase, the dry weight basis of the product after pulverizing with every gram, and described diastatic consumption is the 4-50 enzyme activity unit; The temperature of described enzymolysis is 50-90 ℃, and the time of described enzymolysis is 20-240 minute, and the pH value of described enzymolysis is 3-7.
21. method according to claim 20, wherein, described amylase is α-amylase and/or saccharifying enzyme.
22. method according to claim 1, wherein, in every gram enzymolysis product, the inoculum size of the employed yeast of described fermentation is 10 3-10 8Colony-forming unit, the temperature of described fermentation are 30-36 ℃, and the time of fermentation is 50-75 hour.
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US5245919A (en) * 1993-02-17 1993-09-21 Magnuson Corporation Apparatus for peeling fruits or vegetables
CN1644703A (en) * 2004-12-29 2005-07-27 天津大学 Production of alcohol fuel
CN1772661A (en) * 2005-10-15 2006-05-17 桂林工学院 Combined treatment process for manioc producing effluent
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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US5245919A (en) * 1993-02-17 1993-09-21 Magnuson Corporation Apparatus for peeling fruits or vegetables
CN1644703A (en) * 2004-12-29 2005-07-27 天津大学 Production of alcohol fuel
CN1772661A (en) * 2005-10-15 2006-05-17 桂林工学院 Combined treatment process for manioc producing effluent
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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