CN113957248B - Zinc-cobalt separation method for selective precipitation flotation of cobalt ions in acidic solution - Google Patents
Zinc-cobalt separation method for selective precipitation flotation of cobalt ions in acidic solution Download PDFInfo
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- 229910001429 cobalt ion Inorganic materials 0.000 title claims abstract description 118
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 title claims abstract description 117
- 238000000926 separation method Methods 0.000 title claims abstract description 48
- 238000001556 precipitation Methods 0.000 title claims abstract description 41
- 238000005188 flotation Methods 0.000 title claims abstract description 38
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 title claims abstract description 22
- 239000003929 acidic solution Substances 0.000 title claims description 9
- 239000002245 particle Substances 0.000 claims abstract description 71
- 239000010941 cobalt Substances 0.000 claims abstract description 57
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 57
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 57
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 49
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 40
- 239000011701 zinc Substances 0.000 claims abstract description 40
- 238000000034 method Methods 0.000 claims abstract description 38
- 238000003756 stirring Methods 0.000 claims abstract description 32
- 239000003381 stabilizer Substances 0.000 claims abstract description 20
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 239000002244 precipitate Substances 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 95
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 17
- YXAOOTNFFAQIPZ-UHFFFAOYSA-N 1-nitrosonaphthalen-2-ol Chemical group C1=CC=CC2=C(N=O)C(O)=CC=C21 YXAOOTNFFAQIPZ-UHFFFAOYSA-N 0.000 claims description 9
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical group [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 9
- 230000001276 controlling effect Effects 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 150000007522 mineralic acids Chemical group 0.000 claims description 3
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 2
- 238000006460 hydrolysis reaction Methods 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 abstract description 4
- 239000002253 acid Substances 0.000 abstract description 3
- 239000013522 chelant Substances 0.000 description 11
- 239000003153 chemical reaction reagent Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 9
- 238000000605 extraction Methods 0.000 description 8
- 230000008901 benefit Effects 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 239000012991 xanthate Substances 0.000 description 5
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 239000002893 slag Substances 0.000 description 4
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 3
- 238000003723 Smelting Methods 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 230000005587 bubbling Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000006260 foam Substances 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 235000021110 pickles Nutrition 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 239000002910 solid waste Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- -1 iron ion Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000010813 municipal solid waste Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 239000002341 toxic gas Substances 0.000 description 1
- 239000010926 waste battery Substances 0.000 description 1
Classifications
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- 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
-
- 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
- C22B19/00—Obtaining zinc or zinc oxide
- C22B19/20—Obtaining zinc otherwise than by distilling
-
- 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
-
- 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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- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a zinc-cobalt separation method for selective precipitation flotation of cobalt ions in an acid solution, belongs to the technical field of element separation, and solves the problems of low and incomplete cobalt ion separation efficiency in the prior art. Comprising the following steps: step 1, adjusting the pH value of a solution containing zinc and cobalt ions to be acidic through a pH regulator; step 2, simultaneously adding a cobalt ion chelating precipitant and a particle stabilizer into the solution at a certain temperature, and stirring and mixing to obtain a first intermediate system containing cobalt ion chelating precipitant particles; step 3, adding a surfactant into the first intermediate system, and stirring and mixing uniformly to obtain a second intermediate system containing cobalt precipitation suspended particles; and 4, performing aerated flotation on the second intermediate system by adopting a flotation separation device, and collecting particles containing cobalt precipitate. The method of the invention effectively solves the difficult problem of zinc and cobalt separation.
Description
Technical Field
The invention belongs to the technical field of element separation, and particularly relates to a zinc-cobalt separation method for selective precipitation and flotation of cobalt ions in an acidic solution.
Background
Cobalt is a strategic key metal supporting the development of the high technology field. Along with the popularization of electronic products and the popularization of new energy automobiles, cobalt is increasingly widely applied to battery materials, and the demand of the cobalt is also increasing. At present, china has become the first major country of cobalt consumption. However, cobalt reserves in China only account for 1.1% of global reserves, the external dependence exceeds 90%, and most of cobalt reserves are associated with sulfide ores of metals such as zinc, copper, nickel and the like. Cobalt-containing minerals have generally low cobalt grade, high difficulty and high cost in direct smelting and extraction processes, and the yield of the cobalt-containing minerals is difficult to meet the rapidly-increased cobalt consumption demands in China. Therefore, the development of various cobalt-containing secondary resources (cobalt-containing solid waste, industrial wastewater and the like) is an effective way for guaranteeing the cobalt raw material supply in China.
Smelting slag containing zinc and cobalt, industrial solid waste and waste battery materials are important secondary resources containing cobalt, and metal components can enter the leaching solution through an acid leaching process; in addition, zinc cobalt ions exist in a certain concentration in a part of industrial wastewater. The separation and extraction of cobalt in the secondary resource containing zinc and cobalt and the purification and impurity removal of cobalt in the solution are both required to face the problem of high-efficiency separation of zinc and cobalt ions in the solution.
At present, the separation method of zinc and cobalt in the acid solution mainly comprises a zinc powder replacement method, an extraction method, a precipitation method and the like. The zinc powder replacement method is to replace cobalt ions in the reduction solution by zinc powder and form precipitation by utilizing the potential difference of zinc and cobalt; however, the method needs to add zinc powder of which the theoretical amount is tens times, the formed cobalt-removing slag contains a large amount of unreacted zinc powder, and the extraction of cobalt in the cobalt-removing slag is subjected to zinc-cobalt separation again, so that the problem of difficult zinc-cobalt separation is not thoroughly solved. When a solvent extraction method is adopted to separate zinc and cobalt in the solution, the extraction effect is poor because the content of cobalt ions in the solution is generally low; meanwhile, when zinc and cobalt in the solution are separated by adopting a precipitation method, the available precipitants comprise sulfides, xanthates and the like, but are also influenced by low cobalt ion content, so that larger precipitated particles are difficult to form, the sedimentation process is slow, and the complete separation is difficult.
The root cause of the difficult problem of separating zinc and cobalt in the solution is that the concentration of cobalt ions is generally low, and when the method is adopted to separate zinc and cobalt, the problems of poor selectivity, slow mass transfer process, low separation efficiency, incomplete separation and the like exist. Therefore, how to efficiently separate zinc and cobalt ions is a problem to be solved.
Disclosure of Invention
In view of the analysis, the invention aims to provide a zinc-cobalt separation method for selective precipitation flotation of cobalt ions in an acidic solution, which is used for solving the problems of poor selectivity, low separation efficiency and incomplete separation caused by low concentration of cobalt ions in the solution in the prior art.
The aim of the invention is mainly realized by the following technical scheme:
the invention provides a zinc-cobalt separation method for selective precipitation flotation of cobalt ions in an acidic solution, which comprises the following steps:
step 1, adjusting the pH value of a solution containing zinc and cobalt ions to be acidic through a pH regulator;
step 2, simultaneously adding a cobalt ion chelating precipitant and a particle stabilizer into the solution at a certain temperature, and stirring and mixing to obtain a first intermediate system containing cobalt ion chelating precipitant particles;
step 3, adding a surfactant into the first intermediate system, and stirring and mixing uniformly to obtain a second intermediate system containing cobalt precipitation suspended particles;
and 4, performing aerated flotation on the second intermediate system by adopting a flotation separation device, and collecting particles containing cobalt precipitate.
In the step 1, the concentration of zinc ions in the solution containing zinc and cobalt ions is 0.5-185 g/L, and the concentration of cobalt ions is 1 mg/L-5 g/L.
Further, in the step 1, the pH of the adjusted solution is 2.0 to 3.5.
Further, in the step 1, the pH adjuster is an inorganic acid or a base.
Further, in the step 2, the cobalt ion chelating precipitant is alpha-nitroso-beta-naphthol.
Further, in the step 2, the temperature is 30 to 70 ℃.
Further, in the step 2, the molar ratio of the addition amount of the cobalt ion chelating precipitant to the cobalt ions in the solution is 3:1-10:1.
Further, in the step 2, the particle stabilizer is Fe-containing 3+ A solution.
Further, in the step 2, the molar ratio of the addition amount of the particle stabilizer to cobalt ions in the solution is 0.5:1-1.5:1.
In step 2, the stirring speed is less than or equal to 100rpm, and the stirring time is 10-60 min.
Compared with the prior art, the invention can at least realize one of the following technical effects:
1) The invention applies the chelate precipitation-floatation method to the separation of zinc and cobalt ions in the solution for the first time, utilizes the selective complexation of cobalt ion chelate precipitant (alpha-nitroso-beta-naphthol) and cobalt ions, and the cobalt ion chelate precipitant and cobalt ions in the solution are selectively chelated, and the chelate of cobalt ions and the medicament forms stable suspended particles through the simultaneously added particle stabilizer, and finally realizes the selective extraction of cobalt ions in the solution by virtue of the micro-bubble floatation technology, thereby achieving the purpose of efficiently separating zinc and cobalt ions in the solution. The method can be used for separating zinc and cobalt ions and removing cobalt ions from various solutions containing low-concentration cobalt ions, and has the advantages of good zinc and cobalt separation effect, high cobalt ion recovery rate, low cost and short flow.
2) The existing zinc-cobalt separation technology comprises a zinc powder replacement method and a xanthate precipitation cobalt removal method. Zinc powder displacement method: the zinc powder consumption is large, generally more than 20 times of theoretical amount, the operation time is long, the zinc powder needs to be carried out at about 80 ℃, and AsH is often generated 3 And SbH 3 Toxic gas. The cobalt removal method of xanthate precipitation: because the concentration of cobalt ions in the solution is low, excessive xanthate must be added to enable the reaction to be rapidly carried out and the cobalt to be thoroughly removed, and the dosage is generally 10-15 times of the theoretical dosage. To ensure the quality of the purified solution, it is necessary to remove excess organic agents from the leachate. Compared with the existing method, the method provided by the invention realizes cobalt ion removal by adopting a precipitation-flotation separation method, has a wide application range for the concentration of metal ions in solution, and particularly has stronger applicability in the aspect of low-concentration ion removal, and the dosage of reagents is low; can be continuously carried out, has large solution treatment capacity, high solid-liquid separation rate and more thorough metal ion separation.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. The objects and other advantages of the invention may be realized and obtained by means of the instrumentalities and combinations particularly pointed out in the written description.
Detailed Description
A method for separating zinc from cobalt by selective precipitation and flotation of cobalt ions in an acidic solution is described in further detail below with reference to specific examples, which are for comparison and explanation purposes only, and the invention is not limited to these examples.
A zinc-cobalt separation method for selective precipitation flotation of cobalt ions in an acidic solution comprises the following steps:
step 1, adjusting the pH value of a solution containing zinc and cobalt ions to be acidic through a pH regulator;
step 2, simultaneously adding a cobalt ion chelating precipitant and a particle stabilizer into the solution at a certain temperature, and stirring and mixing to obtain a first intermediate system containing cobalt ion chelating precipitant particles;
step 3, adding a surfactant into the first intermediate system, and stirring and mixing uniformly to obtain a second intermediate system containing cobalt precipitation suspended particles;
and 4, performing air flotation on the second intermediate system by adopting a flotation separation device, collecting particles containing cobalt precipitates, and realizing selective chelate precipitation-flotation removal of cobalt ions in the solution and high-efficiency separation of zinc and cobalt.
Specifically, in the step 1, the solution containing zinc and cobalt ions can be wet zinc smelting pickle liquor, zinc-cobalt solid slag pickle liquor, zinc-cobalt electronic garbage pickle liquor and zinc-cobalt industrial wastewater, and the concentration range of the zinc and cobalt ions is 0.5-185 g/L and 1 mg/L-5 g/L respectively. Wherein the concentration of zinc ions is 0.5 to 185g/L, such as, for example, 0.5g/L, 5g/L, 10g/L, 30g/L, 40g/L, 50g/L, 70g/L, 90g/L, 100g/L, 120g/L, 130g/L, 140g/L, 150g/L, 170g/L, 180g/L; the concentration of cobalt ions is 1mg/L to 5g/L, such as 1mg/L, 10mg/L, 100mg/L, 200mg/L, 300mg/L, 400mg/L, 500mg/L, 600mg/L, 700mg/L, 800mg/L, 900mg/L, 1g/L, 2g/L, 3g/L, 4g/L, 5g/L, for example.
Specifically, in the step 1, the problem that the too high pH of the solution causes hydrolysis and precipitation of zinc ions in the subsequent step is considered, so that the separation efficiency of zinc and cobalt ions is affected; too low a solution pH will affect the efficiency of complex precipitation of the chelating precipitant with cobalt ions in subsequent steps. Thus, the pH of the solution adjusted in step 1 is controlled to be 2.0 to 3.5, such as 2.0, 2.2, 2.5, 2.8, 3.0, 3.3, 3.5, for example.
In the step 1, the pH adjuster is an inorganic acid or base, such as sulfuric acid, hydrochloric acid, or sodium hydroxide.
Specifically, in the step 2, the chelating precipitant is decomposed due to the excessively high temperature, so that unnecessary loss of the chelating precipitant is caused; the difficulty of temperature control in the treatment process is aggravated if the temperature is too low; thus, the temperature is controlled to be 30 to 70 ℃, for example, 30 ℃, 35 ℃, 40 ℃, 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃.
Specifically, in the step 2, the cobalt ion chelating precipitant is alpha-nitroso-beta-naphthol.
Considering that the addition amount of the cobalt ion chelating precipitant is too low, the removal rate of cobalt ions in the solution is low; the excessive addition of the precipitant can cause reagent waste and solution pollution. Thus, in step 2 above, the molar ratio of the added amount of the cobalt ion chelating precipitant to the cobalt ions in the solution is controlled to be 3:1 to 10:1, for example, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1.
Specifically, in the step 2, the particle stabilizer is Fe-containing 3+ The solution can be ferric sulfate solution and/or ferric chloride solution.
Specifically, in the above step 2, fe is contained 3+ The principle of solution stabilization of cobalt ion chelate precipitation products is as follows: in view of the characteristic of low concentration of cobalt ions in the solution, fe is utilized to ensure that the size of cobalt ion chelating precipitation particles meets the requirement of the flotation process 3+ Is easy to hydrolyze to form Fe (OH) 3 The characteristic of floc precipitation realizes the regulation and control of the size of cobalt ion chelating precipitation particles, so that finer precipitation particles grow into particles meeting the flotation requirement.
Considering that the addition amount of the particle stabilizer is too low, the removal rate of cobalt ions in the solution is low; the excessive addition of the particle stabilizer can cause reagent waste and iron ion pollution to the solution. Thus, the molar ratio of the added amount of the particle stabilizer to cobalt ions in the solution is controlled to be 0.5:1 to 1.5:1, for example, 0.5:1, 0.7:1, 0.8:1, 1:1, 1.2:1, 1.3:1, 1.5:1.
Specifically, in the step 2, the particles are difficult to aggregate and grow up due to the too high stirring speed, and the subsequent flotation is adversely affected; too short stirring time can cause insufficient chelating precipitation; too long time affects the processing efficiency. Thus, the stirring rate is controlled to be less than or equal to 100rpm for a stirring time of 10 to 60 minutes, for example, 10 minutes, 15 minutes, 20 minutes, 25 minutes, 30 minutes, 35 minutes, 40 minutes, 45 minutes, 50 minutes, 55 minutes, 60 minutes.
Specifically, in the step 3, the surfactant is one or more of Cetyl Trimethyl Ammonium Bromide (CTAB), sodium Dodecyl Sulfate (SDS) and methyl isobutyl carbinol (MIBC).
Specifically, in the step 3, the surfactant is used for further controlling the particle size and stability. Considering that excessive addition of surfactant can cause surfactant residue in the solution; too small an amount of the additive does not play a role in regulating the particle size. Thus, the amount of the surfactant to be added is controlled to be 10 to 100mg/L, for example, 10mg/L, 15mg/L, 20mg/L, 25mg/L, 30mg/L, 40mg/L, 45mg/L, 50mg/L, 55mg/L, 60mg/L, 65mg/L, 70mg/L, 80mg/L, 85mg/L, 90mg/L, 95mg/L, 100mg/L.
Specifically, in the step 3, the stirring and mixing time is 5-60 min, for example, 5min, 10min, 15min, 20min, 25min, 30min, 35min, 40min, 45min, 50min, 55min, and 60min.
Specifically, in the step 3, factors influencing the particle size of the suspended particles mainly include the addition amount of the particle stabilizer, the stirring and mixing time, the stirring speed, the ion concentration and the like; considering that the particle size of suspended particles is too small, the suspended particles are difficult to adhere to bubbles in the flotation process and then are separated in a flotation mode; the particle size is too large, the mass is large, and the momentum is high, so that the particles are difficult to carry out by bubbles. Thus, the particle diameter of the suspended particles is controlled to be 20 to 50. Mu.m.
It should be noted that, through intensive studies, the inventors found that, due to the low concentration of cobalt ions in the solution, the particles formed are smaller, if a precipitation filtration method is adopted, the filter cloth is easily blocked, if a precipitation filtration method is adopted, large particle precipitation is required to be formed, the production time is long, and more excessive reaction reagent is required to enlarge the particles; the production efficiency is low, the consumption of the reaction reagent is large, and the economical efficiency is poor; thus, in step 4, the second intermediate system is subjected to aerated flotation using a flotation separation device.
Specifically, in the step 4, the flotation separation apparatus includes a flotation machine or a flotation column.
Specifically, in the step 4, the step of air flotation includes: introducing the second intermediate system into a flotation separation device, and performing air flotation; the particles containing cobalt precipitate float up with the bubbles and are concentrated in the upper froth layer, being collected as the froth is discharged.
Or in the steps 1-4, introducing the solution containing zinc and cobalt ions into a flotation separation device, and then adjusting the pH of the solution containing zinc and cobalt ions to be acidic; and then proceeds to step 2-4.
Compared with the prior art, the existing method for separating zinc and cobalt in the solution generally adopts a precipitation method, however, under some conditions, the cobalt ion concentration is lower, larger precipitation particles are difficult to form, and the dosage of the precipitant is required to be increased so as to ensure that the formed precipitation particles meet the requirement of filtering separation on the particle size. Long production times and more excess reagent is required to enlarge the particles; the production efficiency is low, the consumption of the reactant is large, and the economical efficiency is poor. According to the technical scheme, the cobalt ion chelating precipitant alpha-nitroso-beta-naphthol is utilized to selectively chelate cobalt ions in the solution, and the cobalt ions and the cobalt ion chelating precipitant form stable suspended precipitate particles through the particle stabilizer added simultaneously, so that the flotation separation of the cobalt ion chelating precipitate particles in the solution is realized by adopting a microbubble flotation technology, and finally, the selective extraction of low-concentration cobalt ions in the solution is realized, so that the purpose of efficiently separating zinc and cobalt ions in the solution is achieved; the method has the advantages of less reagent consumption, short reaction time, high production efficiency, obvious economic benefit and good zinc-cobalt separation effect.
Example 1
The embodiment provides a zinc-cobalt separation method for selective precipitation flotation of cobalt ions in an acidic solution, which comprises the following steps:
adding a pH regulator into a solution containing 0.5g/L zinc ions and 1mg/L cobalt ions, and regulating the pH value of the solution to 2.0; controlling the temperature of the solution to be 30 ℃, adding a cobalt ion chelating precipitant (alpha-nitroso-beta-naphthol) into the solution, wherein the molar ratio of the addition amount to cobalt ions in the solution is 3:1, and simultaneously adding a particle stabilizer (ferric sulfate solution), and the molar ratio of the addition amount to cobalt ions in the solution is 0.5:1; stirring for 10min at a stirring speed of 50rpm to obtain a solution (a first intermediate system) containing cobalt ion chelate precipitate particles; then adding 10mg/L cetyltrimethylammonium bromide (CTAB) as a surfactant into the mixed solution, and further stirring uniformly to obtain a second intermediate system containing cobalt precipitation suspended particles, wherein the stirring time is 5min; and bubbling air bubbles to carry out floatation, and drying the floated foam product to obtain the cobalt-rich substance. Through the chelating precipitation-floatation process, 85.1% of cobalt ions in the solution can be recovered through floatation, the recovery rate of zinc ion through floatation is 2.1%, the zinc ion content in the obtained cobalt-rich substance is 2.1%, and the zinc-cobalt separation effect is good.
Example 2
Adding a pH regulator into a solution containing 75g/L zinc ions and 1g/L cobalt ions, and regulating the pH value of the solution to be 2.5; controlling the temperature of the solution to be 45 ℃, adding a cobalt ion chelating precipitant (alpha-nitroso-beta-naphthol) into the solution, wherein the molar ratio of the addition amount to cobalt ions in the solution is 5:1, and simultaneously adding a particle stabilizer (ferric chloride solution), and the molar ratio of the addition amount to cobalt ions in the solution is 1:1; stirring for 30min at a stirring speed of 75rpm to obtain a solution (a first intermediate system) containing cobalt ion chelate precipitate particles; then adding 50mg/L cetyltrimethylammonium bromide (CTAB) as a surfactant into the mixed solution, and further stirring uniformly to obtain a second intermediate system containing cobalt precipitation suspended particles, wherein the stirring time is 30min; and bubbling air bubbles to carry out floatation, and drying the floated foam product to obtain the cobalt-rich substance. Through the chelating precipitation-floatation process, 90.8% of cobalt ions in the solution can be recovered through floatation, the recovery rate of zinc ion floatation is 1.3%, the zinc ion content in the obtained cobalt-rich substance is 3.6%, and the zinc-cobalt separation effect is good.
Example 3
Adding a pH regulator into a solution containing 185g/L zinc ions and 5g/L cobalt ions, and regulating the pH value of the solution to 3.5; controlling the temperature of the solution to be 70 ℃, adding a cobalt ion chelating precipitant (alpha-nitroso-beta-naphthol) into the solution, wherein the molar ratio of the addition amount to cobalt ions in the solution is 10:1, and simultaneously adding a particle stabilizer (mixed solution of ferric sulfate and ferric chloride), and the molar ratio of the addition amount to cobalt ions in the solution is 1.5:1; stirring for 60min at a stirring speed of 100rpm to obtain a solution (a first intermediate system) containing cobalt ion chelate precipitate particles; then adding 100mg/L cetyltrimethylammonium bromide (CTAB) as a surfactant into the mixed solution, and further stirring uniformly to obtain a second intermediate system containing cobalt precipitation suspended particles, wherein the stirring time is 60min; and bubbling air bubbles to carry out floatation, and drying the floated foam product to obtain the cobalt-rich substance. Through the chelating precipitation-floatation process, 97.3% of cobalt ions in the solution can be recovered through floatation, the recovery rate of zinc ions through floatation is 1.6%, the zinc ion content in the obtained cobalt-rich substance is 3.9%, and the zinc-cobalt separation effect is good.
Comparative example 1
This comparative example provides a method for separating zinc and cobalt ions, which adopts a xanthate direct precipitation method to treat the same solution containing zinc and cobalt ions as in example 1. The molar ratio of the addition of the chemical reagent to the cobalt ions in the solution is 13:1, a step of; the time of the precipitation treatment is 3-5h; the cobalt ion precipitation of 87.5% in the solution can be recovered, the zinc ion precipitation rate is 8.5%, and the zinc ion content in the obtained cobalt-rich substance is 10.8%. The comparative example has long reaction time, low efficiency, low cobalt recovery rate and poor zinc-cobalt separation effect.
According to the technical scheme, the cobalt ion chelating precipitant (alpha-nitroso-beta-naphthol) is utilized to selectively chelate cobalt ions in the solution, and the cobalt ions and the cobalt ion chelating precipitant form stable suspended precipitate particles through the particle stabilizer added simultaneously, so that the flotation separation of the cobalt ion chelating precipitate particles in the solution is realized by adopting a microbubble flotation technology, and finally, the selective extraction of low-concentration cobalt ions in the solution is realized, so that the purpose of efficiently separating zinc and cobalt ions in the solution is achieved. The method has the advantages of less reagent consumption, short reaction time, high production efficiency, obvious economic benefit and good zinc-cobalt separation effect.
The present invention is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present invention are intended to be included in the scope of the present invention.
Claims (8)
1. A zinc-cobalt separation method for selective precipitation flotation of low-concentration cobalt ions in an acidic solution, which is characterized by comprising the following steps:
step 1, adjusting the pH value of a solution containing zinc and cobalt ions to 2.0-2.5 through a pH regulator;
step 2, simultaneously adding a cobalt ion chelating precipitant and a particle stabilizer into the solution at a certain temperature, and stirring and mixing to obtain a first intermediate system containing cobalt ion chelating suspended particles;
step 3, adding a surfactant into the first intermediate system, and stirring and mixing uniformly to obtain a second intermediate system containing cobalt precipitation suspended particles;
step 4, carrying out aerated flotation on the second intermediate system by adopting a flotation separation device, and collecting particles containing cobalt precipitates;
in the step 1, in the solution containing zinc and cobalt ions, the concentration of the zinc ions is 0.5-185 g/L, and the concentration of the cobalt ions is 1-10 mg/L;
in the step 1, the pH is adjusted to 2.0-2.5 to avoid zinc ion hydrolysis and precipitation in the subsequent step;
in the step 2, the cobalt ion chelating precipitant is alpha-nitroso-beta-naphthol; the molar ratio of the addition amount of the cobalt ion chelating precipitant to cobalt ions in the solution is 3:1-10:1; the particle stabilizer is Fe-containing 3+ A solution; molar ratio of the added amount of the particle stabilizer to cobalt ions in the solution0.5:1 to 1.5:1;
in the step 2, the stirring speed is less than or equal to 100rpm, and the stirring time is 10-60 min;
in the step 3, the surfactant is cetyl trimethyl ammonium bromide, the surfactant is used for further regulating and controlling the particle size and stability, and the addition amount of the surfactant is 10-100 mg/L;
in the step 3, the particle diameter of the suspended particles is 20-50 μm.
2. The method for separating zinc and cobalt according to claim 1, wherein in the step 1, the concentration of zinc ions in the solution containing zinc and cobalt ions is 0.5-170 g/L.
3. The method according to claim 1, wherein in the step 1, the pH of the adjusted solution is 2.0 to 2.2.
4. The method according to claim 1, wherein in the step 1, the pH adjuster is an inorganic acid or a base.
5. The method according to claim 1, wherein in the step 2, the temperature is 30-70 ℃.
6. The method for separating zinc and cobalt according to claim 1, wherein in the step 2, the molar ratio of the addition amount of the cobalt ion chelating precipitant to cobalt ions in the solution is 3:1-9:1.
7. The method for separating zinc and cobalt according to claim 1, wherein in the step 2, the molar ratio of the addition amount of the particle stabilizer to cobalt ions in the solution is 0.5:1 to 1:1.
8. The method for separating zinc from cobalt according to any one of claims 1 to 7, wherein in the step 2, the stirring time is 10 to 55min.
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