CN105316376A - Processing method of starchy raw material - Google Patents
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- CN105316376A CN105316376A CN201410332156.XA CN201410332156A CN105316376A CN 105316376 A CN105316376 A CN 105316376A CN 201410332156 A CN201410332156 A CN 201410332156A CN 105316376 A CN105316376 A CN 105316376A
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Abstract
The invention discloses a processing method of a starchy raw material. The processing method comprises the following steps: (1) mixing starch slurry prepared from a starchy raw material with part of amylase to obtain a mixture, contacting the mixture with steam to raise the temperature of the mixture to 105 to 115 DEG C, and maintaining the temperature for 5 to 8 minutes; (2) subjecting the mixture obtained in the step (1) to flash evaporation, cooling the temperature of the mixture to 95 to 98 DEG C, and mixing the mixture with residual amylase to carry out enzymatic hydrolysis; wherein the weight ratio of amylase used in the step (1) to amylase used in the step (2) is 1:0.3-0.7. Through the technical scheme mentioned above, the residual starch content of residues after enzymatic hydrolysis is reduced, the DE value of enzymatic hydrolysis clear liquid is reduced, the utilization rate of starch is improved, the liquidation is complete, moreover, the provided method increases the light transmittance of enzymatic hydrolysis clear liquid, and the enzymatic hydrolysis effect is prominently improved.
Description
Technical field
The present invention relates to a kind for the treatment of process of starchy material.
Background technology
Current domestic enterprise carries out pretreated method to starchy material (for corn): being added to the water by Semen Maydis powder sizes mixing obtains slurries, then, adding calcium hydroxide regulates the pH value of slurries to be 6.0-6.5, and add amylase, once be injected into 80-95 DEG C, press filtration is carried out, obtained liquefaction clear liquid after the examination of maintenance iodine is qualified.
There is following defect in aforesaid method: (1) amylase is difficult to mix with Semen Maydis powder, and liquefaction effect is unstable.(2) starch utilization ratio is low.(3) liquefaction is not thorough, sugaring grain consumption is high, although add many amylase, but starchy material is still difficult to liquefaction, even if it is qualified finally to make liquefier iodine try reluctantly, but liquefier press filtration is difficult, filter residue viscosity is large, water content is high, not only can part liquid glucose be brought in filter residue, also cause diastatic waste simultaneously.
Summary of the invention
The object of the invention is to overcome above-mentioned defect of the prior art, the starchy material treatment process of the DE value that a kind of residual starch content that can reduce in enzymolysis residue, reduction enzymolysis clear liquid are provided and the transmittance improving enzymolysis clear liquid.
The present inventor finds under study for action, starchy material really dissolves 100-160 DEG C of ability, but diastatic inactivation wholly or in part can be caused then can not to adopt so high gelatinization point owing to considering high temperature in prior art, but first spray once at lesser temps, and maintain the long period, then spray again once at comparatively high temps.The present inventor, through research, changes the technique of existing twice injection, the technique that employing is once sprayed and twice enzyme-added, by controlling gelatinization point and time to certain limit, both gelatinization can have been made thorough, amylase inactivation can not have been caused again, also can reduce the viscosity of gelatinization mucus simultaneously; By adding amylase and control liquefaction holding temperature to diastatic optimum temperuture in batches, thus amylase is played one's part to the full, obtain good hydrolysis result, then complete the present invention.
The invention provides a kind for the treatment of process of starchy material, the method comprises the following steps:
(1) farinaceous size obtained by starchy material is mixed with partial starch enzyme, obtain mixture, contacted with steam by this mixture, the condition of contact makes the temperature of the mixture after contacting with steam be 105-115 DEG C, and keeps 5-8 minute at such a temperature;
(2) by the mixture flash distillation after the contacting with steam of step (1), be cooled to 95-98 DEG C, and mix with the amylase of remainder, carry out enzymolysis,
Wherein, the weight ratio of the diastatic consumption of the remainder in the consumption of the partial starch enzyme in step (1) and step (2) is 1:0.3-0.7.
By above technical scheme, the inventive method can reduce the DE value of residual starch content in enzymolysis residue and enzymolysis clear liquid, thus improves starch utilization ratio, liquefaction thoroughly, and the inventive method improves the transmittance of enzymolysis clear liquid, and hydrolysis result significantly improves.
In a preferred embodiment of the invention, by adjustment liquefaction process, the efficient liquefaction of the farinaceous size of dry matter content higher (32-40 % by weight) can be realized, the water consumption (for the production line consuming 130,000 tons of starchy materials year, at least saving 4.5 ten thousand tons every year) prepared in farinaceous size (sizing mixing) process is saved under the prerequisite ensureing preferably liquefaction and saccharification result.
Other features and advantages of the present invention are described in detail in embodiment part subsequently.
Embodiment
Below the specific embodiment of the present invention is described in detail.Should be understood that, embodiment described herein, only for instruction and explanation of the present invention, is not limited to the present invention.
In the present invention, when not doing contrary explanation, term " DE value " refers to that reducing sugar (with glucose meter) accounts for the per-cent of feed liquid dry-matter.
The treatment process of starchy material provided by the invention comprises the following steps:
(1) farinaceous size obtained by starchy material is mixed with partial starch enzyme, obtain mixture, this mixture is contacted with steam, the condition of contact makes the temperature of the mixture after contacting with steam be 105-125 DEG C (being preferably 110-120 DEG C), and keeps at such a temperature 5-8 minute (being preferably 6-7 minute);
(2) by the mixture flash distillation after the contacting with steam of step (1), be cooled to 95-98 DEG C, and mix with the amylase of remainder, carry out enzymolysis,
Wherein, the weight ratio of the diastatic consumption of the remainder in the consumption of the partial starch enzyme in step (1) and step (2) is 1:0.3-0.7 (being preferably 1:0.4-0.6).
In the present invention, mixture after the contacting with steam of step (1) with can carry out after material is cooled to 95-98 DEG C diastatic mixing of the remainder in step (2), also can carry out before material is cooled to 95-98 DEG C, but preferably carried out before material is cooled to 95-98 DEG C, namely, before carrying out flash distillation, the mixture after the amylase adding remainder makes its contacting with steam with step (1) mixes, and then carries out flash distillation and enzymolysis.
According to the present invention, described diastatic consumption is appropriate as well, comprehensive hydrolysis result and cost consideration, and relative to per ton with the starchy material of dry weight basis, described diastatic total consumption is 400-450g, is preferably 420-450g.
Amylase refers to can the general name of class of enzymes of starch-splitting glycosidic link, and described amylase generally comprises α-amylase, beta-amylase, saccharifying enzyme and isoamylase.
α-amylase is also known as starch Isosorbide-5-Nitrae-dextrinase, and it can cut the α-Isosorbide-5-Nitrae-glycosidic link of starch chain inside at random, brokenly, is maltose, the oligosaccharides containing 6 glucose units and the oligosaccharides with side chain by Starch Hydrolysis.The microorganism producing this enzyme mainly contains Bacillus subtilus, aspergillus niger, aspergillus oryzae and head mold.
Beta-amylase, also known as starch Isosorbide-5-Nitrae-maltoside enzyme, can cut Isosorbide-5-Nitrae-glycosidic link from starch molecule non reducing end, generate maltose.The product that this enzyme acts on starch is maltose and limit dextrin.This enzyme produces primarily of aspergillus, head mold and endomyces.
Saccharifying enzyme is also known as starch α-Isosorbide-5-Nitrae-glucuroide, and this enzyme acts on the non reducing end of starch molecule, in units of glucose, acts on the α-Isosorbide-5-Nitrae-glycosidic link in starch molecule successively, generates glucose.Product after saccharifying enzyme acts on amylopectin has glucose and the oligosaccharides with α-1,6-glycosidic link; Acting on the product after amylose starch is all almost glucose.This enzyme producing strains is aspergillus niger (left U.S. aspergillus, Aspergillus awamori), head mold (snow-white enzyme, De Shi head mold), endomycopsi.sp, monascus mainly.
Isoamylase is also known as starch α-1,6-glucuroide, branching enzyme, and this enzyme acts on α-1, the 6-glycosidic link at branched amylopectin molecules branching-point place, is cut by the whole side chain of amylopectin and becomes amylose starch.This enzyme producing strains mainly dislikes the bacteriums such as gas bacillus, genus bacillus and some Pseudomonas.
According to the present invention, preferably use α-amylase and/or isoamylase.In α-amylase, current multiplex Thermostable α-Amylase, Thermostable α-Amylase has excellent heat resistance, it adopts Bacillus licheniformis through deep drainpipe, the operations such as extraction are refining to be formed, can random hydrolysis starch, glycogen and degradation product inside thereof α-Isosorbide-5-Nitrae glucoside bond the viscosity of colloidal starch solution is declined rapidly, produce soluble dextrins and oligosaccharide, excessive hydrolysis can produce a small amount of glucose and maltose.Therefore, most preferably Thermostable α-Amylase is used in the present invention.
According to the present invention, the method being obtained farinaceous size by starchy material can adopt the method that well known to a person skilled in the art various routine, such as, is pulverized by starchy material, the product after pulverizing and water are mixed to get farinaceous size.The condition pulverize starchy material and mode have no particular limits, as long as starchy material can be made fully broken, under preferable case, the median size of the product after the pulverizing obtained is 10-50 micron.Be mixed to get in the process of farinaceous size by the product after pulverizing and water, the consumption of water is not particularly limited, and with the dry weight basis of starchy material, the concentration controlling described farinaceous size is preferably 32-40 % by weight, is more preferably 35-40 % by weight.The present inventor finds, the enzymolysis of the farinaceous size to higher concentration (32-40 % by weight) can be realized better by above preferred liquefaction condition, thus under the prerequisite ensureing preferably liquefaction and saccharification result, save the water consumption (for the production line consuming 130,000 tons of starchy materials year, at least saving 4.5 ten thousand tons every year) of sizing mixing in process.The pH value of described farinaceous size can be 5.6-5.8.
According to the present invention, in step (1), mix that there is no particular limitation to farinaceous size with diastatic, but temperature is slightly high is conducive to the mixing of the two and follow-up gelatinization, preferably, the temperature of mixing is 50-60 DEG C.In step (1), farinaceous size is wider with the selectable range of the condition that diastatic mixture contacts with steam, as long as farinaceous size and diastatic mixture can reach its suitable temperature respectively after ensureing contact, such as, the condition that described mixture contacts with steam comprises the usage ratio and duration of contact etc. of the temperature of contact, steam and mixture.Under preferable case, in step (1), the temperature that the condition of contact comprises steam is 150-200 DEG C, and the weight ratio of steam and mixture is 0.02-0.1:1, and the time of contact is 1-5 second; More preferably in situation, consider the energy and cost, in step (1), the temperature of steam is 160-180 DEG C, and the ratio of steam and mixture is 0.04-0.06:1, and the time of contact is 1-3 second.
Wherein, the mode that farinaceous size and diastatic mixture are contacted with steam is not particularly limited, under preferable case, and can at injector known in those skilled in the art (such as, the long water heater of million smooth injectors or sky.) in carry out injection contact, that is, by farinaceous size and diastatic mixture and steam while, be ejected in injector and carry out instantaneous touch fast.
According to the present invention, in step (2), in order to reach better brought by temperature variation fast make the expansion of starch molecule more abundant, to such an extent as to macrobead starch swelling fracture can be made to be the object of starch granule, and make the contact better effects if of amylase and starch granules, to reach better hydrolysis result, the present invention adopts the mode of flash distillation that the mixture after the contacting with steam of step (1) is cooled to 95-98 DEG C, and preferably, in quantity-produced process by flash distillation after the steam that obtains return in step (1), for contacting with mixture, the reuse of steam can reduce production cost greatly.In addition, the water of condensation obtained after flash distillation also can return for the preparation of farinaceous size in step (1), that is, for starchy material is pulverized after product after the pulverizing that obtains mix to prepare farinaceous size.Wherein, flash distillation refer to the saturation water of high pressure enter after in the container of relatively low pressure due to the unexpected reduction of pressure make these saturation waters become a part container pressure under saturated steam and saturation water.According to the present invention, the selectable range of the condition of described flash distillation is wider, as long as make it the object of lowering the temperature after reaching flash distillation, such as, the mode of described flash distillation can be atmospheric flashing, and can be also vacuum flashing (vacuum flash), the present invention preferably uses the method for vacuum flashing, the pressure that the condition of described flash distillation comprises flash distillation can be-0.06MPa to-0.09MPa, and the time of flash distillation can be 5-15 second.
According to the present invention, need the step maintaining and carry out enzymolysis that liquefies after flash distillation, preferably, in step (2), the condition of described enzymolysis comprises: pH value is 5.5-7, is more preferably 5.8-6.2, and the time is 60-150 minute, is more preferably 90-120 minute.
According to the present invention, in order to make starchy material be converted into monose as much as possible, described method also preferably includes carries out saccharification by the liquefier obtained after enzymolysis in step (2).
Wherein, have no particular limits the condition of described saccharification, the temperature of described saccharification is preferably 60-70 DEG C.The pH value of described saccharification is preferably 4.2-4.4.The time of described saccharification is preferably 36-48h.The consumption of saccharification saccharifying enzyme used can be the saccharifying enzyme consumption of this area routine, and preferably, relative to the dry-matter in farinaceous size per ton, the amount of saccharification saccharifying enzyme used is 550-650g.
Wherein, saccharifying enzyme is also known as starch α-Isosorbide-5-Nitrae-glucuroide, and this enzyme acts on the non reducing end of starch molecule, in units of glucose, acts on the α-Isosorbide-5-Nitrae-glycosidic link in starch molecule successively, generates glucose.Product after saccharifying enzyme acts on amylopectin has glucose and the oligosaccharides with α-1,6-glycosidic link; Acting on the product after amylose starch is all almost glucose.Described saccharifying enzyme can by commercially available.
To the not special requirement of the mode of described saccharification, can carry out with reference to the usual manner of this area, such as, gained liquefier be added in saccharifying tank, add saccharifying enzyme and stir, generally DE value be reached 98-98.8% as saccharification terminal.
According to the present invention, described method can also comprise carries out solid-liquid separation by the saccharified liquid obtained after saccharification, and concentrates being separated the liquid phase (liquid glucose) obtained, to obtain syrup.Relative to existing treatment process, method of the present invention can process the higher farinaceous size of dry matter content, has not only saved the water consumption of step of sizing mixing, and also helps the energy consumption of saving enrichment step.
According to the present invention, described starchy material can be the various raw material containing starch that may be used for enzymolysis, preparation of citric acid by fermentation well known in the art, such as, can be selected from least one in corn, potato class (as cassava), wheat and Chinese sorghum, in described starchy material, moisture content is preferably less than 16 % by weight.
Below will be described the present invention by embodiment.In following examples, the maize raw material of starchy material for by the mean particle size obtained after corn (moisture content is 13 % by weight) pulverizing being 10 microns of use; The measuring method reference standard QB/T2319-1997 of transmittance, instrument is spectrum SP-752 ultraviolet-visible pectrophotometer (Shanghai Spectrum Apparatus Co., Ltd.), and transmittance is higher, and illustrate that the turbidity of liquid glucose is lower, liquid glucose is purer; DE value adopts fehling reagent titration detection method to record.In following examples, the experimental technique of unreceipted actual conditions, conveniently condition is carried out.
Embodiment 1
(1) in starchy material, adding water move to dry matter content is 35 % by weight, obtain farinaceous size, at 50 DEG C, by the farinaceous size obtained (pH value is adjusted to 6.0) with account for α-amylase gross weight 71 % by weight α-amylase mix (α-amylase that dry-matter per ton adds 420g), obtain mixture, this mixture and the steam of 170 DEG C are carried out spraying in injector and contacts (weight ratio of steam and mixture is 0.05:1), the time of contact is 2 seconds, the temperature of the mixture after contacting with steam is made to be 110 DEG C, and keep 7 minutes at such a temperature,
(2) mixture after above-mentioned steps being contacted with steam carries out flash distillation, and (pressure is-0.06MPa, time is 10 seconds) to 95 DEG C, and with account for α-amylase gross weight 29 % by weight α-amylase mix, adjust ph to 6.0, and at such a temperature keep 100 minutes; And the steam obtained after flash distillation is returned in the step that above-mentioned first time contacts with steam, water of condensation is returned in step (1) and continue on for mixing with the crushed products of corn;
(3) liquefier (DE value is 14%) step (2) obtained adds saccharifying tank, at 60 DEG C, pH value 4.4 times, add saccharifying enzyme (4060 compounded saccharifying enzymes that Genencor Company produces, dry-matter per ton adds the saccharifying enzyme of 550g), stir 48h, namely arrive saccharification terminal (DE value is 98.5%);
(4) saccharified liquid obtained after saccharification is carried out press filtration, the transmittance recording the liquid phase (liquid glucose) that press filtration obtains is 98.3%.
Embodiment 2
(1) in starchy material, adding water move to dry matter content is 40 % by weight, obtain farinaceous size, at 60 DEG C, by the farinaceous size obtained (pH value is adjusted to 7.0) with account for α-amylase gross weight 62.5 % by weight α-amylase mix (α-amylase that dry-matter per ton adds 450g), obtain mixture, this mixture and the steam of 160 DEG C are carried out spraying in injector and contacts (weight ratio of steam and mixture is 0.06:1), the time of contact is 3 seconds, the temperature of the mixture after contacting with steam is made to be 120 DEG C, and keep 6 minutes at such a temperature,
(2) mixture after above-mentioned steps being contacted with steam carries out flash distillation, and (pressure is-0.09MPa, time is 5 seconds) to 98 DEG C, and with account for α-amylase gross weight 37.5 % by weight α-amylase mix, adjust ph to 6.2, and at such a temperature keep 120 minutes; And the steam obtained after flash distillation is returned in the step that above-mentioned first time contacts with steam, water of condensation is returned in step (1) and continue on for mixing with the crushed products of corn;
(3) liquefier (DE value is 16%) step (2) obtained adds saccharifying tank, at 70 DEG C, pH value 4.2 times, add saccharifying enzyme (4060 compounded saccharifying enzymes that Genencor Company produces, dry-matter per ton adds the saccharifying enzyme of 600g), stir 36h, namely arrive saccharification terminal (DE value is 98.8%);
(4) saccharified liquid obtained after saccharification is carried out press filtration, the transmittance recording the liquid phase (liquid glucose) that press filtration obtains is 99%.
Embodiment 3
(1) in starchy material, adding water move to dry matter content is 38 % by weight, obtain farinaceous size, at 55 DEG C, by the farinaceous size obtained (pH value is adjusted to 5.8) with account for α-amylase gross weight 65 % by weight α-amylase mix (α-amylase that dry-matter per ton adds 430g), obtain mixture, this mixture and the steam of 180 DEG C are carried out spraying in injector and contacts (weight ratio of steam and mixture is 0.04:1), the time of contact is 1 second, the temperature of the mixture after contacting with steam is made to be 115 DEG C, and keep 6.5 minutes at such a temperature,
(2) mixture after above-mentioned steps being contacted with steam carries out flash distillation, and (pressure is-0.07MPa, time is 15 seconds) to 97 DEG C, and with account for α-amylase gross weight 35 % by weight α-amylase mix, adjust ph to 5.8, and at such a temperature keep 90 minutes; And the steam obtained after flash distillation is returned in the step that above-mentioned first time contacts with steam, water of condensation is returned in step (1) and continue on for mixing with the crushed products of corn;
(3) liquefier (DE value is 12%) step (2) obtained adds saccharifying tank, at 62 DEG C, pH value 4.3 times, add saccharifying enzyme (4060 compounded saccharifying enzymes that Genencor Company produces, dry-matter per ton adds the saccharifying enzyme of 650g), stir 42h, namely arrive saccharification terminal (DE value is 98.5%);
(4) saccharified liquid obtained after saccharification is carried out press filtration, the transmittance recording the liquid phase (liquid glucose) that press filtration obtains is 99.2%.
Embodiment 4
According to the method process starchy material of embodiment 3, unlike, the content adding water move to dry-matter in starchy material is 30 % by weight, the DE value of the liquefier obtained is 17%, DE value after saccharification is 96.9%, and the transmittance recording the liquid phase (liquid glucose) that press filtration obtains is 96.7%.
Embodiment 5
According to the method process starchy material of embodiment 3, unlike, the temperature of the mixture after contacting with steam in rate-determining steps (1) is 130 DEG C, the DE value of the liquefier obtained is 19%, DE value after saccharification is 95.8%, and the transmittance recording the liquid phase (liquid glucose) that press filtration obtains is 90.4%.
Embodiment 6
According to the method process starchy material of embodiment 3, unlike, the time kept after adding another part α-amylase in step (2) is 3h, the DE value of the liquefier obtained is 20%, DE value after saccharification is 94.6%, and the transmittance recording the liquid phase (liquid glucose) that press filtration obtains is 94%.
Comparative example 1
According to the method process starchy material of embodiment 3, unlike, the weight ratio of the α-amylase used in step (1) and the middle α-amylase used of step (2) is 1:1, the DE value of the liquefier obtained is 17%, DE value after saccharification is 93%, and the transmittance recording the liquid phase (liquid glucose) that press filtration obtains is 96%.
As can be seen from the above embodiments, adopt the inventive method liquefaction thoroughly, starch utilization ratio is high, the transmittance after saccharification and DE value all higher.
Comparing embodiment 3 and comparative example 1 can be found out, the weight ratio of the diastatic consumption of the remainder in the consumption of the partial starch enzyme in rate-determining steps (1) and step (2) can obtain higher transmittance and DE value in the framework of the present definition.Embodiment 3 is compared with embodiment 4-6 and can find out, control DE value and transmittance that the content of dry-matter in farinaceous size and liquefaction condition can improve liquid glucose further in the preferable range that the present invention limits.
More than describe the preferred embodiment of the present invention in detail; but the present invention is not limited to the detail in above-mentioned embodiment, within the scope of technical conceive of the present invention; can carry out multiple simple variant to technical scheme of the present invention, these simple variant all belong to protection scope of the present invention.
It should be noted that in addition, each concrete technical characteristic described in above-mentioned embodiment, in reconcilable situation, can be combined by any suitable mode, in order to avoid unnecessary repetition, the present invention illustrates no longer separately to various possible array mode.
In addition, also can carry out arbitrary combination between various different embodiment of the present invention, as long as it is without prejudice to thought of the present invention, it should be considered as content disclosed in this invention equally.
Claims (9)
1. a treatment process for starchy material, is characterized in that, the method comprises the following steps:
(1) farinaceous size obtained by starchy material is mixed with partial starch enzyme, obtain mixture, contacted with steam by this mixture, the condition of contact makes the temperature of the mixture after contacting with steam be 105-125 DEG C, and keeps 5-8 minute at such a temperature;
(2) by the mixture flash distillation after the contacting with steam of step (1), be cooled to 95-98 DEG C, and mix with the amylase of remainder, carry out enzymolysis,
Wherein, the weight ratio of the diastatic consumption of the remainder in the consumption of the partial starch enzyme in step (1) and step (2) is 1:0.3-0.7.
2. method according to claim 1, wherein, the weight ratio of the diastatic consumption of the remainder in the consumption of the partial starch enzyme in step (1) and step (2) is 1:0.4-0.6.
3. method according to claim 1 and 2, wherein, relative to per ton with the starchy material of dry weight basis, described diastatic total consumption is 400-450g.
4. method according to claim 1 and 2, wherein, relative to per ton with the starchy material of dry weight basis, described diastatic total consumption is 420-450g.
5. method according to claim 1, wherein, in step (1), the condition of contact makes the temperature of the mixture after contacting with steam be 110-120 DEG C, and keeps 6-7 minute at such a temperature.
6. method according to claim 1, wherein, the method being obtained farinaceous size by starchy material comprises starchy material pulverizing, and the product after pulverizing and water are mixed to get farinaceous size, with the dry weight basis of starchy material, the concentration controlling described farinaceous size is 32-40 % by weight; The median size of the product after pulverizing is 10-50 μm.
7. method according to claim 1, wherein, in step (2), the steam obtained being returned for contacting with mixture in step (1), the water of condensation obtained being returned in step (1) for the preparation of farinaceous size after flash distillation after flash distillation.
8. method according to claim 1, wherein, in step (2), the condition of described enzymolysis comprises: pH value is 5.5-7, and the time is 90-120 minute.
9. according to the method in claim 1-8 described in any one, wherein, described starchy material is selected from least one in corn, potato class, wheat and Chinese sorghum.
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| WO2001064934A2 (en) * | 2000-02-28 | 2001-09-07 | Grain Processing Corporation | High purity maltose process and products |
| CN101665843A (en) * | 2008-09-01 | 2010-03-10 | 石济民 | Method for preparing barley maltsyrup by using wheat flour |
| CN102399844A (en) * | 2011-11-03 | 2012-04-04 | 中粮生物化学（安徽）股份有限公司 | Production method of glucose |
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