CN102352440B - Method for recovering palladium sponge and bismuth from multi-metal catalyst utilized in sodium gluconate production - Google Patents
Method for recovering palladium sponge and bismuth from multi-metal catalyst utilized in sodium gluconate production Download PDFInfo
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- CN102352440B CN102352440B CN2011102241738A CN201110224173A CN102352440B CN 102352440 B CN102352440 B CN 102352440B CN 2011102241738 A CN2011102241738 A CN 2011102241738A CN 201110224173 A CN201110224173 A CN 201110224173A CN 102352440 B CN102352440 B CN 102352440B
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- filtrate
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- palladium
- bismuth
- palladium sponge
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 26
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000000034 method Methods 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 title claims abstract description 16
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 8
- 229910052751 metal Inorganic materials 0.000 title abstract description 4
- 239000002184 metal Substances 0.000 title abstract description 4
- AEQDJSLRWYMAQI-UHFFFAOYSA-N 2,3,9,10-tetramethoxy-6,8,13,13a-tetrahydro-5H-isoquinolino[2,1-b]isoquinoline Chemical compound C1CN2CC(C(=C(OC)C=C3)OC)=C3CC2C2=C1C=C(OC)C(OC)=C2 AEQDJSLRWYMAQI-UHFFFAOYSA-N 0.000 title abstract 2
- 239000000176 sodium gluconate Substances 0.000 title abstract 2
- 229940005574 sodium gluconate Drugs 0.000 title abstract 2
- 235000012207 sodium gluconate Nutrition 0.000 title abstract 2
- 239000000706 filtrate Substances 0.000 claims abstract description 46
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 21
- 238000011084 recovery Methods 0.000 claims abstract description 18
- 238000001354 calcination Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000000746 purification Methods 0.000 claims abstract description 9
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims abstract description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 4
- QZPSXPBJTPJTSZ-UHFFFAOYSA-N aqua regia Chemical compound Cl.O[N+]([O-])=O QZPSXPBJTPJTSZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- TUZCOAQWCRRVIP-UHFFFAOYSA-N butoxymethanedithioic acid Chemical compound CCCCOC(S)=S TUZCOAQWCRRVIP-UHFFFAOYSA-N 0.000 claims abstract description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 230000007935 neutral effect Effects 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 239000003863 metallic catalyst Substances 0.000 claims description 10
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 239000007788 liquid Substances 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 125000003963 dichloro group Chemical group Cl* 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 235000010265 sodium sulphite Nutrition 0.000 claims description 3
- 238000012856 packing Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 abstract description 7
- 239000007787 solid Substances 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000047 product Substances 0.000 abstract description 3
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 abstract 2
- 238000009835 boiling Methods 0.000 abstract 1
- 238000001816 cooling Methods 0.000 abstract 1
- 238000001035 drying Methods 0.000 abstract 1
- 238000007654 immersion Methods 0.000 abstract 1
- 239000011259 mixed solution Substances 0.000 abstract 1
- 229910052979 sodium sulfide Inorganic materials 0.000 abstract 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 238000005406 washing Methods 0.000 abstract 1
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000011109 contamination Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- AAJRIJBGDLLRAE-UHFFFAOYSA-M sodium;butoxymethanedithioate Chemical compound [Na+].CCCCOC([S-])=S AAJRIJBGDLLRAE-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention relates to a method for recovering palladium sponge and bismuth from a multi-metal catalyst utilized in sodium gluconate production. The method can solve the problem of recovering palladium sponge and bismuth from a multi-metal catalyst. The method comprises the following steps of calcining a waste catalyst, adding a mixed solution of water and hydrochloric acid into the calcined products, heating, adding sodium chlorate into the heated products for immersion, cooling, filtering to obtain primary filtrate and primary filter residues, adjusting a pH value of the primary filtrate, standing, filtering to obtain secondary filtrate, extracting the primary filter residues twice, heating the extract, adding dropwisely hydrazine hydrate into the heated extract, boiling, filtering, washing the filtered extract to a neutral extract, drying to obtain palladium sponge, adding sodium sulfide into the secondary filtrate for precipitation, filtering to obtain secondary filter residues, dissolving the secondary filter residues in aqua regia, adding butyl xanthate into the solution obtained by the previous step to carry out palladium precipitation, filtering to obtain a solid and tertiary filtrate, carrying out re-purification of the solid to obtain secondary palladium sponge, merging the secondary palladium sponge and the palladium sponge to obtain palladium, adjusting a pH value of the tertiary filtrate to a pH value of 1.5, and filtering to obtain bismuth. The method adopts advanced and unique processes, is easy for operation, has good recovery effects, and saves costs.
Description
Technical field
The present invention relates to chemical field, particularly a kind of recovery method of producing palladium sponge, bismuth in the multi-metallic catalyst that Sunmorl N 60S uses.
Background technology
When producing Sunmorl N 60S, employed catalyzer is the Pd-Bi multi-metallic catalyst take gac as carrier, in use because the activity decreased of catalyzer, be eliminated in use for some time and become spent catalyst, but contained bismuth is to be worth somewhat expensive metal in the catalyzer, and palladium is very worthy especially, thereby has very much recovery value, but how to reclaim, so far there are no good recovery method.Therefore, the recovery method of palladium sponge, bismuth is the problem that people are concerned about in the multi-metallic catalyst of development and production Sunmorl N 60S use.
Summary of the invention
For above-mentioned situation, for overcoming the prior art defective, the present invention's purpose just provides a kind of recovery method of producing palladium sponge, bismuth in the multi-metallic catalyst that Sunmorl N 60S uses, can effectively solve the recovery problem of producing palladium sponge, bismuth in the multi-metallic catalyst that Sunmorl N 60S uses.
The technical scheme that the present invention solves is, on the basis that original palladium carbon catalyst reclaims, spent catalyst packed in the stoving oven, carry out roasting, get calcining matter, calcining matter is packed in the reactor, add the mixing solutions dissolving of entry and hydrochloric acid, heat up, drip sodium chlorate and leach, cooled and filtered gets for the first time filtrate and for the first time filter residue, and filtrate adds ammoniacal liquor and hydrochloric acid adjust pH for the first time, leave standstill filtration, get for the second time filtrate, filter residue gets purification liquid with the inferior palladium method extraction twice of dichloro two amminos for the first time, purification liquid is heated, drip hydrazine hydrate, boil, filter and discard filtrate, get filtrate, to neutral, oven dry gets primary palladium sponge to filtrate with deionized water wash; For the second time filtrate adds sodium sulphite and is precipitated to colourlessly, filters, and discards filtrate, get for the second time filter residue, after filter residue adds aqua regia dissolution for the second time, add the heavy palladium of butyl xanthate, filter, get solids and filtrate for the third time, solids is again by abovementioned steps secondary palladium sponge of purifying to get, merge, realize the sponge recovery of palladium, filtrate hydro-oxidation sodium or potassium hydroxide are adjusted pH to 1.5 for the third time, filter, abandon filtrate, get bismuth.
The inventive method is advanced unique, and easy to operate, the recovering effect of palladium, bismuth is good, realizes utilization of waste material, saves cost, and environmental contamination reduction is the innovation of producing on the remanufacture of palladium sponge, bismuth in the multi-metallic catalyst that Sunmorl N 60S uses.
Embodiment
Below in conjunction with particular case, the specific embodiment of the present invention is elaborated.
In the invention process, realized by following steps:
1, roasting: will produce the used spent catalyst of Sunmorl N 60S, and in the stoving oven of packing into, 140-160 ℃ of lower oven dry 2-3 hour, be warming up to 750 ℃ and passed into air roasting 15 hours, air intake 20L/min gets calcining matter;
2, calcining matter dissolving: calcining matter is packed in the reactor, add the mixing solutions dissolving of water and hydrochloric acid, the add-on of the mixing solutions of water and hydrochloric acid is 4 times of calcining matter weight, content of hydrochloric acid is controlled at 6mol/L, is warming up to 85-95 ℃, then drips sodium chlorate and leaches 3-5 hour, the add-on of sodium chlorate is the 8-10% of calcining matter weight, be cooled to 40-50 ℃, filter, get for the first time filtrate;
3, to the filtrate adjust pH first time: filtrate adds ammoniacal liquor adjustment pH to 7-8 for the first time, and adding the hydrochloric acid adjust pH is 0.5-1.0 again, leaves standstill 2-3 hour, filters, and gets for the second time filtrate and for the first time filter residue;
4, filter residue is purified: the filter residue first time in the step 3 is purified twice with the inferior palladium methods of dichloro two amminos (known technology), get purification liquid;
5, above-mentioned purification liquid is heated to 70-80 ℃, drip hydrazine hydrate to without till the steam bubble generation, boiled 30 minutes, filter, discard filtrate, get filtrate, to neutral, oven dry gets the palladium sponge first time to filtrate with deionized water wash;
6, the filtrate second time in the step 3 is processed: filtrate adds the sodium sulphite precipitation for the second time, until filtrate is filtered to colourless for the second time, gets for the second time filter residue, discards filtrate;
7, after filter residue adds aqua regia dissolution for the second time, add the heavy palladium of butyl xanthate (claiming again sodium n-butyl xanthate), filter, get filter residue and filtrate, wherein, filter residue gets for the second time palladium sponge by step 4,5 again, merge for the first time palladium sponge and for the second time palladium sponge, realize recovery of palladium; Filtrate hydro-oxidation sodium or potassium hydroxide adjust pH 1.5-2.0 filter, and discard filtrate, get bismuth.
Maturing temperature in the described step 1 is preferably 150 ℃, roasting time 2.5 hours; Calcining matter adds the water dissolution intensification in the described step 2, and its temperature preferably rises to 90 ℃, and extraction time is 4 hours; Add the hydrochloric acid adjust pH in the described step 3, be preferably 1.0; The temperature that purification liquid is heated in the described step 5 is preferably 75 ℃; The filtrate adjust pH is preferably 1.5 in the described step 7.
The present invention after tested, in the raw material of spent catalyst, its component is, water accounts for 59-61%, and palladium accounts for 1.9-2.1%, bismuth 1.3-1.5%, all the other components are gac and part organic impurity, through many BT(batch testing)s, in the raw material of spent catalyst, the equal content 60.5% of level, palladium average content 2.02%, bismuth average content 1.4%, surplus is gac and part organic impurity, and after adopting the method to reclaim palladium, bismuth, and reclaim quantity in theory and compare, related results is as follows:
The yield cartogram of Palladium from Wasted Catalyst and bismuth
Data in the above-mentioned table, to measure obtained mean value through repeated multiple times many batches, each spent catalyst of same amount that adopts is repeatedly tested, obtained identical or akin result, fully show, the present invention is reliable and stable, and, can also find out clearly that the present invention is quite high to the palladium in the spent catalyst and the bismuth rate of recovery by above-mentioned test result, wherein the recovery of palladium rate reaches 98%, the rate of recovery of bismuth reaches 96.4%, can reach the recycling level of the palladium carbon catalyst of producing the other products use, particularly when reclaiming palladium, also realized the recovery of bismuth, the palladium that reclaims and bismuth can return in the production and recycle, and effectively reduce the production composition of Sunmorl N 60S, have effectively realized the recycling of refuse, overcome the spent catalyst pollution on the environment, huge economic and social benefit has been arranged.
Claims (3)
1. a recovery method of producing palladium sponge, bismuth in the multi-metallic catalyst that Sunmorl N 60S uses is characterized in that, is realized by following steps:
(1), roasting: will produce the used spent catalyst of Sunmorl N 60S, and in the stoving oven of packing into, 140-160 ℃ of lower oven dry 2-3 hour, be warming up to 750 ℃ and passed into air roasting 15 hours, air intake 20L/min gets calcining matter;
(2), calcining matter dissolving: calcining matter is packed in the reactor, add the mixing solutions dissolving of water and hydrochloric acid, the add-on of the mixing solutions of water and hydrochloric acid is 4 times of calcining matter weight, content of hydrochloric acid is controlled at 6mol/L, is warming up to 85-95 ℃, then drips sodium chlorate and leaches 3-5 hour, the add-on of sodium chlorate is the 8-10% of calcining matter weight, be cooled to 40-50 ℃, filter, get for the first time filtrate;
(3), to the filtrate adjust pH first time: filtrate adds ammoniacal liquor adjustment pH to 7-8 for the first time, and adding the hydrochloric acid adjust pH is 0.5-1.0 again, leaves standstill 2-3 hour, filters, and gets for the second time filtrate and for the first time filter residue;
(4), filter residue is purified: the filter residue first time in the step 3 is purified twice with the inferior palladium method of dichloro two amminos, get purification liquid;
(5), above-mentioned purification liquid is heated to 70-80 ℃, drip hydrazine hydrate till produce without steam bubble, boiled 30 minutes, filter, discard filtrate, get filtrate, to neutral, oven dry gets for the first time palladium sponge to filtrate with deionized water wash;
(6), the filtrate second time in the step (3) is processed: filtrate adds the sodium sulphite precipitation for the second time, until filtrate is filtered to colourless for the second time, gets for the second time filter residue, discards filtrate;
(7), for the second time after filter residue adds aqua regia dissolution, add the heavy palladium of butyl xanthate, filter, get filter residue and filtrate, wherein, filter residue again by step 4,5 palladium sponge for the second time, merge for the first time palladium sponge and for the second time palladium sponge, realize recovery of palladium; Filtrate hydro-oxidation sodium or potassium hydroxide adjust pH 1.5-2.0 filter, and discard filtrate, get bismuth.
2. the recovery method of palladium sponge, bismuth in the multi-metallic catalyst of production Sunmorl N 60S use according to claim 1 is characterized in that adding the hydrochloric acid adjust pH in the described step (3) is 1.0.
3. the recovery method of palladium sponge, bismuth in the multi-metallic catalyst of production Sunmorl N 60S use according to claim 1 is characterized in that the temperature that purification liquid is heated in the described step (5) is 75 ℃.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011102241738A CN102352440B (en) | 2011-08-06 | 2011-08-06 | Method for recovering palladium sponge and bismuth from multi-metal catalyst utilized in sodium gluconate production |
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| Application Number | Priority Date | Filing Date | Title |
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| CN2011102241738A CN102352440B (en) | 2011-08-06 | 2011-08-06 | Method for recovering palladium sponge and bismuth from multi-metal catalyst utilized in sodium gluconate production |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104342558A (en) * | 2014-05-12 | 2015-02-11 | 上海派特贵金属环保科技有限公司 | A method for recycling palladium from a spent precious metal catalyst |
| CN104745837B (en) * | 2015-04-21 | 2017-01-18 | 昆山鸿福泰环保科技有限公司 | Recovery process of palladium in copper-nickel alloy |
| CN107794376B (en) * | 2017-10-12 | 2019-05-31 | 安徽拜善晟制药有限公司 | The recovery method of Metal Palladium in a kind of thin powdered carbon carrier palladium-carbon catalyst |
| CN113151681B (en) * | 2021-02-19 | 2022-07-12 | 石家庄绿色再生资源有限公司 | Process for recovering noble metal palladium from waste palladium catalyst |
| WO2024023055A1 (en) * | 2022-07-26 | 2024-02-01 | Solvay Sa | Hydrometallurgical process for recovering palladium from a spent catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0767243A1 (en) * | 1995-10-07 | 1997-04-09 | BASF Aktiengesellschaft | Recovery of active components from carrier or monolythic catalysts |
| CN101078054A (en) * | 2007-06-22 | 2007-11-28 | 厦门金达威维生素股份有限公司 | Method for reclaiming metal palladium and palladium chloride from waste loading palladium hydrogenation catalyst |
-
2011
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0767243A1 (en) * | 1995-10-07 | 1997-04-09 | BASF Aktiengesellschaft | Recovery of active components from carrier or monolythic catalysts |
| CN101078054A (en) * | 2007-06-22 | 2007-11-28 | 厦门金达威维生素股份有限公司 | Method for reclaiming metal palladium and palladium chloride from waste loading palladium hydrogenation catalyst |
Non-Patent Citations (6)
| Title |
|---|
| 从废催化剂中回收有色和稀有金属;陈耐生;《黑龙江大学自然科学学报》;19861231(第2期);20-22 * |
| 从废钯碳催化剂中回收钯的研究;张永平;《山西化工》;20100228;第30卷(第1期);61-67 * |
| 催化氧化葡糖糖中失活钯铋炭催化剂再生方法探讨;彭方英等;《化工生产与技术》;20101231;第17卷(第3期);17-19 * |
| 张永平.从废钯碳催化剂中回收钯的研究.《山西化工》.2010,第30卷(第1期),20-22. |
| 彭方英等.催化氧化葡糖糖中失活钯铋炭催化剂再生方法探讨.《化工生产与技术》.2010,第17卷(第3期),17-19. |
| 陈耐生.从废催化剂中回收有色和稀有金属.《黑龙江大学自然科学学报》.1986,(第2期),61-67. |
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Free format text: CORRECT: INVENTOR; FROM: AN QINGTANG ZI CONGYUN FENG BINBIN WANG JIANZHONG ZHANG TINGJING TO: AN QINGTANG ZI YUNCONG FENG BINBIN WANG JIANZHONG ZHANG TINGJING |
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Address after: 450008, No. 11, building 12, dragon spirit, the Yellow River East Road, Zheng Dong New District, Henan, Zhengzhou Patentee after: Henan Xingfa Biological Technology Co.,Ltd. Address before: 450008, No. 11, building 12, dragon spirit, the Yellow River East Road, Zheng Dong New District, Henan, Zhengzhou Patentee before: HENAN XINGFA FINE CHEMICAL Co.,Ltd. |
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Granted publication date: 20130109 Termination date: 20210806 |
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