WO2010102471A1

WO2010102471A1 - Method for preparing amino acid chelating copper hydroxychloride crystals and use thereof

Info

Publication number: WO2010102471A1
Application number: PCT/CN2009/072740
Authority: WO
Inventors: 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
Priority date: 2009-03-10
Filing date: 2009-07-13
Publication date: 2010-09-16
Also published as: CN101503415A

Abstract

A method for preparing amino acid chelating copper hydroxychloride crystals and a use thereof are disclosed. The method comprises: a.) powdered crystals of basic copper chloride, amino acid and water are mixed homogeneously by stirring or extruding according to the molar ratio of 1:0~4:1~10 and reacted at the temperature of 10~90ºC for 2-72 hours to obtain amino acid chelating copper hydroxychloride crystals; b.) the resulting amino acid chelating copper hydroxychloride crystals are then dried directly or recrystallized to arrive at the end product. The amino acid chelating copper hydroxychloride crystals prepared by the method can be used as a nutrient additive for animal feed. The method disclosed in the present invention has a low production cost, produces no liquid waste pollution, is a highly pure product, has a high biological absorption and utilization rate and is easy to industrialize.

Description

Preparation method and use of amino acid chelated copper hydroxychloride crystals Preparation method and use of amino acid chelated copper hydroxychloride crystal

[1] [Technical field]

[2] 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.

[3] [Background]

[4] 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 μm 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. For example, 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. However, 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.

[5] Amino acid chelated copper is the third generation of organic copper source. At present, the water system synthesis method is the main method for synthesizing amino acid copper chelate. Although 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. In addition, 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. If the amino acid copper chelate is precipitated by an organic solvent (such as acetone), the yield can be improved, but the production cost is increased and the wastewater treatment difficulty is increased. If 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. However, 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.

[6] [Summary of the Invention]

[7] The present invention aims to solve the above problems, and provides a low production cost, no waste liquid pollution, and high product purity.

The method of preparing bioavailable chelated copper hydroxychloride crystals with high bioavailability and easy to realize industrial production.

[8] It is also an object of the present invention to provide the use of an amino acid prepared by the process to chelate copper hydroxychloride.

[9] In order to achieve the above object, the present invention provides a method for preparing an amino acid chelated copper hydroxychloride crystal, the method comprising the steps of:

[10] a, the powder crystal base copper chloride, amino acid and water in a molar ratio of 1: 0~4: 1~10 mixed under stirring or extrusion conditions, the reaction at a temperature of 10~90 ° C 2 ~72 hours, obtaining amino acid chelated copper hydroxychloride crystals;

[11] b. The amino acid obtained by the mixed reaction is chelated with the copper hydroxychloride crystal product directly by drying or by recrystallization to obtain a product.

[12] In step a, the molar ratio of the powdered basic copper chloride, amino acid and water is 1: 2~3: 1~10.

[13] In step a, 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. A mixed crystal form of one or more of clinochlorite or monoclinic clinoatacamite. 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.

[14] In step a, the reaction formula of the mixed reaction of the powdered basic copper chloride, the amino acid and the water is as follows:

[15] Cu ₂ (OH) ₃ Cl + mAA + H ₂ 0 (AA) _m Cu ₂ (OH) ₃ _ _m Cl . nH ₂ 0

[16] where m is 0 to 3 and n is 0 to 10.

[17] Specifically, in step a, when m is 4吋, the reaction formula of the mixed reaction of the powdered basic copper chloride, the amino acid and the water is as follows:

[18] Cu ₂ (OH) ₃ Cl + 4AA + H ₂ 0

2(AA) ₂ Cu . nH ₂ 0 + HC1

[19] In the step b, 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

, dry to get the product.

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.

[21] In the above method of the present invention, 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.

[22] The three bases coordinated in the basic copper chloride lattice structure are metastable, so its basic group has high reactivity, and it is easy to react with the carboxyl group of the amino acid, so Basic copper chloride powder and amino acids can be reacted in a solid or semi-solid state, even at lower temperatures (eg below 30 ° C below room temperature)

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.

[24] 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.

[25] [Description of the drawing]

BRIEF DESCRIPTION OF THE DRAWINGS 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).

[30] Figure 5 is a method of the present invention (containing a recrystallization step) prepared by glycine chelated copper hydroxychloride

Infrared spectrum of the crystal.

[Detailed Embodiment]

The following examples are intended to further illustrate and explain the present invention and are not to be construed as limiting.

[33] Example 1

[34] In a 1 m3 reactor, the powdered basic copper chloride, lysine hydrochloride, and water were added in a molar ratio of 1:3:8 to 140 kg of monoclinic basic copper chloride. Lysine hydrochloride 360 kg, water 94 kg, evenly mixed, the temperature is raised to 80 ° C, the reaction is kept for 10 hours, the basic copper chloride green powder is all reacted to form lysine copper blue crystal, then After drying and cooling to room temperature, 510 kg of lysine chelated copper hydroxychloride [(Lys.Cl) ₃ Cu ₂ Cl.nH ₂ 0] chelate was obtained.

[35] Recrystallization of synthetic lysine chelated copper hydroxychloride [(Ly _S .Cl) ₃ C _U2 Cl.nH ₂ 0] crystals: 100 g of the composition, 200 ml of water, heated to 80 After stirring for 5 minutes at °C, the solution was a clear transparent sky blue, in which the alkali-free copper chloride green powder and other insoluble materials proved that the solid state reaction was completed. Then, it is naturally cooled to normal temperature, and blue acicular lysine is precipitated to chelate copper hydroxychloride [( Lys.Cl ) ₃ Cu ₂ Cl.nH ₂ 0] crystals, suction filtered, and dried to obtain recrystallized lysine chelate. Hydroxy copper chloride [(Lys.Cl ) ₃ Cu ₂ Cl.nH ₂ 0].

[36] X-ray diffraction analysis of recrystallized lysine chelated copper hydroxychloride [(Ly _S .Cl) ₃ C _U2 Cl.nH ₂ 0] shows that the diffraction peak is obvious, which proves that the material has a crystal structure. Its five strongest diffraction peaks have d values of 3.49, 8.47 , 3.28, 3.59, 3.82 and monoclinic basic copper chloride, the five strongest diffraction peaks d value 5.71, 2.58, 2.57

, 2.41, 2.40 and lysine hydrochloride are significantly different, which proves that the three are different substances.

[37] Infrared spectrum analysis: 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 υ ()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. It also shows that the α-amino group has a coordination reaction with copper, and a strong hydroxyl absorption peak appears at 3443 cm-i, indicating that the hydroxyl group of the powder crystal basic copper chloride participates in the coordination to form the associative crystal water.

[38] Infrared spectra and elemental content analysis of both recrystallized and unrecrystallized lysine chelated copper hydroxychloride [(Ly _S .Cl) ₃ C _U2 Cl.nH ₂ 0]: Infrared The spectrum is similar, the content of both factors is 15.7% copper content, 17.7% chlorine content and 66% lysine (Lys) content, which proves that the molecular formula of the composition is (Lys.Cl) ₃ Cu ₂ Cl.n H ₂ 0 A pure compound (where n is 3 to 6).

[39] Example 2

[40] In a 1 m3 V-shaped double-cone mixer, the powdered basic copper chloride, glycine, and water were added in a molar ratio of 1:3:2 to monoclinic basic copper chloride 200 kg, glycine. 211 kg, 33 kg of water, under mixing conditions, raise the temperature to 40 ° C, react for 12 hours, cool to room temperature, then dry, discharge, to obtain glycine chelated copper hydroxychloride [ ( Gly ) ₃ Cu ₂ Cl.nH ₂ 0] Bright blue crystal 420 kg.

[41] Analysis of the solubility of the synthesized glycine chelated copper hydroxychloride [(Gly) ₃ C _U2 Cl.nH ₂ 0]: Take 20 g of the composition, add 200 ml of water, stir for 5 minutes, and the solution is clear and transparent. Sky blue, in which the alkali-free copper chloride green powder and other insolubles prove that the solid state reaction is complete.

[42] X-ray diffraction analysis of the synthesized copper glycinate chelate: The diffraction peak is obvious, and the material has a crystal structure. The three strongest diffraction peaks have values d 8.35, 4.99, 3.74, 3.60, 3.47 and monoclinic system. Basic copper chloride and glycine are significantly different, demonstrating that the three are different substances.

[43] Infrared spectrum analysis: 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 υ (ΝΗ3) 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 α-amino group has a coordination reaction with copper.

[44] Elemental analysis of synthetic glycine chelated copper hydroxychloride [(Gly) ₃ C _U2 Cl.nH ₂ 0], copper content 27.8%, chlorine content 7.8%, glycine content 48.6%, composition The molecular formula is (Gly) ₃ Cu ₂ C1.4H ₂ 0 . The composition (Gly) ₃ Cu ₂ C1.4H ₂ 0 was recrystallized, and the recrystallized product was analyzed for elemental content, copper content was 27.5%, glycine content was 63.9%, and chlorine was not contained, and the synthesized glycine copper chelate was proved. The active ingredient is very high, and the recrystallized copper glycinate chelate has the formula (Gly) ₂ Cu.H ₂ 0.

[45] Example 3

[46] In a 1 m3 V-shaped double-cone mixer, powdered basic copper chloride, methionine, and water were added in a molar ratio of 1:3:4 to monoclinic copper chloride 200 kg, methionine. 420 kg, water 66 kg, under mixing conditions, raise the temperature to 40 ° C, react 24 hours, cool to room temperature, then dry, discharge, get methionine chelated copper hydroxychloride [(Met) ₃ Cu ₂ Cl.nH ₂ 0] 650 kg of brownish gray crystal.

[47] X-ray diffraction analysis of the synthesized methionine chelated copper hydroxychloride [(Met) ₃ C _U2 Cl. _n H ₂ 0]: The diffraction peak is obvious, and the substance has a crystal structure, and the five strongest diffraction peaks 15.8, 4.4, 8.0, 5.3, 4.3 are significantly different from monoclinic basic copper chloride and methionine, which proves that the three are different substances.

[48] Analysis of solubility of synthetic methionine chelated copper hydroxychloride [(Met) ₃ C _U2 Cl. _n H ₂ 0]: Take 20 g of the composition, add 200 ml of water, stir for 5 minutes, crystallize from brown The gray color turned into a blue water-insoluble precipitate, and no basic copper chloride green powder and other insoluble matter were found, which proved that the solid state reaction proceeded completely.

[49] Elemental analysis of synthetic methionine chelated copper hydroxychloride [(Met) ₃ C _U2 Cl. _n H ₂ 0]: copper content of 17.9%, chlorine content of 5.4%, Met content of 63%, It is presumed that the molecular formula of the composition is (Met) ₃ Cu ₂ C1.5 H ₂ 0.

[50] Example 4

[51] In a 1 m3 V-shaped double-cone mixer, powdered basic copper chloride, methionine, and water were added in a molar ratio of 1:2:3 to 200 kg of monoclinic copper chloride, methionine 280. Kg, water 50 kg, under mixing conditions, raise the temperature to 40 ° C, react 24 hours, cool to room temperature, then dry, discharge, get methionine chelated copper hydroxychloride [(Met) ₂ (OH Cu ₂ Cl.nH ₂ 0] 650 kg of brownish gray crystal.

[52] Analysis of the solubility of the synthesized methionine chelated copper hydroxychloride [(Met) ₂ (OH) C _U2 Cl. _n H ₂ 0]: 20 g of the composition was taken, 200 ml of water was added, and the mixture was stirred for 5 minutes. The crystal changed from brownish gray to blue insoluble in water, and no basic copper chloride green powder was found, which proved that the solid reaction proceeded completely. [53] Elemental analysis of synthetic methionine chelated copper hydroxychloride [(Met) ₂ (OH)C _U2 Cl. _n H ₂ 0], copper content 17.9%, chlorine content 5.4%, methionine (Met The content is 63%, and the molecular formula of the composition is presumed to be (Met) ₂ (OH)Cu ₂ Cl.nH ₂ 0 (where n is 3 to 6).

[54] Example 5

[55] In a 1 m3 V-shaped double-cone mixer, 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-

<15, under the mixing conditions, 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.

[56] The solubility analysis of the synthesized composite amino acid copper was carried out, 20 g of the composition was taken, 200 ml of water was added, and the mixture was stirred for 5 minutes, and the crystal was dissolved into a dark green aqueous solution. No basic copper chloride green powder was found, which proved that the solid reaction was carried out. complete.

[57] 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%.

Claims

Claim

[1] A method for preparing an amino acid chelated copper hydroxychloride crystal, characterized in that the method comprises the following steps:

a, the powder crystal basic copper chloride, amino acid and water in a molar ratio of 1: 0~4: 1~10 mixed under stirring or extrusion conditions, the reaction at a temperature of 10~90 ° C 2~72 small吋, obtaining an amino acid chelate copper hydroxychloride crystal;

b. The amino acid obtained by the mixed reaction is chelated to crystallize the copper hydroxychloride crystal or directly subjected to a recrystallization process to obtain a product.

[2] The preparation method according to claim 1, wherein in the step (a), the molar ratio of the powdered basic copper chloride, the amino acid and the water is 1: 2 to 3: 1 to 10.

[3] The preparation method according to claim 1, wherein in the step (a), the powdery basic copper chloride is a chloroformite having a molecular formula of C (OH) ₃ C 啲 orthorhombic system. Triclinic secondary chlorite

a mixed crystal form of one or more of a monoclinic oblique chlorite or a monoclinic clinoatacamite.

[4] The preparation method according to claim 1, wherein in the step (a), the amino acid is lysine, lysine hydrochloride, lysine sulfate, glycine, tryptophan, Methionine, threonine, valine, histidine, leucine, isoleucine, alanine, phenylalanine, cystine, cysteine, arginine, serine, tyrosine 3.5. A complex amino acid of one or several amino acids of diiodotyrosine, glutamic acid, aspartic acid, proline, hydroxyproline, arginine, citrulline, and ursine.

[5] The preparation method according to claim 1, wherein in the step (a), the reaction formula of the mixed reaction of the powdered basic copper chloride, the amino acid and the water is as follows:

Cu ₂ (OH) ₃ Cl + mAA + H ₂ 0

(AA) _m Cu ₂ (OH) _{3 m} Cl.nH ₂ 0

Where m is 0 to 3 and n is 0 to 10.

[6] The preparation method according to claim 1, wherein in the step (a), the reaction formula of the mixed reaction of the powdered basic copper chloride, the amino acid and the water is as follows: Cu ₂ (OH) ₃ Cl + 4AA + H ₂ 0

2(AA) ₂ Cu.nH ₂ 0 + HC1

[7] The preparation method according to claim 1, wherein in the step (b), the recrystallization process comprises mixing the amino acid chelating copper hydroxychloride crystals with water in a weight ratio of 1:0.5 to 10, Heated and dissolved at a temperature of 60 to 100 ° C, then cooled and recrystallized, filtered, dried to yield

P

[8] The amino acid chelated copper hydroxychloride prepared by the method of claim 1 is used as a nutrient element additive for animal feed.