CN113061724B - Method for eluting nickel sulfide and removing nickel and chloride ions in copper tailings - Google Patents
Method for eluting nickel sulfide and removing nickel and chloride ions in copper tailings Download PDFInfo
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- CN113061724B CN113061724B CN202110255726.XA CN202110255726A CN113061724B CN 113061724 B CN113061724 B CN 113061724B CN 202110255726 A CN202110255726 A CN 202110255726A CN 113061724 B CN113061724 B CN 113061724B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 47
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 29
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 title claims abstract description 26
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title description 13
- 229910052802 copper Inorganic materials 0.000 title description 13
- 239000010949 copper Substances 0.000 title description 13
- 238000005406 washing Methods 0.000 claims abstract description 57
- 239000002002 slurry Substances 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000003825 pressing Methods 0.000 claims abstract description 12
- YFLLTMUVNFGTIW-UHFFFAOYSA-N nickel;sulfanylidenecopper Chemical compound [Ni].[Cu]=S YFLLTMUVNFGTIW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000003599 detergent Substances 0.000 claims abstract description 6
- 239000002893 slag Substances 0.000 claims description 19
- 238000005086 pumping Methods 0.000 claims description 12
- 238000007664 blowing Methods 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 3
- 238000011010 flushing procedure Methods 0.000 claims 1
- 238000000926 separation method Methods 0.000 abstract description 4
- 238000010828 elution Methods 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 3
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 abstract 2
- 239000012141 concentrate Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000570 Cupronickel Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000010310 metallurgical process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 238000011085 pressure filtration Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0067—Leaching or slurrying with acids or salts thereof
- C22B15/0071—Leaching or slurrying with acids or salts thereof containing sulfur
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0065—Leaching or slurrying
- C22B15/0082—Leaching or slurrying with water
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B15/00—Obtaining copper
- C22B15/0063—Hydrometallurgy
- C22B15/0084—Treating solutions
- C22B15/0086—Treating solutions by physical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0407—Leaching processes
- C22B23/0415—Leaching processes with acids or salt solutions except ammonium salts solutions
- C22B23/043—Sulfurated acids or salts thereof
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/06—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese
- C25C1/08—Electrolytic production, recovery or refining of metals by electrolysis of solutions or iron group metals, refractory metals or manganese of nickel or cobalt
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/12—Electrolytic production, recovery or refining of metals by electrolysis of solutions of copper
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
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- 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
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Abstract
The invention discloses a method for eluting nickel and chloride ions in nickel sulfide copper removal tailings. The invention adopts an elution mode of three times of washing and two times of filter pressing to elute nickel and chloride ions in the copper-removing tailings of the nickel sulfide. Firstly, a tubular filter is used as a primary washing container, clean water is used for washing copper-removed tailings of nickel sulfide, and a sulfuric acid detergent is used for washing for secondary washing. And carrying out first filter pressing solid-liquid separation on the washed tailing slurry through a filter press, adding a certain amount of clear water into the filtered tailing to wash nickel and chloride ions mixed with the washed tailing slurry, and carrying out second filter pressing to carry out solid-liquid separation by using the filter press. The elution method can elute nickel and chloride ions in the copper-removing tailings of the nickel sulfide to the maximum extent, improve the recovery rate of nickel metal and reduce the corrosivity of the tailings.
Description
Technical Field
The invention relates to the technical field of metallurgical processes, in particular to a method for eluting nickel and chloride ions in nickel sulfide copper removal tailings.
Background
For a long time, in the using process of the nickel sulfide copper removal process, the nickel sulfide copper removal tailing is limited by high nickel and chloride ions, and cannot be directly sold as secondary copper concentrate. The washing method for removing nickel and chloride ions in copper tailings of nickel sulfide adopts pure water washing, and the nickel content of the washed copper tailings is more than 10%. In order to save mineral resources, the method is generally carried out by leaching the nickel and the chloride ions with chlorine in other workshops, and then filtering and recovering the nickel and the chloride ions. The method can cause the loss of nickel and the enrichment of a large amount of impurities in the process of repeated recycling, increases the production and processing cost, is not beneficial to production and environment-friendly production, brings chloride ions into the downstream pyrometallurgical working procedure, and is easy to cause the corrosion loss of smelting equipment and facilities.
Disclosure of Invention
The invention aims to provide a method for eluting nickel and chloride ions in copper-removing tailings of nickel sulfide, which is mainly suitable for washing the nickel and chloride ions in the copper-removing tailings in the purification process of nickel electrolyte, improves the washing efficiency of the nickel and chloride ions, improves the recovery rate of nickel metal, and reduces the corrosivity of the tailings.
The method for eluting nickel sulfide and removing nickel and chloride ions in copper tailings comprises the following steps:
(1) One-time washing
Adding the copper-removing nickel sulfide tailings into a tubular filter, pumping clear water at the temperature of 50-60 ℃ into the tubular filter, and washing the copper-removing nickel sulfide tailings for 8-12min; and (3) blowing, filtering and carrying out liquid-solid separation on the washed copper-removed tailings of the nickel sulfide through a tubular filter, then discharging slag, and finally pumping the discharged tailings slurry into a washing tank. Wherein the volume ratio of the clear water dosage to the dry weight of the nickel sulfide copper removal tailings is 3.33 to 1, and the volume ratio of the clear water dosage to the dry weight of the nickel sulfide copper removal tailings is 2.22 to 1 to 3.33; the tubular filter serves as a container for one-time washing.
(2) Second washing
Adding clear water into tailing slurry in a washing tank to obtain tailing slurry, heating the tailing slurry to 35-45 ℃ by using steam, adding a washing agent, adjusting the pH value to 2 by using 98% sulfuric acid, stirring and washing for 25-35min, and washing nickel and chloride ions in the tailing slurry. Wherein the volume ratio of the tailing slurry to clear water is 1 to 1; the detergent is sulfuric acid with the mass fraction of 98%, and the volume ratio of the detergent to the tailing slurry is 1.
(3) One-time filter pressing
Pumping the tailing slurry after secondary washing into a filter press, blowing for 3 to 8min after the tailing slurry is fully pressed, discharging slag after entrained water is blown out, and adding the tailing slag into a washing tank;
(4) Three times of washing
Adding clear water into the tailings discharged by the primary filter pressing to obtain tailings slurry, heating to 35-45 ℃ by using steam, stirring and washing for 25-35min, and washing out nickel and chloride ions in the tailings slurry. Wherein the volume ratio of the tailing slag to the clear water is 1.
(5) Secondary filter pressing
Pumping the tailing slurry after the three-time washing into a filter press, blowing for 3 to 8min after the tailing slurry is fully pressed, blowing out entrained water, and then discharging slag to obtain tailing slag with the nickel and chloride ion content not more than 3%.
The finally obtained tailing slag contains less than or equal to 3% of nickel and chloride ions, and the copper-nickel ratio is more than or equal to 15, and the tailing slag can be used as secondary copper concentrate to be sold to a pyrogenic process and used as a raw material of a copper anode plate. Washing the separated high nickel solution for one time, filtering the high nickel solution for one time to obtain an acidic low nickel solution, and filtering the low nickel solution for three times to obtain a neutral low nickel solution, and returning the neutral low nickel solution to the nickel electrolytic solution-making process for recycling.
Compared with the traditional washing mode of copper removal tailings of nickel sulfide, the washing method has the following beneficial effects:
1. in the washing process, the tubular filter is used as a primary washing container, the copper-removing tailings of the nickel sulfide are washed by clean water, and the sulfuric acid detergent is used for washing in the secondary washing process, so that the washing efficiency of nickel and chloride ions is improved;
2. the method adopts an elution mode of three times of washing and two times of filter pressing, so that nickel and chloride ions in the copper sulfide tailings are eluted to the maximum extent to remove nickel and chloride ions, the recovery rate of nickel metal is improved, and the corrosivity of the tailings is reduced;
3. the invention has the advantages of simple process, low cost, cleanness, environmental protection and low labor intensity.
Drawings
FIG. 1 is a process flow diagram of the present invention.
Detailed Description
The method for eluting nickel sulfide and removing nickel and chloride ions in copper tailings is further described by the specific embodiment.
As shown in figure 1, the method for eluting nickel sulfide and removing nickel and chloride ions in copper tailings comprises the following specific steps:
(1) One-time washing
Adding the nickel sulfide copper-removing tailing into a tubular filter, pumping clear water at 50-60 ℃ into the tubular filter, wherein the volume ratio of the clear water usage to the copper-removing tailing (moisture content) is 2.22; and (3) carrying out air-blowing filtration and liquid-solid separation on the washed copper-removed nickel sulfide tailings through a tubular filter, then carrying out slag unloading operation, and finally pumping the unloaded tailing slurry into a primary washing tank.
(2) Second washing
Adding clear water into the tailing slurry in the washing tank to obtain tailing slurry, heating the tailing slurry to 40 ℃ by using steam, adding sulfuric acid with the mass fraction of 98% as a washing agent, adjusting the pH value to 2 by using the sulfuric acid with the mass fraction of 98%, and stirring for 30 minutes. Wherein the volume ratio of the tailing slurry to the clear water is 2; the volume ratio of the washing agent to the tailing slurry is 1.
(3) One-time filter pressing
And pumping the tailing slurry after secondary washing into a filter press by using a pump, blowing for 5 minutes after the tailing slurry is fully pressed, discharging slag, and adding the tailing slag into a washing tank.
(4) Three times of washing
Adding clean water into the tailings subjected to primary pressure filtration according to the volume ratio of 1.
(5) Secondary filter pressing
Pumping the tailings slurry after the three-time washing into a filter press, blowing for 5 minutes after the tailings slurry is fully pressed, and discharging slag after entrained water is blown out. The finally obtained tailing slag contains less than or equal to 3% of nickel and chloride ions, the copper-nickel ratio is more than or equal to 15, and the tailing slag can be used as secondary copper concentrate to be sold to a pyrogenic process and used as a raw material of a copper anode plate.
Claims (6)
1. A method for eluting nickel and chloride ions in copper-removing tailings of nickel sulfide comprises the following steps:
(1) One-time washing
Emptying solution in a tubular filter for filtering nickel sulfide copper-removing tailings, pumping clear water at the temperature of 50-60 ℃ into the tubular filter, and flushing the nickel sulfide copper-removing tailings for 8-12min; blowing, filtering and liquid-solid separating the washed copper-removed tailings of the nickel sulfide in a tubular filter, then discharging slag, and finally pumping the discharged tailings slurry into a secondary washing tank;
(2) Second washing
Adding clear water into tailing slurry in a secondary washing tank to form tailing slurry, heating the tailing slurry to 35-45 ℃ by using steam, adding a washing agent, adjusting the pH value to 2 by using sulfuric acid, stirring and washing for 25-35min, and washing out nickel and chloride ions in the tailing slurry; the detergent is sulfuric acid with the mass fraction of 98%;
(3) One-time filter pressing
Pumping the tailing slurry after secondary washing into a filter press, blowing for 3 to 8min after the tailing slurry is fully pressed, discharging slag after entrained water is blown out, and adding the tailing slag into a three-time washing tank;
(4) Three times of washing
Adding clear water into the tailings discharged by primary filter pressing to form tailing slurry, heating to 35-45 ℃ with steam, stirring and washing for 25-35min, and washing nickel and chloride ions in the tailing slurry;
(5) Secondary filter pressing
Pumping the tailing slurry after the three-time washing into a filter press, blowing for 3 to 8min after the tailing slurry is fully pressed, blowing out entrained water, and then discharging slag to obtain tailing slag with the nickel and chloride ion content not more than 3%.
2. The method for eluting nickel and chloride ions in copper-removing tailings of nickel sulfide as claimed in claim 1, is characterized in that: in the step (1), the volume ratio of the clear water dosage to the dry weight of the nickel sulfide copper removal tailings is 3.33 to 1, and the volume ratio of the clear water dosage to the dry weight of the nickel sulfide copper removal tailings is 2.22 to 1 to 3.33.
3. The method for eluting nickel and chloride ions in the copper-removing tailings of the nickel sulfide as claimed in claim 1, wherein: in the step (1), the tubular filter is used as a primary washing container.
4. The method for eluting nickel and chloride ions in the copper-removing tailings of the nickel sulfide as claimed in claim 1, wherein: in the step (2), the volume ratio of the tailing slurry to clear water is 1 to 1.
5. The method for eluting nickel and chloride ions in copper-removing tailings of nickel sulfide as claimed in claim 1, is characterized in that: in the step (2), the volume ratio of the detergent to the tailing slurry is 1 to 3 to 1.
6. The method for eluting nickel and chloride ions in the copper-removing tailings of the nickel sulfide as claimed in claim 1, wherein: in the step (4), the volume ratio of the tailings to the clear water is 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN202110255726.XA CN113061724B (en) | 2021-03-09 | 2021-03-09 | Method for eluting nickel sulfide and removing nickel and chloride ions in copper tailings |
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| CN202110255726.XA CN113061724B (en) | 2021-03-09 | 2021-03-09 | Method for eluting nickel sulfide and removing nickel and chloride ions in copper tailings |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999060179A1 (en) * | 1998-05-14 | 1999-11-25 | Falconbridge Limited | Recovery of nickel from copper refinery tankhouse electrolyte |
| JP2017155280A (en) * | 2016-03-01 | 2017-09-07 | 住友金属鉱山株式会社 | Method for removing copper ions from copper-containing aqueous nickel chloride solution and method for producing electrolytic nickel |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1032703C (en) * | 1994-06-29 | 1996-09-04 | 北京有色冶金设计研究总院 | Method for removal of copper from electrolytic nickel anodic liquid |
| JP2009046736A (en) * | 2007-08-21 | 2009-03-05 | Sumitomo Metal Mining Co Ltd | Chlorine leaching method of nickel sulfide |
| CN102260795A (en) * | 2011-05-20 | 2011-11-30 | 四川省尼科国润新材料有限公司 | Method for directly producing electrolytic nickel by using copper nickel renewable resources |
| CN102409175A (en) * | 2011-11-09 | 2012-04-11 | 中南大学 | Method for treating purification copper-removing slag of nickel electrolysis anode solution |
| CN103820809B (en) * | 2014-02-28 | 2017-03-01 | 金川集团股份有限公司 | A kind of copper-removing method |
| CN107245585B (en) * | 2017-06-21 | 2022-12-06 | 江西省广德环保科技股份有限公司 | Electroplating waste treatment method |
| CN107287427B (en) * | 2017-07-01 | 2022-01-07 | 江西省广德环保科技股份有限公司 | Electroplating waste treatment method |
| CN109371245B (en) * | 2018-11-13 | 2020-04-28 | 成都理工大学 | Recycling treatment method for copper slag of nickel refining system |
| CN109797410B (en) * | 2019-03-20 | 2020-07-03 | 金川集团股份有限公司 | Two-stage impurity removal process for electrolytic purification of nickel sulfide soluble anode nickel |
| CN109762986A (en) * | 2019-03-20 | 2019-05-17 | 金川集团股份有限公司 | A kind of devices and methods therefor extracting nickel from nickel electrowinning copper ashes |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1999060179A1 (en) * | 1998-05-14 | 1999-11-25 | Falconbridge Limited | Recovery of nickel from copper refinery tankhouse electrolyte |
| JP2017155280A (en) * | 2016-03-01 | 2017-09-07 | 住友金属鉱山株式会社 | Method for removing copper ions from copper-containing aqueous nickel chloride solution and method for producing electrolytic nickel |
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Effective date of registration: 20240412 Address after: 737104 No. 2 Lanzhou Road, Beijing Road Street, Jinchuan District, Jinchang City, Gansu Province Patentee after: Jinchuan Group Nickel Cobalt Co.,Ltd. Country or region after: China Address before: No.98, Jinchuan Road, Jinchuan District, Jinchang City, Gansu Province 737100 Patentee before: JINCHUAN GROUP Co.,Ltd. Country or region before: China |
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