CN109666800A - One kind removing cobalt agent and its application - Google Patents
One kind removing cobalt agent and its application Download PDFInfo
- Publication number
- CN109666800A CN109666800A CN201910057030.9A CN201910057030A CN109666800A CN 109666800 A CN109666800 A CN 109666800A CN 201910057030 A CN201910057030 A CN 201910057030A CN 109666800 A CN109666800 A CN 109666800A
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- China
- Prior art keywords
- cobalt
- except
- zinc
- agent
- leachate
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- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 173
- 239000010941 cobalt Substances 0.000 title claims abstract description 173
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 173
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 46
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 87
- 239000011701 zinc Substances 0.000 claims abstract description 87
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 84
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims abstract description 47
- 238000003723 Smelting Methods 0.000 claims abstract description 36
- 238000000034 method Methods 0.000 claims abstract description 27
- 235000010288 sodium nitrite Nutrition 0.000 claims abstract description 23
- 239000002893 slag Substances 0.000 claims abstract description 16
- MZGNSEAPZQGJRB-UHFFFAOYSA-N dimethyldithiocarbamic acid Chemical compound CN(C)C(S)=S MZGNSEAPZQGJRB-UHFFFAOYSA-N 0.000 claims abstract description 8
- -1 and in mass ratio Chemical compound 0.000 claims abstract description 5
- 238000002386 leaching Methods 0.000 claims abstract description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 37
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 32
- 239000007788 liquid Substances 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 23
- 239000005870 Ziram Substances 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 19
- DUBNHZYBDBBJHD-UHFFFAOYSA-L ziram Chemical compound [Zn+2].CN(C)C([S-])=S.CN(C)C([S-])=S DUBNHZYBDBBJHD-UHFFFAOYSA-L 0.000 claims description 19
- WQOXQRCZOLPYPM-UHFFFAOYSA-N dimethyl disulfide Chemical compound CSSC WQOXQRCZOLPYPM-UHFFFAOYSA-N 0.000 claims description 18
- 238000001556 precipitation Methods 0.000 claims description 15
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 150000004675 formic acid derivatives Chemical class 0.000 claims description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- 239000003792 electrolyte Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 238000012545 processing Methods 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- GSFSVEDCYBDIGW-UHFFFAOYSA-N 2-(1,3-benzothiazol-2-yl)-6-chlorophenol Chemical compound OC1=C(Cl)C=CC=C1C1=NC2=CC=CC=C2S1 GSFSVEDCYBDIGW-UHFFFAOYSA-N 0.000 claims description 4
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001447 ferric ion Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- 239000012265 solid product Substances 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 15
- 238000011084 recovery Methods 0.000 abstract description 14
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 11
- 238000005868 electrolysis reaction Methods 0.000 abstract description 8
- 239000002244 precipitate Substances 0.000 abstract description 3
- 230000001681 protective effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 33
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 28
- 229910052748 manganese Inorganic materials 0.000 description 28
- 239000011572 manganese Substances 0.000 description 28
- 238000001914 filtration Methods 0.000 description 22
- 239000007787 solid Substances 0.000 description 12
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000000706 filtrate Substances 0.000 description 11
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 4
- 238000005554 pickling Methods 0.000 description 4
- 230000001376 precipitating effect Effects 0.000 description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005363 electrowinning Methods 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000012286 potassium permanganate Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- JWAZRIHNYRIHIV-UHFFFAOYSA-N 2-naphthol Chemical compound C1=CC=CC2=CC(O)=CC=C21 JWAZRIHNYRIHIV-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 2
- 239000003818 cinder Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 230000007062 hydrolysis Effects 0.000 description 2
- 238000006460 hydrolysis reaction Methods 0.000 description 2
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 2
- 229910001414 potassium ion Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- OQVYMXCRDHDTTH-UHFFFAOYSA-N 4-(diethoxyphosphorylmethyl)-2-[4-(diethoxyphosphorylmethyl)pyridin-2-yl]pyridine Chemical compound CCOP(=O)(OCC)CC1=CC=NC(C=2N=CC=C(CP(=O)(OCC)OCC)C=2)=C1 OQVYMXCRDHDTTH-UHFFFAOYSA-N 0.000 description 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 239000004280 Sodium formate Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229950011260 betanaphthol Drugs 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- DKVNPHBNOWQYFE-UHFFFAOYSA-N carbamodithioic acid Chemical compound NC(S)=S DKVNPHBNOWQYFE-UHFFFAOYSA-N 0.000 description 1
- SKOLWUPSYHWYAM-UHFFFAOYSA-N carbonodithioic O,S-acid Chemical compound SC(S)=O SKOLWUPSYHWYAM-UHFFFAOYSA-N 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 239000012990 dithiocarbamate Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 1
- 235000019254 sodium formate Nutrition 0.000 description 1
- 238000010563 solid-state fermentation Methods 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 231100000027 toxicology Toxicity 0.000 description 1
- SRWMQSFFRFWREA-UHFFFAOYSA-M zinc formate Chemical compound [Zn+2].[O-]C=O SRWMQSFFRFWREA-UHFFFAOYSA-M 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
- C22B7/007—Wet processes by acid leaching
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B23/00—Obtaining nickel or cobalt
- C22B23/04—Obtaining nickel or cobalt by wet processes
- C22B23/0453—Treatment or purification of solutions, e.g. obtained by leaching
- C22B23/0461—Treatment or purification of solutions, e.g. obtained by leaching by chemical methods
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/44—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes
- C22B3/46—Treatment or purification of solutions, e.g. obtained by leaching by chemical processes by substitution, e.g. by cementation
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Metallurgy (AREA)
- Mechanical Engineering (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Geochemistry & Mineralogy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
本发明公开了一种除钴剂及其应用。所述除钴剂由二甲基二硫代氨基甲酸盐与亚硝酸钠组成，按质量比计，二甲基二硫代甲酸盐：亚硝酸钠＝12‑18:1。将该除钴剂应用于锌冶炼渣浸出液中进行除钴，钴的去除率高达99.7％以上，即近似可以将钴完全除净，使溶液中的钴浓度完全达到锌电解的要求，同时具有极高的选择性，不会除掉溶液中起保护电解作用的锰离子，另外在本发明除钴的过程中，所得钴沉淀经热处理后所得钴渣其品位高达58％以上，具有极大的回收价值。The invention discloses a cobalt removing agent and its application. The cobalt removing agent is composed of dimethyl dithiocarbamate and sodium nitrite, and in mass ratio, dimethyl dithiocarbamate: sodium nitrite=12-18:1. The cobalt removal agent is applied to the zinc smelting slag leaching solution to remove cobalt, and the removal rate of cobalt is as high as 99.7%, that is, the cobalt can be removed almost completely, so that the cobalt concentration in the solution can fully meet the requirements of zinc electrolysis. High selectivity, it will not remove manganese ions that play the role of protective electrolysis in the solution. In addition, in the process of removing cobalt in the present invention, the cobalt slag obtained after heat treatment of the obtained cobalt precipitate has a grade of as high as 58% or more, which has great recovery. value.
Description
Technical field
The present invention relates to one kind to remove cobalt agent and its application, belongs to secondary resource recovery technology field.
Background technique
Global zinc consumption figure is per year over 13000000 tons, it is contemplated that the following whole world zinc demand will sustainable growth.However, with
The increase of zinc consumption figure, the content and grade of primary zinc resource are declining.Meanwhile the discharge and accumulation of a large amount of melting waste slags are led
The serious wasting of resources and environmental problem outstanding are caused.Therefore, in terms of the utilization of resources and environmental protection, as secondary
The high metallurgical slag of the zinc content of resource has to pass through further processing and recycling, to promote the sustainable development of the following Zn Cr coating
Exhibition.
Zinc abstraction Solid state fermentation technique is mainly made of four basic processes: roasting is leached, purification and electroextraction.So
And when with cadmia is leached, other impurities ion, such as iron, cadmium and cobalt inevitably enter percolate together with zinc.These
Foreign ion, especially cobalt can cause serious harm to the electroextraction of zinc.
Meanwhile cobalt is widely used in various products and technique array, such as aviation, space flight, electronics, battery and alloy etc..?
The consumption figure of China's cobalt sharply increases, but Chinese large-sized cobalt ore resource is few, and taste is universal lower, and domestic cobalt output is remote
Far from meet demand.In contrast, the cobalt content in some waste residues is quite high.In addition, cobalt metal ion can cause the mankind refreshing
Through first toxicology disorder, genetoxic and cancer, it in the environment there is a problem of being also one important.These characteristics make
Separating and recovering cobalt and zinc have same importance from cadmia.
Solvent-extracted method is widely used in the separation of zinc cobalt, is extracted from zinc cobalt mixed liquor by using suitable extractant
Then zinc or simultaneously extracting zinc cobalt are stripped to achieve the purpose that the two separation.Used cobalt and zinc extraction agent
Including fatty acid, D2EHPA and N235 extractant etc. is also required to carry out synergic solvent extraction using two or more extractants sometimes.So
And when Zn content is excessively high in solution, it will cause extractant consumption excessive, separative efficiency is lower.But for Zn content compared with
For big solution, extraction and separation are difficult to apply at industrial scale.
For the precipitation method for extraction, what is be simple and efficient is more, more suitable for industrialized production, but it is existing at present
There are some defects in the cobalt agent that removes that the precipitation method use in some, such as using betanaphthol as except cobalt agent removes cobalt, there are costs
Problem high, cobalt concentrate grade is low, while intermediate product amount is more in treatment process, and dosages distribution solution ph is not easily-controllable
System.And oxidation precipitation agent is there are dosage is big, removal rate by pH variation it is big, selectivity is bad the defects of, it is heavy such as sodium hypochlorite
Cobalt amount is up in leachate in Co content 20 times, and can just sink cobalt after preferential precipitation manganese.And for zinc electrolyte, it is appropriate
The quality and current efficiency of zinc can be effectively ensured in manganese ion, if if preferential precipitation, also needing additionally to fill into manganese ion again.
The document " effect that ziram removes cobalt in zinc lixiviating solution " of Liang Huanlong, which is disclosed, to be used as using ziram except cobalt agent,
It, mainly using having xanthic acid group, generates chelate with higher selectivity in conjunction with cobalt ions in the solution, can
Using its deposit solubility product difference, the separation of itself and zinc plasma is effectively realized.But it can be seen that it still from document
There are many defects, first is that dosage is big and is only capable of processing low cobalt solution, content of the additional amount of zinc relative to cobalt needs several hundred
Times.Another needs highly acidity except cobalt efficiency, and acidity is higher, and effect is just better, however highly acidity will lead to ziram decomposition, because
This overall efficiency is not high.
Up to the present, there are no one kind efficiently, selectivity is high, is especially adapted for use in removing in zinc smelting dreg leachate
Cobalt agent.
Summary of the invention
In view of the deficiencies of the prior art, the purpose of the present invention is to provide one kind to remove cobalt agent and its application, by institute of the present invention
With taking except cobalt agent is applied to be carried out in zinc smelting dreg leachate except cobalt, especially have efficiently, the strong feature of selectivity is removed simultaneously
Cobalt cinder grade obtained by cobalt is high.
To achieve the goals above, the present invention uses following scheme.
One kind of the invention removes cobalt agent, is made of dimethyl dithiocarbamate and sodium nitrite, counts in mass ratio, and two
Methyl dithio formate: sodium nitrite=12-18:1.
What the present invention initiated provide it is a kind of by dimethyl dithiocarbamate and sodium nitrite form except cobalt agent,
This has the characteristics that efficient, selectivity is strong except cobalt agent.Dimethyl dithiocarbamate due in independent heavy cobalt dosage it is big,
The problem of various aspects such as low efficiency, not in terms of except cobalt, the zinc smelting dreg leachate of especially high cobalt is answered except cobalt aspect obtains
With, however combined with dimethyl disulfide for formates in the present invention only with a small amount of sodium nitrite, except cobalt effect greatly improves,
Inventors have found that cobalt still exists in precipitating with bivalent form, therefore sodium nitrite, in the combination except cobalt agent, what is played is
Activation, rather than oxidation, so can significantly improve to effect only needing few additional amount.In fact, invention
People has found through a large number of experiments, if the dosage of sodium nitrite increases, not can increase effect, will affect effect instead.
Preferred scheme, is counted in mass ratio, and dimethyl disulfide is for formates: sodium nitrite=12-15:1.
Preferred scheme, the dimethyl disulfide are selected from dimethyl disulfide for sodium formate (Sodium Dimethyldithiocarbamate), diformazan for formates
Base dithiocarbonic acid potassium (good fortune U.S. potassium), dimethyl disulfide are at least one of zinc formate (ziram).
As further preferably, the dimethyl disulfide is selected from ziram for formates.
In the inventive solutions, the heavy cobalt effect of Sodium Dimethyldithiocarbamate, good fortune U.S. potassium is equally preferable, but Sodium Dimethyldithiocarbamate, good fortune U.S. potassium
With slight taste, it is similar to ammonia taste.If in addition sodium, potassium ion enter in electrolyte, since electrolysis rear solution needs follow
Ring uses, and sodium, potassium ion can be accumulated always in aqueous solution, when sodium, potassium concentration reach tens gram per liters in solution, can tie
Brilliant and go out, the zinc ion not being electrolysed for causing to be mingled with, which generates, to be lost.Therefore ziram is selected to belong to most preferred scheme, and this hair
In bright formula, sodium nitrite is since dosage is few, so hardly generating any influence to zinc electrolysis.
A kind of application except cobalt agent of the present invention, by above-mentioned except cobalt agent is applied to carry out in zinc smelting dreg leachate except cobalt, first
By zinc smelting dreg leachate except iron, except obtaining every processing except liquid before cobalt, it is added in liquid before except cobalt and removes cobalt agent, reaction, solid-liquid point
From, obtain zinc electrolyte and containing cobalt precipitate；
The additional amount except cobalt agent is except before cobalt 9-12 times of cobalt element gross mass in liquid.
Preferred scheme, described except zinc concentration is 100-140g/L in liquid before cobalt, the concentration of cobalt is 0.4-0.8g/L, manganese
Concentration be 2-3g/L.
Preferred scheme, the temperature of the reaction are 80-95 DEG C, time 1-2h.
The pH value of preferred scheme, the reaction controls between 4-6.
In technical solution of the present invention, pH value control all has excellent efficiency between 4-6, can effectively avoid in this way
Ziram existing decomposition failure in the case where pH value is too low, certain pH value can not be excessively high, because when pH is excessively high, due to molten
Zinc ion concentration is excessively high in liquid, it is easy to which hydrolysis generates zinc hydroxide precipitation.
Preferred scheme, the reaction carry out under stiring, and mixing speed is 500-700 revs/min.
Preferred scheme, the acquisition methods of the zinc smelting dreg leachate are as follows: using sulfuric acid as leaching agent, to zinc smelting dreg into
Row leaches, and gained leachate is zinc smelting dreg leachate, and the long-pending mass ratio of the liquid solid of the sulfuric acid and zinc smelting dreg is 4-
6ml:1g, the extraction temperature are 75-85 DEG C, extraction time 1-3h.
As a further preference, the sulfuric acid concentration is 1.5-2.5mol/L.
As a further preference, the partial size of the zinc smelting dreg is less than 40 mesh
Preferred scheme, the zinc smelting dreg leachate are that hydrogen peroxide is first added by ferrous ion except the mode of iron
It is oxidized to ferric ion, then makes ferric ions precipitation by adjusting pH to 2.5-4.5.Iron is removed in zinc smelting dreg leachate
Technique, the amount of hydrogen peroxide is added, using the amount reported in the prior art, which is known as neutralizing hydrolysis method.
When zinc electrolysis, divalent manganesetion generates manganese dioxide on anode, is returned in the form of the earth of positive pole and leaches-remove
Miscellaneous-electrowinning process, manganese ion concentration are needed to maintain to balance in systems, when manganese ion concentration is too low in solution, be needed in addition
Supplement manganese.Therefore it is both needed in addition supplement manganese ion except cobalt agent carries out after removing cobalt by the way that selection is some, and in technical side of the invention
It is provided except cobalt agent will not precipitate manganese ion in case, it can effectively guarantee manganese ion in suitable range.Certainly, if
When manganese ion in zinc smelting dreg leachate is excessively high, potassium permanganate precipitating manganese can be added so that manganese is dense after except iron in the present invention
Degree restores the concentration to needed for being electrolysed, and the additional amount of potassium permanganate uses ratio in the prior art, such as counts in mass ratio, high
Potassium manganate: the manganese ion mass ratio with required removing is 1.5:1.
Preferred scheme, the zinc smelting dreg leachate are zinc dust precipitation except the mode of cadmium.
In the inventive solutions, zinc dust precipitation is using condition in the prior art and parameter.
Preferred scheme, it is described to be deposited in 600-800 DEG C of heat treatment 0.5-1.5h acquisition cobalt slag containing cobalt.Pass through heat treatment
Afterwards, the grade of cobalt is more than or equal to 58% in gained cobalt slag.As can be seen that present invention gained cobalt cinder grade is high, has and greatly return
Receive value.
Processing through the above scheme simultaneously, in gained zinc electrolyte, the removal rate of concentration≤1.5mg/L of cobalt, cobalt (are returned
Yield) >=99.7%.It can be seen that the present invention approximately will can all remove the unfavorable cobalt of zinc electrolysis.
In addition, the concentration of manganese is constant in gained zinc electrolyte, it is seen then that of the invention removes cobalt agent with highly selective.
The effect and effect of invention
The present invention provides one kind to remove cobalt agent, should be compounded by dimethyl dithiocarbamate with sodium nitrite except cobalt agent
Composition, be it is a kind of efficiently, selectivity it is strong except cobalt agent.
Since dimethyl dithiocarbamate has as the feasibility in theory for removing cobalt agent, but in practical application
In, but there is a problem of it is a large amount of, be placed in can not really be applied to practice in, inventor is by using a large amount of substance and diformazan
It goes to base dithiocar-bamate and compounds, such as various oxidants, other precipitating reagents, complexing agent and a large amount of adjusting processes
Parameter, the effect that can not have obtained finally find sodium nitrite just unexpected, and when a small amount of sodium nitrite of addition, i.e., desirable
Obtained unexpected effect.
Except cobalt agent, it is applied in zinc smelting dreg leachate by provided by the present invention, carries out except cobalt, the removal rate of cobalt is high
Up to 99.7% or more, i.e. approximation can be completely cleared by cobalt, makes the cobalt concentration in solution that the requirement of zinc electrolysis be fully achieved, simultaneously
With high selectivity, the manganese ion for playing protection electrolysis in solution will not be removed, the process of cobalt is in addition removed in the present invention
In, after heat treatment its grade of gained cobalt slag is up to 58% or more to gained cobalt precipitating, has great recovery value, using this hair
The bright technique carried out except cobalt agent except cobalt, simple possible have considerable economic value, are suitble to heavy industrialization.
Specific embodiment
Embodiment 1
2mol/L sulfuric acid is mixed with zinc smelting dreg with 5:1 liquid-solid ratio, heating stirring 2h filters to obtain leachate, in
Iron, cadmium ion are removed respectively with Hydrolyze method, zinc replacement, are obtained by filtration except liquid before cobalt.Except zinc concentration 110g/L in liquid before cobalt,
Cobalt concentration 650mg/L, manganese concentration 2.4g/L, pH value are adjusted to that 6g ziram, 0.5g sodium nitrite, 90 are added in 4.5,1L solution
It is reacted 2 hours at DEG C with 500 revs/min of stirring rate, filtering, cobalt concentration 1.3mg/L in filtrate, manganese concentration is basically unchanged,
The cobalt rate of recovery 99.8% is dried after precipitation slag pickling, and cobalt taste is 13.8%.Cobalt is deposited in oxidizing roasting 1 hour at 600 DEG C,
Cobalt taste is 59.4% in cobalt slag.
Embodiment 2
2mol/L sulfuric acid is mixed with zinc smelting dreg with 5:1 liquid-solid ratio, heating stirring 2h filters to obtain leachate, in
Iron, cadmium ion are removed respectively with Hydrolyze method, zinc replacement, are obtained by filtration except liquid before cobalt.Except zinc concentration 115g/L in liquid before cobalt,
Cobalt concentration 550mg/L, the concentration of manganese are 2.8g/L, and pH value is adjusted to that 5g ziram is added in 5,1L solution, 0.4g sodium nitrite,
It is reacted 2 hours at 90 DEG C with 500 revs/min of stirring rate, filtering, cobalt concentration 1.5mg/L in filtrate, the concentration of manganese is substantially not
Become, the cobalt rate of recovery 99.7% is dried after precipitation slag pickling, and cobalt taste is 13.5%.It is small that cobalt is deposited in oxidizing roasting 1 at 600 DEG C
When, cobalt taste is 58.4% in cobalt slag.
Embodiment 3
2mol/L sulfuric acid is mixed with zinc smelting dreg with 5:1 liquid-solid ratio, heating stirring 2h filters to obtain leachate, in
Iron, cadmium ion are removed respectively with Hydrolyze method, zinc replacement, are obtained by filtration except liquid before cobalt.Except zinc concentration 108g/L in liquid before cobalt,
Cobalt concentration 600mg/L, the concentration of manganese are 2.3g/L, and pH value is adjusted to that 6g ziram is added in 5,1L solution, 0.4g sodium nitrite,
It is reacted 1.5 hours at 90 DEG C with 500 revs/min of stirring rate, filtering, cobalt concentration 1mg/L in filtrate, the concentration of manganese is substantially not
Become, the cobalt rate of recovery 99.8% is dried after precipitation slag pickling, and cobalt taste is 13.7%.It is small that cobalt is deposited in oxidizing roasting 1 at 800 DEG C
When, cobalt taste is 59.6% in cobalt slag.
Embodiment 4
2mol/L sulfuric acid is mixed with zinc smelting dreg with 5:1 liquid-solid ratio, heating stirring 2h filters to obtain leachate, in
Iron, cadmium ion are removed respectively with Hydrolyze method, zinc replacement, are obtained by filtration except liquid before cobalt.Except zinc concentration 106g/L in liquid before cobalt,
Cobalt concentration 460mg/L, the concentration of manganese are 2.7g/L, and pH value is adjusted to that 5g ziram is added in 4.8,1L solution, 0.4g sodium nitrite,
It is reacted 2 hours at 90 DEG C with 500 revs/min of stirring rate, filtering, cobalt concentration 0.9mg/L in filtrate, the concentration of manganese is basic
Constant, the cobalt rate of recovery 99.8% is dried after precipitation slag pickling, and cobalt taste is 13.5%.Cobalt is deposited in oxidizing roasting 1 at 700 DEG C
Hour, cobalt taste is 58.5% in cobalt slag.
Embodiment 6:
2mol/L sulfuric acid is mixed with zinc smelting dreg with 5:1 liquid-solid ratio, heating stirring 2h filters to obtain leachate, in
Iron, cadmium ion are removed respectively with Hydrolyze method, zinc replacement, are obtained by filtration except liquid before cobalt.Zinc concentration 117g/L in solution, cobalt are dense
680mg/L is spent, the concentration of manganese is 2.5g/L, and pH value is adjusted to that 7g ziram, 0.5g sodium nitrite, at 90 DEG C are added in 5,1L solution
Under reacted 2 hours with 500 revs/min of stirring rate, filtering, cobalt concentration 1.3mg/L in filtrate, the concentration of manganese is basically unchanged,
The cobalt rate of recovery 99.8%.
Comparative example 1
2mol/L sulfuric acid is mixed with zinc smelting dreg with 5:1 liquid-solid ratio, heating stirring 2h filters to obtain leachate, in
Iron, cadmium ion are removed respectively with Hydrolyze method, zinc replacement, are obtained by filtration except liquid before cobalt.Zinc concentration 112g/L in solution, cobalt are dense
510mg/L is spent, the concentration of manganese is 2.6g/L, and pH value is adjusted to that 5g ziram is added in 5,1L solution, with 500 revs/min at 90 DEG C
The stirring rate of clock is reacted 2 hours, filtering, and cobalt concentration 420mg/L in filtrate, the concentration of manganese is to be basically unchanged, the cobalt rate of recovery
17.6%.
Comparative example 2
2mol/L sulfuric acid is mixed with zinc smelting dreg with 5:1 liquid-solid ratio, heating stirring 2h filters to obtain leachate, in
Iron, cadmium ion are removed respectively with Hydrolyze method, zinc replacement, are obtained by filtration except liquid before cobalt.Zinc concentration 107g/L in solution, cobalt are dense
460mg/L is spent, the concentration of manganese is 2.1g/L, and pH value is adjusted to that 5g ziram, 0.4g potassium permanganate, at 90 DEG C are added in 5,1L solution
Under reacted 2 hours with 500 revs/min of stirring rate, filtering, cobalt concentration 262mg/L in filtrate, the concentration of manganese is 2.2g/L,
The cobalt rate of recovery 43%.
Comparative example 3
2mol/L sulfuric acid is mixed with zinc smelting dreg with 5:1 liquid-solid ratio, heating stirring 2h filters to obtain leachate, in
Iron, cadmium ion are removed respectively with Hydrolyze method, zinc replacement, are obtained by filtration except liquid before cobalt.Zinc concentration 116g/L in solution, cobalt are dense
630mg/L is spent, the concentration of manganese is 2.7g/L, and pH value is adjusted to that 8g ziram, 50ml hydrogen peroxide, at 90 DEG C are added in 5,1L solution
Under reacted 2 hours with 500 revs/min of stirring rate, filtering, cobalt concentration 353mg/L in filtrate, the concentration of manganese is basically unchanged,
The cobalt rate of recovery 44%.
Comparative example 4
2mol/L sulfuric acid is mixed with zinc smelting dreg with 5:1 liquid-solid ratio, heating stirring 2h filters to obtain leachate, in
Iron, cadmium ion are removed respectively with Hydrolyze method, zinc replacement, are obtained by filtration except liquid before cobalt.Zinc concentration 109g/L in solution, cobalt are dense
590mg/L is spent, the concentration of manganese is 2.4g/L, and pH value is adjusted to that 5g ziram, 2.5g sodium nitrite, at 90 DEG C are added in 5,1L solution
Under reacted 2 hours with 500 revs/min of stirring rate, filtering, cobalt concentration 165mg/L in filtrate, the concentration of manganese is basically unchanged,
The cobalt rate of recovery 72%.
Comparative example 5
2mol/L sulfuric acid is mixed with zinc smelting dreg with 5:1 liquid-solid ratio, heating stirring 2h filters to obtain leachate, in
Iron, cadmium ion are removed respectively with Hydrolyze method, zinc replacement, are obtained by filtration except liquid before cobalt.Zinc concentration 113g/L in solution, cobalt are dense
480mg/L is spent, the concentration of manganese is 2.5g/L, and pH value is adjusted to that 5g ziram, 0.35g sodium nitrite, 90 are added in 1,1L solution
It is reacted 2 hours at DEG C with 500 revs/min of stirring rate, filtering, cobalt concentration 307mg/L in filtrate, the concentration of manganese is substantially not
Become, the cobalt rate of recovery 36%.
Comparative example 6
2mol/L sulfuric acid is mixed with zinc smelting dreg with 5:1 liquid-solid ratio, heating stirring 2h filters to obtain leachate, in
Iron, cadmium ion are removed respectively with Hydrolyze method, zinc replacement, are obtained by filtration except liquid before cobalt.Zinc concentration 110g/L in solution, cobalt are dense
438mg/L is spent, the concentration of manganese is 2.8g/L, and pH value is adjusted to that 0.45g ziram is added in 4.5,1L solution, 0.3g sodium nitrite,
It is reacted 2 hours at 50 DEG C with 500 revs/min of stirring rate, filtering, cobalt concentration 390mg/L in filtrate, the concentration of manganese is basic
It is constant, the cobalt rate of recovery 11%.
In the above-described embodiments, the ion concentration in solution can be (former using atomic absorption spectrophotometer either ICP
Sub- emission spectrometry) etc. means tested.The present invention can also detect ion concentration using other means of testing.
Claims (10)
1. one kind removes cobalt agent, which is characterized in that be made of dimethyl dithiocarbamate and sodium nitrite, in mass ratio
Meter, dimethyl disulfide is for formates: sodium nitrite=12-18:1.
2. according to claim 1 a kind of except cobalt agent, which is characterized in that count in mass ratio, dimethyl disulfide is for formates:
Sodium nitrite=12-15:1.
3. according to claim 1 or 2 a kind of except cobalt agent, which is characterized in that the dimethyl disulfide is selected from for formates
At least one of Sodium Dimethyldithiocarbamate, good fortune U.S. potassium, ziram.
4. a kind of application except cobalt agent according to claim 1 to 3, which is characterized in that by above-mentioned except cobalt agent is answered
For being carried out in zinc smelting dreg leachate except cobalt, first zinc smelting dreg leachate is being removed except iron, except obtaining every processing except liquid before cobalt
It is added in liquid before cobalt and removes cobalt agent, reacted, is separated by solid-liquid separation, obtain zinc electrolyte and precipitated containing cobalt；
The additional amount except cobalt agent is except before cobalt 9-12 times of cobalt element gross mass in liquid.
5. a kind of application except cobalt agent according to claim 4, which is characterized in that
The temperature of the reaction is 80-95 DEG C, time 1-2h；The pH value of the reaction controls between 4-6.
6. a kind of application except cobalt agent according to claim 4, which is characterized in that the reaction carries out under stiring, stirs
Mixing speed is 500-700 revs/min.
7. a kind of application except cobalt agent according to claim 4, which is characterized in that the acquisition of the zinc smelting dreg leachate
Method are as follows: using sulfuric acid as leaching agent, zinc smelting dreg is leached, gained leachate is zinc smelting dreg leachate, the sulphur
The liquid solid product mass ratio of acid and zinc smelting dreg is 4-6ml:1g, and the extraction temperature is 75-85 DEG C, extraction time 1-3h.
8. a kind of application except cobalt agent according to claim 8, which is characterized in that the concentration of the sulfuric acid is 1.5-
2.5mol/L, the partial size of the zinc smelting dreg is less than 40 mesh.
9. a kind of application except cobalt agent according to claim 4, which is characterized in that
The zinc smelting dreg leachate be except the mode of iron be first added hydrogen peroxide by oxidation of divalent iron ion be ferric iron from
Then son makes ferric ions precipitation by adjusting pH to 2.5-4.5；
The zinc smelting dreg leachate is zinc dust precipitation except the mode of cadmium.
10. a kind of application except cobalt agent according to claim 4, which is characterized in that described to be deposited in 600-800 DEG C containing cobalt
It is heat-treated 0.5-1.5h and obtains cobalt slag.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110629039A (en) * | 2019-08-23 | 2019-12-31 | 白银有色集团股份有限公司 | Deep purification method for zinc, cadmium and cobalt by wet smelting |
| CN110699556A (en) * | 2019-08-23 | 2020-01-17 | 白银有色集团股份有限公司 | Method for deep purification and cadmium and cobalt removal of supernatant in zinc hydrometallurgy |
| CN111748689A (en) * | 2020-06-29 | 2020-10-09 | 中南大学 | A kind of method for separating zinc and iron cobalt in solution |
| CN113265548A (en) * | 2021-04-21 | 2021-08-17 | 内蒙古兴安铜锌冶炼有限公司 | Enrichment and recovery method of cobalt in cobalt removal agent cobalt slag |
| CN113528820A (en) * | 2021-08-25 | 2021-10-22 | 湖南福尔程环保科技有限公司 | Cobalt removing agent and zinc sulfate electrolytic solution cobalt removing method |
| CN113621993A (en) * | 2021-08-25 | 2021-11-09 | 湖南福尔程环保科技有限公司 | Purification method of zinc electrolyte |
| CN114058872A (en) * | 2021-11-24 | 2022-02-18 | 白银有色集团股份有限公司 | Method for improving grade of cobalt slag of zinc hydrometallurgy |
| CN114703013A (en) * | 2022-03-09 | 2022-07-05 | 南京工业职业技术大学 | Method for removing residual cobalt ions in Cu-Zn-Co coating steel cord wet drawing wetting liquid |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108342569A (en) * | 2017-12-29 | 2018-07-31 | 衡阳市坤泰化工实业有限公司 | Method of the foreign metal cobalt to obtain zinc-containing solution is removed from crude zinc raw material |
| CN110592376A (en) * | 2018-06-12 | 2019-12-20 | 济源市华信科技有限公司 | Preparation method and application of zinc hydrometallurgy purifying and cobalt removing agent |
-
2019
- 2019-01-22 CN CN201910057030.9A patent/CN109666800B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108342569A (en) * | 2017-12-29 | 2018-07-31 | 衡阳市坤泰化工实业有限公司 | Method of the foreign metal cobalt to obtain zinc-containing solution is removed from crude zinc raw material |
| CN110592376A (en) * | 2018-06-12 | 2019-12-20 | 济源市华信科技有限公司 | Preparation method and application of zinc hydrometallurgy purifying and cobalt removing agent |
Non-Patent Citations (2)
| Title |
|---|
| 蒋新宇 等: ""高钴硫酸锌溶液中钴的分离研究"", 《有色矿冶》 * |
| 黄守义 等: ""从湿法炼锌硫酸盐溶液中去除钴的试验研究"", 《湿法冶金》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110629039A (en) * | 2019-08-23 | 2019-12-31 | 白银有色集团股份有限公司 | Deep purification method for zinc, cadmium and cobalt by wet smelting |
| CN110699556A (en) * | 2019-08-23 | 2020-01-17 | 白银有色集团股份有限公司 | Method for deep purification and cadmium and cobalt removal of supernatant in zinc hydrometallurgy |
| CN111748689A (en) * | 2020-06-29 | 2020-10-09 | 中南大学 | A kind of method for separating zinc and iron cobalt in solution |
| CN113265548A (en) * | 2021-04-21 | 2021-08-17 | 内蒙古兴安铜锌冶炼有限公司 | Enrichment and recovery method of cobalt in cobalt removal agent cobalt slag |
| CN113528820A (en) * | 2021-08-25 | 2021-10-22 | 湖南福尔程环保科技有限公司 | Cobalt removing agent and zinc sulfate electrolytic solution cobalt removing method |
| CN113621993A (en) * | 2021-08-25 | 2021-11-09 | 湖南福尔程环保科技有限公司 | Purification method of zinc electrolyte |
| CN114058872A (en) * | 2021-11-24 | 2022-02-18 | 白银有色集团股份有限公司 | Method for improving grade of cobalt slag of zinc hydrometallurgy |
| CN114703013A (en) * | 2022-03-09 | 2022-07-05 | 南京工业职业技术大学 | Method for removing residual cobalt ions in Cu-Zn-Co coating steel cord wet drawing wetting liquid |
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Denomination of invention: A cobalt removal agent and its application Granted publication date: 20201124 Pledgee: Changsha Bank Co.,Ltd. Science and Technology Innovation Branch Pledgor: CHANGSHA HASKY ENVIRONMENTAL PROTECTION TECHNOLOGY DEVELOPMENT Co.,Ltd. Registration number: Y2025980008491 |