Background technology: constantly face the especially main and main body of the energy and be non-renewable fossil energy oil the mankind, coal resource is day by day and obviously fast under the exhausted severe situation, regenerative resource particularly rapid research and development and the extensive industrialization thereof of bioenergy has naturally also just become countries in the world and one of the regional subject goal of competing and task and has represented its true national power, strong and weak great sign and one of the standard with the sustainable development ability of the national national power of one of internationally recognized comprehensive judge, the regenerative resource so all spare no effort to research and develop in various countries, the world and area, greatly develop renewable alternative energy source such as clears such as China's Eleventh Five-Year Plan outlines, and reach in the agreement of working in coordination aspect the renewable alternative energy source technical development with the same genus energy resource consumption big country U.S., State Council's energy state basic policy also clear will be strengthened technical research and the deposit of regenerative resource energetically, its each ministries and commissions also all formulate successively one after another and have issued the with it serial policy of supporting enforcement, file is first developed the especially great state basic policy such as fuel alcohol of the recyclable organism energy such as National Development and Reform Committee.It is evident that, in the research and development and industrialization of renewable energy source, the most wide abiotic energy of raw material and market do not belong to, wherein again with chemurgy and growth be harvesting time the regeneration period short, output is big, the starchy material fermentative production fuel alcohol cost of the place of production and area wide (whole world) is minimum and prospect is the most wide.However, little in view of the present global Production of Fuel Ethanol starting time difference, so its fermentation technique and technology substantially all are slightly to improve on traditional wine and alcohol basis and do not have an important breakthrough, heighten as production cycle of very long (more than 150 hours) and corresponding investment wait, all be seriously to restrict the bottleneck that fuel alcohol develops rapidly and lean on present technology to be difficult to go beyond, cause it far can not meet the need of market let alone " substituting " oil; In addition, existing tradition band slag fermentation alcohol Technology is used for the large-scale production fuel alcohol, and volume, energy consumption, water consume and encircle dirty problem and also is difficult to ignore, and should accelerate the correlation technique research and development to seek to achieve breakthrough.
For further strengthening understanding and understand, might as well earlier prior art be briefly introduced following, for your guidance with the usefulness of easy analysis: take a broad view of present wine and Alcohol Production, its fermentation by states of matter be broadly divided into solid-state and liquid two big classes, by technology be broadly divided into interruption and continuous two big classes, other is as semicontinuous etc. then substantially belonging to intervenient transitional type, do not have significant essential distinction, it gets wine, and then substantially all to belong to disposable be ripe method-at every turn just get wine one time after the fermentation ends; Solid state fermentation raw material water content is few far beyond the liquid state fermentation raw material, the alcohol that produces in the yeast body is because of few and mobile little the waiting a moment of raw material water content, be difficult to rapidly diffusion and be accumulated in the yeast cells body in and near all and dense, be understood that according to the product enzyme reaction principle that suppresses namely to slow down the solid state fermentation cycle is long, generally need several months and even nearly 1 year and often need several times, needed nearly 10 months and 6-8 fermentation and get wine and just can finish such as Maotai, although the solid state fermentation cycle is long, but because of the accessory substance that also needs in the beverage wine to produce in some alcoholic fermentation process such as aroma-producing substance etc. to increase quality, and the generation that very long batch solid fermentation is beneficial to these materials and accumulation and each other more complicated reaction and product and high-grade wine valency your pupil widely adopted so far and still accounted for main flow and the principal status of public economy with the characteristics such as expensive that remedy length consuming time, as now still be widely used in valency higher in, high-grade distillation beverage wine such as high-quality world's famous brand of wine Maotai, five-Grain Liquor, Jian Nan Chun, Luzhou Old Cellar etc.Yet intermittent type solid state fermentation and be that to drink advantage the wine obviously low-grade be that low price is drunk wine to high price concerning top grade, especially be not suitable for the production of fuel alcohol, because at first the production cycle is grown and causes cost significantly to improve, and its city field energy is accepted as be that the price of reference price does not have feasibility far below its cost with the petroleum products, secondly, fuel alcohol need not any aroma-producing substance etc. at all, and the 3rd is some material such as the glycerine (mainly being to be produced by yeast in the very long fermentation later stage) that produces in the fermenting process, (pyruvic acid that glucose fermentation generates and amino acid such as Gelucystine effect generate fusel main body of oil primary isoamyl alcohol to potato spirit; In addition, pyruvic acid and acetyl-CoA combine, because the lengthening of carbochain, when sucrose exists as is molasses fermented, promote that also higher alcohols is the generation of potato spirit), (glucose and L-glutamic acid generate succsinic acid, also generate glycerine simultaneously) can expend sugar and reduce alcohol output, the 4th is that long-time tight airtight heap fermentation generation more heat transfer is difficult to distribute easy pollution microbes such as acetic bacteria (directly consuming alcohol) generation acetic acid when causing leavening temperature to be higher than 37 ℃ again, milk-acid bacteria (consuming pyruvic acid is glucose) generates lactic acid, butyric acid is also by glucose, and Yin Wendu is higher than yeast optimum temperuture (30-34 ℃) and suppresses saccharomycetic breeding with active, these factors all reduce alcohol output, the 5th is also to need to isolate from alcohol when distillation these materials, otherwise can influence the especially higher fuel alcohol quality of purity requirement and further increase process complexity and reduce alcohol yield and increase production cycle and plant and equipment investment of alcohol, the 6th is solid-state stepwise fermentation operation of intermittent type and workload, consumption song (repeating with bent) (it is bent to repeat training) consuming time consumption grain (repeats to cultivate and use song and is converted into the thalline consumption grain that can not be transformed into alcohol mostly all to repeat to increase several times: in addition, each fermentation with get wine the wine consumption all arranged: the most common and loss is difficult to again avoid greatly causes rimose " to leak (alcohol and aroma-producing substance etc.) gas " and oxygen enters and weakens zymamsis ability and output and increase oxygen consumption fermentation and product as poorly sealed surface in the fermenting process is withered, carry repeatedly, loosely get alcohol and quality and the production losses such as " spacious gas " that vinasse that ferment that wine uses promptly are commonly called as alcohol and a large amount of volatilizations of aroma-producing substance.More than these factors result single and comprehensive function cause the alcohol yield of solid fermentation to reduce and the cost increase.
Though liquid state fermentation has interruption, semicontinuous and continuous branch, but all tool and above-mentioned solid-state discontinuous fermentation have essence and be the difference of general character: one-period finishes once fermentation and namely abandons after drinking material and no longer repeat to reach again as fermentation raw material and ferment with getting, this just requires liquid state fermentation to ferment as much as possible thoroughly namely to allow starch in the raw material change into as much as possible glucose sugar and make equally as much as possible conversion of glucose is alcohol, and these processes all require continuously once (one-period) property to finish.For aforesaid solid-state batch fermentation, liquid state fermentation truly has high because of moisture and therefore has again certain fluidity to make alcohol be easy to dissolving and comparatively be evenly distributed in the whole liquid, alcohol meltage and content in the liquid are increased, therefore and reduce the inner and nearly all alcohol concentrations of yeast, the enzyme reaction rate that causes generating alcohol because of product be alcohol concentration reduce to be accelerated to shorten fermentation period, and reduce the various alcohol losses of aforesaid solid-state batch fermentation and grain consumption and cost increase etc., thereby substantially overcome or avoided above-mentioned solid-state batch fermentation to be difficult to serial critical defect and the key restraining factors of low-cost large-scale industrialized production fuel alcohol, but for fuel alcohol high-purity and high yield and the fast series key of speed of production and bottleneck requirement, at present liquid state fermentation still has serial major defect, cause Starch Hydrolysis speed slow such as boiling, not thoroughly (be non-glucose as producing the non-direct fermentation sugar such as a large amount of dextrin) and amylodextrin sex change are not aging is difficult to rapidly or thoroughly be hydrolyzed into fermentable sugar and significantly increases fermentation and significantly extend manufacture cycle such as primary fermentation (more than 10 hours) especially after fermentation (more than the 40 hours) time for hydrolysate, equally significantly reduce alcohol output; Starch and dextrin expansion increase liquid viscosity and reduce its flowability, reducing liquid and surface exchange area and the exchange velocity of yeast and the alcoholic fermentation speed that slows down extends manufacture cycle, and easy therefore pollution microbes and reduce alcohol output and quality, only have the high cost that increases the yeast consumption effectively to overcome, or it is mobile to reduce the toughness increase to reduce liquid material concentration, so but this also must be that to reduce unit interval alcohol growing amount be that output is that cost is equally high, though above problem in the prior art can through the agency part of aspergillus carbohydrase generate fermentable sugar and in alcoholic fermentation process the starch in the converted mash and dextrin continue by Glucoamylase hydrolysis namely after saccharification, thoroughly being hydrolyzed into fermentable sugar with respect to the elder generation of the present invention's design is to still have above-mentioned series and the defectives and more serious such as the fermentation of following band slag and accessory substance for fermenting behind the glucose again; The more important thing is band slag boiling and ferment that not only treating capacity is too big, and because increasing, volume takies in a large number equipment and factory building dischargeable capacity and time, space, significantly increase simultaneously and can consume and environmental pollution by water consumption, be that glucose reduces alcohol output because a large amount of proteolysis in the slag cause the thalline excessive multiplication to expend multiple-energy-source also, and as aforementioned same need expend glucose sugar and generate fuel alcohol and do not need and affect its quality and must increase fusel wet goods accessory substance and the corresponding minimizing alcohol outputs of cost to remove such as operation and equipment, time.Above-mentioned series of problems is not as resolving, and the enforcement of Fuel Ethanol Industry and the industry great state basic policy of the inevitable serious national regenerative resource of restriction with regard to being difficult to rapid tremendous development, will seriously restrict the world and human energy resource supply and alternative ability and pace and paces yet.
The state-of-the-art technology progress is for adopting immobilized cell technique to transform traditional technology of alcohol at present, the tool fixed yeast is reusable, useful life is more than 160 days, anti-miscellaneous bacteria ability need not be sterilized by force, no longer need distiller's yeast to cultivate, fermentation time shortens half Zymolysis Equipment production capacity and improves more than 1 times, liquor output rate waits feature ﹠ benefits than traditional zymotic technology raising about 5% under equal fermentation condition, conclude and get up to see mainly be to reduce with bent and cultivation, grain consumption and before, the after fermentation time, but the large-scale production ability of immobilization technology is then littler because of the disposal ability that is subjected to the immobilization post and pass in time processing speed can to reach more and more slowly the restriction higher and the core sexual factor such as cleaned and changed of must stopping work of cost price very limited, and difficulty has essence to break through or takes on a new look in a short time, add that it still fails to solve saccharification and purity and concentration, especially be with slag and treating capacity big, the energy consumption that hard and fast rule are limited in the high serial main body problem of the big cost of the low investment of equipment factory building utilization rate and the 11 5 years development planning outline of the government work report and country, the water consumption, the rigid index of environmental pollution etc. is the serial difficult problem of bottleneck equally, and it is extensive to be difficult to be applicable to that fuel alcohol needs, low-cost production must with the basic demand condition.Also have at present energy-conservation raw material direct fermentation, but fermentation needs above, cycle a couple of days to grow up to this height, fermentation load and treating capacity and volume are too big, and easily microbiological contamination, rotten, corruption etc. are therefore all little for the low-cost feasibility of fuel alcohol high-yield quick and meaning.
Serve the growth that waits industry and desertification to take up an area of along with population and industry and commerce, the universe and everybody are faced with a reality and the long-range existence difficult problem that arable land per capita is fewer and feweri and be difficult to overcome, the production cycle that adds traditional main flow sugaring crop sugarcane reaches 10 months, remaining 2 months because of being shorter than any main energy sources farm crop such as carbohydrate beet, it is long-term that basic growth of oils rape and leguminous crop or starch main source cereal class and tuber crops etc. and ripe former its of cycle have exhausted perennate substantially, cause the price volalility of main flow carbohydrate sucrose soaring, forcing country to employ national treasury deposit sugar again and again on a large scale stabilizes and the sugared valency of regulation and control, but obviously this is temporary transient, because the national treasury gulps down, the amount of telling and ability of regulation and control thereof and regulation and control space are always limited, have only fundamentally to solve source, sugared source and just can reach the regulation and control purpose.Starch sugar then is the only way and wise the selection, because of its crop species, source and distribute extensively, short, the general 3-5 of output height and growth cycle is about individual month, so but 1 year 2-3 is ripe, and be the higher glucose of nutritive value or quality higher, sweeter fruit glucose (slurry) and fructose, add can large-scale industrial production thus price also cheaper, become developed country main flow sugar source at present, the China that developing country especially has a large population and a few land etc. are many also should and can to become inevitable choice and development general trend.The method Patent Prospectus that the CN1070425A maize enzyme acid is directly produced glucose sugar is exactly a well trial of complying with this trend: it removes slag and namely earlier Raw material processing is produced starch slurry or first starch, selectivity principle according to enzyme adopts three sections liquefaction of high temperature enzyme and sour saccharification namely not to be with the direct high-quality of slag fast (with respect to acid described later again, acid enzyme and holoenzyme method) production glucose, thereby the high smart starch of traditional acid system call for bids and high-temperature high-pressure apparatus and heavy with the big environmental pollution of acid amount have been overcome, the problems such as the serious and amount of by-products of recombination reaction is big, also overcome improved method acid-enzyme hydrolysis method (low with sour amount and temperature and accessory substance than acid system), especially the holoenzyme method takes the shortcomings such as long, but its wet-milling legal system starch slurry technology still must consuming timely reach 48-72 hour, starch runs off big, the water consumption is also big with environmental pollution, and starch slurry is processed untimely also easy microbiological contamination, rotten, corrupt; Starch is because of need power consumption drying and because of the low environmental pollution die valency height of dried dust loss yield, also need again water consumption to convert into starch slurry, sulfurous acid (is easily urged glycerine and is generated the reduction alcohol output human body and alcoholic fermentation is unfavorable, specifically see below and state) and the more expensive and acid weak consumption of lactic acid greatly also unstable, and no matter its wet grinding or dry grinding method all require protein, plant skin, the embryo tooth is disconnected from each other and separate with starch and liquid glucose need be made with extra care and complex process, production cycle grows up to this height, the enzyme-added enzyme that kills again of three sections liquefaction processes is valuable and the expensive enzyme wasting of resources, the intensification that matches, cooling and be incubated the corresponding energy consumption that also increases, in time, consumed and (cooling and insulation) water consumption, the more important thing is and be heated to 120-140 ℃ and reach 5-8 minute starch denaturalization coking color depth, the refining difficulty of liquid glucose and yield (comprising that fermentation is such as alcohol) are descended, thus all fail to resolve saccharification and fermentation reach the serial great difficult problems such as thorough fast.
Goal of the invention: the present invention is exactly the fermentation and extraction of fuel alcohol by direct enzymatic liquefaction and acid saccharification of durra method that designs for solving above-mentioned series of problems, and is now that the innovation brief introduction of main scientific and technological principle of the present invention and other outbalance is as follows.The invention solves saccharification quick, thorough, pure and be not with slag and make fermentation same fast, thoroughly, accessory substance is few, recovery rate is high, quality better; Simultaneously slaking of Substratspezifitaet high temperature enzyme liquefaction and except the toxicity that removes slag makes that it is safer, nutrition and mouthfeel better and the feed value height, also thoroughly make saccharification and zymotic fluid concentration height make alcohol output the series of problems such as significantly improve because liquefying, the more important thing is that having solved traditional cooking liquor must qualifiedly have the great innovation of the irreplaceable series of background technology, advantage and advantage because viscosity is high-leveled and difficult with huge workload and high energy consumption, water consumption, environmental pollution and the serial historic difficult problems such as with high investment and cost that slag is processed equally to separate slag.The present invention according to enzyme-to-substrate in conjunction with and the height selectivity principle of catalytic reaction, adopt more than 90 ℃ the high-temperature starch hydrolase and under same temperature in specific manner with the starch in the raw material rapidly and thoroughly liquefaction and to other compositions inoperative and simultaneously slaking with remove the slag poison by high-temperature heating treatment, make feed good palatability livestock and poultry like to eat and be of high nutritive value; The more important thing is because the viscosity of the thorough liquefier that liquefies is low so the separation of slag is easy, and the slag after separating because of the low volume of water content and weight all little again not thickness easily transport and little, the easy drying of freight volume also energy-conservation, when saving, joint equipment and space; Because of separate that liquefier volume behind the slag is little, the low concentration of viscosity is big and good fluidity so the saccharification treating capacity is little; Because saccharified liquid is not with slag purity height, thus adopt the aforesaid enzymatic conversion of acid substitution to make to process easily and fast, as enzymatic conversion needed tens of hours and sour saccharification only needs a few hours; The more important thing is that culture propagation alcohol must remain under the sour environment otherwise fermentation is carried out to the direction that generates glycerine, particularly ferment the later stage, mainly produce in the alcoholic fermentation later stage because of glycerine, although alcoholic fermentation especially the later stage may produce acetic acid, also may pollute that lactic acid bacteria produces lactic acid but living contaminants and produce acid and belong to the strict production accident of taking precautions against with control in the alcoholic fermentation because of living contaminants such as acetic acid bacteria, the present invention is with the hydrochloric acid saccharification and direct fermentation alcohol does not afterwards have these shortcomings and tool is economized on the main advantages such as acid; Of paramount importance is need utilize the zymotic fluid nutriment such as sugar (starch-containing and dextrin etc.) because of yeast, protein and amino acids, trace element is such as proliferative cell quantity such as magnesium, therefore and the fusel oil (introducing before its mechanism) of generation and if the nitrogenous source that easy utilization is arranged in the karusen exists then can stop or postpone the disintegration of yeast and amino acid whose decomposition and, the height selectivity that adds catalyzed by amylase namely kept except starch other all nutriments and as the above-mentioned compositions such as its catalysate sugar can be used for cell proliferation by yeast, when being saccharification in conjunction with acid catalyzed broad spectrum activity again in liquefier and the saccharified liquid the remaining macromolecular substances such as protein also be catalyzed into the small-molecule substances such as nitrogenous source that amino acid is above-mentioned easy utilization, so enzyme liquefaction and sour saccharification not only the time short and because of liquefier, saccharified liquid and zymotic fluid all are not with slag and treating capacity is little and concentration is high, thereby can accelerate the goal of the invention that enzyme reaction principle that enzyme reaction rate improves product concentration realizes producing fast alcohol by utilize improving reactant concentration, also being acid hydrolysis because of materials such as remaining protein and little molecular product is beneficial to Yeast proliferation and the shortening time is beneficial to fermentation alcohol and improves quality, so make that liquefier and saccharified liquid all need not aforementioned CN1070425A refining and again significantly reduce treating capacity and environmental pollution and significantly save time and cost; In addition, the present invention with its fast and the sour saccharified liquid of low-cost production to replace the long-time enzymatic conversion liquid of tradition and improve force of labor also be goal of the invention and the place theoretical and serial major application value thereof that is successfully applied to the alcoholic fermentation production practices, when substantially saving surplus the after fermentation 40 hour very long time and Yin Jie, energy-conservation, water saving, grain consumes and environmental pollution is little and can effectively prevent living contaminants and improve alcohol quality and yield etc.
What is particularly worth mentioning is that also another great innovation of the present invention is that science is the goal of the invention that the fermentation reaction principle realizes producing fast alcohol with the enzyme that rationally utilizes reduction product concentration that enzyme reaction is carried out towards the product direction, existing also that cardinal principle and advantage brief introduction is as follows.Though at present which kind of fermentation alcohol method all be liquid state fermentation treat (solid-state then is each) ferment finish after disposable extraction alcohol, the surface sees that it seems the technology advantages of simple, but analysis will be very easy to find its shortcoming much and be very serious a little, as space is limited, it is for reference now only to make concise and to the point comprehensive analysis: the principle that enzyme reaction is carried out towards the product direction according to above-mentioned reduction product concentration is counter to be pushed away as can be known product and concentration thereof and can seriously hinder fermentation and namely reduce alcohol formation speed and first limiting factor often, it is that the concentration as influencing factor of substrate sugar is much bigger than reducing reactant, because the low product speed that just reduces alcohol of sugared concentration, yeast itself is safe from harm namely can therefore do not weaken internal ability and the potentiality of its fermentation, and improving constantly along with alcohol concentration, it suppresses namely to reduce the wine speed of producing in feedback ground on the one hand, but this also only is equivalent to the impact that above-mentioned sugar reduces, the prior alcohol that also is can cause the irreversible dehydration of cell and albumen irreversible denaturation to make cell and enzyme (albumen) comprise aforesaid traditional enzymatic conversion technology and carbohydrase sex change thereof, inactivation and directly and irreversibility ground by its inhibition, passivation even kill, cause fermenting speed to slow down or stop to make fermentation not thorough fully, or make originally very very long such as liquid phase process 40 hours of traditional handicraft, tens of skies and even the above after fermentation process of several months of solid state process become longer, all can seriously reduce production capacity and output; Owing to causing living contaminants, fermentation time length reduces quality and yield, and make the alcohol separating technology complicated with difficulty, reduce yield equally and increase cost, also because of fermentation period length take volume of equipment and plant area increase significantly reduce production capacity, must increase equipment and factory building invest and remedy for high cost; In addition, long and the mother liquor of fermentation time comprise wherein yeast can not or low grade of recycle and reuse rate will cause its energy consumption, grain consumption, environmental pollution and water to consume loading etc. increasing the weight of synchronously and unfavorable water saving is fallen and can be lowered consumption and the enforcement of environmental protection state basic policy, therefore production cost also can increase and weaken produce market share and competitiveness, and this place of the lifeblood of fuel alcohol enterprise and product just.
This raw materials technology and liquefaction, the saccharification treatment technology makes full use of enzyme effect specificity principle, enzymatic hydrolysis (more than 90 ℃) under comparatively high temps is carried out, thereby realize directly feeding intake production, receive the effect of starch liquefacation rate more than 97%, protein is easy to separate with starch, filter easily, liquefier glucose (DE) value makes follow-up saccharification react very rapid and thorough up to 28-30, thereby make and reach in original technology that saccharification period shortens to several hrs more than 50 hours, and make liquefier quality height in the production process, high purity, by product is little, basically having solved double-enzyme method injects sugared clarity and is difficult for shortcoming up to standard, make and produce injection, oral, edible and industrial sugar is produced in same set of equipment and is come true, for production has brought great handiness.In addition, because the DE value was more than 99.5 after liquid glucose was refining, oral glucose with this liquid glucose production need not crystallization just reach FCC-" U.S.'s edible chemical code " standard and China Ministry of Public Health oral glucose standard promulgated by the ministries or commissions of the Central Government, produce like product by the injection Standard for Sugars and can guarantee that also more than 70 hours crystallizing cycle of old technology shortens about 8-12 hours, and this technology does not play destruction to protein in the raw material etc., only play inspissation, final the mouthfeel that sugared slag is slaking and detoxification that obtains (palatability) is good, the mash concentrate that nutrition is very abundant is desirable food and feed exploitation basic resource.
Below all be important principles, innovation and advantage thereof, advantage and the guarantee that the present invention systematically improves fermentability and alcohol output and quality, especially with solved simultaneously quantity and quality, energy-saving and water-saving, prevent and treat environmental pollution, investment and cost etc. comprehensively, imitate a grand again simple serial historic difficult problem and can be rated as difficultly, be catalytic reaction direction and reactant and product correlation principle headed by the value of production practices with comprehensive scientific and reasonable and flexible Application selectivity (amylase) and non-specific (hydrochloric acid) catalytic reaction and core mechanism thereof again wherein.
Embodiment:
The invention will be further described below in conjunction with accompanying drawing.
The inventive method and principle, advantage are as follows:
1, Chinese sorghum dry grinding method is produced the corn flour breast:
Under the normal temperature with Chinese sorghum with corundum mill add the drinking water such as hard water such as running water (calcic take safeguard with improve follow-up High-temperature Liquefaction technology in the high temperature active of α-amylase with stable) levigate (rotating speed is as 600-800 rev/min) become the powder emulsus, require powder to be about 40% greater than the ratio of 450um, be about 60% less than the ratio of 450um; It is that 6.0-7.0 is the α-amylase Appropriate that hydrochloric acid is transferred PH, make slag capable of using as feed and save the soda acid consumption and avoid the subsequent treatment difficulty, because the hydrochloric acid neutralized reaction product is water-soluble calcium chloride and concentration is very low easily removes in follow-up alcoholic extraction technology, but can maintain also the high active calcium ion of above-mentioned functions and purposes, also can dispelling Chinese sorghum astringent taste material, to be beneficial to follow-up liquid, saccharification and alcoholic fermentation and extraction refining; Transfer newborn concentration, control concentration of slurry about 25-30%.
2, Glucose Liquid is produced in enzyme acid:
Slurries are pressed the disposable adding Ye Huamei of enzyme-added total enzyme concentration of a-amylase 50-60 units/gram dry starch, under 90-93 ℃, carry out high temperature gelatinization and liquefaction, remain to dextrose equivalent value (DE value) 30-35 or disappear to Iod R till the liquefaction degree; Conventional filtration removes slag, and slag is made feed; Filtrate is concentrated in vacuo to 30-35% concentration, adds hydrochloric acid HCl accent pH to 1.2-1.8, is carrying out sour saccharification under the vapour pressure 0.3-0.35 MPa to getting Glucose Liquid more than the DE value 90-95, as the raw material liquid glucose of zymamsis.
The dead starch of the difficulty liquefaction that generally can three sections liquefaction of image height temperature equally will form because amylum body is aging with the liquefaction of this method is fully liquefaction but do not have the hyperchromic problem of starch and when saving water and energy also, can improve sugared and alcohol yield and quality reach and significantly shorten saccharification and alcohol after fermentation time.
3, the production of zymamsis Glucose Liquid:
The raw material liquid glucose is added 10115% yellow soda ash and 1-5% magnesiumcarbonate, and to transfer pH jointly be 4.5-5.1, makes fermented liquid be slightly acidic and get zymamsis with glucose syrup, as zymamsis.
This method guarantee is fermented to alcohol but not the directions such as glycerine are carried out, and as the salt of aforementioned generation because of its solubility in water and stability all height be that good water solubility is very easily removed, the carbonic acid of generation is that volatility and decomposability are all very strong and be original product C O in the alcoholic fermentation process for instability extremely
2Also easily remove all harmless to alcoholic fermentation, the a small amount of salt that generates in addition is for promoting to ferment namely very favourable to Alcohol Production magnesium chloride, this is because generate glucose phosphorylation in the reaction (being called the E-M approach) of pyruvic acid by glucose in alcoholic fermentation process, 1, the 6-diphosphofructose, 3-phoshoglyceric acid, the generation of 2-PEP and pyruvic acid continue the reaction that decarboxylation that degraded produces ethanol generates acetaldehyde by saccharomycete under oxygen free condition all need Mg++ to activate, although also contain magnesium in the light water, but because it mainly is to be insoluble in water and magnesium bicarbonate (calcium in the aforementioned running water is also similar both mainly to be the calcium bicarbonate of indissoluble) that the sediment solubility that is heated is littler, be difficult to guarantee the need of above-mentioned reaction, magnesium chloride is all got well because of solubility and stability and is not had these defectives for the high ionized calcium of activity, then can protect the need of fermentation, as transfer pH then to generate human body and alcoholic fermentation does not need and often harmful as easily make people have loose bowels more than sodium sulphate and magnesium sulfate with sulfuric acid, easily generation can play the sodium hydrogensulfite etc. that addition generates the crystalloid acetaldehyde sodium sulfite addition product of indissoluble with acetaldehyde, force acetaldehyde must not replace it as hydrogen acceptor and generate glycerol 3-phosphate by dihydroxyacetone phosphate as hydrogen acceptor, under the 3-phoshoglyceric acid Lipase catalysis, generate glycerine and reduce alcohol output and quality, so above-mentioned these designs of the present invention and many-sided excellent effect are to realizing that Rapid Fermentation and high yield goal of the invention are necessary and being easy to implement.
4, fuel alcohol fermentation and extraction: primary fermentation is about 2-3 hour by number of yeast cells 1-5 10,000,000/milliliter (deciding on concrete conditions such as different starch source liquid glucoses) with song, disposable adding, yeast phase; For the first time main fermentation, the time is generally about 12 hours, yeast count can reach that 100,000,000/milliliter is above, temperature is controlled at 30-34 ℃ in the mash; Carry for the first time alcohol midway, when the temperature of zymotic fluid reduces gradually but not rises, the zymotic fluid temperature of this moment is controlled at 30-34 ℃, plate and frame filter press separates alcohol liquid and yeast, 30-34 ℃ of boilings of alcohol liquid negative pressure of vacuum are extracted alcohol to protect wherein yeast cells integrality and activity and vigor; For the second time main fermentation and carry alcohol midway, the mother liquor of carrying for the first time alcohol is midway returned former tank with the yeast that separates and add new sugar solution to demarcating volume, carry out the main fermentation second time and extract alcohol midway by the main fermentation first time and the first time putting forward alcohol technology midway; After fermentation and carry alcohol; The mother liquor that extracts for the second time alcohol midway returned former tank with the yeast that separates and add new sugar solution to demarcate volume, change over to after fermentation phase of being equivalent to Traditional Method and technology with operation, continue fermentation and arrive no CO
2Till the generation, this exhausts for glucose sugar and reacts and stops sign.Take turns circulation and equipment is carried out beginning new round circulation behind the cleaning and sterilizing routinely with thorough end one; The yeast slag because of be rich in (more than the dry matter weight 5-8%) RNA nucleic acid and nucleic acid very costly (more than 100,000 yuan/tons), so nucleic acid is carried in the separate case application; Last residue protein content height, event separate case application high protein high-quality feed; Discharge after the mother liquor harmless treatment environment protection standard.
Help to understand the present invention and layout and utilize more rationally to save length, be beneficial to examination and alleviate auditor and censorship amount for better, other asks for an interview following review paper about principle, details and advantage.
Traditional handicraft be with starchy material through boiling make starch be dissolved state, again through the effect generating portion fermentable sugar of aspergillus carbohydrase, in converted mash, insert saccharomycete and change sugar into alcohol and CO
2, separate to obtain alcohol product, (starch in the converted mash and dextrin continuation are by Glucoamylase hydrolysis but because of saccharification after thoroughly not the existing of liquefaction and saccharification, generate sugar) effect, also have protein further to generate the effect of low molecule nitrogen-containing compound such as peptide and amino acid etc. under the hydrolysis at Aspergillus proteinase, these materials of generation have is absorbed synthetic yeast somatic cells, another part and then is fermented and generates alcohol and CO by yeast
2And other accessory substance.Than the present invention not with slag saccharification and fermentation and only the liquefaction of a few hours and saccharification stage just finished these processes, conventional method then with slag and (primary fermentation stage more than 10 hours, after fermentation stage more than 40 hours) the very long time that needs expend surplus in the of 50 hour more just can make starch in the converted mash and the dextrin fermentable sugar of generation that continues to be decomposed; In the mash of alcohol around can any ratio mixing with water, just being dissolved in by the alcohol of discharging in the yeast body, the CO because producing in the fermentation again
2The littler karusen of solubility is will soon be by it saturated and be adsorbed on yeast cell surface until its CO when surpassing the cell adsorption capacity
2Become gaseous state, form little bubble rising, again because CO
2Bubble mutually collides and forms larger bubble and effusion liquid level, CO
2The rising of bubble has also driven the material in the mash and with the yeast cells wander up and down yeast cells can have been contacted more fully namely to be equivalent to increase reactant concentration so that fermentation is faster more abundant and thorough with sugar in the mash, and alcohol is scattered in more namely be equivalent in the liquid reduce product concentration and Alcohol Production speed is accelerated, such fermentation is called the passive type fermentation, if but fermentation liquid than thickness then bubble to arrive the foam that does not break behind the liquid level and forms lastingly diffusing, sometimes foam also may be overflowed by tank deck and cause sugar loss, such fermentation is called bubble and smears fermentation, and oxygen is many even saturatedly also the bubble fermentation phenomenon can take place in the medium, this mainly is because the undue strong breeding of yeast and undue strong fermentation and karusen are done raw material or the song poor quality causes with fresh potato is dried, increase operation and cost though the employing defoamer can be prevented planting here phenomenon also time-consuming bothersome.The present invention's oxygen expenditure in Traditional Method Yin Changwen and the stock media that liquefies for a long time is slow, add big with the contact with air face and the time long so saccharified liquid contains the oxygen height, also greatly easily cause bubble fermentation because of the not thorough viscosity of liquefaction, saccharification, the present invention because of High-temperature Liquefaction, saccharification so gassiness, to contain oxygen all low, and because of liquefaction, the low bubble breaking loose of the thorough fermentation broth viscosity of saccharification, again because of the fast output height of the big fermentation of concentration, quality better, cycle weak point.Thus also visible serial advantage of the present invention and novelty and the importance in alcoholic fermentation is produced thereof.
Distillery yeast does not contain the amylase such as AMS and beta amylase and lactase and can not directly utilize starch or lactose to carry out alcoholic fermentation, therefore must change into fermentable sugar to starch when utilizing starchy material to produce alcohol and could be used to carry out alcoholic fermentation by yeast.Alcoholic fermentation process can be divided into it following three fermentation different stepss by the outward appearance presentation:
The primary fermentation phase is when distiller's yeast and converted mash adding fermentor tank, because of containing minimal amounts of dissolved oxygen and sufficient nutritive substance in the also few and aforesaid mash of the yeast count in the mash, yeast still can be bred rapidly, dextrin in the tradition method mash also continues to be generated sugar by Glucoamylase hydrolysis, but Yin Wendu turns into slow than low sugar, sugar consumption is also few slow because of yeast count, be generally perdurability about 10 hours, because the not strong mash temperature of fermentative action rises unhappy, this moment, the mash temperature was controlled at 26-30 ℃, the too high meeting of temperature causes yeast old and feeble in early days, crossing to hang down to make yeast growth slow again, this phase yeast quantity is easily suppressed to pay close attention to prevent living contaminants by assorted bacterium less, so should strengthen hygiene control.The inventive method is because of no slag and liquefaction, saccharification thoroughly reaches features such as sugared concentration height, can easyly take directly to improve yeast quantity with respect to traditional method is 1-5 10,000,000/milliliter (deciding on particular cases such as different starch source liquid glucoses) and significantly to reduce the primary fermentation phase that reaches more than 10 hours be only about 2-3 hour and therefore effectively prevent, control incident living contaminants of this phase and pour in down a chimney loss and encircle dirty consequence, though initial apparently with the many and cost height of the bent more traditional method of amount (1,000,000 grades), but the time of saving with the present invention and the specially designed reduction resultant of the present invention concentration and yeast are the touring fermentation of mother liquor to be used and not with slag with specializedly produce the production capacity that the high vigor liquid yeast event of high cell count need not the primary fermentation stage and be difficult for feature (asking for an interview following) raisings such as microbiological contamination and compare then and can ignore with the bent medicine of the output value and saving.
This time phase of lord ferment period is generally about 12 hours, yeast count can reach more than 100,000,000/milliliter in the mash, because the oxygen expenditure in the karusen is complete, saccharomycete stops to breed and mainly carrying out anaerobic basically is the alcoholic fermentation effect, sugar rapid decrease, alcohol divide and CO in the mash
2Increase gradually, the temperature of karusen rises also very fast at this moment, should strengthen in the production temperature control of this one-phase, preferably can be controlled at 30-34 ℃, this is the suitableeest fermentation temperature of distillery yeast, temperature Tai Gaoyi makes the early stage aging of yeast, lowers yeast activity and easily cause germ contamination, the easier generation that causes the microbiological contamination phenomenon when especially being higher than 37 ℃ with the karusen temperature.The inventive method is not with slag and saccharification thorough because of saccharified liquid, with Traditional Method band slag and liquefaction and saccharification all not completely with the concentration zymotic fluid compare its reactant be high nearly 1/3, the main fermentation of sugared concentration be the main product time therefore than Traditional Method increase nearly 1/3, production capacity is also corresponding with output increases than Traditional Method, add because not being with slag not only to liquefy thorough with saccharification, and liquefier and saccharified liquid concentration can exceed one times with the concentration of slag 13-15% up to 30-35%, ratio tradition, the viscosity that adds zymotic fluid is low, good fluidity and ferment fast, although fast because fermenting, produce (CO
2) the many and alcohol taken away of gas also many (recovery gets final product, needn't process especially routinely) but still far be not enough to balance, so alcohol generation and dissolving are also many in the zymotic fluid, make its alcohol concentration corresponding than the Traditional Method height, can suppress more by force yeast activity and reproductive capacity and fermentability and speed, so special design of the present invention main fermentation midway to zymotic fluid carry out yeast and wine liquid separate with get wine, the yeast after will separating and the mother liquor of getting after drinking return the technology of carrying out circulating fermentation again.Its principle, necessity and advantage are replenished and to be described below: when the temperature of zymotic fluid reduces gradually but not rises, show that fermentation begins to weaken the heat that namely produces and begins to reduce, sugared content in zymotic fluid this moment is described and the alcohol content rising, because of the two all slow down fermenting speed and alcohol concentration also than Traditional Method height, harm to yeast is just big than Traditional Method, and yeast vigor and proliferative ability at this moment is all just strong, the zymotic fluid of this moment is separated alcohol liquid and yeast with the filter-pressing process that keeps the yeast cells integrality, alcohol liquid negative pressure of vacuum boiling extracted that alcohol has utilized alcohol than the much lower principle of water boiling temperature and energy-conservation, above-mentioned mother liquor and the yeast that separates are returned former tank and add new sugar solution and carry out secondary fermentation to demarcating volume, yeast quantity and proliferation potential in the zymotic fluid can make it again carry out immediately main fermentation at this moment, can go round and begin again in theory and set up benign cycle, but actual from the decay of the continuous dilution of considering living contaminants probability and sugar concentration and the production capacity such as yeast activity and proliferative ability, after finishing twice circulation main fermentation and extracting alcohol midway, change the after fermentation phase (asking for an interview aftermentioned) that is equivalent to Traditional Method over to and take turns circulation with thorough end one, and equipment carried out beginning new round circulation behind the cleaning and sterilizing routinely.Do like this and save in addition song and namely save grain and when joint (one with three, than 2 times at Traditional Method joint), wash number economize on water less and environmental pollution little (three one-periods, only be the Traditional Method of an one-period such as gap method 1/3), in case each fermentation tank is an independently reactor and can just not causing synchronously comprehensively or the serial main advantages such as large tracts of land stopping production, the underproduction or Quality Down because of many fermentation tanks series connection cleanings, maintenance or microbiological contamination as continuous fermentation method.
Sugar major part in the after fermentation phase mash is consumed by saccharomycete, and still remnant dextrin continuation is by the amylo-1:4,1:6-transglucosidase in the song in the mash, and the effect of 41,6-glucuroide generates glucose.Because the very slow steamed bun that this effect is carried out, the sugar of generation are seldom, so fermentation is also very slow.Therefore, alcohol and CO2 produce also fewly in this stage fermentation wine with dregs.
The secondary fermentation stage is because of traditional method band slag fermentation and liquefaction, the not thorough and sugared concentration of saccharification is low, fermentative action weakens but this stage sugar after Primary Fermentation exhausts substantially, the heat that produces also reduces, the temperature of karusen descends gradually and ethanol concn is still not high enough, alcohol needs the secondary fermentation stage so that because of liquefaction and the not thorough and remaining partial starch of saccharification so traditional method starchy material is produced, dextrin continues saccharification during the fermentation to improve the rate of getting alcohol, and this moment, the mash temperature should be controlled at about 30-32 ℃, if the mash temperature is too low, the effect of saccharifying enzyme will weaken and saccharification is slow, fermentation time will prolong, also can influence the rate of getting alcohol.But nonetheless, after fermentation generally still needs about 40 hours very long time just can finish approximately; The alleged after fermentation of the present invention then is because of the liquid glucose of twice circulation main fermentation dilution and above-mentioned for finishing a circulation main fermentation cycle, being fermenting speed 5-10 hour slightly slowly with respect to main fermentation, and this stylish liquid glucose that adds and amount can regulate and control the after fermentation cycle and have very big flexibility and controllability, operability is very strong, so with above-mentioned Traditional Method Starch Hydrolysis and saccharification halfway more than 50 hours long-time after fermentation essential distinction is arranged, all big such as great disparities such as unit interval material treating capacity and alcohol outputs.In addition, although the continuously fermenting of traditional method is in also at the beginning that the Primary Fermentation state promptly also saves the primary fermentation phase than the batch fermentation time for short, but because of saccharification and secondary fermentation total time long (saccharification about 50 hours, fermentation about 60-72 hour, about ATT 115 hours), exceed more than 90 hours about 20 hours than the present invention, deduct that aforesaid the present invention is formerly liquefied and 20 hours of expending approximately of saccharification, still exceed more than 70 hours, so its advantage highly significant still.
Secondary fermentation finishes, method is extracted alcohol routinely, the yeast slag is reclaimed in the mother liquor press filtration, because of compare with traditional secondary fermentation band slag thickness and bulky moisture high mother liquor, especially organic content seldom, short cost of low cycle of harmless treatment oxygen-consumption is low for this mother liquor, so very easily handle the environment protection standard discharging, the yeast slag is quality protein and nucleic acid (RNA) source, can fully utilizes, and stays in other application for a patent for invention and sets forth.
The inventive method also has following main advantages:
1, directly adopt Chinese sorghum make a living malaga sugar starting raw material rather than adopt commodity starch or traditional corn, rice, potato, help enlarging renewable energy source and raw material sources thereof, help the enforcement of national food stability and development renewable energy source and the great state basic policy of rejuvenating the northeast, because of China northeast and national many places all abound with Chinese sorghum, it is not again the daily staple food grain of China people, only Chinese sorghum is made sorghum flour breast (dry grinding method) rather than makes starch milk or starch, help reducing the dust discharge in organic waste water discharging and the drying process, thereby great lot of water resources and energy consumption are saved in the minimizing environmental pollution, the grain consumption; Save factory building, equipment and labor force, improve yield, reduce cost, shorten the production cycle, avoided pollution microbes to become sour and caused loss.
2, rationally utilize enzyme process and acid system to produce glucose advantage and use built-up sequence separately, overcome their shortcomings separately, constant product quality, the short quality of saccharificatinn period is good, and the yield height is so the market adaptability is strong.
3, because of the α-Dian Fenmei in any source all can be cut maltose, the direction unicity and the thoroughness that add acid hydrolytic reaction are very strong, enzymatic liquefaction and acid saccharification all seldom produce difficult disaccharide that utilizes of yeast such as maltose etc., and traditional enzyme glycolysis only contains a α-1 because of saccharifying enzyme is difficult to hydrolysis, the isomaltose of 6 keys, to containing two α-1, the isomaltose of 6 keys then fully can't hydrolysis, add that saccharifying enzyme can cause that the polymerization of glucose and its extent of polymerization also increase with sugared concentration and enzyme concn, transform the about 1-3% of (alcohol) rate and improve throughput and alcohol recovery rate and reduce cost so the present invention is beneficial to behind the further saving alcohol diastatic fermentation time and improves starch.
4, with the Chinese sorghum be starting raw material, adopt the method for enzyme acid direct production glucose only to need Chinese sorghum is made the newborn glucose that is converted into step by step of sorghum flour, Ye Huamei hydrolyzed starch under 85-93 ℃ of high temperature only takes at 1.5 to 2.5 o'clock, saccharification under vapour pressure 0.3-0.35 MPa pressure also only 20 to 25 minutes.
5, this project changes into the generation of adopting earlier enzyme to liquefy to prevent or reduce accessory substance in the glucose process at starch, and rear employing acid saccharification guarantees the stable of product quality and performances.
6, this project sorghum flour breast concentration easily regulate, according to raw starch and water content and water swellability direct regulation and control water consumption, so but direct regulation and control liquefier and be used for transforming glucose concentration.
7, the used enzyme of this project enzymatic liquefaction and acid saccharification production glucose is the high temperature a-amylase of sophisticated large-scale industrial production, and used acid is similarly the hydrochloric acid of large-scale industrial production so raw material is secure and cost is low.
8, this project α-amylase and saccharification acid consumption is few, calculates, reaches 1.2-1.8 calculating with the acid amount by pH value of saccharified liquid by 50-60 units/gram over dry starch with the enzyme amount.
Embodiment:
1, powder emery mill under the red sorghum normal temperature is added tap water levigate (rotating speed is 600 rev/mins) and become the powder emulsus, the control concentration of slurry is about 30%.It is 6.5 that calcium carbonate or hydrochloric acid are transferred PH; The disposable adding α-amylase (press a-amylase 50 units/gram over dry starch and calculate the enzyme amount that always needs) of required total amount that liquefies in liquefier, 90 ℃ of lower liquefactions about 2 hours, Iod R is disappeared, plate and frame filter press filter and remove residue (slag is made feed or food protein raw material), using HCL to transfer pH in stainless cylinder of steel is 1.5, and sour saccharification after 20 minutes under 0.3 MPa vapour pressure, jointly transferring pH with 10% sodium carbonate and 1% magnesium carbonate is 4.9, and evaporation and concentration is 1.3450/45 ℃ concentration to proportion under 0.06 MPa; By number of yeast cells 2,000 ten thousand/milliliter bent, disposable adding, temperature is controlled at 33 ℃; When the temperature of zymotic fluid reduced gradually, plate and frame filter press separated alcohol liquid and yeast, alcohol is extracted in 33 ℃ of boilings of alcohol liquid negative pressure of vacuum; Mother liquor returns former tank with the yeast that separates and adds new sugar solution to demarcating volume, and plate and frame filter press separates alcohol liquid and yeast, alcohol is extracted in 30-34 ℃ of boilings of alcohol liquid negative pressure of vacuum when keeping 33 ℃ to continue fermentation, temperature reduction; Mother liquor returns former tank with the yeast that separates and adds new sugar solution to demarcating volume, change after fermentation phase of being equivalent to Traditional Method and technology and operation over to, continuing fermentation to no CO
2Till the generation, take turns circulation and equipment is carried out beginning new round circulation behind the cleaning and sterilizing routinely with thorough end one; The yeast slag is reclaimed in the mother liquor press filtration, and harmless treatment is to the environment protection standard discharging, the yeast slag because of be rich in (more than the dry matter weight 5-8%) RNA nucleic acid and nucleic acid very costly (more than 100,000 yuan/tons), nucleic acid is carried in former separate case application; Residue protein amount height, event separate case application high protein high-quality feed.
2, powder emery mill under white (glutinous property) Chinese sorghum normal temperature is added tap water levigate (rotating speed is 800 rev/mins) and become the powder emulsus, the control concentration of slurry is about 30%.It is 6.5 that calcium carbonate or hydrochloric acid are transferred PH; The disposable adding α-amylase (press a-amylase 60 units/gram over dry starch and calculate the enzyme amount that always needs) of required total amount that liquefies in liquefier, 90 ℃ of lower liquefactions about 2.5 hours, Iod R is disappeared, plate and frame filter press filter and remove residue (slag is made feed or food protein raw material), using HCL to transfer pH in stainless cylinder of steel is 1.5, and sour saccharification after 20 minutes under 0.3 MPa vapour pressure, jointly transferring pH with 10% sodium carbonate and 1% magnesium carbonate is 5.1, and evaporation and concentration is 1.3450/45 ℃ concentration to proportion under 0.06 MPa; By number of yeast cells 2,000 ten thousand/milliliter bent, disposable adding, temperature is controlled at 33 ℃; When the temperature of zymotic fluid reduced gradually, plate and frame filter press separated alcohol liquid and yeast, alcohol is extracted in 33 ℃ of boilings of alcohol liquid negative pressure of vacuum; Mother liquor returns former tank with the yeast that separates and adds new sugar solution to demarcating volume, and plate and frame filter press separates alcohol liquid and yeast, alcohol is extracted in 30-34 ℃ of boilings of alcohol liquid negative pressure of vacuum when keeping 33 ℃ to continue fermentation, temperature reduction; Mother liquor returns former tank with the yeast that separates and adds new sugar solution to demarcating volume, change after fermentation phase of being equivalent to Traditional Method and technology and operation over to, continuing fermentation to no CO
2Till the generation, take turns circulation and equipment is carried out beginning new round circulation behind the cleaning and sterilizing routinely with thorough end one; Mother liquor and yeast slag are pressed embodiment 1 and are processed.