CN102031370B - Arsenic salt purified cobalt slag seed crystal, and purification method and application thereof - Google Patents
Arsenic salt purified cobalt slag seed crystal, and purification method and application thereof Download PDFInfo
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- CN102031370B CN102031370B CN2010106209879A CN201010620987A CN102031370B CN 102031370 B CN102031370 B CN 102031370B CN 2010106209879 A CN2010106209879 A CN 2010106209879A CN 201010620987 A CN201010620987 A CN 201010620987A CN 102031370 B CN102031370 B CN 102031370B
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Abstract
The invention provides a purification method of arsenic salt purified cobalt slag seed crystal, the arsenic salt purified cobalt slag seed crystal purified by the method and application of the purified seed crystal to the purification of solution of zinc sulfate during wet zinc smelting. The purification method comprises the following steps of: pulping the arsenic salt purified cobalt slag seed crystal to obtain seed crystal pulp; mixing acid and the seed crystal pulp; and performing solid-liquid separation. The purification method can effectively improve the activity of the arsenic salt purified cobalt slag seed crystal produced in the wet zinc smelting process, is easy to operate, reduces production cost, is environmentally-friendly, finally improves the quality of an arsenic salt purified product and has obvious economic benefit, and waste residue, waste gas and waste water are not generated.
Description
Technical field
The present invention relates to a kind of method that improves arsenic salt purified cobalt slag seed crystal activity, the arsenic salt purified cobalt slag seed crystal that utilizes the method purifying to obtain, and the application in the purifying zinc sulfate solution in zinc hydrometallurgy of the crystal seed behind this purifying.
Background technology
In the Zinc Hydrometallurgy Process, cobalt is that one of topmost impurity is separated out in the electrolysis of harm zinc.By solution of zinc sulfate electrolytic preparation zinc simple substance the time, the cobalt contents in the electrolytic solution acquires a certain degree, and just separates out at negative electrode, form microbattery with zinc, zinc is discharged into people's solution, not only reduce the current efficiency of zinc electrolysis, also make " burning plate " phenomenon that occurs the double circular hole shape on the zinc metal sheet.The zinc electrolysis is very strict to the content requirement of impurity in the electrolytic solution, and impurity exceeds standard, and electrolysis just can not normally be carried out, and wherein the control of cobalt contents is particularly important, and the cobalt contents in the liquid of looking for novelty is low as far as possible.Therefore, need aborning to take measures most of cobalt was removed from solution before entering electrowinning process.
The purifying method of solution of zinc sulfate mainly contains in the current zinc wet smelting process: xanthate purification method, 2-Naphthol method, the arsenic salt method of purification, antimony trioxide purification method, alloy zinc powder method etc.
Arsenic salt Cobalt Purification is in certain temperature and has under the condition of cupric ion existence, utilize Cu-Zn microbattery potential difference that cobalt is easy in Cu-Zn microbattery negative electrode discharge reduction, form the principle of Zn-Cu-Co alloy, effect by the white arsenic that in solution, adds and zinc powder and the underflow crystal seed that returns, in solution, form stable As-Cu-Co (Zn) alloy, thereby make the Co2+ in the solution out make the cobalt in the solution of zinc sulfate drop to the degree that is fit to electrolysis with alloy form precipitate and separate from solution.
Main chemical reactions:
2Co
2++2As
3++5Zn＝2CoAs↓+5Zn
2+……………(1)
2Ni
2++2As3++5Zn＝2NiAs↓+5Zn
2+…………(2)
6Cu
2++2As
3++9Zn＝2Cu3As↓+9Zn
2+………(3)
CoAs, NiAs and Cu3As are not arsenide, but the alloy of cobalt, nickel, copper and arsenic.Germanium and antimony also occur coprecipitated, enter filter residue.
Existing operation steps is: the first step, with the white arsenic dissolution of sodium hydroxide, second step, sodium hydroxide solution, zinc powder after the dissolving, cobalt slag (underflow) crystal seed that returns are mixed with the solution of zinc sulfate that contains cobalt, under whipped state, react, obtain containing the mixture of the multiple alloy, solid chemical compound, remaining zinc powder, solution of zinc sulfate etc. of heterogeneity; The 3rd step, the mixture of solution of zinc sulfate and slag is separated (as with pressure filter or thickener with liquid-solid separation equipment, or leave standstill natural separation), the precipitations such as alloy, solid chemical compound, remaining zinc powder enter in the slag, obtain arsenic salt purified cobalt slag, in the 4th step, the amounts of cobalt slag is returned second step as crystal seed use.
The applicant finds that aborning the arsenic salt purified cobalt slag of different batches (underflow cobalt slag) is different on one-tenth is grouped into, thereby its active different except cobalt in be incorporated into except the cobalt system as crystal seed the time.In addition, cobalt slag crystal seed is after long-time the use, and also there is downward trend in activity.If drive away cobalt impurity according to fixing schedule of operation, the cobalt contents less stable after then processing in the material or second-rate.
Summary of the invention
For the different batches crystal seed that solves present existence becomes to be grouped into different problems, the object of the invention is to propose a kind of purification process of arsenic salt purified cobalt slag.
Purification process provided by the invention may further comprise the steps: with the pulp of arsenic salt purified cobalt slag seed crystal, obtain crystal seed pulp liquid; Acid is mixed with crystal seed pulp liquid; And carry out solid-liquid separation.
Further, can adopt the electrolysis waste solution that produces in sulfuric acid or the Zinc Hydrometallurgy Process to mix with crystal seed pulp liquid.
Further, water or solution of zinc sulfate are mixed with described arsenic salt purified cobalt slag seed crystal, obtain crystal seed pulp liquid.
Further, the liquid-solid ratio of crystal seed pulp liquid is 0.5: 1～10: 1.
Further, the system pH that forms after acid mixes with crystal seed pulp liquid is between 0.5～4.5.
Further, the system pH that forms after acid mixes with crystal seed pulp liquid is between 3.0～4.5.
Another object of the present invention is to provide a kind of arsenic salt purified cobalt slag seed crystal, utilize purification process provided by the invention that arsenic salt purified cobalt slag seed crystal crude product is processed, prepare arsenic salt purified cobalt slag seed crystal.
Also purpose of the present invention is, the arsenic salt purified cobalt slag seed crystal behind the purifying provided by the invention is applied in the purification of solution of zinc sulfate in the zinc hydrometallurgy.
Arsenic salt purified cobalt slag seed crystal purification process provided by the invention, Effective Raise the activity of arsenic salt purified cobalt slag seed crystal, and operating process is simple, reduced production cost, do not increase waste residue, waste gas, discharge of wastewater, non-environmental-pollution finally promotes the quality of arsenic salt purified product, remarkable in economical benefits.
Description of drawings
Fig. 1 is an exemplary process flow figure according to the inventive method.
Embodiment
Describe the specific embodiment of the present invention in detail below in conjunction with accompanying drawing 1.
The present invention is the method by the interpolation mineral acid, purifies the cobalt slag crystal seed that produces with arsenic salt and reacts, and generates new crystal seed, and new crystal seed has higher activity.Mineral acid can be sulfuric acid, hydrochloric acid or phosphoric acid.These acid can be without the acid of using, and also can be industrial waste acid.As preferably, sulfuric acid and nitric acid are only, because sulfuric acid has good ionic strength, can not volatilize in addition, and operating worker is not poisoned; And nitric acid also has higher oxidisability except having strength of acid, and processing efficiency can be higher.Consider at cost, preferably use industrial waste acid, vitriolated smelting byproducts for example perhaps contains the industrial waste acid of nitric acid.
In the present invention, the pH value with the cobalt slag crystal seed pulp liquid after the acid adjusting suits between 0.5～4.5.Excessive concentration then is unfavorable for the control of process, is unfavorable for that also it returns rear control to system as new crystal seed; Concentration is excessively low, and then speed of response is too slow.Preferably between 3.0～4.5, the contriver finds that in the pH scope, it is reasonable to process the new crystal seed composition that obtains to this pH value, is beneficial to system's control.It is the most suitable that acid concentration in the acid treatment system is controlled at this scope, can finish in the short period of time and process operation.
The acid-treated time, this time can be adjusted accordingly according to the size of acid concentration usually at 0.1～1 hour.
In a kind of favourable embodiment of the present invention, adopt the electrolysis waste solution that produces in the Zinc Hydrometallurgy Process as acid source, with the reaction of arsenic salt purified cobalt slag seed crystal, to activate this cobalt slag crystal seed.This electrolysis waste solution is provided by the zinc electrowinning process usually, that is after the electrolysis of solution of zinc sulfate process, zine ion is separated out to become and separated out zinc metal sheet, and emits oxygen, and last solution contains acid and remaining zine ion etc., at this moment sulfuric acid content 140～210g/l.
Because arsenic salt Cobalt Purification terminal point acidity is very low, form a large amount of settlings miscellaneous at cobalt slag seed surface, when returning as crystal seed, various settlings have hindered contacting of foreign ion in crystal seed effective constituent and the solution, have reduced the activity of crystal seed.After the process vitriolization, the part that settling in the cobalt slag crystal seed reaches than active metal (zinc) is dissolved in the solution, and so, each effective ingredient in the crystal seed is exposed out, be conducive to solution in the contacting of foreign ion (being mainly cobalt), to reach the order that is removed.
Arsenic salt purified cobalt slag chemical ingredients of the present invention is respectively Co 0.1～10%, Cu 5～70%, Zn 3～45%, As 3～40% by weight percentage, also has a small amount of Cd, Sb, Ge, Au, Ag, Bi, Ni, Mn etc.After acid treatment, the metallic zinc content ratio rises, and the zinc ion content ratio descends, and is dissolved in acid because zine ion is easier.The dissolving of zine ion causes more metallic zinc and alloy exposed, so have high reactivity.
Fig. 1 illustrates a kind of exemplary embodiment of the present invention, and concrete steps are: the first step with solution of zinc sulfate or water slurry, makes it become the soup compound that is easy to carry arsenic salt purified cobalt slag, and makes next step pickling reaction be easy to carry out.Solution of zinc sulfate used herein can be except the new liquid before liquid behind the cobalt or the zinc electrolysis from zinc hydrometallurgy.Carry out at water in the situation of pulp, the liquid-solid ratio after the pulp is 0.5: 1～10: 1.Second step, the arsenic salt purified cobalt slag that pulp is good mixes with acid, opens the stirrer stirring, reacts 0.2～8 hour, obtains containing new crystal seed, contains the mixture of polymictic solution of zinc sulfate etc.; The 3rd step, the mixture of solution of zinc sulfate and slag is separated (as with pressure filter or thickener, or leaving standstill natural separation) with liquid-solid separation equipment, solids is the new crystal seed that obtains.Filtrate then enters next step to reclaim zinc.
The below introduces several specific embodiments.
Embodiment 1:
Arsenic salt purified cobalt slag seed crystal chemical ingredients: Co 1.54%, Zn 25.36%, Cu 25.10%, As 7.23%, manufacturing condition sees Table 1:
Table 1: the processing condition that improve arsenic salt purified cobalt slag seed crystal quality
| Pulp cobalt slag volume (m 3) | Pickling pH | Temperature (℃) | Reaction times (h) |
| 12 | 3.0 | 70 | 0.2 |
The chemical ingredients of new crystal seed after the pickling: Co 1.71%, Zn 19.15%, Cu 28.10%, As 6.88%.
Embodiment 2:
Arsenic salt purified cobalt slag chemical ingredients: Co 1.80%, Zn 28.17%, Cu 26.22%, As 6.58%, the pickle solution that uses is electrolysis spent.Manufacturing condition sees Table 2:
Table 2: the processing condition that improve arsenic salt purified cobalt slag seed crystal quality
| Pulp cobalt slag volume (m 3) | Pickling pH | Temperature (℃) | Reaction times (h) |
| 12 | 4.0 | 75 | 0.3 |
The chemical ingredients of new crystal seed after the pickling: Co 2.0%, Zn 18.76%, Cu 28.63%, As 7.80%.
Embodiment 3:
Arsenic salt purified cobalt slag chemical ingredients: Co 2.75%, Zn 27.68%, Cu 35.22%, As 11.42%, manufacturing condition sees Table 3:
Table 3: the processing condition that improve arsenic salt purified cobalt slag seed crystal quality
| Pulp cobalt slag volume (m 3) | Pickling pH | Temperature (℃) | Reaction times (h) |
| 12 | 4.5 | 73 | 0.4 |
The chemical ingredients of new crystal seed after the pickling: Co 2.91%, Zn 23.52%, Cu 38.35%, As 13.22%.
Among above-mentioned three embodiment, variation has occured in the composition of processing forward and backward cobalt slag crystal seed, wherein cobalt, copper, arsenic content increase, the zinc content, this is that we expect, because this means that crystal seed effective constituent is exposed in a large amount of settling dissolvings miscellaneous of cobalt slag seed surface, be conducive to solution in the contacting of foreign ion, except therefore the cobalt effect can improve.
Embodiment 4
With processing forward and backward cobalt slag crystal seed among the embodiment 1-3, remove cobalt according to following operation: the first step: cobalt slag after the pickling is carried out liquid-solid separation, obtain solid or contain the new crystal seed of a small amount of liquid, second step: new crystal seed is added except the first groove of cobalt groove, in first groove, add simultaneously zinc powder, waste electrolyte and arsenic salt, interior temperature 70-80 ℃ of control flume, pH4.5-5.0.Table 4 list respectively test product except the cobalt result.
The forward and backward crystal seed of table 4 cobalt slag pickling is except the cobalt effect
As can be seen from Table 4: after overpickling, new cobalt slag crystal seed removes cobalt except the cobalt slag crystal seed that the cobalt effect is better than without pickling, and the control quality is more stable.
The slag that the present invention produces during the arsenic salt method of purification is dezincified is reintroduced to except the cobalt system as cobalt slag crystal seed, and uses acid treatment before introducing, and for example sulfuric acid generates new crystal seed, and this new crystal seed has stronger activity.The effect that new crystal seed returns use than pickling before crystal seed be significantly improved.The present invention can make the quality of the cobalt slag crystal seed that produces in the arsenic salt scavenging process be promoted, but Effective Raise improves the quality except liquid behind the cobalt except the effect of cobalt after the retrieval system, reduce production costs simultaneously, do not increase waste residue, waste gas, discharge of wastewater, non-environmental-pollution, remarkable in economical benefits.
Claims (4)
1. the purification process of an arsenic salt purified cobalt slag seed crystal is characterized in that, described purification process comprises:
Water or solution of zinc sulfate are mixed with described arsenic salt purified cobalt slag seed crystal, obtain liquid-solid ratio and be 0.5: 1～10: 1 crystal seed pulp liquid;
Acid is mixed with described crystal seed pulp liquid, form the system of pH value between 0.5～4.5, described acid is the electrolysis waste solution that produces in sulfuric acid or the Zinc Hydrometallurgy Process; And
Carry out solid-liquid separation.
2. purification process according to claim 1 is characterized in that, the system pH that forms after described acid mixes with crystal seed pulp liquid is between 3.0～4.5.
3. an arsenic salt purified cobalt slag seed crystal is characterized in that, utilizes claim 1 or 2 described purification process that arsenic salt purified cobalt slag seed crystal crude product is processed, and is prepared from described arsenic salt purified cobalt slag seed crystal.
4. arsenic salt purified cobalt slag seed crystal claimed in claim 3 application in the purifying zinc sulfate solution in zinc hydrometallurgy.
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| CN102417984B (en) * | 2011-12-09 | 2013-04-24 | 株洲冶炼集团股份有限公司 | Method for purifying zinc sulfate solution |
| CN111074073B (en) * | 2020-01-08 | 2021-07-09 | 昆明理工大学 | Method for purifying and removing cobalt in zinc hydrometallurgy |
| CN113637855B (en) * | 2021-08-13 | 2022-11-15 | 赤峰中色锌业有限公司 | Method for purifying and removing arsenic in zinc hydrometallurgy system |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US5275228A (en) * | 1990-12-13 | 1994-01-04 | Sulzer-Mtu Casting Technology Gmbh | Process and apparatus for production of single-crystal turbine blades |
| CN101713031A (en) * | 2009-10-26 | 2010-05-26 | 德阳市南邡有色金属有限公司 | Method for removing impurities by oxidation in process of zinc hydrometallurgy |
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| US5275228A (en) * | 1990-12-13 | 1994-01-04 | Sulzer-Mtu Casting Technology Gmbh | Process and apparatus for production of single-crystal turbine blades |
| CN101713031A (en) * | 2009-10-26 | 2010-05-26 | 德阳市南邡有色金属有限公司 | Method for removing impurities by oxidation in process of zinc hydrometallurgy |
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| JP特开2004-307592A 2004.11.04 |
| 马杨辉等.湿法炼锌锑盐锌粉除钴的生产实践.《中国有色冶金》.2005,(第1期),22-23，68-69. * |
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