CN114774689B - Extraction agent of nickel-cobalt synergistic extraction system containing organic phosphine oxide extraction agent and nickel-cobalt extraction method - Google Patents
Extraction agent of nickel-cobalt synergistic extraction system containing organic phosphine oxide extraction agent and nickel-cobalt extraction method Download PDFInfo
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- 238000000605 extraction Methods 0.000 title claims abstract description 227
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 49
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 35
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 189
- 239000012074 organic phase Substances 0.000 claims abstract description 91
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 83
- 239000010941 cobalt Substances 0.000 claims abstract description 51
- 229910017052 cobalt Inorganic materials 0.000 claims abstract description 51
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims abstract description 51
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 38
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 32
- 238000000658 coextraction Methods 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 28
- 229910052751 metal Inorganic materials 0.000 claims abstract description 23
- 239000002184 metal Substances 0.000 claims abstract description 19
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims description 50
- 239000007788 liquid Substances 0.000 claims description 44
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid group Chemical group S(O)(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 238000002156 mixing Methods 0.000 claims description 25
- 239000011701 zinc Substances 0.000 claims description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 15
- 229910052725 zinc Inorganic materials 0.000 claims description 15
- 125000004432 carbon atom Chemical group C* 0.000 claims description 10
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 229910052739 hydrogen Inorganic materials 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 claims description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 3
- 238000011084 recovery Methods 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 abstract description 33
- 239000011572 manganese Substances 0.000 abstract description 32
- 239000011575 calcium Substances 0.000 abstract description 28
- 238000000926 separation method Methods 0.000 abstract description 20
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 abstract description 17
- 229910052749 magnesium Inorganic materials 0.000 abstract description 17
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 abstract description 16
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 16
- 229910052791 calcium Inorganic materials 0.000 abstract description 16
- 229910052748 manganese Inorganic materials 0.000 abstract description 16
- 238000005191 phase separation Methods 0.000 abstract description 12
- 230000008569 process Effects 0.000 abstract description 12
- 239000012535 impurity Substances 0.000 abstract description 10
- 150000002739 metals Chemical class 0.000 abstract description 8
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 5
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 5
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000536 complexating effect Effects 0.000 abstract description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 abstract description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 abstract description 2
- 229910001424 calcium ion Inorganic materials 0.000 abstract description 2
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 2
- 229910001437 manganese ion Inorganic materials 0.000 abstract description 2
- KQNPFQTWMSNSAP-UHFFFAOYSA-N isobutyric acid Chemical compound CC(C)C(O)=O KQNPFQTWMSNSAP-UHFFFAOYSA-N 0.000 description 32
- 239000000243 solution Substances 0.000 description 32
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 20
- 230000000694 effects Effects 0.000 description 17
- 239000003350 kerosene Substances 0.000 description 17
- MNZAKDODWSQONA-UHFFFAOYSA-N 1-dibutylphosphorylbutane Chemical compound CCCCP(=O)(CCCC)CCCC MNZAKDODWSQONA-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 239000003085 diluting agent Substances 0.000 description 13
- 238000010828 elution Methods 0.000 description 11
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 description 10
- 239000002253 acid Substances 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- 230000008901 benefit Effects 0.000 description 6
- HSSJULAPNNGXFW-UHFFFAOYSA-N [Co].[Zn] Chemical compound [Co].[Zn] HSSJULAPNNGXFW-UHFFFAOYSA-N 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 230000010355 oscillation Effects 0.000 description 5
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 5
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- GHVNFZFCNZKVNT-UHFFFAOYSA-N decanoic acid Chemical compound CCCCCCCCCC(O)=O GHVNFZFCNZKVNT-UHFFFAOYSA-N 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 239000008346 aqueous phase Substances 0.000 description 3
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 3
- -1 pyridine carboxylate Chemical class 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 235000012054 meals Nutrition 0.000 description 2
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- HVSMSQXVXWYTSI-UHFFFAOYSA-N CCCCCP(O)=O Chemical compound CCCCCP(O)=O HVSMSQXVXWYTSI-UHFFFAOYSA-N 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- IHBCFWWEZXPPLG-UHFFFAOYSA-N [Ca].[Zn] Chemical compound [Ca].[Zn] IHBCFWWEZXPPLG-UHFFFAOYSA-N 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- NAGJZTKCGNOGPW-UHFFFAOYSA-N dithiophosphoric acid Chemical compound OP(O)(S)=S NAGJZTKCGNOGPW-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000010327 methods by industry Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000021110 pickles Nutrition 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007127 saponification reaction Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004088 simulation Methods 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 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
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application relates to the technical field of extraction, in particular to a nickel-cobalt synergistic extraction system containing an organic phosphine oxide extractant and a nickel-cobalt extraction method. An alkyl hydroxyoxime, a carboxylic acid extractant and an organic phosphine oxide extractant of a nickel cobalt synergistic extraction system. The nickel cobalt co-extraction process by using the co-extraction system comprises the following steps: extracting the metal ion solution by using an organic phase containing a synergistic extraction system to obtain a loaded organic phase; and back-extracting the loaded organic phase by using a back-extracting agent to obtain the back-extracting solution enriched with nickel and cobalt. Compared with the impurity metal ions such as magnesium ions, manganese ions, calcium ions and the like, the synergistic extraction system has stronger selective complexing effect on nickel ions and cobalt ions, and realizes the extraction of nickel and/or cobalt at normal temperature and the effective separation of the impurity metals such as calcium, magnesium, manganese and the like. The extraction agent of the synergistic extraction system can be carried out at room temperature in the extraction and back extraction processes, has high efficiency, short time and good phase separation performance in the extraction and back extraction processes, has clear oil-water interface and has wide application prospect.
Description
Technical Field
The application relates to the technical field of extraction, in particular to a nickel-cobalt synergistic extraction system containing an organic phosphine oxide extractant and a nickel-cobalt extraction method.
Background
Nickel and cobalt are important nonferrous metals and are widely applied to the fields of aviation, petrochemical industry, ceramics, electronics, batteries, medicine and the like. Wet leaching is an important method for treating low-grade refractory nickel-cobalt resources. The solvent extraction method has the advantages of low energy consumption, short flow, good purification effect, easy automation control and the like, and is widely applied to the separation and purification of nickel and cobalt in the pickle liquor.
The solvent extraction method mainly comprises an acidic phosphine extraction method, an amine extraction method, a synergistic extraction method and the like, wherein the synergistic extraction method is to extract metal under the same extraction condition after two or more extraction agents are mixed, the distribution ratio of the synergistic extraction agent with the synergistic effect is obviously larger than the sum of the distribution ratios of the extraction metals of the independent extraction agents, and saponification of the acidic phosphine extraction agent can be avoided, so that ammonia nitrogen wastewater cannot occur, and the environment is not damaged. For nickel cobalt synergistic extractant, such as 'bis (2, 4-trimethyl amyl) dithiophosphoric acid+ (2, 4-trimethyl amyl) phosphinic acid', 'alkyl hydroxyoxime + Versatic10 acid', 'pyridine carboxylate + Versatic10 acid', 'alkyl hydroxyoxime + Versatic10 acid + tributyl phosphate' and the like, wherein partial synergistic systems are different in phase, poor in separation coefficient, slow in back extraction rate of nickel and the like. The alkyl hydroxyoxime, versatic10 acid and tributyl phosphate synergistic extraction system has the advantages of better separation coefficient, but still needs to be heated to realize nickel back extraction, so that the process is complex in practical application, and the energy consumption is increased, so that the nickel back extraction is limited.
Disclosure of Invention
The application aims to provide a nickel-cobalt synergistic extraction system containing an organic phosphine oxide extractant, which aims to solve the technical problem of low nickel stripping efficiency in a nickel-cobalt synergistic extraction process in the prior art.
In order to achieve the above purpose, the application adopts the following technical scheme:
a nickel cobalt synergistic extraction system containing an organic phosphine oxide extractant comprises an alkyl hydroxyoxime shown in a formula (1), a carboxylic acid extractant shown in a formula (2) and an organic phosphine oxide extractant shown in a formula (3);
wherein R is 1 And R is 2 Respectively any one of substituted or unsubstituted alkyl with 4-12 carbon atoms; r is R 3 Is hydrogen, or is substitutedOr any one of unsubstituted alkyl groups; r is R 4 Is any one of a substituted or unsubstituted straight-chain alkyl group, a substituted or unsubstituted cycloalkyl group and a substituted or unsubstituted branched-chain alkyl group having 4 to 12 carbon atoms; r is R 5 、R 6 、R 7 Is any one of substituted or unsubstituted alkyl groups having 4 to 12 carbon atoms.
The scheme also provides a nickel-cobalt co-extraction method of the nickel-cobalt co-extraction system containing the organic phosphine oxide extractant, which comprises the following steps in sequence:
s1, extraction: extracting a metal ion solution by using the initial organic phase to obtain a loaded organic phase and a raffinate;
s2, back extraction: and stripping the loaded organic phase by using a stripping agent to obtain an unloaded organic phase and stripping liquid.
The nickel-cobalt co-extraction method of the nickel-cobalt co-extraction system containing the organic phosphine oxide extractant comprises the following steps in sequence:
SS1 extraction: extracting a metal ion solution by using the initial organic phase to obtain a loaded organic phase and a raffinate;
SS2 washing: washing the loaded organic phase by using a washing liquid to obtain a washed loaded organic phase;
SS3 strip: and stripping the washed loaded organic phase by using a stripping agent to obtain an unloaded organic phase and stripping liquid.
The principle and the advantages of the scheme are as follows:
the scheme provides a nickel-cobalt synergistic extraction system extractant comprising an organic phosphine oxide extractant, alkyl hydroxyoxime and carboxylic acid, has a strong selective coordination effect on nickel-cobalt, can be used for extracting and separating nickel-cobalt from other metal impurities, not only realizes the extraction and separation of nickel-cobalt from impurity metals (calcium, magnesium, manganese and the like), but also solves the defect of difficult back extraction of nickel.
The scheme also provides a method for extracting and separating nickel and cobalt from impurity metals (calcium, magnesium, manganese and the like) by utilizing the nickel and cobalt synergistic extractant comprising the organic phosphine oxide extractant, the alkyl hydroxyoxime and the carboxylic acid. In the process engineering of co-extracting nickel and cobalt, the organic phase containing the nickel and cobalt co-extraction system extractant is mixed and extracted relative to the aqueous solution containing nickel ions and/or cobalt ions and impurity metal ions, the extraction balance pH value is controlled to be in a certain range for extraction, and the extracted organic phase is subjected to back extraction to obtain the solution rich in nickel ions and/or cobalt ions for removing impurity ions. The technical proposal simultaneously ensures that nickel is easy to strip, and simplifies the separation process. In addition, the synergistic extractant has the advantages of high selectivity, fast extraction kinetics, fast phase separation, easy back extraction and the like.
In conclusion, the beneficial effects of the technical scheme are as follows:
the extraction agent of the synergistic extraction system realizes the extraction of nickel and/or cobalt and the effective separation of impurity metals such as calcium, magnesium, manganese and the like at normal temperature, and the synergistic extraction system has stronger selective complexing action on nickel ions and cobalt ions compared with impurity metal ions such as magnesium ions, manganese ions, calcium ions and the like, so that the extraction separation of nickel cobalt and impurity metals can be realized, and meanwhile, the complexing action of the synergistic extraction system on nickel ions is stronger than that of cobalt ions, and nickel and cobalt can be further separated.
The chelate formed by alkyl hydroxyoxime and nickel can be changed into nickel complex by adding organic phosphine oxide extractant. Thus, nickel is easily stripped in a short time and at room temperature (without heating), the problem of difficult nickel stripping is solved, and the extraction rate and extraction rate are not affected by the addition of the nickel stripping solution.
The extraction agent of the synergistic extraction system can be carried out at room temperature in the extraction and back extraction processes, has high efficiency, short time, good phase separation performance, clear oil-water interface, good solubility in sulfonated kerosene and aviation kerosene and simple operation.
Further, the molar ratio of the alkyl hydroxyoxime, the carboxylic acid extractant and the organophosphinic oxide extractant is 0.1-2.0:0.1-5.0:0.1-6.0. By adopting the proportion, the ideal effects of extraction, back extraction and washing can be obtained.
Further, the nickel-cobalt synergistic extraction system is used for preparing an initial organic phase, and the volume concentration of the nickel-cobalt synergistic extraction system in the initial organic phase is 0.1-60%. By adopting the proportion and the volume concentration, the ideal effects of extraction, back extraction and washing can be obtained.
Further, the diluent in the organic phase is sulfonated kerosene and/or aviation kerosene. Sulfonated kerosene and aviation kerosene are diluents commonly used in the prior art, are stable in properties and are easy to obtain.
Further, in S1 or SS1, the metal ion solution contains Zn 2+ 、Ni 2+ 、Co 2+ 、Mn 2+ 、Mg 2+ And Ca 2+ ；Ni 2 + 、Co 2+ The ion concentration ranges of the ion concentration ranges are 0.01-10g/L; zn (zinc) 2+ 、Mn 2+ 、Mg 2+ And Ca 2+ The ion concentration ranges of the ion concentration ranges are 0.01-20g/L; the pH value of the metal ion solution is 4.0-6.0, the volume ratio of the initial organic phase to the metal ion solution is 6:1-1:1, and the extraction mixing time is 1-5min; the ambient temperature is-10-45 ℃; the equilibrium pH is 5-5.5. By adopting the parameter conditions, nickel and cobalt can be extracted from the metal ion solution with higher extraction rate, and the separation of the nickel and cobalt from other metal ions can be realized.
Further, in S2, the stripping agent is sulfuric acid solution with the concentration of 20-200 g/L; in S2, the volume ratio of the loaded organic phase to the stripping agent is 5:1-1:5, and the stripping mixing time is 3-10min; the ambient temperature is-10-45 ℃. By adopting the parameter conditions, nickel and cobalt can be extracted from the loaded organic phase with higher meal extraction rate, so that the recovery and enrichment of the two metal ions are realized.
Further, in SS2, the washing liquid contains 0.01-10g/L Ni 2+ The volume ratio of the loaded organic phase to the washing liquid is 0.8:1-50:1, and the washing mixing time is 1-5min; the ambient temperature is-10-45 ℃; the equilibrium pH is 1.0-5.5. By adopting the elution parameter conditions, college elution of zinc and cobalt can be realized, and separation of nickel and zinc cobalt can be realized.
Further, in SS3, the stripping agent is sulfuric acid solution with the concentration of 20-200 g/L; the volume ratio of the loaded organic phase to the stripping agent after washing is 5:1-1:5, and the stripping mixing time is 3-10min; the ambient temperature is-10-45 ℃. By adopting the parameter conditions, nickel can be extracted from the loaded organic phase with higher meal extraction rate, and recovery and enrichment of the nickel are realized.
Drawings
FIG. 1 is a graph showing the pH equilibrium isotherm of metal ion extraction in example 1 of the present application.
FIG. 2 shows the kinetics of metal ion extraction in example 2 of the present application.
FIG. 3 is a graph showing the equilibrium isotherm of the concentration of metal ion stripping acid in example 5 of the present application.
FIG. 4 is a pH equilibrium isotherm of the metal ion wash of example 6 of the present application.
Detailed Description
The present application will be described in further detail with reference to the following embodiments, but the embodiments of the present application are not limited thereto. The technical means used for the following implementation are, unless otherwise indicated, conventional means well known to those skilled in the art: the materials, reagents, and the like used are all commercially available.
The nickel-cobalt co-extraction method of the nickel-cobalt co-extraction system containing the organic phosphine oxide extractant comprises the following steps in sequence:
s1, extraction: and extracting the metal ion solution by using the initial organic phase to obtain a loaded organic phase and raffinate.
The metal ion solution contains Zn 2+ 、Ni 2+ 、Co 2+ 、Mn 2+ 、Mg 2+ And Ca 2+ 。Ni 2+ 、Co 2+ The ion concentration ranges of the ion concentration ranges are 0.01-10g/L; zn (zinc) 2+ 、Mn 2+ 、Mg 2+ And Ca 2+ The ion concentration ranges of 0.01-20g/L. The pH value of the metal ion solution is 4.0-6.0.
The volume ratio of the initial organic phase to the metal ion solution is 5:1-1:5 (preferably 6:1-1:1), and the extraction mixing time is 1-5min; the ambient temperature is-10-45deg.C (which can be performed at room temperature, 0-30deg.C); the equilibrium pH is 5-5.5.
The initial organic phase consists of a nickel cobalt co-extraction system and a diluent. The diluent is sulfonated kerosene and/or aviation kerosene. The volume concentration of the nickel cobalt synergistic extraction system in the initial organic phase is 0.1-60%. The nickel-cobalt synergistic extraction system containing the organic phosphine oxide extractant is characterized by comprising alkyl hydroxyoxime shown in a formula (1), a carboxylic acid extractant shown in a formula (2) and the organic phosphine oxide extractant shown in a formula (3);
wherein R is 1 And R is 2 Respectively any one of substituted or unsubstituted alkyl with 4-12 carbon atoms; r is R 3 Is hydrogen, or is any one of substituted or unsubstituted alkyl; r is R 4 Is any one of a substituted or unsubstituted straight-chain alkyl group, a substituted or unsubstituted cycloalkyl group and a substituted or unsubstituted branched-chain alkyl group having 4 to 12 carbon atoms; r is R 5 、R 6 、R 7 Is any one of substituted or unsubstituted alkyl groups having 4 to 12 carbon atoms. The molar ratio of the alkyl hydroxyoxime, the carboxylic acid extractant and the organic phosphine oxide extractant is 0.1-2.0:0.1-5.0:0.1 to 6.0, preferably 0.1 to 2.0;0.1-5.0;0.1-2.0. Through experimental research, the composition of the three extracting agents with the molar ratio and the concentration range can realize the efficient extraction of nickel and cobalt, and can realize the efficient stripping of nickel and cobalt under the condition that acid is used as a stripping agent; and can also realize the effective separation of nickel and cobalt zinc in the washing process after extraction.
S2, back extraction: and stripping the loaded organic phase by using a stripping agent to obtain an unloaded organic phase and stripping liquid.
The stripping agent is sulfuric acid solution (preferably 20-200 g/L) with concentration of 0.02-2 mol/L. The volume ratio of the loaded organic phase to the back-extraction agent is 5:1-1:5, and the back-extraction mixing time is 3-10min; the ambient temperature is-10-45 ℃.
The nickel-cobalt synergistic extraction system containing the organic phosphine oxide extractant is used for nickel-cobalt co-extraction, and can also realize nickel-cobalt separation by washing, and the specific flow is as follows:
SS1 extraction: and extracting the metal ion solution by using the initial organic phase to obtain a loaded organic phase and raffinate. This step is the same as the S1 extraction described above.
SS2 washing: and washing the loaded organic phase by using a washing liquid to obtain a washed loaded organic phase. More specifically, in SS2, the washing liquid contains 0.01-10g/L Ni 2+ The volume ratio of the loaded organic phase to the washing liquid is 0.8:1-50:1, and the washing mixing time is 1-5min; the ambient temperature is-10-45 ℃; the equilibrium pH is 1.0-5.5.
SS3 strip: and stripping the washed loaded organic phase by using a stripping agent to obtain an unloaded organic phase and stripping liquid. More specifically, in SS3, the stripping agent is sulfuric acid solution with the concentration of 20-200 g/L; the volume ratio of the loaded organic phase to the stripping agent after washing is 5:1-1:5, and the stripping mixing time is 3-10min; the ambient temperature is-10-45 ℃.
The above is a description of the technological process of nickel cobalt co-extraction, and specific examples are as follows:
example 1: sequential experiment of extraction metals
Aqueous feed liquid (metal ion solution): simulation of feed liquid (sulfate system), feed liquid containing Cu 2+ 0.057g/L，Ni 2+ 3.48g/L，Co 2+ 0.79g/L，Zn 2+ 0.34g/L，Ca 2+ 0.98g/L，Mg 2+ 10.78g/L，Mn 2+ 2.97g/L and pH 5.21.
Initial organic phase: sulfonated kerosene is used as a diluent, the concentration of isobutyric acid is 0.5mol/L, the concentration of 3-hydroxy-5-ethyl-nonane-4-oxime is 0.35mol/L, and the concentration of tributylphosphine oxide is 0.5mol/L.
Extraction: the initial organic phase and the aqueous phase are compared with each other at the ratio (O/A) of 1:1, the mixing time is 5min, the oscillating frequency is 300r/min, the temperature is 25 ℃, and the extraction balance pH is adjusted to be 2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 5.5 and 6.5 by using sodium carbonate for extraction.
As can be seen from fig. 1, the metal extraction sequence is: cu > Ni > Zn > Co > Mn > Ca > Mg. As can be seen from the graph, nickel and cobalt can be effectively separated from calcium, magnesium and manganese at ph=5-5.5.
Example 2: kinetic experiments of extraction
Aqueous feed liquid (metal ion solution): to simulate a feed liquid (sulfate system), the feed liquid contains Cu 2+ 0.052g/L，Ni 2+ 3.64g/L，Co 2+ 0.87g/L，Zn 2+ 0.28g/L，Ca 2+ 0.78g/L，Mg 2+ 12.54g/L，Mn 2+ 2.57g/L, pH 5.01;
initial organic phase: sulfonated kerosene is used as a diluent, the concentration of isobutyric acid is 0.5mol/L, the concentration of 3-hydroxy-5-ethyl-nonane-4-oxime is 0.35mol/L, and the concentration of tributylphosphine oxide is 0.5mol/L;
extraction: the ratio of the organic phase to the feed liquid is (O/A) 1:1, the mixing time is 1, 2, 3, 5, 8, 10 and 15min respectively, the oscillating frequency is 300r/min, the temperature is 25 ℃, and the extraction balance pH is adjusted to 5.5 by using sodium carbonate for extraction. The experimental results are shown in FIG. 2.
As can be seen from FIG. 2, the extraction reaction speed is fast, and the extraction rate of nickel is close to 100% when the reaction time is 5 min. The extraction rate of cobalt, calcium, magnesium and manganese tends to decrease along with the extension of time, which is probably because the pH tends to be stable along with the extraction balance, the extraction rate of cobalt, calcium, magnesium and manganese is saturated, the extraction rate of cobalt, calcium, magnesium and manganese is increased and then reduced, and meanwhile, the extraction rate and the extraction rate of nickel are not influenced by the addition of the organic phosphine oxide extractant.
Example 3: influence of different phases on extraction
Aqueous feed liquid (metal ion solution): to simulate a feed liquid (sulfate system), the feed liquid contains Ni 2+ 3.87g/L，Co 2+ 0.35g/L，Ca 2+ 0.58g/L，Mg 2+ 13.47g/L，Mn 2+ 2.25g/L, pH 5.14;
initial organic phase: sulfonated kerosene is used as a diluent, the concentration of isobutyric acid is 0.5mol/L, the concentration of 3-hydroxy-5-ethyl-nonane-4-oxime is 0.35mol/L, and the concentration of tributylphosphine oxide is 0.5mol/L;
extraction: the organic phase and the feed liquid are respectively set to be (O/A) 6:1, 4:1, 2:1, 1:1, 1:2, 1:4 and 1:6, the mixing time is respectively 5min, the oscillation frequency is 300r/min, the temperature is 25 ℃, and sodium carbonate is used for adjusting the extraction balance pH to be 5.5 for extraction. The experimental results are shown in table 1.
Table 1: the effect of different phases on the extraction rate (experimental data in the table are the average of at least three parallel tests)
| Compared (O/A) | 6:1 | 4:1 | 2:1 | 1:1 | 1:2 | 1:4 | 1:6 |
| Nickel extraction yield (%) | 99.78 | 99.78 | 98.45 | 98.78 | 78.45 | 30.74 | 18.04 |
| Cobalt extraction yield (%) | 99.78 | 99.45 | 99.12 | 84.45 | 17.12 | 0 | 0 |
| Calcium extraction yield (%) | 3.55 | 1.52 | 0.99 | 0.67 | 0.22 | 0 | 0 |
| Magnesium extraction yield (%) | 0.11 | 0.1 | 0.08 | 0.08 | 0.04 | 0 | 0 |
| Manganese extraction yield (%) | 9.45 | 9.45 | 5.45 | 1.45 | 5.43 | 0.11 | 0 |
As can be seen from table 1, with the decrease of the ratio O/a, the extraction rate of each metal is rapidly decreased, and under the same conditions, the extraction rate of nickel is significantly higher than that of cobalt, calcium, magnesium and manganese, and when the ratio O/a=2:1 is considered comprehensively, the extraction effect of the synergistic extraction system on each metal is best, the extraction rate of nickel is 98.45%, the extraction rate of cobalt is 99.12%, and the extraction rates of calcium, magnesium and manganese are all kept at lower levels, so that the ideal separation effect is achieved.
Example 4: effect of acidity on stripping Performance
The method for obtaining the loaded organic phase comprises the following steps: the initial organic phase of example 3 above was used to extract the aqueous feed solution of this example. More specifically, the extraction was performed with a mixing time of 5min, an oscillation frequency of 300r/min, a temperature of 25 ℃, and an extraction equilibrium pH of 5.5 adjusted with sodium carbonate, respectively, at a ratio O/a=1:1. Wherein, the aqueous phase feed liquid (metal ion solution) is simulated feed liquid, and the metal concentration of the feed liquid is as follows: ni (Ni) 2+ 3.59g/L，Co 2+ 0.33g/L; extracting to obtain a loaded organic phase containing Ni 2+ 3.58g/L，Co 2+ 0.28g/L。
Stripping agent: the concentration of the sulfuric acid solution is respectively 3g/L, 5g/L, 10g/L, 20g/L, 30g/L, 40g/L, 50g/L, 80g/L, 100g/L and 200g/L.
And (3) back extraction: the stripping was carried out using a loaded organic phase with a (O/A) ratio of 1:1 for 5min and an oscillation frequency of 300r/min at 25℃and the experimental results are shown in Table 2.
Table 2: the effect of different sulfuric acid concentrations on the stripping rate at 25℃C (the experimental data in the table are the average of at least three parallel runs)
| Concentration (g/L) | 3 | 5 | 10 | 20 | 30 | 40 | 50 | 80 | 100 | 200 |
| Nickel stripping Rate (%) | 20.54 | 40.54 | 85.1 | 97.95 | 98.89 | 99.49 | 99.49 | 99.54 | 99.58 | 99.67 |
| Cobalt stripping rate (%) | 78.98 | 90.42 | 98.11 | 98.99 | 99.11 | 99.24 | 99.37 | 99.45 | 99.46 | 99.66 |
According to the experimental results of the stripping agent concentration conditions in Table 2, the stripping of nickel and cobalt is facilitated as the sulfuric acid concentration increases, and the stripping values of nickel and cobalt tend to be balanced when the sulfuric acid concentration is 20g/l.
Example 5: kinetics of back extraction
Aqueous feed liquid (metal ion solution): to simulate a feed liquid (sulfate system), the feed liquid contains Ni 2+ 3.54g/L，Co 2+ 0.35g/L，Zn 2+ 0.18g/L，Ca 2+ 0.5g/L，Mg 2+ 9.54g/L，Mn 2+ 2.25g/L and pH 5.57.
Initial organic phase: sulfonated kerosene is used as a diluent, the concentration of isobutyric acid is 0.5mol/L, the concentration of 3-hydroxy-5-ethyl-nonane-4-oxime is 0.35mol/L, and the concentration of tributylphosphine oxide is 0.5mol/L.
Loaded organic phase: the ratio of the initial organic phase to the feed liquid is (O/A) 1:1, the mixing time is 5min, the oscillating frequency is 300r/min, the temperature is 25 ℃, and the extraction balance pH is adjusted to 5.5 by using sodium carbonate for extraction.
And (3) back extraction: the back extraction is carried out by using a load organic phase and a sulfuric acid (O/A) ratio of 1:1, mixing time of 1, 2, 3, 5, 8, 10 and 15min respectively, oscillation frequency of 300r/min and temperature of 25 ℃, and experimental results are shown in figure 3.
As can be seen from FIG. 3, the stripping reaction rate is fast, and the stripping rate of nickel and cobalt is close to 100% when the reaction time is 5 min. Meanwhile, zinc, calcium, magnesium and manganese are also well reextracted. Under the normal temperature condition, the back extraction rate and the back extraction rate of nickel can be improved by adding the organic phosphine oxide extractant.
Example 6
Aqueous feed liquid (metal ion solution): to simulate a feed liquid (sulfate system), the feed liquid contains Ni 2+ 3.54g/L，Co 2+ 0.35g/L，Zn 2+ 0.18g/L，Ca 2+ 0.5g/L，Mg 2+ 9.54g/L，Mn 2+ 2.25g/L and pH 5.57.
Washing water: to simulate a washing solution (sulfate system), ni-containing 2+ 0.5g/L, pH 2.0.
Initial organic phase: sulfonated kerosene is used as a diluent, the concentration of isobutyric acid is 0.5mol/L, the concentration of 3-hydroxy-5-ethyl-nonane-4-oxime is 0.35mol/L, and the concentration of tributylphosphine oxide is 0.5mol/L.
Extraction: the ratio of the initial organic phase to the feed liquid is (O/A) 1:1, the mixing time is 5min, the oscillating frequency is 300r/min, the temperature is 25 ℃, and the extraction balance pH is adjusted to 5.5 by using sodium carbonate for extraction.
Washing: washing was performed with a ratio of the loaded organic phase to the washing liquid (O/A) of 10:1, a mixing time of 3min, an oscillation frequency of 300r/min, a temperature of 25 ℃, and washing equilibrium pH values of 3.0, 4.0, 4.5, 5.0, 5.5, and 6.0, respectively, adjusted with sodium carbonate. The experimental results are shown in FIG. 4.
As can be seen from fig. 4, when the wash equilibrium pH is between 4.5 and 5.5, the elution rates of cobalt and zinc are high, while the elution rate of nickel is low, enabling the separation of nickel from cobalt zinc.
The prior patent uses alkyl hydroxyoxime, carboxylic acid extractant and organic amine to form a synergistic extraction system (CN 114317961A is a synergistic extraction system for nickel cobalt co-extraction and a co-extraction method thereof). The synergistic extraction system of the prior patent and the synergistic extraction system of the technical proposal have advantages in different aspects, and form good supplement on the efficacy. For example, one great advantage of using an alkyl hydroxyoxime, carboxylic acid extractant and organic amine to make up the co-extraction system is that: the synergistic extraction system contains organic alkali with strong zinc extraction capability, so that the synergistic extraction system can extract zinc under the condition of lower pH value (pH=2.0) without basically extracting nickel cobalt, thereby realizing good separation of zinc and nickel cobalt, and the ideal pH value range for extracting nickel cobalt is 4.5-6.0. The nickel cobalt and the zinc are not required to be separated, so that the separation process is greatly simplified, the energy conservation and emission reduction are facilitated, and the running cost is greatly reduced.
In the technical scheme, organic phosphine oxide extractant is used for replacing organic amine, and the phase separation speed is increased in the extraction and back extraction processes. The chelate formed by alkyl hydroxyoxime and nickel can be changed into nickel complex by adding organic phosphine oxide extractant. Therefore, under the condition of short time and room temperature (without heating), and by using acid as a stripping agent, nickel can be easily stripped, the problem of difficult nickel stripping is solved, and meanwhile, the addition of the nickel stripping agent does not influence the extraction rate and the extraction rate, so that the co-extraction of nickel and cobalt is realized. And if the separation of nickel and cobalt is to be directly realized (instead of the co-stripping of nickel and cobalt), the separation of nickel and cobalt and zinc can be realized by washing, and then the nickel is obtained by stripping. When alkyl hydroxyoxime, carboxylic acid extractant and organic amine are used to form a synergistic extraction system, separation of nickel and cobalt zinc can not be realized through washing, and the process has larger alkali consumption and higher cost. The inventors tried to replace tributylphosphine oxide with methyl tributylamine bromide in equal amount according to the process conditions of this example, and the metal ion washing pH equilibrium isotherm did not appear as regular in fig. 4, i.e. the washing equilibrium pH where the elution rate of cobalt and zinc was high and the elution rate of nickel was low could not be found. The inventors have also tried the process conditions according to this example, without tributylphosphine oxide (i.e. the initial organic phase contains only isobutyric acid and 3-hydroxy-5-ethyl-nonane-4-oxime), no wash equilibrium pH could be found where the elution rates of cobalt and zinc are high and the elution rate of nickel is low. In terms of the phase separation speed, in this example, the extraction, stripping and washing of the homogeneous phase are all accelerated, especially the washing of the phase separation. More specifically, the extraction phase separation only needs 30s, the washing phase separation only needs 50s, and the back extraction phase separation only needs 40s. According to the process conditions of this example, the same amount of tributylphosphine oxide was replaced with methyltributylamine bromide, 50s was required for the extraction phase separation and 60s for the stripping phase separation.
Example 7
Aqueous feed liquid (metal ion solution): to simulate a feed liquid (sulfate system), the feed liquid contains Ni 2+ 3.54g/L，Co 2+ 0.35g/L，Zn 2+ 0.18g/L，Ca 2+ 0.5g/L，Mg 2+ 9.54g/L，Mn 2+ 2.25g/L and pH 5.57.
Washing water: to simulate a washing solution (sulfate system), ni-containing 2+ 0.5g/L, pH 2.0.
Back extract: to simulate the strip (sulfate system), ni-containing 2+ 6g/L，H 2 SO 4 20g/L。
Initial organic phase: sulfonated kerosene is used as a diluent, the concentration of isobutyric acid is 0.5mol/L, the concentration of 3-hydroxy-5-ethyl-nonane-4-oxime is 0.35mol/L, and the concentration of tributylphosphine oxide is 0.5mol/L.
The process conditions are as follows: the process of two extraction, two washing and two reversing.
Extraction: the initial organic phase is (O/A) 2:1, the mixing time is 5min, the oscillating frequency is 300r/min, the temperature is 25 ℃, the extraction balance pH is regulated by sodium carbonate, the first-stage extraction balance pH=5.3, and the second-stage extraction balance pH=5.6.
Washing: the ratio of the extracted organic phase to the washing liquid is (O/A) 10:1, the mixing time is 5min, the oscillating frequency is 300r/min, the temperature is 25 ℃, the extraction equilibrium pH is regulated by sodium carbonate, the first-stage washing equilibrium pH=4.5, and the second-stage washing equilibrium pH=4.5.
And (3) back extraction: the loaded organic phase is compared with 20g/L sulfuric acid (O/A) at a ratio of 1:1, the mixing time is 5min, the oscillating frequency is 300r/min, and the temperature is 25 ℃, and two-stage back extraction is carried out. The experimental results are shown in table 3.
As can be seen from the data in the table, cobalt, zinc, calcium, magnesium, manganese can be effectively separated from nickel by the washing stage, and the loss rate of nickel is below 4%.
Table 3: extraction, back extraction and elution efficiency under the process conditions of double extraction, double washing and double back extraction
| Metallic element | Cobalt (Co) | Nickel (Ni) | Manganese (Mn) | Magnesium (Mg) | Calcium | Zinc alloy |
| Two-stage extraction yield (%) | 99.68 | 99.97 | 10.89 | 1.28 | 1.05 | 99.57 |
| Two-stage stripping rate (%) | 99.98 | 99.98 | \ | \ | \ | 99.95 |
| Two-stage elution Rate (%) | 96.78 | 3.21 | 99.99 | 99.98 | 99.97 | 97.35 |
Example 8:
this example is essentially the same as example 7, except that the organophosphine oxide extractant, R 5 、R 6 、R 7 All are n-alkyl groups with 12 carbon atoms. See table 4 for experimental data.
Table 4: extraction, back extraction and elution efficiency under the process conditions of double extraction, double washing and double back extraction
Comparative example 1:
aqueous feed liquid (metal ion solution): to simulate a feed liquid (sulfate system), the feed liquid contains Ni 2+ 3.48g/L，Co 2+ 0.79g/L，Ca 2+ 0.98g/L，Mg 2+ 10.78g/L，Mn 2+ 2.97g/L and pH 5.21.
Initial organic phase: sulfonated kerosene is used as a diluent, the concentration of isobutyric acid is 0.5mol/L, and the concentration of 3-hydroxy-5-ethyl-nonane-4-oxime is 0.35mol/L.
Extraction and back extraction: the initial organic phase is compared with the metal ion solution at (O/A) of 1:1, the mixing time is 5min, the oscillating frequency is 300r/min, the temperature is 25 ℃, and the extraction balance pH is adjusted to 5.5 by using sodium carbonate for extraction. Phase separation to obtain a loaded organic phase and raffinate, mixing the loaded organic phase and the 50g/L sulfuric acid (O/A) for 5min at the oscillating frequency of 300r/min at the room temperature of 25 ℃ for back extraction to obtain an unloaded organic phase and back extract. And detecting the concentration of each metal ion in the loaded organic phase after extraction and the empty organic phase after back extraction and the back extraction liquid in the raffinate, and calculating the extraction rate (%) and the back extraction rate (%) of each metal ion. The extraction rate is calculated by the following formula: e=c 1 /C 0 Wherein C 1 For extraction to target metal concentration in the organic phase, C 0 To extract the target metal to a concentration in the metal ion solution prior to extraction. The calculation formula of the back extraction rate is as follows: s=c 2 /C 1 ，C 1 For extraction to target metal concentration in the organic phase, C 2 Is the concentration of the target metal back extracted into the aqueous phase. The results shown in Table 5 were obtained by detection and calculation.
Table 5: the extraction and back extraction effect of the synergistic extraction system "isobutyric acid +3-hydroxy-5-ethyl-nonane-4-oxime" (experimental data in the table are average values of at least three parallel tests)
| Metallic element | Cobalt (Co) | Nickel (Ni) | Manganese (Mn) | Magnesium (Mg) | Calcium |
| Extraction yield (%) | 99.12 | 97.51 | 5.41 | 0.22 | 0.11 |
| Back extraction yield (%) | 98.78 | 40.45 | 99.11 | 99.98 | 99.97 |
As is clear from Table 5, when the synergistic extraction system "isobutyric acid +3-hydroxy-5-ethyl-nonane-4-oxime" was extracted (without using an organic phosphine oxide extractant), the extraction rates of cobalt and nickel were 99.13% and 97.51%, respectively, but the stripping effect of nickel was poor and the stripping rate was only 40.45%. Therefore, the synergistic extraction system cannot effectively strip nickel.
In contrast, 0.5mol/L tributylphosphine oxide is added into the initial organic phase, other conditions are unchanged, the extraction rate of cobalt and nickel can be kept to be 80% -98% or more, and the stripping rate of cobalt and nickel can be kept to be 99% -98% or more. The addition of tributylphosphine oxide is described, and the back extraction rate of cobalt and nickel is ensured on the basis of keeping the extraction rate of cobalt and nickel.
Comparative example 2
This comparative example is substantially the same as comparative example 1, except that the initial organic phase: sulfonated kerosene is used as a diluent, the concentration of isobutyric acid is 0.5mol/L, the concentration of 3-hydroxy-5-ethyl-nonane-4-oxime is 0.35mol/L, and the concentration of tributyl phosphate is 0.5mol/L. The experimental results are shown in table 6.
Table 6: extraction and back extraction effects of synergistic extraction system isobutyric acid +3-hydroxy-5-ethyl-nonane-4-oxime +tributyl phosphate
| Metallic element | Cobalt (Co) | Nickel (Ni) | Manganese (Mn) | Magnesium (Mg) | Calcium |
| Extraction yield (%) | 96.89 | 98.75 | 3.41 | 0.28 | 0.18 |
| Back extraction yield (%) | 99.25 | 55.78 | 99.55 | 99.91 | 99.93 |
As is clear from Table 6, the extraction of cobalt and nickel was good, but the stripping effect of nickel was poor at 25℃when the extraction was carried out by the synergistic system "isobutyric acid +3-hydroxy-5-ethyl-nonane-4-oxime +tributyl phosphate". Therefore, the synergistic extraction system cannot effectively strip nickel at room temperature. If the stripping effect of nickel is to be improved by using the stripping system of the comparative example, the stripping volume must be heated (at least 40 ℃), which results in a certain energy waste and an increase in equipment cost.
Comparative example 3
This comparative example is substantially the same as comparative example 1, except that the initial organic phase: sulfonated kerosene is used as a diluent, the concentration of isobutyric acid is 0.5mol/L, the concentration of 3-hydroxy-5-ethyl-nonane-4-oxime is 0.35mol/L, and the concentration of (2, 4-trimethylpentyl) phosphinic acid is 0.5mol/L. The experimental results are shown in table 7.
Table 7: extraction and back extraction effects of synergistic extraction system isobutyric acid +3-hydroxy-5-ethyl-nonane-4-oxime +2, 4-trimethyl amyl phosphinic acid
| Metallic element | Cobalt (Co) | Nickel (Ni) | Manganese (Mn) | Magnesium (Mg) | Calcium |
| Extraction yield (%) | 94.35 | 96.05 | 6.74 | 0.58 | 0.99 |
| Back extraction yield (%) | 99.88 | 45.38 | 99.88 | 99.34 | 99.75 |
As is clear from Table 7, the extraction of cobalt and nickel was good, but the stripping effect of nickel was poor at 25℃when the synergistic extraction system "isobutyric acid +3-hydroxy-5-ethyl-nonane-4-oxime+ (2, 4-trimethylpentyl) phosphinic acid" was extracted.
Comparative example 4
This comparative example was basically the same as example 7, except that tributylphosphine oxide was 2.05mol/L in concentration, which was higher than the ideal range, resulting in a decrease in extraction rate. The two-stage extraction rate of cobalt is 60.78%, and the two-stage extraction rate of nickel is 70.83%.
Comparative example 5
This comparative example was substantially the same as in example 7, except that tributylphosphine oxide was 0.05mol/L in concentration, and the concentration was lower than the ideal range, resulting in a decrease in stripping rate. The nickel two-stage stripping rate is 51.24%.
Combining the results of comparative examples 4 and 5, either too high or too low tributylphosphine oxide concentrations are detrimental to achieving the desired process results. In example 7, the tributylphosphine oxide concentration of 0.5mol/L was used, and the extraction rate and the stripping were both satisfactory compared to comparative example 4 and comparative example 5. The concentration of tributylphosphine oxide in the initial organic phase is controlled between 0.1 and 2.0mol/L, so that the high-efficiency extraction of nickel and cobalt can be realized, and the high-efficiency stripping of nickel and cobalt can be realized under the condition that acid is used as a stripping agent; and can also realize the effective separation of nickel and cobalt zinc in the washing process after extraction.
The foregoing is merely exemplary of the present application, and specific technical solutions and/or features that are well known in the art have not been described in detail herein. It should be noted that, for those skilled in the art, several variations and modifications can be made without departing from the technical solution of the present application, and these should also be regarded as the protection scope of the present application, which does not affect the effect of the implementation of the present application and the practical applicability of the patent. The protection scope of the present application is subject to the content of the claims, and the description of the specific embodiments and the like in the specification can be used for explaining the content of the claims.
Claims (6)
1. A nickel-cobalt co-extraction method using a nickel-cobalt co-extraction system containing organic phosphine oxide extractant is characterized in that,
the method comprises the following steps of:
s1, extraction: extracting the metal ion solution with an initial organic phase to obtain a loaded organic phase and a raffinate; the initial organic phase contains a nickel cobalt synergistic extraction system with the volume concentration of 0.1-60%;
s2, back extraction: back-extracting the loaded organic phase by using a back-extracting agent to obtain an unloaded organic phase and a back-extracting solution; the back extractant is sulfuric acid solution with the concentration of 20-200 g/L; nickel and cobalt are recovered and enriched after back extraction;
or comprises the following steps sequentially:
SS1 extraction: extracting the metal ion solution with an initial organic phase to obtain a loaded organic phase and a raffinate; the initial organic phase contains a nickel cobalt synergistic extraction system;
SS2 washing: washing the loaded organic phase by using a washing liquid to obtain a washed loaded organic phase; after washing, separating nickel from zinc and cobalt;
SS3 strip: carrying out back extraction on the washed loaded organic phase by using a back extraction agent to obtain an unloaded organic phase and a back extraction liquid; the back extractant is sulfuric acid solution with the concentration of 20-200 g/L; nickel recovery and enrichment are realized after back extraction;
the nickel cobalt synergistic extraction system comprises alkyl hydroxyoxime shown in a formula (1), a carboxylic acid extractant shown in a formula (2) and an organic phosphine oxide extractant shown in a formula (3);
wherein R is 1 And R is 2 Respectively any one of substituted or unsubstituted alkyl with 4-12 carbon atoms; r is R 3 Is hydrogen, or is any one of substituted or unsubstituted alkyl; r is R 4 Is any one of a substituted or unsubstituted straight-chain alkyl group, a substituted or unsubstituted cycloalkyl group and a substituted or unsubstituted branched-chain alkyl group having 4 to 12 carbon atoms; r is R 5 、R 6 、R 7 Is any one of substituted or unsubstituted alkyl groups having 4 to 12 carbon atoms.
2. The method for nickel cobalt co-extraction using a nickel cobalt co-extraction system containing an organophosphine oxide extractant according to claim 1, wherein the molar ratio of the alkyl hydroxyoxime, the carboxylic acid extractant, and the organophosphine oxide extractant is 0.1-2.0:0.1-5.0:0.1-6.0.
3. The method for nickel-cobalt co-extraction of a nickel-cobalt co-extraction system containing an organic phosphine oxide extractant according to claim 1, wherein the metal ion solution contains Zn in S1 or SS1 2+ 、Ni 2+ 、Co 2+ 、Mn 2+ 、Mg 2+ And Ca 2+ ；Ni 2+ 、Co 2+ The ion concentration ranges of the ion concentration ranges are 0.01-10g/L; zn (zinc) 2+ 、Mn 2+ 、Mg 2+ And Ca 2+ The ion concentration ranges of the ion concentration ranges are 0.01-20g/L; the pH value of the metal ion solution is 4.0-6.0, and the initial organic phase and the metal phaseThe volume ratio of the ion solution is 6:1-1:1, and the extraction mixing time is 1-5min; the ambient temperature is-10-45 ℃; the equilibrium pH is 5-5.5.
4. The method for nickel-cobalt co-extraction of a nickel-cobalt co-extraction system containing an organic phosphine oxide extractant according to claim 1, wherein in the step S2, the volume ratio of the loaded organic phase to the stripping agent is 5:1-1:5, and the stripping mixing time is 3-10min; the ambient temperature is-10-45 ℃.
5. The method for nickel-cobalt co-extraction of nickel-cobalt co-extraction system containing organic phosphine oxide extractant according to claim 1, wherein in SS2, the washing solution contains 0.01-10g/L Ni 2+ The volume ratio of the loaded organic phase to the washing liquid is 0.8:1-50:1, and the washing mixing time is 1-5min; the ambient temperature is-10-45 ℃; the equilibrium pH is 1.0-5.5.
6. The method for nickel-cobalt co-extraction of a nickel-cobalt co-extraction system containing an organic phosphine oxide extractant according to claim 1, wherein in SS3, the volume ratio of the loaded organic phase to the stripping agent after washing is 5:1-1:5, and the stripping mixing time is 3-10min; the ambient temperature is-10-45 ℃.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0892665A (en) * | 1994-09-20 | 1996-04-09 | Catalysts & Chem Ind Co Ltd | Method for selectively separating and recovering nickel and/or cobalt |
| WO2006029439A1 (en) * | 2004-09-13 | 2006-03-23 | Canopean Pty. Ltd | Process for preparing nickel loaded organic extractant solution |
| CN105803197A (en) * | 2014-12-29 | 2016-07-27 | 北京有色金属研究总院 | Method for removing calcium and magnesium from bioleaching solution of nickel cobalt by synergetic extraction method |
| CN108642283A (en) * | 2018-05-25 | 2018-10-12 | 中南大学 | A kind of nickel cobalt synergic reagent and its method detached with impurity extraction for nickel cobalt |
| CN114317961A (en) * | 2021-12-30 | 2022-04-12 | 重庆康普化学工业股份有限公司 | Co-extraction system for nickel-cobalt co-extraction and co-extraction method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP1330555A4 (en) * | 2000-09-15 | 2005-08-31 | Commw Scient Ind Res Org | Solvent extraction process for recovering nickel and cobalt from leach solutions |
-
2022
- 2022-05-26 CN CN202210588587.7A patent/CN114774689B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0892665A (en) * | 1994-09-20 | 1996-04-09 | Catalysts & Chem Ind Co Ltd | Method for selectively separating and recovering nickel and/or cobalt |
| WO2006029439A1 (en) * | 2004-09-13 | 2006-03-23 | Canopean Pty. Ltd | Process for preparing nickel loaded organic extractant solution |
| CN105803197A (en) * | 2014-12-29 | 2016-07-27 | 北京有色金属研究总院 | Method for removing calcium and magnesium from bioleaching solution of nickel cobalt by synergetic extraction method |
| CN108642283A (en) * | 2018-05-25 | 2018-10-12 | 中南大学 | A kind of nickel cobalt synergic reagent and its method detached with impurity extraction for nickel cobalt |
| CN114317961A (en) * | 2021-12-30 | 2022-04-12 | 重庆康普化学工业股份有限公司 | Co-extraction system for nickel-cobalt co-extraction and co-extraction method thereof |
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