CN1557959A - Enzyme hydrolysis protein liquor and deposition removal production process - Google Patents
Enzyme hydrolysis protein liquor and deposition removal production process Download PDFInfo
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- CN1557959A CN1557959A CNA2004100216996A CN200410021699A CN1557959A CN 1557959 A CN1557959 A CN 1557959A CN A2004100216996 A CNA2004100216996 A CN A2004100216996A CN 200410021699 A CN200410021699 A CN 200410021699A CN 1557959 A CN1557959 A CN 1557959A
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Abstract
The present invention is enzyme hydrolyzed protein liquid and its precipitate eliminating process, and belongs to the field of hydrolyzed protein liquid producing technology. Proteinase hydrolyzed protein liquid is first added with assistant and filtered; the calcium ion and other matter is eliminated with cationic exchange resin, free oxidized derivative sulfoxide, sulfone and sulfurous radical are oxidized into sulfuric radical with H2O2 and L-ascorbic acid, and the sulfuric radical is eliminated with silkworm chrysalis chitosan-glutamic acid cationic exchange resin; and finally, the hydrolyzed protein liquid is vacuum concentrated to required concentration and compounded into the product. The hydrolyzed protein liquid product of the present invention has the features of low salt content, light color, no bad smell, no waste produced, no harmful matter, etc. and may be used widely in food product, medicine, feed, etc.
Description
One, technical field
The invention belongs to the Hydrolyzed protein liquid production technical field, particularly protein hydrolysis liquid and precipitation remove production technique.
Two, technical background
Hydrolyzed protein liquid is the fraction of mainly being made up of small-molecular peptides that protein raw material forms after part is decomposed, and its main application is a food enrichment, flavour of food products conditioning agent, pharmaceutical injection or oral nitrogen nutrition liquid.Existing method of producing Hydrolyzed protein liquid mainly contains acid hydrolysis and enzymic hydrolysis two big classes.Acid hydrolysis mainly is to come the protolysate raw material with hydrochloric acid, uses activated carbon decolorizing again, and vacuum concentration is to needs concentration then.Though this method production cost is low; but sodium chloride content is very high in the product; color is dark; peculiar smell obviously and contain carcinogenic objectionable impuritiess such as propylene chlorohydrin; but also serious environment pollution and etching apparatus; therefore make the requirement of protolysate technology incompatibility modern environment protection with acid hydrolysis, belong to superseded Technology.Enzymic hydrolysis mainly is to use proteolytic enzyme to come the protolysate raw material, and vacuum concentration is to needs concentration then.Though the Hydrolyzed protein liquid sodium chloride-containing of producing with the protease hydrolysis method is low, of light color, do not have obvious peculiar smell and do not have carcinogenic objectionable impuritiess such as propylene chlorohydrin, there are not " three disasters " yet, but since in production process and storage because the oxidized generation vitriol of sulfur-containing amino acid, therefore be easy to generate calcium sulfate precipitation, thereby influenced the quality of product and apply.
Three, summary of the invention
The purpose of this invention is to provide a kind of protein hydrolysis liquid and precipitation and remove production technique; not only can overcome existing deficiency of producing Hydrolyzed protein liquid, and keep the advantage of protein hydrolysis liquid, also can make full use of protein raw material; help environment protection, easy to utilize.
The object of the present invention is achieved like this: a kind of protein hydrolysis liquid and precipitation remove production technique, its principal character is to use the proteolytic enzyme protolysate raw material, adding after flocculating aids filters, removing and filtering calcium ion in the protein liquid etc., using micro-H again with Zeo-karb of the present invention
2O
2And the L-xitix is to partial oxidation derivative sulfone, sulfoxide, the HSO of free sulfur-containing amino acid
3 -Carry out oxidation, generate SO respectively
4 2-, remove SO with anionite-exchange resin then
4 2-, vacuum concentration is mixed with finished product at last to the concentration that needs again, for using.
Mechanism of the present invention is:
In Hydrolyzed protein liquid, the amino of small-molecular peptides and carboxyl have the ability of complexing or chelating calcium ion, and therefore, the calcium ion that exists in the protein raw material is that the form with peptide chelate complex or inner complex exists.The new synthetic silkworm chitosan of the present invention-L-glutamic acid Zeo-karb can form inner complex with positively charged ion such as calcium with the free carboxy of L-glutamic acid, therefore the calcium ion in the Hydrolyzed protein liquid etc. can be removed; In Hydrolyzed protein liquid, sulfur-containing amino acid has two kinds, and a kind of is methionine(Met), in solution under the oxidation of oxygen by partial oxidation, generate sulfoxide or sulfone.Another kind is that (S-S-), the sulfydryl of halfcystine (SH) is reoxidised into HSO by-S-S-for halfcystine and partial oxidation products disulfide linkage thereof
3 -Under subacidity pH, H
2O
2With L-xitix synergy, H
2O
2Form and the effect of L-xitix with OH generate L-xitix peroxy acid, and latter's oxidation capacity is stronger than the former, can be with sulfoxide, sulfone and HSO
3 -Finally be oxidized to SO
4 2-, SO
4 2-The exchange of anionite-exchange resin such as available D315 removes, otherwise, if SO
4 2-After concentration and calcium ion concn product met or exceeded the solubility product of calcium sulfate generation, calcium sulfate precipitation promptly generated.In addition, remaining OH can form H again
2O, therefore, the L-xitix also can make unnecessary H
2O
2Reduction.
Production craft step of the present invention is as follows:
1. preparation protein liquid
At first protein raw material is dissolved in temperature and is in 50 ℃~60 ℃ the water, can quicken its dissolving, prepare protein concn and be 5%~20% protein liquid, and to regulate its pH value be 8.5~11.0 by measures such as stirrings;
2. preparation Hydrolyzed protein liquid
In the protein liquid of preparing, add proteolytic enzyme, prepare Hydrolyzed protein liquid, the ratio of its proteolytic enzyme and Hydrolyzed protein liquid is 1: 800~1: 2500 (W/V), and the insulation that stirs under agitation is hydrolyzed, and its hydrolysis temperature is 50~65 ℃, hydrolysis time is 30~60 minutes, sodium chloride content is few, of light color in its Hydrolyzed protein liquid of preparing, and does not have carcinogenic materials such as propylene chlorohydrin;
3. filtration Hydrolyzed protein liquid
In the Hydrolyzed protein liquid of preparation, the flocculating aids (as diatomite, gac etc.) that adds 1: 10~1: 20 (W/V) is warming up to 85 ℃~95 ℃ and kept 15~30 minutes after stirring, use vacuum filtration, remove by filter impurity in the Hydrolyzed protein liquid etc., make the Hydrolyzed protein liquid clear;
4. prepare the decalcification Hydrolyzed protein liquid
In the Hydrolyzed protein liquid after filtration, add 1: 30~1: the 20 crosslinked silkworm chitosan of the new synthetic of (W/V) the present invention-L-glutamic acid Zeo-karb, stir and under agitation carry out cation exchange reaction, the permutoid reaction time is 60~120 minutes, exchange out the also filtrations such as calcium ion that easily generate sedimentary calcium sulfate in the hydrolyzed solution, prepare the decalcification Hydrolyzed protein liquid, its filter residue is mainly used Zeo-karb, after this used Zeo-karb can be regenerated with ordinary method, for using next time, to reduce production costs;
5. preparation contains SO
4 2-Hydrolyzed protein liquid
In the decalcification Hydrolyzed protein liquid of preparation, add the H of 1: 500~1: 400 (V/V)
2O
2With the L-xitix of 1: 250~1: 200 (W/V), in 60 ℃~80 ℃ temperature, keep reacting in 50~60 minutes, prepare and contain S0
4 2-Hydrolyzed protein liquid;
6. SO is taken off in preparation
4 2-Hydrolyzed protein liquid
The SO that contains in preparation
4 2-Hydrolyzed protein liquid in, add acidulous anion exchange resins such as the D301 of 1: 40~1: 30 (W/V) or D315, stir and under agitation carried out anion exchange reaction 60~120 minutes, exchange out and easily produce sedimentary SO in the Hydrolyzed protein liquid
4 2-, prepare and take off SO
4 2-Hydrolyzed protein liquid after the filtration, is prepared and is taken off SO
4 2-Hydrolyzed protein liquid, its filter residue is mainly used anionite-exchange resin, after this used anionite-exchange resin can be regenerated with ordinary method, for using next time, to reduce production costs;
7. preparation concentrates Hydrolyzed protein liquid
At last, the SO to preparing
4 2-Hydrolyzed protein liquid carries out vacuum concentration, is concentrated into the concentration that needs, and is configured to finished product then as required.The feature of technology of the present invention is as follows:
(1) adopt the crosslinked silkworm chitosan of the new synthetic of the present invention-L-glutamic acid Zeo-karb exchange cation, the present invention of this resin system is also synthetic first, and calcium magnesium and zinc etc. are had very strong exchange capacity, and nontoxic, and degradable also uses repeatedly.
(2) adopt H in the technology
2O
2And L-xitix promote the oxidation sulfoxide, sulfone and HSO under slightly acidic condition
3 -, make to generate SO
4 2-, so that subsequent technique is removed.Remaining H
2O
2Under the effect of L-xitix, be reduced into H
2O.
(3) adopt the acidulous anion exchange resin to remove SO
4 2-
Therefore, with the Hydrolyzed protein liquid that production technique of the present invention is produced, it is low to have saltiness, of light color, does not have obvious peculiar smell, does not have " three wastes " and produces no carcinogenic characteristics such as objectionable impurities such as propylene chlorohydrin; Production cost of the present invention is low, in production process and product storage, does not have precipitation and produces.Therefore, the present invention produces the Perfected process that Hydrolyzed protein liquid is suitable for.The Hydrolyzed protein liquid of producing with this method can be widely used in industries such as food, medicine, daily use chemicals and feed.
Four, embodiment
Below in conjunction with embodiment, further specify the present invention.
Embodiment 1
Get 100 kilograms of soybean protein isolates, adding 850 kg of water disperses, regulate pH value to 9.5 with 20%NaOH, under agitation heat to 55 ℃, add 1 kilogram of papoid, hydrolysis is after 120 minutes, add 10 kilograms of super-cells then, be warming up to 85 ℃ and kept 15 minutes after stirring, use the vacuum filter suction filtration, clear filtrate.Crosslinked silkworm chitosan-L-glutamic acid the Zeo-karb that in clear liquor, adds 28.3 kilograms, stir exchange down 60 minutes, suction filtration, filter residue are used crosslinked silkworm chitosan-L-glutamic acid Zeo-karb, and this resin can be regenerated with ordinary method, and the back is next uses.Filtrate is decalcification ion Hydrolyzed protein liquid, is used for further processing.Promptly in this filtrate, add 1.7 kilograms of 30%H
2O
2And 3.75 kilograms of L-xitix, be warming up to 65 ℃ after stirring, reacted 1 hour.The D301 weak-type anionite-exchange resin that adds 22.5 kilograms then stirs 1 hour after-filtration of exchange down, and filter residue is used D301 weak-type anionite-exchange resin.This resin can use with ordinary method regeneration back next time.Filtrate being taken off SO
4 2-The ion Hydrolyzed protein liquid.This filtrate is carried out vacuum concentration, be concentrated into soluble solid and reach at 40% o'clock only.At last concentrated solution is mixed with finished product.
Embodiment 2
Get 100 kilograms of freshly prepd silkworm separated proteins (butt), adding 850 kg of water disperses, regulate pH value to 10.5 with 20%NaOH, under agitation heat to 60 ℃, be incubated and be cooled to 2 kilograms of Esperase proteolytic enzyme of 60 ℃ of addings after 30 minutes, hydrolysis was reduced to 55 ℃ with the hydrolyzed solution temperature after 60 minutes, add 1 kilogram of flavor protease once more, hydrolysis 2~3 hours.Add 20 kilograms of gacs then, be warming up to 93 ℃ and kept 25 minutes after stirring, use the vacuum filter suction filtration, faint yellow clear filtrate.Crosslinked silkworm chitosan-L-glutamic acid the Zeo-karb that in clear liquor, adds 42.5 kilograms, stir exchange down 60 minutes, suction filtration, filter residue are used crosslinked silkworm chitosan-L-glutamic acid Zeo-karb, and this resin can be regenerated with ordinary method, and the back is next uses.Filtrate is decalcification ion Hydrolyzed protein liquid, is used for further processing.In this filtrate, add 2.13 kilograms of 30%H
2O
2And 4.25 kilograms of L-xitix, be warming up to 65 ℃ after stirring, reacted 1 hour.The D315 weak-type anionite-exchange resin that adds 28.3 kilograms then stirs exchange SO down
4 2-Ion, 1 hour after-filtration, filter residue are used D315 weak-type anionite-exchange resin.This resin can use with ordinary method regeneration back next time.Filtrate being taken off SO
4 2-The ion Hydrolyzed protein liquid.This filtrate is carried out vacuum concentration, be concentrated into soluble solid and reach at 40% o'clock only.At last concentrated solution is mixed with finished product.
Claims (3)
1. protein hydrolysis liquid and precipitation remove production technique, it is characterized in that its production technique, and step is as follows:
(1) preparation protein liquid
At first protein raw material is dissolved in the water of 50 ℃~60 ℃ of temperature and stirs, prepare concentration and be 5%~20% protein liquid, and regulate its pH value;
(2) preparation Hydrolyzed protein liquid
In the protein liquid of preparing, add proteolytic enzyme, the ratio of proteolytic enzyme and Hydrolyzed protein liquid is 1: 800~1: 2500, and stirs, insulation under agitation is hydrolyzed;
(3) filter Hydrolyzed protein liquid
In the Hydrolyzed protein liquid of preparing, add 1: 10~1: 20 diatomite or gac flocculating aids, be warming up to 85 ℃~95 ℃ after stirring, keep after 15~30 minutes vacuum filtration;
(4) preparation decalcification Hydrolyzed protein liquid
In the Hydrolyzed protein liquid after filtration, add Zeo-karb, stir, under agitation carry out the cation exchange reaction after-filtration, its filter residue can be regenerated with ordinary method;
(5) preparation contains SO
4 2-Hydrolyzed protein liquid
In the decalcification Hydrolyzed protein liquid of preparation, add H
2O
2With the L-xitix, react;
(6) SO is taken off in preparation
4 2-Hydrolyzed protein liquid
The SO that contains that is preparing
4 2-Hydrolyzed protein liquid in, add anionite-exchange resin, stir, under agitation carry out anion exchange reaction, filter, its filter residue can be regenerated with ordinary method;
(7) preparation concentrates Hydrolyzed protein liquid
At last, the SO that takes off to preparing
4 2-Hydrolyzed protein liquid carries out vacuum concentration.
2. remove production technique according to described protein hydrolysis liquid of claim 1 and precipitation, the pH value that it is characterized in that regulating protein liquid is 8.5~11.0; The hydrolysis temperature of preparation Hydrolyzed protein liquid is 50 ℃~65 ℃, and hydrolysis time is 30~60 minutes; The add-on of the Zeo-karb of preparation decalcification protein liquid is 1: 30~1: 20, and the permutoid reaction time is 60~120 minutes; Preparation contains SO
4 2-The H of Hydrolyzed protein liquid
2O
2Add-on be 1: 500~1: 400, L-xitix add-on is 1: 250~1: 200, its temperature of reaction is 60 ℃~80 ℃, the hold-time is 50~60 minutes; SO is taken off in preparation
4 2-The add-on of the anionite-exchange resin of Hydrolyzed protein liquid is 1: 40~1: 30, and the permutoid reaction time is 60~120 minutes.
3. remove production technique according to described protein hydrolysis liquid of claim 1 and precipitation, it is characterized in that described Zeo-karb is crosslinked silkworm chitosan-L-glutamic acid; Described anionite-exchange resin is D
301Or D
315The acidulous anion exchange resin.
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CNA2004100216996A CN1557959A (en) | 2004-01-15 | 2004-01-15 | Enzyme hydrolysis protein liquor and deposition removal production process |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100393229C (en) * | 2006-02-23 | 2008-06-11 | 重庆大学 | Preparation method of foreign flavor free hydrolyzed protein liquid |
CN102718831A (en) * | 2012-06-12 | 2012-10-10 | 成都起点投资有限公司 | Preparation method for manufacturing silkworm pupa protein of protein filament |
CN103305573A (en) * | 2013-03-07 | 2013-09-18 | 重庆海帆生化科技有限公司 | Method for preparing undecene-hydrolysate protein derivative |
CN116837064A (en) * | 2023-09-04 | 2023-10-03 | 成都速攻痛风病研究集团有限公司 | Preparation method of silkworm chrysalis protein peptide |
-
2004
- 2004-01-15 CN CNA2004100216996A patent/CN1557959A/en active Pending
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100393229C (en) * | 2006-02-23 | 2008-06-11 | 重庆大学 | Preparation method of foreign flavor free hydrolyzed protein liquid |
CN102718831A (en) * | 2012-06-12 | 2012-10-10 | 成都起点投资有限公司 | Preparation method for manufacturing silkworm pupa protein of protein filament |
CN102718831B (en) * | 2012-06-12 | 2013-10-02 | 成都起点投资有限公司 | Preparation method for manufacturing silkworm pupa protein of protein filament |
CN103305573A (en) * | 2013-03-07 | 2013-09-18 | 重庆海帆生化科技有限公司 | Method for preparing undecene-hydrolysate protein derivative |
CN103305573B (en) * | 2013-03-07 | 2015-01-07 | 重庆海帆生化科技有限公司 | Method for preparing undecene-hydrolysate protein derivative |
CN116837064A (en) * | 2023-09-04 | 2023-10-03 | 成都速攻痛风病研究集团有限公司 | Preparation method of silkworm chrysalis protein peptide |
CN116837064B (en) * | 2023-09-04 | 2023-11-28 | 成都速攻痛风病研究集团有限公司 | Preparation method of silkworm chrysalis protein peptide |
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