CN114774711A - Method for extracting zinc and enriching cobalt from zinc and cobalt-containing solution - Google Patents
Method for extracting zinc and enriching cobalt from zinc and cobalt-containing solution Download PDFInfo
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 123
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 122
- 239000011701 zinc Substances 0.000 title claims abstract description 122
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title claims abstract description 115
- 239000010941 cobalt Substances 0.000 title claims abstract description 114
- 229910017052 cobalt Inorganic materials 0.000 title claims abstract description 114
- 238000000034 method Methods 0.000 title claims abstract description 40
- 238000000605 extraction Methods 0.000 claims abstract description 161
- 239000000243 solution Substances 0.000 claims abstract description 54
- 239000007788 liquid Substances 0.000 claims abstract description 39
- 239000012074 organic phase Substances 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 239000007790 solid phase Substances 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012071 phase Substances 0.000 claims abstract description 11
- 239000003350 kerosene Substances 0.000 claims abstract description 9
- 239000012266 salt solution Substances 0.000 claims abstract description 9
- 230000008021 deposition Effects 0.000 claims abstract description 7
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000284 extract Substances 0.000 claims abstract description 7
- 239000008346 aqueous phase Substances 0.000 claims abstract description 3
- 230000010355 oscillation Effects 0.000 claims abstract description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 18
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 16
- 229910000859 α-Fe Inorganic materials 0.000 claims description 8
- 239000012156 elution solvent Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 238000000151 deposition Methods 0.000 claims description 6
- 150000001412 amines Chemical class 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 5
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 5
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 5
- 229960001763 zinc sulfate Drugs 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- 238000005868 electrolysis reaction Methods 0.000 claims description 3
- 238000002444 silanisation Methods 0.000 claims description 3
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 2
- 230000029936 alkylation Effects 0.000 claims description 2
- 238000005804 alkylation reaction Methods 0.000 claims description 2
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 claims 2
- 239000012535 impurity Substances 0.000 abstract description 5
- 230000002349 favourable effect Effects 0.000 abstract description 2
- 239000002893 slag Substances 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000009854 hydrometallurgy Methods 0.000 description 7
- 238000000746 purification Methods 0.000 description 5
- 230000001186 cumulative effect Effects 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000006247 magnetic powder Substances 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- OXSWKJLAKXNIFG-UHFFFAOYSA-N azane sulfuric acid Chemical compound N.N.N.OS(O)(=O)=O OXSWKJLAKXNIFG-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
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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
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a method for extracting zinc and enriching cobalt from a zinc and cobalt-containing solution, which comprises the following steps: adopting di (2-ethylhexyl) phosphate and sulfonated kerosene to form an extraction organic phase, oscillating for primary extraction to obtain primary extraction liquid and primary raffinate, and washing the primary extraction liquid with a zinc-containing salt solution to obtain a loaded organic phase and a washing water phase; combining the washing aqueous phase and the primary raffinate, and performing secondary extraction by adopting composite extractant oscillation to obtain a secondary extract and a secondary raffinate; and respectively performing back extraction on the primary extraction liquid and the secondary extraction liquid, combining the back extraction liquids, recovering zinc through electrolytic deposition, and enriching cobalt in the secondary extraction raffinate by adopting a magnetic solid phase. The method has the advantages of simple process, no special equipment requirement, easy realization of industrialization, cost investment saving, no introduction of new impurities in the processes of extraction and the like, high purity of the recovered zinc, less impurities, creation of favorable conditions for effective utilization of the cobalt by enrichment of the cobalt, and good economic value.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy, and particularly relates to a method for extracting zinc and enriching cobalt from a zinc and cobalt-containing solution.
Background
The metal cobalt is widely used in the industries of aerospace, mechanical manufacturing, chemistry, ceramics and the like. With the development of economy in China, the consumption of cobalt is continuously increased, but the cobalt resource in China is scarce, large cobalt-containing ore deposits are scarce, and most of cobalt is associated with other metal ore deposits at a lower grade. At present, in the process of mining and utilizing metal zinc, a small amount of cobalt associated in zinc ore is enriched in the beneficiation process of the zinc ore, and then is separated in the form of purified slag in the zinc hydrometallurgy process. Along with the continuous expansion of the zinc hydrometallurgy capacity in China, the purification slag (cobalt-containing waste slag) generated by zinc hydrometallurgy is also continuously increased, and the cobalt-containing waste slag can not be randomly discharged due to certain environmental pollution, so that the cobalt in the zinc hydrometallurgy purification slag is extracted and utilized, the environmental protection pressure of enterprises can be relieved, the scarce metal cobalt can be recycled, and the resource utilization rate is improved.
At present, the following method is generally adopted for treating the cobalt-containing waste residue: (1) selective leaching method: the process leaches cobalt-containing slag under certain conditions, so that most of zinc is dissolved in a solution, and cobalt is left in the leached slag, thereby achieving the purpose of separating and enriching zinc and cobalt, but the process can only partially separate zinc and cobalt in practical application, and cannot achieve the purpose of efficiently separating and recycling zinc and cobalt; (2) ammonia-ammonium sulfate process: the prior paper (Zhao YanKai, Tang-Rong. New treatment process for purifying cobalt slag by zinc hydrometallurgy [ J ]. proceedings of university of south-middle industry, 2001,32(4):371- & 375.) adopts an ammonia water and ammonium sulfate system, the roasted cobalt-containing slag is leached out under the action of an oxidant, then a zinc powder purification method is adopted to carry out deep purification on the leached supernatant and separate zinc, cadmium, cobalt, copper and the like, the solution after cobalt removal adopts an ammonium solution electrolysis method to produce electrolytic zinc, and the cobalt-containing slag is further treated, and the method does not effectively enrich and recycle cobalt.
Because the content of zinc element in the zinc hydrometallurgy purification slag is far higher than that of cobalt, the recovery and the utilization of the cobalt are seriously interfered, and therefore, the effective separation of the zinc and the cobalt from the solution containing the zinc and the cobalt is the main problem to be solved for recovering the cobalt.
Disclosure of Invention
In order to realize the effective separation of zinc and cobalt in the zinc and cobalt solution, the invention provides a method for extracting zinc and enriching cobalt from the zinc and cobalt-containing solution, wherein the zinc is extracted from the solution through primary extraction and secondary extraction, the recovery is realized through back extraction and electrolytic deposition, the purpose of enriching cobalt is achieved through magnetic solid phase extraction of raffinate, the process flow is short, and manpower and material resources are saved.
In order to achieve the purpose, the invention adopts the technical scheme that:
a method for extracting zinc and enriching cobalt from a zinc and cobalt-containing solution comprises the following steps of adopting di (2-ethylhexyl) phosphate (P204) and sulfonated kerosene (No. 260 aviation kerosene) to form an extraction organic phase, oscillating for primary extraction to obtain a primary extraction liquid and a primary raffinate, and washing the primary extraction liquid with a zinc-containing salt solution to obtain a loaded organic phase and a washing water phase; combining the washing aqueous phase and the primary raffinate, and oscillating by adopting a composite extracting agent to perform secondary extraction to obtain a composite extraction liquid and a composite raffinate; respectively back extracting the loaded organic phase and the complex extract, combining the back extract, recovering zinc through electrolytic deposition, and enriching cobalt in the complex raffinate by adopting a magnetic solid phase;
the composite extracting agent comprises 2-ethylhexyl mono-2-ethylhexyl phosphate (P507), tributyl phosphate (TBP) and sulfonated kerosene, wherein in the composite extracting agent, the 2-ethylhexyl mono-2-ethylhexyl phosphate accounts for 20-30% by mass, and the tributyl phosphate accounts for 3-10% by mass; the magnetic solid phase is formed by taking ferrite as a magnetic core and sequentially carrying out silanization and amine grafting on the surface.
Preferably, before primary extraction, dilute sulfuric acid is used for adjusting the pH value of the zinc-containing and cobalt-containing solution to 2.5-5.
Preferably, during the initial extraction, the usage amount of the extraction organic phase is 0.8-3 times of the volume of the zinc-containing and cobalt-containing solution, the shaking extraction time is 5-15 minutes, and the mass percentage of the di (2-ethylhexyl) phosphate in the extraction organic phase is 10-20%.
Preferably, when the zinc-containing salt solution is washed, the zinc-containing salt solution is 0.2-0.6 mol/L zinc sulfate solution, the usage amount of the zinc-containing salt solution is 0.05-0.2 time of the volume of the primary extraction liquid, and the washing time is 3-10 minutes.
Preferably, during the secondary extraction, the usage amount of the composite extracting agent is 0.8-2 times of the total volume of the washing water phase and the primary raffinate, and the oscillation extraction time is 5-10 minutes.
Preferably, during the back extraction, 10-20% of dilute sulfuric acid is used as a back extraction agent to perform 2-3 levels of back extraction, the time of each level of back extraction is 3-10 minutes, and the total usage amount of the back extraction agent is 1-2 times of the total volume of the loaded organic phase and the complex extraction liquid.
Preferably, the electrolytic deposition adopts direct electrolysis of the solution after stripping, and the control conditions are as follows: at a temperature of 25 to 40 ℃ and a current density of 300 to 500A/m2The voltage is 3.0-5.0V, and the processing efficiency is 0.3-0.8L/h.
Preferably, when the magnetic solid phase is enriched with cobalt, the magnetic solid phase extracts cobalt from the complex raffinate in an oscillating mode, and then the magnetic solid phase is transferred to an elution solvent to be eluted under the action of an external magnetic field, so that the separation and concentration effects are achieved.
Preferably, the alkylation is carried out by using gamma-aminopropyltriethoxysilane, the amine grafting is carried out by using diethylenetriamine, and the elution solvent is dilute sulfuric acid with the temperature of 35-50 ℃ and the mass percent of 1.5-2.5%.
Preferably, the organic liquid obtained after the back extraction of the primary extraction liquid returns to the primary extraction cycle, and the organic liquid obtained after the back extraction of the secondary extraction liquid returns to the extraction cycle.
When the cobalt concentration in the zinc-containing and cobalt-containing solution is low, the removal effect is not ideal in both oxidation precipitation and replacement, and other impurities may be introduced. Therefore, the invention adopts the solvent extraction method to extract zinc from the solution, then enriches cobalt from the extracted solution, realizes the separation of zinc and cobalt by controlling the conditions of pH and organic phase in the extraction process, and the organic phase has stable performance in multiple recycling use without the phenomena of emulsification and third phase in the extraction process. During initial extraction, P204 with strong extraction capacity is selected, and H separated out during zinc extraction by P204+Will dissolveThe pH value of the solution is reduced, so that the solution containing zinc and cobalt is adjusted to be acidic before primary extraction, but the pH value is not easy to be too low, and the higher extraction rate of zinc can be ensured; and during secondary extraction, P507 with good selectivity is adopted, and a small amount of TBP is added to form an extraction system with good synergistic effect, so that the generation of a third phase is inhibited, and the extraction of zinc is further completed.
The method has the advantages of simple process, no special equipment requirement, easy realization of industrialization, short extraction period, no introduction of new impurities in the working procedures of extraction and the like, return reuse of organic liquid used in the extraction, cost investment saving, high purity of recovered zinc, less impurities, creation of favorable conditions for effective utilization of the zinc due to cobalt enrichment and good economic value.
Drawings
Fig. 1 is a flow chart of the process for extracting zinc and enriching cobalt from a zinc and cobalt-containing solution.
Detailed Description
In order to make the technical purpose, technical solutions and advantages of the present invention clearer, the technical solutions of the present invention are further described with reference to specific examples, which are intended to explain the present invention and are not to be construed as limiting the present invention, and those who do not specify a specific technique or condition in the examples follow the techniques or conditions described in the literature in the art or follow the product specification.
Example 1
A process for extracting zinc and enriching cobalt from a zinc and cobalt containing solution, as shown in figure 1, comprising the steps of:
(1) preparing a zinc-containing and cobalt-containing solution (containing 0.60 g/L zinc and 0.15 g/L cobalt) by adopting zinc sulfate and cobalt sulfate, and adjusting the pH value of the zinc-containing and cobalt-containing solution to be 4 by using dilute sulfuric acid;
(2) forming an extraction organic phase (15 wt% of P204) by adopting P204 and No. 260 aviation kerosene, wherein the volume ratio (namely the ratio of O/A) of the extraction organic phase to a zinc-containing and cobalt-containing solution is 1:1, and oscillating for 10 min for primary extraction to obtain primary extraction liquid and primary raffinate;
(3) washing the primary extraction liquid obtained in the step (2) by using a zinc sulfate solution of 0.4 mol/L, wherein the volume ratio (namely the ratio A/O) of the zinc sulfate solution to the primary extraction liquid is 1:10, and washing for 5 minutes to obtain a loaded organic phase and a washing water phase;
(4) combining the washing water phase obtained in the step (3) with the primary raffinate obtained in the step (2), adopting P507, TBP and No. 260 aviation kerosene to form a composite extracting agent (25 wt% of P507 and 5wt% of TBP), wherein the total volume of the composite extracting agent is the same as that of the washing water phase and the primary raffinate (compared with O/A1: 1), and oscillating for 8 min for carrying out complex extraction to obtain a complex extraction liquid and a complex raffinate;
(5) carrying out three-stage back extraction on the loaded organic phase obtained in the step (3) and the complex extraction liquid obtained in the step (4) by respectively adopting 15% dilute sulfuric acid as a back extraction agent, wherein the using amount of the back extraction agent in each stage is 0.5:1 in terms of the ratio of A/O (namely the total using amount of the back extraction agent is 1.5 times of the total volume of the loaded organic phase and the complex extraction liquid), and the time of each stage of back extraction is 4 minutes; returning organic liquid obtained after the primary extraction liquid is subjected to back extraction to the primary extraction cycle, returning organic liquid obtained after the secondary extraction liquid is subjected to back extraction to the extraction cycle, and combining the primary extraction liquid and the secondary extraction liquid to obtain back extraction liquid after the back extraction;
(6) directly electrolyzing the combined back extraction solution obtained in the step (5) by adopting electrolytic deposition, and collecting cathode zinc; the control conditions are as follows: the temperature is 30 ℃, and the current density is 400A/m2The voltage is 3.0-5.0V, and the treatment efficiency is 0.6L/h;
(7) and (3) adding a magnetic solid phase (the using amount is 1 g/L) into the complex raffinate obtained in the step (4), oscillating and extracting for 10 min, and transferring the magnetic solid phase into an elution solvent to desorb under the action of an external magnetic field to achieve the effect of enriching cobalt.
The influence of the adjustment of each parameter on the effect is detected from the adjustment of pH in step (1), the ratio of P204 in step (2), and the ratios of P507 and TBP in step (4) as influencing factors, respectively, wherein when one influencing factor is adjusted, the other two influencing factors remain the same according to the parameters given in example 1.
a) Adjusting the pH value in the step (1): respectively using dilute sulfuric acid to regulate the pH values of zinc-containing solution and cobalt-containing solution to be 2, 3, 4, 5 and 6, detecting the contents of zinc and cobalt in the primary extraction, then calculating the extraction rates of zinc and cobalt, and obtaining the results: when the pH is =2, the zinc extraction rate is 32.6% and the cobalt extraction rate is 0.73%; when the pH is =3, the zinc extraction rate is 42.4% and the cobalt extraction rate is 0.63%; when the pH is =4, the zinc extraction rate is 48.3% and the cobalt extraction rate is 0.82%; when the pH is =5, the zinc extraction rate is 40.8% and the cobalt extraction rate is 1.21%; when the pH =6, the zinc extraction rate was 27.3% and the cobalt extraction rate was 2.46%.
b) In the step (2), the proportion of P204 is respectively adjusted to 10wt%, 15wt%, 20wt% and 25wt%, the content of zinc and cobalt in the primary extraction is detected, and then the extraction rates of zinc and cobalt are calculated, and the result is as follows: when the P204 accounts for 10wt%, the zinc extraction rate is 40.1% and the cobalt extraction rate is 0.72%; when the P204 accounts for 15wt%, the zinc extraction rate is 47.6% and the cobalt extraction rate is 0.84%; when the P204 accounts for 20wt%, the zinc extraction rate is 50.5%, and the cobalt extraction rate is 1.20%; when P204 accounts for 25wt%, the zinc extraction rate is 52.6% and the cobalt extraction rate is 2.27%.
c) In the step (4), the proportion of P507 is respectively adjusted to 15wt%, 20wt%, 25wt% and 30wt%, the content of zinc in the re-extraction is detected, and then the cumulative extraction rate of zinc is calculated, and the result is as follows: when P507 accounts for 15wt%, the accumulative extraction rate of zinc is 78.4%; when P507 accounts for 20wt%, the accumulative extraction rate of zinc is 90.1%; when P507 accounts for 25wt%, the accumulative extraction rate of zinc is 96.2%; when P507 accounts for 30wt%, the accumulative extraction rate of zinc is 98.0%.
d) Adjusting the TBP ratio in the step (4) to be 0, 3wt%, 5wt% and 10wt% respectively, detecting the content of zinc in the re-extraction, and then calculating the cumulative extraction rate of zinc, wherein the result is as follows: when the TBP is not contained, the accumulative extraction rate of zinc is 66.7 percent; when TBP accounts for 3wt%, the accumulative extraction rate of zinc is 83.5%; when TBP accounts for 5wt%, the accumulative extraction rate of zinc is 96.8%; when TBP accounts for 10wt%, the cumulative extraction rate of zinc is 91.7%.
From the above detection results, it can be seen that when P204 is used as an extractant, the extraction rate of cobalt is much lower than that of zinc, and although the extraction of zinc by P204 needs to be performed under acidic conditions, H precipitated during the extraction process+The pH of the solution can be reduced, so that the pH is not easy to be too low before the initial extraction; when the pH value of the extraction water phase is 4, the difference between the extraction rates of zinc and cobalt is the largest, the extraction rate of zinc is the largest at this moment, nearly half of zinc can be separated out through primary extraction, and most of cobalt still remains in the aqueous solution. The higher the concentration of P204 is, the higher the extraction rate of zinc and cobalt is, considering the problems of dosage and cost of an extracting agent and reducing the loss of cobalt in primary extraction, 15wt% of P204 (No. 260 aviation kerosene) is selectedAs a diluting solvent). In addition, the detection data of P507 and TBP show that the addition of TBP can greatly increase the extraction rate of P507, and the cumulative extraction rate of zinc can reach 98.0% after repeated extraction. The recovery rate of the zinc extracted by the embodiment reaches more than 95 percent.
Example 2
On the basis of the embodiment 1, the magnetic solid phase in the step (7) is formed by taking ferrite as a magnetic core and sequentially performing silanization and amine grafting on the surface, and the specific steps are as follows:
crushing and sieving ferrite to obtain ferrite powder with the granularity of 1250 meshes (common commercial products are adopted, the specific saturation magnetic moment is about 10-70 Am/kg, and the coercive force is 80-600A/m), washing, drying water, and drying for 2 hours in vacuum; then dispersing 15 g of ferrite powder in 250 mL of mixed solution of ethanol and acetone (v: v =7: 3), heating to 60 ℃ in the nitrogen atmosphere, adding 10 mL of gamma-aminopropyltrimethoxysilane, keeping the closed reflux of the solution system, stirring for 8 hours at constant temperature, then carrying out solid-liquid separation, washing the solid with ethanol, and carrying out vacuum drying for 4 hours at 90 ℃ to obtain silanized magnetic powder; dispersing 10 g of silanized magnetic powder in a mixed solution of 225 mL of ethanol and water (v: v =7: 3), heating to 80 ℃ in a nitrogen atmosphere, adding 11.3 mL of diethylenetriamine, keeping the closed reflux of a solution system, stirring at a constant temperature for 8 hours, then carrying out solid-liquid separation, taking the solid, alternately washing with ethanol and water, controlling the water content to be dry, and carrying out vacuum drying at 90 ℃ for 3 hours to obtain amino grafted magnetic powder, namely a magnetic solid phase. The method has the advantages that the diethylenetriamine is coupled and grafted to the surface of the ferrite through the bridging action of the gamma-aminopropyltrimethoxysilane, so that the acid resistance, the ion exchange property and the affinity of the ferrite are improved, and the cobalt in the solution can be extracted by forming coordination bonding with the cobalt.
When desorbing after magnetic solid phase extraction of cobalt, dilute sulfuric acid with the temperature of 40 ℃ and the concentration of 2% is used as an elution solvent, and the volume ratio (namely, the ratio A/O) of the elution solvent to the re-extraction raffinate is 1: 20. The final cobalt-enriched solution of this example was found to contain 2.51 g/L cobalt.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A method for extracting zinc and enriching cobalt from a zinc and cobalt-containing solution comprises the following steps of adopting di (2-ethylhexyl) phosphate and sulfonated kerosene to form an extraction organic phase, oscillating for primary extraction to obtain a primary extraction liquid and a primary raffinate, and is characterized in that: washing the primary extraction liquid with a zinc-containing salt solution to obtain a loaded organic phase and a washing water phase; combining the washing aqueous phase and the primary raffinate, and oscillating by adopting a composite extracting agent to perform secondary extraction to obtain a composite extraction liquid and a composite raffinate; respectively back extracting the loaded organic phase and the complex extract, combining the back extract, recovering zinc through electrolytic deposition, and enriching cobalt in the complex raffinate by adopting a magnetic solid phase;
the composite extracting agent comprises 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester, tributyl phosphate and sulfonated kerosene, wherein in the composite extracting agent, the 2-ethylhexyl phosphoric acid mono-2-ethylhexyl ester accounts for 20-30% by mass, and the tributyl phosphate accounts for 3-10% by mass; the magnetic solid phase is formed by taking ferrite as a magnetic core and sequentially carrying out silanization and amine grafting on the surface.
2. A process for the extraction of zinc and enrichment of cobalt from a zinc and cobalt containing solution according to claim 1, characterized in that: before primary extraction, dilute sulfuric acid is used for adjusting the pH value of a zinc-containing and cobalt-containing solution to 2.5-5.
3. The process of claim 1 for extracting zinc and enriching cobalt from a zinc and cobalt containing solution, wherein: during primary extraction, the usage amount of an extraction organic phase is 0.8-3 times of the volume of a zinc-containing and cobalt-containing solution, the shaking extraction time is 5-15 minutes, and the mass percentage of di (2-ethylhexyl) phosphate in the extraction organic phase is 10-20%.
4. A process for the extraction of zinc and enrichment of cobalt from a zinc and cobalt containing solution according to claim 1, characterized in that: when the zinc-containing salt solution is washed, the zinc-containing salt solution is 0.2-0.6 mol/L zinc sulfate solution, the usage amount of the zinc-containing salt solution is 0.05-0.2 time of the volume of the primary extraction liquid, and the washing time is 3-10 minutes.
5. A process for the extraction of zinc and enrichment of cobalt from a zinc and cobalt containing solution according to claim 1, characterized in that: and during secondary extraction, the usage amount of the composite extracting agent is 0.8-2 times of the total volume of the washing water phase and the primary raffinate, and the oscillation extraction time is 5-10 minutes.
6. The process of claim 1 for extracting zinc and enriching cobalt from a zinc and cobalt containing solution, wherein: during back extraction, 10-20% of dilute sulfuric acid is used as a back extraction agent to perform 2-3 levels of back extraction, the time of each level of back extraction is 3-10 minutes, and the total usage amount of the back extraction agent is 1-2 times of the total volume of the loaded organic phase and the complex extraction liquid.
7. A process for the extraction of zinc and enrichment of cobalt from a zinc and cobalt containing solution according to claim 1, characterized in that: the electrolytic deposition adopts the direct electrolysis of the solution after back extraction, and the control conditions are as follows: the temperature is 25-40 ℃, and the current density is 300-500A/m2The voltage is 3.0-5.0V, and the processing efficiency is 0.3-0.8L/h.
8. A process for the extraction of zinc and enrichment of cobalt from a zinc and cobalt containing solution according to claim 1, characterized in that: when the magnetic solid phase is enriched with cobalt, the magnetic solid phase extracts cobalt from the complex raffinate in an oscillating mode, and then the magnetic solid phase is transferred into an elution solvent to be eluted under the action of an external magnetic field, so that the separation and concentration effects are achieved.
9. A process for the extraction of zinc and enrichment of cobalt from a zinc and cobalt containing solution according to claim 8, characterized in that: the alkylation is carried out by using gamma-aminopropyltriethoxysilane, the amine grafting is carried out by using diethylenetriamine, and the elution solvent is dilute sulfuric acid with the temperature of 35-50 ℃ and the mass percent of 1.5-2.5%.
10. A process for the extraction of zinc and the enrichment of cobalt from a zinc and cobalt containing solution according to any one of claims 1 to 9, characterized in that: and returning the organic liquid obtained after the primary extraction liquid is subjected to back extraction to the primary extraction cycle, and returning the organic liquid obtained after the secondary extraction liquid is subjected to back extraction to the extraction cycle.
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