CN113444883B - Mixed extracting agent and method for enriching rare earth by using same - Google Patents
Mixed extracting agent and method for enriching rare earth by using same Download PDFInfo
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- CN113444883B CN113444883B CN202010224192.XA CN202010224192A CN113444883B CN 113444883 B CN113444883 B CN 113444883B CN 202010224192 A CN202010224192 A CN 202010224192A CN 113444883 B CN113444883 B CN 113444883B
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 96
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims description 42
- GPLFPJQMVKFQMK-UHFFFAOYSA-N 2-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]acetic acid Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(OCC(O)=O)C=C1 GPLFPJQMVKFQMK-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000010828 elution Methods 0.000 claims abstract description 44
- -1 alkylphenyl ether Chemical compound 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 33
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000002844 melting Methods 0.000 claims abstract description 20
- 230000008018 melting Effects 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000002244 precipitate Substances 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 28
- 239000003795 chemical substances by application Substances 0.000 claims description 27
- 239000007788 liquid Substances 0.000 claims description 27
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 22
- 238000001556 precipitation Methods 0.000 claims description 20
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 claims description 19
- 150000007522 mineralic acids Chemical class 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- CQMDBLRKZWOZIW-UHFFFAOYSA-N 2-Methyl-2-phenyl-undecane Chemical compound CC(C)(C)CC(C)(C)C1=CC=CC=C1 CQMDBLRKZWOZIW-UHFFFAOYSA-N 0.000 claims description 12
- 150000007529 inorganic bases Chemical class 0.000 claims description 12
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 9
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- AUYPJCDTURCDRS-UHFFFAOYSA-N 1-tert-butyl-4-dodecoxybenzene Chemical compound CCCCCCCCCCCCOC1=CC=C(C(C)(C)C)C=C1 AUYPJCDTURCDRS-UHFFFAOYSA-N 0.000 claims description 7
- GPHMTWRHAYOWDW-UHFFFAOYSA-N 1-tert-butyl-4-octoxybenzene Chemical compound CCCCCCCCOC1=CC=C(C(C)(C)C)C=C1 GPHMTWRHAYOWDW-UHFFFAOYSA-N 0.000 claims description 7
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 claims description 7
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 claims description 7
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 150000001555 benzenes Chemical class 0.000 claims description 5
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 5
- 238000007127 saponification reaction Methods 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 3
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 3
- 229910052691 Erbium Inorganic materials 0.000 claims description 3
- 229910052693 Europium Inorganic materials 0.000 claims description 3
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 3
- 229910052689 Holmium Inorganic materials 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910052779 Neodymium Inorganic materials 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 3
- 229910052772 Samarium Inorganic materials 0.000 claims description 3
- 229910052771 Terbium Inorganic materials 0.000 claims description 3
- 229910052775 Thulium Inorganic materials 0.000 claims description 3
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 3
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 3
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 3
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 3
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 3
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 3
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 3
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 3
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 3
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 1
- 239000007864 aqueous solution Substances 0.000 abstract description 8
- 238000004945 emulsification Methods 0.000 abstract description 5
- 239000000243 solution Substances 0.000 description 30
- 238000000605 extraction Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 13
- 238000002360 preparation method Methods 0.000 description 13
- 239000007787 solid Substances 0.000 description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- AJDONJVWDSZZQF-UHFFFAOYSA-N 1-(2,4,4-trimethylpentan-2-yl)-4-[4-(2,4,4-trimethylpentan-2-yl)phenoxy]benzene Chemical compound C1=CC(C(C)(C)CC(C)(C)C)=CC=C1OC1=CC=C(C(C)(C)CC(C)(C)C)C=C1 AJDONJVWDSZZQF-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 238000002386 leaching Methods 0.000 description 5
- 230000000536 complexating effect Effects 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000011777 magnesium Substances 0.000 description 3
- 229910052749 magnesium Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000005416 organic matter Substances 0.000 description 3
- 239000012074 organic phase Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000002195 synergetic effect Effects 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- VMKOFRJSULQZRM-UHFFFAOYSA-N 1-bromooctane Chemical compound CCCCCCCCBr VMKOFRJSULQZRM-UHFFFAOYSA-N 0.000 description 2
- CYEJMVLDXAUOPN-UHFFFAOYSA-N 2-dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=CC=C1O CYEJMVLDXAUOPN-UHFFFAOYSA-N 0.000 description 2
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 2
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 2
- 239000001099 ammonium carbonate Substances 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- JZCCFEFSEZPSOG-UHFFFAOYSA-L copper(II) sulfate pentahydrate Chemical compound O.O.O.O.O.[Cu+2].[O-]S([O-])(=O)=O JZCCFEFSEZPSOG-UHFFFAOYSA-L 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- KQGAIKIRKNMYOR-UHFFFAOYSA-N 1-tert-butyl-4-(4-tert-butylphenoxy)benzene Chemical compound C1=CC(C(C)(C)C)=CC=C1OC1=CC=C(C(C)(C)C)C=C1 KQGAIKIRKNMYOR-UHFFFAOYSA-N 0.000 description 1
- XRTANKYQJQXSFP-UHFFFAOYSA-N 1-tert-butyl-4-chlorobenzene Chemical compound CC(C)(C)C1=CC=C(Cl)C=C1 XRTANKYQJQXSFP-UHFFFAOYSA-N 0.000 description 1
- DWUYSEMDJQMICY-UHFFFAOYSA-N 2-(4-octylphenoxy)acetic acid Chemical compound CCCCCCCCC1=CC=C(OCC(O)=O)C=C1 DWUYSEMDJQMICY-UHFFFAOYSA-N 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- GDNCXORZAMVMIW-UHFFFAOYSA-N dodecane Chemical compound [CH2]CCCCCCCCCCC GDNCXORZAMVMIW-UHFFFAOYSA-N 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- LCPDWSOZIOUXRV-UHFFFAOYSA-N phenoxy-acetic acid Natural products OC(=O)COC1=CC=CC=C1 LCPDWSOZIOUXRV-UHFFFAOYSA-N 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- YTZKOQUCBOVLHL-UHFFFAOYSA-N tert-butylbenzene Chemical compound CC(C)(C)C1=CC=CC=C1 YTZKOQUCBOVLHL-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing 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
- C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
- C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
-
- 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
- C22B59/00—Obtaining rare earth metals
-
- 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)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention provides a mixed extractant which is characterized by comprising p-tert-octylphenoxyacetic acid and a compound with a structure shown in a formula (I). According to the invention, after the p-tert-octyl phenoxy acetic acid component and the alkylphenol or the alkylphenyl ether component are mixed, the melting point of the p-tert-octyl phenoxy acetic acid is obviously reduced, and the p-tert-octyl phenoxy acetic acid can form hydrogen bonds with the alkylphenol or the alkylphenyl ether so as to obviously reduce the solubility of the p-tert-octyl phenoxy acetic acid in an aqueous solution. The mixed extractant provided by the invention is used for enriching rare earth, can avoid emulsification, reduce elution temperature and obviously improve the total enrichment rate of rare earth.
Description
Technical Field
The invention belongs to the technical field of rare earth enrichment and separation, and particularly relates to a mixed extractant and a rare earth enrichment method thereof.
Background
The ionic rare earth ore is a rare earth ore which is special in China and is rich in medium and heavy rare earth elements with higher value. With the continuous development and utilization of rare earth ore resources, the grade of the rare earth ore is gradually reduced, generally to less than one per thousand, even to less than four ten thousandths. In the existing extraction process of ionic rare earth ore, ammonium sulfate or other solutions are used as leaching agents for in-situ leaching to obtain rare earth leaching solution with low concentration, and then ammonium bicarbonate or oxalic acid is used as a precipitator for rare earth enrichment. The prior art includes: and (1) oxalic acid precipitation. The method has high rare earth precipitation rate, but the rare earth precipitation needs 800 ℃ ignition, the dissolution of concentrated hydrochloric acid and high cost. The precipitation mother liquor has high oxalic acid content and high toxicity. (2) ammonium bicarbonate precipitation. The method has the disadvantages of low production cost, slow precipitation, difficult solid-liquid separation and long production period because the rare earth precipitates into amorphous precipitates. (3) centrifugal extraction method of naphthenic acid or P507-sulfonated kerosene. The disadvantages are that the residual amount of naphthenic acid or P507 and sulfonated kerosene in the extraction raffinate is large, the price of centrifugal extraction equipment is expensive, and the maintenance is difficult.
Patent CN107828961A discloses an extraction method of rare earth element ions and the rare earth enrichment liquid obtained by the method, bubbles coated with extraction liquid on the surface are added into aqueous solution containing rare earth ions, the bubbles float upward and then break, and the organic phase is extracted reversely to obtain the rare earth enrichment liquid. But the extractant loss is greater.
Patent CN108383713A discloses an organic matter of alkyl phenoxy acetic acid and a method for enriching rare earth elements in a low-concentration rare earth solution. CN110408777A discloses a method for extracting metal ions from fatty acid organic matters. The common defects are that when a single compound is adopted for precipitating the rare earth, the organic matter is easy to emulsify, so that the concentration of the residual organic matter is high, and the melting point of the single compound is very high, so that when the rare earth is eluted from the rare earth precipitate, the elution temperature requirement is high, and the elution rate is low.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a mixed extractant and a method for enriching rare earth, wherein the mixed extractant provided by the present invention is used for enriching rare earth, so that emulsification can be avoided, elution temperature can be reduced, and total enrichment rate of rare earth can be significantly increased.
The invention provides a mixed extractant, which comprises p-tert-octyl phenoxyacetic acid and a compound with a structure shown in a formula (I),
wherein R is 1 Selected from C1-C12 alkyl; r 2 Selected from hydrogen, C1-C12 alkyl or C1-C12 alkyl substituted benzene.
Preferably, the mass ratio of the p-tert-octylphenoxyacetic acid to the compound with the structure shown in the formula (I) is 1: (0.05-5).
Preferably, R in the compound having the structure shown in the formula (I) 1 Is selected from C4-C12 alkyl; r is 2 Selected from hydrogen, C4-C12 alkyl or C4-C12 alkyl substituted benzene.
Preferably, the compound having the structure represented by formula (I) is selected from one or more of di (p-tert-octylphenyl) ether, p-tert-octylphenol, nonylphenol, p-tert-butylphenyl (dodecyl-substituted phenyl) ether, p-tert-butylphenyl octylether, and p-tert-butylphenyl dodecyl ether.
The invention also provides a method for enriching rare earth, which comprises the following steps:
a) Mixing the saponified mixed extracting agent with a feed liquid containing rare earth ions, and carrying out a complex precipitation reaction to obtain a complex precipitate, wherein the mixed extracting agent is selected from the mixed extracting agents;
b) Eluting the complex precipitate with inorganic acid to obtain a rare earth enrichment solution; the elution temperature is more than or equal to the melting point of the mixed extractant.
Preferably, the saponified mixed extraction agent is obtained by mixing a mixed extraction agent and an inorganic base to perform a saponification reaction, and the mass ratio of the mixed extraction agent to the inorganic base is 1: (0.01-0.25).
Preferably, the inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide and ammonia water.
Preferably, the inorganic acid is selected from one or more of hydrochloric acid, nitric acid and sulfuric acid, the concentration of the inorganic acid is 0.5-12 mol/L, and the molar ratio of the inorganic acid to the complex precipitate is (1-10): 1.
preferably, the temperature range of the elution is 30 to 100 ℃.
Preferably, in the feed liquid containing rare earth ions, the rare earth ions comprise one or more of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium, the concentration range of the rare earth ions is 0.05-50 g/L, and the pH value range of the feed liquid is 1-7.
Compared with the prior art, the invention provides a mixed extractant which is characterized by comprising p-tert-octyl phenoxyacetic acid and a compound with a structure shown in a formula (I). After the p-tert-octyl phenoxy acetic acid component and the alkylphenol or the alkylphenyl ether component are mixed, the melting point of the p-tert-octyl phenoxy acetic acid is obviously reduced, and the p-tert-octyl phenoxy acetic acid can form a hydrogen bond with the alkylphenol or the alkylphenyl ether so as to obviously reduce the solubility of the p-tert-octyl phenoxy acetic acid in an aqueous solution. In addition, in the extraction process, the components of the mixed extractant generate synergistic extraction, so that the emulsification tendency of the extractant is effectively avoided, and the extractant residue in the aqueous solution is reduced. In the elution process, when the complexing precipitate is eluted at a certain temperature by using inorganic acid, the complexing precipitate can be melted into a liquid state from a solid state only when the elution temperature is more than or equal to the melting point of an extracting agent in the complexing precipitate, and the inorganic acid can fully transfer mass with the complexing precipitate, so that the rare earth enters an inorganic acid solution. In the present invention, the mixed extractant has a low melting point, so that the elution temperature can be significantly reduced. The method for enriching rare earth adopts the mixed extractant, the extraction process is not emulsified, the extractant residue in the aqueous solution is very low, the elution temperature in the elution process is low, and the elution rate is high. The mixed extractant provided by the invention can be recycled after being used. In addition, the mixed extractant provided by the invention has no biotoxicity and is environment-friendly.
Detailed Description
The invention provides a mixed extractant, which comprises p-tert-octyl phenoxyacetic acid and a compound with a structure shown in a formula (I),
wherein R is 1 Selected from C1-C12 alkyl; r 2 Selected from hydrogen, C1-C12 alkyl or C1-C12 alkyl substituted benzene.
In some embodiments of the present invention, R in the compound having the structure shown in formula (I) 1 Selected from C4-C12 alkyl; r 2 Selected from C4-C12 alkyl or C4-C12 alkyl substituted benzene.
In some embodiments of the invention, the compound having the structure of formula (I) is selected from one or more of di (p-tert-octylphenyl) ether, p-tert-octylphenol, nonylphenol, p-tert-butylphenyl (dodecylsubstituted phenyl) ether, p-tert-butylphenyl octylether, and p-tert-butylphenyl dodecylether.
In some embodiments of the invention, the compound having the structure of formula (I) is selected from di (p-tert-octylphenyl) ether;
in some embodiments of the invention, the compound having the structure of formula (I) is selected from the group consisting of a mixture of p-tert-octylphenol and nonylphenol;
in some embodiments of the invention, the compound having the structure shown in formula (I) is selected from the group consisting of p-tert-octylphenol and a mixture of di (p-tert-octylphenyl) ether;
in some embodiments of the invention, the compound having the structure of formula (I) is selected from the group consisting of p-tert-butyl phenyl (dodecyl substituted phenyl) ether;
in some embodiments of the invention, the compound having the structure of formula (I) is selected from the group consisting of p-tert-butyl phenyl octyl ether;
in some embodiments of the present invention, the compound having the structure of formula (I) is selected from p-tert-butylphenyl dodecyl ether.
In the present invention, the di (p-tert-octylbenzene) ether is prepared as follows:
under the condition of catalyst, 1-diphenyl ether and bromooctane are mixed in an organic solvent to react to obtain di (p-tert-octylbenzene) ether.
In the present invention, the source of the p-tert-butyl phenyl (dodecyl-substituted phenyl) ether is not particularly limited, and may be a self-made one or a commercially available one. In the present invention, the p-tert-butyl phenyl (dodecyl-substituted phenyl) ether is prepared as follows:
under the condition of protective atmosphere, mixing dodecylphenol, sodium hydroxide solid and copper sulfate pentahydrate powder for heating reaction, and then adding p-tert-butyl chlorobenzene-xylene solution for reaction under the vacuum condition to obtain a reaction product;
and sequentially acidifying, extracting, washing and distilling the reaction product to obtain the p-tert-butyl benzene (dodecyl substituted benzene) ether.
In the invention, the mixed extractant also comprises p-tert-octyl phenoxyacetic acid. The p-tert-octyl phenoxyacetic acid is prepared according to the following method:
mixing p-tert-octylphenol, sodium hydroxide solid, sodium chloroacetate solution and propanol, and carrying out heating reaction under a vacuum condition to obtain reaction liquid;
and acidifying the reaction solution to obtain the p-tert-octyl phenoxyacetic acid.
In the invention, the mass ratio of the p-tert-octylphenoxyacetic acid to the compound with the structure shown in the formula (I) is 1: (0.05 to 5), preferably 1: (0.1 to 2), more preferably 1: (0.11-1).
The invention also provides a method for enriching rare earth, which is characterized by comprising the following steps:
a) Mixing the saponified mixed extracting agent with a feed liquid containing rare earth ions, and carrying out a complex precipitation reaction to obtain a complex precipitate, wherein the mixed extracting agent is selected from the mixed extracting agent of any one of claims 1 to 4;
b) Eluting the complex precipitate with inorganic acid to obtain a rare earth enrichment solution; the elution temperature is more than or equal to the melting point of the mixed extractant.
The invention firstly prepares a mixed extractant, namely, the p-tert-octyl phenoxyacetic acid and the compound with the structure shown in the formula (I) are mixed to obtain the mixed extractant.
And then saponifying the mixed extracting agent to obtain the saponified mixed extracting agent. Specifically, the saponified mixed extraction agent is obtained by mixing a mixed extraction agent and an inorganic base to perform a saponification reaction, wherein the mass ratio of the mixed extraction agent to the inorganic base is 1: (0.01 to 0.25), preferably 1: (0.05 to 0.20), more preferably 1: (0.10-0.15). The inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide and ammonia water. The temperature and time for the saponification in the present invention are not particularly limited, and those known to those skilled in the art may be used.
And then, mixing the saponified mixed extracting agent with a feed liquid containing rare earth ions to perform a complex precipitation reaction to obtain a complex precipitate.
Wherein the feed liquid containing rare earth ions is prepared according to the following method: 1kg of ion type rare earth ore raw ore is taken and added with 1L of 2% ammonium sulfate solution for leaching.
In the feed liquid containing the rare earth ions, the rare earth ions comprise one or more of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium, the concentration range is 0.05-50 g/L, and the pH value range is 1-7.
After the mixed extractant is used for extracting rare earth, a complex precipitate is formed with rare earth ions, the complex precipitate is separated from the solution, and other impurities are still remained in the solution.
And then, eluting the complex precipitate by using inorganic acid to obtain a rare earth enrichment solution.
The inorganic acid is selected from one or more of hydrochloric acid, nitric acid and sulfuric acid, and the concentration of the inorganic acid is 0.5-12 mol/L, preferably 1.0-10 mol/L, and more preferably 4-7 mol/L;
the molar ratio of the inorganic acid to the complex precipitate is (1-10): 1, preferably (3 to 8): 1, more preferably (4 to 7): 1.
in the invention, the elution temperature is not lower than the melting point of the extracting agent, and is 30-100 ℃, preferably 40-90 ℃, and more preferably 50-80 ℃. The elution time is 1 to 30 minutes, preferably 5 to 25 minutes, and more preferably 10 to 20 minutes.
The preparation of p-octylphenoxyacetic acid is not particularly limited in the present invention, and can be prepared by a known method by those skilled in the art or can be purchased from the market.
The present invention is not particularly limited to the production of the alkylphenol or alkylphenyl ether, and those skilled in the art can produce the alkylphenol or alkylphenyl ether by a known method or by a commercially available method.
The present invention is not particularly limited to the specific method for elution, and any elution method known to those skilled in the art may be used.
The alkylphenol or alkylphenyl ether component can obviously reduce the melting point of the mixed extractant, obviously reduce the elution temperature in the elution process, and the components of the mixed extractant generate synergistic extraction in the extraction process, so that the emulsification of the extractant and the extractant residue in the solution can be effectively avoided, and the total enrichment rate of the rare earth is obviously improved. The mixed extractant is suitable for enriching rare earth from low-concentration rare earth solution to high concentration. The mixed extractant is simple to prepare, low in cost and recyclable.
The p-tert-octylphenoxyacetic acid component and the alkylphenol or alkylphenyl ether component are mixed, the melting point of the p-tert-octylphenoxyacetic acid component is obviously reduced, and the p-tert-octylphenoxyacetic acid component can form hydrogen bonds with the alkylphenol or alkylphenyl ether, so that the solubility of the p-tert-octylphenoxyacetic acid component in an aqueous solution is obviously reduced. In addition, in the extraction process, the components of the mixed extractant have synergistic extraction effect, so that the emulsification tendency of the extractant is effectively avoided, and the extractant residue in the aqueous solution is reduced. In the elution process, when the complex precipitate is eluted at a certain temperature by using inorganic acid, the complex precipitate is melted into a liquid state from a solid state only when the elution temperature is more than or equal to the melting point of an extracting agent in the complex precipitate, the inorganic acid can be fully transferred with the complex precipitate, so that the rare earth enters the inorganic acid solution, and the mixed extracting agent just can obviously reduce the elution temperature.
By adopting the technical scheme, the invention has the beneficial effects that: the method for enriching the rare earth adopts the mixed extractant, the extraction process is not emulsified, the extractant residue in the aqueous solution is low, the elution temperature in the elution process is low, and the elution rate is high. The mixed extractant provided by the invention can be recycled after being used. In addition, the mixed extracting agent provided by the invention has no biotoxicity and is environment-friendly.
For further understanding of the present invention, the mixed extractant and the rare earth enrichment method thereof provided by the present invention are illustrated below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
In the following examples and comparative examples, the following characterization was carried out by "chemical analysis method of rare earth metals and compounds thereof — determination of total amount of rare earth" GB/T14635-2008 ". The precipitation P, elution St and total enrichment E (total) are calculated as follows: the concentrations of the water-phase rare earth ions before and after precipitation are respectively C0 and C1, and the volumes of the water-phase rare earth ions before and after precipitation are respectively V0 and V1. Assuming that the concentration and volume of the rare earth ions in the water phase after elution are Cst and Vst respectively, then:
examples 1 to 3
The first compound and the second compound are p-tert-octylphenoxyacetic acid and di (p-tert-octylphenyl) ether, respectively, i.e., in formula (I), R is 1 Is p-tert-octyl, R 2 Is p-tert-octylphenyl.
(1) Preparation of p-tert-octylphenoxyacetic acid and di (p-tert-octylbenzene) ether: in the embodiment, the p-tert-octylphenoxyacetic acid and the di (p-tert-octylbenzene) ether are prepared by self.
Preparation of p-tert-octyl phenoxyacetic acid: 2L of propanol is added into a reaction kettle, 8mol (1.66 kg) of p-tert-octylphenol, 320g of sodium hydroxide solid and 1.82kg of 50 percent sodium chloride solution are added, the reaction temperature is maintained at 95 ℃, the relative vacuum degree is kept at minus 0.05MPa, and the reaction time is 0.5 hour, thus obtaining the reaction solution. After the reaction is finished, cooling to room temperature, adding 900mL of 6mol/L hydrochloric acid, acidifying for 5 minutes, and distilling under reduced pressure at 150 ℃ to obtain the p-tert-octyl phenoxyacetic acid.
Preparation of di (p-tert-octylbenzene) ether: 500mL of anhydrous dichloromethane, 425.5g of 1, 1-diphenyl ether and 300g of anhydrous aluminum trichloride are added into a reaction kettle, and after the temperature is raised to 75 ℃, 1930g of bromooctane is added dropwise to maintain the reaction for 6 hours. After the reaction, the reaction mixture was cooled to room temperature, 2L of water was added to wash the organic phase, and the organic phase was distilled under reduced pressure at 120 ℃ to obtain di (p-tert-octylphenyl) ether.
(2) Preparation of saponified Mixed extractant: a mixed extractant was prepared by mixing 8.7g of p-tert-octylphenoxy acetic acid with 0.97g (example 1), or 2.17g (example 2), or 3.73g (example 3) of di (p-tert-octylbenzene) ether.
Then 5mL of water was added, 1.05g of sodium hydroxide solid was added, and the mixture was stirred to prepare a saponified mixed extractant, i.e., the mass ratio of the mixed extractant of examples 1 to 3 to the inorganic base was 1.
(3) Preparing a feed liquid containing rare earth: taking ionic rare earth leaching liquid in Longyan city, and adjusting the pH to be =6. 2.0L of the rare earth is taken, and the total amount of the rare earth is measured to be 0.67g/L. The pH was 4. The main impurities comprise: al (Al) 2 O 3 ＝0.4g/L，Fe 2 O 3 And the total amount of calcium and magnesium is =0.1/L and 0.2g/L. The proportion of each rare earth element (calculated as oxide) to the total rare earth is shown inTable 1.
TABLE 1 proportions of respective rare earth elements to total rare earths used in examples 1 to 3 of the present invention
| Rare earth oxide | La | Ce | Pr | Nd | Sm | Eu | Gd | Tb |
| Mass ratio (%) | 27.5 | 2.50 | 5.86 | 21.7 | 5.12 | 0.35 | 4.76 | 0.70 |
| Rare earth oxide | Dy | Ho | Er | Tm | Yb | Lu | Y | Sc |
| Mass ratio (%) | 3.77 | 0.63 | 1.98 | 0.29 | 1.79 | 0.26 | 22.9 | <0.02 |
(4) And (3) precipitation process: and (3) adding the saponified mixed extractant in the step (2) into the rare earth-containing feed liquid in the step (3), continuing stirring for 10 minutes, and finally adding the rare earth into the mixed extractant to form complex precipitates.
(5) And (3) an elution process: and (5) eluting the complex precipitate in the step (4) at 100 ℃ by using 6mL of 5mol/L hydrochloric acid for 10min, so that the rare earth enters the hydrochloric acid solution, and the mixed extractant can be recycled.
The results showed that the melting points of the mixed extractants of examples 1,2 and 3 were 99.8, 95.0 and 86.8 deg.c, respectively. The elution rates for examples 1,2 and 3, when eluted at 100 ℃, were: 86.3%,99.7% and 100%. The total enrichment ratio for examples 1,2 and 3 were: 81.8%,94.6% and 95.8%. The residual amounts of extractant in the solution were 15.1, 16.3 and 17.0ppm. The specific parameters are shown in Table 2.
Comparative examples 1,2
The difference from example 1 is: the extractant of the comparative examples was a single extractant, containing only p-tert-octylphenoxyacetic acid (comparative example 1), or only the di (p-tert-octylbenzene) ether component (comparative example 2).
In comparative example 1 8.7g of p-tert-octylphenoxyacetic acid were taken as the sole extractant. The single extractant of comparative example 1 was tested to have a melting point of 124 ℃. The preparation, precipitation and elution of the rare earth-containing feed solution were the same as in example 1. The results show that the melting point of comparative example 1 is 124 ℃. When the extraction solution is eluted at 100 ℃, the single extractant in the comparative example 1 can not be melted at all and still is in a solid state, the elution rate is only 21.0 percent, and the total enrichment rate is only 20.5 percent. The residual amount of extractant in the solution was 32.8ppm.
In comparative example 2, 9.7g of di (p-tert-octylphenyl) ether was taken as the sole extractant, and the melting point of the sole extractant of comparative example 2 was tested to be 83.5 ℃. The preparation, precipitation and elution of the rare earth-containing feed solution were the same as in example 1. The results show that the di (p-tert-octylbenzene) ether of comparative example 2 has no enriching effect at all. The specific parameters are shown in Table 2.
Examples 4 to 6
The first compound is p-tert-octylphenoxyacetic acid. The second compound is p-tert-octylphenol, or a mixture of p-tert-octylphenol and nonylphenol, or a mixture of p-tert-octylphenol and di (p-tert-octylbenzene) ether.
(1) Preparation of p-tert-octylphenoxyacetic acid and di (p-tert-octylbenzene) ether: the same as in example 1.
Para-tert-octylphenol and nonylphenol were purchased from Shandong-West Asia chemical industries, ltd.
(2) Preparation of saponified mixed extractant:
in example 4, 17.4g of p-tert-octylphenoxyacetic acid and 4.34g of p-tert-octylphenol were mixed to prepare a mixed extractant.
In example 5, a mixed extractant was prepared by mixing 17.4g of p-tert-octylphenoxyacetic acid, 5.8g of p-tert-octylphenol, and 5.8g of nonylphenol.
In example 6, a mixed extractant was prepared by mixing 17.4g of p-tert-octylphenoxyacetic acid, 8.7g of p-tert-octylphenol, and 8.7g of di (p-tert-octylbenzene) ether.
The mixed extractant was further added with 10mL of water and 2.10g of solid sodium hydroxide, and stirred to prepare a saponified mixed extractant. That is, the mass ratio of the mixed extractant to the inorganic base in examples 4 to 6 was 1.
(3) Preparing a feed liquid containing rare earth: taking the ionic rare earth leachate in Longyan city, and adjusting the pH to be =5. Taking 8.0L, and measuring the total amount of the rare earth to be 0.335g/L. The pH was 5. The main impurities comprise: al (aluminum) 2 O 3 ＝0.2g/L，Fe 2 O 3 And the total amount of calcium and magnesium is =0.05/L and 0.10g/L. The proportions of the respective rare earth elements (calculated as oxides) in the total rare earth are shown in Table 1.
(4) And (3) precipitation process: and (3) adding the saponified mixed extracting agent obtained in the step (2) into the rare earth-containing feed liquid obtained in the step (3), continuously stirring for 30 minutes, and finally allowing the rare earth to enter the mixed extracting agent to form complex precipitates.
(5) And (3) an elution process: and (5 mL of 10mol/L hydrochloric acid is used for eluting the complex precipitate in the step (4) at 95 ℃, the elution time is 10min, the rare earth enters the hydrochloric acid solution, and the mixed extractant can be recycled.
The results show that the mixed extractants of examples 4, 5 and 6 have melting points of 92.8, 78.8 and 55.0 c, respectively. The mixed extractants of examples 4, 5 and 6 were fully melted into a liquid state when eluted at 95 ℃, and the elution rates were: 98.1%,99.0% and 100%. The total enrichment ratio for examples 4, 5 and 6 were: 94.0%,94.6% and 94.8%. The residual amounts of extractant in the solution were 16.5, 15.5 and 15.4ppm, respectively. Specific parameters are shown in table 2.
Table 2 examples and comparative examples precipitation process and elution process parameters
As can be seen from Table 2, the melting point of the mixed extractant provided by the invention is obviously lower than that of a single extractant, so that the elution rate of rare earth is also obviously improved. The residual concentration of the mixed extractant in the solution after extraction is also significantly lower than that of the single extractant.
Example 7
The first compound is p-tert-octylphenoxyacetic acid. The second compound is p-tert-butyl phenyl (dodecyl substituted phenyl) ether. That is, in the formula (I), R 1 Is p-tert-butyl, R 2 Is dodecyl substituted phenyl. Due to the symmetry of the ether compound, the second compound is completely equivalent to dodecyl substituted benzene (p-tert-butyl) ether, i.e., R in formula (I) 1 Is dodecyl radical, R 2 Is p-tert-butylphenyl.
(1) Preparation of p-tert-butylbenzene (dodecyl-substituted phenyl) ether: under the protection of argon, 105g of dodecylphenol, 17g of sodium hydroxide solid and 2g of copper sulfate pentahydrate powder are added into a 500mL three-neck flask, the temperature is raised to 110 ℃, and the reaction is carried out for 1h. Heating to 200 ℃, dropwise adding p-tert-butyl chlorobenzene-xylene solution (containing 85g of p-tert-butyl chlorobenzene), starting a water circulation vacuum pump, and maintaining the relative vacuum degree of a reaction system at-0.02 MPa for 5 hours. After cooling to room temperature, the mixture was acidified by adding 90mL of 6mol/L hydrochloric acid, extracted by adding 150mL of petroleum ether (boiling point at 90 ℃ C.) and washed with 150mL of deionized water. Vacuum distilling at 150 deg.C to obtain dodecyl substituted benzene (p-tert-butyl phenyl) ether product. The product purity is 97 percent, and the product yield is 94.5 percent.
(2) Preparation of saponified Mixed extractant:
17.4g of p-tert-octylphenoxyacetic acid and 4.34g of p-tert-butyl phenyl (dodecyl substituted benzene) ether are mixed to prepare the mixed extractant. The mass ratio of p-tert-butyl phenyl (dodecyl-substituted phenyl) ether was 20%. The melting point of the mixed extractant was measured to be 90.1 ℃.
The mixed extractant was further added with 10mL of water and 2.10g of solid sodium hydroxide, and stirred to prepare a saponified mixed extractant. The mass ratio of the mixed extractant to the inorganic base is 1.
(3) Preparing a feed liquid containing rare earth: taking Vietnam containing scandiumAnd (5) adjusting the pH of the ionic rare earth leachate to be 5. Taking 1.0L, measuring the total amount of rare earth to be 2.68g/L, wherein the scandium content is 0.029g/L. The pH was 5. The main impurities comprise: al (aluminum) 2 O 3 ＝1.2g/L，Fe 2 O 3 =0.15/L, and the calcium and magnesium content =0.50g/L.
(4) And (3) precipitation process: and (3) adding the saponified mixed extractant in the step (2) into the rare earth-containing feed liquid in the step (3), continuously stirring for 15 minutes, and finally adding the rare earth into the mixed extractant to form complex precipitation.
(5) And (3) elution process: and (3) eluting the complex precipitate in the step (4) at 95 ℃ by using 15mL of 10mol/L hydrochloric acid for 10min, so that the rare earth enters the hydrochloric acid solution, and the mixed extractant can be recycled.
The results show that when the mixed extractant is eluted at 95 ℃, the mixed extractant can be fully melted into liquid, and the elution rate is as follows: 98.5 percent. The total enrichment ratio is respectively: 94.5 percent. The residual amount of extractant in the solution was 16.0ppm. The specific parameters are shown in Table 2.
Examples 8 to 9
The first compound is p-tert-octylphenoxyacetic acid. The second compound was p-tert-butylphenyl octyl ether (example 8) or p-tert-butylphenyl dodecyl ether (example 9). That is, in the formula (I), R1 is p-tert-butyl, and R2 is octyl or dodecyl.
(1) Preparation of p-tert-octyl phenoxyacetic acid: p-tert-octylphenoxyacetic acid was prepared as in example 1. P-tert-butylphenyl octyl ether and p-tert-butylphenyl dodecyl ether are available from Shandong-Xiya chemical industries, ltd.
(2) Preparation of saponified Mixed extractant:
in example 8, a mixed extractant was prepared by mixing 17.4g of p-tert-octylphenoxyacetic acid and 0.92g of p-tert-butylphenyl octyl ether.
In example 9, 17.4g of p-tert-octylphenoxyacetic acid and 87.0g of p-tert-butylphenyl dodecyl ether were mixed to prepare a mixed extractant.
The mixed extractant was further added with 10mL of water and 2.10g of solid sodium hydroxide, and stirred to prepare a saponified mixed extractant.
(3) Preparing a rare earth-containing feed liquid: the same as in example 1.
(4) And (3) precipitation process: and (3) adding the saponified mixed extractant in the step (2) into the rare earth-containing feed liquid in the step (3), continuing stirring for 30 minutes, and finally adding the rare earth into the mixed extractant to form complex precipitates.
(5) And (3) an elution process: and (3) eluting the complex precipitate in the step (4) at 95 ℃ by using 5mL of 10mol/L hydrochloric acid for 10min, so that the rare earth enters the hydrochloric acid solution, and the mixed extractant can be recycled.
The results show that the melting points of the mixed extractants of examples 8 and 9 are 101 and 29.8 deg.C, respectively. When the elution is carried out at 95 ℃, the elution rates are respectively as follows: 84.4% and 100%. The total enrichment ratio is respectively: 81.7% and 97.5%. The residual amounts of extractant in the solution were 34.9ppm and 16.4ppm, respectively. The specific parameters are shown in Table 2.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A mixed extractant is characterized by comprising p-tert-octylphenoxyacetic acid and a compound with a structure shown in a formula (I),
wherein R is 1 Selected from C1-C12 alkyl; r is 2 Selected from hydrogen, C1-C12 alkyl or C1-C12 alkyl substituted benzene;
the mass ratio of the p-tert-octyl phenoxyacetic acid to the compound with the structure shown in the formula (I) is 1: (0.05-5);
the compound with the structure shown in the formula (I) is selected from one or more of di (p-tert-octylbenzene) ether, p-tert-octylphenol, nonylphenol, p-tert-butyl phenyl (dodecyl substituted benzene) ether, p-tert-butyl phenyl octyl ether and p-tert-butyl phenyl dodecyl ether.
2. The mixed extractant of claim 1, wherein R in the compound having the structure of formula (I) 1 Selected from C4-C12 alkyl; r 2 Selected from hydrogen, C4-C12 alkyl or C4-C12 alkyl substituted benzene.
3. A method for enriching rare earth is characterized by comprising the following steps:
a) Mixing the saponified mixed extracting agent with a feed liquid containing rare earth ions, and carrying out a complex precipitation reaction to obtain a complex precipitate, wherein the mixed extracting agent is selected from the mixed extracting agent of any one of claims 1-2;
b) Eluting the complex precipitate with inorganic acid to obtain a rare earth enrichment solution; the elution temperature is more than or equal to the melting point of the mixed extractant.
4. The method according to claim 3, wherein the saponified mixed extractant is obtained by mixing a mixed extractant and an inorganic base to perform saponification, and the mass ratio of the mixed extractant to the inorganic base is 1: (0.01-0.25).
5. The method according to claim 4, wherein the inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide and aqueous ammonia.
6. The method according to claim 3, wherein the inorganic acid is selected from one or more of hydrochloric acid, nitric acid and sulfuric acid, the concentration of the inorganic acid is 0.5-12 mol/L, and the molar ratio of the inorganic acid to the complex precipitate is (1-10): 1.
7. the method according to claim 3, wherein the temperature of the elution is in the range of 30 to 100 ℃.
8. The method according to claim 3, wherein the rare earth ions in the feed liquid containing rare earth ions comprise one or more of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium and yttrium, the concentration of the rare earth ions ranges from 0.05 to 50g/L, and the pH value of the feed liquid ranges from 1 to 7.
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|---|---|---|---|---|
| CN1034818C (en) * | 1993-07-23 | 1997-05-07 | 中国科学院上海有机化学研究所 | Extractant for separating rare-earth metal |
| JP5035788B2 (en) * | 2006-06-06 | 2012-09-26 | 独立行政法人日本原子力研究開発機構 | Rare earth metal extractant and extraction method |
| CA2925149C (en) * | 2015-05-25 | 2022-10-04 | Xiamen Institute Of Rare Earth Materials | Extractant and method for extracting and separating yttrium |
| CN108456792B (en) * | 2017-02-17 | 2019-11-26 | 厦门稀土材料研究所 | A kind of rare earth extraction separation extractant and preparation method thereof and extraction separating method |
| CN109666792B (en) * | 2017-10-16 | 2020-12-01 | 厦门熙途科技有限公司 | Rare earth extractant and method for separating rare earth yttrium |
| CN108726555B (en) * | 2017-10-19 | 2020-02-14 | 厦门稀土材料研究所 | Method for recovering rare earth through precipitation based on ionic liquid |
| CN109022839A (en) * | 2018-09-28 | 2018-12-18 | 中国恩菲工程技术有限公司 | The method of scandium-enriched |
| CN110042234B (en) * | 2019-01-29 | 2021-08-03 | 厦门稀土材料研究所 | Extracting agent and preparation method and application thereof |
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2020
- 2020-03-26 CN CN202010224192.XA patent/CN113444883B/en active Active
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