CN109180510B - Preparation method of high-purity ferrous glutamate - Google Patents
Preparation method of high-purity ferrous glutamate Download PDFInfo
- Publication number
- CN109180510B CN109180510B CN201810995723.8A CN201810995723A CN109180510B CN 109180510 B CN109180510 B CN 109180510B CN 201810995723 A CN201810995723 A CN 201810995723A CN 109180510 B CN109180510 B CN 109180510B
- Authority
- CN
- China
- Prior art keywords
- ferrous
- reaction
- carbonate
- glutamate
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a preparation method of high-purity ferrous glutamate, which comprises the following steps: adding glutamic acid into the ferrous carbonate suspension, reacting at constant temperature under the vacuum condition of-0.02-0.099 MPa, controlling the pH value of the reaction end point, cooling to below 40 ℃ after the reaction is finished, discharging the vacuum, filtering and drying to obtain the high-purity ferrous glutamate.
Description
Technical Field
The invention belongs to the technical field of preparation of feed additives, and particularly relates to a preparation method of high-purity ferrous glutamate.
Background
Glutamic acid is one of the basic amino acids of nitrogen metabolism in organisms, and has important significance in metabolism, and is a main constituent of protein. Glutamate is ubiquitous in nature and is contained in a variety of foods as well as in the human body.
Glutamic acid (2-aminoglutaric acid) has a levorotatory isomer, a dextrorotatory isomer and a racemic body. The levorotatory isomer, L-glutamic acid, is a flaky or powdery crystal, is slightly acidic, non-toxic, insoluble in water, hardly soluble in diethyl ether, acetone and cold acetic acid, and insoluble in ethanol and methanol.
Since glutamic acid is hardly soluble in water, glutamic acid is hardly soluble in an aqueous solutionThe iron salts form chelate complexes, and the synthesis is also rarely reported in the literature. The patent CN101822316A only describes the application of ferrous glutamate as a trace element chelate animal feed additive, and does not mention the preparation method. A process for preparing ferrous glutamate by response surface method includes such steps as using ferrous chloride and sodium glutamate as raw materials, analyzing response surface to optimize the conditions of ferrous glutamate by solid-liquid phase method, selecting pH value, reaction temp and reaction time, and central combination test to build up a quadratic regression equation. The results show that the quantity ratio of reactant substances, the pH value of a medium, the reaction time and the temperature all have certain influence on the yield of the reaction product, and the optimized preparation process conditions are glutamic acid and Fe2+The mass ratio of the substances is 1:1, the pH value of the medium is 5.76, the reaction time is 0.75h, the reaction temperature is 58.9 ℃, the yield is 77.79 percent, and the composition of the ferrous glutamate chelate of the reaction product is Fe (C)5H7NO4)·2H2And O. However, in this production method, iron powder is added in order to reduce the generation of trivalent iron, but in the actual reaction process, iron powder hardly participates in the reaction in a weakly acidic environment, and on the contrary, impurities are introduced, so that the yield is lowered.
Disclosure of Invention
The technical problem to be solved by the invention is to provide a preparation method of high-purity ferrous glutamate, which overcomes the defects and shortcomings in the background technology.
In order to solve the technical problems, the technical scheme provided by the invention is as follows:
a preparation method of high-purity ferrous glutamate comprises the following steps:
adding glutamic acid into ferrous carbonate, reacting at constant temperature under the vacuum condition of-0.02-0.099 MPa, controlling the pH value of the reaction end point, cooling to below 40 ℃ after the reaction is finished, discharging the vacuum, filtering and drying to obtain the high-purity ferrous glutamate.
In the above production method, preferably, the reaction end point has a pH of 4.0 to 7.0.
In the preparation method, the constant-temperature reaction time is preferably 1-5 h.
In the preparation method, the temperature of the isothermal reaction is preferably 50-90 ℃.
The ferrous carbonate reacts with glutamic acid under the conditions of heating and vacuum to generate ferrous glutamate, and the chemical reaction equation is as follows:
synthesizing ferrous carbonate: FeSO4+Na2CO3——FeCO3↓+Na2SO4；
Synthesizing ferrous glutamate: FeCO3+C5H9NO4——FeC5H7NO4+H2O+CO2↑。
The invention utilizes the reaction of glutamic acid and ferrous carbonate to generate CO gas2The method is characterized in that CO is continuously removed under the vacuum condition of-0.02-0.099 MPa by changing the chemical equilibrium2The reaction is promoted to continuously proceed to the right, thereby improving the yield of the target product of the reaction, and Fe is used2+The conversion rate can reach more than 90 percent, and the high-purity ferrous glutamate is obtained.
In the above preparation method, preferably, the ferrous carbonate is a ferrous carbonate suspension, and the specific preparation process includes:
(1) adding ferrous sulfate into water to completely dissolve the ferrous sulfate to obtain a ferrous sulfate solution;
adding sodium carbonate into water to completely dissolve the sodium carbonate to obtain a sodium carbonate solution;
(2) adding the sodium carbonate solution into the ferrous sulfate solution for reaction, filtering and washing to obtain an active ferrous carbonate wet filter cake;
(3) and adding the active ferrous carbonate wet filter cake into water, and stirring to prepare a ferrous carbonate suspension.
The prepared ferrous carbonate has more active reaction property, does not contain ferric carbonate impurities in the ferrous carbonate, and has high activity. The invention utilizes the reaction activity of the active ferrous carbonate, can reduce the activation energy of the reaction with the organic weak acid glutamic acid, and leads the two to be easier to react, and the defect of slow reaction of the commercial ferrous carbonate and the glutamic acid is changed by adopting the active ferrous carbonate.
In the above preparation method, preferably, in the step (2), the molar ratio of the ferrous sulfate to the sodium carbonate is 1: 1.
in the above preparation method, the molar ratio of the glutamic acid to the ferrous carbonate is preferably 1 (1-1.1).
In the preparation method, the drying temperature is 50-80 ℃, the drying time is 1-3h, and the drying is carried out under the vacuum condition of-0.02-0.099 MPa. The invention is dried at low temperature in vacuum, avoids the oxidation of ferrous, the ferrous content in the product can reach 27.0 percent, the ferric iron is less than or equal to 0.5 percent, and ensures the high purity of the ferrous glutamate.
In the above preparation method, preferably, the carbon dioxide gas generated in the isothermal reaction process is continuously discharged from the reaction system. Continuous CO removal2The reaction for synthesizing the ferrous glutamate is promoted to be continuously carried out rightwards, thereby improving the yield of the target product of the reaction,
compared with the prior art, the invention has the advantages that:
according to the preparation method, ferrous sulfate and sodium carbonate are respectively prepared into solutions to generate active ferrous carbonate, and the reaction activity of the active ferrous carbonate is utilized to reduce the activation energy of the reaction with organic weak acid glutamic acid, so that the two are easier to react, and the defect that the commercial ferrous carbonate and the glutamic acid react slowly is overcome; the reaction is carried out under the vacuum condition of-0.02-0.099 MPa, the chemical balance of the reaction is changed, the reaction is promoted to be continuously carried out rightwards, thereby the yield of the target product of the reaction is improved, and Fe is used2+The yield can reach more than 90%; because the solubility of the glutamic acid is poor, the glutamic acid ferrous is easy to oxidize, and the oxygen concentration is low under the vacuum condition, the introduction of impurity iron powder is avoided on the premise that the glutamic acid ferrous is not oxidized, and the high-purity glutamic acid ferrous is prepared; the preparation method of the invention avoids the characteristic that ferrous iron is easy to oxidize under oxygen-rich and high-temperature conditions, and the purity of the ferrous glutamate product prepared by the preparation method of the invention can reach more than 95%.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
Fig. 1 is an XRD diffractogram of the ferrous glutamate product prepared in example 1 of the present invention.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
The total iron content of the products of the following examples was determined by potassium dichromate titration, the ferrous content was determined by uv spectrophotometry, the ferric content was the total iron content minus the ferrous content, and the glutamic acid was determined by azotometry.
Example 1:
the preparation method of the high-purity ferrous glutamate comprises the following steps:
(1) weighing 26.6g of ferrous sulfate pentahydrate, adding into 100g of water, stirring and dissolving to obtain a ferrous sulfate solution;
weighing 11.7g of sodium carbonate, adding the sodium carbonate into 100g of water, and stirring for dissolving to obtain a sodium carbonate solution;
(2) adding a sodium carbonate solution into a ferrous sulfate solution, fully mixing and stirring for 20min, filtering and washing to obtain an active ferrous carbonate wet filter cake;
(3) adding the ferrous carbonate wet filter cake prepared in the step (2) into 250mL of water, and stirring to prepare a ferrous carbonate suspension;
(4) adding 14.7g of glutamic acid into the ferrous carbonate suspension in the step (3), reacting for 2h at 50 ℃ under the vacuum of-0.09 MPa (carbon dioxide gas generated in the reaction process is continuously discharged out of a reaction system), wherein the end-point pH of the reaction liquid is 5.4, vacuumizing, heating and concentrating for 160min (about 50mL of concentrated solution), cooling to 40 ℃, discharging vacuum, and performing suction filtration to obtain an earthy yellow ferrous glutamate wet filter cake;
(5) drying the wet filter cake for 1h under vacuum of-0.08 MPa at 55 ℃ to obtain 18.4g of ferrous glutamate product.
Measuring the yield of the ferrous glutamate product as Fe2+Calculated as 90.1%, the water loss at 104 ℃ was 1.1%, the ferrous content was 27.1%, the ferric content was 0.24%, the glutamic acid content was 71.2%, the purity was 98.6%, i.e. the molar ratio of glutamic acid to iron was about 1: 1.
The XRD diffraction pattern of the product prepared in this example is shown in fig. 1, the first, second, third and fourth rows of the abscissa are the XRD diffraction patterns of the product, glutamic acid, ferrous sulfate pentahydrate and ferrous sulfate heptahydrate in this example in turn, and it can be seen from the patterns that the peaks of the product are shifted, split and combined, rather than the superposition of the peaks of glutamic acid and ferrous sulfate, i.e. a new substance is generated by the reaction, thereby determining that the molecular formula thereof is FeC5H7NO4。
Example 2:
the preparation method of the high-purity ferrous glutamate comprises the following steps:
(1) weighing 15.5g of anhydrous ferrous sulfate, adding the anhydrous ferrous sulfate into 100g of water, and stirring for dissolving to obtain a ferrous sulfate solution;
weighing 10.6g of sodium carbonate, adding the sodium carbonate into 100g of water, and stirring for dissolving to obtain a sodium carbonate solution;
(2) adding a sodium carbonate solution into a ferrous sulfate solution, fully mixing and stirring for 15min, filtering and washing to obtain a white active ferrous carbonate wet filter cake;
(3) adding the ferrous carbonate wet filter cake prepared in the step (2) into 250mL of water, and stirring to prepare a ferrous carbonate suspension;
(4) adding 14.7g of glutamic acid into the ferrous carbonate suspension, reacting for 5h at 50 ℃ under the vacuum of-0.03 MPa (carbon dioxide gas generated in the reaction process is continuously discharged out of the reaction system), wherein the end point pH of the reaction liquid is 4.0, then vacuumizing, heating and concentrating for 160min (about 60mL of concentrated solution), cooling to 40 ℃, discharging vacuum, and performing suction filtration to obtain an earthy yellow ferrous glutamate wet filter cake;
(5) the wet filter cake was dried under vacuum of-0.08 MPa at 50 ℃ for 3h to obtain 20.6g of ferrous glutamate product.
Measuring the yield of the ferrous glutamate product as Fe2+Calculated as 97.9%, the water loss at 104 ℃ is 3.2%, the ferrous content is 26.6%, the ferric content is 0.12%, the glutamic acid content is 69.7%, the purity is 96.5%, namely the molar ratio of glutamic acid to iron in the product is about 1:1, and the molecular formula is FeC5H7NO4。
Example 3:
the preparation method of the high-purity ferrous glutamate comprises the following steps:
(1) weighing 31.1g of ferrous sulfate heptahydrate, adding into 100g of water, stirring and dissolving to obtain a ferrous sulfate solution;
weighing 11.1g of sodium carbonate, adding the sodium carbonate into 100g of water, and stirring for dissolving to obtain a sodium carbonate solution;
(2) adding a sodium carbonate solution into a ferrous sulfate solution, fully mixing and stirring for 25min, filtering and washing to obtain a white active ferrous carbonate wet filter cake;
(3) adding the ferrous carbonate wet filter cake prepared in the step (2) into 250mL of water, and stirring to prepare a ferrous carbonate suspension;
(4) adding 14.7g of glutamic acid into the ferrous carbonate suspension, reacting for 1h at 90 ℃ under the vacuum of-0.02 MPa (carbon dioxide gas generated in the reaction process is continuously discharged out of the reaction system), wherein the end point pH of the reaction liquid is 7.0, then vacuumizing, heating and concentrating for 160min (about 50mL of concentrated solution), cooling to 40 ℃, discharging vacuum, and performing suction filtration to obtain an earthy yellow ferrous glutamate wet filter cake;
(5) drying the wet filter cake for 1h at the temperature of 80 ℃ under the vacuum of-0.04 MPa to obtain 19.4g of ferrous glutamate product.
Determination of ferrous glutamate productYield as Fe2+Calculated as 91.8%, the water loss at 104 ℃ is 0.7%, the ferrous content is 27.3%, the ferric content is 0.08%, the glutamic acid content is 71.4%, the purity is 98.8%, namely the ratio of glutamic acid to iron in the product is about 1:1, the molecular formula is determined to be FeC5H7NO4。
Claims (8)
1. A preparation method of ferrous glutamate is characterized by comprising the following steps:
adding glutamic acid into ferrous carbonate, reacting at constant temperature under the vacuum condition of-0.02 to-0.099 MPa, continuously discharging carbon dioxide gas generated in the reaction at constant temperature out of a reaction system, controlling the pH value of a reaction end point, cooling to below 40 ℃ after the reaction is finished, discharging vacuum, filtering, and drying to obtain the ferrous glutamate.
2. The method according to claim 1, wherein the pH at the end of the reaction is 4.0 to 7.0.
3. The method according to claim 1, wherein the isothermal reaction time is 1 to 5 hours.
4. The method according to claim 1, wherein the isothermal reaction temperature is 50-90 ℃.
5. The preparation method according to any one of claims 1 to 4, wherein the ferrous carbonate is a ferrous carbonate suspension, and the preparation process comprises the following steps:
(1) adding ferrous sulfate into water to completely dissolve the ferrous sulfate to obtain a ferrous sulfate solution;
adding sodium carbonate into water to completely dissolve the sodium carbonate to obtain a sodium carbonate solution;
(2) adding the sodium carbonate solution into the ferrous sulfate solution for reaction, filtering and washing to obtain an active ferrous carbonate wet filter cake;
(3) and adding the active ferrous carbonate wet filter cake into water, and stirring to prepare a ferrous carbonate suspension.
6. The method according to claim 5, wherein in the step (2), the molar ratio of the ferrous sulfate to the sodium carbonate is 1: 1.
7. the method according to any one of claims 1 to 4, wherein the molar ratio of glutamic acid to ferrous carbonate is 1 (1 to 1.1).
8. The method according to any one of claims 1 to 4, wherein the drying temperature is 50 to 80 ℃, the drying time is 1 to 3 hours, and the drying is performed under a vacuum condition of-0.02 to-0.099 MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810995723.8A CN109180510B (en) | 2018-08-29 | 2018-08-29 | Preparation method of high-purity ferrous glutamate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810995723.8A CN109180510B (en) | 2018-08-29 | 2018-08-29 | Preparation method of high-purity ferrous glutamate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109180510A CN109180510A (en) | 2019-01-11 |
| CN109180510B true CN109180510B (en) | 2021-08-24 |
Family
ID=64916476
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810995723.8A Active CN109180510B (en) | 2018-08-29 | 2018-08-29 | Preparation method of high-purity ferrous glutamate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109180510B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110041213A (en) * | 2019-04-11 | 2019-07-23 | 中国农业科学院兰州畜牧与兽药研究所 | A kind of preparation method of glutamate chelate iron |
| CN111116390B (en) * | 2019-12-25 | 2024-06-21 | 长沙兴嘉生物工程股份有限公司 | Preparation method of calcium glutamate |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1529775A1 (en) * | 2001-12-17 | 2005-05-11 | JH Biotech, Inc. | Method for preparation of metal organic acid chelates |
| CN1720249A (en) * | 2002-12-05 | 2006-01-11 | Md白奥阿尔法有限公司 | Method for preparation of amino acid chelate |
| CN101671263A (en) * | 2009-10-12 | 2010-03-17 | 北京中国科学院老专家技术中心 | Method for preparing novel amino acid chelate |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU1832123C (en) * | 1991-02-15 | 1993-08-07 | Институт Органической Химии Ан Киргсср | Method of iron (ii) diglutamate synthesis |
-
2018
- 2018-08-29 CN CN201810995723.8A patent/CN109180510B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1529775A1 (en) * | 2001-12-17 | 2005-05-11 | JH Biotech, Inc. | Method for preparation of metal organic acid chelates |
| CN1720249A (en) * | 2002-12-05 | 2006-01-11 | Md白奥阿尔法有限公司 | Method for preparation of amino acid chelate |
| CN101671263A (en) * | 2009-10-12 | 2010-03-17 | 北京中国科学院老专家技术中心 | Method for preparing novel amino acid chelate |
Non-Patent Citations (1)
| Title |
|---|
| 谷氨酸亚铁螯合物的合成与表征;黄杰;《中国优秀硕士学位论文全文数据库 工程科技第I辑》;20160215;正文第18-19页第2.2.1节 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109180510A (en) | 2019-01-11 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109180510B (en) | Preparation method of high-purity ferrous glutamate | |
| AU2010255849B2 (en) | Non-caking salt composition, preparation process and use thereof | |
| CN101381327B (en) | Method for preparing aminoguanidin carbonate | |
| CN112142028B (en) | Preparation method of manganese phosphate | |
| Plass et al. | Synthesis, reactivity, and structural characterization of dioxovanadium (V) complexes with tridentate schiff base ligand: vanadium complexes in supramolecular networks | |
| CN107118115B (en) | Preparation method of ferrous glycinate chelate | |
| CN104891576B (en) | A kind of preparation method of Manganous sulfate monohydrate | |
| Chen et al. | Transformations and reductions of γ-octamolybdates with their monomeric and dimeric amino polycarboxylates | |
| CA2797442A1 (en) | Process for the production of ferrous sulphate monohydrate | |
| CN101731628B (en) | Method for preparing casein peptide chelated iron | |
| CN116143093A (en) | Method for preparing battery-grade anhydrous ferric phosphate by utilizing industrial waste iron mud | |
| CN102702032A (en) | Synthesis method of guanidinoacetic acid | |
| CN101987747A (en) | Preparation method of reagent-grade ammonium molybdate | |
| VuČKović et al. | Preparation, characterization and redox properties of o, o′‐geometrical isomers of μ‐α and μ‐β‐aminoisobuty‐rato co (ii) complexes with n, n′, n′, n‴‐tetrakis (2‐pyridylmethyl)‐1, 4, 8, 11‐tetraazacyclotetradecane | |
| EP3653633B1 (en) | Methionine-metal chelate and production method thereof | |
| CN102618064B (en) | Synthesizing process of Janus green B | |
| Nawi et al. | Model complexes for amavadine, a vanadium natural product | |
| CN116022757B (en) | Preparation method of battery-grade hydrated ferric phosphate | |
| CN106831399A (en) | A kind of 2 thylhexoic acid rhodiums（Ⅱ）Synthetic method | |
| CN109179475A (en) | A kind of preparation method of strontium chloride | |
| CN110357777B (en) | Synthetic method of high-purity ferrous oxalate | |
| CN102476829A (en) | Preparation method of vanadyl sulfate | |
| KR20100030292A (en) | Method for preparing liquefied fertilizer using dolomite or limestone | |
| AU743601B2 (en) | Iron alkali salt of S,S-ethylenediamine-N,N'-disuccinic acid and process for producing the same | |
| CN116924365A (en) | Method for preparing ferric phosphate dihydrate by decomplexing ferric phosphate complex |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |