CN109678745B - Refining method of low-titanium ferric glycine - Google Patents
Refining method of low-titanium ferric glycine Download PDFInfo
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- 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
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- glycinate
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- titanium
- iron
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- 239000010936 titanium Substances 0.000 title claims abstract description 40
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 12
- 238000007670 refining Methods 0.000 title claims abstract description 10
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 title claims description 58
- 239000004471 Glycine Substances 0.000 title claims description 29
- AKLSSKNRPSKJBO-UHFFFAOYSA-K 2-aminoacetate;iron(3+) Chemical compound [Fe+3].NCC([O-])=O.NCC([O-])=O.NCC([O-])=O AKLSSKNRPSKJBO-UHFFFAOYSA-K 0.000 claims abstract description 41
- GIPOFCXYHMWROH-UHFFFAOYSA-L 2-aminoacetate;iron(2+) Chemical compound [Fe+2].NCC([O-])=O.NCC([O-])=O GIPOFCXYHMWROH-UHFFFAOYSA-L 0.000 claims abstract description 26
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000012535 impurity Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- LPOSZYSKJWFIQH-UHFFFAOYSA-N 2-aminoacetic acid;iron Chemical compound [Fe].NCC(O)=O LPOSZYSKJWFIQH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000007710 freezing Methods 0.000 claims abstract description 6
- 230000008014 freezing Effects 0.000 claims abstract description 6
- 239000013078 crystal Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 17
- 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
- 238000003756 stirring Methods 0.000 claims description 11
- 238000005189 flocculation Methods 0.000 claims description 9
- 230000016615 flocculation Effects 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 239000012452 mother liquor Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 5
- 230000008025 crystallization Effects 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 239000010413 mother solution Substances 0.000 claims description 2
- 239000012267 brine Substances 0.000 claims 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims 1
- 238000002845 discoloration Methods 0.000 abstract description 4
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 230000003311 flocculating effect Effects 0.000 abstract 1
- 239000000047 product Substances 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 238000003860 storage Methods 0.000 description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 3
- 239000003674 animal food additive Substances 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- -1 iron ion Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 239000013589 supplement 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
- 239000011782 vitamin Substances 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)
- 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.
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| 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 | A kind of preparation method of complex of ferrous glycine |
| 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 |
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2019
- 2019-01-25 CN CN201910075346.0A patent/CN109678745B/en active Active
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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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| WO2018111756A1 (en) * | 2016-12-12 | 2018-06-21 | Novus International Inc. | Metal complexes |
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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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| 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 |