CN104480306A - Method for processing hydrochloric acid leaching liquid of zinc-containing nickel-cobalt hydroxide material - Google Patents
Method for processing hydrochloric acid leaching liquid of zinc-containing nickel-cobalt hydroxide material Download PDFInfo
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- CN104480306A CN104480306A CN201410733195.0A CN201410733195A CN104480306A CN 104480306 A CN104480306 A CN 104480306A CN 201410733195 A CN201410733195 A CN 201410733195A CN 104480306 A CN104480306 A CN 104480306A
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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
Abstract
The invention relates to a method for processing a hydrochloric acid leaching liquid of a zinc-containing nickel-cobalt hydroxide material, and particularly relates to a method for separating nickel, cobalt and zinc by extracting the hydrochloric acid leaching liquid of a nickel-cobalt hydroxide material which is an intermediate material in the treatment process of laterite. The treatment process comprises the following steps: extracting the hydrochloric acid leaching liquid of the zinc-containing nickel-cobalt hydroxide material by using N235 extract liquor, organically carrying out nickel washing and cobalt stripping on loads, and adding ammoniac strip liquor into a zinc-loaded organic phase to carry out zinc stripping; and separating to obtain a zinc-loaded water phase and an organic phase. The ammoniac zinc stripping liquor is treated for cycle use. Zinc after accumulation can be opened in a zinc residue form, chlorine roots brought by ammonium ions and the organic phase form ammonium chloride crystal substances so as to be opened through filtering, and the phase splitting process is quick, no influence on the organic phase is generated and waste water is not exhausted. The process is simple, has a cost far lower than the existing production cost and is easy to implement.
Description
Technical field
Containing a treatment process for zinc nickel hydroxide cobalt material salt pickling liquor, relate to the method for the hydrochloric acid leachate extracting and separating nickel of the intermediate material nickel hydroxide cobalt material of output in a kind of laterite treating processes, cobalt, zinc.
Background technology
Nickel hydroxide cobalt material is a kind of intermediate material in laterite treating processes, higher containing zinc in raw material, and by the process of Leaching in Hydrochloric Acid production electrodeposited cobalt or other nickel products, zinc is a kind of impurity that must deviate from.Deviate from the method for zinc in conventional Leaching in Hydrochloric Acid solution, be adopt resin to dezincify, cost is higher, and more applicable to the solution of zinc content lower (being less than 0.1g/L); Or adopt extraction process to dezincify, as P204, P507 and N235 extraction agent etc., although all zinc can be extracted in organic phase.But P204, P507 zinc supported is organic, need adopt high acid solution back extraction, the zinc that gets off of back extraction is difficult to open circuit process, sinks zinc according to neutralisation, and one is the significantly rising that the anti-zinc liquid of peracid brings alkaline consumption; Two is cause other valuable metals in anti-zinc liquid to be difficult to recycle.And N235 zinc supported organic phase, adopt the alkali lye of proper concn, salpeter solution and oxalic acid solution etc. all zinc back extraction can be got off, but anti-zinc liquid can not recycle, the wastewater flow rate of outer row is very large, and the consumption of reagent consumption and water is all very large, and enterprise is difficult to bear.
Therefore, for the hydrochloric acid leachate that Zn content is higher, lack treatment process that is economic, low cost for a long time.
Summary of the invention
Object of the present invention is exactly the deficiency existed for above-mentioned prior art, there is provided a kind of reasonable open circuit problem that effectively can solve zinc, treating processes does not have the treatment process containing the pickling liquor of zinc nickel hydroxide cobalt material salt that ammonia discharge of wastewater, organic phase are capable of circulation, process facility is simple, reagent consumption is low, easy to implement.
The object of the invention is to be achieved through the following technical solutions.
Containing a treatment process for zinc nickel hydroxide cobalt material salt pickling liquor, the step of its treating processes comprises:
(1) N235 extraction liquid will be adopted to extract containing the pickling liquor of zinc nickel hydroxide cobalt material salt;
(2) separation obtains the organic phase of Supported Co and zinc and the aqueous phase of nickel-loaded;
(3) organic phase being separated Supported Co and the zinc obtained is carried out the reaction of water back extraction cobalt;
(4) separation obtains the organic phase of zinc supported and the aqueous phase of Supported Co;
It is characterized in that its step also comprises:
(5) be separated the zinc supported organic phase obtained and add the back extraction that ammonia strip liquor carries out zinc;
(6) separation obtains the aqueous phase of zinc supported and does not contain the organic phase of zinc.
A kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt of the present invention, is characterized in that the volume proportion of the N235 extraction liquid of its step (1) is: 25% N235+7% isooctyl alcohol+68% solvent oil.
A kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt of the present invention, it is characterized in that the organic phase being separated the zinc supported obtained is carried out water extraction and reacted the ammonia water extraction liquid added by its step (5), for the mixing solutions of ammoniacal liquor and volatile salt or bicarbonate of ammonia, containing ammonia weight concentration in water extraction liquid is 2%-3%, and the concentration containing volatile salt or bicarbonate of ammonia is 80-150g/L; What water extraction was reacted is in a ratio of 3-4:1(O/A), after mix and blend 3-10min, clarification phase-splitting 5-15min.
A kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt of the present invention, is characterized in that its step (6) is separated the organic phase obtained and returns step (1).
A kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt of the present invention, after it is characterized in that aqueous phase that its step (6) is separated the zinc supported obtained supplements ammoniacal liquor and volatile salt or bicarbonate of ammonia, returns step (5).
A kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt of the present invention, is characterized in that aqueous phase that its step (6) is separated the zinc supported obtained is crossed and filters crystallisate, then return step (5), recycle.
A kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt of the present invention, it is characterized in that its step (6) is separated the aqueous phase obtaining zinc supported and returns step (5) the aqueous phase zinc content carrying out being circulated to containing zinc when being greater than 10g/L, add ammonium sulfide or hydrogen sulfide ammonium carries out heavy zinc reaction, filtering-depositing isolates zinc sulphide, after adding ammoniacal liquor and volatile salt or bicarbonate of ammonia by ratio requirement again, return step (5) again, continue to recycle.
A kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt of the present invention, N235 extraction liquid will be adopted to extract containing the pickling liquor of zinc nickel hydroxide cobalt material salt, hydrochloric acid soln through separating nickel, cobalt enters conventional nickel, cobalt Production Flow Chart, is separated the organic phase obtaining zinc supported and adds the back extraction that ammonia strip liquor carries out zinc; Adding ammonium ion object is make the zinc in organic phase and ammonia form ammonium complex ion, add carbonic acid in order in and organic phase in acid, effectively improve the efficiency of back extraction zinc.
A kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt of the present invention, ammonia knock back zinc liquid process Posterior circle uses, zinc is opened a way with cadmia form, the chlorine root that ammonium ion and organic phase are brought into can form ammonium chloride crystals thing and filter and open a way, process phase-splitting is fast, organic phase is not had any impact, there is no efflux wastewater.And technique is simple, far below existing production cost, easy to implement.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of method of the present invention.
Embodiment
Containing a treatment process for zinc nickel hydroxide cobalt material salt pickling liquor, the step of its treating processes comprises:
(1) N235 extraction liquid is adopted to carry out (proportioning 25% N235+7% isooctyl alcohol+68% solvent oil) extraction containing the pickling liquor of zinc nickel hydroxide cobalt material salt;
(2) separation obtains the organic phase of Supported Co and zinc and the aqueous phase of nickel-loaded;
(3) organic phase being separated Supported Co and the zinc obtained is carried out the reaction of water back extraction cobalt;
(4) separation obtains the organic phase of zinc supported and the aqueous phase of Supported Co;
(5) be separated the zinc supported organic phase obtained and add the back extraction that ammonia strip liquor carries out zinc; The anti-zinc liquid of ammonia is the mixing solutions of ammoniacal liquor and volatile salt (or bicarbonate of ammonia), and matched proportion density, for being 2%-3% containing ammonia density, is 80-150g/L containing volatile salt (or bicarbonate of ammonia) concentration; Its stripping process is by 3-4:1(O/A) compare and add the anti-zinc liquid of ammonia, after mix and blend 3-10min, clarification phase-splitting 5-15min;
6) separation obtains the aqueous phase of zinc supported and does not contain the organic phase of zinc; Organic phase Returning process uses, and adds ammoniacal liquor and volatile salt (or bicarbonate of ammonia) recycles as anti-zinc liquid containing the aqueous phase of zinc by ratio requirement;
When described back extraction zinc liquid recycles in process, constantly raise containing zinc, when being greater than 10g/L, the amount risen by per kilogram zinc 4-7 adds industrial ammonium sulfide or hydrogen sulfide ammonium solution and sinks zinc, and heavy zinc technology condition is normal temperature, reaction times 20-30min, sulfuration cadmia is obtained, containing zinc about 55% after filtration; After heavy zinc, filtrate is as after the anti-zinc of anti-zinc liquid condition, then after adding ammoniacal liquor and volatile salt or bicarbonate of ammonia by ratio requirement, continues to recycle, so circulate, whole process non-wastewater discharge.
(more than 5 times) in process are recycled when back extraction zinc liquid, the chlorine root that the ammonium ion added and organic phase are brought into can form the crystallization (not affecting phase-splitting) of ammonium chloride in anti-zinc liquid, crossed by anti-zinc liquid in process and filter crystallisate, ammonium ion and chlorine root can obtain opening a way and process.
Embodiment 1
To zinc 2.01g/L, nickeliferous 169.11g/L be contained, adopt N235(proportioning 25% N235+7% isooctyl alcohol+68% solvent oil containing the Leaching in Hydrochloric Acid solution of cobalt 5.75 g/L) extracting and separating nickel cobalt (comparing 3:1), organic phase, after washing nickel, anti-cobalt process, obtains the N235 organic phase containing zinc 0.68g/L.Organicly add anti-zinc liquid by comparing of 3:1 by what obtain, anti-zinc liquid, containing ammonia 2.0%, prepare containing volatile salt 80 g/L, mix and blend 10min, after clarification phase-splitting 5min, organic containing zinc 0.066g/L after anti-zinc, Returning process use, the anti-zinc rate 91% of process; Anti-zinc liquid fills into ammonia by the concentration of 2.0%, after filling into volatile salt, recycles as anti-zinc liquid by the concentration of 80 g/L; After recycling 4 times, in aqueous phase, producing a small amount of ammonium chloride crystals thing, filtering by crossing; When being accumulated to 13g/L containing zinc in anti-zinc liquid, adding industrial ammonium sulfide solution sink zinc by the amount of 6 liters, per kilogram zinc, heavy zink rod part is normal temperature, and time 20min, obtains sulfuration cadmia after filtration, containing zinc 53.33%; The outer row of sulfuration cadmia open circuit, filtrate Returning process, as anti-zinc liquid, continues to recycle as previously mentioned.
Embodiment 2
To contain zinc 1.57g/L, nickeliferous 171.0g/L, adopt N235 extracting and separating nickel cobalt (comparing 3:1) containing the Leaching in Hydrochloric Acid solution of cobalt 6.31 g/L, organic phase, after washing nickel, anti-cobalt process, obtains the N235 organic phase containing zinc 0.57g/L; Organicly add anti-zinc liquid by comparing of 4:1 by what obtain, anti-zinc liquid, containing ammonia 2.5%, prepare containing bicarbonate of ammonia 110g/L, mix and blend 5min, after clarification phase-splitting 10min, organic containing zinc 0.035g/L after anti-zinc, Returning process use, the anti-zinc rate 94% of process; Anti-zinc liquid fills into ammonia by the concentration of 2.5%, after filling into bicarbonate of ammonia, recycles as anti-zinc liquid by the concentration of 110g/L; After recycling 4 times, in aqueous phase, producing a small amount of ammonium chloride crystals thing, filtering by crossing; When being accumulated to 12g/L containing zinc in anti-zinc liquid, adding industrial ammonium sulfide solution sink zinc by the amount of 5 liters, per kilogram zinc, heavy zink rod part is normal temperature, and reaction times 30min, obtains sulfuration cadmia after filtration, containing zinc 54.63%; The outer row of sulfuration cadmia open circuit, filtrate Returning process, as anti-zinc liquid, continues to recycle as previously mentioned.
Embodiment 3
To contain zinc 1.35g/L, nickeliferous 161.81g/L, adopt N235 extracting and separating nickel cobalt (comparing 3:1) containing the Leaching in Hydrochloric Acid solution of cobalt 5.03 g/L, organic phase, after washing nickel, anti-cobalt process, obtains the N235 organic phase containing zinc 0.48g/L; Organicly add anti-zinc liquid by comparing of 3:1 by what obtain, anti-zinc liquid, containing ammonia 3.0%, prepare containing bicarbonate of ammonia 150g/L, mix and blend 3min, after clarification phase-splitting 15min, organic containing zinc 0.0047g/L after anti-zinc, Returning process use, the anti-zinc rate 99% of process; Anti-zinc liquid fills into ammonia by the concentration of 3.0% again, after filling into bicarbonate of ammonia, recycles as anti-zinc liquid by the concentration of 150g/L; After recycling 6 times, in aqueous phase, producing a small amount of ammonium chloride crystals thing, filtering by crossing; When being accumulated to 15g/L containing zinc in anti-zinc liquid, adding industrial ammonium sulfide solution sink zinc by the amount of 7 liters, per kilogram zinc, heavy zink rod part is normal temperature, and reaction times 30min, obtains sulfuration cadmia after filtration, containing zinc 51.56%; The outer row of sulfuration cadmia open circuit, filtrate Returning process, as anti-zinc liquid, continues to recycle as previously mentioned.
Claims (7)
1. containing a treatment process for zinc nickel hydroxide cobalt material salt pickling liquor, the step of its treating processes comprises: (1) will adopt N235 extraction liquid to extract containing the pickling liquor of zinc nickel hydroxide cobalt material salt;
(2) separation obtains the organic phase of Supported Co and zinc and the aqueous phase of nickel-loaded;
(3) organic phase being separated Supported Co and the zinc obtained is carried out the reaction of water back extraction cobalt;
(4) separation obtains the organic phase of zinc supported and the aqueous phase of Supported Co;
It is characterized in that its step also comprises:
(5) be separated the zinc supported organic phase obtained and add the back extraction that ammonia strip liquor carries out zinc;
(6) aqueous phase and the organic phase that obtain zinc supported is separated.
2. a kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt according to claim 1, is characterized in that the volume proportion of the N235 extraction liquid of its step (1) is: 25% N235+7% isooctyl alcohol+68% solvent oil.
3. a kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt according to claim 1, it is characterized in that the organic phase being separated the zinc supported obtained is carried out water extraction and reacted the ammonia water extraction liquid added by its step (5), for the mixing solutions of ammoniacal liquor and volatile salt or bicarbonate of ammonia, containing ammonia weight concentration in water extraction liquid is 2%-3%, and the concentration containing volatile salt or bicarbonate of ammonia is 80-150g/L; What water extraction was reacted is in a ratio of 3-4:1(O/A), after mix and blend 3-10min, clarification phase-splitting 5-15min.
4. a kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt according to claim 1, is characterized in that its step (6) is separated the organic phase obtained and returns step (1).
5. a kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt according to claim 1, after it is characterized in that aqueous phase that its step (6) is separated the zinc supported obtained supplements ammoniacal liquor and volatile salt or bicarbonate of ammonia, returns step (5).
6. a kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt according to claim 1, is characterized in that aqueous phase that its step (6) is separated the zinc supported obtained is crossed and filters crystallisate, then return step (5), recycle.
7. a kind for the treatment of process containing the pickling liquor of zinc nickel hydroxide cobalt material salt according to claim 1, it is characterized in that its step (6) is separated the aqueous phase obtaining zinc supported and returns step (5) the aqueous phase zinc content carrying out being circulated to containing zinc when being greater than 10g/L, add ammonium sulfide or hydrogen sulfide ammonium carries out heavy zinc reaction, filtering-depositing isolates zinc, after adding ammoniacal liquor and volatile salt or bicarbonate of ammonia by ratio requirement again, return step (5) again, continue to recycle.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410733195.0A CN104480306A (en) | 2014-12-07 | 2014-12-07 | Method for processing hydrochloric acid leaching liquid of zinc-containing nickel-cobalt hydroxide material |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201410733195.0A CN104480306A (en) | 2014-12-07 | 2014-12-07 | Method for processing hydrochloric acid leaching liquid of zinc-containing nickel-cobalt hydroxide material |
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| CN104480306A true CN104480306A (en) | 2015-04-01 |
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| CN201410733195.0A Pending CN104480306A (en) | 2014-12-07 | 2014-12-07 | Method for processing hydrochloric acid leaching liquid of zinc-containing nickel-cobalt hydroxide material |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109266856A (en) * | 2018-09-13 | 2019-01-25 | 桐乡市思远环保科技有限公司 | The method of zinc is recycled from pickle liquor using solvent extraction |
Citations (3)
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|---|---|---|---|---|
| CN1148029A (en) * | 1995-10-16 | 1997-04-23 | 李寅高 | Method for treating waste water contg. ammonia and zinc from dry cell factory |
| CN1827803A (en) * | 2006-03-30 | 2006-09-06 | 中南大学 | Iron slag free wet-method zinc smelting and indium extracting method and method for preparing zinc ferrite |
| CN102242266A (en) * | 2011-06-15 | 2011-11-16 | 金川集团有限公司 | Process for recovering cobalt, copper, zinc and manganese in manganese chloride residual liquid |
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2014
- 2014-12-07 CN CN201410733195.0A patent/CN104480306A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1148029A (en) * | 1995-10-16 | 1997-04-23 | 李寅高 | Method for treating waste water contg. ammonia and zinc from dry cell factory |
| CN1827803A (en) * | 2006-03-30 | 2006-09-06 | 中南大学 | Iron slag free wet-method zinc smelting and indium extracting method and method for preparing zinc ferrite |
| CN102242266A (en) * | 2011-06-15 | 2011-11-16 | 金川集团有限公司 | Process for recovering cobalt, copper, zinc and manganese in manganese chloride residual liquid |
Non-Patent Citations (2)
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| 包福毅等: "氯化浸出镍溶液中钴的分离和回收", 《有色冶金》 * |
| 汪家鼎等主编: "《溶剂萃取手册》", 31 January 2001 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109266856A (en) * | 2018-09-13 | 2019-01-25 | 桐乡市思远环保科技有限公司 | The method of zinc is recycled from pickle liquor using solvent extraction |
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