CN115710637A - Extractant and application thereof in extraction of lithium rubidium cesium - Google Patents
Extractant and application thereof in extraction of lithium rubidium cesium Download PDFInfo
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- 238000000605 extraction Methods 0.000 title claims abstract description 121
- BHKCBKMUUHAIAX-UHFFFAOYSA-N [Rb].[Cs].[Li] Chemical compound [Rb].[Cs].[Li] BHKCBKMUUHAIAX-UHFFFAOYSA-N 0.000 title abstract description 8
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 81
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 59
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 38
- 238000002156 mixing Methods 0.000 claims abstract description 29
- 239000012074 organic phase Substances 0.000 claims abstract description 29
- 239000007788 liquid Substances 0.000 claims abstract description 27
- 239000012071 phase Substances 0.000 claims abstract description 23
- 150000001875 compounds Chemical class 0.000 claims abstract description 17
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000001556 precipitation Methods 0.000 claims abstract description 15
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000011084 recovery Methods 0.000 claims abstract description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 13
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 12
- 239000003085 diluting agent Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 43
- -1 n-octyl Chemical group 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- 239000003350 kerosene Substances 0.000 claims description 17
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical group [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000008346 aqueous phase Substances 0.000 claims description 16
- 239000011734 sodium Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000543 intermediate Substances 0.000 claims description 11
- 238000002386 leaching Methods 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 10
- 238000001308 synthesis method Methods 0.000 claims description 10
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 7
- 230000002378 acidificating effect Effects 0.000 claims description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- ZRZHXNCATOYMJH-UHFFFAOYSA-N 1-(chloromethyl)-4-ethenylbenzene Chemical compound ClCC1=CC=C(C=C)C=C1 ZRZHXNCATOYMJH-UHFFFAOYSA-N 0.000 claims description 6
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- 239000003929 acidic solution Substances 0.000 claims description 6
- 239000012267 brine Substances 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 6
- 238000000967 suction filtration Methods 0.000 claims description 6
- 239000002699 waste material Substances 0.000 claims description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 claims description 5
- 238000006722 reduction reaction Methods 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 4
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 238000006460 hydrolysis reaction Methods 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 4
- 229910001392 phosphorus oxide Inorganic materials 0.000 claims description 4
- VSAISIQCTGDGPU-UHFFFAOYSA-N tetraphosphorus hexaoxide Chemical compound O1P(O2)OP3OP1OP2O3 VSAISIQCTGDGPU-UHFFFAOYSA-N 0.000 claims description 4
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 3
- 239000003513 alkali Substances 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 3
- 239000001630 malic acid Substances 0.000 claims description 3
- 235000011090 malic acid Nutrition 0.000 claims description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 3
- 230000001376 precipitating effect Effects 0.000 claims description 3
- 238000003512 Claisen condensation reaction Methods 0.000 claims description 2
- 238000007259 addition reaction Methods 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000001728 carbonyl compounds Chemical class 0.000 claims description 2
- 150000001733 carboxylic acid esters Chemical class 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 239000012141 concentrate Substances 0.000 claims description 2
- DJMZKFUAQIEDKC-UHFFFAOYSA-N lithium rubidium Chemical compound [Li].[Rb] DJMZKFUAQIEDKC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 abstract description 21
- 238000000034 method Methods 0.000 abstract description 16
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000003912 environmental pollution Methods 0.000 abstract description 4
- 150000002739 metals Chemical class 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 4
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 18
- 238000002360 preparation method Methods 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 239000013522 chelant Substances 0.000 description 7
- 239000012535 impurity Substances 0.000 description 7
- ZZSSCCQEJRAFTD-UHFFFAOYSA-N 1-octylphosphonoyloctane Chemical compound CCCCCCCCP(=O)CCCCCCCC ZZSSCCQEJRAFTD-UHFFFAOYSA-N 0.000 description 6
- 239000004342 Benzoyl peroxide Substances 0.000 description 6
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 6
- 235000019400 benzoyl peroxide Nutrition 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000005292 vacuum distillation Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000002253 acid Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- PQJJJMRNHATNKG-UHFFFAOYSA-N ethyl bromoacetate Chemical compound CCOC(=O)CBr PQJJJMRNHATNKG-UHFFFAOYSA-N 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000010413 mother solution Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ZDHXKXAHOVTTAH-UHFFFAOYSA-N trichlorosilane Chemical compound Cl[SiH](Cl)Cl ZDHXKXAHOVTTAH-UHFFFAOYSA-N 0.000 description 3
- 239000005052 trichlorosilane Substances 0.000 description 3
- AFOOTTNDNHOWBV-UHFFFAOYSA-N 1-phenyl-3-propylheptan-1-one Chemical compound CCCCC(CCC)CC(=O)C1=CC=CC=C1 AFOOTTNDNHOWBV-UHFFFAOYSA-N 0.000 description 2
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- AFCIMSXHQSIHQW-UHFFFAOYSA-N [O].[P] Chemical group [O].[P] AFCIMSXHQSIHQW-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000012452 mother liquor Substances 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000000638 solvent extraction Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- PWRSUUUQEQAMEV-UHFFFAOYSA-N 1-(4-nonylphenyl)ethanone Chemical compound CCCCCCCCCC1=CC=C(C(C)=O)C=C1 PWRSUUUQEQAMEV-UHFFFAOYSA-N 0.000 description 1
- XTVRLCUJHGUXCP-UHFFFAOYSA-N 3-methyleneheptane Chemical compound CCCCC(=C)CC XTVRLCUJHGUXCP-UHFFFAOYSA-N 0.000 description 1
- KJWMCPYEODZESQ-UHFFFAOYSA-N 4-Dodecylphenol Chemical compound CCCCCCCCCCCCC1=CC=C(O)C=C1 KJWMCPYEODZESQ-UHFFFAOYSA-N 0.000 description 1
- JVJMRLZNFIEHGR-UHFFFAOYSA-N 4-tert-butyl-2-(1-phenylethyl)phenol Chemical compound C=1C(C(C)(C)C)=CC=C(O)C=1C(C)C1=CC=CC=C1 JVJMRLZNFIEHGR-UHFFFAOYSA-N 0.000 description 1
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 125000005594 diketone group Chemical group 0.000 description 1
- 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 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000002587 enol group Chemical group 0.000 description 1
- 239000012527 feed solution Substances 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- NWOGWXZLSXEADL-UHFFFAOYSA-N hexyl(oxido)phosphanium Chemical compound CCCCCC[PH2]=O NWOGWXZLSXEADL-UHFFFAOYSA-N 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 125000000468 ketone group Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052629 lepidolite Inorganic materials 0.000 description 1
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 1
- 229910052808 lithium carbonate Inorganic materials 0.000 description 1
- 229910003002 lithium salt Inorganic materials 0.000 description 1
- 159000000002 lithium salts Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 238000005502 peroxidation Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 150000003018 phosphorus compounds Chemical class 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 229910021653 sulphate ion Inorganic materials 0.000 description 1
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical group CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 description 1
Images
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
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- Extraction Or Liquid Replacement (AREA)
Abstract
The invention relates to an extractant and application thereof in extraction of lithium, rubidium and cesium, wherein the extractant comprises a compound with a structure shown as a formula I or a formula II; the application comprises the following steps: (1) Mixing an extracting agent and a diluting agent to form an extraction system, and mixing the extraction system with feed liquid containing alkali metal under an alkaline condition for extraction; (2) Mixing the organic phase obtained after extraction with a back extraction solution, and back extracting to a water phase; (3) And carrying out precipitation or heating treatment on the obtained water phase, and separating to obtain an alkali metal-containing compound or an enriched substance. The extraction agent has the advantages of simple synthesis steps, wide source of synthesis raw materials, low water solubility and strong stability, and can reduce environmental pollution and cost; the method can be used for extracting valuable metals Li, rb and Cs with a large amount of Na in lithium rubidium cesium extraction process + 、K + Or NH 4 + ImpuritiesAnd the recovery rate of valuable metals Li, rb and Cs is high, the product purity is high, and the method has a good industrial application prospect.
Description
Technical Field
The invention relates to the technical field of chemical separation, in particular to an extracting agent and application thereof in lithium, rubidium and cesium extraction.
Background
Lithium, rubidium and cesium are precious rare elements, belonging to the first main group, and are often present in ores and brines together with sodium and potassium. With the rapid development of batteries and advanced materials, the consumption of Li, rb and Cs in production is rapidly increasing, with Li increasing from about 15 million tons (as lithium carbonate) in 2011 to about 50 million tons at present; the total consumption of Rb and Cs also increases from under a thousand tons (as metal salts) to nearly ten thousand tons. High-valence metal ions, particularly divalent metal ions, generated in the extraction process of Li, rb and Cs can be separated and removed by the technologies of precipitation, membrane separation and the like, but a large amount of monovalent ions Na + And K + Difficult to remove. For example, after lepidolite mineral salt roasting and water leaching, a feed liquid containing Li, na, K, rb and Cs is obtained; the carbonate type salt lake rich in reserves in the Tibet region of China contains Li, rb, cs valuable resources and a large amount of Na + And K + Impurities; leaching by peroxidation in the recovery process of the secondary ternary battery material to obtain an immersion liquid containing Ni, co, mn and Li, extracting the Ni, co and Mn to obtain a solution containing Li, and if ammonia water is adopted for neutralization in the extraction process, the solution also contains a large amount of NH 4 + . Therefore, in order to obtain products of high-purity Li, rb and Cs, the Li, rb and Cs and other univalent metal ions Na are realized + 、K + Or NH 4 + The high-efficiency separation has important significance.
At present, a plurality of documents report that a solvent extraction method is adopted to recover Li from a solution containing alkali metal ions such as Na, K, li, rb or Cs, and CN107779612A discloses a process for extracting lithium from alkaline brine. However, the method has complex composition of a synergistic system, wherein a fluorine-containing extracting agent is easy to damage the environment, an organic phase needs to consume alkali for regeneration, and the process flow is long. CN111057848A discloses a method for extracting lithium from lithium-containing solution by adopting a solvent extraction method, which adopts a composite synergistic extraction system consisting of dodecyl phenyl-methyl-beta-diketone and trioctyl/hexyl phosphine oxide to separate lithium from lithium-containing and monovalent metal impurity solution, and the lithium is subjected to back extraction to obtain high-purity lithium-containing solution which can be used for further preparing lithium salt products of different types. The method has short process flow and reduces the environmental pollution, but the composite extraction system adopted by the method is quite complex. CN110656239B discloses a method for extracting lithium by extraction-stripping separation and purification, which adopts a composite extraction system composed of ketone chelate and neutral phosphorus compounds to separate lithium and monovalent impurities at a higher pH value, and then carries out gas-liquid three-phase continuous stripping, and the stripping liquid is subjected to heat treatment to obtain a lithium product. The methods all adopt a complex composite extraction system, can realize the effective separation of Li and univalent impurities Na and K, but cannot comprehensively utilize valuable metals such as Rb, cs and the like in an alkaline solution, thereby causing resource waste.
CN107460344A discloses a method for extracting rubidium and cesium in salt lake brine, which adopts t-BAMBP organic phase saponified by alkaline solution to extract Cs and Rb in salt lake brine, and obtains a strip liquor containing Cs and Rb and a blank organic phase after back extraction of a loaded organic phase.
In view of the problems of the above documents, it is an urgent need to solve the problems of high recovery rate and high product purity of Li, rb and Cs, short extraction process, low cost and easy industrialization, and therefore, it is necessary to develop an extractant and apply the same to a process containing a large amount of Na + 、K + Or NH 4 + It is necessary to extract Li, rb and Cs with high selectivity in the feed solution of impurities.
Disclosure of Invention
In view of the problems of the prior art, the present invention provides an extractant and its application in extraction of lithium, rubidium and cesium, which can realize high-efficiency extraction of Li, rb and Cs, and simultaneously can be mixed with monovalent impurity Na + 、K + Or NH 4 + And (4) separating.
In order to achieve the technical effect, the invention adopts the following technical scheme:
the invention provides an extracting agent, which comprises an extracting agent A shown as a formula I or an extracting agent B shown as a formula II:
wherein R in the formula I 1 Is a C4-C12 (e.g. C4, C5, C6, C7, C8, C9, C10, C11 or C12) straight or branched alkyl, R 2 Is n-octyl or isooctyl; r in the formula II 3 Is a C8-C12 (e.g. C8, C9, C10, C11 or C12) straight or branched alkyl radical, R 4 Is n-octyl or isooctyl.
In the present invention, the extractant A may be any one of (4- (1- (5-butyl-2-hydroxyphenyl) ethyl) phenyl) dioctylphosphine oxide, (4- (1- (5-pentyl-2-hydroxyphenyl) ethyl) phenyl) dioctylphosphine oxide, (4- (1- (5-octyl-2-hydroxyphenyl) ethyl) phenyl) diisooctylphosphine oxide, (4- (1- (5-butyl-2-hydroxyphenyl) ethyl) phenyl) diisooctylphosphine oxide or (4- (1- (5-heptyl-2-hydroxyphenyl) ethyl) phenyl) dioctylphosphine oxide, but is not limited to the exemplified compounds, R 1 And R 2 Other compounds not listed in the scope are equally suitable.
In the present invention, the extractant B may be any one of 4-dioctylphosphoryl-1- (4-octylphenyl) butane-1,3-dione, 4-dioctylphosphoryl-1- (4-nonylphenyl) butane-1,3-dione, 4-diisooctylphosphoryl-1- (4-octylphenyl) butane-1,3-dione, or 4-diisooctylphosphoryl-1- (4-decylphenyl) butane-1,3-dione, but is not limited to the exemplified compounds, R is 3 And R 4 Other compounds not listed in the scope are equally suitable.
Preferably, the synthesis method of the extractant A comprises the following steps: the extraction agent A is prepared by carrying out addition reaction on 4-chloromethyl styrene and alkylphenol to obtain an alkyl-2- (1- (4- (chloromethyl) phenyl) ethyl) phenol intermediate, carrying out addition-reduction reaction on sodium hypophosphite and unsaturated olefin to obtain a dialkyl phosphorus oxide intermediate, and carrying out addition-hydrolysis reaction on the two intermediates.
Preferably, the synthesis method of the extractant B comprises the following steps: performing a claisen condensation reaction on a carbonyl compound containing a benzene ring and halogenated carboxylic acid ester under the catalysis of alkali to obtain a beta-diketone intermediate, performing an addition-reduction reaction on sodium hypophosphite and unsaturated olefin to obtain a dialkyl phosphorus oxide intermediate, and performing an addition-hydrolysis reaction on the two intermediates to obtain the extractant B.
In the invention, the synthetic raw materials of the extracting agent have wide sources, simple synthetic steps, low water solubility of the extracting agent and strong stability, so that the subsequent extraction process is stable, and the environmental pollution is reduced. Since both extractant A and extractant B have-OH and P = O groups (the carbonyl group in B has a keto-and enol-tautomeric equilibrium), it can react with Li + Stable neutral chelate is formed after coordination, so that two extracting agents can obviously improve Li + The extraction rate of (a); meanwhile, the benzene ring connected with the phenolic hydroxyl group of the extracting agent A has a strong electron-withdrawing effect, so that the extracting agent A also has strong binding capacity with Rb and Cs, and the extraction rate of Rb and Cs is improved.
The invention also provides the use of an extractant as described above for the extraction of lithium rubidium caesium, said use comprising the following steps:
(1) Mixing the extracting agent A or the extracting agent B with a diluent to form an extraction system, and mixing the extraction system with feed liquid containing alkali metal under an alkaline condition for extraction;
(2) Mixing the organic phase obtained after extraction in the step (1) with a stripping solution, and performing stripping to obtain a water phase;
(3) And (3) carrying out precipitation or heating treatment on the water phase obtained in the step (2), and separating to obtain an alkali metal-containing compound or an enriched substance.
As a preferred embodiment of the present invention, the concentration of the extractant A in the extraction system in the step (1) is 0.2 to 1.0mol/L, and may be, for example, 0.2mol/L, 0.4mol/L, 0.6mol/L, 0.8mol/L or 1.0mol/L, but not limited to the values mentioned above, and other values not mentioned above within the range of values are also applicable.
Preferably, the concentration of the extractant B in the extraction system in the step (1) is 0.2 to 1.0mol/L, for example, 0.2mol/L, 0.4mol/L, 0.6mol/L, 0.8mol/L or 1.0mol/L, etc., but is not limited to the enumerated values, and other values in the numerical range are also applicable.
As a preferred technical solution of the present invention, the diluent in the step (1) comprises any one or at least two combinations of hydrogenated kerosene, sulfonated kerosene, aliphatic hydrocarbon or aromatic hydrocarbon, and the combinations are exemplified by the following typical but non-limiting examples: a combination of hydrogenated kerosene and sulfonated kerosene, a combination of hydrogenated kerosene and aliphatic hydrocarbon, or a combination of aliphatic hydrocarbon and aromatic hydrocarbon, and the like.
Preferably, the feed liquid in step (1) comprises any one or at least two of a leaching liquid of lithium ore, a lithium precipitation mother liquid, a leaching liquid of lithium battery waste, a salt lake brine or a solution for secondary resource recovery, and the combinations are exemplified by, but not limited to: the combination of the leaching solution of the lithium ore and the lithium precipitation mother solution, the combination of the lithium precipitation mother solution and the leaching solution of the lithium battery waste, the combination of the lithium precipitation mother solution and salt lake brine and the like.
Preferably, the alkaline conditions in step (1) are to adjust the pH to 8-14, which may be, for example, 8, 9, 10, 11.5, 12.5, 13 or 14, etc., but are not limited to the recited values, and other values not recited within the range of values are equally applicable, preferably 11.5-12.5.
Preferably, the pH adjusting agent comprises any one or a combination of at least two of sodium hydroxide, potassium hydroxide, or aqueous ammonia, and the combination is typically but not limited to: a combination of sodium hydroxide and potassium hydroxide, a combination of sodium hydroxide and an aqueous ammonia solution, a combination of potassium hydroxide and an aqueous ammonia solution, or the like.
Preferably, the alkali metal in the feed liquid in step (1) comprises any one or at least two combinations of Li, rb or Cs, and the combinations are exemplified by the following typical but non-limiting examples: combinations of Li and Rb, li and Cs, or Li, rb and Cs, and the like.
Preferably, the Li, rb or Cs concentration is independently 0.1 to 5g/L, and may be, for example, 0.1g/L, 0.5g/L, 1g/L, 2g/L, 3g/L, 4g/L or 5g/L, etc., but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the feed liquid in the step (1)Further comprises Na + 、K + Or NH 4 + Any one or at least two combinations of the following, typical but non-limiting examples being: na (Na) + And K + Combination of (A) and (B), na + And NH 4 + Combination of (A) or (B) + And NH 4 + Combinations of (a), (b), and the like.
Preferably, the Na + 、K + And/or NH 4 + The total concentration of (B) is 10 to 200g/L, and may be, for example, 10g/L, 50g/L, 90g/L, 130g/L, 170g/L or 200g/L, etc., but is not limited to the values listed, and other values not listed in the numerical range are also applicable.
As a preferable technical scheme of the invention, the strip liquor in the step (2) is an acidic solution or a mixed solution of a weakly acidic gas and water.
Preferably, the acidic solution comprises any one or a combination of at least two of a hydrochloric acid solution, a sulfuric acid solution, a phosphoric acid solution, a citric acid solution, or a malic acid solution, as typical but non-limiting examples: a combination of a hydrochloric acid solution and a sulfuric acid solution, a combination of a sulfuric acid solution and a phosphoric acid solution, a combination of a citric acid solution and a malic acid solution, or the like.
Preferably, the weakly acidic gas comprises CO 2 And/or SO 2 。
Preferably, the total concentration of alkali metal ions contained in the aqueous phase in step (2) is greater than 6g/L, and may be, for example, 7g/L, 8g/L, 9g/L, 10g/L, or 11g/L, etc., but is not limited to the recited values, and other values not recited in the range of values are also applicable.
Preferably, the pH of the aqueous phase in step (2) is 3 to 7.5, and may be, for example, 3, 3.5, 4, 4.5, 5, 5.5, 6, 6.5, 7 or 7.5, etc., but is not limited to the recited values, and other values not recited in the range of values are equally applicable.
As a preferable technical scheme of the invention, the precipitation treatment in the step (3) is to add a precipitator.
Preferably, the precipitating agent is sodium carbonate and/or a sodium carbonate solution.
Preferably, the temperature of the heat treatment in step (3) is 80-110 ℃, for example, 80 ℃, 85 ℃, 90 ℃, 95 ℃,100 ℃, 105 ℃ or 110 ℃, etc., but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the time of the heat treatment in step (3) is 0.5-2h, such as 0.5h, 1h, 1.5h or 2h, but not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the separation means of step (3) comprises any one or at least two combinations of filtration, suction filtration or centrifugation, typical but non-limiting examples being: a combination of filtration and suction filtration, a combination of filtration and centrifugation, or a combination of suction filtration and centrifugation, and the like.
Preferably, the alkali metal containing compound or concentrate of step (3) is a chloride, sulphate or carbonate of Li or Li, rb and Cs. The extraction agent A is adopted to easily obtain enrichment matters of Li, rb and Cs, and the extraction agent B is adopted to easily obtain compounds of Li.
As a preferred embodiment of the present invention, the application of the extraction agent to extraction of lithium, rubidium and cesium specifically includes the following steps:
(1) Mixing 0.2-1.0mol/L extractant A or 0.2-1.0mol/L extractant B with diluent to form extraction system, and under the condition of pH 8-14, respectively and independently containing Li, rb or Cs alkali metal with concentration of 0.1-5g/L and Na with total concentration of 10-200g/L + 、K + And/or NH 4 + Mixing the feed liquid and extracting;
(2) Mixing the organic phase obtained after extraction in the step (1) with an acidic solution or mixing the organic phase with a mixed solution of weakly acidic gas and water, and back-extracting to obtain a water phase, wherein the total concentration of alkali metal ions in the water phase is more than 6g/L, and the pH value of the water phase is 3-7.5;
(3) And (3) carrying out precipitation treatment on the water phase obtained in the step (2) or heating the water phase at the temperature of 80-110 ℃ for 0.5-2h, and separating to obtain chloride, sulfate or carbonate containing Li or Li, rb and Cs.
Compared with the prior art, the invention has the following beneficial effects:
(1) The extractant of the invention can be extracted efficientlyThe valuable metal lithium rubidium cesium, and a large amount of Na + 、K + Or NH 4 + Impurities are separated, the obtained product has high purity, the back extraction rates of Li, rb and Cs are all more than 95 percent, and the recovery rates of Li, rb and Cs are all more than 90 percent;
(2) The extraction agent has the advantages of simple synthesis steps, wide source of synthetic raw materials, low water solubility, strong stability, low oil content of raffinate discharge and environmental pollution reduction;
(3) The extraction process flow used in the invention is simple and convenient, reduces the production cost, is efficient and environment-friendly, and has good industrial application prospect.
Drawings
FIG. 1 shows the extractant A vs Li + The extraction process of (2);
FIG. 2 shows the extractant B vs Li + The process of (2).
Detailed Description
The technical solution of the present invention is further explained by the following embodiments. It should be understood by those skilled in the art that the preparation examples and application examples are only for the understanding of the present invention and should not be construed as specifically limiting the present invention.
Preparation example 1
The preparation example provides an extracting agent, which comprises an extracting agent A or an extracting agent B;
the synthesis method of the extractant A comprises the following steps:
(1) In a 500mL round-bottom flask were added 152.6g of 4-chloromethylstyrene, 75g of p-tert-butylphenol, 10g of concentrated phosphoric acid in this order, and reacted at 150 ℃ for 6 hours. After the reaction, concentrated phosphoric acid was washed off with sodium carbonate, and low boiling substances were removed by distillation under reduced pressure to obtain 145g of 4- (tert-butyl) -2- (1- (4- (chloromethyl) phenyl) ethyl) phenol in a yield of 91%.
(2) 280g of 1-octene, 88g of sodium hypophosphite, 3.6g of Benzoyl Peroxide (BPO) and 100g of acetic acid were added in this order to a 1L round bottom flask and stirred at 135 ℃ for 4h. After the reaction was complete the solid was filtered and the filtrate was washed 2 times with 1M sulfuric acid. After liquid separation, organic phase is subjected to vacuum distillation to remove low-boiling-point substances, 200mL of toluene and 300g of trichlorosilane are added to react for 4 hours at the temperature of 80 ℃, and the low-boiling-point substances are removed by vacuum distillation to obtain 252g of dioctylphosphine oxide with the yield of 95%.
(3) 145g of 4- (tert-butyl) -2- (1- (4- (chloromethyl) phenyl) ethyl) phenol and 126g of dioctylphosphine oxide were charged in a 500mL round-bottomed flask, and reacted at 100 ℃ for 3 hours, after cooling and cooling, 100mL of distilled water was added thereto and refluxed for 5 hours to obtain 244g of (4- (1- (5- (tert-butyl) -2-hydroxyphenyl) ethyl) phenyl) dioctylphosphine oxide in 93% yield.
The synthesis method of the extractant B comprises the following steps:
(1) 248g of 4-octylacetophenone, 83.5g of ethyl bromoacetate, 10g of sodium ethoxide and 100mL of DMF were successively charged in a 500mL round-bottomed flask, and the reaction was stirred at 120 ℃ for 6 hours. After the reaction was complete, the organic phase was washed 2 times with deionized water. The low boiling point compound was distilled off under reduced pressure to give 172g of 4-bromo-1- (4-octylphenyl) butane-1,3-dione as a pale yellow liquid for further use.
(2) 145g of 4-bromo-1- (4-octylphenyl) butane-1,3-dione and 126g of dioctylphosphine oxide are added into a 500mL round bottom flask, and reacted at 100 ℃ for 3h, and after cooling and cooling, 100mL of distilled water is added and refluxed for 5h to obtain 256g of 4- (dioctylphosphoryl) -1- (4-octylphenyl) butane-1,3-dione with a yield of 94%.
Preparation example 2
The preparation example provides an extracting agent, which comprises an extracting agent A or an extracting agent B;
the synthesis method of the extractant A comprises the following steps:
(1) In a 500mL round-bottom flask were added 152.6g of 4-chloromethylstyrene, 75g of p-tert-butylphenol, 10g of concentrated phosphoric acid in this order, and reacted at 150 ℃ for 6 hours. After the reaction, concentrated phosphoric acid was washed with sodium carbonate, and low boiling substances were removed by distillation under reduced pressure to obtain 145g of 4- (tert-butyl) -2- (1- (4- (chloromethyl) phenyl) ethyl) phenol in a yield of 91%.
(2) 280g of 2-ethyl-1-hexene, 88g of sodium hypophosphite, 3.6g of Benzoyl Peroxide (BPO) and 100g of acetic acid were added in this order to a 1L round bottom flask and stirred at 135 ℃ for 4h. After the reaction was complete the solid was filtered and the filtrate was washed 2 times with 1M sulfuric acid. After liquid separation, organic phase is subjected to vacuum distillation to remove low-boiling-point substances, 200mL of toluene and 300g of trichlorosilane are added to react for 4 hours at the temperature of 80 ℃, vacuum distillation is carried out to remove the low-boiling-point substances, and 252g of diisooctylphosphine oxide is obtained, wherein the yield is 95%.
(3) 145g of 4- (tert-butyl) -2- (1- (4- (chloromethyl) phenyl) ethyl) phenol and 126g of diisooctylphosphine oxide were charged in a 500mL round-bottomed flask, and reacted at 100 ℃ for 3 hours, and after cooling and cooling, 100mL of distilled water was added and refluxed for 5 hours to obtain 244g of (4- (1- (5- (tert-butyl) -2-hydroxyphenyl) ethyl) phenyl) diisooctylphosphine oxide in 93% yield.
The synthesis method of the extractant B comprises the following steps:
(1) 248g of 4-octylacetophenone, 83.5g of ethyl bromoacetate, 10g of sodium ethoxide and 100mL of DMF were sequentially added to a 500mL round-bottomed flask, and the reaction was stirred at 120 ℃ for 6 hours. After the reaction was complete, the organic phase was washed 2 times with deionized water. The low boiling point compound was distilled off under reduced pressure to give 172g of 4-bromo-1- (4-octylphenyl) butane-1,3-dione as a pale yellow liquid for further use.
(2) 145g of 4-bromo-1- (4-octylphenyl) butane-1,3-dione and 126g of diisooctylphosphine oxide are added into a 500mL round bottom flask, the mixture is reacted for 3h at 100 ℃,100 mL of distilled water is added after cooling and temperature reduction, and reflux is carried out for 5h to obtain 256g of 4- (diisooctylphosphoryl) -1- (4-octylphenyl) butane-1,3-dione with the yield of 94%.
Preparation example 3
The preparation example provides an extracting agent, which comprises an extracting agent A or an extracting agent B;
the synthesis method of the extractant A comprises the following steps:
(1) In a 500mL round-bottom flask were charged 152.6g of 4-chloromethylstyrene, 131.2g of p-dodecylphenol, 12g of concentrated phosphoric acid, and reacted at 170 ℃ for 8 hours. After the reaction, concentrated phosphoric acid was washed away with sodium carbonate, and excess 4-chloromethylstyrene was removed by distillation under reduced pressure to obtain 200g of 2- (1- (4- (chloromethyl) phenyl) ethyl) -4-dodecylphenol in a yield of 96%.
(2) 280g of 1-octene, 88g of sodium hypophosphite, 3.6g of Benzoyl Peroxide (BPO) and 100g of acetic acid were added in this order to a 1L round bottom flask and stirred at 135 ℃ for 4h. After the reaction was complete the solid was filtered and the filtrate was washed 2 times with 1M sulfuric acid. After liquid separation, organic phase is subjected to vacuum distillation to remove low-boiling-point substances, 200mL of toluene and 300g of trichlorosilane are added to react for 4 hours at the temperature of 80 ℃, vacuum distillation is carried out to remove the low-boiling-point substances, and then 249g of dioctylphosphine oxide is obtained, wherein the yield is 94%.
(3) 200g of 2- (1- (4- (chloromethyl) phenyl) ethyl) -4-dodecylphenol and 141g of dioctylphosphine oxide are added into a 500mL round-bottom flask, and reacted for 3h at 100 ℃, and then 100mL of distilled water is added after cooling and cooling, and refluxing is carried out for 5h, so as to obtain 268.6g of (4- (1- (5-dodecyl-2-hydroxyphenyl) ethyl) phenyl) dioctylphosphine oxide with 88% yield.
The synthesis method of the extractant B comprises the following steps:
(1) 246g of 4-n-nonylacetophenone, 83.5g of ethyl bromoacetate, 10g of sodium ethoxide and 100mL of DMF are successively added to a 500mL round-bottom flask, and the reaction is stirred at 120 ℃ for 6 hours. After the reaction was complete, the organic phase was washed 2 times with deionized water. The low boilers were distilled off under reduced pressure to give 178g of 4-bromo-1- (4-n-nonylphenyl) butane-1,3-dione as a pale yellow liquid.
(2) 178g of 4-bromo-1- (4-n-nonylphenyl) butane-1,3-dione and 146g of dioctylphosphine oxide were charged in a 500mL round-bottomed flask, and reacted at 100 ℃ for 3 hours, followed by cooling and cooling, and then 100mL of distilled water was added thereto and refluxed for 5 hours, whereby 252g of 4- (dioctylphosphoryl) -1- (4-n-nonylphenyl) butane-1,3-dione was obtained in 90% yield.
The extractant A is opposite to Li + The extraction process of (2) is shown in FIG. 1. [ Li (H) 2 O)] + Easily matches with-OH and P = O in a compound containing phenolic hydroxyl and phosphorus oxygen functional groups to form a stable neutral chelate, wherein Li + After coordination, a stable seven-membered chelate ring is formed. The benzene ring connected with the phenolic hydroxyl group has a strong electron-withdrawing effect, so that the phenolic hydroxyl group and Li + A tighter bond is possible. Meanwhile, the phenolic hydroxyl is easy to combine with Rb and Cs to form a corresponding extract compound. Will carry [ Li (H) ] 2 O)] + Is mixed with a weak acid by Li + And H + Ion exchange of (2), can realize Li + And (4) back extraction.
The extractant B is opposite to Li + The extraction process of (2) is shown in FIG. 2. The beta-diketone and phosphorus-oxygen functional compound has tautomeric equilibrium of its keto form and enol form, and during extraction, [ Li (H) 2 O)] + Is easy to be matched with-OH and P = O to form stable neutral chelate, wherein Li + After coordination, a stable seven-membered chelate ring is formed. Because the benzene ring contained in the compound has stronger electron-withdrawing effect, li + The chelate formed is more stable.
Application example 1
The application example provides application of the extracting agent in extraction of lithium, rubidium and cesium, and the application comprises the following steps:
(1) The extracting agent A obtained in the preparation example 1 is mixed with hydrogenated kerosene to form an extraction system, the pH value of the extraction system is adjusted to 11.5 by utilizing sodium hydroxide, and under the condition, the extraction system and the mixture containing Li with the concentration of 1g/L, rb with the concentration of 0.1g/L, cs with the concentration of 0.1g/L, na + The concentration is 10g/L, K + The concentration is 10g/L and NH 4 + Mixing the lithium precipitation mother liquor with the concentration of 10g/L for extraction;
(2) Mixing the loaded organic phase containing Li, rb and Cs obtained in the step (1) with a hydrochloric acid solution for back extraction, wherein compared with (volume of the organic phase to volume of the aqueous phase) 35;
(3) And (3) heating the water phase obtained in the step (2) at 95 ℃ for 1h, and performing suction filtration to obtain LiCl, rbCl and CsCl products with the purity of 99%, 98% and 98% respectively.
Application example 2
The application example provides application of the extracting agent in extraction of lithium, rubidium and cesium, and the application comprises the following steps:
(1) The extracting agent A obtained in the preparation example 2 is mixed with hydrogenated kerosene to form an extraction system, the pH of the extraction system is adjusted to 12.5 by utilizing sodium hydroxide, and under the condition, the extraction system and the hydrogenated kerosene with the Li concentration of 0.5g/L, rb concentration of 0.5g/L, cs concentration of 0.5g/L, na + The concentration is 10g/L and K + Mixing the lithium precipitation mother liquor with the concentration of 10g/L for extraction;
(2) Mixing the loaded organic phase containing Li, rb and Cs obtained in the step (1) with a hydrochloric acid solution for back extraction, wherein compared with (volume of the organic phase to volume of the aqueous phase) 20;
(3) And (3) heating the water phase obtained in the step (2) at 80 ℃ for 2h, and performing suction filtration to obtain LiCl, rbCl and CsCl products with the purity of 98%, 96% and 97% respectively.
Application example 3
The application example provides application of the extracting agent in extraction of lithium, rubidium and cesium, and the application comprises the following steps:
(1) The extracting agent A obtained in the preparation example 3 and sulfonated kerosene are mixed to form an extraction system, the pH of the extraction system is adjusted to 8 by utilizing potassium hydroxide, and under the condition, the extraction system and the sulfonated kerosene with the Li concentration of 2g/L, rb of 0.6g/L, cs of 0.6g/L, na are mixed + The concentration is 20g/L, K + The concentration is 20g/L and NH 4 + Mixing the lithium battery waste leachate with the concentration of 20g/L for extraction;
(2) Mixing the loaded organic phase containing Li, rb and Cs obtained in the step (1) with a sulfuric acid solution for back extraction, wherein compared with (volume of the organic phase to volume of the aqueous phase) 15;
(3) Heating the water phase obtained in the step (2) at 110 ℃ for 0.5h, and centrifuging to obtain Li 2 SO 4 、Rb 2 SO 4 And Cs 2 SO 4 The purity of the product is 98%, 96% and 97% respectively.
Application example 4
The application example provides an application of the extractant in lithium rubidium cesium extraction, and the application comprises the following steps:
(1) The extractant B obtained in the preparation example 1 and sulfonated kerosene are mixed to form an extraction system, the pH of the extraction system is adjusted to 14 by using potassium hydroxide, and under the condition, the extraction system and the Li-containing concentration are 5g/L, na + The concentration is 20g/L and K + Mixing the lithium battery waste leachate with the concentration of 20g/L for extraction;
(2) Mixing the Li-containing loaded organic phase obtained in the step (1) with a sulfuric acid solution for back extraction, and obtaining an aqueous phase containing 38.4g/L Li after back extraction compared with 8:1 (volume of organic phase to volume of aqueous phase), wherein the pH value of the obtained aqueous phase is 5, the back extraction rate of Li is 99%, and the recovery rate of Li is 96%;
(3) Heating the water phase obtained in the step (2) at 100 ℃ for 1h, and centrifuging to obtain Li 2 SO 4 The product has the purity of 97%.
Application example 5
The application example provides application of the extracting agent in extraction of lithium, rubidium and cesium, and the application comprises the following steps:
(1) The extracting agent B obtained in the preparation example 2 is mixed with hydrogenated kerosene to form an extraction system, the pH of the extraction system is adjusted to 11.5 by ammonia water, and under the condition, the extraction system and the Li-containing concentration are 1g/L, na + The concentration is 30g/L, K + The concentration is 5g/L and NH 4 + Mixing leaching solutions of 5g/L lithium ores for extraction;
(2) The Li-containing loaded organic phase obtained in the step (1) is mixed with CO 2 Weak acid solution formed by continuously introducing water is mixed for back extraction, compared with the condition that the volume of an organic phase is 1 to the volume of an aqueous phase, the aqueous phase containing 3.69g/L of Li is obtained after the back extraction, the pH value of the obtained aqueous phase is 6, the back extraction rate of the Li is 95 percent, and the recovery rate of the Li is 92 percent;
(3) Heating the water phase obtained in the step (2) at 100 ℃ for 1h, and centrifuging to obtain Li 2 CO 3 The product has a purity of 99%.
Application example 6
The application example provides application of the extracting agent in extraction of lithium, rubidium and cesium, and the application comprises the following steps:
(1) The extractant B obtained in the preparation example 3 is mixed with sulfonated kerosene to form an extraction system, the pH of the extraction system is adjusted to 9 by ammonia water, and the extraction system and the Li-containing solution with the concentration of 3g/L, na are mixed under the condition + The concentration is 30g/L, K + The concentration is 5g/L and NH 4 + Mixing leaching solutions of 5g/L lithium ores for extraction;
(2) Carrying out phase separation on the Li-containing loaded organic phase obtained in the step (1) and SO 2 Continuously introducing a weak acid solution formed in water, mixing and back-extracting, wherein compared with (volume of an organic phase to volume of an aqueous phase) 1.5, after back-extraction, an aqueous phase containing 5.76g/L of Li is obtained, the pH value of the obtained aqueous phase is 6, the back-extraction rate of Li is 99%, and the recovery rate of Li is 96%;
(3) Adding sodium carbonate into the water phase obtained in the step (2), heating for 1h at 100 ℃, and centrifuging to obtain Li 2 CO 3 The product has the purity of 98 percent.
Comparative application example 1
This comparative example provides the use of the extraction agent in lithium rubidium cesium extraction, which is the same as in application example 1 except that the step (1) of adjusting the pH of the extraction system to 11.5 using sodium hydroxide is replaced with the step of adjusting the pH of the extraction system to 5 using hydrochloric acid.
The back extraction rates of Li, rb and Cs are respectively 35%, 5% and 6%, and the recovery rates of Li, rb and Cs are respectively 65%, 20% and 10%; liCl, rbCl and CsCl products are obtained, and the purity is 79%, 35% and 20% respectively.
Comparative application example 2
This comparative example provides the use of the extraction reagent in extraction of lithium, rubidium and cesium, which is the same as in application example 1 except that no diluent is added to the extraction system in step (1).
The back extraction rates of Li, rb and Cs are 85%, 77% and 69%, respectively, and the recovery rates of Li, rb and Cs are 68%, 55% and 46%, respectively; liCl, rbCl and CsCl products are obtained, and the purity is 88%, 55% and 45% respectively.
Comparative application example 3
This comparative example provides an application of the extractant in lithium rubidium cesium extraction, wherein the step (1) is to replace the extractant A obtained in preparation example 1 with 4-tert-butyl-2- (alpha-methylbenzyl) phenol (t-BAMBP) to be mixed with hydrogenated kerosene to form an extraction system, and the rest steps are the same as the application example 1.
The back extraction rates of Li, rb and Cs are respectively 5%, 67% and 69%, and the recovery rates of Li, rb and Cs are respectively 15%, 57% and 66%; liCl, rbCl and CsCl products are obtained, and the purity is 20%, 50% and 69%, respectively.
Comparative application example 4
This comparative example provides an application of the extractant in lithium rubidium cesium extraction, wherein the step (1) replaces the extractant B obtained in preparation example 1 with dodecylphenyl-methyl-beta-diketone (LIX 54) to be mixed with hydrogenated kerosene to form an extraction system, and the rest is the same as application example 4.
The back extraction rate of Li is 51%, and the recovery rate of Li is 25%; to obtain Li 2 SO 4 The product has a purity of 18%.
Comparing the application example 1 with the comparative application examples 1-2, if the pH value of the extraction system is acidic or no diluent exists in the extraction system, the extraction and recovery of Li, rb and Cs are not facilitated, and the purity of the obtained product is not high; therefore, the existence of alkaline environment and diluent in the extraction system is an important condition for ensuring that the extracting agent can efficiently extract the valuable metals Li, rb and Cs.
Comparing the application example 1 with the comparative application example 3, the extracting agent t-BAMBP containing the benzene ring connected with the phenolic hydroxyl group can extract Cs and Rb but can not recover Li resources in the solution; comparing the application example 4 with the comparative application example 4, the valuable metal Li can be extracted by using the diketone extracting agent LIX54, but the extraction rate of the Li is poor, and the purity of the obtained product is not high; therefore, the great difference in extraction effect still exists between the homologues, and the extractant can realize high-efficiency extraction of Li, rb and Cs.
The applicant declares that the present invention is illustrated in detail in the structural features and the application flow of the present invention through the above preparation examples and application examples, but the present invention is not limited to the above detailed structural features and the application flow, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features and the application flow. It should be understood by those skilled in the art that any modification of the present invention, equivalent replacement of the raw materials of the product of the present invention, addition of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
Claims (10)
1. An extractant, which is characterized by comprising an extractant A shown as a formula I or an extractant B shown as a formula II:
wherein R in the formula I 1 Is a C4-C12 linear or branched alkyl group, R 2 Is n-octyl or isooctyl; r in the formula II 3 Is a C8-C12 linear or branched alkyl radical, R 4 Is n-octyl or isooctyl.
2. The extractant according to claim 1, characterized in that the synthesis method of the extractant A comprises the following steps: the extraction agent A is prepared by carrying out addition reaction on 4-chloromethyl styrene and alkylphenol to obtain an alkyl-2- (1- (4- (chloromethyl) phenyl) ethyl) phenol intermediate, carrying out addition-reduction reaction on sodium hypophosphite and unsaturated olefin to obtain a dialkyl phosphorus oxide intermediate, and carrying out addition-hydrolysis reaction on the two intermediates.
3. The extractant of claim 1, wherein the synthesis method of the extractant B comprises the following steps: performing a claisen condensation reaction on a carbonyl compound containing a benzene ring and halogenated carboxylic ester under the catalysis of alkali to obtain a beta-diketone intermediate, and performing an addition-hydrolysis reaction on the beta-diketone intermediate and dialkyl phosphorus oxide to obtain the extractant B.
4. Use of an extractant according to any one of claims 1 to 3 for lithium rubidium caesium extraction, characterized in that it comprises the following steps:
(1) Mixing an extracting agent as defined in any one of claims 1 to 3 with a diluent to form an extraction system, and mixing the extraction system with an alkali metal-containing feed liquid under an alkaline condition for extraction;
(2) Mixing the organic phase obtained after extraction in the step (1) with a stripping solution, and performing stripping to obtain a water phase;
(3) And (3) carrying out precipitation or heating treatment on the water phase obtained in the step (2), and separating to obtain an alkali metal-containing compound or an enriched substance.
5. The use of claim 4, wherein the concentration of the extractant A in the extraction system in the step (1) is 0.2-1.0mol/L;
preferably, the concentration of the extractant B in the extraction system in the step (1) is 0.2-1.0mol/L.
6. The use according to claim 4 or 5, wherein the diluent of step (1) comprises any one or a combination of at least two of hydrogenated kerosene, sulfonated kerosene, aliphatic hydrocarbon or aromatic hydrocarbon;
preferably, the feed liquid in the step (1) comprises any one or at least two of a leaching liquid of lithium ore, a lithium precipitation mother liquid, a leaching liquid of lithium battery waste, salt lake brine or a solution for secondary resource recovery;
preferably, the alkaline conditions in step (1) are adjusting the pH to 8-14, preferably 11.5-12.5;
preferably, the regulator used for adjusting the pH comprises any one or at least two of sodium hydroxide, potassium hydroxide or ammonia water solution.
7. The use according to any one of claims 4 to 6, wherein the alkali metal in the feed liquid in step (1) comprises any one or a combination of at least two of Li, rb or Cs;
preferably, the concentrations of Li, rb or Cs are respectively and independently 0.1-5g/L;
preferably, the feed liquid in the step (1) further comprises Na + 、K + Or NH 4 + Any one or a combination of at least two of;
preferably, the Na + 、K + And/or NH 4 + The total concentration of (A) is 10-200g/L.
8. The use according to any one of claims 4 to 7, wherein the strip liquor in step (2) is an acidic solution or a mixed solution of a weakly acidic gas and water;
preferably, the acidic solution comprises any one or at least two of hydrochloric acid solution, sulfuric acid solution, phosphoric acid solution, citric acid solution or malic acid solution;
preferably, the weakly acidic gas comprises CO 2 And/or SO 2 ；
Preferably, the total concentration of alkali metal ions in the aqueous phase of step (2) is greater than 6g/L;
preferably, the pH of the aqueous phase of step (2) is from 3 to 7.5.
9. The use according to any one of claims 4 to 8, wherein the precipitation treatment in step (3) is the addition of a precipitating agent;
preferably, the precipitating agent is sodium carbonate and/or a sodium carbonate solution;
preferably, the temperature of the heating treatment in the step (3) is 80-110 ℃;
preferably, the time of the heat treatment in the step (3) is 0.5-2h;
preferably, the separation mode of the step (3) comprises any one or at least two combinations of filtration, suction filtration or centrifugation;
preferably, the alkali metal containing compound or concentrate of step (3) is a chloride, sulfate or carbonate of Li or Li, rb and Cs.
10. Use according to any of claims 4-9, characterized in that it comprises the following steps:
(1) Mixing 0.2-1.0mol/L of the extractant A or 0.2-1.0mol/L of the extractant B as described in any one of claims 1 to 3 with a diluent to form an extraction system, and mixing the extraction system with the alkali metal containing Li, rb or Cs at a concentration of 0.1-5g/L and the alkali metal containing Na at a total concentration of 10-200g/L respectively and under the condition of pH 8-14 + 、K + And/or NH 4 + Mixing the feed liquid and extracting;
(2) Mixing the organic phase obtained after extraction in the step (1) with an acidic solution or mixing the organic phase with a mixed solution of weakly acidic gas and water, and back-extracting to obtain a water phase, wherein the total concentration of alkali metal ions in the water phase is more than 6g/L, and the pH value of the water phase is 3-7.5;
(3) And (3) carrying out precipitation treatment on the water phase obtained in the step (2) or heating the water phase at the temperature of 80-110 ℃ for 0.5-2h, and separating to obtain chloride, sulfate or carbonate containing Li or Li, rb and Cs.
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