CN102242266A - Process for recovering cobalt, copper, zinc and manganese in manganese chloride residual liquid - Google Patents
Process for recovering cobalt, copper, zinc and manganese in manganese chloride residual liquid Download PDFInfo
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- CN102242266A CN102242266A CN2011101599562A CN201110159956A CN102242266A CN 102242266 A CN102242266 A CN 102242266A CN 2011101599562 A CN2011101599562 A CN 2011101599562A CN 201110159956 A CN201110159956 A CN 201110159956A CN 102242266 A CN102242266 A CN 102242266A
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- Prior art keywords
- manganese
- zinc
- cobalt
- copper
- raffinate
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000011701 zinc Substances 0.000 title claims abstract description 44
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 44
- 239000010941 cobalt Substances 0.000 title claims abstract description 43
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 43
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 43
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 42
- 239000010949 copper Substances 0.000 title claims abstract description 42
- 239000011572 manganese Substances 0.000 title claims abstract description 37
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 25
- 229910021380 Manganese Chloride Inorganic materials 0.000 title claims abstract description 8
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 title claims abstract description 8
- 239000011565 manganese chloride Substances 0.000 title claims abstract description 8
- 235000002867 manganese chloride Nutrition 0.000 title claims abstract description 8
- 229940099607 manganese chloride Drugs 0.000 title claims abstract description 8
- 239000007788 liquid Substances 0.000 title abstract 4
- 239000012074 organic phase Substances 0.000 claims abstract description 23
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims abstract description 19
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 13
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000011787 zinc oxide Substances 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 8
- 238000002425 crystallisation Methods 0.000 claims abstract description 6
- 230000008025 crystallization Effects 0.000 claims abstract description 6
- 238000001704 evaporation Methods 0.000 claims abstract description 6
- 230000008020 evaporation Effects 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000000605 extraction Methods 0.000 claims description 44
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- CNFDGXZLMLFIJV-UHFFFAOYSA-L manganese(II) chloride tetrahydrate Chemical compound O.O.O.O.[Cl-].[Cl-].[Mn+2] CNFDGXZLMLFIJV-UHFFFAOYSA-L 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 10
- 150000002500 ions Chemical class 0.000 claims description 10
- 239000003350 kerosene Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 229960003280 cupric chloride Drugs 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 8
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 8
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- 238000007127 saponification reaction Methods 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 235000017550 sodium carbonate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000002386 leaching Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000000047 product Substances 0.000 abstract description 18
- 238000011084 recovery Methods 0.000 abstract description 13
- 239000012535 impurity Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 4
- 239000002184 metal Substances 0.000 abstract description 4
- 239000002244 precipitate Substances 0.000 abstract description 3
- 150000002696 manganese Chemical class 0.000 abstract 3
- 239000012266 salt solution Substances 0.000 abstract 2
- 239000002253 acid Substances 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- -1 chlorine ions Chemical class 0.000 abstract 1
- 230000001105 regulatory effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- ALKWJXWZUTYERW-UHFFFAOYSA-L O.O.O.O.[Mn](=O)(Cl)Cl Chemical class O.O.O.O.[Mn](=O)(Cl)Cl ALKWJXWZUTYERW-UHFFFAOYSA-L 0.000 description 3
- WIINZSNDMQYCIR-UHFFFAOYSA-N [Mn].[Zn].[Co].[Cu] Chemical compound [Mn].[Zn].[Co].[Cu] WIINZSNDMQYCIR-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 2
- VSEWZMQQQHLHQT-UHFFFAOYSA-N manganese;sulfuric acid;hydrate Chemical compound O.[Mn].OS(O)(=O)=O VSEWZMQQQHLHQT-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000001698 pyrogenic effect Effects 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 238000000247 postprecipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011667 zinc carbonate Substances 0.000 description 1
- 235000004416 zinc carbonate Nutrition 0.000 description 1
- 229910000010 zinc carbonate Inorganic materials 0.000 description 1
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 1
- 229940007718 zinc hydroxide Drugs 0.000 description 1
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 1
- ZPEJZWGMHAKWNL-UHFFFAOYSA-L zinc;oxalate Chemical compound [Zn+2].[O-]C(=O)C([O-])=O ZPEJZWGMHAKWNL-UHFFFAOYSA-L 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
Landscapes
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a process for recovering cobalt, copper, zinc and manganese in a manganese chloride residual liquid. By using the process, the recovery rates of cobalt, copper, zinc and manganese are above 90%, the contents of impurities in recovered cobalt, copper, zinc and manganese products are below 1g/L, and the contents of the impurities in the manganese product are below 2%. The process mainly comprises the following steps: regulating the concentration of chlorine ions in the manganese chloride residual liquid to 250-350g/L; extracting cobalt, copper and zinc in the manganese chloride residual liquid with N235, and reserving manganese in raffinate; then stripping cobalt, copper and zinc in an organic phase with a stripping agent so as to obtain pure cobalt chloride, a copper chloride solution and a zinc precipitate, washing, drying and calculating the zinc precipitate so as to obtain a zinc oxide product; extracting manganese in the raffinate with P204, stripping with an acid so as to obtain a manganese salt solution; and carrying out evaporation, crystallization and drying on the manganese salt solution so as to obtain the manganese salt product. The process has the advantages of short process flow, high valuable metal recovery, high recovered product purity and low recover cost.
Description
Technical field
The invention belongs to hydrometallurgy, chemical field, particularly a kind of method that reclaims cobalt, copper, zinc, manganese in the Manganous chloride tetrahydrate raffinate.
Background technology
When processing contained the ore of cobalt, copper, zinc, manganese simultaneously, after usually the cobalt in the ore, copper, zinc, manganese being leached, extraction agents such as first Lix984 were separated the copper in the leach liquor, use P more at present
20
4Isolate cobalt Deng extraction agent, the solution that will contain zinc, manganese (carrying part cobalt, copper secretly) returns pyrogenic process system recoveries cobalt, copper wherein with post precipitations such as carbonate, wherein zinc vapors away when pyrogenic process reclaims, manganese is discarded by slag making, the rate of recovery of this method cobalt, copper is extremely low, zinc, manganese can not get reclaiming, and have caused the great wasting of resources and environmental pollution; When containing this seabed, the cobalt-bearing crust ore deposit polymetallic ore of cobalt, copper, zinc, manganese, processing often adopts Lix984 extracting copper, P
204The technology that extracting zinc, HA-1 extraction cobalt separates manganese, this technical process is long, and cost height, recovery rate of valuable metals are low.
Summary of the invention
Technical problem to be solved by this invention is at problems of the prior art, the method of cobalt, copper, zinc, manganese in a kind of comprehensive recovery Manganous chloride tetrahydrate raffinate is provided, to shorten the comprehensive recycling process flow process, reduce production costs, improve the purity of recovery rate of valuable metals and recovery product.
The present invention adopts following technical scheme for solving the problems of the technologies described above:
A kind of method that reclaims cobalt, copper, zinc, manganese in the Manganous chloride tetrahydrate raffinate, this method may further comprise the steps:
A concentration is that 24%～35% hydrochloric acid soln is adjusted to 250～350g/L with chlorine ion concentration in the Manganous chloride tetrahydrate raffinate;
B is with containing 5%～30%N
235, the extraction agent of 5%～20% isooctyl alcohol and 50%～90% sulfonated kerosene is being compared O/A=1:0.5～5, and cobalt, copper, zine ion in the extraction Manganous chloride tetrahydrate raffinate are stayed in the raffinate;
The c chlorine ion concentration is sodium chloride solution or the hydrochloric acid soln of 60g/L～80g/L, is comparing O/A=1:0.5～5, and the cobalt in the reextraction raffinate organic phase obtains the cobalt chloride throw out; Comparing O/A=1:0.5～5 with pure water, the copper in the reextraction raffinate load organic phases obtains the cupric chloride throw out; Comparing O/A=1:0.5～5 with strippant oxalic acid, yellow soda ash, potassium hydroxide, the zinc in the reextraction raffinate load organic phases obtains the throw out of zinc;
D is with containing 10%～30%P
204, 90%～70% sulfonated kerosene, saponification degree be that 50%～80% extraction agent is being compared O/A=1:0.5～5, extraction is through N
235Mn ion in the gained raffinate of extraction back; Comparing O/A=1:1～5 with strippant sulfuric acid or hydrochloric acid soln, stripping through P
204Manganese in the gained load organic phases of extraction back;
Zinc washing of precipitate, drying, calcining that e takes out back extraction promptly get the zinc oxide product that the present invention is recovered to; Manganese containing solution evaporation, crystallization, drying with back extraction is taken out promptly obtain the manganese product salt that the present invention is recovered to.
Described Manganous chloride tetrahydrate raffinate is for containing the manganese chloride solution that contains cobalt, copper, zinc that produced in the ore process of manganese, cobalt, copper, zinc or leaching when containing the ore of manganese, cobalt, copper, zinc resulting Manganous chloride tetrahydrate leach liquor with hydrochloric acid in processing.
The described P that strips that is used to
204When extracting the manganese in the gained load organic phases of back, the concentration of used strippant sulfuric acid or hydrochloric acid soln is 1mol/L～4mol/L.
The present invention has the high advantage of product purity that technical process is short, production cost is low, recovery rate of valuable metals is high, be recovered to.Utilize the rate of recovery that the present invention reclaims cobalt, copper, zinc, manganese more than 90%, reclaim that foreign matter content is below 1g/L in the cobalt that obtains, copper, the zinc product, foreign matter content is below 2% in the manganese product.
Embodiment:
Embodiment 1:
A concentration is that 24% hydrochloric acid soln contains processing that chlorine ion concentration is adjusted to 300g/L in the manganese chloride solution that contains cobalt, copper, zinc that is produced in the ore process of manganese, cobalt, copper, zinc;
B is with containing 5%N
235, the extraction agent of 5% isooctyl alcohol and 90% sulfonated kerosene is being compared O/A=1:0.5, and cobalt, copper, zine ion in the extraction Manganous chloride tetrahydrate raffinate are stayed in the raffinate;
The c chlorine ion concentration is that the sodium chloride solution of 60g/L is being compared O/A=1:0.5, and the cobalt in the reextraction raffinate organic phase obtains the cobalt chloride throw out; Comparing O/A=1:0.5 with pure water, the copper in the reextraction raffinate load organic phases obtains the cupric chloride throw out; Comparing O/A=1:0.5 with strippant yellow soda ash, the zinc in the reextraction raffinate load organic phases obtains the throw out of zinc;
D is with containing 10%P
204With 90% sulfonated kerosene, saponification degree is 50% extraction agent, is comparing O/A=1:0.5, and extraction is through N
235Mn ion in the gained raffinate of extraction back; Hydrochloric acid with 1mol/L is being compared under the O/A=1:1, strips through P
204Manganese in the gained load organic phases of extraction back;
The zinc oxalate washing that e takes out back extraction, dry, calcining promptly get the zinc oxide product that the present invention is recovered to; Manganese chloride solution evaporation, crystallization, drying with back extraction is taken out promptly obtain the five water Manganous chloride tetrahydrate products that the present invention is recovered to.
Embodiment 1 result is as shown in table 1 below:
Table 1 embodiment 1 result
| ? | Cobalt chloride solution | Cupric Chloride Solution | Zinc oxide | Five water Manganous chloride tetrahydrates |
| Total impurities content | 1g/L | 0.7 g/L | 2% | 1.3% |
| ? | Cobalt | Copper | Zinc | Manganese |
| The rate of recovery | 97.4% | 95.1% | 95.8% | 92.4% |
Embodiment 2:
To be 35% hydrochloric acid soln leach hydrochloric acid when containing the ore of manganese, cobalt, copper, zinc a concentration, and chlorine ion concentration is adjusted to 350g/L in the resulting Manganous chloride tetrahydrate leach liquor;
B is with containing 30%N
235, the N of 20% isooctyl alcohol and 50% sulfonated kerosene
235Extraction agent is being compared under the O/A=1:5, and cobalt, copper, zine ion in the extraction Manganous chloride tetrahydrate raffinate are stayed in the raffinate;
The c chlorine ion concentration is that the hydrochloric acid soln of 80g/L is being compared O/A=1:5, and the cobalt in the reextraction raffinate organic phase obtains the cobalt chloride throw out; Comparing O/A=1:5 with pure water, the copper in the reextraction raffinate load organic phases obtains the cupric chloride throw out; Comparing O/A=1:5 with strippant oxalic acid, the zinc in the reextraction raffinate load organic phases obtains the throw out of zinc;
D is with containing 30%P
204With 70% sulfonated kerosene, saponification degree is that 80% extraction agent is being compared O/A=1:5, and extraction is through N
235Mn ion in the gained raffinate of extraction back; Sulfuric acid with 4mol/L is being compared under the O/A=1:5, strips through P
204Manganese in the gained load organic phases of extraction back;
The zinc carbonate washing that e takes out back extraction, dry, calcining promptly get the zinc oxide product that the present invention is recovered to; Manganous sulfate evaporation, crystallization, drying with back extraction is taken out promptly obtain the sulfuric acid monohydrate manganese product that the present invention is recovered to.
Embodiment 2 results are as shown in table 2 below:
Table 2 embodiment 2 results
| ? | Cobalt chloride solution | Cupric Chloride Solution | Zinc oxide | Five water Manganous chloride tetrahydrates |
| Total impurities content | 0.8g/L | 0.4 g/L | 1.7% | 1.3% |
| ? | Cobalt | Copper | Zinc | Manganese |
| The rate of recovery | 97.8% | 96.2% | 93.7% | 93.3% |
Embodiment 3:
A concentration is that 30% hydrochloric acid soln is adjusted to 250g/L with chlorine ion concentration in the Manganous chloride tetrahydrate raffinate;
B is with containing 20%N
235, the N of 15% isooctyl alcohol and 65% sulfonated kerosene
235Extraction agent is being compared under the O/A=1:3, cobalt, copper, zine ion in the extraction Manganous chloride tetrahydrate raffinate;
The c chlorine ion concentration is that the sodium chloride solution of 70g/L is being compared under the O/A=1:2 cobalt in the reextraction organic phase; Comparing under the O/A=1:3 copper in the reextraction load organic phases with pure water; Comparing under the O/A=1:3.5 zinc in the reextraction load organic phases with potassium hydroxide; Cobalt chloride, cupric chloride that back extraction is taken out are cobalt chloride, the cupric chloride product that the present invention is recovered to;
D is with containing 25%P
204With 75% sulfonated kerosene, saponification degree is 75% P
204Extraction agent is being compared under the O/A=1:3, and extraction is through N
235Mn ion in the gained raffinate of extraction back; Sulfuric acid with 2mol/L is being compared under the O/A=1:4, strips through P
204Manganese in the gained load organic phases of extraction back;
The zinc hydroxide washing that e takes out back extraction, dry, calcining promptly get the zinc oxide product that the present invention is recovered to; Manganese sulfate solution evaporation, crystallization, drying with back extraction is taken out promptly obtain the sulfuric acid monohydrate manganese product that the present invention is recovered to.
Embodiment 3 results are as shown in table 3 below:
Table 3 embodiment 3 results
| ? | Cobalt chloride solution | Cupric Chloride Solution | Zinc oxide | Five water Manganous chloride tetrahydrates |
| Total impurities content | 0.4g/L | 0.6 g/L | 1.2% | 1.0% |
| ? | Cobalt | Copper | Zinc | Manganese |
| The rate of recovery | 95.3% | 96.4% | 90.7% | 93.3% |
Claims (3)
1. method that reclaims cobalt, copper, zinc, manganese in the Manganous chloride tetrahydrate raffinate is characterized in that this method may further comprise the steps:
A concentration is that 24%～35% hydrochloric acid soln is adjusted to 250～350g/L with chlorine ion concentration in the Manganous chloride tetrahydrate raffinate;
B is with containing 5%～30%N
235, the extraction agent of 5%～20% isooctyl alcohol and 50%～90% sulfonated kerosene is being compared O/A=1:0.5～5, and cobalt, copper, zine ion in the extraction Manganous chloride tetrahydrate raffinate are stayed in the raffinate;
The c chlorine ion concentration is sodium chloride solution or the hydrochloric acid soln of 60g/L～80g/L, is comparing O/A=1:0.5～5, and the cobalt in the reextraction raffinate organic phase obtains the cobalt chloride throw out; Comparing O/A=1:0.5～5 with pure water, the copper in the reextraction raffinate load organic phases obtains the cupric chloride throw out; Comparing O/A=1:0.5～5 with strippant oxalic acid, yellow soda ash, potassium hydroxide, the zinc in the reextraction raffinate load organic phases obtains the throw out of zinc;
D is with containing 10%～30%P
204, 70%～90% sulfonated kerosene, saponification degree is that 50%～80% extraction agent is being compared O/A=1:0.5～5, extraction is through N
235Mn ion in the gained raffinate of extraction back; With concentration is that 1～4mol/L strippant sulfuric acid or hydrochloric acid soln are being compared O/A=1:1～5, strips through P
204Manganese in the gained load organic phases of extraction back;
The zinc throw out washing that e takes out back extraction, dry, calcining promptly get the zinc oxide product that the present invention reclaims; With manganese containing solution evaporation, crystallization, the drying that back extraction is taken out, promptly obtain the manganese product salt that the present invention reclaims.
2. a kind of method that reclaims cobalt, copper, zinc, manganese in the Manganous chloride tetrahydrate raffinate according to claim 1, it is characterized in that described Manganous chloride tetrahydrate raffinate is for containing the manganese chloride solution that contains cobalt, copper, zinc that produced in the ore process of manganese, cobalt, copper, zinc or leaching when containing the ore of manganese, cobalt, copper, zinc resulting Manganous chloride tetrahydrate leach liquor with hydrochloric acid in processing.
3. a kind of method that reclaims cobalt, copper, zinc, manganese in the Manganous chloride tetrahydrate raffinate according to claim 1 is characterized in that the described P that strips that is used to
204When extracting the manganese in the gained load organic phases of back, the concentration of used strippant sulfuric acid or hydrochloric acid soln is 1mol/L～4mol/L.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110159956.2A CN102242266B (en) | 2011-06-15 | 2011-06-15 | A kind of method reclaiming cobalt, copper, zinc, manganese in Manganous chloride tetrahydrate raffinate |
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|---|---|---|---|
| CN201110159956.2A CN102242266B (en) | 2011-06-15 | 2011-06-15 | A kind of method reclaiming cobalt, copper, zinc, manganese in Manganous chloride tetrahydrate raffinate |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102560156A (en) * | 2012-02-23 | 2012-07-11 | 中国恩菲工程技术有限公司 | Method for recycling manganese from P204 manganese back extraction solution in nickel laterite hydrometallurgical process |
| CN102888513A (en) * | 2012-10-15 | 2013-01-23 | 甘肃民族师范学院 | Method of fully separating copper, manganese, zinc, cobalt and calcium chloride solution |
| CN103409626A (en) * | 2013-07-29 | 2013-11-27 | 中国科学院过程工程研究所 | Method for asynchronously extracting and separating vanadium and manganese from solution containing V (IV) and Mn (II) |
| CN104060097A (en) * | 2014-07-04 | 2014-09-24 | 江西省广德环保科技有限公司 | Separating and recycling method of nickel, cobalt, copper manganese and zinc in electroplating sludge |
| CN104480306A (en) * | 2014-12-07 | 2015-04-01 | 金川集团股份有限公司 | Method for processing hydrochloric acid leaching liquid of zinc-containing nickel-cobalt hydroxide material |
| CN107723485A (en) * | 2017-10-24 | 2018-02-23 | 闻喜县远华冶金材料有限公司 | The recycling method of manganese in magnesium alloy flux waste residue |
| CN112456676A (en) * | 2020-11-05 | 2021-03-09 | 中国恩菲工程技术有限公司 | Method for treating organic wastewater |
| US11359260B2 (en) * | 2019-09-04 | 2022-06-14 | Korea Resources Corporation | Method of inhibiting degradation of extractant by anhydrous environment avoiding and metal stripping |
| CN115109943A (en) * | 2022-06-30 | 2022-09-27 | 金川集团股份有限公司 | Method for extracting and recovering copper, zinc, cobalt and manganese metals from copper chloride manganese zinc cobalt solution step by step |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101519222A (en) * | 2009-03-19 | 2009-09-02 | 金川集团有限公司 | Method for processing mixed waste liquor containing zinc sulfate and manganese sulfate in nickel salt production process |
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| CN102888513A (en) * | 2012-10-15 | 2013-01-23 | 甘肃民族师范学院 | Method of fully separating copper, manganese, zinc, cobalt and calcium chloride solution |
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| CN104060097A (en) * | 2014-07-04 | 2014-09-24 | 江西省广德环保科技有限公司 | Separating and recycling method of nickel, cobalt, copper manganese and zinc in electroplating sludge |
| CN104480306A (en) * | 2014-12-07 | 2015-04-01 | 金川集团股份有限公司 | Method for processing hydrochloric acid leaching liquid of zinc-containing nickel-cobalt hydroxide material |
| CN107723485A (en) * | 2017-10-24 | 2018-02-23 | 闻喜县远华冶金材料有限公司 | The recycling method of manganese in magnesium alloy flux waste residue |
| CN107723485B (en) * | 2017-10-24 | 2019-08-30 | 闻喜县远华冶金材料有限公司 | The recycling method of manganese in magnesium alloy flux waste residue |
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| CN112456676A (en) * | 2020-11-05 | 2021-03-09 | 中国恩菲工程技术有限公司 | Method for treating organic wastewater |
| CN115109943A (en) * | 2022-06-30 | 2022-09-27 | 金川集团股份有限公司 | Method for extracting and recovering copper, zinc, cobalt and manganese metals from copper chloride manganese zinc cobalt solution step by step |
| CN115109943B (en) * | 2022-06-30 | 2023-08-25 | 金川集团股份有限公司 | Method for extracting and recovering copper, zinc, cobalt and manganese metals from copper-manganese-zinc-cobalt chloride solution step by step |
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