CN101787382A - Method for recovering coin protein sugar dregs and preparing protein nitrogen sources and nitrogen-containing syrup - Google Patents

Method for recovering coin protein sugar dregs and preparing protein nitrogen sources and nitrogen-containing syrup Download PDF

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CN101787382A
CN101787382A CN201010019495A CN201010019495A CN101787382A CN 101787382 A CN101787382 A CN 101787382A CN 201010019495 A CN201010019495 A CN 201010019495A CN 201010019495 A CN201010019495 A CN 201010019495A CN 101787382 A CN101787382 A CN 101787382A
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protein
sugar
saccharification
poor
starch
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CN101787382B (en
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黄立新
徐正康
赵谋明
周彦斌
罗建勇
琚长霄
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Guangzhou Shuangqiao (Chongqing) Co., Ltd.
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GUANGZHOU SHUANGQIAO CO Ltd
South China University of Technology SCUT
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Abstract

The invention discloses a method for recovering coin protein sugar dregs and preparing protein nitrogen sources and nitrogen-containing syrup in the production of enzymatic corn starch sugar, comprising the steps of size mixing, liquefying, saccharifying, standing separation, centrifugal separation, proteolysis, concentration, drying, compounding, and the like. In the invention, protein is condensed under the heat flash of liquefying, the protein sugar dregs concentrate and float upwards in saccharifying, the sugar dregs are recovered through the steps of standing separation and centrifugal separation, the sugar dregs are dried into protein, or the sugar dregs are hydrolyzed to prepare protein nitrogen sources, and the nitrogen sources can be compounded with syrup to form nitrogen-containing starch syrup for fermenting. Clarified saccharification liquid after centrifugal separation is decolored, filtered, refined and concentrated, and starch syrup products are obtained. The majority of lentous sugar dregs in the saccharification liquid are removed before the treatment of decoloring and filtering, and the decoloring and filtering performance of the material is better. The use level of active carbon, and the like can be properly reduced, the production capability of filtering equipment is improved, and the frequency of the loading and unloading of filters as well as the consumption of washing waste water and various kinds of loss are greatly reduced.

Description

Reclaim coin protein sugar dregs and preparation albumen nitrogenous source and nitrogenous syrupy method
Technical field
The present invention relates in enzyme process corn starch sugar production process, the impurity recovery of protein is utilized in the starch material, is specifically related to reclaim coin protein sugar dregs and preparation albumen nitrogenous source and nitrogenous syrupy method.
Background technology
Corn is the world, also is one of economic cereal of Chinese important food, and plantation is extensive, and the output height both can be used as grain and directly eaten, and also had been widely used industrial.Corn (grain) mainly contains starch, and its starch content accounts for more than 70% of corn grain dry weight, contains compositions such as protein, fat, fiber, ash content and soluble saccharide in addition, and corn is most important Starch Production raw material.The ratio that W-Gum accounts for world's starch ultimate production holds a safe lead, and also is so in China, more than 75%.Wet milling process is the universal method that world today W-Gum is produced, by products such as the corn leaching solution that can produce production process, skin slag, plumule, seitan reclaim and fully utilize, adopt modern starch-making equipment line and advanced production control technology thereof, the rate of recovery height of corn dry substance, starch product purity height, quality better, price is cheap with respect to starch such as potato, cassava, wheats, becomes to produce various Dian Fentangs, leavened prod (antibiotic, monosodium glutamate, citric acid, Methionin, lactic acid and alcohol etc.) most important material.
The W-Gum purity of general industry scale operation is very high, but except moisture, still contains certain non-starch impurities, and these impurity are mainly protein, fat and ash content, wherein again with proteinic quantity maximum.The national standard of W-Gum product sees the following form 1 to the requirement of protein content physical and chemical index.
Table 1
Project/grade Top grade One-level Secondary
Protein (butt), % ??≤0.40 ??≤0.50 ??≤0.80
These large-scale Dian Fentang enterprises of Bei Fang Lu Zhou group, western Wang Jituan, the emerging trade in Zhucheng, COFCO and southern Guangzhou Shuangqiao Corp or the like (producing few hundred thousand tonnes of per year) at home to up to a million tons Dian Fentang product, and the msg product of these Chinese brand names such as doube bridge, lotus flower, plum blossom, be that raw material is produced at present basically with the W-Gum.The Dian Fentang of the U.S. and alcohol product also are so, almost all come from the hydrolysis deep processing of W-Gum.Adopt the Production by Enzymes Dian Fentang to have very many superiority, become the starch hydrolysis produce the Dian Fentang product, as the most important method of fermenting carbon source.In the process of W-Gum Production by Enzymes Dian Fentang, starch is become the glycan molecule of various low polymerization degrees by enzyme liquefaction, saccharification, as oligose and monose.These impurity such as protein, fat are not diastatic action, but in process of production owing to effects such as being subjected to heat, iso-electric point is flocculated, the sex change polymerization, their are removed through refinement treatment such as absorption, decolouring and filtrations such as gac, diatomite, finally obtain the very high Dian Fentang of purity (slurry) product.The enzyme process starch refine dsugar technological process of production of domestic current be W-Gum through sizing mixing, liquefy, after the cooling, saccharification, starch is become the glycan molecule of various low polymerization degrees by enzyme liquefaction, saccharification, these impurity such as protein, fat are not diastatic action, handle and after removing through absorption such as gac, diatomite, decolouring, press filtration, further refining, concentrate and obtain starch syrup.
Though the Protein content of W-Gum is low, but it all has many adverse influences to the quality of starch refine dsugar and Dian Fentang, such as, in the sugaring process, protein easily and the sugar colorific material that reacts, perhaps the colorific material of self decomposes needs stronger decolouring to handle.Protein easily produces bubble, and influence is from friendship.Protein is heated through liquefaction and wait handles and sex change is flocculated, these protein sugar be pickled with grains or in wine when saccharification can on float to the upper strata of saccharification liquid, generally adopt vacuum suction filter to filter as flocculating aids with diatomite, adopt plate-and-frame filter press to carry out press filtration after perhaps adding activated carbon decolorizing, remove protein sugar and be pickled with grains or in wine impurity such as grade and obtain clarifying liquid glucose.Because the poor suction of the protein sugar of flocculation is many, density is littler than liquid glucose, loosely organized, viscosity is big, very easily seals the filter opening of blocking filtering medium, makes it filter factor and reduces, the resistance multiplication, the processing property of filter plant is sharply descended, and the filtration capacity of the liquid glucose in operation of equipment cycle diminishes, and becomes to hinder one of further key point that enlarges of Dian Fentang production line production capacity.In addition, what filter plant was more frequent unpicks and washes, and has also increased diatomite, washes waste water, sugar decreases, cloth consumption and workman's labor capacity, and the health production environment is had a negative impact.These contain the poor filter cake filter mud of protein sugar, owing to be mixed with waste and old activated carbon or diatomite, have lost due value, become solid waste substantially.And these contain the poor filter cake filter mud of protein sugar, if do not dealt carefully with or transport as early as possible, also very easily are subjected to action of microorganisms and smelly, become source of pollution.
With the low W-Gum of protein content (as the top grade W-Gum) is the raw material production Dian Fentang, can reduce this negative impact of protein to producing, but, the top grade W-Gum is because protein content is lower, purity is higher, price is also higher naturally, therefore, and the general W-Gum that uses one-level in the production.The protein content of a domestic cornstarch is many about 0.45% at present, the corn starch sugar of 100,000 tons of butts can produce the protein of about 420 tons~450 tons of butts, amount to 750 tons~820 tons of the protein raw materials (moisture is by 8%) that are equivalent to content 60%, value (is being used as the protein raw materials of feed more than 2,200,000 yuan, about 3000 yuan/ton of price, with the rule of feedstuff industry, calculate for about 50 yuan) according to each albumen percentage point.
By above-mentioned production status both domestic and external and analyze as seen, be used for producing Dian Fentang or as the W-Gum in sugar fermentation source, though its protein content is lower, but for the huge Dian Fentang enterprise of industrial scale, if W-Gum protein wherein can access recovery, its annual amount is still considerable, and the leavened prod that corn protein and hydrolysate thereof have been widely used for food, medicine has good effect as the organic protein nitrogenous source.Its two, if in the corn starch sugar production process, the protein of the recovery system of taking measures before filtering press filtration can also overcome the poor above-mentioned multiple adverse influence of protein sugar.
In fact, above-mentioned this imagination and processing method have been implemented to realize abroad in practice, Changsha high fructose factory, the high fructose in Jiangyin factory that China builds for introduction technology and equipment produced in USA nineteen ninety, after liquefaction, before the saccharification, the flocculation corn protein that disk centrifugal separator separates liquefaction and heat effect formation is set, remove the solid impurity in the liquefier, and then deglycation, decolouring, filtration, refining and operation such as concentrate.Stage after liquefaction is removed the poor operation of protein sugar to liquefier, except the proteinic elementary object of removal system, also have other benefit: the temperature during the liquefaction insulation is more than 90 ℃, and saccharification needs it is reduced to the suitable operative temperature of 50 ℃~65 ℃ saccharifying enzyme.The cooling of lowering the temperature of domestic present employing water cooler.Isolated protein process at disk centrifugal separator also is the temperature-fall period of liquefier, and isolated clarifying liquefier available pipe is led to saccharifying tank, from the processing unit flow process and see the simplest preferably in theory, kills two birds with one stone.But, to put into practice from the operation of the high fructose in Changsha at home factory, the high fructose in Jiangyin factory, this method is in actual production, and the separating effect of disk centrifugal separator is extremely unstable, is difficult to stable control.Main reason has:
(1) in liquefaction and long soaking period of time thereof, the tissue morphology of protein floculation and matter structure thereof be complete stability not also, also is on the turn.
(2) disk centrifugal separator also is the process of the rapid cooling of liquefier in the process of isolated protein, and under the state of alternating temperature, the iso-electric point of protein floculation, tissue morphology and matter structure thereof still change in the system.
(3) disk centrifugal separator is in higher temperature and have under the situation of moisture evaporation of a great deal of and separate, and device control and operating environment condition complicate, and also the stable smooth working to whizzer has a negative impact, and big fluctuation takes place also belong to unavoidably.
Therefore, disk centrifugal separator separating effect extremely unstable even isolate a large amount of liquefiers, yield rate reduces, and the poor mixture of these sugar with many liquefiers and protein floculation is behind cool to room temperature, very easily become paste, and be subjected to microbiological contamination easily.Enterprise did not have the good method of utilizing to the poor by product of these protein sugar yet at that time, can only be as solid waste.Because the saccharification liquid of sugaring back segment also will decolour, press filtration is handled, these enterprises simply just cancelled the proteinic step of this disk centrifugal separator removal liquefier afterwards, become the starch refine dsugar technological process of production of domestic current: starch → size mixing → liquefy → cool off → saccharification → decolouring → filtration → refining → concentrate → starch syrup, impurity such as the protein in the starch mainly are removed in the filtering stage, and therefore proteinic disadvantageous effect does not still overcome.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, a kind of recovery coin protein sugar dregs and preparation albumen nitrogenous source and nitrogenous syrupy method are provided, the inventive method be through sizing mixing, liquefaction, saccharification, standing separation, centrifugation, proteolysis, step such as concentrated, dry, composite, reach the purpose that the protein in the production process of enzyme process corn starch sugar is reclaimed and utilizes.This method can be dried to albumen with the protein that reclaims, and perhaps creates the used albumen nitrogenous sources in field such as food fermentation, biochemical pharmacy through hydrolysis again with the protein sugar that reclaims is poor, these nitrogenous sources can also with the composite nitrogenous starch syrup of making fermentation usefulness of syrup.
The object of the invention is achieved through the following technical solutions:
Reclaim coin protein sugar dregs and preparation albumen nitrogenous source and nitrogenous syrupy method, may further comprise the steps:
(1) size mixing: add entry at the jar of sizing mixing, start stirring, add W-Gum, the concentration of dry substance is 32%~46% weight in the control slurries, adds calcium chloride, Ca in the control slurries 2+Content be 20~45mg/kg, the pH value of regulating slurries is 5.6~6.4, adds high-temperature again, consumption is 0.2~1.2kg/t butt starch, mixes;
(2) liquefaction: slurries are carried out the insulation processing of continuous injection liquefaction and 95~100 ℃, time 60~140min;
(3) saccharification: liquefier is cooled to 50~65 ℃ through flash distillation or heat exchange, and pH is 4.1~6.0, adds the saccharifying enzyme of 0.06~1.50kg/t butt starch, hydrolysis 25~70 hours, the DE value of control saccharification liquid;
(4) leave standstill enrichment: stop to stir in the saccharification later stage, leave standstill more than 4 hours;
(5) standing separation: open the bleeder valve on saccharifying tank top from top to bottom one by one, make saccharifying tank top be enriched with the poor saccharification liquid of flocculation protein sugar and all flow out or extraction, regulate isolated material pH to 4.8~5.2, carry out next step centrifugation;
(6) centrifugation: adopt whizzer with saccharification liquid with protein sugar is poor separates, the saccharification liquid behind the separating clarifying with make with extra care after the bottom saccharification liquid of same saccharifying tank mixes, the concentrated starch syrup of making;
(7) protein sugar that step (6) centrifugation is come out poor dehydrate, crushing screening, be packaged to be protein product; Perhaps poor acid system hydrolysis or the enzymatic hydrolysis of carrying out of the protein sugar that step (6) is obtained obtains the albumen nitrogenous source through neutralizing, make with extra care and concentrating, the composite nitrogenous starch syrup of making fermentation usefulness of albumen nitrogenous source and syrup.
The described high-temperature of step (1) is Termamyl, Liquozyme or Suhong AA Plus high-temperature.
The described saccharifying enzyme of step (3) is one or more a mixture in glucoamylase, Pullulanase or beta-amylase or the fungal amylase.
Described saccharifying enzyme is one or more the mixture in Dextrozyme compounded saccharifying enzyme, AMG glucoamylase, Promozyme Pullulanase, Fungamyl fungal amylase or the Optimalt BBA beta-amylase.
When the concentration of dry substance in the slurries was 40%~46% weight, second spraying liquefaction was preferably adopted in the described liquefaction of step (2), and the temperature of steam ejection liquefaction is below 110 ℃ for the first time, and the temperature of steam ejection liquefaction is at 130 ℃~135 ℃ for the second time; 95~100 ℃ of insulations, soaking time is 60~100min.
Described whizzer is high speed dish type whizzer, filtering centrifuge or horizontal helical type whizzer, and rotating speed is more than the 3000r/min.
Described enzymatic hydrolysis is to add the water that is equivalent to 3~6 times of its weight at the protein sugar groove, temperature is 50 ℃~65 ℃, pH is 5.0~8.0, adds the animal and plant protease and/or the microbial protease of the poor weight 0.1%~1.0% of protein sugar, stirring reaction 10~20 hours.
Described animal and plant protease comprises one or more the mixture in stomach en-, trypsinase, papoid or the bromeline; Described microbial protease is one or more the mixture in neutral, the acid or alkaline microbial protease.
Described microbial protease comprises Neutrase, Alcalase or Flavourzyme.
1, size mixing, liquefy, cooling, saccharification: of the present inventionly size mixing, processing step and method thereof such as liquefaction, saccharification, basic identical with the production technique of the corn starch sugar of present routine.
(1) size mixing step and control thereof is the same substantially with the production technique of the present corn starch sugar of routine.
At jar an amount of water of adding of sizing mixing, start stirring, add W-Gum, the concentration of control powder slurries dry substance is 32%~46%.Powder slurry concentration is too low, and it is high that the back concentrates power consumption; Concentration is too high, and refining unfavorable to liquefaction, saccharification and filtration, recovery rate reduces, and production cost improves equally.The present invention is according to the technical requirements of existing condition, equipment and invention, and the concentration of powder slurries dry substance is preferably 40%~46%, and the concentration of saccharification liquid of back operation is higher with making, and relative density is higher, the poor come-up that is easier to of protein sugar.Add calcium chloride, content 20~45mg/kg of control slurries Ca2+, the pH value of regulating the powder slurries is 5.6~6.4 (perhaps operating according to characteristic, specification and the instruction explanation of the high-temperature zymin commodity that use), the high-temperature that adds 0.4~1.2kg/t starch butt at last, mix, prepare liquefaction.
(2) Ye Hua operation, processing method and existing method are basic identical, adopt high-temperature, liquefy with the continuous injection liquefier.
Can operate the insulation of liquefying by general continuous injection liquefaction and handle with 95~100 ℃, time 60~140min, generally at 70~110min, the dextrose equivalent value DE of liquefier is controlled to be 8~20.If the concentration of slurries dry substance is 40%~46% higher concentration, in order to make the better sex change cohesion of protein in the W-Gum, preferably adopt the technology of second spraying liquefaction, the temperature of steam ejection liquefaction is below 110 ℃ for the first time, the temperature of steam ejection liquefaction is higher for the second time, at 130 ℃~135 ℃, insulation is handled at 95~100 ℃, and the time gets final product at 60~100min.Liquefaction processing can make damaged starch granules disperse fully by the enzyme effect like this, the abundant sex change dehydration of protein, and heat-coagulation is better, for these proteinic separation of next stage, recycling are laid a good foundation.
(3) processing method of saccharification is identical with existing method, operates basic identical.
Liquefier is through flash distillation or heat exchange, be cooled to 50~65 ℃, regulating the pH value is 4.1~6.0, the various saccharifying enzyme that add 0.06~1.50kg/t carry out synergetic hydrolysis, hydrolysis time (was perhaps operated according to characteristic, specification and the instruction explanation of the various glucoamylase enzyme preparation commodity that use in general 25~70 hours, detect the sugar component variation of the saccharification liquid of saccharifying again with high-efficient liquid phase chromatogram discuss, control the saccharification terminal point and the time of dissimilar starch sugar procuts), the DE value of control saccharification liquid;
Make the saccharification liquid of high glucose content, adopt the blue enzyme of glucoamylase Jia Pulu to carry out saccharification, the DE value of saccharification liquid is controlled at more than 97; The glucose that transforms in the production (liquid), adopt glucoamylase or the more blue enzyme of Jia Pulu carry out saccharification, the DE value of saccharification liquid is controlled at 35~75; Produce malt syrup or high maltose syrup, beer with sugar adopt fungal enzyme, beta-amylase or again Jia Pulu indigo plant enzyme carry out saccharification, the DE value of saccharification liquid is controlled at more than 42.
(4) saccharification leave standstill processing: the time of liquefaction and insulation thereof generally in 2.0 hours, just enters next step.The time of saccharification is then longer, generally more than 20 hours, produces high-purity Glucose Liquid, generally more than 40 hours.The present invention's requirement stopped to stir in the saccharification later stage, left standstill, and leaves time enough the protein come-up of volume flocculation is assembled, and carried out the enrichment and the fastening of weave construction of protein floculation and stablized.The present invention require before saccharification finishes more than 4 hours, saccharifying tank stops to stir, and leaves standstill the gathering of the poor fully come-up of the protein sugar of waiting for flocculation.
2, standing separation: the top of saccharifying tank (account for saccharifying tank height 30%), the different heights position has discharge port from top to bottom, go out more protein suspending thing with " decant ", improve the content concn of the poor solid insoluble of the flocculation protein sugar of material to be processed, reduce the quantity of the saccharification liquid of wanting the centrifugation processing, improved the end-use performance of separating device, costs such as energy efficient, power consumption.
Open the decant bleeder valve on saccharifying tank top from top to bottom one by one, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (be generally saccharifying tank liquid glucose height 10%~25%) can all flow out or be retracted to insulated tank, regulate the isoelectric points of proteins of pH to 4.8~5.2 of material, prepare to carry out centrifugation.
The residue saccharification liquid of bottom in the saccharifying tank owing to isolated most poor impurity of solid protein sugar, can directly go the diatomite vacuum suction filter to filter, and perhaps mixes with the clarification saccharification liquid that centrifugation is come out, and carries out next step refinement treatment again.
3, centrifugation: adopt high speed dish type whizzer/filtering centrifuge/horizontal helical type whizzer to carry out saccharification liquid and poor the separating of protein sugar, the clarifying saccharification liquid that comes out or mix again with the bottom saccharification liquid of same saccharifying tank, that carries out next step again makes with extra care, is condensed into starch syrup, starch syrup can be the finished product, perhaps makes nitrogenous starch syrup with the albumen nitrogenous source is composite.
The separating effect of whizzer depends on material factor (the matter structure that temperature, solid content, viscosity and the protein sugar that saccharification liquid, protein sugar are poor is poor and with the difference of specific gravity of liquid glucose etc.), apparatus factor (device structure size, rotating speed etc.) and operation factors (inlet amount, temperature etc.).With regard to whizzer, rotating speed is high more, and separating effect is good more.The present invention requires the minimum 3000r/min of being of the rotating speed of whizzer, preferably reaches more than the 5000r/min.
The poor sugar liquid that is mingled with certainly of the protein sugar that centrifugation goes out, the present invention does not advocate to wash sugar is poor in this centrifugal separation processes, and the sugar that reclaims this part is back to it in ative starch sugaring flow process again.As if do the sugar dry substance that has lost this part like this, reason of the present invention has:
(1) the purposes aspect of separated product: the poor sugar that is mingled with of the protein sugar after the centrifugation, sugar also is the nutritive element of microbial fermentation, do not influence the poor and hydrolysate of protein sugar as the used albumen nitrogenous source in fields such as food fermentation, biochemical pharmacy, perhaps be used for composite nitrogenous starch syrup.The sugar of these " losses " still is utilized, and does not just get back to the starch syrup product.
(2) the control aspect of lock out operation: if the high speed centrifugation separating device has the function of separation, washing, the operation that separates simultaneously, washs, not only the price of equipment is higher, under the separation that main is at high-speed high capacity, the work of washing, compare with pure lock out operation, increased influence factors such as washing water temperature, flow, increased one new washing water material, the capital makes the device separates system become complicated and fluctuates greatly, and equipment is difficult for stable control and turns round.In addition, if wash with the drinkable water of room temperature, big temperature head between the poor and washing water of protein sugar then, the weave construction that protein sugar is poor will produce bigger variation, might destroyedly disperse the separating effect variation again.If adopt the hot water (more than 50 ℃) close to wash, can reduce this adverse influence, but will add hot-water cylinder and water temperature control device thereof, increase equipment and troublesome poeration with the temperature of charge of separating, washing.
(3) source of washings: the operation that separating device separates simultaneously, washs, if washing effect will be got well, the washing water yield generally will strengthen, therefore, the dry solids content of washings is not high certainly, in 10%, even, also unavoidably have the protein throw out of part less than 5%.This part washings dry substance concentration is low, and albumen foreign matter content height utilizes its Production Flow Chart that is back to ative starch sugar again, and cost performance is uneconomical.This part washings is if be used to prepare the nitrogenous starch syrup of usefulness of fermenting, still can omit the poor washing of protein sugar in fact, isolate that the protein sugar that contains more sugar is poor can directly to remove to prepare the nitrogenous starch syrup of usefulness of ferment, the cost of concentration and evaporation also hangs down.
(4) others: the protein sugar that centrifugation is come out is poor to be washed with other equipment again, can improve the poor protein content of sugar, can avoid the troublesome problem of the lock out operation of above-mentioned (2), (3) high speed dish type whizzer again.But, for a production line of producing 100000 tons of corn starch sugars of butt per year, the content 60% protein by product about 800 tons (moisture is by 8%) of Hui Shouing like this, limited amount, and the protein that these sugar are poor has passed through the elevated temperature heat sex change, by product with general W-Gum wet milling process---Zein powder is compared (protein content 60%~65%, special purified protein content can reach more than 70%), and its nutrition and use value greatly reduce.The present price of Zein powder about 3500 yuan/ton, as the protein raw materials that feed is used, price also than the poor height of the protein sugar that reclaims from enzyme process corn starch sugar production process not what.Therefore, if the zein deep processed product of the high-grade high value of Development and Production, select the by product of W-Gum wet milling process for use---Zein powder is as processing raw material, more suitable, convenient and economy.If it is refining that this coin protein sugar dregs is thought to wash again, improve protein content, the zein deep processed product of other high-grade high value of Development and Production, it is the processing technology routine of raw material that its Technological Economy was still competed with the Zein powder.So, these are poor from the protein sugar that enzyme process corn starch sugar production process reclaims, be dried to albumen, perhaps again with used albumen nitrogenous sources in field such as its process hydrolysis food prepared therefrom fermentation, biochemical pharmacies, perhaps again with the composite nitrogenous starch syrup of making fermentation usefulness of syrup, be all more feasible comprehensive utilization of Technological Economy by way of.
4, drying: the protein sugar that step 3 centrifugation is come out is poor to dewater with Vacuumdrier or spray-drier or the like drying plant, crushing screening then, and weighing is packaged to be protein product, can be used as the protein raw materials of feed, food and fermentation usefulness.
5, proteolysis, concentrated, composite etc.: with the protein sugar groove that step 3 obtains, adopt acid system or enzyme process to be hydrolyzed, through neutralization, refining and concentrate the albumen nitrogenous source used of fermentation and food, can be again and the composite nitrogenous starch syrup of making fermentation usefulness of syrup.
Above-mentioned liquefying amylase is the high temperature Ye Huamei, as Termamyl, and the Liquozym high-temperature; Above-mentioned saccharifying enzyme is glucoamylase, Pullulanase, beta-amylase, fungal amylase, as in Dextrozyme compounded saccharifying enzyme, AMG glucoamylase, Promozyme Pullulanase, Fungamyl fungal amylase or the Optimalt BBA beta-amylase one or more.All zymins are food grade, and are as follows.
In the step 5, acid system hydrolysis calpastatin nitrogenous source: the poor edible acid that adds of sugar, preferably adopt edible hydrochloric acid, adopt the acid (sulfuric acid, phosphoric acid etc.) of other kind to come hydrolysis, purified economy and effect are all relatively poor.At normal pressure or add and depress, carry out acid hydrolysis according to general hydrochloric acid hydrolysis method of protein, technology, with the edible acid of 2.5~5.0mol/L (preferably hydrochloric acid) between 95~130 ℃, heating hydrolysis 3~24 hours, adopt edible yellow soda ash or sodium hydroxide solution neutralizing hydrolysis liquid pH to 4.4~5.0, with 0.5%~1% (to the albumen butt) activated carbon deodorization, filtration, vacuum concentration to concentration is 70%~80%, make the sodium chloride content of the sodium chloride content of enriched material and soy sauce commodity close or higher, product at room temperature storage property is good; After the acid hydrolysis liquid process activated carbon deodorization that perhaps sugar is poor, the filtration, pass through OH -The most Cl of the refining removal of type anionite-exchange resin -, being neutralized to pH6~7, vacuum concentration to concentration is 70%~80%, perhaps is dried to solid phase prod again, all can be used as the albumen nitrogenous source of fermentation usefulness.
In the step 5, enzymatic hydrolysis calpastatin nitrogenous source: the poor water that adds 3~6 times of weight of sugar, temperature regulation is 50~65 ℃, the pH value is 5.0~8.0, adds the animal and plant protease and/or the microbial protease that are equivalent to white 0.1%~1.0% weight of sugared Egg preserved in wine, and constantly stirring reaction is 10~20 hours, smart filter, vacuum concentration to concentration is 70%~80%, perhaps is dried to solid phase prod again, all can be used as the albumen nitrogenous source of fermentation usefulness.
Preferred version: above-mentioned animal and plant protease is stomach en-, trypsinase, papoid or bromeline; Microbial protease is Neutrase, Alcalase, Protamex or Flavourzyme etc.
With W-Gum is that raw material adopts the Production by Enzymes starch syrup, and the protein in the W-Gum is taken as major impurity and removes, and forms the component of filter residue waste material.As previously mentioned, protein, amino acid nitrogenous substances residual in the starch syrup finished product can influence syrupy outward appearance, and in Application in Food Processing, cause ill effect.Yet when this kind of starch syrupy product is not to be used to food-processing, but when being used as the carbon source of fermenting process of leavened food, biochemical pharmacy etc., carbon source is enough obviously, and organic nitrogen source content is obviously not enough.Corn grain contains the protein of a great deal of, and edible safety is good, is a kind of good organic protein nitrogenous source.Corn steep liquor in that W-Gum wet production process is produced contains the protein more than 40%, is the auxiliary material that well ferments, and has been widely used among the fermentation of products such as monosodium glutamate, soy sauce, alcohol, organic acid, antibiotic.At the Zein powder that W-Gum wet production process is produced, also be good feedstuff protein raw material.Therefore, retrieve from this contained percentage several poor by product of corn protein sugar and hydrolysate thereof at zero point of starch material, be suitable for use as the used albumen nitrogenous sources in field such as food fermentation, biochemical pharmacy equally, can with syrup composite make the fermentation usefulness nitrogenous starch syrup.Thisly not only contained sugar, but also contained the starch syrup in organic protein-n source, the purposes that is more suitable for processing leavened prods such as soy sauce, monosodium glutamate, beer, organic acid, antibiotic than the starch syrup of general purified glucose, maltose.Employed in the method various zymins, acid supplement must meet certain rules and quality standard, are permitted among the food-processing.
Advantage and beneficial effect that the present invention has with respect to prior art:
(1) concentration of the dry substance of farinaceous size is 40%~46% higher concentration, adopt the technology of second spraying liquefaction, the temperature of steam ejection liquefaction mainly is to make protein dissociation open starch granules and molecule below 110 ℃ for the first time, the protein molecule chain can fully stretch, not over-drastic sex change.The temperature of steam ejection liquefaction is higher for the second time, at 130 ℃~135 ℃, damaged starch granules is disperseed fully by the enzyme effect, the abundant sex change dehydration of protein, and heat-coagulation is better.Temperature is high again, also can make protein molecule generation thermal destruction, and the albumen of cohesion sex change is " redissolution " again, has lost centrifugation and has obtained the poor basic substance of protein sugar.Liquefaction process and method thereof are the keys that the protein in the W-Gum raw material forms insoluble coin protein sugar dregs.
(2) in the saccharification stage, adopt the synergetic hydrolysis effect of multiple saccharifying enzyme, can access glucose content height (can surpass 96.0%), perhaps the higher dissimilar starch syrups of forming with sugar such as (can surpass 55.0%) of maltose content can be suitable for the different requirements of different fermentations product to the substrate sugar component.
(3) the present invention makes full use of the long characteristics of saccharification time, carried out the stabilization of organizing the matter structure of protein floculation, and stop to stir in the saccharification later stage, leave standstill, leave time enough (more than 4 hours) the protein come-up of a large amount of flocculations is assembled, carry out the fastening stable of poor enrichment of protein sugar and weave construction.
In addition, discharge port is opened in different heights position on saccharifying tank top, can " decant " go out more protein suspending thing, improve the content concn of the poor solid insoluble of the flocculation protein sugar of material to be processed, reduced the volume amount of the saccharification liquid of wanting the centrifugation processing, improved the end-use performance of separating device, costs such as energy efficient, power consumption.
Compare with the whole centrifugations of liquefaction back liquefier, leave standstill enrichment and isolating processing by the saccharification later stage, make the poor content concn of protein sugar of isolated material improve 2~3 times, it is about 80% to need the volume amount of the treatment solution of centrifugation to reduce, and the most solid protein floculation in whole jar of saccharification liquid is removed; In addition, protein sugar is poor to be organized the matter structure to become through long saccharifying to stablize fastening, and the centrifugal settling characteristic is better; The temperature of different batches treatment solution, pH (iso-electric points in pH4.8~5.2) are also unanimous on the whole, therefore, the operation control stabilization of centrifugal separation equipment, separation efficiency improves, and result of use is good.
(4) in the poor process of centrifugation protein sugar, do not wash, reduced cost, when saccharification liquid activated carbon decolorizing or diatomite help filter, the viscid protein sugar poor can the coating active charcoal, diatomite, perhaps by gac, diatomite adsorption, thereby reduced the function of the auxiliary agent that is added.Because saccharification liquid to be processed removed most solid protein floculation, reduced the poor parcel of this part viscid protein sugar, adsorption aid particulate negative interaction, therefore, decoloration active carbon and help the diatomaceous consumption of filter can be than original minimizing.
(5) having removed most of viscid flocculation protein sugar owing to saccharification liquid is centrifugal is pickled with grains or in wine, the strainability of material greatly improves, and the syrupy ability of the filtration of pressure filter is original 2~3 times, the filter operation cycle stretch-out, equipment capacity improves, and has increased the accessibility of production scheduling; Pressure filter loading and unloading number of times reduces, and labor strength reduces; Total washing water, the rare liquid glucose that washs out, sugar decrease and the filter cloth loss all significantly reduces, be about original 50%, can remedy in the process of centrifugation and not wash that part of sugar of institute's " loss ", also reduce the quantity discharged of washes protein sugar is poor.These all are before filtering, and remove the poor benefit of being brought to producing of protein sugar.
(6) the nitrogenous starch syrup of the inventive method preparation contains the required organic nitrogen source nutritive elements of microbial fermentation such as more rich protolysate and alpha-amino nitrogen, add suitable and abundant carbon source, can simplify fermentation application technology flow process, be suitable for the zymotechnique that high dense stream adds, improve leavening property and unit production capacity, reduce production costs.Such nitrogenous starch syrup is used for different fields such as food fermentation, biochemical pharmacy and has good application benefit, is that to be suitable for very much with the coin protein sugar dregs be the product that raw material carries out comprehensive development and utilization.
(7) adopt method of the present invention, the utilization ratio of the dry substance of W-Gum increases, and meaning to be discharged into needs the BOD and the COD that handle to reduce in the outside environment.
Embodiment
Embodiment 1
(1) size mixing: at jar an amount of water of adding of sizing mixing, start stirring, add W-Gum, the concentration of control powder slurries dry substance is 40%wt, adds calcium chloride, control slurries Ca 2+Content 20mg/kg, the pH value of regulating the powder slurries is 5.6~5.8, adds the Liquozyme Supra high-temperature of 1.2kg/t butt starch at last, mixes, and prepares to liquefy.
(2) liquefaction: adopt the technology of second spraying liquefaction, the steam ejection liquefaction temperature is 108 ℃ for the first time, time 3min, and the temperature of steam ejection liquefaction is 130 ℃ for the second time, time 5min, 100 ℃ of insulations, time 60min.
(3) saccharification and leave standstill processing: liquefier is cooled to 50~55 ℃, the pH value is 5.6~5.9, adds the beta-amylase of 1.3kg/t butt starch, the Promozyme D2 Propiram debranching factor cooperative saccharification of 0.06kg/t butt starch, 25 hours time, product D E value gets final product greater than 48.0.Before saccharification finishes 5 hours, saccharifying tank stops to stir, and leaves standstill the gathering of the poor fully come-up of the protein sugar of waiting for flocculation.
(4) standing separation: the decant bleeder valve of opening saccharifying tank top from top to bottom one by one, control fluid speed, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (for saccharifying tank liquid glucose height 18%), be retracted to 50~55 ℃ insulated tank, regulate pH to 4.8~5.0 of material, prepare to carry out centrifugation.
(5) centrifugation: adopt the Alfa Laval disk centrifugal separator of 5000r/min to carry out saccharification liquid and poor the separating of protein sugar, the clarifying liquid glucose that comes out mixes again with the bottom saccharification liquid of same saccharifying tank, and that carries out next step again makes with extra care, is condensed into starch syrup.
(6) drying: the albumen by product that step (5) centrifugation is come out dewaters with spray drying device, crushing screening then, and weighing is packaged to be protein product, can be used as the protein raw materials of feed, food and fermentation usefulness.
Present embodiment makes full use of the long characteristics of saccharification time, carried out the stabilization of organizing the matter structure of protein floculation, and stop to stir in the saccharification later stage, leave standstill, leave time enough (5 hours) the protein come-up of a large amount of flocculations is assembled, carry out the fastening stable of poor enrichment of protein sugar and weave construction.
In addition, the different heights position of (saccharifying tank height 30% part) has discharge port on saccharifying tank top, decant goes out to account for the upper strata saccharification liquid of liquid glucose height 18% in the saccharifying tank, but decant goes out more protein suspending thing, improve the content concn of the poor solid insoluble of the flocculation protein sugar of material to be processed, reduce the volume amount of the saccharification liquid that needs the centrifugation processing, improved the end-use performance of separating device, costs such as energy efficient, power consumption.
Compare with the whole centrifugations of liquefaction back liquefier, present embodiment leaves standstill enrichment and isolating processing by the saccharification later stage, make the poor content concn of isolated protein sugar improve about 2 times, it is about 80% to need the volume amount of the treatment solution of centrifugation to reduce, and the most solid protein floculation in whole jar of saccharification liquid is removed; In addition, protein sugar is poor to be organized the matter structure to become through long saccharifying to stablize fastening, and the centrifugal settling characteristic is better; The temperature of different batches treatment solution, pH (iso-electric points in pH4.8~5.0) are also unanimous on the whole, therefore, the operation control stabilization of centrifugal separation equipment, separation efficiency improves, and result of use is good.
When saccharification liquid activated carbon decolorizing or diatomite help filter, the viscid protein sugar poor can the coating active charcoal, diatomite, perhaps by gac, diatomite adsorption, thereby reduced the function of the auxiliary agent that is added.Because saccharification liquid to be processed removed most solid protein floculation, reduced the poor parcel of this part viscid protein sugar, adsorption aid particulate negative interaction, therefore, decoloration active carbon and help the diatomaceous consumption of filter can be than original minimizing.
Removed most of viscid flocculation protein sugar owing to saccharification liquid is centrifugal poor, the strainability of material greatly improves, and the syrupy ability of the filtration of pressure filter is about original 2 times, the filter operation cycle stretch-out, equipment capacity improves, and has increased the accessibility of production scheduling; Pressure filter loading and unloading number of times reduces, and labor strength reduces; Total washing water, the rare liquid glucose that washs out, sugar decrease and the filter cloth loss all significantly reduces, be about original 50%, can remedy in the process of centrifugation and not wash that part of sugar of institute's " loss ", also reduce the quantity discharged of washes protein sugar is poor.These all are before filtering, and remove the poor benefit of being brought to producing of protein sugar.
The nitrogenous starch syrup of the inventive method preparation contains the required organic nitrogen source nutritive elements of microbial fermentation such as more rich protolysate and alpha-amino nitrogen, add suitable and abundant carbon source, can simplify fermentation application technology flow process, be suitable for the zymotechnique that high dense stream adds, improve leavening property and unit production capacity, reduce production costs.Such nitrogenous starch syrup is used for different fields such as food fermentation, biochemical pharmacy and has good application benefit, is that to be suitable for very much with the coin protein sugar dregs be the product that raw material carries out comprehensive development and utilization.
Adopt method of the present invention, the utilization ratio of the dry substance of W-Gum increases, and meaning to be discharged into needs the BOD and the COD that handle to reduce in the outside environment, has economical and social double benefit.
Embodiment 2
(1) size mixing: at jar an amount of water of adding of sizing mixing, start stirring, add W-Gum, the concentration of control powder slurries dry substance is 40%wt, adds calcium chloride, control slurries Ca 2+Content 20mg/kg, the pH value of regulating the powder slurries is 5.6~5.8, adds the Liquozyme Supra high-temperature of 1.2kg/t butt starch at last, mixes, and prepares to liquefy.
(2) liquefaction: adopt the technology of second spraying liquefaction, the steam ejection liquefaction temperature is 108 ℃ for the first time, time 3min, and the temperature of steam ejection liquefaction is 130 ℃ for the second time, time 5min, 100 ℃ of insulations, time 60min.
(3) saccharification and leave standstill processing: liquefier is cooled to 50~55 ℃, the pH value is 5.6~5.9, adds the beta-amylase of 1.3kg/t butt starch, the Promozyme D2 Propiram debranching factor cooperative saccharification of 0.06kg/t butt starch, 25 hours time, product D E value gets final product greater than 48.0.Before saccharification finishes 5 hours, saccharifying tank stops to stir, and leaves standstill the gathering of the poor fully come-up of the protein sugar of waiting for flocculation.
(4) standing separation: the decant bleeder valve of opening saccharifying tank top from top to bottom one by one, control fluid speed, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (for saccharifying tank liquid glucose height 18%), be retracted to 50~55 ℃ insulated tank, regulate pH to 4.8~5.0 of material, prepare to carry out centrifugation.
(5) centrifugation: adopt the Alfa Laval disk centrifugal separator of 5000r/min to carry out saccharification liquid and poor the separating of protein sugar, the clarifying liquid glucose that comes out mixes again with the bottom saccharification liquid of same saccharifying tank, and that carries out next step again makes with extra care, is condensed into starch syrup.
(6) acid hydrolysis: the protein sugar that step (5) centrifugation is come out is poor, with the food grade hydrochloric acid of 3.5mol/L 130 ℃ of hydrolysis 6 hours, adopt 10% sodium carbonate solution to be neutralized to pH4.8~5.0, activated carbon deodorization, filtration with 0.5% pair of albumen dry weight (as follows), at vacuum concentration to dry solids content is 72%, can be used as the albumen nitrogenous source that fermentation and food are used.
Embodiment 3
(1) size mixing: at jar an amount of water of adding of sizing mixing, start stirring, add W-Gum, the concentration of control powder slurries dry substance is 40%wt, adds calcium chloride, control slurries Ca 2+Content 20mg/kg, the pH value of regulating the powder slurries is 5.6~5.8, adds the Liquozyme Supra high-temperature of 1.2kg/t butt starch at last, mixes, and prepares to liquefy.
(2) liquefaction: adopt the technology of second spraying liquefaction, the steam ejection liquefaction temperature is 108 ℃ for the first time, time 3min, and the temperature of steam ejection liquefaction is 130 ℃ for the second time, time 5min, 100 ℃ of insulations, time 60min.
(3) saccharification and leave standstill processing: liquefier is cooled to 50~55 ℃, the pH value is 5.6~5.9, adds the beta-amylase of 1.3kg/t butt starch, the Promozyme D2 Propiram debranching factor cooperative saccharification of 0.06kg/t butt starch, 25 hours time, product D E value gets final product greater than 48.0.Before saccharification finishes 5 hours, saccharifying tank stops to stir, and leaves standstill the gathering of the poor fully come-up of the protein sugar of waiting for flocculation.
(4) standing separation: the decant bleeder valve of opening saccharifying tank top from top to bottom one by one, control fluid speed, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (for saccharifying tank liquid glucose height 18%), be retracted to 50~55 ℃ insulated tank, regulate pH to 4.8~5.0 of material, prepare to carry out centrifugation.
(5) centrifugation: adopt the Alfa Laval disk centrifugal separator of 5000r/min to carry out saccharification liquid and poor the separating of protein sugar, the clarifying liquid glucose that comes out mixes again with the bottom saccharification liquid of same saccharifying tank, and that carries out next step again makes with extra care, is condensed into starch syrup.
(6) acid hydrolysis, drying: the protein sugar that step (5) centrifugation is come out is poor, with the hydrochloric acid of 4.0mol/L 110 ℃ of hydrolysis 18 hours, the activated carbon deodorization with 1%, filter after, remove most Cl with OH-type anionite-exchange resin -, being neutralized to pH6~7, vacuum concentration to concentration is 80%, perhaps concentrated solution is dried to solid product again, can be used as the albumen nitrogenous source that fermentation and food are used.
Embodiment 4
(1) size mixing: at jar an amount of water of adding of sizing mixing, start stirring, add W-Gum, the concentration of control powder slurries dry substance is 40%wt, adds calcium chloride, control slurries Ca 2+Content 20mg/kg, the pH value of regulating the powder slurries is 5.6~5.8, adds the Liquozyme Supra high-temperature of 1.2kg/t butt starch at last, mixes, and prepares to liquefy.
(2) liquefaction: adopt the technology of second spraying liquefaction, the steam ejection liquefaction temperature is 108 ℃ for the first time, time 3min, and the temperature of steam ejection liquefaction is 130 ℃ for the second time, time 5min, 100 ℃ of insulations, time 60min.
(3) saccharification and leave standstill processing: liquefier is cooled to 50~55 ℃, the pH value is 5.6~5.9, adds the beta-amylase of 1.3kg/t butt starch, the Promozyme D2 Propiram debranching factor cooperative saccharification of 0.06kg/t butt starch, 25 hours time, product D E value gets final product greater than 48.0.Before saccharification finishes 5 hours, saccharifying tank stops to stir, and leaves standstill the gathering of the poor fully come-up of the protein sugar of waiting for flocculation.
(4) standing separation: the decant bleeder valve of opening saccharifying tank top from top to bottom one by one, control fluid speed, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (for saccharifying tank liquid glucose height 18%), be retracted to 50~55 ℃ insulated tank, regulate pH to 4.8~5.0 of material, prepare to carry out centrifugation.
(5) centrifugation: adopt the Alfa Laval disk centrifugal separator of 5000r/min to carry out saccharification liquid and poor the separating of protein sugar, the clarifying liquid glucose that comes out mixes again with the bottom saccharification liquid of same saccharifying tank, and that carries out next step again makes with extra care, is condensed into starch syrup.
(6) enzymic hydrolysis: the protein sugar that step (5) centrifugation is come out is poor, the water that adds 3 times, attemperation is 62 ℃~65 ℃, the pH value is about 6.5, adds 0.8 weight part papoid, reacts 20 hours, impurity such as smart filtering fiber, vacuum concentration to concentration is 80%, perhaps concentrated solution is dried to solid product again, can be used as the albumen nitrogenous source that fermentation and food are used.
(7) composite: the solid that step (6) is obtained or the albumen nitrogenous source of liquid, make the starch syrup of high malt sugar content type with present method step (5), carry out compositely according to 100: 0.3 ratio of sugared nitrogen butt, can obtain the nitrogenous starch syrup of fermentation.
Embodiment 5
(1) size mixing: at jar an amount of water of adding of sizing mixing, start stirring, add W-Gum, the concentration of control powder slurries dry substance is 40%wt, adds calcium chloride, control slurries Ca 2+Content 20mg/kg, the pH value of regulating the powder slurries is 5.6~5.8, adds the Liquozyme Supra high-temperature of 1.2kg/t butt starch at last, mixes, and prepares to liquefy.
(2) liquefaction: adopt the technology of second spraying liquefaction, the steam ejection liquefaction temperature is 108 ℃ for the first time, time 3min, and the temperature of steam ejection liquefaction is 130 ℃ for the second time, time 5min, 100 ℃ of insulations, time 60min.
(3) saccharification and leave standstill processing: liquefier is cooled to 50~55 ℃, the pH value is 5.6~5.9, adds the beta-amylase of 1.3kg/t butt starch, the Promozyme D2 Propiram debranching factor cooperative saccharification of 0.06kg/t butt starch, 25 hours time, product D E value gets final product greater than 48.0.Before saccharification finishes 5 hours, saccharifying tank stops to stir, and leaves standstill the gathering of the poor fully come-up of the protein sugar of waiting for flocculation.
(4) standing separation: the decant bleeder valve of opening saccharifying tank top from top to bottom one by one, control fluid speed, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (for saccharifying tank liquid glucose height 18%), be retracted to 50~55 ℃ insulated tank, regulate pH to 4.8~5.0 of material, prepare to carry out centrifugation.
(5) centrifugation: adopt the Alfa Laval disk centrifugal separator of 5000r/min to carry out saccharification liquid and poor the separating of protein sugar, the clarifying liquid glucose that comes out mixes again with the bottom saccharification liquid of same saccharifying tank, and that carries out next step again makes with extra care, is condensed into starch syrup.
(6) enzymic hydrolysis: the water that the protein sugar that step (5) centrifugation is come out is pickled with grains or in wine and adds 5 times, regulating temperature of charge is 60 ℃~63 ℃, pH value about 7.3, added the Flavourzyme 500MG proteolytic enzyme of 0.6 weight part and Protamex mmp reaction 10 hours, impurity such as smart filtering fiber, vacuum concentration to concentration is 78%, perhaps concentrated solution is dried to solid phase prod, the product local flavor is pure, and tasty mouthfeel can be used as the albumen nitrogenous source that fermentation and food are used.
(7) composite: the solid that step (6) is obtained or the albumen nitrogenous source of lotion, the starch syrup of the high malt sugar type that makes with present method step (5) carries out compositely according to 100: 0.5 ratio of sugared nitrogen butt, obtain the nitrogenous starch syrup of fermentation.
Embodiment 6
(1) size mixing: at jar an amount of water of adding of sizing mixing, start stirring, add W-Gum, the concentration of control powder slurries dry substance is 46%, adds calcium chloride, control slurries Ca 2+Content 45mg/kg, the pH value of regulating the powder slurries is 6.3~6.4, adds the Termamyl 120L high-temperature of 1.0kg/t butt starch at last,
(2) liquefaction: adopt the technology of second spraying liquefaction, the steam ejection liquefaction temperature is 105 ℃ for the first time, time 5min, and the temperature of steam ejection liquefaction is 135 ℃ for the second time, 8 minutes time, 95 ℃ of insulations, time 100min.
(3) saccharification and leave standstill processing: liquefier is cooled to 55~60 ℃, and the pH value is 4.1~4.3, adds the Dextrozyme DX compounded saccharifying enzyme of 1.2kg/t butt starch, effect hydrolysis time 70 hours, and product D E value is 97.8.Before saccharification finishes 4 hours, saccharifying tank stops to stir, and leaves standstill the gathering of the poor fully come-up of the protein sugar of waiting for flocculation.
(4) standing separation: the decant bleeder valve of opening saccharifying tank top from top to bottom one by one, control fluid speed, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (for saccharifying tank liquid glucose height 10%), be retracted to 50~55 ℃ insulated tank, regulate pH to 5.0~5.2 of material, prepare to carry out centrifugation.
(5) centrifugation: adopt the Alfa Laval disk centrifugal separator of 3000r/min to carry out saccharification liquid and poor the separating of protein sugar, the clarifying liquid glucose that comes out and the bottom saccharification liquid of same saccharifying tank mix again carry out next step again make with extra care, be condensed into starch syrup.
(6) drying: the albumen by product that step (5) centrifugation is come out dewaters with vacuum dryer, crushing screening then, and weighing is packaged to be protein product, can be used as the protein raw materials of feed, food and fermentation usefulness.
(7) composite: the solid that step (6) is obtained or the albumen nitrogenous source of lotion, the starch syrup of the high glucose type that makes with present method step (5) carries out compositely according to 100: 1 ratio of sugared nitrogen butt, obtain the nitrogenous starch syrup of fermentation.
Embodiment 7
(1) size mixing: at jar an amount of water of adding of sizing mixing, start stirring, add W-Gum, the concentration of control powder slurries dry substance is 46%, adds calcium chloride, control slurries Ca 2+Content 45mg/kg, the pH value of regulating the powder slurries is 6.3~6.4, adds the Termamyl 120L high-temperature of 1.0kg/t butt starch at last,
(2) liquefaction: adopt the technology of second spraying liquefaction, the steam ejection liquefaction temperature is 105 ℃ for the first time, time 5min, 135 ℃ of the temperature of second steam ejection liquefaction, 8 minutes time, 95 ℃ of insulations, time 100min.
(3) saccharification and leave standstill processing: liquefier is cooled to 50 ℃~53 ℃, and the pH value is 5.6~5.8, adds the germination Fructus Hordei Germinatus of 1.4kg/t butt starch, the Promozyme D2 Propiram debranching factor cooperative saccharification of 0.1kg/t butt starch, hydrolysis time 25 hours.Product D E value is 52.6.Before saccharification finishes 4 hours, saccharifying tank stops to stir, and leaves standstill the gathering of the poor fully come-up of the protein sugar that makes flocculation.
(4) standing separation: the decant bleeder valve of opening saccharifying tank top from top to bottom one by one, control fluid speed, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (for saccharifying tank liquid glucose height 15%), be retracted to 50~55 ℃ insulated tank, regulate pH to 5.0~5.2 of material, prepare to carry out centrifugation.
(5) centrifugation: adopt 3000r/min or the higher Alfa Laval disk centrifugal separator of rotating speed to carry out saccharification liquid and poor the separating of protein sugar, the clarifying liquid glucose that comes out and the bottom saccharification liquid of same saccharifying tank mix again carry out next step again make with extra care, be condensed into starch syrup.
(6) the poor acid hydrolysis of protein sugar: the albumen by product that step (5) centrifugation is come out, with the hydrochloric acid of 5.0mol/L 130 ℃ of hydrolysis 3 hours, adopt sodium hydroxide solution to be neutralized to pH4.4~4.6, the activated carbon deodorization with 0.5%, filtration, vacuum concentration to dry solids content is 70%.
(7) composite: the solid that step (6) is obtained or the albumen nitrogenous source of lotion, the starch syrup of the high malt sugar type that makes with present method step (5) carries out compositely according to 100: 0.5 ratio of sugared nitrogen butt, obtain the nitrogenous starch syrup of fermentation.
Embodiment 8
(1) size mixing: at jar an amount of water of adding of sizing mixing, start stirring, add W-Gum, the concentration of control powder slurries dry substance is 46%, adds calcium chloride, control slurries Ca 2+Content 45mg/kg, the pH value of regulating the powder slurries is 6.3~6.4, adds the Termamyl 120L high-temperature of 1.0kg/t butt starch at last,
(2) liquefaction: adopt the technology of second spraying liquefaction, the steam ejection liquefaction temperature is 105 ℃ for the first time, time 5min, 135 ℃ of the temperature of second steam ejection liquefaction, 8 minutes time, 95 ℃ of insulations, time 100min.
(3) saccharification and leave standstill processing: liquefier is cooled to 59~61 ℃, and the pH value is 5.2~5.5, and the Promozyme 400L debranching factor that adds 0.8kg/t Fungamyl800 fungal amylase and 0.06kg/t butt starch is hydrolyzed hydrolysis time 36 hours.Product D E value is 50.3.After 31 hours, saccharifying tank stops to stir in saccharification, leaves standstill the poor fully come-up of the protein sugar of waiting for flocculation and assembles.
(4) standing separation: the decant bleeder valve of opening saccharifying tank top from top to bottom one by one, control fluid speed, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (for saccharifying tank liquid glucose height 12%), be retracted to 50~55 ℃ insulated tank, regulate pH to 5.0~5.2 of material, prepare to carry out centrifugation.
(5) centrifugation: adopt 3000r/min or the higher Alfa Laval disk centrifugal separator of rotating speed to carry out saccharification liquid and poor the separating of protein sugar, the clarifying liquid glucose that comes out and the bottom saccharification liquid of same saccharifying tank mix again carry out next step again make with extra care, be condensed into starch syrup.
(6) the poor acid hydrolysis of protein sugar: with the hydrochloric acid of 3.6mol/L 95 ℃ of hydrolysis 24 hours, the activated carbon deodorization with 1%, filter after, use OH -Type anionite-exchange resin is removed most Cl -, being neutralized to pH6, vacuum concentration to concentration is 80%, perhaps is spray dried to solid product again, can be used as the albumen nitrogenous source that fermentation and food are used.
Embodiment 9
(1) size mixing: at jar an amount of water of adding of sizing mixing, start stirring, add W-Gum, the concentration of control powder slurries dry substance is 46%, adds calcium chloride, control slurries Ca 2+Content 45mg/kg, the pH value of regulating the powder slurries is 6.3~6.4, adds the Termamyl 120L high-temperature of 1.0kg/t butt starch at last,
(2) liquefaction: adopt the technology of second spraying liquefaction, the steam ejection liquefaction temperature is 105 ℃ for the first time, time 5min, 135 ℃ of the temperature of second steam ejection liquefaction, 8 minutes time, 95 ℃ of insulations, time 100min.
(3) saccharification and leave standstill processing: liquefier is cooled to 59~61 ℃, and the pH value is 5.2~5.5, and the Promozyme 400L debranching factor that adds 0.8kg/t Fungamyl800 fungal amylase and 0.06kg/t butt starch is hydrolyzed hydrolysis time 36 hours.Product D E value is 50.3.After 31 hours, saccharifying tank stops to stir in saccharification, leaves standstill the poor fully come-up of the protein sugar of waiting for flocculation and assembles.
(4) standing separation: the decant bleeder valve of opening saccharifying tank top from top to bottom one by one, control fluid speed, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (for saccharifying tank liquid glucose height 12%), be retracted to 50~55 ℃ insulated tank, regulate pH to 5.0~5.2 of material, prepare to carry out centrifugation.
(5) centrifugation: adopt 3000r/min or the higher Alfa Laval disk centrifugal separator of rotating speed to carry out saccharification liquid and poor the separating of protein sugar, the clarifying liquid glucose that comes out and the bottom saccharification liquid of same saccharifying tank mix again carry out next step again make with extra care, be condensed into starch syrup.
(6) the poor enzymic hydrolysis of protein sugar: the water that the protein sugar that step (5) centrifugation is come out is pickled with grains or in wine and adds 3 times, attemperation is 62 ℃~65 ℃, the pH value is 7.5, add 1 weight part papoid and Alcalase 2.4L FG proteolytic enzyme (two kinds of enzyme weight ratios are 1: 1), reacted 10 hours, impurity such as smart filtering fiber, vacuum concentration to concentration is 80%, perhaps be spray dried to solid product again, can be used as the albumen nitrogenous source that fermentation and food are used.
(7) composite: the solid that step (6) is obtained or the albumen nitrogenous source of lotion, the starch syrup of the high malt sugar type that makes with present method step (5) carries out compositely according to 100: 2 ratio of sugared nitrogen butt, obtain the nitrogenous starch syrup of fermentation.
Embodiment 10
(1) size mixing: at jar an amount of water of adding of sizing mixing, start stirring, add W-Gum, the concentration of control powder slurries dry substance is 46%, adds calcium chloride, control slurries Ca 2+Content 45mg/kg, the pH value of regulating the powder slurries is 6.3~6.4, adds the Termamyl 120L high-temperature of 1.0kg/t butt starch at last,
(2) liquefaction: adopt the technology of second spraying liquefaction, the steam ejection liquefaction temperature is 105 ℃ for the first time, time 5min, 135 ℃ of the temperature of second steam ejection liquefaction, 8 minutes time, 95 ℃ of insulations, time 100min.
(3) saccharification and leave standstill processing: liquefier is cooled to 59~61 ℃, the pH value is 5.2~5.5, the Promozyme 400L debranching factor that adds 0.8kg/t butt starch Fungamyl 800 fungal amylases and 0.06kg/t butt starch is hydrolyzed hydrolysis time 36 hours.Product D E value is 50.3.After 31 hours, saccharifying tank stops to stir in saccharification, leaves standstill the poor fully come-up of the protein sugar of waiting for flocculation and assembles.
(4) standing separation: the decant bleeder valve of opening saccharifying tank top from top to bottom one by one, control fluid speed, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (for saccharifying tank liquid glucose height 12%), be retracted to 50~55 ℃ insulated tank, regulate pH to 5.0~5.2 of material, prepare to carry out centrifugation.
(5) centrifugation: adopt the Alfa Laval disk centrifugal separator of 3000r/min to carry out saccharification liquid and poor the separating of protein sugar, the clarifying liquid glucose that comes out and the bottom saccharification liquid of same saccharifying tank mix again carry out next step again make with extra care, be condensed into starch syrup.
(6) the poor enzymic hydrolysis of protein sugar: the water that the protein sugar that step (5) centrifugation is come out is pickled with grains or in wine and adds 5 times, regulating temperature of charge is 58 ℃~62 ℃, the pH value is 6.0~6.3, add 0.6 weight part bromeline and 0.1 weight part trypsin protein sugar groove is 100 weight parts), reacted 20 hours, smart filter, vacuum concentration to concentration is 75%, perhaps be spray dried to solid product again, can be used as the albumen nitrogenous source that fermentation and food are used.
Embodiment 11
(1) size mixing: add an an amount of water sizing mixing jar, start stirring, add W-Gum, the concentration of control powder slurries dry substance is about 32%, adds calcium chloride, control slurries Ca 2+Content 40mg/kg, the pH value of regulating the powder slurries is 6.0~6.2, adds the Suhong AA Plus high-temperature of 0.2kg/t butt starch at last, mixes, and prepares to liquefy.
(2) liquefaction: under 108~110 ℃, carry out continuous injection liquefaction, time 8min, liquefier is handled time 140min 95~98 ℃ insulation.
(3) saccharification and leave standstill processing: liquefier is cooled to 54~58 ℃, and the pH value is 4.1~4.4, adds 1.0kg/t SuhongGA II or Dextrozyme GA glucase and carries out saccharification 65 hours, and product D E value is 97.1.Before saccharification finishes 7 hours, saccharifying tank stops to stir, and leaves standstill the gathering of the poor fully come-up of the protein sugar of waiting for flocculation.
(4) standing separation: the decant bleeder valve of opening saccharifying tank top from top to bottom one by one, control fluid speed, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (for saccharifying tank liquid glucose height 25%), be retracted to 50~55 ℃ insulated tank, regulate pH to 5.0~5.2 of material, prepare to carry out centrifugation.
(5) centrifugation: adopt the yeast whizzer of 8000r/min to carry out saccharification liquid and poor the separating of protein sugar, the clarifying liquid glucose that comes out and the bottom saccharification liquid of same saccharifying tank mix again carry out next step again make with extra care, be condensed into starch syrup.
(6) the poor acid hydrolysis of protein sugar: with the hydrochloric acid of 2.5mol/L 105 ℃ of hydrolysis 24 hours, the activated carbon deodorization with 0.8%, filter after, use OH -Type anionite-exchange resin is removed most Cl -, being neutralized to pH6.5, vacuum concentration to concentration is 75%, perhaps is spray dried to solid product again, can be used as the albumen nitrogenous source that fermentation and food are used.
Embodiment 12
(1) size mixing: add an an amount of water sizing mixing jar, start stirring, add W-Gum, the concentration of control powder slurries dry substance is about 32%, adds calcium chloride, control slurries Ca 2+Content 40mg/kg, the pH value of regulating the powder slurries is 6.0~6.2, adds the SuhongAAPlus high-temperature of 0.2kg/t butt starch at last, mixes, and prepares to liquefy.
(2) liquefaction: under 108~110 ℃, carry out continuous injection liquefaction, time 8min, liquefier is handled time 140min 95~98 ℃ insulation.
(3) saccharification and leave standstill processing: liquefier is cooled to 50~55 ℃, and the pH value is 4.1~4.4, adds 0.65kg/t AMGE type glucase and carries out saccharification 24 hours, and product D E value is 67.0.Before saccharification finishes 6 hours, saccharifying tank stops to stir, and leaves standstill the gathering of the poor fully come-up of the protein sugar of waiting for flocculation.
(4) standing separation: the decant bleeder valve of opening saccharifying tank top from top to bottom one by one, control fluid speed, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (for saccharifying tank liquid glucose height 28%), be retracted to 50~55 ℃ insulated tank, regulate pH to 5.0~5.2 of material, prepare to carry out centrifugation.
(5) centrifugation: adopt the yeast whizzer of 8000r/min to carry out saccharification liquid and poor the separating of protein sugar, the clarifying liquid glucose that comes out and the bottom saccharification liquid of same saccharifying tank mix again carry out next step again make with extra care, be condensed into starch syrup.
(6) the poor enzymic hydrolysis of protein sugar: the water that the protein sugar that step (5) centrifugation is come out is pickled with grains or in wine and adds 6 times, regulating temperature of charge is 50 ℃~52 ℃, the pH value is 7.8~8.0, the Alcalase 3.0T basic protein enzyme reaction 15 hours that adds 1 weight part, impurity such as smart filtering fiber, vacuum concentration to concentration is 80%, perhaps is spray dried to solid product again, can be used as the albumen nitrogenous source that fermentation and food are used.
(7) composite: the solid that step (6) is obtained or the albumen nitrogenous source of lotion, the starch syrup of the middle conversion type that makes with present method step (5) carries out compositely according to 100: 3 ratio of sugared nitrogen butt, obtain the nitrogenous starch syrup of fermentation.
Embodiment 13
(1) sizes mixing: at jar an amount of water of adding of sizing mixing, start stirring, add W-Gum, the concentration of control powder slurries dry substance is about 32%, adds calcium chloride, the content 40mg/kg of control slurries Ca2+, the pH value of regulating the powder slurries is 6.0~6.2, add the SuhongAAPlus high-temperature of 0.2kg/t butt starch at last, mix, prepare liquefaction.
(2) liquefaction: under 108~110 ℃, carry out continuous injection liquefaction, time 8min, liquefier is handled time 140min 95~98 ℃ insulation.
(3) saccharification and leave standstill processing: liquefier is cooled to 50~55 ℃, and the pH value is 4.1~4.4, adds 0.65kg/t butt starch AMG E type glucase and carries out saccharification 24 hours, and product D E value is 67.0.Before saccharification finishes 6 hours, saccharifying tank stops to stir, and leaves standstill the gathering of the poor fully come-up of the protein sugar of waiting for flocculation.
(4) standing separation: the decant bleeder valve of opening saccharifying tank top from top to bottom one by one, control fluid speed, make the poor upper strata saccharification liquid of the flocculation of enrichment in saccharifying tank egg sugar (for saccharifying tank liquid glucose height 28%), be retracted to 50~55 ℃ insulated tank, regulate pH to 5.0~5.2 of material, prepare to carry out centrifugation.
(5) centrifugation: adopt the yeast whizzer of 8000r/min to carry out saccharification liquid and poor the separating of protein sugar, the clarifying liquid glucose that comes out and the bottom saccharification liquid of same saccharifying tank mix again carry out next step again make with extra care, be condensed into starch syrup.
(6) the poor enzymic hydrolysis of protein sugar: the poor water that adds 5 times of the protein sugar that step (5) centrifugation is come out, attemperation is 50 ℃~52 ℃, the pH value is 5.0, the NovoCor aspartic protease that adds 0.1 weight part stomach en-and 0.5 weight part, reacted 20 hours, impurity such as smart filtering fiber, vacuum concentration to concentration is 78%, perhaps be spray dried to solid product again, can be used as the albumen nitrogenous source that fermentation and food are used.

Claims (9)

1. reclaim coin protein sugar dregs and preparation albumen nitrogenous source and nitrogenous syrupy method, it is characterized in that, may further comprise the steps:
(1) size mixing: add entry at the jar of sizing mixing, start stirring, add W-Gum, the concentration of dry substance is 32%~46% weight in the control slurries, adds calcium chloride, Ca in the control slurries 2+Content be 20~45mg/kg, the pH value of regulating slurries is 5.6~6.4, adds high-temperature again, consumption is 0.2~1.2kg/t butt starch, mixes;
(2) liquefaction: slurries are carried out the insulation processing of continuous injection liquefaction and 95~100 ℃, time 60~140min;
(3) saccharification: liquefier is cooled to 50~65 ℃ through flash distillation or heat exchange, and pH is 4.1~6.0, adds the saccharifying enzyme of 0.06~1.50kg/t butt starch, hydrolysis 25~70 hours, the DE value of control saccharification liquid;
(4) leave standstill enrichment: stop to stir in the saccharification later stage, leave standstill more than 4 hours;
(5) standing separation: open the bleeder valve on saccharifying tank top from top to bottom one by one, make saccharifying tank top be enriched with the poor saccharification liquid of flocculation protein sugar and all flow out or extraction, regulate isolated material pH to 4.8~5.2, carry out next step centrifugation;
(6) centrifugation: adopt whizzer with saccharification liquid with protein sugar is poor separates, the saccharification liquid behind the separating clarifying with make with extra care after the bottom saccharification liquid of same saccharifying tank mixes, the concentrated starch syrup of making;
(7) protein sugar that step (6) centrifugation is come out poor dehydrate, crushing screening, be packaged to be protein product; Perhaps poor acid system hydrolysis or the enzymatic hydrolysis of carrying out of the protein sugar that step (6) is obtained obtains the albumen nitrogenous source through neutralizing, make with extra care and concentrating, the composite nitrogenous starch syrup of making fermentation usefulness of albumen nitrogenous source and syrup.
2. method according to claim 1 is characterized in that the described high-temperature of step (1) is Termamyl, Liquozyme or Suhong AA Plus high-temperature.
3. preparation method according to claim 1 is characterized in that the described saccharifying enzyme of step (3) is one or more a mixture in glucoamylase, Pullulanase or beta-amylase or the fungal amylase.
4. method according to claim 3 is characterized in that the described saccharifying enzyme of step (3) is one or more the mixture in Dextrozyme compounded saccharifying enzyme, AMG glucoamylase, Promozyme Pullulanase, Fungamyl fungal amylase or the Optimalt BBA beta-amylase.
5. method according to claim 1, it is characterized in that when the concentration of dry substance was 40%~46% weight in the slurries, second spraying liquefaction was adopted in described liquefaction, the temperature of steam ejection liquefaction is below 110 ℃ for the first time, and the temperature of steam ejection liquefaction is at 130 ℃~135 ℃ for the second time; 95~100 ℃ of insulations, soaking time is 60~100min.
6. method according to claim 1 is characterized in that described whizzer is high speed dish type whizzer, filtering centrifuge or horizontal helical type whizzer, and rotating speed is more than the 3000r/min.
7. method according to claim 1, it is characterized in that, described enzymatic hydrolysis is to add the water that is equivalent to 3~6 times of its weight at the protein sugar groove, temperature is 50 ℃~65 ℃, pH is 5.0~8.0, the animal and plant protease and/or the microbial protease that add the poor weight 0.1%~1.0% of protein sugar, stirring reaction 10~20 hours.
8. method according to claim 7 is characterized in that, described animal and plant protease comprises one or more the mixture in stomach en-, trypsinase, papoid or the bromeline; Described microbial protease is one or more the mixture in neutral, the acid or alkaline microbial protease.
9. method according to claim 8 is characterized in that described microbial protease comprises Neutrase, Alcalase or Flavourzyme.
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