CN109678745A - A kind of refining methd of low titanium ferrous glycine - Google Patents
A kind of refining methd of low titanium ferrous glycine Download PDFInfo
- Publication number
- CN109678745A CN109678745A CN201910075346.0A CN201910075346A CN109678745A CN 109678745 A CN109678745 A CN 109678745A CN 201910075346 A CN201910075346 A CN 201910075346A CN 109678745 A CN109678745 A CN 109678745A
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- Prior art keywords
- ferrous glycine
- glycine
- ferrous
- low titanium
- crystal
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- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims abstract description 187
- 239000004471 Glycine Substances 0.000 title claims abstract description 93
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 title claims abstract description 84
- 239000010936 titanium Substances 0.000 title claims abstract description 40
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 37
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 238000007670 refining Methods 0.000 title claims abstract description 10
- 239000012535 impurity Substances 0.000 claims abstract description 17
- 238000001953 recrystallisation Methods 0.000 claims abstract description 10
- 238000001914 filtration Methods 0.000 claims abstract description 9
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 230000003311 flocculating effect Effects 0.000 claims abstract description 7
- 239000013078 crystal Substances 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 20
- 238000002425 crystallisation Methods 0.000 claims description 19
- 230000008025 crystallization Effects 0.000 claims description 19
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000004062 sedimentation Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005119 centrifugation Methods 0.000 claims description 7
- 239000012452 mother liquor Substances 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 239000012267 brine Substances 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 229920002401 polyacrylamide Polymers 0.000 claims description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims 1
- 239000011790 ferrous sulphate Substances 0.000 claims 1
- 230000003647 oxidation Effects 0.000 abstract description 5
- 238000007254 oxidation reaction Methods 0.000 abstract description 5
- 238000004321 preservation Methods 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000005054 agglomeration Methods 0.000 abstract description 3
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000002845 discoloration Methods 0.000 abstract description 3
- 230000007774 longterm Effects 0.000 abstract description 3
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 235000009508 confectionery Nutrition 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- VUKOXQIVNYFVAY-RGMNGODLSA-N [Fe].C(CC)N[C@@H](CCO)C(=O)O Chemical compound [Fe].C(CC)N[C@@H](CCO)C(=O)O VUKOXQIVNYFVAY-RGMNGODLSA-N 0.000 description 5
- -1 iron ion Chemical class 0.000 description 4
- 238000005189 flocculation Methods 0.000 description 3
- 230000016615 flocculation Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- DWNBOPVKNPVNQG-LURJTMIESA-N (2s)-4-hydroxy-2-(propylamino)butanoic acid Chemical compound CCCN[C@H](C(O)=O)CCO DWNBOPVKNPVNQG-LURJTMIESA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241000040710 Chela Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 150000003722 vitamin derivatives Chemical class 0.000 description 1
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)
- Crystallography & Structural Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A kind of refining methd of low titanium ferrous glycine, comprising the following steps: (1) synthesize ferrous glycine；(2) flocculating setting；(3) filtering and impurity removing；(4) frozen recrystallization；(5) separation washing；(6) dry.Ti content≤0.05% in low titanium ferrous glycine prepared by the present invention, even if can also be long-term preservation 6 months or more under the conditions of summer high temperature high humidity (temperature >=35 DEG C, relative humidity >=70%), No oxidation discoloration, stay in grade, agglomeration not easy to moisture absorption.
Description
Technical field
The invention belongs to organic feed additive preparation technical fields, and in particular to a kind of purification side of low titanium ferrous glycine
Method.
Background technique
It is a kind of novel fodder additive that ferrous glycine network (chela), which closes object (hereinafter referred to as ferrous glycine), it is by animal institute
Required metallic element iron ion and glycine are chemically synthesized the chelate with cyclic structure of generation.It synthesizes at present sweet
The common raw material of propylhomoserin iron is glycine and ferrous sulfate heptahydrate (i.e. green vitriol), but contains titanium impurity in ferrous sulfate heptahydrate,
Content is about 0.2%~0.3%.In the technical process of production ferrous glycine, if using containing, titanium is miscellaneous without drop titanium processing
Also there can be titanium impurity in ferrous glycine prepared by the ferrous sulfate heptahydrate of matter.And the appearance of excessive titanium impurity will affect it is sweet
The stability of propylhomoserin iron causes the moisture absorption quickly in the case where summer high temperature high humidity of ferrous glycine product, and oxidation stain is agglomerated,
Vitamin can be destroyed after adding in feed, feed quality is caused to decline, cost improves.
Currently, not occurring the refining methd of low titanium ferrous glycine also on the market, it is therefore necessary to the production to ferrous glycine
Technique improves, and reduces the Ti content in ferrous glycine, maintains the stability and biological value of ferrous glycine, extends glycine
There is the time of oxidation stain in iron.
Summary of the invention
The technical problem to be solved by the present invention is to overcome drawbacks described above of the existing technology, providing one kind can be long-term
It saves, stay in grade, agglomeration not easy to moisture absorption, the refining methd of holding 6 months or more the low titanium ferrous glycines of No oxidation discoloration.
The technical solution adopted by the present invention to solve the technical problems is as follows: a kind of refining methd of low titanium ferrous glycine,
The following steps are included:
(1) it synthesizes ferrous glycine: ferrous sulfate heptahydrate is dissolved in water, be heated to 60~70 DEG C, it is completely molten to ferrous sulfate heptahydrate
Glycine is added after solution, keeps stirring reaction 30min~60min, is then cooled to 25~35 DEG C, makes the coarse crystallization of ferrous glycine
It is precipitated, is separated ferrous glycine crystal with mother liquor by being centrifuged, obtaining the thick purity of ferrous glycine is 96%~98% crystallization；
(2) flocculating setting: ferrous glycine coarse crystallization obtained by step (1) is dissolved in 60~70 DEG C of hot water, and flocculant both sexes are added
Polyacrylamide stirs evenly again standing sedimentation 2 hours~4 hours, obtains ferrous glycine sedimentation solution；
(3) filtering and impurity removing: the titanium that the sedimentation solution of ferrous glycine obtained by step (2) is filtered to remove in ferrous glycine sedimentation solution is miscellaneous
Matter obtains low titanium ferrous glycine filtrate；
(4) frozen recrystallization: being transferred to crystallization tank for low titanium ferrous glycine filtrate obtained by step (3), cold using -10 DEG C -0 DEG C
Freeze the indirect cooling down of salt water, 98%~99% ferrous glycine crystal is precipitated again；
(5) separation washing: as centrifugation by ferrous glycine crystal step (4) obtained by and mother liquor separation, to ferrous glycine crystallize into
Row washing；
(6) dry: ferrous glycine crystal obtained by step (5) being dried, the ferrous glycine of low titanium can be obtained.Further,
The molar ratio of ferrous sulfate heptahydrate and glycine is 1:1~1:1.2 in step (1).
Further, the additional amount of the flocculant is the 0.05%-0.15% of ferrous glycine coarse crystallization.
Further, in step (1) and step (5), the mother liquor after ferrous glycine recrystallization is centrifuged can repeat to make
With.
The invention has the advantages that: Ti content≤0.05% in low titanium ferrous glycine prepared by the present invention, even if in summer high temperature
Under the conditions of high humidity (temperature >=35 DEG C, relative humidity >=70%) can also long-term preservation 6 months or more No oxidation discolorations, stay in grade,
Agglomeration not easy to moisture absorption.
Specific embodiment
Below with reference to embodiment, the invention will be further described.
Chemical reagent used in the embodiment of the present invention is obtained by routine business approach unless otherwise specified.
Embodiment 1
The present embodiment the following steps are included:
(1) it takes 100g ferrous sulfate heptahydrate to be dissolved in 60ml water, is heated to 65 DEG C, 26.9g glycine is added, keeps stirring, protect
Thermotonus 45min is held, is cooled to 30 DEG C, ferrous glycine crystallization is precipitated, centrifugation obtains ferrous glycine coarse crystal；
(2) flocculating setting: taking ferrous glycine coarse crystal 50g, and 100ml water is added, and is heated to 70 DEG C, after being completely dissolved, and is added
0.025g polyacrylamide, stir evenly keep temperature standing sedimentation 2h, be centrifuged again, by after flocculation sedimentation titanium impurity with it is sweet
The separation of propylhomoserin ferrous solution；
(3) filtering and impurity removing: filtering solution removes titanium impurity；
(4) frozen recrystallization: being transferred to crystallization tank for filtered solution, and using the indirect cooling down of chilled brine, utilization is sweet
Propylhomoserin iron solubility reduces and reduced characteristic with temperature, and ferrous glycine crystal is precipitated again；
(5) separation washing: the crystal and mother liquor for recrystallizing ferrous glycine with the method for centrifugation separate, and carry out water to ferrous glycine
It washes,；
(6) dry: ferrous glycine crystal being dried, the ferrous glycine of low titanium can be obtained.
Comparative example
It takes 100g ferrous sulfate heptahydrate to be dissolved in 60ml water, is heated to 65 DEG C, 26.9g glycine is added, keeps stirring, keep temperature
Degree reaction 45min, is cooled to 30 DEG C, and ferrous glycine crystallization is precipitated, and centrifugation obtains ferrous glycine crystal；(the conventional preparation of supplement
Method)
Performance after the present embodiment product and comparative example save 30 days under conditions of 35 DEG C, relative humidity 72% compares
1 the present embodiment product of table is compared with the performance after comparative example preservation 30 days
Embodiment 2
The present embodiment the following steps are included:
(1) by the mother liquid obtained 90ml in 1 step of embodiment (5), ferrous sulfate heptahydrate 150g is added, is heated to 70 DEG C, is added
44.5g glycine, keeps stirring, and keeps thermotonus 45min, is cooled to 30 DEG C, and ferrous glycine crystallization is precipitated, and centrifugation obtains
To ferrous glycine coarse crystal；
(2) flocculating setting: taking ferrous glycine coarse crystallization 100g to be re-dissolved in 67 DEG C of hot water, keeps water temperature, and it is poly- that flocculant both sexes are added
Acrylamide 0.1g stirs evenly again standing sedimentation 3 hours, settles titanium impurity；It is centrifuged again, by the titanium after flocculation sedimentation
Impurity is separated with ferrous glycine solution.
(3) filtering and impurity removing: filtering solution removes titanium impurity；
(4) frozen recrystallization: being transferred to crystallization tank for filtered solution, and using the indirect cooling down of chilled brine, utilization is sweet
Propylhomoserin iron solubility reduces and reduced characteristic with temperature, and ferrous glycine crystal is precipitated again；
(5) separation washing: the crystal of ferrous glycine recrystallization and solution are centrifugated, ferrous glycine is washed；
(6) dry: ferrous glycine crystal being dried, the ferrous glycine of low titanium can be obtained.
Performance after the present embodiment product and comparative example save 90 days under conditions of 35 DEG C, relative humidity 72% compares
2 the present embodiment product of table is compared with the performance after comparative example preservation 90 days
Embodiment 3
The present embodiment the following steps are included:
(1) by the mother liquid obtained 120ml in 2 step of embodiment (5), ferrous sulfate heptahydrate 200g is added, is heated to 70 DEG C, is added
64.7g glycine, keeps stirring, and keeps thermotonus 45min, is cooled to 30 DEG C, and ferrous glycine crystallization is precipitated, and centrifugation obtains
To ferrous glycine coarse crystal；
(2) flocculating setting: flocculating setting: taking ferrous glycine coarse crystallization 100g to be re-dissolved in 63 DEG C of hot water, keeps water temperature, and flocculation is added
Agent amphiprotic polyacrylamide 0.15g, stirs evenly again standing sedimentation 4 hours, settles titanium impurity；It is centrifuged, will flocculate again
Titanium impurity after precipitating is separated with ferrous glycine solution.
(3) filtering and impurity removing: filtering solution removes titanium impurity；
(4) frozen recrystallization: being transferred to crystallization tank for filtered solution, and using the indirect cooling down of chilled brine, utilization is sweet
Propylhomoserin iron solubility reduces and reduced characteristic with temperature, and ferrous glycine crystal is precipitated again；
(5) washing separation: the crystal of ferrous glycine recrystallization and solution are centrifugated, ferrous glycine is washed；
(6) dry: ferrous glycine crystal being dried, the ferrous glycine of low titanium can be obtained.
Performance after the present embodiment product and comparative example save 180 days under conditions of 35 DEG C, relative humidity 72% compares
3 the present embodiment product of table is compared with the performance after comparative example preservation 180 days
Claims (4)
1. a kind of refining methd of low titanium ferrous glycine, which comprises the following steps:
(1) it synthesizes ferrous glycine: ferrous sulfate heptahydrate is dissolved in water, be heated to 60~70 DEG C, it is completely molten to ferrous sulfate heptahydrate
Glycine is added after solution, keeps stirring reaction 30min~60min, is then cooled to 25~35 DEG C, makes the coarse crystallization of ferrous glycine
It is precipitated, is separated ferrous glycine crystal with mother liquor by being centrifuged, obtaining purity is 96%~98% ferrous glycine coarse crystallization；
(2) flocculating setting: ferrous glycine coarse crystallization obtained by step (1) is dissolved in 60~70 DEG C of hot water, and flocculant both sexes are added
Polyacrylamide stirs evenly again standing sedimentation 2 hours~4 hours, obtains ferrous glycine sedimentation solution；
(3) filtering and impurity removing: the titanium that the sedimentation solution of ferrous glycine obtained by step (2) is filtered to remove in ferrous glycine sedimentation solution is miscellaneous
Matter obtains low titanium ferrous glycine filtrate；
(4) frozen recrystallization: low titanium ferrous glycine filtrate obtained by step (3) is transferred to crystallization tank, using -10 DEG C~0 DEG C
The indirect cooling down of chilled brine, it is 98%~99% ferrous glycine crystal that purity is precipitated again；
(5) separation washing: as centrifugation by ferrous glycine crystal step (4) obtained by and mother liquor separation, to ferrous glycine crystallize into
Row washing；
(6) dry: ferrous glycine crystal obtained by step (5) being dried, the ferrous glycine of low titanium can be obtained.
2. the refining methd of low titanium ferrous glycine according to claim 1, which is characterized in that in step (1), seven water
The molar ratio of ferrous sulfate and glycine is 1:1~1.2.
3. the refining methd of low titanium ferrous glycine according to claim 1 or claim 2, which is characterized in that in step (2), the wadding
The additional amount of solidifying agent is the 0.05%~0.15% of ferrous glycine coarse crystallization.
4. the refining methd of low titanium ferrous glycine described according to claim 1~one of 3, which is characterized in that step (1) and step
(5) in, the mother liquor after ferrous glycine recrystallization is centrifuged may be 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 |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910075346.0A CN109678745B (en) | 2019-01-25 | 2019-01-25 | Refining method of low-titanium ferric glycine |
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| CN109678745B CN109678745B (en) | 2021-12-10 |
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Cited By (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 |
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| 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 |
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2019
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Cited By (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 |
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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 |
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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. |
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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 |