CN102191381B - Method for removing calcium and manganese from nickel sulfate solution without saponification extraction - Google Patents
Method for removing calcium and manganese from nickel sulfate solution without saponification extraction Download PDFInfo
- Publication number
- CN102191381B CN102191381B CN2010101287015A CN201010128701A CN102191381B CN 102191381 B CN102191381 B CN 102191381B CN 2010101287015 A CN2010101287015 A CN 2010101287015A CN 201010128701 A CN201010128701 A CN 201010128701A CN 102191381 B CN102191381 B CN 102191381B
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- CN
- China
- Prior art keywords
- extraction
- solution
- nickel sulfate
- sulfate solution
- manganese
- 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.)
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Links
- 238000000605 extraction Methods 0.000 title claims abstract description 38
- 239000011575 calcium Substances 0.000 title claims abstract description 25
- 239000011572 manganese Substances 0.000 title claims abstract description 21
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 19
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title claims abstract description 17
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 title claims abstract description 14
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 title claims abstract description 14
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims abstract description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 238000007127 saponification reaction Methods 0.000 title abstract description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000012074 organic phase Substances 0.000 claims abstract description 7
- 238000002474 experimental method Methods 0.000 claims abstract description 3
- 239000003350 kerosene Substances 0.000 claims abstract description 3
- 239000000463 material Substances 0.000 claims abstract description 3
- 238000006386 neutralization reaction Methods 0.000 claims abstract description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 2
- 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 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 150000004965 peroxy acids Chemical class 0.000 claims description 2
- 239000002244 precipitate Substances 0.000 claims description 2
- 229910052925 anhydrite Inorganic materials 0.000 abstract 1
- 239000008346 aqueous phase Substances 0.000 abstract 1
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 abstract 1
- 239000012071 phase Substances 0.000 abstract 1
- 239000000126 substance Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 14
- 150000002815 nickel Chemical class 0.000 description 7
- 239000012452 mother liquor Substances 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000004160 Ammonium persulphate Substances 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 1
- 235000019395 ammonium persulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- HIRWGWMTAVZIPF-UHFFFAOYSA-N nickel;sulfuric acid Chemical compound [Ni].OS(O)(=O)=O HIRWGWMTAVZIPF-UHFFFAOYSA-N 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000007704 transition Effects 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)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention discloses a method for removing calcium and manganese from a nickel sulfate solution without saponification extraction, which is characterized in that an extractant does not need saponification treatment, and Ca and Mn are removed directly through extraction. The extractant used in the invention is P204; in order to guarantee the removal rate of Ca and Mn from the nickel sulfate solution, the extraction process disclosed by the invention employs a neutralization form to maintain the pH value of the solution during the extraction process at 3.0-3.5. The experiment conditions are as follows: the organic phase is composed of 25% of P204 and 75% of sulfonated kerosene; the stripping agent is a sulfuric acid solution with the pH value of 0.5; the washing agent is pure water; the phase ratios meet extraction O/A (organic phase/aqueous phase) = 1:1.5, reverse extraction O/A ratio = 1:0.5, and washing O/A ratio = 1:1; and the pre-extraction solution meets pH value >= 4.5. In order to further recover Ni from the reverse extraction solution, concentrated sulfuric acid is added to the reverse extraction solution to precipitate Ca in the form of CaSO4, the solution is filtered, and the obtained high-acidity Ni-containing water is returned to a chemical material process for use.
Description
Technical field
The present invention relates to a kind of method of in nickel sulfate solution, removing most of calcium, manganese, particularly a kind of from the single nickel salt crystalline mother solution, go on foot the method that saponifiable extraction is removed calcium in the nickel sulfate solution, manganese of exempting from of removing most of calcium, manganese with discontinuous single-stage extraction one.
Background technology
Qualified nickel sulfate solution is produced qualified crystalline sulfuric acid nickel through condensing crystal, and in the mother liquor after the crystallization enrichment Ca, Mn, just can not continue again condensing crystal, if produce qualified product, just need to carry out again purifying treatment.About from nickel sulfate solution, removing the treatment process of most of Ca, Mn:
1, individual curing:
A. with NaF or NiF
2Except Ca
B. remove Mn with ammonium persulphate
Owing to brought again Na in the single nickel salt mother liquor
+And NH
+With F-thickening equipment is had corrosion, the quality that has affected again the single nickel salt crystallization is difficult to adopt this method.
2, extraction treatment:
Organic phase at first will form the P204 soda soap with the saponification of NaOH solution, uses NiSO again
4Could extract except Ca, Mn behind the solution formation transition P204Ni soap.
Use this kind treatment process need increase extraction equipment newly, so facility investment is large, processing cost is high, and generally speaking, the single nickel salt mother liquor is processed again just as raw material.
Summary of the invention
The technical problem to be solved in the present invention is shortcoming and the problem that exists for above-mentioned technology, in order to overcome the technical deficiency of individual curing single nickel salt mother liquor, the invention provides a kind of method that saponifiable extraction is removed Ca in the nickel sulfate solution, Mn of exempting from.The method technique is simple, and convenient and reliable operation and facility investment are few, and be effective, and processing cost is cheap.
The technical solution adopted for the present invention to solve the technical problems is:
Extraction agent needn't carry out saponification to be processed, and directly extracts and removes most of Ca, Mn.The extraction agent that the present invention adopts is P204, and for guaranteeing the clearance of Ca, Mn in the nickel sulfate solution, the present invention adopts the form of neutralization in extraction process, to keep the pH value of solution=3.0-3.5 of extraction process.
Experiment condition:
Organic phase forms: P204 25%, sulfonated kerosene 75%;
Reverse-extraction agent: pH=0.5 sulphuric acid soln;
Washing composition: pure water;
Compare: extraction O/A=1: 1.5,
Anti-leather O/A=1: 0.5,
Washing O/A=1: 1;
Extraction stoste: pH 〉=4.5.
Be further to reclaim the Ni in the strip liquor, adopt the method that adds the vitriol oil in the strip liquor, impel most of Ca, with CaSO
4Form precipitates after filtering, and this peracid nickel water returns the material operation and uses.
The invention has the beneficial effects as follows:
1. eliminated the P204 extraction agent and must carry out saponification, the consciousness of ability separation of C a, Mn;
2. the present invention separates Ca, Mn from nickel sulfate solution, continues to produce qualified product thereby make the single nickel salt mother liquor can return the condensing crystal operation;
3. the present invention processes Ca, Mn only needs sulfuric acid pure water cost low;
4. present device is simple, meets industry standard HG/T2824-1997, less investment and operation is simple and reliable, safety non-pollution;
5. the present invention has the versatility of removing Ca, Mn in sulfate liquor.
Embodiment
The present invention will be further described below in conjunction with embodiment:
Embodiment:
The single nickel salt mother liquor solution is adjusted pH 〉=4.5, V=2800L.
During extraction: O/A=1: 1.5, extraction kept pH value of solution=3.0-3.5 more than 10 minutes, clarified after 20 minutes, emitted raffinate by the bottom;
During back extraction: O/A=1: 0.5, to strip with the pH=0.5 sulphuric acid soln, back-extraction time was clarified 20 minutes more than 10 minutes, emitted strip liquor by the bottom;
During washing: O/A=1: 1, wash with pure water, its objective is in order to improve organic phase pH value, clarified 2 hours the about 20-30 of washing time second, emit washing water by the bottom, organic phase extracts again.
Extraction equipment: volume 6M3 cone end plastic cylinder, 60 rev/mins stirring system, acid proof recycle pump.
The effect of extracting instruction card:
Its except Ca lead 〉=80%, except Mn lead 〉=60%
Claims (2)
1. exempt from the method that saponifiable extraction is removed calcium in the nickel sulfate solution, manganese for one kind, it is characterized in that: the extraction agent of employing is P204, for guaranteeing the clearance of Ca, Mn in the nickel sulfate solution, in extraction process, adopt the form of neutralization, to keep the pH value of solution=3.0-3.5 of extraction process; Experiment condition: organic phase forms: P204 25%, sulfonated kerosene 75%; Reverse-extraction agent: pH=0.5 sulphuric acid soln; Washing composition: pure water; Compare: extraction O/A=1: 1.5, back extraction O/A=1: 0.5, washing O/A=1: 1; Extraction stoste: pH 〉=4.5.
2. as claimed in claim 1ly exempt from the method that saponifiable extraction is removed calcium in the nickel sulfate solution, manganese, it is characterized in that: be the Ni that further reclaims in the strip liquor, adopt the method that adds the vitriol oil in the strip liquor, impel most of Ca, with CaSO
4Form precipitates after filtering, and this peracid nickel water returns the material operation and uses.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101287015A CN102191381B (en) | 2010-03-19 | 2010-03-19 | Method for removing calcium and manganese from nickel sulfate solution without saponification extraction |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2010101287015A CN102191381B (en) | 2010-03-19 | 2010-03-19 | Method for removing calcium and manganese from nickel sulfate solution without saponification extraction |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102191381A CN102191381A (en) | 2011-09-21 |
| CN102191381B true CN102191381B (en) | 2013-01-02 |
Family
ID=44600244
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2010101287015A Withdrawn - After Issue CN102191381B (en) | 2010-03-19 | 2010-03-19 | Method for removing calcium and manganese from nickel sulfate solution without saponification extraction |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102191381B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102010999B (en) * | 2010-12-24 | 2013-08-28 | 湖南邦普循环科技有限公司 | Method for separating impurities from cobalt and/or nickel solution by non-saponifiable extraction |
| CN102392132A (en) * | 2011-11-29 | 2012-03-28 | 南通库博新材料有限公司 | Iron stripping method without saponification |
| CN103789539A (en) * | 2014-01-24 | 2014-05-14 | 江苏凯力克钴业股份有限公司 | Equipment for removing calcium in cobalt hydrometallurgy process |
| CN106756011A (en) * | 2016-11-25 | 2017-05-31 | 桂林理工大学 | The method that saponification directly extracts calcium is exempted from a kind of synergic solvent extraction from solution |
| CN112760482B (en) * | 2019-11-05 | 2023-01-17 | 格林美股份有限公司 | Method for reducing calcium sulfate deposition in P204 extraction impurity removal process |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730680A (en) * | 2005-09-05 | 2006-02-08 | 有研稀土新材料股份有限公司 | Rare-earth element extraction separation process using nonsaponifying organic extractant |
| CN1986849A (en) * | 2005-12-21 | 2007-06-27 | 北京方正稀土科技研究所有限公司 | No-saponifying pre-grouped extraction and separation process of ion adsorbing RE mineral |
| CN101126127A (en) * | 2007-09-07 | 2008-02-20 | 金川集团有限公司 | Method for eliminating impurity from nickel sulfate solution |
| CN101126128A (en) * | 2007-09-07 | 2008-02-20 | 金川集团有限公司 | Copper eliminating method by extracting nickel chloride solution |
-
2010
- 2010-03-19 CN CN2010101287015A patent/CN102191381B/en not_active Withdrawn - After Issue
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1730680A (en) * | 2005-09-05 | 2006-02-08 | 有研稀土新材料股份有限公司 | Rare-earth element extraction separation process using nonsaponifying organic extractant |
| CN1986849A (en) * | 2005-12-21 | 2007-06-27 | 北京方正稀土科技研究所有限公司 | No-saponifying pre-grouped extraction and separation process of ion adsorbing RE mineral |
| CN101126127A (en) * | 2007-09-07 | 2008-02-20 | 金川集团有限公司 | Method for eliminating impurity from nickel sulfate solution |
| CN101126128A (en) * | 2007-09-07 | 2008-02-20 | 金川集团有限公司 | Copper eliminating method by extracting nickel chloride solution |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102191381A (en) | 2011-09-21 |
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