WO2010102471A1 - Procédé de fabrication de cristaux de chlorhydrate de cuivre chélatant les acides aminés et leur utilisation - Google Patents

Procédé de fabrication de cristaux de chlorhydrate de cuivre chélatant les acides aminés et leur utilisation Download PDF

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Publication number
WO2010102471A1
WO2010102471A1 PCT/CN2009/072740 CN2009072740W WO2010102471A1 WO 2010102471 A1 WO2010102471 A1 WO 2010102471A1 CN 2009072740 W CN2009072740 W CN 2009072740W WO 2010102471 A1 WO2010102471 A1 WO 2010102471A1
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WO
WIPO (PCT)
Prior art keywords
amino acid
copper
hydroxychloride
water
crystals
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PCT/CN2009/072740
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English (en)
Chinese (zh)
Inventor
陈昌铭
温炎燊
陈志传
毛鹏举
刘艳帅
Original Assignee
深圳市危险废物处理站有限公司
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Publication of WO2010102471A1 publication Critical patent/WO2010102471A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/54—Organic compounds
    • A—HUMAN NECESSITIES
    • A23—FOODS OR FOODSTUFFS; TREATMENT THEREOF, NOT COVERED BY OTHER CLASSES
    • A23K—FODDER
    • A23K20/00—Accessory food factors for animal feeding-stuffs
    • A23K20/10—Organic substances
    • A23K20/142—Amino acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C229/00—Compounds containing amino and carboxyl groups bound to the same carbon skeleton
    • C07C229/76—Metal complexes of amino carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions

Definitions

  • the present invention relates to a method for preparing an amino acid chelate compound, and more particularly to a method for preparing an amino acid chelate copper hydroxychloride crystal which can be used as a nutrient element additive for animal feed, and a use thereof.
  • the basic copper chloride powder crystal has the molecular formula C (0H) 3 C1, which has the following crystal structure: orthorhombic chloroformite (atacamite), triclinic secondary chlorite (paratacamite), monoclinic borallackite and monoclinic clinoatacamite, or a mixed crystal form of several of them.
  • the basic copper chloride powder is a fine-grained powder with an average particle size of 10 to 300 ⁇ m and a uniform particle size. It has good fluidity, no dust, no water, no corrosion, and is easy to destroy. It has good physicochemical properties, such as separation from other water-soluble background salts, high purity, easy mixing and so on, and therefore has important applications in the feed industry.
  • Chinese Patent No. ZL95192983.6 discloses a method for using orthorhombic basic copper chloride powder for animal feed additives.
  • ZL200610060144.1 China Invention Patent discloses a use of monoclinic basic copper chloride powder for animal feed additives.
  • 2008100 67243.1 Chinese patent application discloses a method for preparing monoclinic crystalline copper oxide by using basic copper chloride powder crystal.
  • the basic copper chloride powder is an inorganic mineral micronutrient additive, and its bioabsorption utilization rate is still low compared to the organic amino acid chelated copper.
  • Amino acid chelated copper is the third generation of organic copper source.
  • the water system synthesis method is the main method for synthesizing amino acid copper chelate.
  • the water system synthesis method is widely used, in the production technology, this method has a long hydrolysis process period, and requires a large amount of alkali neutralization in the synthesis process. It produces a large number of salts, low content of trace elements in the final product, and low purity of the amino acid copper complex.
  • the water system synthesis method also has the disadvantages of high cost, intractable waste liquid, serious pollution, etc., which affects the promotion and use of amino acid copper chelate in feed additives.
  • the yield can be improved, but the production cost is increased and the wastewater treatment difficulty is increased.
  • an organic solvent such as acetone
  • the mixed amino acid hydrolyzed by protein is used as a ligand, many types of ligands are formed during the production process, and the trace elements are strongly bonded to the ligand. The degree is not high, the product quality is not high, and the effect is unstable in actual use.
  • the advantage of solid phase reaction for synthesizing amino acid chelates is that the synthesis operation is simple, the consumption is small, and the cost is low.
  • the general metal salt and amino acid have low reactivity, the reaction is not easy to carry out, and the microwave heating technology is required for the catalytic reaction, but the microwave catalytic solid phase
  • the reaction synthesis of amino acid chelates is not easy to control, the temperature is not uniform, the product is likely to cause burnt, the energy consumption is high, and the industrial production is not easy to be realized.
  • the present invention aims to solve the above problems, and provides a low production cost, no waste liquid pollution, and high product purity.
  • the present invention provides a method for preparing an amino acid chelated copper hydroxychloride crystal, the method comprising the steps of:
  • step a the molar ratio of the powdered basic copper chloride, amino acid and water is 1: 2 ⁇ 3: 1 ⁇ 10.
  • the powder crystal basic copper chloride is an orthorhombic chloroformite of a molecular formula of C(OH) 3 Cl, a triclinic para-copperite or a monoclinic system.
  • the amino acids are lysine, lysine hydrochloride, lysine sulfate, glycine, tryptophan, methionine, threonine, valine, histidine, leucine, isoleucine, Alanine, phenylalanine, cystine, cysteine, arginine, serine, tyrosine, 3.5. diiodotyrosine, glutamic acid, aspartic acid, proline, hydroxy A complex amino acid of one or several amino acids of proline, arginine, citrulline, and ursine.
  • step a the reaction formula of the mixed reaction of the powdered basic copper chloride, the amino acid and the water is as follows:
  • step a when m is 4 ⁇ , the reaction formula of the mixed reaction of the powdered basic copper chloride, the amino acid and the water is as follows:
  • the recrystallization process comprises mixing amino acid chelating copper hydroxychloride crystals with water in a weight ratio of 1:0.5 to 10, heating and dissolving at a temperature of 60 to 100 ° C, and then cooling and performing Recrystallization, filtered
  • the present invention also provides the use of an amino acid prepared by the method to chelate copper hydroxychloride, the amino acid chelated copper hydroxychloride prepared by the method being used as a nutrient element additive for animal feed.
  • the basic copper chloride powder crystal provides a basic group required for complexing with an amino acid, so that no other basic compound raw material is required, and the same reaction does not produce other by-products.
  • the resulting amino acid copper complex has no impurities and is highly pure.
  • the reaction can also be carried out, except that a complete reaction requires a long period of time (for example, 1 to 3 days) in which water acts as a solid reaction initiator.
  • the present invention also provides the use of an amino acid prepared by the method to chelate copper hydroxychloride, the amino acid chelated copper hydroxychloride prepared by the method being used as a nutrient element additive for animal feed.
  • the method of the invention makes the mixing reaction complete in one step, the operation is very simple, no waste liquid is generated, the environment is very environmentally friendly, the product yield is 100%, and the production cost is extremely low. Due to the low moisture content, the drying cost is also low, and industrial production is easy to achieve.
  • the amino acid copper chelate prepared by the method of the invention has low cost, high purity of amino acid copper chelate and high content of biological active ingredients, and the obtained product is used for feeding additives to supplement amino acids and copper micronutrients required by animals. Improve the absorption and utilization rate of copper in animals, and effectively increase the growth rate of animals, reduce feed consumption, and enhance disease resistance. Lower dose of amino acid copper The growth promoting effect of high-dose inorganic copper is obtained. Tongyu also overcomes the mineral poisoning and excessive consumption caused by adding too much inorganic salt product in the feed, which can reduce the environmental impact of the remaining excrement, reduce the amount of copper added in the feed, save resources and protect the environment. Significance.
  • Figure 1 is a X-ray diffraction spectrum of a lysine-chelating copper hydroxychloride crystal prepared by the method of the present invention (containing a recrystallization step).
  • Figure 2 is a X-ray diffraction spectrum of a glycine-chelating copper hydroxychloride crystal prepared by the method of the present invention (containing a recrystallization step).
  • Figure 3 is an X-ray diffraction spectrum of a methionine chelated copper hydroxychloride crystal prepared by the method of the present invention.
  • Figure 4 is an infrared spectrum of a lysine-chelating copper hydroxychloride crystal prepared by the method of the present invention (containing a recrystallization step).
  • Figure 5 is a method of the present invention (containing a recrystallization step) prepared by glycine chelated copper hydroxychloride
  • Lysine has a characteristic absorption peak at 2137 cm-i, disappears in the infrared spectrum of lysine copper chelate, and has a characteristic absorption peak near 2100 cm-i with a-amino acid. The conclusion that the peak disappeared after the coordination was consistent, indicating that the lysine reacted with the powdered basic copper chloride.
  • the ⁇ ()3) absorption band of lysine is shifted from 2862 and 2937 cm- 1 , and the lysine copper chelate appears at 2933 cm- 1 and 301 lcm- 1 (NH2), vs (NH2) absorption peak.
  • Glycine has a characteristic absorption peak at 2120 cm-i, disappeared in the infrared spectrum of glycine copper chelate, and has a characteristic absorption peak near 2100 cm-i with a-amino acid, after coordination The conclusion that the peak disappeared is consistent, indicating that the glycine is coordinated and chelated with the powdered basic copper chloride.
  • the glycine ⁇ ( ⁇ 3) absorption band is shifted from 3170cm- 1 , and the glycine copper chelate is at 3314cm- 1 and 3264cm- 1.
  • the "as (NH2), vs (NH2) absorption peak appeared in both places, indicating that the ⁇ -amino group has a coordination reaction with copper.
  • the monoclinic basic chlorination is added in a molar ratio of powdered basic copper chloride, lysine sulfate complex amino acid to water 1:2.5:3. 140 kg of copper, 616 kg of 65% lysine sulfate, 50 kg of water, wherein the composition of lysine sulfate complex amino acid is: L-lysine content ⁇ 51%, other amino acids ⁇ 10%, sulfate ( S0 4 2-
  • the temperature is raised to 40 ° C, the reaction is 24 hours, the temperature is lowered to normal temperature, and then dried, and discharged, to obtain 760 kg of lysine sulfate complex amino acid copper chelate green crystal.
  • the elemental content of the synthesized complex amino acid copper was 10.7%, the lysine content was 41%, and the sulfate (S042-) content was 11.3%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Polymers & Plastics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Metallurgy (AREA)
  • Zoology (AREA)
  • Food Science & Technology (AREA)
  • Animal Husbandry (AREA)
  • Proteomics, Peptides & Aminoacids (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Fodder In General (AREA)

Abstract

L'invention porte sur un procédé de fabrication de cristaux de chlorhydrate de cuivre chélatant les acides aminés et sur leur utilisation. Le procédé comprend : a. des cristaux de poudre de chlorure de cuivre basique, un acide aminé et de l'eau sont mélangés de façon homogène selon le rapport molaire de 1:0~4:1~10 dans les conditions d'agitation ou d'extrusion et mis à réagir à la température de 10~90°C pendant 2-72 h pour obtenir des cristaux de chlorhydrate de cuivre chélatant les acides aminés; b. le produit de cristaux de chlorhydrate de cuivre chélatant les acides aminés obtenu par la réaction de mélange est séché directement ou soumis à une recristallisation pour obtenir le produit. Les cristaux de chlorhydrate de cuivre chélatant les acides aminés préparés par le procédé peuvent être utilisés comme additif d'élément nutritif pour l'alimentation animale. Le procédé selon l'invention est de faible coût de production, ne présente pas de pollution par un liquide résiduaire, donne des produits de haute pureté, une absorption biologique élevée et un rapport d'utilisation élevé, et est également aisé à faire passer à l'échelle industrielle.
PCT/CN2009/072740 2009-03-10 2009-07-13 Procédé de fabrication de cristaux de chlorhydrate de cuivre chélatant les acides aminés et leur utilisation WO2010102471A1 (fr)

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CNA2009101059533A CN101503415A (zh) 2009-03-10 2009-03-10 氨基酸螯合羟基氯化铜结晶的制备方法及用途
CN200910105953.3 2009-03-10

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Cited By (1)

* Cited by examiner, † Cited by third party
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CN112624933A (zh) * 2020-12-31 2021-04-09 河北力维素科技有限公司 一种支链氨基酸螯合铜的制备方法

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CN102659823B (zh) * 2012-06-02 2015-08-05 维尔信科技（潍坊）有限公司 一种防脱发、生发、护肤作用的氨基酸铜络合物、制备方法及应用
CN104761462B (zh) * 2015-03-23 2017-03-15 长沙兴嘉生物工程股份有限公司 一种苏氨酸铜的制备方法
CN108264083A (zh) * 2018-04-23 2018-07-10 南京信息工程大学 一种六棱柱状羟基氯化铜及其制备方法和电化学用途
DE102018113243A1 (de) * 2018-06-04 2019-12-05 BIOCHEM Zusatzstoffe Handels- und Produktionsgesellschaft mbH Verfahren zur Herstellung einer Zusammensetzung enthaltend zumindest eine Metall-Aminosäure-Verbindung sowie Zusammensetzung erhältlich durch ein derartiges Verfahren
CN113740282A (zh) * 2021-08-19 2021-12-03 广东有机宝生物科技股份有限公司 一种铜元素含量的测试方法
CN114195180B (zh) * 2021-11-29 2024-04-19 天宝动物营养科技股份有限公司 一种分散型碱式氯化铜及其制备方法
CN116283669A (zh) * 2023-02-27 2023-06-23 长沙兴嘉生物工程股份有限公司 一种精氨酸铜螯合物单晶及其制备方法

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4900561A (en) * 1989-01-03 1990-02-13 Zinpro Corporation Copper complexes of alpha-amino acids that contain terminal amino groups, and their use as nutritional supplements
CN1069181C (zh) * 1994-03-15 2001-08-08 传统环境服务有限公司 微量营养素添加剂
CN1230092C (zh) * 2003-10-16 2005-12-07 黄逸强 碱式氯化铜饲料添加剂及其制备方法
CN1995015A (zh) * 2006-01-06 2007-07-11 深圳市危险废物处理站 利用蚀刻废液制备饲料级蛋氨酸铜螯合物的方法
CN1328245C (zh) * 2002-10-16 2007-07-25 金宝公司 α氨基二羧酸的金属络合物

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4900561A (en) * 1989-01-03 1990-02-13 Zinpro Corporation Copper complexes of alpha-amino acids that contain terminal amino groups, and their use as nutritional supplements
CN1069181C (zh) * 1994-03-15 2001-08-08 传统环境服务有限公司 微量营养素添加剂
CN1328245C (zh) * 2002-10-16 2007-07-25 金宝公司 α氨基二羧酸的金属络合物
CN1230092C (zh) * 2003-10-16 2005-12-07 黄逸强 碱式氯化铜饲料添加剂及其制备方法
CN1995015A (zh) * 2006-01-06 2007-07-11 深圳市危险废物处理站 利用蚀刻废液制备饲料级蛋氨酸铜螯合物的方法

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN112624933A (zh) * 2020-12-31 2021-04-09 河北力维素科技有限公司 一种支链氨基酸螯合铜的制备方法

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