CN109678745B - Refining method of low-titanium ferric glycine - Google Patents
Refining method of low-titanium ferric glycine Download PDFInfo
- Publication number
- CN109678745B CN109678745B CN201910075346.0A CN201910075346A CN109678745B CN 109678745 B CN109678745 B CN 109678745B CN 201910075346 A CN201910075346 A CN 201910075346A CN 109678745 B CN109678745 B CN 109678745B
- Authority
- CN
- China
- Prior art keywords
- glycinate
- ferric
- glycine
- titanium
- iron
- 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
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
- C07C227/16—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 not involving the amino or carboxyl groups
-
- 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
- C07C227/38—Separation; Purification; Stabilisation; Use of additives
- C07C227/40—Separation; Purification
- C07C227/42—Crystallisation
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A refining method of low-titanium ferric glycinate comprises the following steps: (1) synthesizing glycine iron; (2) flocculating and settling; (3) filtering to remove impurities; (4) freezing and recrystallizing; (5) separating and washing; (6) and (5) drying. The low-titanium ferrous glycinate prepared by the invention has the titanium content of less than or equal to 0.05 percent, can be stored for more than 6 months even under the conditions of high temperature and high humidity (the temperature is more than or equal to 35 ℃ and the relative humidity is more than or equal to 70 percent) in summer, has no oxidation discoloration, has stable quality, and is not easy to absorb moisture and agglomerate.
Description
Technical Field
The invention belongs to the technical field of preparation of organic feed additives, and particularly relates to a refining method of low-titanium ferric glycine.
Background
A glycine iron complex (chelate) compound (glycine iron) is a new type of feed additive, which is a chelate compound with cyclic structure produced by chemical synthesis of iron ion as metal element necessary for animals and glycine. Currently, raw materials commonly used for synthesizing glycine iron are glycine and ferrous sulfate heptahydrate (namely copperas), but the ferrous sulfate heptahydrate contains titanium impurities, and the content of the titanium impurities is about 0.2-0.3%. In the process of producing the ferrous glycinate, titanium impurities also exist in the ferrous glycinate prepared by utilizing ferrous sulfate heptahydrate containing the titanium impurities if the titanium reduction treatment is not carried out. The occurrence of excessive titanium impurities can affect the stability of the glycine iron, so that the glycine iron product can quickly absorb moisture, oxidize and discolor and cake under the conditions of high temperature and high humidity in summer, vitamins can be damaged after the glycine iron product is added into the feed, the quality of the feed is reduced, and the cost is increased.
At present, no refining method of low-titanium iron glycinate exists in the market, so that improvement on the production process of the iron glycinate is needed, the titanium content in the iron glycinate is reduced, the stability and the biological potency of the iron glycinate are maintained, and the time for the iron glycinate to generate oxidative discoloration is prolonged.
Disclosure of Invention
The invention aims to solve the technical problem of overcoming the defects in the prior art and provide a refining method of low-titanium ferrous glycinate, which has the advantages of long-term storage, stable quality, difficult moisture absorption and agglomeration, and no oxidative discoloration for more than 6 months.
The technical scheme adopted by the invention for solving the technical problems is as follows: a refining method of low-titanium ferric glycinate comprises the following steps:
(1) synthesis of iron glycinate: dissolving ferrous sulfate heptahydrate in water, heating to 60-70 ℃, adding glycine after the ferrous sulfate heptahydrate is completely dissolved, reacting for 30-60 min without stopping stirring, then cooling to 25-35 ℃, separating out coarse crystals of ferric glycinate, and separating the ferric glycinate crystals from a mother solution through centrifugation to obtain crystals with the coarse purity of 96-98% of the ferric glycinate;
(2) flocculation and sedimentation: dissolving the coarse crystals of the ferric glycinate obtained in the step (1) in hot water at 60-70 ℃, adding flocculant amphoteric polyacrylamide, uniformly stirring, standing and settling for 2-4 hours to obtain a ferric glycinate settling solution;
(3) and (3) filtering and removing impurities: filtering the ferric glycine sediment solution obtained in the step (2) to remove titanium impurities in the ferric glycine sediment solution, so as to obtain a low-titanium ferric glycine filtrate;
(4) freezing and recrystallizing: transferring the low-titanium ferric glycine filtrate obtained in the step (3) to a crystallization tank, and indirectly cooling by adopting frozen saline water at the temperature of-10-0 ℃ to re-precipitate 98-99% of ferric glycine crystals;
(5) separation and water washing: separating the ferric glycinate crystal obtained in the step (4) from the mother liquor by centrifugation, and washing the ferric glycinate crystal with water;
(6) and (3) drying: and (5) drying the ferric glycinate crystal obtained in the step (5) to obtain the low-titanium ferric glycinate. Further, the molar ratio of the ferrous sulfate heptahydrate to the glycine in the step (1) is 1: 1-1: 1.2.
Further, the addition amount of the flocculant is 0.05-0.15% of the coarse crystal of the ferric glycinate.
Further, in the step (1) and the step (5), mother liquor obtained after the ferric glycinate is recrystallized and centrifugally separated can be reused.
The invention has the beneficial effects that: the low-titanium ferrous glycinate prepared by the invention has the titanium content of less than or equal to 0.05 percent, can be stored for more than 6 months for a long time without oxidation and discoloration even under the conditions of high temperature and high humidity (the temperature is more than or equal to 35 ℃ and the relative humidity is more than or equal to 70 percent) in summer, has stable quality, and is not easy to absorb moisture and agglomerate.
Detailed Description
The present invention will be further described with reference to the following examples.
The chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
Example 1
The embodiment comprises the following steps:
(1) dissolving 100g of ferrous sulfate heptahydrate in 60ml of water, heating to 65 ℃, adding 26.9g of glycine, continuously stirring, keeping the temperature for reacting for 45min, cooling to 30 ℃, crystallizing and separating out ferric glycinate, and centrifuging to obtain a coarse ferric glycinate crystal;
(2) flocculation and sedimentation: taking 50g of coarse crystals of the ferric glycinate, adding 100ml of water, heating to 70 ℃, adding 0.025g of polyacrylamide after complete dissolution, uniformly stirring, keeping the temperature, standing and settling for 2 hours, centrifuging again, and separating titanium impurities after flocculation precipitation from the ferric glycinate solution;
(3) and (3) filtering and removing impurities: filtering the solution to remove titanium impurities;
(4) freezing and recrystallizing: transferring the filtered solution to a crystallization tank, adopting frozen saline water to indirectly cool, and utilizing the characteristic that the solubility of the ferric glycine is reduced along with the reduction of the temperature to re-precipitate the ferric glycine crystal;
(5) separation and water washing: separating the crystal of iron glycinate recrystallization from the mother liquor by a centrifugal method, and washing the iron glycinate with water;
(6) and (3) drying: and drying the iron glycinate crystal to obtain the low-titanium iron glycinate.
Comparative example
Dissolving 100g of ferrous sulfate heptahydrate in 60ml of water, heating to 65 ℃, adding 26.9g of glycine, continuously stirring, keeping the temperature for reacting for 45min, cooling to 30 ℃, crystallizing and separating out ferric glycinate, and centrifuging to obtain ferric glycinate crystals; (supplement conventional production method)
The product of this example was compared with the comparative example in terms of performance after 30 days storage at 35 ℃ and 72% relative humidity
TABLE 1 comparison of the properties of the product of this example with those of the comparative example after 30 days storage
Example 2
The embodiment comprises the following steps:
(1) adding 150g of ferrous sulfate heptahydrate into 90ml of the mother liquor obtained in the step (5) in the embodiment 1, heating to 70 ℃, adding 44.5g of glycine, continuously stirring, keeping the temperature for reacting for 45min, cooling to 30 ℃, crystallizing and separating out ferric glycinate, and centrifuging to obtain coarse ferric glycinate crystals;
(2) flocculation and sedimentation: dissolving 100g of coarse ferric glycinate crystals in hot water at 67 ℃, keeping the water temperature, adding 0.1g of flocculant amphoteric polyacrylamide, uniformly stirring, standing and settling for 3 hours to enable titanium impurities to be settled; and centrifuging again, and separating the titanium impurities after the flocculation precipitation from the ferric glycinate solution.
(3) And (3) filtering and removing impurities: filtering the solution to remove titanium impurities;
(4) freezing and recrystallizing: transferring the filtered solution to a crystallization tank, adopting frozen saline water to indirectly cool, and utilizing the characteristic that the solubility of the ferric glycine is reduced along with the reduction of the temperature to re-precipitate the ferric glycine crystal;
(5) separation and water washing: centrifugally separating the recrystallized crystal of the ferric glycinate from the solution, and washing the ferric glycinate with water;
(6) and (3) drying: and drying the iron glycinate crystal to obtain the low-titanium iron glycinate.
The product of this example was compared with the comparative example in terms of performance after 90 days storage at 35 ℃ and 72% relative humidity
TABLE 2 comparison of the properties of the product of this example with those of the comparative example after storage for 90 days
Example 3
The embodiment comprises the following steps:
(1) adding 200g of ferrous sulfate heptahydrate into 120ml of the mother liquor obtained in the step (5) in the embodiment 2, heating to 70 ℃, adding 64.7g of glycine, continuously stirring, keeping the temperature for reacting for 45min, cooling to 30 ℃, crystallizing and separating out ferric glycinate, and centrifuging to obtain coarse ferric glycinate crystals;
(2) flocculation and sedimentation: flocculation and sedimentation: dissolving 100g of coarse ferric glycinate crystals in hot water at 63 ℃, keeping the water temperature, adding 0.15g of flocculant amphoteric polyacrylamide, uniformly stirring, standing and settling for 4 hours to enable titanium impurities to be settled; and centrifuging again, and separating the titanium impurities after the flocculation precipitation from the ferric glycinate solution.
(3) And (3) filtering and removing impurities: filtering the solution to remove titanium impurities;
(4) freezing and recrystallizing: transferring the filtered solution to a crystallization tank, adopting frozen saline water to indirectly cool, and utilizing the characteristic that the solubility of the ferric glycine is reduced along with the reduction of the temperature to re-precipitate the ferric glycine crystal;
(5) washing and separating: centrifugally separating the recrystallized crystal of the ferric glycinate from the solution, and washing the ferric glycinate with water;
(6) and (3) drying: and drying the iron glycinate crystal to obtain the low-titanium iron glycinate.
The product of this example was compared with the comparative example in terms of performance after storage for 180 days at 35 ℃ and 72% relative humidity
TABLE 3 comparison of the properties of the product of this example with those of the comparative example after storage for 180 days
Claims (3)
1. A refining method of low-titanium ferric glycinate is characterized by comprising the following steps:
(1) synthesis of iron glycinate: dissolving ferrous sulfate heptahydrate in water, heating to 60-70 ℃, adding glycine after the ferrous sulfate heptahydrate is completely dissolved, reacting for 30-60 min without stopping stirring, then cooling to 25-35 ℃, separating out coarse crystals of ferric glycinate, and separating the ferric glycinate crystals from a mother solution through centrifugation to obtain the coarse crystals of the ferric glycinate with the purity of 96-98%;
(2) flocculation and sedimentation: dissolving the coarse crystals of the ferric glycinate obtained in the step (1) in hot water at 60-70 ℃, adding flocculant amphoteric polyacrylamide, uniformly stirring, standing and settling for 2-4 hours to obtain a ferric glycinate settling solution;
(3) and (3) filtering and removing impurities: filtering the ferric glycine sediment solution obtained in the step (2) to remove titanium impurities in the ferric glycine sediment solution, so as to obtain a low-titanium ferric glycine filtrate;
(4) freezing and recrystallizing: transferring the low-titanium ferric glycine filtrate obtained in the step (3) to a crystallization tank, and indirectly cooling by adopting frozen brine at the temperature of-10-0 ℃ to re-precipitate ferric glycine crystals with the purity of 98-99%;
(5) separation and water washing: separating the ferric glycinate crystal obtained in the step (4) from the mother liquor by centrifugation, and washing the ferric glycinate crystal with water;
(6) and (3) drying: drying the ferric glycinate crystal obtained in the step (5) to obtain low-titanium ferric glycinate;
in the step (1), the molar ratio of the ferrous sulfate heptahydrate to the glycine is 1: 1-1.2; in the step (2), the addition amount of the flocculant is 0.05-0.15% of the coarse crystal of the glycine iron.
2. The method for refining iron glycinate with low titanium content as claimed in claim 1, wherein the mother liquor obtained by recrystallizing iron glycinate and centrifuging the recrystallized iron glycinate in step (1) and step (5) is reused.
3. The method for refining iron glycinate with low titanium content as claimed in claim 2, wherein the mother liquor obtained by recrystallizing iron glycinate and centrifuging the recrystallized iron glycinate in step (1) and step (5) is reused.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910075346.0A CN109678745B (en) | 2019-01-25 | 2019-01-25 | Refining method of low-titanium ferric glycine |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910075346.0A CN109678745B (en) | 2019-01-25 | 2019-01-25 | Refining method of low-titanium ferric glycine |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109678745A CN109678745A (en) | 2019-04-26 |
| CN109678745B true CN109678745B (en) | 2021-12-10 |
Family
ID=66194070
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910075346.0A Active CN109678745B (en) | 2019-01-25 | 2019-01-25 | Refining method of low-titanium ferric glycine |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109678745B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110170179A (en) * | 2019-06-03 | 2019-08-27 | 无锡市前洲无缝钢管有限公司 | A kind of seamless steel pipe acid-washing waste acid cerium sulphate crystal method |
| CN111777523A (en) * | 2020-06-08 | 2020-10-16 | 四川爱隆植物营养科技有限公司 | Preparation method of glycine iron chelate |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05229996A (en) * | 1992-02-20 | 1993-09-07 | Norihiko Fujita | Production of glycine |
| WO2002030947A2 (en) * | 2000-10-11 | 2002-04-18 | Albion International, Inc. | Compositions and methods of preparing amino acid chelates and complexes |
| US6458981B1 (en) * | 2000-10-11 | 2002-10-01 | Albion International, Inc. | Composition and method for preparing amino acid chelate hydroxides free of interfering ions |
| FR2843752B1 (en) * | 2002-08-26 | 2007-05-18 | Pancosma Sa Pour L Ind Des Pro | CRYSTALLINE OLIGO-ELEMENTS AND PROCESSES FOR THEIR MANUFACTURE |
| CN103086901A (en) * | 2011-11-03 | 2013-05-08 | 青岛康地恩药业股份有限公司 | Preparation method of amino acid ferrous sulfate chelate |
| CN106187797A (en) * | 2016-07-08 | 2016-12-07 | 仲恺农业工程学院 | Preparation method of ferrous glycinate complex |
| CN107118115A (en) * | 2017-06-28 | 2017-09-01 | 北京博农利生物科技有限公司 | A kind of preparation method of Ferrous glycinate |
| WO2018111756A1 (en) * | 2016-12-12 | 2018-06-21 | Novus International Inc. | Metal complexes |
-
2019
- 2019-01-25 CN CN201910075346.0A patent/CN109678745B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05229996A (en) * | 1992-02-20 | 1993-09-07 | Norihiko Fujita | Production of glycine |
| WO2002030947A2 (en) * | 2000-10-11 | 2002-04-18 | Albion International, Inc. | Compositions and methods of preparing amino acid chelates and complexes |
| US6458981B1 (en) * | 2000-10-11 | 2002-10-01 | Albion International, Inc. | Composition and method for preparing amino acid chelate hydroxides free of interfering ions |
| FR2843752B1 (en) * | 2002-08-26 | 2007-05-18 | Pancosma Sa Pour L Ind Des Pro | CRYSTALLINE OLIGO-ELEMENTS AND PROCESSES FOR THEIR MANUFACTURE |
| CN103086901A (en) * | 2011-11-03 | 2013-05-08 | 青岛康地恩药业股份有限公司 | Preparation method of amino acid ferrous sulfate chelate |
| CN106187797A (en) * | 2016-07-08 | 2016-12-07 | 仲恺农业工程学院 | Preparation method of ferrous glycinate complex |
| WO2018111756A1 (en) * | 2016-12-12 | 2018-06-21 | Novus International Inc. | Metal complexes |
| CN107118115A (en) * | 2017-06-28 | 2017-09-01 | 北京博农利生物科技有限公司 | A kind of preparation method of Ferrous glycinate |
Non-Patent Citations (1)
| Title |
|---|
| 甘氨酸亚铁的合成和晶体结构研究;舒绪刚等;《江西农业学报》;20141231;第26卷(第9期);第103-104页1.2部分 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109678745A (en) | 2019-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP3854765B2 (en) | Method for purifying long-chain dicarboxylic acids | |
| CN109678745B (en) | Refining method of low-titanium ferric glycine | |
| KR102085016B1 (en) | Purification of lithium carbonate by removing sulfate ion impurities | |
| CN103074499B (en) | Method for producing high-quality copper sulfate through low-pressure oxygen leaching of copper slag | |
| CN112158858A (en) | Method for preparing ammonium bifluoride by using BOE waste liquid | |
| CN110040708B (en) | Preparation method of high-purity optical glass additive lanthanum metaphosphate | |
| US5227007A (en) | Process for producing crystals of salt of acidic amino acid and basic amino acid | |
| CN117658799B (en) | Cobalt acetate crystallization process | |
| CN107963669A (en) | A kind of calcium removal methods of technical grade sulfuric acid manganese | |
| CN106044838A (en) | Production technology of low-sulfur lanthanum hydroxide | |
| CN105837431B (en) | A kind of method that sodium acetate is detached in sodium acetate and sodium sulphate mixed system | |
| CN103708566A (en) | Method for improving filtering performance of ferrous sulfate | |
| KR830001465B1 (en) | Isoleucine Purification Method | |
| CN114149477A (en) | Crystallization method of high-purity vitamin B12 crystal and product thereof | |
| CN109053456B (en) | Method for refining Jina | |
| US6214302B1 (en) | Production of aluminum sulfate from coal ash | |
| CN106220520B (en) | A kind of processing method of beet alkali hydrochlorate calcium method production technology waste liquor | |
| CN112939032A (en) | Method for preparing potassium nitrate by nitric acid method | |
| CN111777523A (en) | Preparation method of glycine iron chelate | |
| CN113754717B (en) | A method for preparing reduced glutathione alpha-type crystals | |
| US2303607A (en) | Tartaric acid production from calcium tartrate | |
| CN102701291A (en) | Purification technology of ferrous sulphate heptahydrate | |
| CN107720833A (en) | The process for effectively purifying of byproduct ferrous sulfate of titanium dioxide | |
| CN111517918B (en) | Preparation method of D-mannitol alpha crystal form | |
| US20230322575A1 (en) | Preparation method for electronic-grade copper chloride dihydrate |
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 | ||
| CB02 | Change of applicant information | ||
| CB02 | Change of applicant information |
Address after: 421500 Xinyuan Road, Shuikoushan Economic Development Zone, Changning City, Hengyang City, Hunan Province Applicant after: Hunan Debang Biotechnology Co.,Ltd. Address before: 421500 No. 68 Shuikoushan Town Bridge Road, Changning City, Hengyang City, Hunan Province Applicant before: CHANGNING DEBANG BIOTECHNOLOGY Co.,Ltd. |
|
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A refining method of low titanium glycine iron Effective date of registration: 20220307 Granted publication date: 20211210 Pledgee: Hengyang Branch of China Everbright Bank Co.,Ltd. Pledgor: Hunan Debang Biotechnology Co.,Ltd. Registration number: Y2022430000016 |
|
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder |
Address after: 421500 Xinyuan Road, Shuikoushan Economic Development Zone, Changning City, Hengyang City, Hunan Province Patentee after: Hunan Debang Biotechnology Co.,Ltd. Address before: 421500 Xinyuan Road, Shuikoushan Economic Development Zone, Changning City, Hengyang City, Hunan Province Patentee before: Hunan Debang Biotechnology Co.,Ltd. |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20230511 Granted publication date: 20211210 Pledgee: Hengyang Branch of China Everbright Bank Co.,Ltd. Pledgor: Hunan Debang Biotechnology Co.,Ltd. Registration number: Y2022430000016 |