CN107815542B - A kind of synergic reagent and method for nickel selective extraction in acid solution - Google Patents
A kind of synergic reagent and method for nickel selective extraction in acid solution Download PDFInfo
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 170
- 238000000605 extraction Methods 0.000 title claims abstract description 106
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 82
- 230000002195 synergetic effect Effects 0.000 title claims abstract description 31
- 238000000034 method Methods 0.000 title claims abstract description 23
- 239000003153 chemical reaction reagent Substances 0.000 title abstract description 6
- 239000002253 acid Substances 0.000 title abstract description 5
- 239000012074 organic phase Substances 0.000 claims abstract description 51
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 28
- 239000010452 phosphate Substances 0.000 claims abstract description 28
- 239000012535 impurity Substances 0.000 claims abstract description 23
- SIOXPEMLGUPBBT-UHFFFAOYSA-N Picolinic acid Natural products OC(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-N 0.000 claims abstract description 18
- -1 picolinic acid ester Chemical class 0.000 claims abstract description 18
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 16
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 15
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims abstract description 14
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001424 calcium ion Inorganic materials 0.000 claims abstract description 14
- 229910001425 magnesium ion Inorganic materials 0.000 claims abstract description 14
- 229910001437 manganese ion Inorganic materials 0.000 claims abstract description 10
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- 150000007522 mineralic acids Chemical class 0.000 claims abstract description 7
- 239000000243 solution Substances 0.000 claims description 26
- 239000003929 acidic solution Substances 0.000 claims description 20
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 claims description 16
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 16
- 230000002378 acidificating effect Effects 0.000 claims description 13
- 239000003350 kerosene Substances 0.000 claims description 11
- 239000003085 diluting agent Substances 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 229910001413 alkali metal ion Chemical group 0.000 claims description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical group [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 13
- 150000003839 salts Chemical class 0.000 abstract description 4
- 238000011084 recovery Methods 0.000 abstract description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 abstract description 2
- 229940081066 picolinic acid Drugs 0.000 abstract 1
- 238000000926 separation method Methods 0.000 description 24
- 239000003795 chemical substances by application Substances 0.000 description 16
- 239000011575 calcium Substances 0.000 description 15
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 14
- 229910052791 calcium Inorganic materials 0.000 description 14
- 229910052749 magnesium Inorganic materials 0.000 description 13
- 239000011777 magnesium Substances 0.000 description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 12
- 239000007788 liquid Substances 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- BWCBBUTYNHNXTR-UHFFFAOYSA-N octanoic acid;pyridine Chemical compound C1=CC=[NH+]C=C1.CCCCCCCC([O-])=O BWCBBUTYNHNXTR-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 7
- 239000011572 manganese Substances 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- 238000007127 saponification reaction Methods 0.000 description 7
- 229910052748 manganese Inorganic materials 0.000 description 5
- 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 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 239000012527 feed solution Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 239000010953 base metal Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 229910001710 laterite Inorganic materials 0.000 description 2
- 239000011504 laterite Substances 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- NPXOKRUENSOPAO-UHFFFAOYSA-N Raney nickel Chemical compound [Al].[Ni] NPXOKRUENSOPAO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- PSZYNBSKGUBXEH-UHFFFAOYSA-N naphthalene-1-sulfonic acid Chemical compound C1=CC=C2C(S(=O)(=O)O)=CC=CC2=C1 PSZYNBSKGUBXEH-UHFFFAOYSA-N 0.000 description 1
- 238000005192 partition Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- SIOXPEMLGUPBBT-UHFFFAOYSA-M picolinate Chemical compound [O-]C(=O)C1=CC=CC=N1 SIOXPEMLGUPBBT-UHFFFAOYSA-M 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 230000002829 reductive effect Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Manufacturing & Machinery (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention discloses a kind of synergic reagents and method for nickel selective extraction in acid solution, synergic reagent is made of phosphate (salt) with picolinic acid ester, using the organic phase containing synergic reagent from acid solution selective extraction nickel, it can be realized efficiently separating for the foreign ions such as nickel ion and manganese ion, magnesium ion, calcium ion, load organic phases carry out the solution containing nickel that back extraction obtains high-purity using inorganic acid.This method is to nickel recovery height, and nickel and impurity good separating effect, process are short, it is easy to accomplish industrialization.
Description
Technical Field
The invention relates to a synergistic extraction agent, in particular to a synergistic extraction agent consisting of pyridine carboxylic ester and phosphate ester or phosphate ester salt, and a method for selectively extracting nickel from an acidic nickel-containing solution by utilizing the synergistic extraction agent, belonging to the technical field of chemical extraction.
Background
Nickel is an important strategic rare metal and has wide industrial applications. Hydrometallurgy of acidic systems is one of the major methods for extracting nickel from low-grade nickel-containing resources (such as nickel laterite, nickel-containing spent catalysts, nickel-molybdenum ores, electroplating sludge, etc.). Acidic nickel-containing solutions containing impurities, such as nickel laterite sulfuric acid leach liquor, electroplating sludge sulfuric acid leach liquor, spent nickel-containing catalyst sulfuric acid leach liquor, and the like, are produced during hydrometallurgical processing of acidic systems containing nickel materials. These acidic nickel-containing solutions contain, in addition to the nickel ions of the metal of value, a large amount of base metal cation impurities such as iron, aluminum, manganese, magnesium, calcium, chromium, and the like. Some efforts have been made by researchers for many years to extract nickel from nickel acid leach solution, for example, chinese patent No. ZL201310332212.5 discloses a synergistic extractant and a method for selectively extracting nickel from acidic nickel-containing aqueous solution, which solves the problem of separating nickel from base metal impurities such as iron, aluminum, manganese, magnesium, calcium, chromium, etc., can selectively extract nickel from spent catalyst sulfuric acid leachate containing 2g/L nickel, 30g/L aluminum and 1g/L ferric iron (pH <2), the single-stage extraction rate of nickel reaches more than 96%, the separation coefficients of nickel iron and nickel aluminum reach 2524 and 4346, respectively, the loaded organic phase is back-extracted with dilute sulfuric acid, and the back-extraction rate of nickel is more than 99% by 3-stage counter-current back-extraction. However, the synthesis process of naphthalenesulfonic acid, one of the components of the synergistic extractant adopted in the patent technology, is complex and high in cost, and the extraction and recovery cost of nickel is high.
Disclosure of Invention
Aiming at the defects of high cost, complex process, incomplete impurity separation and the like of the traditional process for extracting nickel from a nickel-containing acidic solution and the defects of high cost and the like of the prior invention patent (ZL201310332212.5) technology, the invention aims to provide a synergistic extractant which has low cost and can selectively extract nickel from the acidic nickel-containing solution containing various impurity ions such as manganese ions, magnesium ions, calcium ions and the like.
Another objective of the present invention is to provide a method for selectively extracting nickel from an acidic nickel-containing solution by using the synergistic extraction agent, which can realize effective separation of nickel ions from manganese ions, magnesium ions, calcium ions, etc., and has the advantages of high nickel extraction yield, short process, low cost, and easy realization of industrial application.
In order to achieve the technical purpose, the invention provides a synergistic extraction agent for selective extraction of nickel in an acidic solution, which consists of pyridine carboxylic ester and phosphate and/or phosphate ester salt; the pyridine carboxylic ester has a structure shown in a formula I; the phosphate or the phosphate salt has a structure shown in a formula II;
wherein,
r is selected from C6～12Alkyl groups of (a);
m is hydrogen ion, calcium ion, magnesium ion, ammonium ion or alkali metal ion;
n is the valence number of M.
The synergistic extraction agent disclosed by the invention is composed of pyridine carboxylic ester and phosphate ester (salt), and a large number of experiments show that the combination of pyridine carboxylic ester and phosphate ester (salt) has an obvious synergistic effect on nickel extraction in an acidic solution, and when the phosphate ester (salt) or pyridine carboxylic ester is used as the extraction agent for extracting nickel in the acidic solution, the extraction rate of nickel ions is low, the selectivity is poor, and the separation effect of the nickel ions from impurity ions such as manganese ions, calcium ions and magnesium ions is poor; when phosphate and pyridine carboxylate are used as extracting agents to extract nickel in the acidic solution synergistically, the extraction rate of nickel ions is high, and the extraction rates of magnesium ions, calcium ions and manganese ions are low, so that the pyridine carboxylate and the phosphate have an obvious positive synergistic extraction effect on the nickel ions, and have an obvious extraction inhibiting effect on the manganese ions, the calcium ions, the magnesium ions and the like, and thus the extraction separation of the nickel ions from the manganese ions, the magnesium ions, the calcium ions and the like can be realized.
Preferably, the ratio of the number of moles of pyridine carboxylic ester to the total number of moles of phosphate ester and phosphate ester salt is 1-6: 1. Within the preferable proportion range, the synergistic effect of the two can be fully exerted, and the best extraction effect is achieved.
The invention also provides a method for selectively extracting nickel from the acidic solution, which comprises the steps of carrying out single-stage or multi-stage countercurrent extraction on the acidic aqueous solution containing at least one impurity ion of manganese ions, magnesium ions and calcium ions and nickel ions by adopting an organic phase containing a synergistic extractant, selectively extracting the nickel ions into the organic phase, and leaving the impurity ions in raffinate; and washing the loaded organic phase, and performing single-stage or multi-stage countercurrent back extraction by using an inorganic acid solution to obtain a pure nickel-containing solution.
In a preferable scheme, the pH value of the acidic aqueous solution is 1.2-5.0.
In a preferred embodiment, the organic phase consists of a synergistic extractant and an organic diluent.
In a preferable scheme, the total concentration of the phosphate and the phosphate ester salt in the organic phase is between 0.1 and 0.6 mol/L.
More preferably, the organic diluent is sulfonated kerosene, No. 260 solvent oil, aviation kerosene, Escaid110, C8～13At least one of the higher alcohols of (1).
In a preferred embodiment, the inorganic acid solution is H+Sulfuric acid solution, hydrochloric acid solution and nitric acid solution with the concentration of 0.5-4.0 mol/LAt least one of them.
In the preferable scheme, the number of extraction stages is 1-10.
Preferably, the volume flow ratio of the organic phase to the aqueous phase in the extraction process is 1/5-10/1.
In the preferred scheme, the number of the back extraction stages is 1-10.
In a more preferable scheme, the volume flow ratio of the organic phase to the inorganic acid solution in the back extraction process is 1/1-10/1.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
1) the synergistic extracting agent has obvious synergistic effect in the extraction process of nickel ions in the acidic nickel solution, has the effect of inhibiting extraction of impurity metal ions such as manganese ions, calcium ions, magnesium ions and the like, and can extract nickel ions from the acidic solution with higher selectivity.
2) The synergistic extraction agent disclosed by the invention is a conventional reagent sold in the market, is low in cost and is beneficial to reducing the use cost of the synergistic extraction agent.
3) The method for selectively extracting nickel in the acidic solution by utilizing the synergistic extraction agent has the advantages of short flow, high nickel yield, good impurity removal effect, low consumption of chemical reagents, low cost and easy realization of industrialization.
Detailed Description
The following examples are intended to illustrate the invention without further limiting its scope.
In the examples, the partition ratio D, the separation coefficient β, and the extraction ratio E1(%), back extraction E2And the removal rate Y (%) were calculated according to the following formulae (1) to (5):
D＝CMO/CMR (1)
βNi/M＝DNi/DM (2)
E1＝(CFVF-CRVR)/(CFVF)×100％ (3)
E2＝Cs/(Co×R)×100％ (4)
Y＝(CMF/CNiF-CMS/CNiS)/(CMF/CNiF)×100％ (5)
in the formula (1), CMO,CMRRespectively representing the concentration (g/L) of the metal ions M in the loaded organic phase and the raffinate; in the formula (2), betaNi/MDenotes the separation coefficient of Ni from the impurity M, DNi,DMRespectively represent the distribution ratio of Ni to the impurity M; c in formula (3)F,CRRespectively representing the concentrations (g/L) of metal ions in feed liquid and raffinate; vF,VRRespectively representing the volumes of feed liquid and raffinate; in the formula (4), Cs,CoRespectively representing the concentrations (g/L) of metal ions in the stripping solution and the loaded organic phase, wherein R represents the volume flow ratio of the organic phase to the aqueous phase; in the formula (5), CMF，CNiFRespectively represents the concentrations (g/L) of impurity metal ions M and nickel ions, CMS，CNiSRespectively shows the concentrations (g/L) of the impurity metal ions M and the nickel ions in the stripping solution.
Example 1
Water phase feed liquid: the pH value of the feed liquid is 2.0, and the concentration of each metal ion in the feed liquid is as follows: ni2+：3.102g/L，Mn2+：2.801g/L，Mg2+：1.447g/L，Ca2+：0.487g/L。
Organic phase: preparing three organic phases with different compositions, wherein the serial numbers of the three organic phases are 1,2 and 3 respectively, wherein a diluent in the organic phases is sulfonated kerosene, a sulfonated kerosene solution with 1.0mol/L pyridine caprylate in the No. 1 organic phase, a P204 sulfonated kerosene solution with 0.25mol/L in the No. 2 organic phase and a sulfonated kerosene solution with 0.25mol/L P204+1.0mol/L pyridine caprylate in the No. 3 organic phase.
Extraction and separation: the 3 organic phases are respectively subjected to single-stage extraction with the feed liquid under the condition that the phase ratio (volume ratio of the organic phase to the water phase) is 1/1, the extraction equilibrium time is 10min, and the temperature is 25 ℃. The results of the experiment are shown in table 1.
TABLE 1 synergistic Effect of P204 and pyridine octanoate on Nickel extraction
As can be seen from Table 1, the nickel extraction rate was very low when the phosphate extractant P204 or picolinate alone was used to extract nickel (Ni-O-R) (II) ((III))<1%); when the phosphate extractant P204 is used alone, the extraction rate of calcium is 7.0 percent; when the pyridine carboxylic ester is used independently, the extraction rates of manganese and calcium are respectively 7.21 percent and 33.41 percent, and magnesium is not extracted basically; when the mixed extractant consisting of the phosphate extractant P204 and the pyridine carboxylate is used for synergistically extracting nickel, Ni2+The extraction rate reaches 53.68 percent, and the extraction rates of magnesium and calcium are lower than 1 percent. The distribution ratio of nickel in the extraction of the mixed extractant is far greater than that of nickel in the extraction of phosphate or pyridine carboxylic ester alone and the sum of the phosphate and pyridine carboxylic ester; however, the extraction rate of manganese, magnesium and calcium is still even lower than that of P204 or pyridine carboxylic ester alone, and the separation coefficients of Ni/Mn, Ni/Mg and Ni/Ca respectively reach 3.62, 5368 and 1789 when the mixed extractant is used for extraction. Therefore, the mixed extractant consisting of the phosphate P204 and the pyridine acid ester has obvious positive synergistic extraction effect on nickel, has obvious reverse synergistic extraction effect on magnesium and calcium, and can extract Mn from Mn-containing substances2+、Mg2+、Ca2+And the like, and selectively extracting nickel from the acidic solution of impurities.
Example 2
The aqueous feed solution was the same as in example 1.
Organic phase: six organic phases with different compositions and the serial numbers of 1,2,3, 4, 5 and 6 respectively are prepared, wherein the diluent in the organic phases is sulfonated kerosene, the concentration of pyridine caprylate is 1mol/L, and the concentration of P204 is 0mol/L, 0.05mol/L, 0.15mol/L, 0.25mol/L, 0.4mol/L and 0.5mol/L respectively.
Extraction and separation: the 6 organic phases are respectively subjected to single-stage extraction with the feed liquid under the condition that the phase ratio (volume ratio of the organic phase to the water phase) is 1/1, the extraction equilibrium time is 30min, and the temperature is 25 ℃. The results of the experiment are shown in table 2.
TABLE 2 extraction test results
As can be seen from Table 2, the separation coefficients of nickel, magnesium and calcium increase with the increase of the concentration of the extractant P204, and the separation coefficients of nickel, magnesium and calcium are respectively 6.18, 389.76 and 267.8 when the concentration of the extractant P204 reaches 0.5 mol/L. The result shows that under the extraction system, the separation effect of nickel and impurities, particularly magnesium and calcium, is remarkably improved by increasing the concentration of P204.
Example 3
The aqueous feed solution was the same as in example 1.
Organic phase: six organic phases with different compositions and the serial numbers of 1,2,3, 4, 5 and 6 respectively are prepared, wherein the diluent in the organic phases is sulfonated kerosene, the concentration of P204 is 0.25mol/L, and the concentrations of pyridine caprylate are 0, 0.25mol/L, 0.55mol/L, 0.75mol/L, 1mol/L and 1.25mol/L respectively.
Extraction and separation: the 6 organic phases are respectively subjected to single-stage extraction with the feed liquid under the condition that the phase ratio (volume ratio of the organic phase to the water phase) is 1/1, the extraction equilibrium time is 30min, and the temperature is 25 ℃. The results of the experiment are shown in table 3.
TABLE 3 extraction test results
As can be seen from Table 3, the extraction rate of nickel increases with the increase of the concentration of pyridine octoate as the extractant, and reaches 57.9% without adjusting pH when the concentration of pyridine octoate is 1.25 mol/L. Meanwhile, the concentration of pyridine caprylate serving as an extracting agent is increased, and the separation effect of nickel and other metals is better. In addition, the phase separation time is not substantially changed by increasing the concentration of pyridine caprylate. The result shows that under the extraction system, the separation effect of nickel and impurity manganese, magnesium and calcium is obviously improved by properly increasing the concentration of pyridine caprylate.
Example 4
The aqueous feed solution was the same as in example 1.
Organic phase: five organic phases with different compositions are prepared, wherein the serial numbers of the five organic phases are 1,2,3, 4 and 5 respectively, the diluent in the organic phases is sulfonated kerosene, the concentration of pyridine caprylate is 1.25mol/L, the concentration of P204 is 0.25mol/L, 5 parts of organic phases are saponified by using sodium hydroxide, and the saponification rates are 0%, 10%, 20%, 30% and 40% respectively. Extraction and separation: the 5 organic phases are respectively subjected to single-stage extraction with the feed liquid under the condition that the phase ratio (volume ratio of the organic phase to the water phase) is 1/1, the extraction equilibrium time is 30min, and the temperature is 25 ℃. The results of the experiment are shown in table 4.
TABLE 4 extraction test results
As can be seen from table 4, the extraction rates of nickel and manganese both increased significantly with increasing saponification rate during the extraction, with the nickel extraction rate varying particularly significantly from 59% to 78%. The separation coefficient of nickel and magnesium is reduced and kept constant along with the increase of the saponification rate, and the separation coefficient of nickel, manganese and calcium is increased along with the increase of the saponification rate. At a saponification rate of 40%, the separation coefficients of nickel and manganese, magnesium and calcium were 9.67, 108.31 and 41.31, respectively. The result shows that under the extraction system, the separation effect of nickel and impurities of manganese and calcium is obviously improved by increasing the organic saponification rate.
Example 5
The aqueous feed solution was the same as in example 1.
Organic phase: the concentration of P204 in the organic phase is 0.25mol/L, and the concentration of 4PC is 1.25 mol/L; the organic phase saponification rate was 40%.
Cascade extraction and separation: the organic phase-contrast feed liquid is adopted to carry out 5-stage countercurrent extraction, the extraction equilibrium time is 10min, and the temperature is 25 ℃. The results of the experiment are shown in Table 5.
TABLE 5 results of extraction tests
As can be seen from Table 5, the extraction rate of nickel reaches 98.7% after 5-stage countercurrent extraction, while the extraction rates of other impurity metals are basically below 5%, and are lower than the extraction rates of the respective single-stage extraction. The result shows that under the extraction system, the recovery rate of nickel is greatly improved through 5-stage countercurrent extraction, and the separation effect of nickel and other impurity metals is obvious.
Example 6
Stripping agent: 0.5mol/L dilute sulfuric acid
The concentration of nickel in the loaded organic phase is 2.85g/L
Extraction and separation: carrying out single-stage extraction on the loaded organic phase by using a stripping agent under the condition of phase ratio 1/1, wherein the extraction balance time is respectively 1min, 3min, 5min, 8min, 10min and 15 min; the temperature was 25 ℃. The results of the experiment are shown in Table 6.
TABLE 6 extraction test results
As can be seen from Table 6, after the stripping time reaches 3min, the stripping rate is maintained at about 91%, indicating that the stripping is balanced about 3min and the stripping kinetics is fast.
Claims (10)
1. A synergistic extractant for selective extraction of nickel in acidic solution, characterized in that: consists of pyridine carboxylic ester and phosphate and/or phosphate ester salt; the pyridine carboxylic ester has a structure shown in a formula I; the phosphate or the phosphate salt has a structure shown in a formula II;
wherein,
r is selected from C6～12Alkyl groups of (a);
m is hydrogen ion, calcium ion, magnesium ion, ammonium ion or alkali metal ion;
n is the valence number of M.
2. A synergistic extractant for the selective extraction of nickel in acidic solution in accordance with claim 1, characterized in that: the ratio of the number of moles of pyridine carboxylic ester to the total number of moles of phosphate ester and phosphate ester salt is 1-6: 1.
3. A process for the selective extraction of nickel from an acidic solution, characterized by: carrying out single-stage or multi-stage countercurrent extraction on an acidic aqueous solution containing at least one impurity ion of manganese ions, magnesium ions and calcium ions and nickel ions by using an organic phase containing the synergistic extractant of claim 1 or 2, wherein the nickel ions are selectively extracted into the organic phase, and the impurity ions are left in a raffinate; and washing the loaded organic phase, and performing single-stage or multi-stage countercurrent back extraction by using an inorganic acid solution to obtain a pure nickel-containing solution.
4. A process for the selective extraction of nickel from an acidic solution according to claim 3, characterized in that: the pH value of the acidic aqueous solution is 1.2-5.0.
5. A process for the selective extraction of nickel from an acidic solution according to claim 3, characterized in that:
the organic phase consists of a synergistic extractant and an organic diluent;
the total concentration of the phosphate and the phosphate ester salt in the organic phase is between 0.1 and 0.6 mol/L;
the organic diluent is sulfonated kerosene, No. 260 solvent oil, aviation kerosene, Escaid110 and C8～13At least one of the higher alcohols of (1).
6. A process for the selective extraction of nickel from an acidic solution according to claim 3, characterized in that: the inorganic acid solution is H+At least one of a sulfuric acid solution, a hydrochloric acid solution and a nitric acid solution with the concentration of 0.5-4.0 mol/L.
7. The process for the selective extraction of nickel from an acidic solution according to any one of claims 3 to 6, characterized in that: the number of extraction stages is 1-10 stages.
8. The process for selective extraction of nickel from acidic solutions according to claim 7, characterized in that: the volume flow ratio of the organic phase to the aqueous phase in the extraction process is 1/5-10/1.
9. The process for the selective extraction of nickel from an acidic solution according to any one of claims 3 to 6, characterized in that: the number of stages of the back extraction is 1-10 stages.
10. The process for selective extraction of nickel from an acidic solution according to claim 9, characterized in that: the volume flow ratio of the organic phase to the inorganic acid solution in the back extraction process is 1/1-10/1.
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