CN1757633A - Method for organic acid hydrolytic producing amino-acid - Google Patents
Method for organic acid hydrolytic producing amino-acid Download PDFInfo
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Abstract
The invention relates to a method of amino-acid with hydrolysis of organic acid or mixed acid (mixing an organic acid and hydrogen chloride with different proportion based on various salt-containing of different products), including the following steps: (1) pre-treatment of raw material; (2) hydrolysis, neutralization; (3) produced amino-acid solution after blending and filtration; (4) going to market after sterilizing, filling in tins, labelling, inspecting and packing. More steps needed for producing amino-acid powder: after adding additives and fillings needed, dissolving, stirring, appropriate concentrating and drying in drying machine, the amino-acid powder is produced, then going to market after packing, labelling, inspecting and packing in boxes. Based on different kind of raw material hydrolysis animal albumen (HAP) and hydrolysis plant albumen (HVP) and various kind of amino-acid preparation may be made with amino-acid. The amino-acid met pharmaceutical grade may be provided as raw material of amino-acid injection solution.
Description
Technical field
The present invention relates to a kind of method of organic acid hydrolytic producing amino-acid, the raw material of use comprises: cereal tankage such as corn chop, dregs of beans; The fowl poultry kind tankage; Sea (fresh water) product or its tankage; Low-value aquatic product product etc.The requirement raw material must be very clean, fresh.
Background technology
Amino acid is Source of life, is the basic material of constitutive protein matter, and is very important to human body! Produce amino acid and require eight kinds of essential amino acid equilibriums, ratio is suitable mutually, meets the Food and Argriculture OrganizationFAO and the World Health Organization (FAO/WHO) pattern.Its production method has acid (hydrochloric acid) hydrolysis method, enzyme hydrolysis method, chemical synthesis and microbe fermentation method etc.Acid-hydrolysis method wherein is with a long history, and advantage is the production efficiency height, and raw material is cheap and easy to get, equipment is simple, can produce the almost amino acid of all categories simultaneously, and shortcoming is: the acid that (1) hydrolysis is used is difficult for separating with amino acid, can stay a large amount of salt after the neutralization, remove very hard; (2) smelly difficult an elimination of the hydrolysis of acid hydrolysis generation, and contaminate environment! Also may produce carcinogenic trichloropropanol for high-fat beans raw grains material.Because these these technical barriers can not get solving for a long time, the great potential performance of acid-hydrolysis method is not come out, and has been in the edge that is eliminated; Other production methods are just arisen at the historic moment, and are able to large development, but they neitherly possess acid-hydrolysis method institute potential technical superiority.Though some researchist utilizes the volatility of hydrochloric acid that it is separated with aminoacids solution now, even but with liquid burn near do also can residual a large amount of hydrochloric acid, and this measure meeting consumes amino acid, also can stay a large amount of salt (NaCl) after the neutralization, must adopt membrane sepn or from exchange resin, very complicated poor efficiency.
The great advantage of enzyme hydrolysis method is a mild condition, does not need high temperature, high pressure and acid-resistant system.Shortcoming is a long reaction time, and hydrolysis is fully difficult, and the peptide that is produced has bad allergy to answer to the part human body, needs special cultivation enzyme condition; And product is difficult to filter; Many proteolytic enzyme have high selectivity, a kind of special peptide tendon of an often a kind of enzyme hydrolysis.
Traditional extraction method, enzyme process and chemical synthesis be because the cost height of precursor, and complex process is difficult to reach the purpose of suitability for industrialized production.
To produce amino acid whose big country and be Japan and German. it is the Big Three that world's amino acid is produced that the aginomoto of Japan, the moral of consonance fermentation and Germany fix the sand. they can produce high-quality amino acid, can be directly used in the production of infusion preparation.
No matter scale and quality product also are difficult to and abroad contend with at present in domestic amino acid production. in the middle and later periods eighties, introduce the manufacturing technology and the counterfeit products of infusion preparation from Japan, but raw materials for production are dependence on import all, amino acid market is still based on imported product, and " three side chains " amino acid (Xie Ansuan, leucine, Isoleucine) is most of still to be to use import.
Mass production amino acid also reduces cost and market value is the necessary means of human health longevity.Market outlook are very considerable.World market aggregate demand average annual growth 56%.
Domestic industry is just making great efforts the amino acid product is all realized production domesticization, but the focus of amino acid market competition mainly is its production cost at present, the domestic production cost is 100,000-120,000 yuan/ton, and the international marketing valency is 1.0 ten thousand-1.2 ten thousand dollars/ton, still have big gap, this year, situation was particularly severe, and how to reduce production costs is the ten minutes urgent task.Therefore; The utilization of tankage is highly significant!
Utilizing cereal tankage such as pressing oily corn chop, dregs of beans to produce amino acid is to kill two birds with one stone, and their protein content is very high.Though: present global cereal generally is subjected to the pollution of the flavacin of severe toxicity, but just can handle this problem as long as adopt acid-hydrolysis method, because the toxicity of some materials is caused by its protein, can be through acid hydrolysis with the clear amino acid that is hydrolyzed into of protein, not protein, do not had toxicity.
Pig blood contains various trace elements such as the iron, copper, zinc of a large amount of protein and needed by human, aminoacids complex with its production, the essential amino acid total amount accounts for total amino acid content more than 50%, the amino acid A wide selection of colours and designs, the essential amino acid equilibrium meets the Food and Argriculture OrganizationFAO and the World Health Organization (FAO/WHO) pattern.But pig blood is sneaked into a large amount of dung urine in the massacre process, and is very dirty not easily separated.
Silkworm chrysalis contains a large amount of protein and abundant constant and trace element, as calcium, phosphorus, zinc etc., is a kind of high zinc protein, and essential amino acid accounts for total amount about 40% in its amino acid.Silkworm chrysalis protein also is a complete protein, thus the amino acid A wide selection of colours and designs, eight kinds of essential amino acid equilibriums, ratio is suitable mutually, meets the Food and Argriculture OrganizationFAO and the World Health Organization (FAO/WHO) pattern.But silkworm chrysalis produces stench in hydrolytic process, polluted air, bad processing.
Sea (fresh water) product closes and rich in proteins amino acid all such as tankage, low-value aquatic product product; also contain more nonprotein amino acid---taurine; it is very important to human body; it is the essential material of newborn infant's brain development; and have a protection cardiac muscle, effects such as Jiang Shi blood pressure, blood fat and blood sugar.In addition, also contain the element of needed by human and trace element as calcium, potassium, magnesium, zinc, iodine, selenium and phosphorus etc., ten minutes helps producing seafood amino acid.
The amino acid that adopts beef or bird tankage to produce needs near human body very much, and mouthfeel is also fine!
Summary of the invention
The objective of the invention is to the shortcoming that exists at prior art, a kind of organic acid-hydrolyzed method is provided, solved acid and amino acid separation problem after the hydrolysis easily, the product saltiness can arbitrarily be controlled; The proportion of composing of its indispensable amino acid can be adjusted to arbitrarily and meets FAO/WHO (1985) standard; Do not contain the smelly and carcinogenic trichloropropanol of hydrolysis; Free from environmental pollution and air; Hydrolysis fully, the incomplete peptide that produces of no hydrolysis is to the bad anaphylaxis of part human body; Technology is simple, the production efficiency height, and output is big, and raw material is cheap and easy to get, can produce aminoacids solution, amino acid powder or protolysate, and various amino acid preparation, and the pharmaceutical grade product can be made for the raw material of amino acid injection.
The amino acid production technology is the high-tech area of worldwide attention, and the organic acid technology for hydrolyzing at home and abroad all is blank field! Belong to the forward position high-tech, present technique at home and abroad maintains the leading position!
Our another patent: " method of producing condiment by organic acid hydrolysis " (number of patent application: 200410092043, publication number: 1615741), its basic fundamental similarly, but this patent is to produce high-grade products----amino acid.
Some requirement of producing seasonings is lower, as long as contained amino nitrogen reaches lower aq, and no matter have which kind of amino acid or how many essential amino acids are arranged, contains a great deal of protein so only require raw material, the good extraction, and mouthfeel is well just; As for raw material whether adopt fresh or refrigeration it doesn't matter, even refrigeration is also less demanding for using what antidegenerative agent; Product often needs additive color; Because seasonings mainly is liquid, and higher, the contained amino nitrogen of saltiness is lower, needs thin up after the modulation, with salt, so needn't consider result's saltiness control in hydrolytic process.But the necessary color of seasonings is various: existing purplish red or yellow gloss, state clarification do not have precipitation; Bright fragrance of meat or fish and sauce perfume (or spice) that fish, shellfish, shrimps uniqueness are arranged again; Also must delicate flavour strong, the degree of saltiness is agreeable to the taste, taste is mellow, soft cotton long, free from extraneous odour.These need good technical skill!
Then need to ask eight kinds of essential amino acid equilibriums yet produce amino acid, ratio is suitable mutually, meets the Food and Argriculture OrganizationFAO and the World Health Organization (FAO/WHO) pattern, thereby must select raw material in view of the above, and require the raw material must be very clean, fresh; If very need refrigeration really, then adopt the carboxylic-acid antidegenerative agent as far as possible, in order to avoid cause other such as Maillard reaction etc.; Therefore the amino acid whose content of product requirement require the selected organic acid catalysic coefficient of hydrolysis α big slightly than higher, and strengthen the conditions such as molconcentration C of acid in the hydrating solution, makes hydrolysis more complete; Product is preferably colourless, and main what consider is curative effect but not mouthfeel; Because the amino acid product has liquid and solid-state, require not saliferous or saltiness lower, and amino acid contained higher, need after the modulation to concentrate or dry, so must strictness control result's saltiness in hydrolytic process.
Technical scheme:
The method of organic acid hydrolytic producing amino-acid comprises the steps:
1. raw materials pretreatment. for cereal such as corn chop, dregs of beans etc., sort out silt foreign material etc. earlier, soaked in advance 6～12 hours, carry out necessary fragmentation; Must sort out big slightly bone to fowl poultry kind meat, fat etc. rub; To shellfish, shrimps, sort out wherein shell and impurity sandstone etc.; Barbel removes head and internal organ, must add poach earlier to the fish raw material of diameter more than 4cm and open to stir kindred is separated, and removes bone. and require the raw material must be very clean, fresh;
2. hydrolysis, neutralization: in extractor, add raw material and an amount of water; Add an amount of organic acid according to different raw materials, make the molconcentration of acid in total solution reach 0.8～4mol/L; Being incubated 10～24 hours down at 100～125 ℃ is hydrolyzed; Hydrolysis finishes with corresponding alkali neutralization, and waste obtains hydrolysising original liquid;
3. modulation is filtered: add additive by the prescription requirement, filter through modulation, obtain aminoacids solution.
The prescription that above-mentioned modulation step is related and other processing parameters are known technology in the present technique field, and those of ordinary skill all can be grasped preferably.
4. products obtained therefrom is through can, and sterilization is labelled, check, and just can dispatch from the factory in the vanning back;
Produce amino acid powder must: add additive and weighting agent on demand, an amount of through dissolve, stir evenly, being concentrated into, obtain amino acid powder more after drying, packing is labelled, check just can be dispatched from the factory after the vanning.
Amino acid ligand can be made hydrolyzed animal protein (HAP) and hydrolyzed vegetable protein (HVP) and various amino acid preparation by raw material type; The pharmaceutical grade product can be made for the raw material of amino acid injection.
The organic acid that the present invention uses is oxysuccinic acid, phosphoric acid, tartrate, citric acid, oxalic acid, lactic acid etc.For the product of different purposes, an influence of residual calcium salt quantity after the acid neutralization that must consider to be adopted!
The effect of hydrolysis is different because of the protein content of raw material, and for example soyabean expeller contains 40% protein approximately, approximately is 3～5 times of animal class raw material. and hydrolysis also must correspondingly improve with acid; To certain hydrolysis object, hydrolysis effect becomes positive correlation with molconcentration C (mol/L), hydrolysis temperature T sour in sour catalysic coefficient α, the solution with time t with selected hydrolysis, must take all factors into consideration definite hydrolysising condition.
1. if selected hydrolysis acid is weak acid, catalysic coefficient α is less, then can consider to improve hydrolysis temperature T, prolongs hydrolysis time t or increase molconcentration C sour in the solution;
2. if selected hydrolysis acid is than strong acid, catalysic coefficient α is bigger, then can consider to reduce hydrolysis temperature T, shortens hydrolysis time t or reduce molconcentration C sour in the solution;
3. reduce the molconcentration C of hydrolysis as wanting, can consider to improve hydrolysis temperature T or prolong hydrolysis time t with acid;
4. as wanting to shorten hydrolysis time t, can consider the molconcentration C that improves hydrolysis temperature T or increase acid in the solution or adopt the bigger acid of catalysic coefficient α to increase work efficiency.
Main innovate point:
1. the organic acid method for hydrolysis has solved acid and amino acid separation problem after the hydrolysis easily, adopts the neutralization of calcium alkali, and the solubleness C of the calcium salt that is produced in water is very low, and very easy mistake filters to remove.
2. the product saltiness can arbitrarily be controlled, and the proportion of composing of its indispensable amino acid can be adjusted to arbitrarily and meets FAO/WHO (1985) standard;
3. product does not contain the smelly and carcinogenic trichloropropanol of hydrolysis, does not pollute the environment and air;
4. hydrolysis fully, the incomplete peptide that produces of no hydrolysis is to the bad anaphylaxis of part human body;
5. technology is simple, the production efficiency height, output is big, raw material is cheap and easy to get, and solved product put for a long time the precipitation this a great problem;
6. studies show that of trophology, the metal ion in the food comprises calcium and trace element etc., has only the part that is combined into complex compound or inner complex form with amino acid, in small intestine by the upper part, utilization just can be absorbed by the body.In our sea-food amino acid, have a large amount of needed by human element and the trace element exist simultaneously with amino acid as calcium, potassium, magnesium, zinc, iodine, selenium and phosphorus etc., enter digestive tube after, environment pH is in a single day suitable, they are combined into the form of complex compound or inner complex immediately, and assimilation effect is fairly good!
Sea-food also contains more nonprotein amino acid---taurine in addition, and it is very important to human body, is the essential material of newborn infant's brain development, and has protection cardiac muscle, brings high blood pressure down, effects such as blood fat and blood sugar.
7. utilization of waste material is turned waste into wealth, and becomes beans cereal tankage, fowl poultry kind tankage or sea (fresh water) product tankage and is high value product.Help the update and the reasonable resources development and use of China's processing technology.
8. in order reducing cost, to raise the efficiency, also can to adopt organic acid to become by a certain percentage with hydrochloric acid---the mixed-acid hydrolysis method.The amino acid product is not that whole needs are salt-free according to the purposes difference, can consider the saltiness of the add-on of hydrochloric acid with the control product on demand.Notice that different acid must neutralize with corresponding alkali.
Embodiment
The invention will be further described below in conjunction with specific embodiment.
Embodiment 1. uses phosphoric acid hydrolysis and produces oyster amino acid energy liquid.
1. raw material gives processing: sort out shell in the Oyster and impurity sandstone etc.;
2. hydrolysis, neutralization: throw Oyster connect 370 kilograms+water of juice an amount of+phosphoric acid [making the molconcentration C ≈ 1mol/L of acid in the solution], at T=110 ℃, insulation 20 hours, stir, with lime carbonate neutralization, waste, hydrolysising original liquid;
3. modulation is filtered, and is concentrated into suitable concentration, obtains oyster amino acid energy liquid;
4. through sterilization, can is labelled, check, and just can dispatch from the factory in the vanning back.
Oyster amino acid energy liquid contains 18 kinds of gal4 amino acids and is flavor nucleic acid; And contain more taurine, and it is the essential material of newborn infant's brain development, and has protection cardiac muscle, anti-heart disorder brings high blood pressure down, effects such as blood fat and blood sugar.In addition, also contain a large amount of zinc: lacking zinc influences childhood development; And to man's reproductive organ important influence; The pregnant woman lacks zinc could cause fetal brain underdevelopment!
Embodiment 2. uses the mixed-acid hydrolysis of citric acid and hydrochloric acid and produces the beef aminoacids solution.
1. raw materials pretreatment: remove the bone in the beef tankage, fat etc. rub;
2. hydrolysis, neutralization: the beef 370Kg+ water that feeds intake is an amount of+and [citric acid+hydrochloric acid makes the molconcentration C of acid in the solution to mixing acid
Lemon≈ 1.5mol/L, C
HCl≈ 0.25mol/L], at T=115 ℃, insulation 15 hours, stir, neutralize citric acid and hydrochloric acid respectively with corresponding alkali, waste must hydrolysising original liquid;
3. modulation is filtered, and is concentrated into suitable concentration, obtains the beef aminoacids solution;
4. through sterilization, can is labelled, check, and just can dispatch from the factory in the vanning back.
The nearly kind more than 300 of fragrance ingredient in the beef aminoacids solution, the amino acid of needed by human is complete, and nutritive value is very high, and mouthfeel is very good, helps human body and recovers after being ill!
Embodiment 3. uses the oxalic acid hydrolysis and produces the fish aminoacids solution.
1. raw materials pretreatment: cod chop 500Kg and water is an amount of, boil stirring kindred is separated, remove bone and impurity sandstone, stay meat and juice;
2. hydrolysis, neutralization: add oxalic acid [make in the solution acid molconcentration C ≈ 1.0mol/L], at T=120 ℃, insulation 18 hours, stir, with lime carbonate neutralization, waste, hydrolysising original liquid;
3. modulation is filtered, and is concentrated into suitable concentration, obtains the fish aminoacids solution;
4. through sterilization, can is labelled, check, and just can dispatch from the factory in the vanning back.
The fish aminoacids solution contains 16 kinds of gal4 amino acids and is flavor nucleic acid, wherein contains more arginine, and it is that the man makes one of raw material of sperm.
Embodiment 4. uses the citric acid hydrolysis and produces amino acid powder.
1. raw materials pretreatment: it is an amount of that dregs of beans 470Kg is added water, soaked 6～12 hours, and fragmentation;
2. hydrolysis, neutralization: adding citric acid makes in the solution molconcentration C ≈ 4.0mol/L of acid], at T=116 ℃, insulation 20 hours, stir, with lime carbonate neutralization, waste, hydrolysising original liquid;
3. modulation is filtered;
4. add additive and weighting agent, dissolve, stir evenly;
5. be concentrated into an amount of;
6. obtain amino acid powder after drying;
7. through packing, label, check, just can dispatch from the factory in the vanning back.
Canclin liquid contains 18 kinds of gal4 amino acids and is flavor nucleic acid, and amino acid A wide selection of colours and designs, nutritive value are very high.
Claims (2)
1. the method with organic acid hydrolytic producing amino-acid is characterized in that comprising the following steps:
(1) raw materials pretreatment. for cereal such as corn chop, dregs of beans etc., sort out silt foreign material etc. earlier, soaked in advance 6～12 hours, carry out necessary fragmentation; Must sort out big slightly bone to fowl poultry kind meat, fat etc. rub; To shellfish, shrimps, sort out bone wherein, shell and impurity sandstone etc.; Barbel removes head and internal organ, must add poach earlier to the fish raw material of diameter more than 4cm and open to stir kindred is separated, and removes bone. and require the raw material must be very clean, fresh;
(2) hydrolysis, neutralization: in extractor, add raw material and an amount of water; Add an amount of organic acid according to different raw materials, make the molconcentration of acid in total solution reach 0.8～4mol/L; Being incubated 10～24 hours down at 100～125 ℃ is hydrolyzed; Hydrolysis finishes with corresponding alkali neutralization, and waste obtains hydrolysising original liquid;
The organic acid that the present invention uses is oxysuccinic acid, phosphoric acid, tartrate, citric acid, oxalic acid, lactic acid etc.For the product of different purposes, an influence of residual calcium salt quantity after the acid neutralization that must consider to be adopted!
(3) modulation is filtered: add additive by the prescription requirement, filter through modulation, obtain aminoacids solution.
The prescription that above-mentioned modulation step is related and other processing parameters are known technology in the present technique field, and those of ordinary skill all can be grasped preferably.
(4) products obtained therefrom is through can, and sterilization is labelled, check, and just can dispatch from the factory in the vanning back;
Produce amino acid powder and add additive and weighting agent by still needing, dissolve, stir evenly, concentrate, dry, obtain amino acid powder, through packing, label, check just can be dispatched from the factory after the vanning.
Amino acid ligand can be made hydrolyzed animal protein (HAP) and hydrolyzed vegetable protein (HVP) and various amino acid preparation by raw material type, the pharmaceutical grade product can be made for the raw material of amino acid injection.
2. a kind of organic acid of usefulness according to claim 1 is produced amino acid whose method, it is characterized in that adding a kind of organic acid simultaneously, the ratio that needs by the control of variant production saltiness, add appropriate hydrochloric acid in addition and form the single organic acid of planting of mixing acid replacement, make concentration sour in total solution reach 0.8～4mol/L and be hydrolyzed, different acid must neutralize with corresponding alkali.All the other steps obtain the above various product by the above.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830966A (en) * | 2010-04-01 | 2010-09-15 | 北京金波绿泰科技有限公司 | Protein hydrolysis process and application thereof |
| CN103584055A (en) * | 2013-11-19 | 2014-02-19 | 广东嘉豪食品股份有限公司 | Method for preparing odor-free delicious amino acids by graded acid hydrolysis of wheat bran proteins |
| CN105105125A (en) * | 2015-09-09 | 2015-12-02 | 陈俊豪 | Pearl oyster amino acid liquid and pearl oyster and ginseng amino acid liquid production method |
| CN105105078A (en) * | 2015-09-09 | 2015-12-02 | 陈俊豪 | Delicious scallop juice producing method |
| CN105124516A (en) * | 2015-09-09 | 2015-12-09 | 陈贵卿 | Astaxanthin containing penaeus orientalis juice production method |
| CN105168257A (en) * | 2015-09-09 | 2015-12-23 | 陈贵卿 | Processing method of pearl liquid, pearl ginseng liquid and pearl powder easily absorbed by human body |
| CN106831465A (en) * | 2016-12-28 | 2017-06-13 | 安徽省虹升生物股份有限公司 | A kind of method by hydrolyzing refinement beta Alanine in gelatine |
| CN109451722A (en) * | 2016-05-02 | 2019-03-08 | 奥塔哥创新有限公司 | The processing of biomaterial containing keratin |
| CN110668907A (en) * | 2019-10-09 | 2020-01-10 | 福州三合元生物科技有限公司 | Preparation method of hydrolyzed amino acid |
| CN115736089A (en) * | 2022-11-21 | 2023-03-07 | 华南理工大学 | Acid hydrolysis plant protein liquid and preparation method thereof |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101830966A (en) * | 2010-04-01 | 2010-09-15 | 北京金波绿泰科技有限公司 | Protein hydrolysis process and application thereof |
| CN101830966B (en) * | 2010-04-01 | 2012-09-26 | 北京金波绿泰科技有限公司 | Protein hydrolysis process and application thereof |
| CN103584055A (en) * | 2013-11-19 | 2014-02-19 | 广东嘉豪食品股份有限公司 | Method for preparing odor-free delicious amino acids by graded acid hydrolysis of wheat bran proteins |
| CN105105125A (en) * | 2015-09-09 | 2015-12-02 | 陈俊豪 | Pearl oyster amino acid liquid and pearl oyster and ginseng amino acid liquid production method |
| CN105105078A (en) * | 2015-09-09 | 2015-12-02 | 陈俊豪 | Delicious scallop juice producing method |
| CN105124516A (en) * | 2015-09-09 | 2015-12-09 | 陈贵卿 | Astaxanthin containing penaeus orientalis juice production method |
| CN105168257A (en) * | 2015-09-09 | 2015-12-23 | 陈贵卿 | Processing method of pearl liquid, pearl ginseng liquid and pearl powder easily absorbed by human body |
| CN109451722A (en) * | 2016-05-02 | 2019-03-08 | 奥塔哥创新有限公司 | The processing of biomaterial containing keratin |
| US11613557B2 (en) | 2016-05-02 | 2023-03-28 | Wool Research Organisation Of New Zealand Incorporated | Treatment of keratin-containing biological materials |
| CN106831465A (en) * | 2016-12-28 | 2017-06-13 | 安徽省虹升生物股份有限公司 | A kind of method by hydrolyzing refinement beta Alanine in gelatine |
| CN110668907A (en) * | 2019-10-09 | 2020-01-10 | 福州三合元生物科技有限公司 | Preparation method of hydrolyzed amino acid |
| CN115736089A (en) * | 2022-11-21 | 2023-03-07 | 华南理工大学 | Acid hydrolysis plant protein liquid and preparation method thereof |
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