CN117004830B - Method for recovering nickel from nickel-containing iron material liquid - Google Patents
Method for recovering nickel from nickel-containing iron material liquid Download PDFInfo
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- CN117004830B CN117004830B CN202311268900.XA CN202311268900A CN117004830B CN 117004830 B CN117004830 B CN 117004830B CN 202311268900 A CN202311268900 A CN 202311268900A CN 117004830 B CN117004830 B CN 117004830B
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 121
- 239000007788 liquid Substances 0.000 title claims abstract description 87
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 56
- 238000000034 method Methods 0.000 title claims abstract description 37
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title abstract description 41
- 229910052742 iron Inorganic materials 0.000 title abstract description 18
- 239000000463 material Substances 0.000 title description 3
- 238000000605 extraction Methods 0.000 claims abstract description 106
- 239000007790 solid phase Substances 0.000 claims abstract description 80
- 238000005406 washing Methods 0.000 claims abstract description 63
- 238000002414 normal-phase solid-phase extraction Methods 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims description 84
- 229920001429 chelating resin Polymers 0.000 claims description 51
- 229920005989 resin Polymers 0.000 claims description 49
- 239000011347 resin Substances 0.000 claims description 49
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 239000010949 copper Substances 0.000 claims description 17
- 229920005990 polystyrene resin Polymers 0.000 claims description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 14
- 239000012527 feed solution Substances 0.000 claims description 14
- 125000000623 heterocyclic group Chemical group 0.000 claims description 13
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 13
- 229920001577 copolymer Polymers 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- 229920001568 phenolic resin Polymers 0.000 claims description 6
- 239000005011 phenolic resin Substances 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- 150000003440 styrenes Chemical class 0.000 claims description 6
- 229920001296 polysiloxane Polymers 0.000 claims description 4
- 125000002252 acyl group Chemical group 0.000 claims description 3
- 230000001172 regenerating effect Effects 0.000 claims description 3
- JYEUMXHLPRZUAT-UHFFFAOYSA-N 1,2,3-triazine Chemical group C1=CN=NN=C1 JYEUMXHLPRZUAT-UHFFFAOYSA-N 0.000 claims description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- 125000003785 benzimidazolyl group Chemical group N1=C(NC2=C1C=CC=C2)* 0.000 claims description 2
- 125000002883 imidazolyl group Chemical group 0.000 claims description 2
- NBZBKCUXIYYUSX-UHFFFAOYSA-N iminodiacetic acid Chemical compound OC(=O)CNCC(O)=O NBZBKCUXIYYUSX-UHFFFAOYSA-N 0.000 claims description 2
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 claims description 2
- 125000003373 pyrazinyl group Chemical group 0.000 claims description 2
- 125000003226 pyrazolyl group Chemical group 0.000 claims description 2
- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 125000001425 triazolyl group Chemical group 0.000 claims description 2
- 239000012535 impurity Substances 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 6
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 abstract 1
- 239000013522 chelant Substances 0.000 description 16
- 239000012071 phase Substances 0.000 description 13
- 238000011084 recovery Methods 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000004005 microsphere Substances 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000004064 recycling Methods 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 229910000365 copper sulfate Inorganic materials 0.000 description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 5
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 5
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- 229910017709 Ni Co Inorganic materials 0.000 description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 2
- 235000011941 Tilia x europaea Nutrition 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000004571 lime Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000012492 regenerant Substances 0.000 description 2
- 239000012266 salt solution Substances 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910000863 Ferronickel Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001868 cobalt Chemical class 0.000 description 1
- 229910000361 cobalt sulfate Inorganic materials 0.000 description 1
- 229940044175 cobalt sulfate Drugs 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- YTBWYQYUOZHUKJ-UHFFFAOYSA-N oxocobalt;oxonickel Chemical compound [Co]=O.[Ni]=O YTBWYQYUOZHUKJ-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- -1 preferably Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000008234 soft water Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000008399 tap water Substances 0.000 description 1
- 235000020679 tap water Nutrition 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
-
- 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
- C22B3/36—Heterocyclic compounds
-
- 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
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)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The application relates to a method for recovering nickel from nickel-copper-containing feed liquid with a pH value of 0.5-3, which comprises the following steps: step 1): carrying out first solid-phase extraction on the feed liquid, and then carrying out solid-liquid separation to obtain a first liquid phase and a first solid phase with the pH value less than or equal to 3.5; and step 2): and washing and back-extracting the first solid phase in sequence to obtain nickel-rich back-extracted liquid and back-extracted first solid phase. The method has high extraction efficiency on nickel, so that the separation effect of nickel and impurity iron and the like is good.
Description
Technical Field
The application relates to the technical field of metal recovery. In particular, the application relates to a method for recovering nickel from a nickel-containing iron feed solution.
Background
The nickel sources mainly include nickel cobalt ore, nickel cobalt intermediate products, nickel cobalt oxide, waste lithium ion batteries and the like, and the nickel has important economic and strategic values for extracting and recycling the nickel in the nickel cobalt ore.
In the prior art, a resin solid-phase extraction method is generally adopted to recover metal, wherein the resin containing specific functional groups is utilized to realize metal extraction. The resin solid-phase extraction method has the characteristics of good metal selectivity, high phase separation speed, simple operation and environmental friendliness.
However, the resin solid-phase extraction method is not ideal for separating impurities such as nickel and iron, and therefore, a new method for effectively separating impurity metals such as nickel and iron is required.
Disclosure of Invention
An object of the present application is to provide a method for efficiently recovering nickel from a nickel-containing iron-containing material liquid.
Accordingly, the present application provides a process for recovering nickel from a nickel-containing iron-containing feed solution having a pH of from 0.5 to 3, comprising:
step 1): carrying out first solid phase extraction on the feed liquid by using a first extractant, and then carrying out solid-liquid separation to obtain a first liquid phase and a first solid phase with the pH value less than or equal to 3.5; and
step 2): washing and back-extracting the first solid phase in sequence to obtain nickel-rich back-extracting solution and back-extracted first solid phase,
wherein,
the first extractant comprises a chelating resin of formula (I):
(I)
wherein:
p is a base resin;
R 1 and R is 2 Each independently is a nitrogen-containing heterocyclic group;
m is%) x ;
n and m are independently integers from 2 to 10; and
x is 0 or 1.
The method has high extraction efficiency on nickel, so that the separation effect of nickel and impurity iron and the like is good.
Detailed Description
Various aspects, as well as further objects, features, and advantages of the present application will be more fully apparent hereinafter.
As described above, the present application provides a method for recovering nickel from a nickel-containing iron-containing feed solution having a pH of 0.5 to 3, comprising:
step 1): carrying out first solid phase extraction on the feed liquid by using a first extractant, and then carrying out solid-liquid separation to obtain a first liquid phase and a first solid phase with the pH value less than or equal to 3.5; and
step 2): washing and back-extracting the first solid phase in sequence to obtain nickel-rich back-extracting solution and back-extracted first solid phase,
wherein,
the first extractant comprises a chelating resin of formula (I):
(I)
wherein:
p is a base resin;
R 1 and R is 2 Each independently is a nitrogen-containing heterocyclic group;
m is%) x ;
n and m are independently integers from 2 to 10; and
x is 0 or 1.
The nickel-containing iron feed solution may be, for example, an aqueous dispersion or an aqueous solution.
Advantageously, the feed liquid comprises Ni 0.1-20 g/L, preferably Ni 0.1-10 g/L, by weight relative to the volume of the feed liquid.
Advantageously, the feed liquid comprises Fe 0.1-120 g/L, preferably Fe 1-80 g/L, by weight relative to the volume of the feed liquid.
In some embodiments, the feed solution further comprises Cu.ltoreq.15 g/L, preferably.ltoreq.10 g/L, by weight relative to the volume of the feed solution.
In the case of copper in the feed liquid, preferably, copper is first extracted and removed, that is, the feed liquid is subjected to a second solid phase extraction using a second extractant, then subjected to solid-liquid separation to obtain a second liquid phase and a second solid phase, and then subjected to a first solid phase extraction with respect to the second liquid phase.
Preferably, the pH of the first liquid phase is in the range of 0.7-3.5.
Preferably, the second extractant of the present application comprises a chelating resin selected from the group consisting of chelating resins of formula (IA), chelating resins of formula (IIA), chelating resins of formula (IIIA), chelating resins of formula (IVA), iminodiacetic acid chelating resins, and combinations thereof:
(IA),/>(IIA),
(IIIA),/>(IVA),
wherein:
p is a base resin;
R 11 and R is 21 Each independently is a nitrogen-containing heterocyclic group;
R 31 is an acyl-containing group;
m is%) x ;
n and m are independently integers from 2 to 10; and
x is 0 or 1.
Advantageously, the pH of the second liquid phase is controlled to be between 0.5 and 3 for use as the feed liquid in step 1).
After the second extractant solid phase extraction, the method can realize the full removal of copper.
In some embodiments, the pH of the second liquid phase is controlled to be between 0.5 and 1.
In some embodiments, the feed solution comprises Co.ltoreq.20 g/L by weight relative to the volume of the feed solution.
In some embodiments, the feed solution optionally may further comprise one or more of Mn, zn, cd, cr, al, ca, mg, li, ti, si, F.
In some embodiments, the feed solution comprises Cd 10 g/L or less and/or Zn 10 g/L or less, by weight relative to the volume of the feed solution.
In some embodiments, the first extractant further comprises a chelating resin of formula (II):
(II),
wherein:
R 1 is a nitrogen-containing heterocyclic group, and is a nitrogen-containing heterocyclic group,
R 3 is an acyl-containing group;
m is%) x ;
n and m are independently integers from 2 to 10; and
x is 0 or 1.
In some embodiments, the second extractant is the same as the first extractant.
Preferably, the second extractant comprises a chelating resin of formula (IIA).
In some embodiments, the second extractant is a chelating resin of formula (IIA), and the first extractant consists of a chelating resin of formula (I) and a chelating resin of formula (II).
Preferably, the molar ratio of chelating resin of formula (I) to chelating resin of formula (II) in the first extractant is not less than 0.6:1, in some embodiments the ratio is in the range of 1-5:1.
In some embodiments, the second extractant comprises a chelating resin of formula (IA) and a chelating resin of formula (IIA).
In some embodiments, the second extractant consists of a chelating resin of formula (IA) and a chelating resin of formula (IIA).
In some embodiments, the molar ratio of chelating resin of formula (IA) to chelating resin of formula (IIA) in the second extractant is not less than 0.6:1, in some embodiments the ratio is in the range of 1-5:1.
In some embodiments, the second extractant consists of the chelate resin of formula (IA) and the chelate resin of formula (IIA), and the first extractant consists of the chelate resin of formula (I) and the chelate resin of formula (II), preferably the molar ratio of the chelate resin of formula (IA) to the chelate resin of formula (IIA) in the second extractant is in the range of 1-5:1 and/or the molar ratio of the chelate resin of formula (I) to the chelate resin of formula (II) in the first extractant is in the range of 1-5:1.
In some embodiments, the second extractant comprises a chelating resin of formula (IA) and a chelating resin of formula (IIIA).
In some embodiments, the second extractant consists of a chelating resin of formula (IA) and a chelating resin of formula (IIIA).
In some embodiments, the molar ratio of chelating resin of formula (IA) to chelating resin of formula (IIIA) in the second extractant is not less than 0.6:1, in some embodiments the ratio is in the range of 1-5:1.
In some embodiments, the second extractant consists of the chelate resin of formula (IA) and the chelate resin of formula (IIIA), and the first extractant consists of the chelate resin of formula (I) and the chelate resin of formula (II), preferably the molar ratio of the chelate resin of formula (IA) to the chelate resin of formula (IIIA) in the second extractant is in the range of 1-5:1 and/or the molar ratio of the chelate resin of formula (I) to the chelate resin of formula (II) in the first extractant is in the range of 1-5:1.
The present application is not particularly limited with respect to the base resin P, and preferably the base resin P is selected from the group consisting of polystyrene resin, copolymer of styrene and divinylbenzene, phenolic resin polymer, polyacrylic resin and silicon-based resin. More preferably, the base resin P is selected from polystyrene resins and copolymers of styrene and divinylbenzene.
Specifically, n and m are independently 2, 3, 4, 5, 6, 7, 8, 9 or 10.
Preferably, the nitrogen-containing heterocyclic group R 1 、R 2 、R 11 And R is 21 Each independently selected from the group consisting of a pyridine group, an imidazole group, a benzimidazole group, a pyrazole group, a quinoline group, a pyrazine group, a triazine group, and a triazole group.
More specifically, the nitrogen-containing heterocyclic group R 1 、R 2 、R 11 And R is 21 Each independently selected from the following groups:
、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、、/>、/>、/>、/>、/>、、/>、/>、/>、、/>、/>、/>、/>、、/>、/>、/>、/>、/>、、/>、/>、/>、/>、、/>and->。
Preferably, the nitrogen-containing heterocyclic group R 1 、R 2 、R 11 And R is 21 Each independently selected from the following groups:
、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、、/>、/>、/>、/>、/>、、/>、/>、、/>、/>、/>、/>、、/>、/>、/>、/>、/>、、/>、/>and->。
Preferably, R 3 And R is 31 Each independently is- (CO) R 4 or-CH 2 (CO)R 4 Wherein R is 4 Is a straight-chain or branched alkyl group with a carbon chain number of 1-5, -N- (R) 5 ) 2 Or for R 1 、R 2 、R 11 Or R is 21 A nitrogen-containing heterocyclic group as defined, wherein R 5 Is a straight or branched alkyl group having a carbon chain number of 1 to 5.
More specifically, the chelating resins of formula (I) and formula (IA) each independently have a structure selected from the group consisting of:
、/>、/>、/>、/>、/>、、/>、/>、/>、、/>、/>and->,
Wherein P is independently selected from the group consisting of polystyrene resins, copolymers of styrenes and divinylbenzene, phenolic resin polymers, polyacrylic resins, and silicone-based resins.
More preferably, the chelating resins of formula (I) and formula (IA) each independently have a structure selected from the group consisting of:
、/>、/>、/>、/>and,
wherein P is independently selected from the group consisting of polystyrene resins, copolymers of styrenes and divinylbenzene.
Preferably, the chelating resins of formula (II) and formula (IIA) each independently have a structure selected from the group consisting of:
、/>、/>、/>、、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、、/>、/>、/>、、/>、/>、/>,
wherein P is independently selected from the group consisting of polystyrene resins, copolymers of styrenes and divinylbenzene, phenolic resin polymers, polyacrylic resins, and silicone-based resins.
More preferably, the chelating resins of formula (II) and formula (IIA) each independently have a structure selected from the group consisting of:
、/>、/>and->、/>And,
wherein P is independently selected from the group consisting of polystyrene resins, copolymers of styrenes and divinylbenzene.
Preferably, the chelating resin of formula (IIIA) has a structure selected from the group consisting of:
、/>、/>、/>、/>,
wherein P is independently selected from the group consisting of polystyrene resins, copolymers of styrenes and divinylbenzene, phenolic resin polymers, polyacrylic resins, and silicone-based resins.
Further, the solid to liquid ratio of the second extractant to the feed liquid is 1g:1-30 mL, preferably 1 g:1-10 mL.
Further, the second solid phase extraction is counter-current and/or cross-current extraction, preferably counter-current extraction.
Further, the extraction stage number is 1 to 10 stages, preferably 2 to 8 stages.
Further, the extraction mixing time in the second solid phase extraction is 10 to 60 min, and more preferably 20 to 50 min.
Further, the first solid phase extraction in step 1) is a countercurrent and/or cross-current extraction, preferably a countercurrent extraction.
Further, the extraction stage number in the first solid phase extraction is 1 to 15 stages, preferably 2 to 8 stages.
Further, the solid to liquid ratio of the first extractant to the feed liquid or second liquid phase in step 1) is 1 g:0.5-30 mL, preferably 1 g:0.8-10 mL.
Further, the mixing time in the first solid phase extraction in step 1) is 10 to 60 minutes, and more preferably 20 to 50 minutes.
Further, the washing in step 2) is counter-current and/or cross-current washing, the number of washing stages being from 1 to 20 stages, preferably from 2 to 15 stages.
Further, the pH of the washing solution used for washing the first solid phase is 0.5 to 7, more preferably 0.5 to 2. Preferably, the ratio of the washing liquid to the first solid phase is 0.2-10 mL/1 g, and the washing time is 10-60 min, more preferably 20-50 min.
Preferably, the second solid phase is subjected to back extraction after multistage countercurrent washing to obtain a copper-containing solution and a back extracted second solid phase, and the second solid phase is regenerated and returned to be used as an extractant, wherein the pH value of the regenerated effluent is controlled to be 0.5-3.0.
Further, the washing of the second solid phase is counter-current and/or cross-current washing, with a washing stage number of 1-20, preferably 2-15.
Further, the pH of the washing solution used for washing the second solid phase is 0.5 to 7, more preferably 0.5 to 2. The ratio of the washing liquid to the second solid phase is 0.2-10 mL/1 g, and the washing time is 10-60 min, and more preferably 20-50 min.
The back extraction can be carried out by adopting an acid solution; the acid solution comprises sulfuric acid and/or hydrochloric acid.
The ratio of the acid solution to the first solid phase or the second solid phase is 0.2-10 mL/1 g, the back extraction time is 10-60 min, more preferably 20-50 min, the concentration of hydrochloric acid is 1-8 mol/L, and the concentration of sulfuric acid is 0.5-6 mol/L, more preferably 2-3 mol/L.
Preferably, the process of the application further comprises regenerating the first solid phase after back-extraction after step 2), the pH of the regenerated effluent being controlled to be between 0.5 and 7, preferably between 0.5 and 3.0.
The regenerant used for the regeneration in the present application is not particularly limited, and preferably the regenerant includes one or a combination of at least two of water, sodium hydroxide solution, ammonia water, sodium carbonate solution, nickel salt solution, cobalt salt solution, nickel hydroxide suspension, cobalt hydroxide suspension, magnesium oxide suspension, and lime suspension.
It is further preferable that the first solid phase after the back extraction is regenerated using one or a combination of at least two selected from pure water, tap water, and soft water as a regenerating agent.
The method has good metal ion separation effect, realizes the separation and recovery of the nitrogen-containing heterocyclic resin on nickel by controlling the extraction pH value, has good impurity ion separation effect, is simple to operate and has low process cost.
The method ensures that the removal rate of impurity copper (if present) is more than or equal to 99 percent, the nickel recovery rate is more than or equal to 98 percent, and the nickel-iron ratio in the nickel-rich strip liquor is not lower than 350.
In addition, the resin used in the method can be recycled after being recovered, the operation cost is low, and the method has good economic benefit.
In the present application, the term "and/or" encompasses situations involving one or both of the mentioned elements.
In the present application, the terms "comprising" and "including" encompass the situation in which other elements not explicitly mentioned are also included or included, as well as the situation in which the elements mentioned are composed.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. To the extent that the definitions of terms in this specification are inconsistent with the ordinary understanding of those skilled in the art to which this application pertains, the definitions described herein control.
Unless otherwise indicated, all numbers expressing quantities of ingredients, temperatures, times, and so forth used in the specification and claims are to be understood as being modified in the term "about". Accordingly, unless indicated to the contrary, the numerical parameters set forth herein are approximations that may vary depending upon the desired properties to be obtained.
Examples
The conception, specific structure, and technical effects of the present application will be further described with reference to examples so that those skilled in the art can fully understand the objects, features, and effects of the present application. It will be readily appreciated by those skilled in the art that the embodiments herein are for illustrative purposes only and that the scope of the present application is not limited thereto.
Example 1
The feed liquid in this embodiment is a nickel-containing iron feed liquid, the pH of the feed liquid is 1.3, and the feed liquid contains the following components:
composition of the components | Ni | Co | Mn | Ca | Mg | Fe |
Content (g/L) | 5.6 | 0.17 | 0.16 | 0.50 | 1.3 | 50.3 |
Composition of the components | Cr | Cd | Si | Li | Zn | Al |
Content (g/L) | 0.057 | 0.1 | 0.76 | 0.01 | 0.06 | 0.4 |
The first extractant is adopted (the structural formula is shown as the molar ratio of 3:1And->Wherein P is polystyrene resin microsphere) is used for carrying out 5-level countercurrent extraction on the feed liquid, the extraction equipment is a continuous ion exchange resin column, the ratio of the first extractant to the feed liquid is 1g to 1 mL, the mixing time is 30 min, and a solid phase 1 and a water phase 1 with a pH value of 1.15 are obtained.
And (3) carrying out 10-level countercurrent washing on the solid phase 1 by adopting sulfuric acid solution with the pH value of 0.8, wherein the ratio of the washing solution to the solid phase 1 is 1.5 mL/1 g, the mixing time is 30 min, the washed solid phase 1 is obtained, then, 4-level countercurrent back extraction is carried out by adopting 2.5 mol/L sulfuric acid solution, the ratio of the back extraction solution to the washed solid phase 1 is 1.5 mL/1 g, the mixing time is 30 min, the solid phase 1 after back extraction and the back extraction solution are obtained, the washing solution obtained after washing is recycled and then is merged into the feed liquid, the back extraction solution after back extraction is recycled, the nickel-cobalt-rich back extraction solution is obtained after the nickel concentration in the back extraction solution reaches 30 g/L, the nickel sulfate and the cobalt sulfate are obtained after evaporation and concentration, and the solid phase 1 after back extraction is washed to the pH value of effluent through 0.5% lime suspension for recycling.
In the embodiment, the recovery rates of Ni and Co are 98.9% and 27.6%, respectively, and the ratio of nickel to iron impurity element in the nickel-cobalt-rich strip liquor is 350.
Example 2
The feed liquid in this embodiment is ferronickel liquid, the pH value of the feed liquid is 1.0, and the feed liquid contains the following components:
the second extractant is adopted (the molar ratio is 4:1 and the structural formula is shown as followsAnd->Wherein P is polystyrene resin microspheres), carrying out 1-level cross-flow extraction on the feed liquid, wherein an extraction device is a fixed bed resin column, the ratio of a second extractant to the feed liquid is 1 g:20 mL, the mixing time is 60 min, the extraction is completed to obtain a solid phase 2 and a water phase 2 with a pH value of 0.95, after the resin column reaches extraction saturation, carrying out 1-level cross-flow washing on the solid phase 2 by adopting sulfuric acid solution with a pH value of 1.0, the ratio of a washing solution to the solid phase 2 is 0.5 mL:1 g, the mixing time is 20 min, back extraction is carried out 3 times by adopting 6 mol/L sulfuric acid solution, the ratio of the back extraction solution to the washed solid phase 2 is 0.5 mL:1 g, the mixing time is 20 min, the obtained solid phase 2 after back extraction and the back extraction solution are recycled and are then merged into the feed liquid, and the back extraction solution is recycled for multiple times, and after the copper concentration in the back extraction solution reaches 20g/L, the copper sulfate solution is obtained, and then the metal copper is prepared by electrowinning.
The solid phase 2 after back extraction is washed by pure water until the pH value of the effluent is 1.0, and then is recycled.
The first extractant is adopted (the structural formula is shown as the molar ratio of 2.5:1And->Wherein P is polystyrene resin microsphere) to carry out 5-level countercurrent extraction on the water phase 2, the extraction equipment adopts centrifugal extraction equipment, the ratio of the first extractant to the water phase 2 is 1g to 10 mL, the mixing time is 30 min, and the solid-liquid separation is carried out to obtain a solid phase 1 and a water phase 1 with the pH value of 0.8.
And (3) carrying out 8-level countercurrent washing on the solid phase 1 by adopting sulfuric acid solution with the pH value of 1, carrying out back extraction on the solid phase 1 for 4 times by adopting 2 mol/L sulfuric acid solution, wherein the ratio of the washing solution or the back extraction solution to the solid phase 1 is 1 mL:1 g, and the mixing time is 30 min, so as to obtain a back extracted solid phase 1 and a back extracted solution, recycling the back extracted solution obtained after washing, and then merging the back extracted solution into a feed liquid, recycling the back extracted solution for multiple times, obtaining a nickel-rich back extraction solution after the nickel concentration in the back extraction solution reaches 30 g/L, evaporating and concentrating to obtain nickel sulfate, and washing the back extracted solid phase 1 to the pH value of water of 1.0 by pure water for recycling.
The copper removal rate in this example was 99.6%; the recovery rate of Ni is 99.1%, and the ratio of nickel to iron in the nickel-rich strip liquor is 560.
Example 3
The feed liquid in this embodiment is a nickel-cobalt-containing battery feed liquid, the pH of the feed liquid is 3.0, and the feed liquid contains the following metal components:
composition of the components | Ni | Co | Mn | Ca | Mg | Fe | Al | Zn | Li | Cu |
Content (g/L) | 20 | 9.6 | 9.0 | 0.5 | 0.2 | 0.16 | 0.005 | 0.15 | 4.2 | 0.25 |
The second extractant is adopted (the molar ratio is 3:1 and the structural formula is shown as followsAnd->Wherein P is polystyrene resin microsphere) is used for carrying out 2-level countercurrent extraction on the feed liquid, the extraction equipment is a fixed bed resin column, the ratio of the second extractant to the feed liquid is 1 g:2.5 mL, the mixing time is 25 min, the extraction is completed to obtain a solid phase 2 and a water phase 2 with the pH value of 2.0, after the resin column reaches extraction saturation, sulfuric acid solution with the pH value of 2 is used for carrying out 3-level cross-flow washing on the solid phase 2, 2.5 mol/L sulfuric acid solution is used for carrying out back extraction for 4 times, the ratio of washing solution or back extraction solution to the solid phase 2 is 5 mL:1 g, and the mixture is mixedThe synthesis time is 60 min, a solid phase 2 after back extraction and a liquid after back extraction are obtained, the liquid after washing is recycled for multiple times and then is merged into the feed liquid, the liquid after back extraction is recycled for multiple times, copper concentration in the liquid after back extraction reaches 20g/L, copper sulfate solution is obtained, and copper sulfate is obtained through evaporation and concentration.
And washing the solid phase 2 after back extraction by pure water until the pH value of the effluent is 2, and recycling.
The first extractant is adopted (the molar ratio is 2:1 and the structural formula is shown as followsAnd->Wherein P is polystyrene resin microsphere) to carry out 8-level countercurrent extraction on the water phase 2, centrifuging the extraction equipment of the extraction equipment, mixing the first extractant with the water phase 2 in a ratio of 1g to 0.8 mL for 40 min, and carrying out solid-liquid separation to obtain a solid phase 1 and a water phase 1 with a pH value of 1.5.
And (3) carrying out 15-level countercurrent washing on the solid phase 1 by adopting sulfuric acid solution with the pH value of 2.5, carrying out back extraction on the solid phase 1 for 3 times by adopting 3 mol/L sulfuric acid solution, wherein the ratio of the washing solution or the back extraction solution to the solid phase 1 is 0.5 mL/1 g, the mixing time is 20 min, the washing solution obtained after washing is recycled for multiple times and then is mixed into the feed liquid, the back extraction solution obtained after back extraction is recycled for multiple times, the nickel-rich back extraction solution is obtained after the nickel concentration in the back extraction solution reaches 30 g/L, the nickel sulfate is obtained after evaporation and concentration, and the solid phase 1 after back extraction is washed by pure water until the pH value of effluent is 0.5 and then is recycled.
The copper removal rate in this example was 99.4%; the recovery rate of Ni is 99.0%, and the ratio of nickel to iron and zinc in the nickel-rich back extraction liquid is 2500.
Example 4
The feed liquid in this embodiment is a feed liquid containing nickel and cobalt, the pH of the feed liquid is 0.75, and the feed liquid contains the following metal components:
composition of the components | Ni | Co | Fe | Zn | Cu |
Content (g/L) | 1.4 | 0.13 | 26.5 | 2.0 | 5.5 |
Using a second extractant (structural formulaWherein P is a copolymer of styrene and divinylbenzene) is used for carrying out 4-level countercurrent extraction on the feed liquid, the extraction equipment is a fixed bed resin column, the ratio of resin 1 to the feed liquid is 1g to 1 mL, the mixing time is 30 min, the extraction is completed to obtain a solid phase 2 and a water phase 2 with the pH value of 0.72, after the resin column reaches extraction saturation, pure water is used for carrying out 2-level countercurrent washing on the solid phase 2, then 3 mol/L sulfuric acid solution is used for carrying out back extraction for 3 times, the ratio of washing solution to back extraction solution to the solid phase 2 is 1 mL to 1g, the mixing time is 30 min, the obtained washed solution is recycled for multiple times and then is mixed into the feed liquid, the obtained back extraction solution is recycled for multiple times, and the copper concentration in the back extraction solution is 20g/L to obtain copper sulfate solution, and the copper sulfate is obtained through evaporation and concentration.
The solid phase 2 after back extraction is washed by 1% sodium carbonate solution until the pH value of the effluent is 3.0, and then is recycled.
The first extractant is adopted (the structural formula is shown as the molar ratio of 4.5:1And->Wherein P is polystyrene resin microsphere) to carry out 3-level countercurrent extraction on the water phase 2, centrifuging the extraction equipment of the extraction equipment, mixing the first extractant with the copper-removed feed liquid at a ratio of 1g to 10 mL for 25 min, and carrying out solid-liquid separation to obtain a solid phase 1 and a water phase 1 with a pH value of 0.7.
And (3) carrying out 6-level countercurrent washing on the solid phase 1 by adopting a sulfuric acid solution with the pH value of 1, carrying out back extraction on the solid phase 1 for 4 times by adopting a sulfuric acid solution with the concentration of 1.5 mol/L, wherein the ratio of the washing solution or the back extraction solution to the solid phase 1 is 0.5 mL/1 g, the mixing time is 25 min, the washing solution obtained after washing is recycled for multiple times and then is mixed into the feed liquid, the back extraction solution obtained after back extraction is recycled for multiple times, the nickel-rich back extraction solution is obtained after the nickel concentration in the back extraction solution reaches 30 g/L, the nickel sulfate is obtained after evaporation and concentration, and the solid phase 1 after back extraction is washed by pure water until the pH value of effluent is 2.5 and then recycled.
The copper removal rate in this example was 99.5%; the recovery rate of Ni is 99.3%, and the ratio of nickel to iron impurity element in the nickel-rich back extraction solution is 380.
Example 5
The difference from example 4 is the second extractant
The molar ratio is 1:1 is of the structureAnd->And P is polystyrene resin microsphere.
In this example, the copper removal rates were 99.4%, the recovery rate of Ni was 99.3%, and the ratio of nickel to iron impurity element in the nickel strip solution was 400.
Example 6
The difference from example 3 is that the pH value of the aqueous phase 2 is adjusted to 1.1 by sulfuric acid, the first extractant is saponified by 2% sodium hydroxide, the pH value of the saponified solution is controlled to 7, the first extractant is extracted after saponification, and the aqueous phase 1 with the pH value of 3.5 is obtained.
In this example, the recovery rate of Ni was 99.4%, and the ratio of Ni to Fe impurity element in the nickel stripping solution was 380.
Example 7
The feed liquid in this embodiment is a feed liquid containing nickel and cobalt, the pH of the feed liquid is 0.5, and the feed liquid contains the following metal components:
composition of the components | Ni | Co | Fe | Zn | Mn | Cd | Al | Ca | Mg |
Content (g/L) | 0.1 | 0.11 | 39 | 0.08 | 0.13 | 0.07 | 0.35 | 0.5 | 1.3 |
The first extractant is subjected to ammonia water with the concentration of 4 percent (the molar ratio is 3:1 and the structural formula is shown as the specificationAnd->Wherein P is polystyrene resin microsphere), controlling pH value of the saponified solution to be 5, obtaining a first extractant after saponification, carrying out 2-level countercurrent extraction on the feed liquid, centrifuging the extraction equipment, extracting the first extractant with the feed liquid by a ratio of 1g to 30 mL, mixing for 60 min, and carrying out solid-liquid separation to obtain a solid phase 1 and a water phase 1 with pH value of 1.0.
And (3) carrying out 8-level countercurrent washing on the solid phase 1 by adopting sulfuric acid solution with the pH value of 1, carrying out back extraction on the solid phase 1 for 3 times by adopting 3 mol/L sulfuric acid solution, wherein the ratio of the washing solution or the back extraction solution to the solid phase 1 is 2 mL:1 g, the time is 40 min, the washing solution obtained after washing is recycled for multiple times and then is mixed into the feed liquid, the back extraction solution obtained after back extraction is recycled for multiple times, the nickel-rich back extraction solution is obtained after the nickel concentration in the back extraction solution reaches 30 g/L, the nickel sulfate is obtained after evaporation and concentration, and the solid phase 1 after back extraction is washed by pure water until the pH value of effluent is 1.5 and then is recycled.
In the embodiment, the recovery rate of Ni is 99.1%, and the ratio of nickel to iron impurity element in the nickel-rich back extraction liquid is more than 400.
The foregoing describes only exemplary embodiments or examples of the present application and is not intended to limit the present application. The present application is susceptible to various modifications and changes by those skilled in the art. Any modification, equivalent replacement, improvement, etc. which come within the spirit and principles of the application are within the scope of the following claims.
Claims (16)
1. A method for recovering nickel from a nickel-iron-containing feed solution having a pH of 0.5-3, comprising:
step 1): carrying out first solid phase extraction on the feed liquid by using a first extractant, and then carrying out solid-liquid separation to obtain a first liquid phase and a first solid phase with the pH value less than or equal to 3.5; and
step 2): washing and back-extracting the first solid phase in sequence to obtain nickel-rich back-extracting solution and back-extracted first solid phase,
wherein,
the first extractant comprises a chelating resin of formula (I) and a chelating resin of formula (II):
(I),/>(II),
wherein:
p is a base resin;
R 1 and R is 2 Each independently selected from:
、/>、/>、/>、/>、、/>、/>、/>、/>、/>、/>、/>、/>、/>、/>、、/>and->;
R 3 Is- (CO) R 4 or-CH 2 (CO)R 4 Wherein R is 4 Is a straight-chain or branched alkyl group having a carbon chain number of 1-5 or-N- (R) 5 ) 2 Wherein R is 5 Is a straight chain or a straight chain with a carbon chain number of 1-5Branched alkyl;
m is%) x ;
n and m are independently integers from 2 to 10; and
x is 0 or 1 and the number of the groups,
in the first extractant, the molar ratio of chelating resin of formula (I) to chelating resin of formula (II) is in the range of 1-5:1.
2. The method of claim 1, wherein the feed liquid comprises Ni 0.1-20 g/L by weight relative to the volume of the feed liquid.
3. The process of claim 1, wherein the feed solution further comprises Cu, the process further comprising subjecting the feed solution to a second solid phase extraction with a second extractant followed by solid-liquid separation to obtain a second liquid phase and a second solid phase prior to the solid phase extraction with the first extractant, and subsequently subjecting the second liquid phase to a first solid phase extraction with the first extractant, the second extractant comprising a chelating resin selected from the group consisting of chelating resins of formula (IA), chelating resins of formula (IIA), chelating resins of formula (IIIA), chelating resins of formula (IVA), iminodiacetic acid chelating resins, and combinations thereof:
(IA), />(IIA),
(IIIA), />(IVA),
in formulae (IA), (IIA), (IIIA) and (IVA):
p is a base resin;
R 11 and R is 21 Each independently is a nitrogen-containing heterocyclic group;
R 31 is an acyl-containing group;
m is%) x ;
n and m are independently integers from 2 to 10; and
x is 0 or 1.
4. A process according to claim 3, wherein the second extractant comprises a chelating resin of formula (IA) and formula (IIA), wherein the molar ratio of chelating resin of formula (IA) to chelating resin of formula (IIA) is in the range of 1-5:1.
5. A process according to claim 3, wherein the second extractant comprises a chelating resin of formula (IA) and formula (IIIA), wherein the molar ratio of chelating resin of formula (IA) to chelating resin of formula (IIIA) is in the range of 1-5:1.
6. The method according to any one of claims 1 to 5, wherein the base resin P is selected from the group consisting of polystyrene resins, copolymers of styrene and divinylbenzene, phenolic resin polymers, polyacrylic resins and silicon-based resins.
7. A process according to claim 3, characterized in that for the second extractant, the nitrogen-containing heterocyclic group R 11 And R is 21 Each independently selected from the group consisting of a pyridine group, an imidazole group, a benzimidazole group, a pyrazole group, a quinoline group, a pyrazine group, a triazine group, and a triazole group, R 31 Is- (CO) R 4 or-CH 2 (CO)R 4 Wherein R is 4 Is a straight-chain or branched alkyl group with a carbon chain number of 1-5, -N- (R) 5 ) 2 Or for R 11 Or R is 21 A nitrogen-containing heterocyclic group as defined, wherein R 5 Is of carbon chain number 1-5Linear or branched alkyl.
8. A process according to claim 3, characterized in that for the second extractant, the nitrogen-containing heterocyclic group R 11 And R is 21 Each independently selected from the following groups:
、/>、/>、/>、/>、/>、、/>、/>、/>、/>、、/>、/>、/>、/>、/>、、/>、/>、/>、、/>、/>、/>、/>、、/>、/>、/>、/>、/>、、/>、/>、/>、/>、、/>and->,
R 31 Is- (CO) R 4 or-CH 2 (CO)R 4 Wherein R is 4 Is a straight-chain or branched alkyl group with a carbon chain number of 1-5 or-N- (R) 5 ) 2 Wherein R is 5 Is a straight chain or branched chain with a carbon chain number of 1-5An alkyl group.
9. The process according to any one of claims 1 to 5, characterized in that for the second extractant, the chelating resin of formula (IA) has a structure selected from:
、/>、/>、/>、/>、/>、、/>,
the chelating resin of formula (IIA) has a structure selected from the group consisting of:
、/>、/>、/>、/>、/>、、/>、/>、/>、/>,
the chelating resin of formula (IIIA) has a structure selected from the group consisting of:
、/>、/>、/>、/>,
wherein P is independently selected from the group consisting of polystyrene resins, copolymers of styrenes and divinylbenzene, phenolic resin polymers, polyacrylic resins, and silicone-based resins.
10. A method according to claim 3, wherein the second solid phase extraction is one or a combination of countercurrent extraction and cross-current extraction, the extraction stage number is 1-10, the solid-to-liquid ratio of the second extractant to the feed liquid is 1g:1-30 mL, and the extraction mixing time in the second solid phase extraction is 10-60 min.
11. The method according to any one of claims 1 to 5, wherein the first solid phase extraction is one or a combination of countercurrent extraction and cross-current extraction, the number of extraction stages in the first solid phase extraction is 1-15, the solid-liquid ratio of the first extractant to the feed liquid or the second liquid phase in claim 3 is 1 g:0.5-30 mL, and the mixing time in the first solid phase extraction is 10-60 min.
12. The method according to any one of claims 1 to 5, wherein the washing in step 2) is one or a combination of two of countercurrent washing and cross-current washing, the number of washing stages is 1-20, or
The pH value of the washing liquid adopted for washing the first solid phase is 0.5-7, the ratio of the washing liquid to the first solid phase is 0.2-10 mL/1 g, and the washing time is 10-60 min.
13. A method according to claim 3, characterized in that the second solid phase is subjected to counter-current washing in multiple stages and subjected to back extraction to obtain a copper-containing solution and a back extracted second solid phase, the back extracted second solid phase is regenerated, and the pH of the regenerated effluent is controlled to be 0.5-3.0.
14. The method according to claim 13, wherein the washing of the second solid phase is one or a combination of countercurrent washing and cross-current washing, the number of washing stages is 1-20, the pH of the washing liquid used for the washing of the second solid phase is 0.5-7, and the ratio of the washing liquid to the second solid phase is 0.2-10 ml:1 g.
15. The process according to any one of claims 1-5 and 13, characterized in that the stripping in step 2) or in claim 13 is performed with an acid solution; the acid solution comprises sulfuric acid or hydrochloric acid, the concentration of the hydrochloric acid is 1-8 mol/L, the concentration of the sulfuric acid is 0.5-6 mol/L, and the ratio of the acid solution to the first solid phase or the second solid phase in claim 13 is 0.2-10 mL/1 g.
16. The method according to any one of claims 1 to 5, further comprising regenerating the first solid phase after the back extraction after step 2), the pH of the regenerated water being controlled to be 0.5 to 7.
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CN110453070A (en) * | 2019-03-11 | 2019-11-15 | 西安蓝晓科技新材料股份有限公司 | A method of extracting recycling nickel directly from lateritic nickel ore leaching liquor |
CN113293293A (en) * | 2021-05-26 | 2021-08-24 | 中国恩菲工程技术有限公司 | Method for recovering nickel and cobalt from laterite-nickel ore by resin adsorption method |
CN115433832A (en) * | 2021-06-02 | 2022-12-06 | 中国科学院过程工程研究所 | Nickel and cobalt synergistic extraction agent and application thereof |
CN114044844A (en) * | 2021-11-11 | 2022-02-15 | 上海应用技术大学 | Chelate resin and preparation method and application thereof |
CN114057915A (en) * | 2021-11-11 | 2022-02-18 | 上海应用技术大学 | Dicarbonyl chelate resin and preparation method and application thereof |
CN116479237A (en) * | 2022-01-14 | 2023-07-25 | 中国科学院过程工程研究所 | Extractant, preparation method and application thereof |
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