CN111138271A - Preparation method of organic metal salt additive - Google Patents

Preparation method of organic metal salt additive Download PDF

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Publication number
CN111138271A
CN111138271A CN202010063165.9A CN202010063165A CN111138271A CN 111138271 A CN111138271 A CN 111138271A CN 202010063165 A CN202010063165 A CN 202010063165A CN 111138271 A CN111138271 A CN 111138271A
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ammonium
zinc
salt additive
source
calcium
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马建超
庞进
冯国瑞
王雨昕
马清亮
王欣
郭春丽
张思宇
郝海东
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Taiyuan University of Technology
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Taiyuan University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part

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Abstract

The invention discloses a preparation method of an organic metal salt additive, which comprises the following steps: (1) mixing short-chain organic acid serving as an acid source and ammonia water serving as an alkali source in an aqueous solution to prepare organic acid ammonium; (2) and (2) mixing an iron source, a calcium source or a zinc source with the solution obtained in the step (1), stirring, filtering, washing and drying to obtain the high-purity organic metal salt additive. The organic metal salt has a good crystal structure and high purity, the raw materials used are wide in source and low in price, the problems of complexity, high production cost, low yield and the like of the existing process are well solved, and the organic metal salt has a good industrial application prospect.

Description

Preparation method of organic metal salt additive
Technical Field
The invention relates to a preparation method of an organic metal salt additive, belonging to the field of feed additives and medicament additives.
Background
The metal elements are essential elements in animal body, such as calcium, zinc, iron, etc., and have effects of strengthening bone, regulating appetite, improving digestive system secretion function, and enhancing animal body immunity. Compared with inorganic metal element additives, the organic metal element additives have the characteristics of high efficiency, low toxicity, low pollution, easy absorption and the like. The short-chain organic metal salt is used as an organic metal element additive with extremely high metal element content, and is beneficial to the absorption of calcium, zinc and ferrous ions by animals and human bodies. Meanwhile, short-chain organic acid radical ions can participate in tricarboxylic acid cycle to form ATP to provide energy for metabolism of organisms, and can also be used as a carbon skeleton to form amino acid to further synthesize protein. Therefore, researchers have increasingly strengthened research on the organometallic salt additives.
Zinc fumarate has been The first concern of researchers because of its high zinc content (Gupta M P, Sahu R D, MaulikP R. The crystalline structure of zinc (II) fumarate hydrate [ J]Zeitschriff ü r Kristallographie, 1983, 163(1-2): 151-154.) since then, researchers developed a grinding method to prepare zinc fumarate (Yang bin. microwave radiation solid phase method to synthesize zinc fumarate [ J bin ]]Application chemical, 2005 (9); tomislav Fri š č i ć, L a szl Louvbi, mechanical conversion of a metal oxide polymerization and pore frame using liquid-assisted formation (LAG) J]CrystEngComm, 2009, 11.). However, this method is gradually abandoned because it is difficult to realize industrial production. Instead, there is the sodium carbonate process (Xie Hong Zhen et al. Synthesis and crystallization of Zn (H)2O)4(C4H2O4)]·H2O[J]Journal of coding Chemistry,2003, 56(15): 1291-1297; zhoujian-zinc fumarate complex, its preparation and application, China 201710723397.0P]The method for catalytically synthesizing the zinc fumarate [ J ] by using maleic anhydride and maleic anhydride in one kettle (Jianyi, maleic anhydride in one kettle)]Shanghai chemical industry (10): 14-16.) and zinc hypoxide process (Method for synthesizing zinc fumarate as feed additive from zinc hypoxide, China 201010223550.1P]A new process for preparing zinc fumarate or calcium fumarate (Shesxin, etc.; Chinese 201110339486.8P].) and zinc acetate process (Bats J W et al, One-dimensional zinc (II) fumarate complexation polymers [ J W et al]Journal of coding Chemistry 2015, 68(1): 118-129.), and the like. With the development of zinc fumarate preparation process, the growth research of zinc succinate (Zhang GJUN, et al, non-linear optical crystal zinc succinate [ J)]The artificial crystal bulletin, 2008(06), 189-193), zinc lysine (Ronchi, etc., a preparation method and application of zinc lysine feed additive with medium chelating strength, China, 201610237068.0 [ P ]]) Preparation method of lysine chelated calcium with scallop shell as calcium source, China, 201710002171.1 [ P ]]) Chinese iron malate (Liyungzheng, a method for producing ferrous malate: 201810774797.9 [ P ]]) The preparation process of the organic metal salt is also developed successively. However, most of the existing processes for preparing the organic metal salt have the defects of low yield, easy corrosion equipment, complex process and the like, and the direction is pointed for the research of the subsequent organic metal salt additive production process.
Disclosure of Invention
The invention aims to provide a preparation method of an organic metal salt additive, and the scheme has the advantages of simple process, greenness, low cost, high product purity and the like.
In the present invention, taking zinc fumarate as an example, the reaction equation is as follows:
Figure RE-330425DEST_PATH_IMAGE002
the invention provides a preparation method of an organic metal salt additive, which comprises the following two steps:
(1) mixing short-chain organic acid serving as an acid source and ammonia water serving as an alkali source in an aqueous solution to prepare organic acid ammonium;
(2) and (2) mixing an iron source, a calcium source or a zinc source with the solution obtained in the step (1), stirring, filtering, washing and drying to obtain the high-purity organic metal salt additive.
The short-chain organic acid in the step (1) is one of fumaric acid, succinic acid, malic acid and lysine; the organic acid ammonium is one of ammonium fumarate, ammonium succinate, ammonium malate, and ammonium lysinate; in the step (2), the iron source is ferrous sulfate heptahydrate; the zinc source is one of zinc sulfate heptahydrate and zinc acetate dihydrate; the calcium source is calcium chloride dihydrate; the organic metal salt additive is one of zinc fumarate, zinc succinate, zinc malate, zinc lysine, ferrous succinate, ferrous malate, ferrous lysine, calcium fumarate, calcium succinate, calcium malate or calcium lysine;
the above-described method for preparing an organic metal salt additive,
preferably, in the step (1), the pH value of the prepared organic acid ammonium solution is controlled to be 1-8, and the concentration of the organic acid ammonium is 0.5-2.5 moL/L.
Preferably, in the step (2), the molar charge ratio of the organic acid ammonium to the zinc sulfate heptahydrate, the zinc acetate dihydrate, the ferrous sulfate heptahydrate and the calcium chloride dihydrate is 2: 1-1: 5, the reaction temperature is 20-80 ℃, the reaction time is 20-120 min, the filter cake drying temperature is 50-70 ℃, and the drying time is 2-6 h.
Preferably, in the step (2), when washing with deionized water, the stirring time is 10min to 30min, and the mass ratio of the deionized water to the filter cake is 1:1 to 5: 1.
The invention has the beneficial effects that:
the invention has the beneficial effects that the organic metal salt prepared by the process has better crystal structure and higher purity, the raw materials used are wide in source and low in price, and the problems of complex process, high production cost, low yield and the like in the prior art are solved.
Detailed Description
The present invention is further illustrated by, but is not limited to, the following examples.
Example 1:
adding 11.6g of fumaric acid, 85mL of deionized water and 15mL of 25-28 mass percent ammonia water into a 100mL beaker to ensure that the pH value is about 5, uniformly mixing, and filtering to remove trace insoluble matters for later use.
28.76g of zinc sulfate heptahydrate is added into a 250mL flask, the prepared ammonium fumarate solution is transferred into the 250mL flask, stirred and reacted for 50min, and filtered by suction. Stirring and washing the mixture for 10min by using 100mL of deionized water, filtering the mixture, and drying the mixture for 6h at the temperature of 60 ℃ to obtain a zinc fumarate product. The results are shown in Table 1.
Example 2
Adding 118g of succinic acid 852mL of deionized water and 148mL of ammonia water with the mass fraction of 25% -28% into a 1000mL beaker to enable the pH value to be about 5, uniformly mixing, and filtering to remove trace insoluble matters for later use.
166g of calcium chloride dihydrate was added to a 2000mL beaker, and the prepared ammonium succinate solution was transferred to the 2000mL flask, stirred for reaction for 1 hour, and filtered with suction. Stirring and washing the mixture for 15min by using 500mL of deionized water, filtering the mixture, and drying the mixture for 6h at 70 ℃ to obtain the calcium succinate product. The results are shown in Table 1.
Example 3
Adding 13.4g of malic acid, 85mL of deionized water and 15mL of ammonia water with the mass fraction of 25% -28% into a 100mL beaker to enable the pH value to be about 5, uniformly mixing, and filtering to remove trace insoluble matters for later use.
14.7g of calcium chloride dihydrate was added to a 250mL flask, and the prepared ammonium malate solution was transferred to the 250mL flask, stirred for 40min and filtered. Stirring and washing the mixture for 10min by using 100mL of deionized water, filtering the mixture, and drying the mixture for 6h at 70 ℃ to obtain the calcium malate product. The results are shown in Table 1.
Example 4
Adding 146g of lysine 850mL of deionized water and 150mL of ammonia water with the mass fraction of 25% -28% into a 1000mL beaker to enable the pH value to be about 5, uniformly mixing, and filtering to remove trace insoluble matters for later use.
140g of ferrous sulfate heptahydrate is added into a 2000mL beaker, the prepared lysine ammonium solution is transferred into the 2000mL flask, stirred and reacted for 1 hour, and then filtered. Stirring and washing the mixture for 15min by using 1000mL of deionized water, filtering the mixture, and drying the mixture for 6h at 70 ℃ to obtain a ferrous lysine product. The results are shown in Table 1.
Example 5
146g of 855mL of deionized water containing lysine and 145mL of ammonia water with the mass fraction of 25% -28% are added into a 1000mL beaker, the pH value is kept at about 6, the materials are uniformly mixed, and the trace insoluble matter is removed by filtration for later use.
120g of zinc acetate dihydrate was added to a 2000mL beaker, and the prepared ammonium lysine solution was transferred to the 2000mL flask, reacted for 1 hour with stirring, and filtered with suction. And stirring and washing the mixture for 15min by using 1000mL of deionized water, filtering the mixture, and drying the filtered product for 6h at the temperature of 60 ℃ to obtain the lysine zinc product. The results are shown in Table 1.
Example 6
Adding 146g of lysine 850mL of deionized water and 150mL of ammonia water with the mass fraction of 25% -28% into a 1000mL beaker to enable the pH value to be about 6, uniformly mixing, and filtering to remove trace insoluble matters for later use.
80g of calcium chloride dihydrate was added to a 2000mL beaker, and the prepared ammonium lysine solution was transferred to the 2000mL flask, reacted for 1 hour with stirring, and filtered with suction. Stirring and washing the mixture for 15min by using 1000mL of deionized water, filtering the mixture, and drying the mixture for 6h at the temperature of 60 ℃ to obtain a lysine calcium product. The results are shown in Table 1.
Example 7
Adding 11.6g of fumaric acid 85mL of deionized water and 15mL of ammonia water with the mass fraction of 25% -28% into a 100mL beaker to enable the pH value to be about 6, uniformly mixing, and filtering to remove trace insoluble matters for later use.
15g of calcium chloride dihydrate was added to a 250mL beaker, and the prepared ammonium fumarate solution was transferred to a 250mL flask, stirred for 1 hour, and filtered with suction. Stirring and washing the mixture for 15min by using 100mL of deionized water, filtering the mixture, and drying the mixture for 6h at 70 ℃ to obtain a calcium fumarate product. The results are shown in Table 1.
Example 8
Adding 118g of succinic acid 850mL of deionized water and 150mL of ammonia water with the mass fraction of 25% -28% into a 1000mL beaker to enable the pH value to be about 5, uniformly mixing, and filtering to remove trace insoluble matters for later use.
300g of zinc sulfate heptahydrate is added into a 2000mL beaker, the prepared ammonium succinate solution is transferred into the 2000mL flask, stirred and reacted for 1 hour, and then filtered. Stirring and washing the mixture for 15min by using 1000mL of deionized water, filtering the mixture, and drying the mixture for 6h at the temperature of 60 ℃ to obtain the zinc succinate product. The results are shown in Table 1.
Example 9
850mL of deionized water containing 134g of malic acid and 150mL of ammonia water with the mass fraction of 25% -28% are added into a 1000mL beaker, the pH value is kept at about 6, the mixture is uniformly mixed, and the small amount of insoluble matter is removed by filtration for later use.
287g of zinc sulfate heptahydrate is added into a 2000mL beaker, and the prepared ammonium malate solution is transferred into the 2000mL flask, stirred for reaction for 1 hour, and filtered. Stirring and washing the mixture for 15min by using 1000mL of deionized water, filtering the mixture, and drying the mixture for 6h at 70 ℃ to obtain the zinc malate product. The results are shown in Table 1.
Example 10
Adding 118g of succinic acid 850mL of deionized water and 150mL of ammonia water with the mass fraction of 25% -28% into a 1000mL beaker to enable the pH value to be about 6, uniformly mixing, and filtering to remove trace insoluble matters for later use.
290g of ferrous sulfate heptahydrate is added into a 2000mL beaker, the prepared ammonium succinate solution is transferred into the 2000mL flask, stirred and reacted for 1 hour, and then filtered. Stirring and washing the mixture for 15min by using 1000mL of deionized water, filtering the mixture, and drying the mixture for 6h at the temperature of 60 ℃ to obtain a ferrous succinate product. The results are shown in Table 1.
Example 11
Adding 85mL deionized water of 14g malic acid and 15mL ammonia water with the mass fraction of 25% -28% into a 100mL beaker to ensure that the pH value is in the range of 7, uniformly mixing, and filtering to remove trace insoluble matters for later use.
18g of ferrous sulfate heptahydrate is added into a 250mL beaker, the prepared ammonium malate solution is transferred into a 250mL flask, stirred and reacted for 1 hour, and filtered. Stirring and washing the mixture for 15min by using 1000mL of deionized water, filtering the mixture, and drying the mixture for 6h at 70 ℃ to obtain a ferrous malate product. The results are shown in Table 1.
TABLE 1 product-related data
Item Yield of Purity of
Example 1 0.71 ≥0.96
Example 2 0.79 ≥0.96
Example 3 0.70 ≥0.94
Example 4 0.72 ≥0.94
Example 5 0.72 ≥0.94
Example 6 0.75 ≥0.94
Example 7 0.70 ≥0.94
Example 8 0.72 ≥0.94
Example 9 0.76 ≥0.94
Example 10 0.68 ≥0.94
Example 11 0.78 ≥0.94

Claims (9)

1. A method for preparing an organometallic salt additive, characterized by comprising two steps:
(1) mixing short-chain organic acid serving as an acid source and ammonia water serving as an alkali source in an aqueous solution to prepare organic acid ammonium;
(2) mixing an iron source, a calcium source or a zinc source with the solution obtained in the step (1), stirring for reaction, filtering, washing and drying to obtain a high-purity organic metal salt additive;
the short-chain organic acid is one of fumaric acid, succinic acid, malic acid and lysine;
the iron source is ferrous sulfate heptahydrate; the zinc source is one of zinc sulfate heptahydrate or zinc acetate dihydrate; the calcium source is calcium chloride dihydrate.
2. The method of preparing an organometallic salt additive according to claim 1, characterized in that: the organic acid ammonium prepared in the step (1) is one of ammonium fumarate, ammonium succinate, ammonium malate and ammonium lysinate.
3. The method of preparing an organometallic salt additive according to claim 2, characterized in that: and (2) controlling the pH value of the ammonium fumarate, ammonium succinate, ammonium malate or lysine ammonium solution prepared in the step (1) to be 1-8.
4. The method of preparing an organometallic salt additive according to claim 2, characterized in that: the concentration of the ammonium fumarate, the ammonium succinate, the ammonium malate and the ammonium lysinate prepared in the step (1) is 0.5 moL/L-2.5 moL/L.
5. The method of preparing an organometallic salt additive according to claim 2, characterized in that: in the step (2), the molar feeding ratio of the ammonium fumarate, the ammonium succinate, the ammonium malate or the ammonium lysinate to the zinc sulfate heptahydrate, the zinc acetate dihydrate, the ferrous sulfate heptahydrate and the calcium chloride dihydrate is 2: 1-1: 5.
6. The method of preparing an organometallic salt additive according to claim 1, characterized in that: the obtained organic metal salt additive is one of zinc fumarate, zinc succinate, zinc malate, zinc lysine, ferrous succinate, ferrous malate, ferrous lysine, calcium fumarate, calcium succinate, calcium malate or calcium lysine.
7. The method of preparing an organometallic salt additive according to claim 1, characterized in that: the reaction temperature is 20-80 ℃, and the reaction time is 20-120 min.
8. The method of preparing an organometallic salt additive according to claim 1, characterized in that: the drying temperature of the filter cake is 50-70 ℃, and the drying time is 2-6 h.
9. The method of preparing an organometallic salt additive according to claim 1, characterized in that: in the step (2), when washing with deionized water, stirring for 10-30 min, wherein the mass ratio of the deionized water to the filter cake is 1: 1-5: 1.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113277954A (en) * 2021-06-17 2021-08-20 英德市匠心新材料股份有限公司 Amino acid metal chelate micro-nano powder and preparation method thereof
CN114891502A (en) * 2022-05-23 2022-08-12 北京兴德通医药科技股份有限公司 Method for auxiliary synthesis of fluorescent probe by eutectic solvent and application
CN116217384A (en) * 2023-03-17 2023-06-06 金陵药业股份有限公司 Ferrous succinate basic salt crystal form, preparation method and composition

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GB1328494A (en) * 1969-08-28 1973-08-30 Laso Martinez V Process for preparing a ferrous fumarate product
CN101870645A (en) * 2010-07-09 2010-10-27 深圳市危险废物处理站有限公司 Method for synthesizing copper fumarate by using waste printed circuit board etching liquid
CN102367224A (en) * 2011-10-31 2012-03-07 宜兴市前成生物有限公司 Method for preparing calcium fumarate or zinc fumarate
US20120195822A1 (en) * 2011-01-27 2012-08-02 Honeywell International Inc. Method for the preparation of high purity stannous oxide
CN107473956A (en) * 2017-08-29 2017-12-15 南京雪郎化工科技有限公司 A kind of production method of ferrous fumarate

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2848366A (en) * 1956-05-18 1958-08-19 Mallinckrodt Chemical Works Non-hydrated ferrous fumarate and hematinic composition thereof
GB1328494A (en) * 1969-08-28 1973-08-30 Laso Martinez V Process for preparing a ferrous fumarate product
CN101870645A (en) * 2010-07-09 2010-10-27 深圳市危险废物处理站有限公司 Method for synthesizing copper fumarate by using waste printed circuit board etching liquid
US20120195822A1 (en) * 2011-01-27 2012-08-02 Honeywell International Inc. Method for the preparation of high purity stannous oxide
CN102367224A (en) * 2011-10-31 2012-03-07 宜兴市前成生物有限公司 Method for preparing calcium fumarate or zinc fumarate
CN107473956A (en) * 2017-08-29 2017-12-15 南京雪郎化工科技有限公司 A kind of production method of ferrous fumarate

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113277954A (en) * 2021-06-17 2021-08-20 英德市匠心新材料股份有限公司 Amino acid metal chelate micro-nano powder and preparation method thereof
CN113277954B (en) * 2021-06-17 2023-04-28 英德市匠心新材料股份有限公司 Amino acid metal chelate micro-nano powder and preparation method thereof
CN114891502A (en) * 2022-05-23 2022-08-12 北京兴德通医药科技股份有限公司 Method for auxiliary synthesis of fluorescent probe by eutectic solvent and application
CN114891502B (en) * 2022-05-23 2023-09-15 北京兴德通医药科技股份有限公司 Method for synthesizing fluorescent probe with assistance of eutectic solvent and application
CN116217384A (en) * 2023-03-17 2023-06-06 金陵药业股份有限公司 Ferrous succinate basic salt crystal form, preparation method and composition

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Application publication date: 20200512