CN101671263A - Method for preparing novel amino acid chelate - Google Patents
Method for preparing novel amino acid chelate Download PDFInfo
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- CN101671263A CN101671263A CN200910181131A CN200910181131A CN101671263A CN 101671263 A CN101671263 A CN 101671263A CN 200910181131 A CN200910181131 A CN 200910181131A CN 200910181131 A CN200910181131 A CN 200910181131A CN 101671263 A CN101671263 A CN 101671263A
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- amino acid
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Abstract
The invention relates to a method for preparing a novel food additive amino acid chelate, and the method comprises the following steps: acidic amino acid and calcium oxide or calcium hydroxide are chelated in a proper condition to obtain the calcium amino acid chelate; and the calcium amino acid chelate reacts with sulphates of zinc, iron, magnesium, copper, manganese and cobaltic to obtain the corresponding amino acid chelate. The amino acid micro-element chelate produced by the method is characterized in that the products are electric neutrality, do not carry other ions besides amino acid and microelements and have simple process, no environment pollution; the byproduct calcium sulphate is taken as raw auxiliary materials in food and medical fields. Due to the advantages of large dissolubility quality, stable properties, safety and effectiveness and no toxic side effect and the like, the stable amino acid micro-element chelate can bring new commercial opportunities for future healthcare products and medicinal markets.
Description
Technical field
The present invention relates to a kind of method for preparing novel amino acid chelate.Its specific practice is with acidic amino acid and calcium oxide or calcium hydroxide chelating under proper condition, obtains calcium amino acid chelate, with the vitriol reaction of calcium amino acid chelate and zinc, iron, magnesium, copper, manganese, cobalt, obtains corresponding amino-acid chelate again.
Background technology
Microelement product has experienced three developmental stage: first-generation product is an inorganic salts, as ferrous sulfate, copper sulfate, zinc sulfate etc.; S-generation product is an organic acid salt, and as ferrous citrate, zinc fumarate, magnesium lactate etc., but all there is the defective that absorbs rate variance in above two series products, have antagonistic action between the trace element, therefore can not fully satisfy the demand of animal body growth; Third generation product is an organism, it and inorganic salt structurally have very big difference, inorganic salt only are to form the ionic linkage structure between the zwitterion, and inner complex is the compound with ring texture that is formed by coordinate bond by N, O, S atom and Zn, Cu, Fe, Mg, Mn, Co etc. two or Tricationic by one or more amino acid.Amino-acid trace element chela compound is a kind of trace element replenisher that approaches natural form in the human body, has to improve metal ion absorption in vivo and utilization, prevent that trace element from forming insoluble substance, improving the effect of body's immunity.Trace element and amino acid all are the necessary important nutritive factors of organism, trace element participates in nearly all physiology of body and biological process directly or indirectly, vital movement to biology plays an important role, and amino acid then is to constitute proteinic basic structural unit.In addition, the amino-acid trace element chelate has that chemical property is stable, and the bioavailability height is is easily digested and assimilated, and advantage such as have no side effect is the ideal trace element replenisher.
Based on the above-mentioned advantage of amino acid trace element chelated thing, the research of amino-acid chelate has had the development of advancing by leaps and bounds, and makes scientific and technical literature and patent constantly weed out the old and bring forth the new.Make a general survey of patent or the application relevant, still exist many places that have much room for improvement with the amino-acid trace element chelate.
Described a kind of calcium amino acid chelate of patent application patent (03137615.0) and preparation thereof and application are: glycine and carbaminothioic acid (methionine(Met), cysteine plus cystine) are mixed the back by a certain percentage make calcium amino acid chelate as part and calcium containing compound (calcium chloride, calcium oxide or its mixture) reaction.The weak point of this patent is: 1. do not have concrete preparation method and reaction conditions such as temperature, the time etc. of calcium amino acid chelate, lack operability; 2. glycine and sulfo-amino acid mixture are as part, and the two proportioning number of times (mol ratio) is too many, and whole patent application has more than 10 places, is not easy to actually operating; 3. with calcium chloride CaCl
2As the calcium source, (acid increasing) is unfavorable for that the direction of reacting to generating inner complex carries out will to cause the pH value of solution in the chelating process to reduce; Simultaneously, chlorion also is difficult to remove, and can introduce a large amount of chlorion Cl in product
-, be unfavorable for the health of human body; 4. find in test that when glycine, carbaminothioic acid carried out chelating as part and calcium ion, their mol ratio did not reach 2: 1, that is to say, the existence of a large amount of total free aminoacidss and calcium ion will be arranged.
The preparation method of the described a kind of food enrichment Ferrous glycinate of patent application patent (200410065260.3) is: with glycine and iron protochloride or iron protocarbonate is raw material, in water medium, add a certain amount of antioxidant, feed nitrogen simultaneously, under stirring state with above-mentioned raw materials according to 2～3: 1 mixes, temperature of reaction is 20～80 ℃, and the reaction times is 10～60min, filters then.Add anhydrous ethanol solvent and precipitate extraction in filtrate, with methyl alcohol the precipitation extract is carried out the washing dehydration impurity elimination again, drying is pulverized, and obtains the food grade Ferrous glycinate.The weak point of this method is: 1. be source of iron with the iron protochloride, will make and introduce a large amount of chlorions in the product; Iron protocarbonate (K
Sp=2 * 10
-11) be insoluble salt, iron protocarbonate carries out chelating as source of iron and glycine, will be very slow; 3. with dehydrated alcohol inner complex is purified, not only can not extract all inner complexs fully, and will consume a large amount of ethanol,, production cost will be improved greatly even ethanol is reclaimed; 3. with methyl alcohol the precipitation extract is washed, because methyl alcohol is bigger than alcoholic acid toxicity, methyl alcohol boiling point (65 ℃) is also low than ethanol (79 ℃), causes operating environment poor, has also improved production cost simultaneously.
The described amino-acid chelate preparation method of patent application patent (200380105098.7) is: lime carbonate is disperseed in 500ml water, stirring and dissolving, react to wherein adding L-glutamic acid, this solution is dissolved up to lime carbonate and L-glutamic acid fully by lasting the stirring then.The reaction soln that obtains is not tolerant through centrifugal removal, gets clarified supernatant, gets calcium amino acid chelate through lyophilize.Gained chelating calcium reacts with the vitriol continuation of zinc, manganese, copper, iron, magnesium, chromium again, makes corresponding inner complex.The weak point of this method is: 1. when preparing chelating calcium, use lime carbonate and Protanal TXF 200 as raw material.This raw material is insoluble calcium, and slow with the chelating amino acids speed of response, the time is long, reacts not thorough.By product carbonic acid raises the pH value of solution value, makes chelatropic reaction be unfavorable for carrying out; 2. in this patent application, in the unreceipted reaction times, temperature of reaction in actual production, can't be operated according to the cited example of this patent; 3. when producing except that chelating calcium other inner complexs, byproduct calcium sulfate reclaims, and not only environment is polluted, and also can cause the wasting of resources.
Summary of the invention
By analysis to the foregoing invention patent application, be not difficult to find out, also there is certain weak point in existing method of producing amino acid trace element chelated thing, mainly show as the following aspects: 1. the amino acid starting material of selecting for use is not ideal enough, glycine, carbaminothioic acid are as part, with the metal ion-chelant weak effect, in product, will there be a large amount of total free aminoacidss and free metal ion to exist; 2. metal ion raw material such as calcium chloride, iron protochloride, iron protocarbonate, lime carbonate all can make the pH value of chelating liquid reduce, and are unfavorable for the carrying out of chelatropic reaction; Chlorion in the reaction solution also will be brought product into, and too much chlorion is unfavorable to health; Iron protocarbonate, lime carbonate are insoluble salt, and the chelating process duration is long, and reaction is not thorough; Reaction conditions such as temperature, time indeterminate, the proportioning raw materials complexity is various, lacks operability; 4. adopt ethanol, methyl alcohol as solvent product to be separated, washs, the two is noxious solvent, and boiling point is low, and saturated vapor pressure is big, causes operating environment poor, influences enterprise employee health, brings potential safety hazard simultaneously; 5. all recovery and utilizations of not mentioned by product of above-mentioned three pieces of patent applications not only cause the waste of resource, and have polluted environment.
At above-mentioned situation, the present invention adopts acidic amino acid L-glutamic acid, aspartic acid or its mixture as amino acid source, the mol ratio of pressing amino acid and calcium adds calcium oxide or calcium hydroxide at 2: 1, at 70～100 ℃, stir 30min, regulate pH7～8, obtain colourless clear liquid, naturally cool to room temperature, filter and obtain purified calcium amino acid chelate.As prepare other microelement chelates beyond the calcium amino acid chelate, above-mentioned solution (need not to filter) is continued to react 30min with the equimolar ferrous sulfate of calcium ion, sal epsom, zinc sulfate, manganous sulfate and rose vitriol down at 60～80 ℃ respectively as raw material, the pH value is controlled at pH7 ± 0.5, remove by filter the calcium sulfate precipitation of generation, filtrate is amino-acid chelate, the spray-dried finished product that gets.Copper amino acid chelate is controlled at 55～65 ℃ and pH value with temperature to carry out between being controlled at 5～6 as stated above; Iron-amino acid chelate is on the basis that produces chelated copper, reacts under adding antioxidant vitamin C and the nitrogen atmosphere, by spraying drying, obtains amino acid chela iron again.
Embodiment
Embodiment 1 (calcium-glutamate chelate preparation)
Take by weighing food grade L-glutamic acid 100.00g and calcium hydroxide Ca (OH)
223.29g put into beaker, add water 300ml, be heated to 70～80 ℃, stir 30min, regulating pH is 7 ± 0.5.Naturally cool to room temperature, filter, get clear and bright weak yellow liquid.Carry out spraying drying again, get faint yellow bulk powder, i.e. calcium-glutamate chelate.
Embodiment 2 (preparation of glutamate chelate zinc)
Take by weighing food grade L-glutamic acid 100.00g and calcium hydroxide Ca (OH) 224.05g puts into beaker, add water 300ml, be heated to 70～80 ℃, stir 30min, regulating pH is 7～8, achromatism and clarity solution.In solution, add 97.76g Zinc Sulphate Heptahydrate (ZnSO while hot
47H
2O), temperature maintenance continues to stir 30min at 70～80 ℃, and the pH value is filtered in pH7 ± 0.5, and filtrate is zinc-amino acid chelate, the spray-dried finished product that gets.Be precipitated as calcium sulfate, can use as food grade calcium sulfate after the drying.
Embodiment 3 (the glutamate chelate copper is equipped with)
Take by weighing food grade L-glutamic acid 100.00g and calcium hydroxide Ca (OH)
223.54g put into beaker, add water 300ml, be heated to 70～80 ℃, stir 30min, regulating pH is 7～8, gets achromatism and clarity solution.After cold slightly, solution temperature adds 74.98g cupric sulfate pentahydrate CuSO in solution in the time of 55～65 ℃
45H
2O stirs 30min, and keeps pH6～7.After being cooled to room temperature, leach the calcium sulfate precipitation of generation, obtain purified blue chelating amino acids copper solutions, spraying drying gets composite aminoacid chelating copper.Can use as food grade calcium sulfate after the calcium sulfate drying.
Embodiment 4 (the ferrous preparation of glutamate chelate)
Take by weighing food grade L-glutamic acid 100.00g and calcium hydroxide Ca (OH)
224.19g put into beaker, add water 300ml, be heated to 70～80 ℃, stir 30min, regulating pH is 7～8, gets achromatism and clarity solution.Treat that solution temperature reduces to about 60 ℃, add the 1.5g xitix after, add 84.53g iron vitriol (FeSO
47H
2O), charge into nitrogen, and temperature is controlled at 55～65 ℃, stir 30min, and keep pH6～7.After being quickly cooled to room temperature, leach the calcium sulfate precipitation of generation, obtain purified composite aminoacid chelating ferrous solution, spraying drying gets composite aminoacid chelating iron.Can use as food grade calcium sulfate after the calcium sulfate drying.
Embodiment 5 (preparation of aspartic acid chelating calcium)
Take by weighing food grade L-glutamic acid 100.00g and calcium hydroxide Ca (OH)
224.73g 25.19g puts into beaker, adds water 500ml, is heated to 70～80 ℃, stirs 30min, regulating pH is 7 ± 0.5.Naturally cool to room temperature, filter, get clear and bright weak yellow liquid.Carry out spraying drying again, get faint yellow bulk powder, i.e. aspartic acid chelating calcium.
Embodiment 6 (preparation of aspartic acid chelated magnesium)
Take by weighing food grade aspartic acid 100.00g and calcium oxide CaO 22.13g puts into beaker, add water 500ml, be heated to 70～80 ℃, stir 30min, regulating pH is 7～8, achromatism and clarity solution.In solution, add 82.24g magnesium sulfate heptahydrate (MgSO while hot
47H
2O), temperature maintenance continues to stir 30min at 70～80 ℃, and the pH value is filtered in pH7 ± 0.5, and filtrate is amino acid chelated magnesium, the spray-dried finished product that gets.Be precipitated as calcium sulfate, can use as food grade calcium sulfate after the drying.
Claims (7)
1. the preparation method of a novel amino acid chelate, it is characterized in that acidic amino acid and calcium oxide or calcium hydroxide chelating under proper condition, obtain calcium amino acid chelate, with the vitriol reaction of calcium amino acid chelate and zinc, iron, magnesium, copper, manganese, cobalt, obtain corresponding amino-acid chelate again.
2. according to the preparation method of right 1 described a kind of novel amino acid chelate, it is characterized in that used amino acid is acidic amino acid aspartic acid, L-glutamic acid or its mixture.
3. according to the preparation method of right 1 described a kind of novel amino acid chelate, it is characterized in that used calcium source is calcium oxide CaO, calcium hydroxide Ca (OH)
2Or its mixture.
4. according to the preparation method of right 1,2,3 described a kind of novel amino acid chelates, it is characterized in that amino acid and calcium source chelating temperature are 70～80 ℃, the time is 30min, and the pH value is 7 ± 0.5.
5. according to the preparation method of right 1,2,3,4 described a kind of novel amino acid chelates, when it is characterized in that other the amino acid trace element chelated things beyond the preparation deliming, use calcium amino acid chelate to be raw material and copper sulfate CuSO
4, ferrous sulfate FeSO
4, zinc sulfate ZnSO
4, rose vitriol CoSO
4, sal epsom MgSO
4, manganous sulfate MnSO
4Or its hydrate carries out chelating.
6. according to the preparation method of right 1,5 described a kind of novel amino acid chelates, when it is characterized in that other the amino acid trace element chelated things beyond the preparation deliming, temperature of reaction is 60～80 ℃, and the time is 30min, and the pH value is 5.5～7.5.
7. according to the preparation method of right 1,5,6 described a kind of novel amino acid chelates, it is characterized in that can be used as the use of food grade calcium sulfate after the byproduct calcium sulfate drying.
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Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276633A (en) * | 2011-06-23 | 2011-12-14 | 辽宁中医药大学 | Quercetin-glutamic acid Cu (II) complex and preparation method and application thereof |
| CN102626180A (en) * | 2012-04-10 | 2012-08-08 | 南宁市泽威尔饲料有限责任公司 | Amino acid chelating compound organic feed additive and production method thereof |
| CN102627585A (en) * | 2012-03-26 | 2012-08-08 | 广州九益生物技术有限公司 | Carbamyl glycine dipeptide chelated zinc and preparation method thereof |
| CN102627584A (en) * | 2012-03-26 | 2012-08-08 | 广州九益生物技术有限公司 | Carbamyl glycine dipeptide chelated copper and preparation method thereof |
| CN103739509A (en) * | 2014-01-09 | 2014-04-23 | 山东祥维斯生物科技有限公司 | Industrial production and preparation process of glycine chelated manganese |
| CN104432096A (en) * | 2014-12-09 | 2015-03-25 | 重庆综艺营养科技有限责任公司 | Amino acid complex trace element vitamin health product |
| CN105777567A (en) * | 2016-03-07 | 2016-07-20 | 湖北工业大学 | Preparation method of complex amino acid chelated calcium |
| CN107445868A (en) * | 2017-08-04 | 2017-12-08 | 仲恺农业工程学院 | N carbamylglutamic acid Chelated Manganeses and preparation method thereof |
| CN107821942A (en) * | 2017-11-24 | 2018-03-23 | 淮南市春风粮油食品有限公司 | A kind of processing method of the function intensified flour of amino acid chelated iron |
| CN108264546A (en) * | 2016-12-30 | 2018-07-10 | 河北凯盛医药科技有限公司 | Succinyl casein-ferrous iron and its preparation method and application |
| CN108373421A (en) * | 2018-02-13 | 2018-08-07 | 云南宁康生物科技有限公司 | A kind of preparation method of calcium L-aspartate chelate |
| CN109081786A (en) * | 2018-10-15 | 2018-12-25 | 禄丰天宝磷化工有限公司 | A kind of preparation method of amino acid ferrous chelate compound |
| CN109180510A (en) * | 2018-08-29 | 2019-01-11 | 长沙兴嘉生物工程股份有限公司 | A kind of preparation method of high-purity ferrous glutamate |
| CN110663823A (en) * | 2019-11-05 | 2020-01-10 | 化学工业（全国）饲料添加剂工程技术中心山东科技公司 | Preparation method of feed additive copper methionine |
| CN112724032A (en) * | 2020-12-28 | 2021-04-30 | 宁波盈前科技有限公司 | Threonine calcium product and production method thereof |
| CN113735729A (en) * | 2021-08-03 | 2021-12-03 | 四川吉隆达生物科技集团有限公司 | Production process of feed-grade ferrous glutamate |
-
2009
- 2009-10-12 CN CN200910181131A patent/CN101671263A/en active Pending
Cited By (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102276633B (en) * | 2011-06-23 | 2014-08-27 | 辽宁中医药大学 | Quercetin-glutamic acid Cu (II) complex and preparation method and application thereof |
| CN102276633A (en) * | 2011-06-23 | 2011-12-14 | 辽宁中医药大学 | Quercetin-glutamic acid Cu (II) complex and preparation method and application thereof |
| CN102627585A (en) * | 2012-03-26 | 2012-08-08 | 广州九益生物技术有限公司 | Carbamyl glycine dipeptide chelated zinc and preparation method thereof |
| CN102627584A (en) * | 2012-03-26 | 2012-08-08 | 广州九益生物技术有限公司 | Carbamyl glycine dipeptide chelated copper and preparation method thereof |
| CN102626180A (en) * | 2012-04-10 | 2012-08-08 | 南宁市泽威尔饲料有限责任公司 | Amino acid chelating compound organic feed additive and production method thereof |
| CN102626180B (en) * | 2012-04-10 | 2014-11-12 | 南宁市泽威尔饲料有限责任公司 | Amino acid chelating compound organic feed additive and production method thereof |
| CN103739509A (en) * | 2014-01-09 | 2014-04-23 | 山东祥维斯生物科技有限公司 | Industrial production and preparation process of glycine chelated manganese |
| CN104432096A (en) * | 2014-12-09 | 2015-03-25 | 重庆综艺营养科技有限责任公司 | Amino acid complex trace element vitamin health product |
| CN105777567A (en) * | 2016-03-07 | 2016-07-20 | 湖北工业大学 | Preparation method of complex amino acid chelated calcium |
| CN108264546A (en) * | 2016-12-30 | 2018-07-10 | 河北凯盛医药科技有限公司 | Succinyl casein-ferrous iron and its preparation method and application |
| CN107445868A (en) * | 2017-08-04 | 2017-12-08 | 仲恺农业工程学院 | N carbamylglutamic acid Chelated Manganeses and preparation method thereof |
| CN107821942A (en) * | 2017-11-24 | 2018-03-23 | 淮南市春风粮油食品有限公司 | A kind of processing method of the function intensified flour of amino acid chelated iron |
| CN108373421A (en) * | 2018-02-13 | 2018-08-07 | 云南宁康生物科技有限公司 | A kind of preparation method of calcium L-aspartate chelate |
| CN108373421B (en) * | 2018-02-13 | 2021-05-14 | 云南宁康生物科技有限公司 | Preparation method of L-aspartic acid chelated calcium |
| CN109180510A (en) * | 2018-08-29 | 2019-01-11 | 长沙兴嘉生物工程股份有限公司 | A kind of preparation method of high-purity ferrous glutamate |
| CN109180510B (en) * | 2018-08-29 | 2021-08-24 | 长沙兴嘉生物工程股份有限公司 | Preparation method of high-purity ferrous glutamate |
| CN109081786A (en) * | 2018-10-15 | 2018-12-25 | 禄丰天宝磷化工有限公司 | A kind of preparation method of amino acid ferrous chelate compound |
| CN110663823A (en) * | 2019-11-05 | 2020-01-10 | 化学工业（全国）饲料添加剂工程技术中心山东科技公司 | Preparation method of feed additive copper methionine |
| CN112724032A (en) * | 2020-12-28 | 2021-04-30 | 宁波盈前科技有限公司 | Threonine calcium product and production method thereof |
| CN113735729A (en) * | 2021-08-03 | 2021-12-03 | 四川吉隆达生物科技集团有限公司 | Production process of feed-grade ferrous glutamate |
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Application publication date: 20100317 |