Corn high-low-temperature rapid soaking wet-milling residue-less fermentation extraction of fuel alcohol method
Technical field: the invention belongs to agricultural byproducts deep processing, sugar and alcohol industrial field.
Background technology: it is especially main with main body and be that non-renewable fossil energy oil, coal resource are day by day and obviously fast under the severe situation of exhaustion constantly to face the energy the mankind; Renewable energy source particularly rapid research and development and the subject goal that extensive industrialization has also just become countries in the world and area competition naturally thereof of bioenergy with one of task and representing its true national power, be one of great sign and standard of the strong and weak and sustainable development ability of national national power of internationally recognized multifactorial evaluation; The renewable energy source so all spare no effort to research and develop in various countries, the world and area; As China's Eleventh Five-Year Plan outline etc. clearly regulation greatly develop renewable substitute energy and reach in the agreement of working in coordination aspect the renewable substitute energy technical development with the same genus energy consumption big country U.S.; Also clearly the regulation technical research that will strengthen renewable energy source energetically and deposit, its each ministries and commissions are also all numerous and confused has formulated and issued serial policy, the file of supporting enforcement with it successively for State Council's energy state basic policy, first develop especially great state basic policy such as fuel alcohol of the recyclable organism energy like National Development and Reform Committee.It is obvious 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 prodn 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 basically all are on traditional wine and alcohol basis, slightly to improve and do not have an important breakthrough; Heighten like production cycle of very long (more than 60-80 hour) and corresponding investment wait, all be to restrict seriously that fuel alcohol develops rapidly and by the bottleneck that present technology is difficult to go beyond, cause it far can not meet the need of market let alone " substituting " oil; Though corn etc. are than the slag much less of potato class, 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 as follows, for your guidance with the usefulness of easy analysis: take a broad view of present wine and Alcohol Production; Its fermentation is broadly divided into solid-state and liquid two big types, is broadly divided into by technology and is interrupted and continuous two big classes, other is as semicontinuous etc. then belonging to intervenient transitional type, do not have significant essential distinction basically by states of matter, and it gets wine, and then basically all to belong to disposable be ripe method-at every turn just get wine one time after the fermentation ends; The alcohol that solid state fermentation raw material water content is few far beyond the liquid state fermentation raw material, produce in the yeast body wait a moment for a short time because of the raw material water content is few and mobile, be difficult to diffusion rapidly be accumulated in the yeast cells body and nearly week dense; Be understood that based on the product enzyme reaction principle that suppresses promptly to slow down the solid state fermentation cycle is long, generally need several months and even nearly 1 year and often need ferment again several times and get that wine such as Maotai needed nearly 10 months and 6-8 fermentation and get wine and could accomplish; Though the solid state fermentation cycle is long; But widely adopted with the characteristics such as expensive that remedy length consuming time with the generation that increases the very long batch (-type) solid fermentation of quality and be beneficial to these materials and accumulation and complicated more each other reaction and product and high-grade wine valency your pupil and accounted for the main flow and the principal status of public economy so far and still because of drinking the accessory substance that also needs in the wine to produce in some alcoholic fermentation process such as aroma-producing substance etc., distill and drink wine such as high-quality world's famous brand of wine Maotai, five-Grain Liquor, Jian Nan Chun, Luzhou Old Cellar etc. like the existing higher middle and high shelves of valency that still are widely used in.Yet the intermittent type solid state fermentation and concerning top grade be high price drink advantage the wine obviously be not suitable for fuel alcohol and low-grade be the production that low price is drunk wine; Because at first the production cycle long causes cost significantly to improve and its city's 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 of producing in the fermenting process such as glycerine (mainly being to be produced by yeast in the very long fermentation later stage), potato spirit (pyruvic acid that glucose fermentation generates and amino acid such as Gelucystine effect generation fusel main body of oil primary isoamyl alcohol; 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), succsinic acid (glucose and L-glutamic acid generate, also generate simultaneously glycerine) can expend sugar and reduce alcohol output; The 4th is that long-time tight airtight heap fermentation produces more heat transfer and is difficult to again distribute when causing leavening temperature to be higher than 37 ℃ and is prone to pollution microbes such as acetic bacteria (directly consuming alcohol) and generates that acetic acid, milk-acid bacteria (consuming pyruvic acid glucose) generate lactic acid, butyric acid also is higher than yeast optimum temperuture (30-34 ℃) by glucose and Yin Wendu and suppresses saccharomycetic breeding and all reduce alcohol output with activity, these factors; The 5th is also to need when distillation, from alcohol, isolate 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, and the 6th is that the solid-state stepwise fermentation operation of intermittent type and workload repeat to increase times and consumption bent (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 that can not be transformed into alcohol mostly and consume grain; 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 " with oxygen getting into weakening zymamsis ability and output and increasing oxygen consumption fermentation and product as poorly sealed surface in the fermenting process is withered, carrying repeatedly, loosely get alcohol and quality and the output such as " opening gas " that vinasse that ferment that wine uses promptly are commonly called as alcohol and a large amount of volatilizations of aroma-producing substance) lose.More than these factors result single and comprehensive action cause alcohol yield to reduce and the cost increase.
Though liquid state fermentation have be interrupted, 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 is accomplished fermentation once and is promptly abandoned material after drinking 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 promptly to let starch in the raw material change into glucose sugar as much as possible and make conversion of glucose equally as much as possible is alcohol, and these processes all require continuously once the completion of (one-period) property.During with respect to aforesaid solid-state intermittence for the fermentation; Liquid state fermentation truly has high and therefore have certain flowability to make alcohol be easy to dissolve again and comparatively be evenly distributed in the whole liquid, alcohol meltage and content in the liquid are heightened because of moisture content; And therefore reduce the inner and nearly all ethanol concns of yeast, the enzyme reaction rate that causes generating alcohol because of resultant be ethanol concn reduce to be able to accelerate to shorten fermentation period; And various alcohol losses and the grain consumption and the cost that reduce aforesaid solid-state batch fermentation increase, thereby overcome basically or avoided above-mentioned solid-state batch fermentation to be difficult to the serial critical defect and the key restraining factors of low-cost large-scale industrialized production fuel alcohol.But with respect to fuel alcohol high-purity and high yield and the fast series of speed of production is crucial require with bottleneck for, liquid state fermentation at present still has serial major defect; Cause the starch hydrolysis rate slow like boiling, not thoroughly (is non-glucose as producing 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 and equally significantly reduce alcohol output like primary fermentation (more than 10 hours) especially after fermentation (more than the 40 hours) time for hydrolysate; Starch and dextrin expand and increase liquid viscosity and reduce its flowability, reduce surface exchange area and the exchange velocity of liquid and yeast and slow down alcoholic fermentation lengthening rate production cycle and easy so pollution microbes and reduce alcohol output and quality; Have only the high cost that increases the yeast consumption effectively to overcome; Or reduce liquid material concentration to reduce toughness and increase mobile but this also must be to be that output is so that cost is high equally to reduce unit interval alcohol growing amount; Though above problem can pass through in the prior art that the agency part of aspergillus carbohydrase generates fermentable sugar and in alcoholic fermentation process the starch in the converted mash continue by the i.e. back saccharification of Glucoamylase hydrolysis with dextrin, 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 following band slag to ferment for fermenting behind the glucose and defectives and more serious such as accessory substance again; The more important thing is band slag boiling and ferment that not only treating capacity is too big; And, volume takies equipment and factory building dischargeable capacity and time, space in a large number because of heightening; Significantly increase simultaneously and can consume with ring dirty by water consumption; Be that glucose reduces alcohol output also, and need expend glucose sugar as described above equally and generate fuel alcohol and do not need and influence 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 because of a large amount of proteolysis in the slag cause the thalline excessive multiplication to expend the too much energy.Above-mentioned serial problem is not as resolving, and the enforcement of Fuel Ethanol Industry and the industry great state basic policy of the inevitable serious national renewable energy source 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 rate of advance and paces yet.
The state-of-the-art technology progress is transformed traditional technology of alcohol for adopting immobilized cell technique at present; The tool fixed yeast is reusable, time limit of service more than 160 days, anti-assorted bacterium ability need not sterilize by force, no longer need that distiller's yeast is cultivated, fermentation time shortens that half fermentation equipment throughput improves more than 1 times, liquor output rate improves characteristic and advantages such as about 5% than traditional zymotic technology under equal fermentation condition; Conclude and get up to see mainly be to reduce with song and cultivation, grain consumption and forward and backward fermentation time; But the scale prodn ability of immobilization technology then less because of the processing power that receives the immobilization post with the restriction more high core sexual factor of cost price very limited and in a short time difficulty have essence to break through or take on a new look; Add its still fail to resolve saccharification and purity and concentration, especially aforesaid National Development and Reform Committee intend the band slag of adjustment and handle big, the high serial main body problem of the big cost of the low investment of equipment factory building utilization ratio and the 11 5 years development planning outline of the government work report and country in the energy consumption that limits of hard and fast rule, water consumption, the dirty rigid index of ring etc. be the serial difficult problem of bottleneck equally, be difficult to be applicable to fuel alcohol need extensive, low cost prodn must with the basic demand condition.Also has energy-conservation raw material direct fermentation at present; But fermentation period needs a couple of days in the above cycle to grow up to this height; Fermentation load and treatment capacity are too big with volume, are prone to microbiological contamination, rotten, corruption etc., and be therefore all little as far as low-cost indispensable requirement feasibility of fuel alcohol high-yield quick and meaning.
Along with the growth of industry such as population and industrial and commercial service and desertification occupation of land, 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 reach 10 months, remaining 2 months because of the basic growth and the event of maturation cycle that are shorter than any main energy sources property farm crop such as carbohydrate beet, oils rape and leguminous crop or starch main source cereal class and tuber crops etc. its to have exhausted perennate basically long-term; Causing main flow carbohydrate sucrose price constantly to rise, force 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 be temporary transient, because national treasury and ability of regulation and control thereof are always limited with the regulation and control space, have only fundamentally to solve sugared source and originate and just can reach the regulation and control purpose.Dian Fentang then is that the only way is selected with wise; 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 higher glucose of nutritive value or quality higher, sweeter high fructose syrup (slurry) and fructose, add the ability large-scale industrial production so price is 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. also should and can become inevitable choice and development general trend.The method patent of invention prospectus of CN1070425A maize enzyme acid direct production glucose sugar is exactly to comply with of this trend well to attempt: it remove slag promptly earlier the raw material processing become starch slurry or just starch, again according to the specificity principle of enzyme adopt three sections liquefaction of high temperature enzyme and sour saccharification promptly not with the direct high-quality of slag fast (with respect to after for acid, sour enzyme and the full-enzyme method stated) production glucose; Thereby high smart starch of traditional acid system call for bids and high-temperature high-pressure apparatus have been overcome and with dirty heavy, the problem such as complex reaction is serious and amount of by-products is big of the big ring of acid amount; Also overcome improved method acid-enzyme hydrolysis method (low with sour amount and temperature and by product), especially full-enzyme method and taken shortcomings such as long than acid system; But its wet-milling legal system starch slurry technology still must consuming timely reach 48-72 hour; Starch runs off greatly, the water consumption is also big with the ring dirt; Starch slurry is handled the untimely microbiological contamination, rotten, corrupt that also is prone to; The dirty die valency of ring is high, also water consumption is converted into starch slurry again because of need power consumption drying and because of dried dust loss yield hangs down for starch; Sulphur (is prone to short glycerine and generates reduction ethanol production and yield etc. human body and zymamsis is unfavorable in the immersion anticorrosion process; See after and state-corn high-low-temperature rapid soaking wet milling process production milk of starch) and lactic acid is more expensive and acid weak consumption is greatly also unstable; And no matter the enzyme-added enzyme that kills again of three sections liquefaction processes of its wet milling process or dry grinding method is valuable and the expensive enzyme wasting of resources; The intensification that matches, cooling and insulation be corresponding also increase energy consumption, the time consumption and (cooling and insulation) water consumption; The more important thing is to be heated to 120-140 ℃ and reach 5-8 minute starch denaturalization coking color depth, refining difficulty of liquid glucose and yield (comprising that fermentation is like alcohol) are descended, thus all fail to resolve saccharification and fermentation reach serial great difficult problems such as thorough fast.
Summary of the invention:
Goal of the invention: the present invention is exactly for solving the corn high-low-temperature rapid soaking wet-milling residue-less fermentation extraction of fuel alcohol method that above-mentioned serial problem designs, and the invention solves above-mentioned three aspects all and be existing newer documents (requiring to many) also unsolved altogether serial problem such as saccharification far beyond the convention that generally is no more than three pieces of documents quick, thorough, pure and be not with slag make fermentation same quick, thorough, by product is few, yield is high, quality better; The slaking simultaneously of Substratspezifitaet high temperature enzyme liquefaction and remove that the toxicity that removes slag makes that it is safer, nutrition and mouthfeel better and feed value is high; Also thoroughly make saccharification and fermented liquid concentration height that alcohol output is significantly improved, the more important thing is to have solved traditional cooking liquor because of high-leveled and difficult huge workload and high energy consumption, the water that must be with slag to handle with the separation slag of viscosity consumes, ring is dirty and serial historic difficult problems such as with high investment and cost qualifiedly have the at present technological irreplaceable great innovation of above-mentioned series, advantage and advantage equally because of liquefying.Now again with the innovation brief introduction of main scientific and technological principle of the present invention and other outbalance: 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 selectivity ground with the starch in the raw material rapidly and thoroughly liquefaction and to other compositions inoperative and slaking simultaneously 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 of the viscosity of the thorough liquefier that liquefies is low so the separation of slag is easy, and the slag after separating because of low volume of water content and weight all little again not thickness be prone to transportation and freight volume is little, be prone to dry 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 of saccharification liquid is not with slag purity high, thus adopt the aforesaid enzymatic conversion of acid substitution to make to handle easily and fast, as enzymatic conversion need 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 because of glycerine in the alcoholic fermentation later stage; Though especially the later stage maybe because of living contaminants such as acetic acid bacteria produces acetic acid but it is a volatile acid in alcoholic fermentation; Possibly pollute also 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; Though tradition can keep stable acidity of later stage but can produce the material (stating after seeing for details) that people and environment and alcoholic fermentation all be harmful to particularly of full phase of alcoholic fermentation with non-volatile acid sulfuric acid, direct fermentation alcohol does not afterwards have these shortcomings and tool is economized on main advantages such as acid (stating after seeing for details) and the present invention reaches with the hydrochloric acid saccharification; Of paramount importance is need utilize the zymotic fluid nutriment like sugar (starch-containing with dextrin etc.), protein and amino acid, micro-like proliferative cell quantity such as magnesium because of yeast; And if the nitrogenous source that easy utilization is arranged in the karusen exists then can stop or postpone disintegration and the amino acid whose decomposition of yeast and therefore and the fusel oil (introducing before its mechanism) of generation; The height selectivity that adds catalyzed by amylase promptly kept except that starch other all nutriments and as above-mentioned compositions such as its catalysate sugar can be used for cell proliferation by yeast, liquefier and the remaining macromolecular substances such as protein of saccharification liquid also are catalyzed into the small-molecule substances such as nitrogenous source that amino acid is above-mentioned easy utilization when being saccharification in conjunction with acid catalyzed broad spectrum activity again; So enzyme liquefaction and sour saccharification not only the time short and all be not with the slag treating capacity little and concentration is high because of liquefier, saccharification liquid and zymotic fluid; 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 beneficial to fermentation alcohol and improving quality and make liquefier and saccharification liquid all need not make with extra care, significantly reduce once more treating capacity and the ring dirt significantly saves time and cost because of above-mentioned materials such as the remaining protein of need supply acidolysis and acid hydrolysis products thereof; In addition, the present invention with its fast and the sour saccharification liquid of low-cost production replace the long-time enzymatic conversion liquid of tradition improve force of labor also be the successful Application enzyme-to-substrate agree with can carry out immediately and accelerate the enzyme reaction principle in the goal of the invention of alcoholic fermentation production practices and theoretical and serial major application thereof be worth as save primary fermentation basically 10 hours, after fermentation 40 surplus hour altogether surplus in the of about 50 when hour very long time and Yin Jie, energy-conservation, water saving, grain consumption and to encircle dirt little and can effectively prevent living contaminants and improve alcohol quality and yield etc.
Also What is worth mentioning is that 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; It is existing also with cardinal principle and advantage brief introduction: no matter which kind of liquid state fermentation alcohol method all is to treat (solid-state then is each) the disposable extraction alcohol after the completion that ferments at present; The surface sees that it seems the technology advantages of simple but analyzes a little and will find at an easy rate that its shortcoming much but also very serious; It is as space is limited, existing that only to make concise and to the point comprehensive analysis for reference: the principle that enzyme reaction is carried out towards the product direction based on above-mentioned reduction product concentration is counter push away can know product and concentration thereof can seriously hinder fermentation promptly reduce the alcohol formation speed and often first limiting factor, it is that the influence of concentration of substrate sugar is much bigger than reducing reactant; Because sugared concentration is low just to reduce the product speed of alcohol, yeast itself is safe from harm promptly can therefore weaken the internal ability and the potentiality of its fermentation; And improving constantly along with alcohol concentration; Its one side feedback ground suppresses promptly to reduce product wine speed but this also only is equivalent to the influence that above-mentioned sugar reduces; Prior also be alcohol can cause 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 40 hours of the originally very very long as liquid phase process of traditional handicraft, tens of days of solid state process and even the after fermentation process more than the several months 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 heighten and significantly reduce production capacity, must be with in proportion increase equipment and factory building at least (look production capacity, yield and quality more than 30% and even at double) and invest and remedy for high cost because of fermentation period length takies volume of equipment and plant area; In addition; Fermentation time long with mother liquor comprise wherein yeast can not or low grade of recycle and reuse rate will cause its energy consumption, grain consumption, ring dirt and water to consume loading etc. increasing the weight of synchronously and unfavorable falling can be lowered consumption and the enforcement of environmental protection state basic policy; Therefore production cost also can heighten and weaken produce market share and competitiveness, and this place of lifeblood of enterprise and product just.
This raw materials technology and liquefaction, saccharification treatment technology make full use of enzyme effect specificity principle and good zymin, enzymatic hydrolysis (90 ℃) under comparatively high temps is carried out, thereby solved the realization that directly feeds intake; Received the effect of starch-liquefying rate more than 97%, protein is easy to separate with starch, filters easily; Liquefier glucose (DE) value is up to 28-30, make saccharification react very rapidly with thoroughly, reach in original technology that saccharification period shortens to several hrs more than 50 hours thereby make; And make liquefier quality height in the production process; High purity, by product is little, has solved double-enzyme method basically and has injected sugared clarity and be difficult for shortcoming up to standard; Make production injection, oral, edible and industrial sugar in same set of equipment, produce and come true, for production has brought great handiness.In addition; Because the refining back of liquid glucose DE value is more than 99.5; Oral glucose with this liquid glucose production need not crystallization just reach FCC-" U.S.'s edible chemical code " standard and China Ministry of 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 more than 70 hours crystallizing cycle of old technology shortens about 8-12 hour yet, and this technology do not play destruction to the protein in the raw material etc., only play inspissated; The liquefaction slag is the mash concentrate that slaking and toxicide mouthfeel (palatability) are good, nutrition is very abundant, is ideal food and feed development basic resource.
Below all be important principles, innovation and advantage thereof, advantage and the guarantee that the present invention improves fermentation capacity and alcohol output and quality systemicly; Especially output and quality, energy-saving and water-saving, control ring are dirty to have solved simultaneously, investment and cost etc. comprehensively, imitate a grand simple again serial historic difficult problem and can be rated as difficultly, be catalyzed reaction direction and reactant and resultant mutual relationship principle headed by the value of production practice with comprehensive scientific and reasonable and flexible Application specificity (glycase) and non-specificity (hydrochloric acid) catalyzed reaction and core mechanism thereof again wherein.
Description of drawings:
Fig. 1 is the process flow diagram of Technology of the present invention.
Embodiment:
Below in conjunction with accompanying drawing the present invention is described further.
The inventive method is following.
1, the corn high-low-temperature rapid soaking wet milling process is produced milk of starch: commodity corn is sieved to remove sand, foreign matter and granule; Soak.Make starch granules and protein be easy to separate for shortening soak time with preventing the organism corruption and destroying the protein net; Hydrochloric acid soln (temperature is in 45-55 ℃ of scope) with 0.1-0.4% soaked 1-2 hour; Be warmed up to 75-85 ℃, partly moisture about 60% up to plumule, endosperm is moisture about 38-43% partly; The moisture about 45-50% of whole kernel corn is with the very easy strip off corn grain of nail; Separated plumule and kind skin (the two often connects together); Universalpulverizer with sieve plate is housed is broken into the 6-8 lobe with corn grain; Again with the germ separation device with plumule and skin with after corn grain and milk of starch separate; Plumule is through washing, except that dry rapidly peeling behind the destarching is used for oil expression, and the water evaporation concentration of bubble corn becomes steeping water to be used as the microbiotic substratum; 800-1000 rev/min of hard water of powder emery mill rotating speed under the normal temperature (it is active and stable that institute's calcic improves following high temperature Ye Huamei) is levigate like tap water, concentration is about 30-35%; Whizzer separates (rotating speed 1000-1500 rev/min) milk of starch and corn protein (yellow slurry) and slag; Starch quality can reach primary standard (fat, protein contnt are below 0.1%); Yellow slurry whiz gets Zein powder and is rich in carrotenoid; Be good food and medicine raw material, slag is made feed; Can produce medical glucose-injection sugar and oral glucose, when save than CN1070425A 45-70 hour, improve (comprising the mother liquor that crystallization extracts after the injection sugar ferments) alcohol yield (sulfur-bearing and do not have aforesaid glycerine generation not; See after state-zymamsis is with the production of glucose syrup), invention " three property " is remarkable.
2, maize enzyme acid is produced Glucose Liquid: the disposable adding Ye Huamei of enzyme-added total enzyme concentration of milk of starch being pressed a-glycase 50-60 units/gram dry starch; Looking acid-basicity lime carbonate or hydrochloric acid accent PH is 6.0-7.0; Concentration is about 30-35%; Under 90-93 ℃, carry out high temperature gelatinization and liquefaction, remain to dextrose equivalent value (DE value) 25-30 or disappear to Iod R till the liquefaction degree, with this method liquefaction corn starch milk; The dead starch of the difficulty liquefaction that generally can three sections liquefaction of image height temperature equally will form because of starch small grain is aging is fully liquefaction but do not have starch coking color depth problem and save water and energy when saving also; Can improve sugar and alcohol yield and quality and significantly shorten saccharification and alcohol secondary fermentation time, conventional filtration removes slag, and slag is made feed; Filtrating adds hydrochloric acid HCl (associated viscera that its serial important effect and advantage are seen after and stated) and transfers PH to 1.2-1.8, under vp 0.3-0.35 MPa, carries out sour saccharification, keeps getting in 20-25 minute Glucose Liquid.
3, zymamsis is with the production of Glucose Liquid: above-mentioned Glucose Liquid is added 10-15% yellow soda ash and 1-5% magnesiumcarbonate liquid, and to transfer PH jointly be 4.5-5.1; Make fermented liquid be slightly acidic, with ensure fermentation to alcohol but not directions such as glycerine carry out; And the salt that generates be mainly to all harmless sodium-chlor of fermentation and human body and because of the equal height of its solubleness in water and stability be that good water solubility is very easily removed; The carbonic acid that generates for instability extremely be volatility with decomposability all very by force and be prone to remove, die harmless equally for the original product in the alcoholic fermentation process to zymamsis; The a small amount of salt that generates in addition is promptly very favourable to the ethanol produce magnesium chloride that can promote to ferment; This is because in alcoholic fermentation process, generate the glucose phosphorylation, 1 in the reaction (being called the E-M approach) of pyruvic acid by glucose; The generation of 6-hexose diphosphate, 3-phoshoglyceric acid, 2-PEP and pyruvic acid all need Mg++ to activate by the reaction of yeast continuation degraded generation alcoholic acid decarboxylation generation acetaldehyde under oxygen free condition; Though also contain magnesium in the ortho-water but be to be insoluble in water and the littler magnesiumcarbonate of resolution of precipitate degree that is heated, to be difficult to guarantee the need of above-mentioned reaction because of it; Magnesium chloride is all got well the need that do not have these defectives, then can protect fermentation because of solubleness and stability; Transfer PH then to generate human body with sulfuric acid with zymamsis does not need and often harmful in being prone to make people have loose bowels more than sodium sulfate and sal epsom; Easy generation can play sodium sulfite anhy 96 etc. that addition generates the crystalloid acetaldehyde S-WAT affixture of indissoluble with acetaldehyde, force the acetaldehyde can not be as hydrogen acceptor and must replace it as hydrogen acceptor and generate glycerol 3-phosphate, under the catalysis of 3-phoshoglyceric acid lipase, generate glycerine and reduce alcohol output and quality by phosphodihydroxyacetone, so above-mentioned these designs of the present invention and many-sided excellent effect are to realizing fermenting quick and the high yield goal of the invention is necessary and be easy to implement.
4, fuel alcohol fermentation: traditional technology is starchy material to be made through boiling starch is dissolved state, the effect through the aspergillus saccharifying enzyme generates the part fermentable sugar, in converted mash, inserts yeast and change sugar into alcohol and CO again
2, separate to obtain alcohol product; (starch in the converted mash and dextrin continuation are by Glucoamylase hydrolysis but because of the back saccharification that thoroughly do not exist of liquefaction and saccharification; Generate sugar) act on, also have protein under the further hydrolysis of Aspergillus proteinase, to generate the effect of low molecule nitrogenous compound such as peptide and amino acid etc., absorbed by yeast synthetic yeast somatic cells, another part that these materials of generation have are then generated alcohol and CO by fermentation
2And other by product.Than the present invention be not with slag saccharification and liquefaction, saccharification is thorough and only several hours, traditional method then with slag and (primary fermentation stage more than 10 hours, secondary fermentation stage more than 40 hours) the very long time that needs expend surplus in the of 50 hour more just can make starch and dextrin in the converted mash fermentable sugar of generation that continues to be decomposed; In the mash of alcohol around can any ratio mixing, just being dissolved in by the alcohol of discharging in the yeast body with water, the CO because of producing in the fermentation again
2The less beer of solubleness is will soon be by it saturated and be adsorbed on yeast cell surface CO when it surpasses the cell adsorptive power
2Become gaseous state, form little bubble rising, again because CO
2Bubble collides formation each other than air pocket and effusion liquid level, CO
2The rising of bubble also driven the material in the mash and yeast cell wander up and down make yeast cell can be more fully with mash in sugar contact promptly be equivalent to increase reactant concn make fermentative action sooner more fully with thoroughly and alcohol is scattered in more promptly be equivalent in the liquid reduce resultant concentration and makes that ethanol produce speed is able to accelerate, such fermentation is called the passive type fermentation; If but fermentation liquid is than thickness then bubble arrives that the foam that does not break behind the liquid level and forms does not loose lastingly, foam also possibly overflowed by tank deck and cause sugar loss, such fermentation to be called bubble fermentation sometimes, though in the medium oxygen many in addition saturated the bubble fermentation phenomenon also can take place, this mainly is because the undue strong breeding of yeast and undue strong fermentation and beer are done raw material or the song poor quality causes, adopts skimmer can prevent planting here phenomenon increase operation and cost is also time-consuming takes a lot of trouble with fresh potato is dried.Than traditional method because of normal temperature and in the stock media that liquefies for a long time oxygen depletion slow, add big and the time long so saccharification liquid contains the oxygen height with the air contact surface; Also be prone to cause bubble fermentation greatly because of the not thorough viscosity of liquefaction, saccharification; Yin Gaowen of the present invention liquefies, gassiness is died in saccharification, it is all low to contain oxygen; And because of hanging down bubble, liquefaction, the thorough fermentation broth viscosity of saccharification be prone to broken loosing, again because of the fast output height of the big fermentation of concentration, quality better, cycle weak point.Also visible thus serial advantage of the present invention and novelty and the importance in zymamsis is produced thereof.
Distillery yeast does not contain glycase such as AMS and beta-amylase and Sumylact L and can not directly utilize starch or lactose to carry out zymamsis, therefore when utilizing starchy material to produce alcohol, must change into fermentable sugar to starch and could be used to carry out zymamsis by yeast.Alcoholic fermentation process can be divided into following three fermentation different stepss with it 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 in the also few and aforesaid mash of the yeast count in the mash and sufficient nutritive substance, yeast still can be bred rapidly; Dextrin in the tradition method mash also continues to be generated sugar by Glucoamylase hydrolysis; But Yin Wendu than low sugar turn into slowly, sugar consumption also is generally about 10 hours because of yeast count few slow, perdurability; Because the strong mash temperature rising of fermentative action is unhappy, the mash temperature is controlled at 26-30 ℃ at this moment; The too high meeting of temperature cause yeast early stage old and feeble, cross and lowly can make yeast growth slow again, this phase yeast quantity is prone to suppressed to pay close attention to prevent living contaminants by assorted bacterium less, so should strengthen hygiene control.The inventive method thoroughly reaches characteristic such as sugared concentration height, can easyly take directly to improve yeast quantity with respect to traditional method with liquefaction, saccharification because of no slag be that 1-5 10,000,000/milliliter particular cases such as (look different decide) starch source liquid glucoses significantly reduces primary fermentation phase of reaching more than 10 hours and is 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 be that the touring fermentation of mother liquor is used and do not produced the production capacity that the high vigor liquid yeast event of high cell count need not the primary fermentation stage and be difficult for characteristic (asking for an interview following) raisings such as microbiological contamination with slag and specialized and compare then and can ignore with the bent medicine of the output value and saving with high time of practicing thrift with the present invention of the many costs of the bent more traditional method of amount (1,000,000 grades) and the specially designed reduction resultant of the present invention concentration and yeast.
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 depletion in the beer finishes, to stop breeding basically and mainly carry out anaerobic is the zymamsis effect to yeast, sugar descends rapidly in the mash, alcohol divides and CO
2Increase gradually, the temperature of beer rises also very fast at this moment; Should strengthen in the production temperature control in this stage, preferably can be controlled at 30-34 ℃, this is the righttest leavening temperature of distillery yeast; Temperature Tai Gaoyi makes the early stage aging of yeast, lowers yeast activity and be prone to cause bacterial contamination, more is prone to cause the generation of microbiological contamination phenomenon when being higher than 37 ℃ with the beer temperature especially.The inventive method is not with slag and saccharification thorough because of saccharification liquid; With traditional method band slag and liquefaction and saccharification all very halfway with the concentration fermented liquid compare its reactant be high nearly 1/3, the Primary Fermentation of sugared concentration be the main product time therefore more traditional method increase nearly 1/3, the also corresponding more traditional method of production capacity and increase with output; Add because of not being with slag not only to liquefy thorough with saccharification; And liquefier and saccharification liquid concentration can exceed one times up to the concentration of 25-30%, ratio tradition band slag 13-15%; The viscosity that adds fermented liquid is low, good fluidity and ferment fast, though fast because of fermenting, produce (CO
2) the many and alcohol that take away also many (get final product, needn't handle especially by the routine recovery) of gas but still far be not enough to balance; So alcohol generation and dissolving are also many in the fermented liquid; Make the corresponding more traditional method height of its ethanol concn, can suppress yeast activity and reproductivity and fermentation capacity and speed more by force; So the present invention designed especially Primary Fermentation midway to fermented liquid carry out yeast and wine liquid separate with get wine, the yeast after will separating and the mother liquor got after drinking return the technology of carrying out circulating fermentation again; Its principle, necessity and advantage replenish to be introduced as follows: when the temperature of fermented liquid reduces gradually but not rises; The heat that the demonstration fermentative action begins to weaken i.e. generation begins to reduce, explains sugared content reduction in fermented liquid this moment and the ethanol content rising; Also high because of the two all slow down fermenting speed and ethanol concn, just all just strong than vigor and the proliferative ability of the big yeast of traditional method this moment to zymic harm than traditional method; The fermented liquid of this moment is separated alcohol liquid and yeast, alcohol liquid routine is extracted alcohol with the 1000-3000 rev/min of rotating speed that keeps the yeast cell integrity; Adopt the thermotolerant yeast of the present invention fermentation then needn't separate fermentation liquid, because of it can bear 60-62 ℃ of high temperature, though under the normal pressure alcohol boiling point be 78 ℃ this boiling point of 100 ℃ than water is low many; Add the alcohol highly volatile, just can extract alcohol smoothly so need only simple and regular adopt lower negative pressure of vacuum method that its boiling point is dropped to below 60 ℃; Above-mentioned mother liquor and isolating yeast are returned former jar and add new sugar solution and can make it carry out Primary Fermentation immediately once more to demarcating yeast quantity and the proliferation potential that volume carries out in Secondary Fermentation, this moment fermented liquid, can go round and begin again in theory set up benign cycle but from the decay reality of the continuous dilution of considering living contaminants probability and sugar concentration and throughput such as yeast activity and proliferative ability, change after accomplishing twice circulation Primary Fermentation and extracting alcohol midway that the secondary fermentation phase (stating after asking for an interview) that is equivalent to traditional method is taken turns circulation with thorough end one over to and equipment carried out cleaning and sterilizing by routine after a beginning new round circulate.Do like this and save song in addition and promptly save grain and when joint (bent three usefulness, more traditional method save 2 times); Wash number is economized on water less and is encircled dirty little (three one-period, the traditional method that is merely an one-period such as gap methods 1/3), in case each fermentor tank all is an independently reactor drum and can as continuous fermentation method, just not causing synchronously comprehensively or serial main advantages such as big area stopping production, the underproduction or downgrade because of many fermentor tanks series connection cleanings, maintenance or microbiological contamination.
Sugar major part in the secondary fermentation phase mash is consumed by yeast, in the mash still the remnant dextrin continue by the amylo-1:4,1:6-transglucosidase in the song, 41, the effect of 6-glucuroide generates glucose.Because the very slow steamed bun that this effect is carried out, the sugar of generation are seldom, fermentative action also very slowly.Therefore, alcohol and CO2 produce also fewly in this stage fermentation wine with dregs.
The secondary fermentation stage is low because of traditional method band slag fermentation and liquefaction, the not thorough and sugared concentration of saccharification; The fermentative action heat that weakens, produce also reduces but this stage sugar after Primary Fermentation exhausts basically, the temperature of beer descends gradually and ethanol concn is still not high enough; So traditional method starchy material produces that alcohol needs the secondary fermentation stage because of liquefaction and not thorough and remaining partial starch, the dextrin of saccharification continue saccharification during the fermentation improving the rate of getting alcohol, if this moment, the mash temperature should be controlled at about 30-32 ℃ that the effect too low, saccharifying enzyme of mash temperature will weaken and saccharification is slow, fermentation time will prolong, also can influence the rate of getting alcohol.But nonetheless, secondary fermentation generally still needs about 40 hours very long time to accomplish approximately; The alleged secondary fermentation of the present invention then be because of the dilution of the liquid glucose of circulating fermentation with above-mentioned for finishing a circulation Primary Fermentation cycle, being fermenting speed 5-10 hour slightly slowly with respect to Primary Fermentation; So with the hydrolysis of above-mentioned traditional method starch and saccharification halfway more than 50 hours secondary fermentation for a long time essential distinction is arranged, all big like great disparities such as unit time material treatment 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, exceed more than 90 hours about 20 hours than the present invention because of saccharification and secondary fermentation total time long (saccharification about 50 hours, fermentation about 60-72 hour, ATT is about 115 hours); Deduct aforesaid the present invention formerly liquefy 20 hours of expending approximately with saccharification, still exceed more than 70 hours, so its advantage highly significant still.
Secondary fermentation finishes the back gets wine or conventional method midway by aforementioned Primary Fermentation and extracts waste behind the alcohol, and the yeast slag is quality protein and nucleic acid (RNA) source, can fully utilizes, and stays elaboration again in other application for a patent for invention.
The inventive method also has following main advantages:
1, directly adopt corn make a living malaga sugar starting raw material rather than adopt commodity starch, help reducing cost and fully utilizing; Only corn is processed milk of starch (wet milling process) rather than processed starch, help reducing the dust discharge in organic waste water discharging and the drying process, thereby reduce environmental pollution, practice thrift great lot of water resources and energy consumption, 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 utilized enzyme process and acid system to produce glucose advantage and use built-up sequence separately; Overcome their shortcomings separately, constant product quality, saccharification time is short; Crystalline quality is good; Yield is high, and can be according to the demands of different adjustment simplified and traditional degree of production technique and the operation of quality, and the market adaptability is strong; As can add partly converting apparatus on this basis and produce high fructose syrup, thereby also can in same main product line, keep and use dual-enzymatic process etc. to obtain the optimum economic benefit and the market competitiveness flexibly.
3, the AMS because of any source all can cut SANMALT-S, add that the direction unicity of acid hydrolytic reaction and thoroughness are very strong; Enzymatic liquefaction and acid saccharification all seldom produce difficult disaccharide that utilizes of yeast such as SANMALT-S 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, so the present invention is beneficial to behind the further saving alcohol diastatic fermentation time and improves starch and transform (alcohol) rate about 3% and improve throughput and alcohol yield and reduce cost.
4, with the corn be starting raw material; The method of employing enzyme acid direct production glucose only needs that corn is processed milk of starch and is converted into glucose step by step; Ye Huamei hydrolyzed starch under 85-93 ℃ of high temperature only takes at 1.5 to 2.5 o'clock, saccharification under vp 0.3-0.35 MPa pressure also only 20 to 25 minutes.
5, this project changes at starch and adopts enzyme liquefaction to prevent or to reduce production of by-products that the back adopts sour saccharification to guarantee the stable of product quality and performances in the glucose process earlier.
6, this project corn starch milk can directly be adjusted concentration and is used for transforming glucose.
7, the used enzyme of this project enzymatic liquefaction and acid saccharification production glucose is the high temperature a-glycase of sophisticated large-scale industrial production, and used acid is similarly the hydrochloric acid of large-scale industrial production so raw materials cost is low secure.
8, this project enzyme and sour consumption few, press 50-60 units/gram over dry starch with the enzyme amount and calculate, reach 1.2-1.8 calculating with the acid amount by saccharification liquid pH value.
Embodiment:
1, Semen Maydis is sieved, and in stainless steel cask, with 50 ℃ of warm water soaking 1.5 hours (adding hydrochloric acid solution makes soak solution acid reach 0.3% concentration), is warmed up to 80 ℃ about 1.5 hours, Universalpulverizer broken (soak solution produce steeping water with).Germ separation device removal plumule and kind skin (plumule cleans and separates kind of a skin after drying oil expression, and the dregs of fat and kind skin are made feed), powder emery grinds levigate (900 rev/mins of rotating speeds); It is 30% that whizzer separates (1200 rev/mins of rotating speeds) accent starch concentration; PH6.5, in liquefier disposable adding liquefy required total amount Ye Huamei (press a-glycase 50 units ./gram over dry starch calculates the enzyme amount that always needs), 90 times ℃ of liquefaction about 2 hours; Make the DE value reach 26; Plate-and-frame filter press filter and remove residue (slag is made feed or food protein raw material), in stainless cylinder of steel, using HCL to transfer PH is 1.8, and sour saccharification after 20 minutes under 0.3 MPa vp; Using 10% yellow soda ash and 2% magnesiumcarbonate liquid to transfer PH is 4.9, and evaporation concentration is 1.3450/45 ℃ concentration to proportion under 0.06 MPa; Press yeast cell quantity 1,000 ten thousand/milliliter with bent, disposable adding, temperature is controlled at 33 ℃; When the temperature of fermented liquid 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 and isolating yeast return former jar and add new sugar solution to demarcating volume, keeps 33 ℃ continue fermentation, when temperature reduces plate-and-frame filter press separate alcohol liquid and yeast, with 30-34 ℃ of boiling extraction of alcohol liquid negative pressure of vacuum alcohol; Mother liquor and isolating yeast return former jar and add new sugar solution to demarcating volume, change the secondary fermentation phase and technology and the operation that are equivalent to traditional method over to, continuing to ferment to no CO
2Till the generation, take turns circulation and equipment is carried out beginning new round circulation behind the cleaning and sterilizing by routine 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/ton), nucleic acid is carried in the separate case of dying application; The residue protein amount is high, event separate case application protein-high high-quality feed.
2, white (glutinous property) corn sieves, and in stainless steel cask, soaks 1 hour with 55 ℃ of warm water (lactic acid concn 0.2%), be warmed up to 75 ℃ about 1 hour to improve the separation rate of plumule and kind skin; Universalpulverizer broken (soak solution contains the low emission of the organism utmost point), germ separation device are isolated plumule and are planted skin (plumule kind skin treatment process is with embodiment 1), powder emery mill levigate (1000 rev/mins); Transferring powder slurry concentration is 35%; PH is 6.8, and liquefier liquefaction is always disposable enzyme-added with the enzyme amount by the metering of 60 units/gram dry starch content; 93 ℃ of insulation liquefaction made Iod R disappear in 2.5 hours; Filter press (slag is made feed or food protein raw material), in stainless steel cask, adding HCL, to transfer PH be sour saccharification 20 minutes under 1.5,0.35 MPas; Using 15% yellow soda ash and 2% magnesiumcarbonate liquid to transfer PH is 5, and evaporation concentration is 1.3450/45 ℃ concentration to proportion under 0.06 MPa; Press yeast cell quantity 2,000 ten thousand/milliliter with bent, disposable adding, temperature is controlled at 33 ℃; When the temperature of fermented liquid 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 and isolating yeast return former jar and add new sugar solution to demarcating volume, keeps 33 ℃ continue fermentation, when temperature reduces plate-and-frame filter press separate alcohol liquid and yeast, with 30-34 ℃ of boiling extraction of alcohol liquid negative pressure of vacuum alcohol; Mother liquor and isolating yeast return former jar and add new sugar solution to demarcating volume, change the secondary fermentation phase and technology and the operation that are equivalent to traditional method over to, continuing to ferment to no CO
2Till the generation, take turns circulation and equipment is carried out beginning new round circulation behind the cleaning and sterilizing by routine with thorough end one; The processing of mother liquor and yeast slag is with embodiment 1.