CN101704545A - Method for preparing basic zinc chloride - Google Patents
Method for preparing basic zinc chloride Download PDFInfo
- Publication number
- CN101704545A CN101704545A CN200910310422A CN200910310422A CN101704545A CN 101704545 A CN101704545 A CN 101704545A CN 200910310422 A CN200910310422 A CN 200910310422A CN 200910310422 A CN200910310422 A CN 200910310422A CN 101704545 A CN101704545 A CN 101704545A
- Authority
- CN
- China
- Prior art keywords
- zinc
- zinc chloride
- basic zinc
- reaction
- basic
- 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.)
- Granted
Links
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 title claims abstract description 88
- 239000011592 zinc chloride Substances 0.000 title claims abstract description 44
- 235000005074 zinc chloride Nutrition 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 22
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims abstract description 33
- 229940007718 zinc hydroxide Drugs 0.000 claims abstract description 33
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims abstract description 33
- 238000002360 preparation method Methods 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 28
- 239000011701 zinc Substances 0.000 claims description 28
- 229910052725 zinc Inorganic materials 0.000 claims description 27
- 239000002994 raw material Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- IPCXNCATNBAPKW-UHFFFAOYSA-N zinc;hydrate Chemical compound O.[Zn] IPCXNCATNBAPKW-UHFFFAOYSA-N 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 21
- 238000004519 manufacturing process Methods 0.000 abstract description 11
- 239000002699 waste material Substances 0.000 abstract description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000654 additive Substances 0.000 description 5
- 229910052785 arsenic Inorganic materials 0.000 description 5
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 5
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- 239000011787 zinc oxide Substances 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 3
- 229960001763 zinc sulfate Drugs 0.000 description 3
- 229910000368 zinc sulfate Inorganic materials 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 201000010099 disease Diseases 0.000 description 2
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 2
- 230000003053 immunization Effects 0.000 description 2
- 239000002440 industrial waste Substances 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 206010012735 Diarrhoea Diseases 0.000 description 1
- 241000282887 Suidae Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000003674 animal food additive Substances 0.000 description 1
- 230000002180 anti-stress Effects 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 210000003746 feather Anatomy 0.000 description 1
- 230000003031 feeding effect Effects 0.000 description 1
- 230000037308 hair color Effects 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 235000019629 palatability Nutrition 0.000 description 1
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000003245 working effect Effects 0.000 description 1
Abstract
The invention discloses a method for preparing basic zinc chloride, which comprises the following steps: adding zinc hydroxide slurry into zinc chloride solution in a molar ratio of the zinc hydroxide to the zinc chloride being 3-4.5:1 to perform reaction at the temperature between 70 and 105DEG C and a pH value between 5 and 9, and obtaining a reaction product after the reaction; washing the reaction product with water, and centrifuging and drying the reaction product to obtain the basic zinc chloride. The preparation method has sample and safe operation, low waste emission and low production cost; and the product has better quality.
Description
Technical field
The present invention relates to a kind of preparation method of compound of zinc, relate in particular to a kind of halid preparation method of zinc.
Background technology
Basic zinc chloride is as a kind of new zinc source feed additive; with respect to conventional zinc sources such as zinc oxide and zinc sulfate; have that the interpolation level is low, consumption is few, advantage such as good palatability, biological value height and feeding effect are good; and more help protecting environment, be a kind of safe, efficient, environmental protection and comprehensive effects novel fodder additive.In the process for producing of present existing basic zinc chloride, useful useless zinc is produced, useful zinc chloride and zinc oxide reaction are produced, also useful hydrochloric acid and zinc oxide or react with hydrochloric acid and zinc subcarbonate and to produce, in these preparation methods, the method production cost that has is too high, and the raw materials used price of the method that has is relatively costly, the preparation method's gained by product that has causes environmental pollution easily, all has certain limitation.
Summary of the invention
The technical problem to be solved in the present invention is to overcome the deficiencies in the prior art, and a kind of safety simple to operate, waste discharge is few, production cost is low and the product quality is better preparation method of basic zinc chloride are provided.
For solving the problems of the technologies described above, the technical scheme that the present invention proposes is a kind of preparation method of basic zinc chloride, may further comprise the steps: the zinc hydroxide slurry is added in the liquor zinci chloridi, the mol ratio of described zinc hydroxide and zinc chloride is 3～4.5: 1, in temperature is that 70 ℃～105 ℃, pH value are to react under 5～9 the condition, obtains reaction product after reaction is finished; To make basic zinc chloride after reaction product washing, centrifugal, the drying.The chemical equation of this reaction is as follows:
4Zn(OH)
2+ZnCl
2+H
2O＝Zn
5(OH)
8Cl
2·H
2O
As a further improvement on the present invention, in the technique scheme, zinc hydroxide preferably utilizes useless zinc raw material (as industrial wastes such as secondary zinc oxide, cadmia, useless zinc powders) to process, its concrete working method can for: behind will give up earlier zinc raw material and the vitriol lixiviation through removal of impurities, press filtration, and then go out zinc hydroxide by generating the throw out sedimentation, and then obtain the zinc hydroxide finished product by press filtration with sodium hydroxide or ammoniacal liquor and zinc sulfate.Generally can obtain moisture 45% zinc hydroxide wet feed after machining.Adopt useless zinc raw material processing zinc hydroxide, not only can effectively handle and contain the zinc waste, reduce environment damage and pollution, and the zinc hydroxide wet feed that obtains at last needn't carry out drying, can be directly used in preparation zinc hydroxide slurry and carry out the synthetic production of basic zinc chloride, to reduce production costs.Useless zinc of the prior art generally is meant the useless zinc powder that produces in the very high zinc course of processing of (heavy metal is very low) free from foreign meter, purity, and described herein " useless zinc raw material " be meant contain a large amount of impurity contain the zinc waste, the raw materials cost that therefore should improve the technology use is lower, be utilization of waste material fully, can not only reduce enterprise's production cost greatly, and meet the development trend of recycling economy.
In the technique scheme, the suspension liquid that described zinc hydroxide slurry preferably is mixed with by zinc hydroxide and water.After pulling an oar into suspension liquid zinc hydroxide and zinc chloride contact area are increased, help the carrying out that reacts.
In the technique scheme, the mass concentration of described liquor zinci chloridi is preferably 10%～30% in known scope.Concentration crosses that low then mother liquor is too many, and energy consumption of reaction increases, and excessive concentration then viscosity is too big, and reaction has some setbacks.
In the technique scheme, the reaction times of described reaction is preferably 0.5h～4h.By optimal control, can when guaranteeing quality product, improve the efficient of preparation feedback to the reaction times.
In the technique scheme, described rotating speed when centrifugal is preferably 300r/min～1600r/min, and temperature is preferably 80 ℃～120 ℃ when dry, and the water content that generally is dried to described reaction product is less than 10%.
The above-mentioned basic zinc chloride that makes is pulverized, and after packing, can be obtained basic zinc chloride finished product as fodder additives, zinc content can reach 58%～60% in the finished product, arsenic content≤5ppm, lead content≤5ppm, cadmium content≤8ppm, the XRD figure spectrum of product is consistent with standard diagram.
Compared with prior art, the invention has the advantages that: under the situation of water that responds, directly react by utilizing zinc chloride and zinc hydroxide, need not to add other promotion reagent, reacted product carries out can obtaining basic zinc chloride after centrifugation, the drying.By the basic zinc chloride of method preparation of the present invention, not only can improve the purity of basic zinc chloride, and the generation of reactionless by product, almost non-pollutant discharge more helps environment protection.Preferred version of the present invention also can effectively be handled and contain zinc waste, minimizing to environment damage and pollution, and the zinc hydroxide wet feed of generation needn't carry out drying, packing and transportation, can directly carry out the synthetic production of basic zinc chloride, to reduce production costs.Operational path of the present invention is simple, operation easily, and the price of raw materials for production is lower, and production cost is little, and constant product quality and detrimental impurity content are low, and can satisfy the requirement of environment protection and cleaner production.In addition, with the basic zinc chloride feeding animals that the present invention makes, animal not only absorbs soon, and the absorption rate height.
For example: the basic zinc chloride that makes with the present invention feeds pigs as the standard consumption of fodder additives by the zinc source, can promote growth, improves feedstuff-meat ratio, improves yellowish pink, improves its resistance against diseases, and makes the pigskin skin ruddy, the hair color light; Feed piglet and can improve anti-stress ability and the immunizing power of piglet, promote its growth, prevention suckling piglet diarrhea; Feed boar and can prolong the breeding work-ing life of boar;
Feed poultry as fodder additives by the standard consumption in zinc source with the basic zinc chloride that the present invention makes, its speed of growth is improved, feedstuff-meat ratio descends, and strengthens the feather glossiness, improves its stress ability, reduces mortality ratio;
Feed aquatic animal as fodder additives by the standard consumption in zinc source with the basic zinc chloride that the present invention makes, can strengthen its immunizing power, reduce incidence and mortality, promote to produce, reduce disease and take place, improve efficiency of feed utilization thereby reduce water-soluble loss.
Embodiment
Embodiment 1:
A kind of preparation method of basic zinc chloride of the present invention, may further comprise the steps: the first water of interpolation 100ml in the reactor, open whipping appts then, in reactor, drop into the zinc chloride of 18.5g, be warming up to 75 ℃ then, slowly add 200g zinc hydroxide slurry (the zinc hydroxide wet feed that 120g contains zinc hydroxide 45% add to pull an oar behind the 80g water form) again, the pH value is under 5～9 the condition behind the isothermal reaction 1h, blanking is centrifugal, centrifugal rotational speed is 1000r/min, go into dry under 85 ℃ in the drying room to water ratio less than 10%, pulverized 60 mesh sieves, prepare finished product at last.
XRD detection method by routine detects the crystal of finished product to be formed and structure, in conjunction with the ultimate principle of chemical reaction, can determine that finished product is a basic zinc chloride simultaneously.Zinc content is 58.9% in the finished product, arsenic content is 1.1ppm, lead content is 3.9ppm, cadmium content is 2.2ppm, the XRD figure spectrum of product is consistent with standard diagram, and the assay of zinc content in the finished product and arsenic, lead, cadmium is measured with reference to national standard (GB/T 22546-2008) method of basic zinc chloride.
Embodiment 2:
A kind of preparation method of basic zinc chloride of the present invention, may further comprise the steps: the first water of interpolation 500ml in the reactor, open whipping appts then, in reactor, drop into the zinc chloride of 150g, be warming up to 100 ℃ then, slowly add 1370g zinc hydroxide slurries (the zinc hydroxide wet feed that contains zinc hydroxide 50% with 870g add 500g water pull an oar form) again, the pH value is under 5～9 the condition behind the isothermal reaction 2h, blanking is centrifugal, centrifugal rotational speed is 1500r/min, go into dry under 115 ℃ in the drying room to water ratio less than 10%, to pulverize 60 mesh sieves, prepared the basic zinc chloride finished product at last. the zinc content in this finished product is 59.12%, and arsenic content is 1.3ppm, lead content is 2.5ppm, and cadmium content is that the detection method of 2.8ppm. product is identical with embodiment 1.
Embodiment 3:
A kind of preparation method of basic zinc chloride of the present invention, may further comprise the steps: the first water of interpolation 500Kg in the reactor, open whipping appts then, in reactor, drop into the zinc chloride of 150Kg, be warming up to 90 ℃ then, slowly add 1180Kg zinc hydroxide slurries (the zinc hydroxide wet feed that contains zinc hydroxide 50% with 680Kg add 500Kg water pull an oar form) again, the pH value is under 5～9 the condition behind the isothermal reaction 3.5h, blanking is centrifugal, centrifugal rotational speed is 500r/min, go into dry under 95 ℃ in the drying room to water ratio less than 10%, pulverized 60 mesh sieves, prepare the basic zinc chloride finished product at last.Zinc content is 58.62% in this finished product, and arsenic content is 1.5ppm, and lead content is 2.0ppm, and cadmium content is 2.3ppm.The detection method of product is identical with embodiment 1.
Zinc hydroxide wet feed in the various embodiments described above is to utilize useless zinc raw material (as industrial wastes such as secondary zinc oxide, cadmia, useless zinc powders) to process, its concrete working method is: behind will give up earlier zinc raw material and the vitriol lixiviation through removal of impurities, press filtration, and then go out zinc hydroxide by generating the throw out sedimentation, and then obtain moisture 50%～55% zinc hydroxide wet feed by press filtration with sodium hydroxide or ammoniacal liquor and zinc sulfate.
Claims (6)
1. preparation method of basic zinc chloride, may further comprise the steps: the zinc hydroxide slurry is added in the liquor zinci chloridi, the mol ratio of described zinc hydroxide and zinc chloride is 3～4.5: 1, in temperature is that 70 ℃～105 ℃, pH value are to react under 5～9 the condition, obtains reaction product after reaction is finished; To make basic zinc chloride after reaction product washing, centrifugal, the drying.
2. the method for basic zinc chloride according to claim 1 is characterized in that, described zinc hydroxide is to utilize useless zinc raw material to process.
3. the method for basic zinc chloride according to claim 1 and 2, it is characterized in that: described zinc hydroxide slurry is the suspension liquid that is mixed with by zinc hydroxide and water.
4. the method for basic zinc chloride according to claim 1 and 2, it is characterized in that: the mass concentration of described liquor zinci chloridi is 10%～30%.
5. the method for basic zinc chloride according to claim 1 and 2, it is characterized in that: the reaction times of described reaction is 0.5h～4h.
6. the method for basic zinc chloride according to claim 1 and 2 is characterized in that: described rotating speed when centrifugal is 300r/min～1600r/min, and temperature is 80 ℃～120 ℃ when dry, and the water content that is dried to described reaction product is less than 10%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103104228A CN101704545B (en) | 2009-11-25 | 2009-11-25 | Method for preparing basic zinc chloride |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009103104228A CN101704545B (en) | 2009-11-25 | 2009-11-25 | Method for preparing basic zinc chloride |
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| Publication Number | Publication Date |
|---|---|
| CN101704545A true CN101704545A (en) | 2010-05-12 |
| CN101704545B CN101704545B (en) | 2011-10-05 |
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|---|---|---|---|
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108741A (en) * | 2014-07-14 | 2014-10-22 | 上海理工大学 | Preparation method of alkaline zinc chloride particles |
| CN105399132A (en) * | 2015-12-14 | 2016-03-16 | 广州科城环保科技有限公司 | Technology for preparing tribasic copper chloride and tetrabasic zinc chloride by utilization of brass slag and zinc-containing flue ash |
| CN109198192A (en) * | 2018-10-30 | 2019-01-15 | 长沙兴嘉生物工程股份有限公司 | The preparation method and applications of hydroxy chloride calcium |
| CN110980799A (en) * | 2019-12-26 | 2020-04-10 | 江西省愚人纳米科技有限公司 | Preparation method of basic zinc chloride for feed |
| CN111607124A (en) * | 2020-05-21 | 2020-09-01 | 科迈特新材料有限公司 | Calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material and preparation method thereof |
| CN112209426A (en) * | 2020-10-23 | 2021-01-12 | 深圳市环保科技集团有限公司 | Basic zinc chloride and preparation method thereof |
| CN114057218A (en) * | 2021-11-29 | 2022-02-18 | 天宝动物营养科技股份有限公司 | Preparation method of basic zinc chloride |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103043708B (en) * | 2013-01-09 | 2015-02-11 | 长沙嘉源生物科技有限公司 | Preparation method of beta-tetrabasic zinc chloride, and application of beta-tetrabasic zinc chloride serving as animal feed additive |
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2009
- 2009-11-25 CN CN2009103104228A patent/CN101704545B/en active Active
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104108741A (en) * | 2014-07-14 | 2014-10-22 | 上海理工大学 | Preparation method of alkaline zinc chloride particles |
| CN104108741B (en) * | 2014-07-14 | 2016-02-03 | 上海理工大学 | A kind of preparation method of basic zinc chloride particle |
| CN105399132A (en) * | 2015-12-14 | 2016-03-16 | 广州科城环保科技有限公司 | Technology for preparing tribasic copper chloride and tetrabasic zinc chloride by utilization of brass slag and zinc-containing flue ash |
| CN105399132B (en) * | 2015-12-14 | 2017-10-10 | 广州科城环保科技有限公司 | A kind of technique for preparing basic copper chloride and basic zinc chloride with brass clinker and flue dust containing zinc |
| CN109198192B (en) * | 2018-10-30 | 2022-03-08 | 长沙兴嘉生物工程股份有限公司 | Preparation method and application of calcium hydroxychloride |
| CN109198192A (en) * | 2018-10-30 | 2019-01-15 | 长沙兴嘉生物工程股份有限公司 | The preparation method and applications of hydroxy chloride calcium |
| CN110980799A (en) * | 2019-12-26 | 2020-04-10 | 江西省愚人纳米科技有限公司 | Preparation method of basic zinc chloride for feed |
| CN110980799B (en) * | 2019-12-26 | 2022-05-31 | 江西省愚人纳米科技有限公司 | Preparation method of basic zinc chloride for feed |
| CN111607124A (en) * | 2020-05-21 | 2020-09-01 | 科迈特新材料有限公司 | Calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material and preparation method thereof |
| CN111607124B (en) * | 2020-05-21 | 2022-05-27 | 科迈特新材料有限公司 | Calcium-doped zinc-aluminum hydrotalcite-nano zinc oxide composite material and preparation method thereof |
| CN112209426A (en) * | 2020-10-23 | 2021-01-12 | 深圳市环保科技集团有限公司 | Basic zinc chloride and preparation method thereof |
| CN114057218A (en) * | 2021-11-29 | 2022-02-18 | 天宝动物营养科技股份有限公司 | Preparation method of basic zinc chloride |
| CN114057218B (en) * | 2021-11-29 | 2024-03-26 | 天宝动物营养科技股份有限公司 | Preparation method of basic zinc chloride |
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| Publication number | Publication date |
|---|---|
| CN101704545B (en) | 2011-10-05 |
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Denomination of invention: Method for preparing basic zinc chloride Effective date of registration: 20170915 Granted publication date: 20111005 Pledgee: Hunan Jinxin Company Limited by Guarantee Pledgor: Changsha Xingjia Bio-engineering Co., Ltd. Registration number: 2017430000064 |
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Address after: Kang Ning Lu Hunan province 410300 Changsha Changsha Liuyang national biological industry base No. 370 Patentee after: CHANGSHA XINGJIA BIO-ENGINEERING Co.,Ltd. Address before: Room 1017-1025, building 1, Xiangyu central, 235 Wuyi Avenue, Changsha Patentee before: CHANGSHA XINGJIA BIO-ENGINEERING Co.,Ltd. |