CN104513899A - Process for treating xanthate cobalt slag - Google Patents
Process for treating xanthate cobalt slag Download PDFInfo
- Publication number
- CN104513899A CN104513899A CN201310445483.1A CN201310445483A CN104513899A CN 104513899 A CN104513899 A CN 104513899A CN 201310445483 A CN201310445483 A CN 201310445483A CN 104513899 A CN104513899 A CN 104513899A
- Authority
- CN
- China
- Prior art keywords
- cobalt
- xanthate
- zinc
- leaching
- processing method
- 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.)
- Pending
Links
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 discloses a process for treating xanthate cobalt slag. The recovery rates of zinc, copper and cobalt can reach 95% or more. The xanthate cobalt slag produced in the purification step of zinc hydrometallurgy is subjected to first section leaching at first, in the first section leaching, the xanthate cobalt slag is washed by water and then soaked in acid, the leaching yield of zinc can reach 95% or more, and the leaching yield of cadmium can reach 90% or more. The first-section leachate is subjected to zinc powder replacement and then enriched by a GX series heavy metal adsorption material so as to obtain a liquid with enriched zinc. The first-section leaching slag is subjected to second section leaching, in the second section leaching, the slag is burned and then soaked in acid, and the leaching yields of copper and cobalt can reach 95% or more. The leachate obtained in the second-section leaching is processed by a GX series heavy metal adsorption material so as to separate the copper and cobalt. The copper solution can be directly processed by a copper electro-deposition technology to produce metal copper, and at the same time the zinc solution is returned to the zinc smelting.
Description
Technical field
The invention belongs to mineral to produce and technical field of comprehensive utilization, relate to the Comprehensive recycle technology of xanthate cobalt slag in the production of a kind of zinc hydrometallurgy.
Background technology
At present, zinc hydrometallurgy is topmost zinc metallurgy method in the world, and along with the development of technology be ever-increasing trend.The master operation of zinc hydrometallurgy is divided into roasting, leaching, clean liquid, electrodeposition and founding five operations.Zinc roasted ore is after leaching, zinc enters into solution in the form of an ion, but other impurity, as the elements such as copper cadmium cobalt nickel arsenic antimony germanium then also enter in zinc sulfate leaching liquid, if these foreign matter contents are too high, Zinc electrolysis technico-economical comparison and Eletrolytic zinc quality are had a significant impact, the requirement that electrolytic deposition process can not normally carry out to reach Zinc electrolysis can be caused time serious, the detrimental impurity such as the copper cadmium cobalt nickel arsenic antimony germanium in zinc sulfate leaching liquid must be purified to below specified standards, make the valuable metals such as copper cadmium cobalt nickel obtain good enrichment in this course simultaneously, so that recycle.Therefore purification is one of most important operation of zinc hydrometallurgy.
Xanthate Cobalt Purification method
Xanthate is also a kind of organic reagent, common as potassium xanthonate (C
2h
5and sodium xanthonate (C OCSSK)
2h
5etc. OCSSNa) be used to zinc hydrometallurgy Cobalt Purification xanthate and can form insoluble compound with many metals, a lot of metals, as Cu
2+, Cd
2+, Fe
3+, Co
3+sulfonate than the sulfonate indissoluble of zinc, so add xanthate can remove these foreign ions in solution in zinc sulfate liquid, and not disturb by zine ion.Mainly sodium ethyl xanthate (the C adopted in production practice
2h
5oCSSNa), its action principle is that the sodium ethyl xanthate added and rose vitriol react based under having copper sulfate existent condition in solution, generates cobalt xanthate precipitation, thus reaching the object of Cobalt Purification, oxygenant copper sulfate is then play xanthate to be oxidized to xanthogenic acid (C
2h
5oCSS)
2s
2effect, also can adopt air in reaction, potassium permanganate etc. use as oxygenant.
The reaction process that xanthate method removes cobalt is as follows
First be the reaction of xanthate and copper sulfate:
4C
2H
5OCSSNa+2CuSO
4=(C2H5OCSS)
2S
2+Cu
2(C
2H
5OCSS)
2+2Na
2SO
4
Two xanthogenic acid that the first step reaction generates make the divalence xanthogenic acid cobalt oxidation of generation be trivalent xanthogenic acid cobalt precipitation, and its reaction formula is as follows:
2C
2H
5OCSSNa+CoSO
4=Co(C
2H
5OCSS)
2+Na
2SO
4
Co(C
2H
5OCSS)
2+(C
2H
5OCSS)
2S
2=2Co(C
2H
5OCSS)
3↓
Remain in removing solution while cobalt, reaction formula is as follows:
CdSO
4+2C
2H
5OCSSNa=Cd(C
2H
5OCSS)
2↓
Xanthate removes cobalt process should carry out in neutral solution, and generally the pH value of solution controls easily to decompose in an acidic solution because of xanthate between 5.2-5.4, its consumption can be made to increase and reduce except cobalt efficiency; When temperature is more than 50 DEG C, xanthate also easily decomposes, so the control temperature that xanthate removes cobalt should be 35-40 DEG C of cobalt of being advisable to remove lower concentration in solution, xanthate consumption is generally the 10-15 of cobalt amount in solution doubly, and copper sulfate add-on is 1/3-1/5 times of xanthate consumption.
Expensive due to xanthate, and can not regenerate, there is in reaction process very strong stink, make labor condition not good enough, the most important thing is except cobalt and nickel thorough all not, and the process extracting cobalt from wbolt sulfonate slag also unusual complexity, after purification, to remain xanthate also very unfavorable to follow-up electrodeposition for liquid, thus now both at home and abroad only minority producer adopt this method.
During hydrometallurgy metallic zinc, normal containing a small amount of cobalt in raw material, cobalt is one of the most harmful impurity in zinc hydrometallurgy, therefore has to pass through strict with the clean liquid process of cobalt on stream.Chifeng's zinc cobalt ore slag is through xanthate except the slag obtained after cobalt method, xanthate (C
4h
9oCS
2k) except principal reaction in cobalt process is as follows:
Cu
2++Co
2+→Cu
++Co
3+
CoSO
4+2C
4H
9OCS
2K+(C
4H
9OCS
2)
2Cu
→K
2SO
4+C
4H
9OCS
2Cu+(C
4H
9OCS
2)
3Co↓
Also containing metallic compounds such as a large amount of Zn, Cd, Cu, Ni in slag, wherein cobalt and copper are xanthate, and zinc is mainly the solution of zinc sulfate form of basic zinc sulfate and absorption and is present in slag.
At present for xanthate except the comprehensive recycling process of metal in the Zn-Co sludge formed after cobalt is less, this patent primary study is a kind of processes the technique of xanthate except cobalt slag, and the rate of recovery of Qi Zhongxin, copper, cobalt can reach more than 95% respectively.
Summary of the invention
The invention provides a kind of leaching by two sections and obtain metal leach liquor, recycling heavy-metal adsorption material realizes the processing method of the process xanthate cobalt slag of separation of metal ions.
Concrete steps are as follows:
S1, first washes xanthate cobalt slag.
S2, then carries out acidleach to the washing slag obtained.
S3, utilizes zinc dust precipitation to remove cadmium after water lotion mixes with leach liquor.
S4, utilizes GX series heavy-metal adsorption material to carry out enrichment to it to the zinc-containing solution after having replaced.After enrichment, liquid enters Zinc electrolysis.
Above step is that first paragraph leaches step, and first paragraph leaches takes the method for washing-acidleach to leach metal target zinc, cadmium.The electrodeposition stage is entered after utilizing GX series heavy-metal adsorption material to carry out enrichment to leach liquor.
S5, carries out roasting to the first paragraph leached mud obtained.
S6, carries out acidleach to the slag after roasting.
S7, leached mud returns acidleach part, leach liquor utilize GX series heavy-metal adsorption material it is separated, enrichment.
Above step is that second segment leaches step, and second segment leaches takes the method for oxidizing roasting-acidleach to leach metal target copper, cobalt.GX series heavy-metal adsorption material is utilized to be separated leach liquor, to enter the electrodeposition stage after enrichment.
Below the present invention is described further:
The processing method proposing the process xanthate cobalt slag that leaching matches with materials adsorption of novelty of the present invention, the experiment proved that, the modes that the method is leached by two sections, and each metal all can obtain higher metal leaching rate and the rate of recovery.And after the process of GX series heavy-metal adsorption material, each metal can realize detached from each other, all reaches the requirement standard entering electrodeposition link separately.And whole technique is arranged outward without waste water and gas, comprehensively recovering valuable metal, reaches cleaner production requirement.Therefore, the technical process utilizing leaching and GX series heavy-metal adsorption material Adsorption Phase to be combined provided by the invention, can be applicable in the production of process xanthate cobalt slag.
Accompanying drawing explanation
Fig. 1 is schematic flow sheet of the present invention (xanthate cobalt residues processing technique schema).
embodiment
Below with reference to embodiment, content of the present invention is described further.
Embodiment one
1, xanthate removes cobalt slag supplied materials is that sorrel is block, and composition is as shown in table 1, mainly containing metals such as zinc, cadmium, copper, cobalt, nickel.
table 1 xanthate is except cobalt slag results of elemental analyses
| Chemical composition | Cu | Co | Zn | Cd | Ni |
| Content | 1.27% | 1.89% | 10.13% | 1.37% | 0.15% |
2, remove cobalt slag to xanthate and carry out first paragraph leaching, metal target is zinc, cadmium.Leaching way is washing-acidleach, first paragraph leaching condition: room temperature 20 DEG C, solid-to-liquid ratio 5:1, stirring velocity 50 ~ 100 r/min, churning time 0.5h, pickling acidity 10g/L, and now the leaching yield of zinc is 95.6%, and the leaching yield of cadmium is 90.5%.
3, carry out pre-treatment to one section of leach liquor, first utilize zinc dust precipitation to go out cadmium, now in solution, zinc concentration is 15-20g/L.Recycling GX heavy-metal adsorption material carries out enrichment to clean liquid, and the zinc solution concentration after enrichment can reach 50-60g/L, and foreign matter content is low, meets Zinc electrolysis requirement.
4, carry out second segment leaching to first paragraph leached mud, metal target is copper, cobalt.Leaching way is roasting-acidleach.Maturing temperature is 400 DEG C, roasting time 0.5-1h, and leach liquid-solid ratio 5:1, sulfuric acid dosage is 120g/L, and oxygenant consumption is 5% ~ 10%, heats 80 DEG C of agitation leach 1h, stirring velocity 50 ~ 100r/min.The leaching yield of copper, cobalt is respectively 95.7%, 96.3%.
5, GX heavy-metal adsorption material is utilized to carry out fractionation by adsorption to second segment leach liquor.The scope of absorption leach liquor pH is 3.5-4.5.Copper liquid concentration after fractionation by adsorption can reach 40-50g/L, directly can enter copper process, carry out electrodeposition, production of copper product.Cobalt liquid enters cobalt operation, carries out electrodeposition, produces cobalt product.
Embodiment two
1, xanthate removes cobalt slag supplied materials is that sorrel is block, and composition is as shown in table 2, mainly containing metals such as zinc, cadmium, copper, cobalt, nickel.
table 2 xanthate is except cobalt slag results of elemental analyses
| Chemical composition | Cu | Co | Zn | Cd | Fe |
| Content | 0.87% | 3.10% | 9.13% | 1.97% | 0.98% |
2, remove cobalt slag to xanthate and carry out first paragraph leaching, metal target is zinc, cadmium.Leaching way is washing-acidleach, first paragraph leaching condition: room temperature 20 DEG C, solid-to-liquid ratio 5:1, stirring velocity 50 ~ 100 r/min, churning time 0.5h, pickling acidity 10g/L, and the leaching yield of zinc can reach more than 95%, and the leaching yield of cadmium can reach more than 90%.
3, carry out pre-treatment to one section of leach liquor, first utilize zinc dust precipitation to go out cadmium, now in solution, zinc concentration is 10-15g/L.Recycling GX heavy-metal adsorption material carries out enrichment to clean liquid, and the zinc solution concentration after enrichment can reach 50-60g/L, and foreign matter content is low, meets Zinc electrolysis requirement.
4, carry out second segment leaching to first paragraph leached mud, metal target is copper, cobalt.Leaching way is roasting-acidleach.Maturing temperature is 400 DEG C, roasting time 0.5-1h, and leach liquid-solid ratio 5:1, sulfuric acid dosage is 120g/L, and oxygenant consumption is 5% ~ 10%, heats 80 DEG C of agitation leach 1h, stirring velocity 50 ~ 100r/min.The leaching yield of copper, cobalt all reaches more than 95%.
5, GX heavy-metal adsorption material is utilized to carry out fractionation by adsorption to second segment leach liquor.The scope of absorption leach liquor pH is 4.5-5.5.Copper liquid concentration after fractionation by adsorption can reach 40-50g/L, directly can enter copper process, carry out electrodeposition, production of copper product.Cobalt liquid enters cobalt operation, carries out electrodeposition, produces cobalt product.
Claims (7)
1. process a processing method for xanthate cobalt slag, it is characterized in that: main technique is two sections of leachings, and in conjunction with the GX series fractionation by adsorption of heavy-metal adsorption material, extraction.
2. the processing method of process xanthate cobalt slag according to claim 1, is characterized in that, two sections of extract technologies refer to that first paragraph leaches as washing-acidleach, and second segment leaches as roasting-acidleach.
3. according to the processing method of process xanthate cobalt slag according to claim 1 or claim 2, it is characterized in that in first paragraph leaching process, top condition is: extraction temperature 20-50 DEG C, liquid-solid ratio 1:1-10:1, stirring velocity 50-500 r/min, churning time 0.2-2h, acidleach acidity 5-50g/L.
4. according to the processing method of process xanthate cobalt slag according to claim 1 or claim 2, it is characterized in that in second segment leaching process, top condition is: maturing temperature is 200-800 DEG C, roasting time 0.2-2h, leach liquid-solid ratio 1:1-10:1, acid consumption is 20-200g/L, oxygenant consumption is 1%-20%, heats 50-100 DEG C of agitation leach 0.2-2h, stirring velocity 50-100r/min.
5. according to the processing method of process xanthate cobalt slag according to claim 1 or claim 2, it is characterized in that, in acidleach, comprise one or more in the acid of the routine such as sulfuric acid or hydrochloric acid with acid.
6., according to the processing method of process xanthate cobalt slag according to claim 1 or claim 2, it is characterized in that using GX heavy-metal adsorption material process leach liquor optimum PH range to be 2.5-6.0.
7. the processing method of process wbolt sulfonate slag according to claim 1 and 2, it is characterized in that, described heavy-metal adsorption material is produced by the following method: the production method of described heavy-metal adsorption material is shown in patent ZL 03126366.6, and name is called " producing the processing method of toxic heavy metal waste water conditioner ".
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310445483.1A CN104513899A (en) | 2013-09-27 | 2013-09-27 | Process for treating xanthate cobalt slag |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310445483.1A CN104513899A (en) | 2013-09-27 | 2013-09-27 | Process for treating xanthate cobalt slag |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104513899A true CN104513899A (en) | 2015-04-15 |
Family
ID=52789771
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310445483.1A Pending CN104513899A (en) | 2013-09-27 | 2013-09-27 | Process for treating xanthate cobalt slag |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104513899A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105950875A (en) * | 2016-05-09 | 2016-09-21 | 钟庆文 | Processing method for purified cobalt residues of zinc and manganese hydrometallurgy |
| CN112520790A (en) * | 2020-11-12 | 2021-03-19 | 四川顺应动力电池材料有限公司 | Method for producing cobalt sulfate by using organic cobalt slag of zinc smelting plant |
| CN113265547A (en) * | 2021-05-26 | 2021-08-17 | 昆明冶金研究院有限公司 | Comprehensive recovery process for zinc hydrometallurgy organic purification cobalt slag |
| CN113881857A (en) * | 2021-09-09 | 2022-01-04 | 云南云铜锌业股份有限公司 | Method for treating cobalt-containing solution produced in wet zinc smelting cadmium recovery process |
-
2013
- 2013-09-27 CN CN201310445483.1A patent/CN104513899A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105950875A (en) * | 2016-05-09 | 2016-09-21 | 钟庆文 | Processing method for purified cobalt residues of zinc and manganese hydrometallurgy |
| CN112520790A (en) * | 2020-11-12 | 2021-03-19 | 四川顺应动力电池材料有限公司 | Method for producing cobalt sulfate by using organic cobalt slag of zinc smelting plant |
| CN113265547A (en) * | 2021-05-26 | 2021-08-17 | 昆明冶金研究院有限公司 | Comprehensive recovery process for zinc hydrometallurgy organic purification cobalt slag |
| CN113881857A (en) * | 2021-09-09 | 2022-01-04 | 云南云铜锌业股份有限公司 | Method for treating cobalt-containing solution produced in wet zinc smelting cadmium recovery process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102851693B (en) | Technology for recovering production of electrolytic copper and zinc from smelting ash | |
| CN103643044B (en) | The direct extracting copper of a kind of Bellamya aeruginosa wet method, zinc technology | |
| CN106119560B (en) | Zinc-cobalt separation method | |
| CN113549766B (en) | Method for removing arsenic from lead smelting smoke dust and recovering valuable metals | |
| CN102534235B (en) | Method for recovering valued metals from cobalt-nickel residue obtained through antimony trioxide purification in zinc hydrometallurgy | |
| CN103160688B (en) | Zinc replacement prepares the method for germanium concentrate from germanic leach liquor | |
| CN106868307A (en) | A kind of pyrite cinder arsenic removal is enriched with the comprehensive utilization process of gold and silver | |
| Herrero et al. | Hydrometallurgical process development for the production of a zinc sulphate liquor suitable for electrowinning | |
| CN102888515A (en) | Comprehensive utilization method of amarillite slag | |
| CN106834693A (en) | A kind of smelting zinc replacement slag wet method comprehensive reutilization method | |
| EA020759B1 (en) | Method of processing nickel bearing raw material | |
| CN109824096A (en) | A method of nickel sulfate is produced by raw material of the low nickel matte of high-speed rail | |
| CN106315682B (en) | A kind of method of richness rhenium slag production ammonium perrhenate | |
| CN104513899A (en) | Process for treating xanthate cobalt slag | |
| CN104195345A (en) | Process for recovering sulfur, lead, zinc and silver from oxygen-enriched directly leached residues of zinc concentrates or lead-zinc mixed ores | |
| CN102994753A (en) | Method for separating and enriching nickel from leach liquor used for pickling and vulcanizing tailing | |
| CN113088710A (en) | Method for separating copper and germanium from copper and germanium replacement slag | |
| CN105907972B (en) | A kind of method of a variety of valuable metals of the synthetical recovery from electroplating sludge | |
| CN105734293B (en) | A kind of high-grade lead copper matte resource comprehensive utilization technique | |
| CN102703700B (en) | Two-stage ammonia leaching-flow distributing extraction method for copper oxide ore | |
| CN114752767A (en) | Method for recovering copper, zinc and nickel from electroplating sludge | |
| CN107142378A (en) | The extracting method of lead in a kind of sintering flue dust | |
| CN108239701B (en) | Method for comprehensively recovering lead and zinc in high-mud carbonate type lead-zinc oxide ore | |
| CN107916434B (en) | A kind of purification method of the in-pulp electrolysis liquid containing antimony concentrate | |
| CN107555469B (en) | A kind of technique preparing zinc sulfate combined producting ammonium chloride with high chlorine cadmia |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20150415 |
|
| WD01 | Invention patent application deemed withdrawn after publication |