CN106521190B - The phosphine of neutrality containing amino extractant is used for the purposes and method of extracting and separating zirconium and/or hafnium - Google Patents
The phosphine of neutrality containing amino extractant is used for the purposes and method of extracting and separating zirconium and/or hafnium Download PDFInfo
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- CN106521190B CN106521190B CN201611012369.XA CN201611012369A CN106521190B CN 106521190 B CN106521190 B CN 106521190B CN 201611012369 A CN201611012369 A CN 201611012369A CN 106521190 B CN106521190 B CN 106521190B
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- Prior art keywords
- hafnium
- zirconium
- ethylhexyl
- extraction
- extractant
- Prior art date
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- 229910052735 hafnium Inorganic materials 0.000 title claims abstract description 242
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 title claims abstract description 242
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 title claims abstract description 232
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 title claims abstract description 232
- 229910052726 zirconium Inorganic materials 0.000 title claims abstract description 232
- 238000000034 method Methods 0.000 title claims abstract description 128
- 229910000073 phosphorus hydride Inorganic materials 0.000 title claims abstract description 116
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 title claims abstract description 71
- 238000000605 extraction Methods 0.000 claims abstract description 191
- 239000007788 liquid Substances 0.000 claims abstract description 143
- 230000007935 neutral effect Effects 0.000 claims abstract description 116
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000000926 separation method Methods 0.000 claims abstract description 40
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 34
- 239000001257 hydrogen Substances 0.000 claims abstract description 34
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 21
- 238000001556 precipitation Methods 0.000 claims abstract description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 4
- -1 bis (2-ethylhexyl) 1- (2-ethylhexylamino) methylphosphonic acid Chemical compound 0.000 claims description 130
- 239000000243 solution Substances 0.000 claims description 88
- 238000005406 washing Methods 0.000 claims description 88
- 239000003795 chemical substances by application Substances 0.000 claims description 53
- GVOLZAKHRKGRRM-UHFFFAOYSA-N hafnium(4+) Chemical compound [Hf+4] GVOLZAKHRKGRRM-UHFFFAOYSA-N 0.000 claims description 39
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 28
- 125000000217 alkyl group Chemical group 0.000 claims description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 24
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 239000002253 acid Substances 0.000 claims description 22
- 150000003254 radicals Chemical class 0.000 claims description 21
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 20
- 238000000638 solvent extraction Methods 0.000 claims description 18
- 239000003350 kerosene Substances 0.000 claims description 17
- 239000011259 mixed solution Substances 0.000 claims description 17
- 125000001424 substituent group Chemical group 0.000 claims description 17
- 229910017604 nitric acid Inorganic materials 0.000 claims description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 15
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 14
- 239000003085 diluting agent Substances 0.000 claims description 14
- 239000003607 modifier Substances 0.000 claims description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 13
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 9
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 9
- 239000003513 alkali Substances 0.000 claims description 8
- 239000012527 feed solution Substances 0.000 claims description 8
- 150000007513 acids Chemical class 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 238000004090 dissolution Methods 0.000 claims description 7
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 7
- 229940039748 oxalate Drugs 0.000 claims description 7
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 6
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical group CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 6
- 125000003545 alkoxy group Chemical group 0.000 claims description 6
- KBPLFHHGFOOTCA-UHFFFAOYSA-N caprylic alcohol Natural products CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 claims description 6
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical class C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 6
- YCOZIPAWZNQLMR-UHFFFAOYSA-N pentadecane Chemical compound CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 claims description 6
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 claims description 6
- IIYFAKIEWZDVMP-UHFFFAOYSA-N tridecane Chemical compound CCCCCCCCCCCCC IIYFAKIEWZDVMP-UHFFFAOYSA-N 0.000 claims description 6
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 claims description 6
- 239000008096 xylene Substances 0.000 claims description 6
- QZESEQBMSFFHRY-UHFFFAOYSA-N 2-methylheptan-1-ol Chemical compound CCCCCC(C)CO QZESEQBMSFFHRY-UHFFFAOYSA-N 0.000 claims description 5
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 5
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 5
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 5
- DIOQZVSQGTUSAI-UHFFFAOYSA-N n-butylhexane Natural products CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 5
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 239000000446 fuel Substances 0.000 claims description 4
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- BWDBEAQIHAEVLV-UHFFFAOYSA-N 6-methylheptan-1-ol Chemical compound CC(C)CCCCCO BWDBEAQIHAEVLV-UHFFFAOYSA-N 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- 150000001298 alcohols Chemical class 0.000 claims description 3
- 229940057995 liquid paraffin Drugs 0.000 claims description 3
- ZCYXXKJEDCHMGH-UHFFFAOYSA-N nonane Chemical compound CCCC[CH]CCCC ZCYXXKJEDCHMGH-UHFFFAOYSA-N 0.000 claims description 3
- BKIMMITUMNQMOS-UHFFFAOYSA-N normal nonane Natural products CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 claims description 3
- YOCZZJWFWDUAAR-UHFFFAOYSA-N sulfanyl-sulfanylidene-bis(2,4,4-trimethylpentyl)-$l^{5}-phosphane Chemical group CC(C)(C)CC(C)CP(S)(=S)CC(C)CC(C)(C)C YOCZZJWFWDUAAR-UHFFFAOYSA-N 0.000 claims description 3
- ZMBHCYHQLYEYDV-UHFFFAOYSA-N trioctylphosphine oxide Chemical compound CCCCCCCCP(=O)(CCCCCCCC)CCCCCCCC ZMBHCYHQLYEYDV-UHFFFAOYSA-N 0.000 claims description 3
- OFOUIYGUOUTLLP-UHFFFAOYSA-N 2,4,4-trimethyl-1-(2,4,4-trimethylpentoxyphosphonoyloxy)pentane Chemical compound CC(C)(C)CC(C)COP(=O)OCC(C)CC(C)(C)C OFOUIYGUOUTLLP-UHFFFAOYSA-N 0.000 claims description 2
- ZDFBXXSHBTVQMB-UHFFFAOYSA-N 2-ethylhexoxy(2-ethylhexyl)phosphinic acid Chemical compound CCCCC(CC)COP(O)(=O)CC(CC)CCCC ZDFBXXSHBTVQMB-UHFFFAOYSA-N 0.000 claims description 2
- GOCVCBDBQYEFQD-UHFFFAOYSA-N 3-[[2-ethylhexoxy(2-ethylhexyl)phosphoryl]oxymethyl]heptane Chemical compound CCCCC(CC)COP(=O)(CC(CC)CCCC)OCC(CC)CCCC GOCVCBDBQYEFQD-UHFFFAOYSA-N 0.000 claims description 2
- HFKNKTQWWBVCQC-UHFFFAOYSA-N C(C(C)C)NP(=O)(NOCCCCCC(C)C)NCC(C)C Chemical compound C(C(C)C)NP(=O)(NOCCCCCC(C)C)NCC(C)C HFKNKTQWWBVCQC-UHFFFAOYSA-N 0.000 claims description 2
- WBLGXIFKKXGJGJ-UHFFFAOYSA-N CC(CCCCCC)(C)OP(O)(=O)C Chemical compound CC(CCCCCC)(C)OP(O)(=O)C WBLGXIFKKXGJGJ-UHFFFAOYSA-N 0.000 claims description 2
- XJTKJBYXOMXALF-UHFFFAOYSA-N CC(COP(OCC(CC(C)(C)C)C)=S)CC(C)(C)C Chemical compound CC(COP(OCC(CC(C)(C)C)C)=S)CC(C)(C)C XJTKJBYXOMXALF-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- XOVGHMTUWWTYDF-UHFFFAOYSA-N N-[amino-(2-methylpropylamino)phosphoryl]-2-methylpropan-1-amine Chemical compound P(=O)(NCC(C)C)(NCC(C)C)N XOVGHMTUWWTYDF-UHFFFAOYSA-N 0.000 claims description 2
- ZLMKQJQJURXYLC-UHFFFAOYSA-N bis(2-ethylhexoxy)-oxophosphanium Chemical compound CCCCC(CC)CO[P+](=O)OCC(CC)CCCC ZLMKQJQJURXYLC-UHFFFAOYSA-N 0.000 claims description 2
- DMSZORWOGDLWGN-UHFFFAOYSA-N ctk1a3526 Chemical compound NP(N)(N)=O DMSZORWOGDLWGN-UHFFFAOYSA-N 0.000 claims description 2
- SEGLCEQVOFDUPX-UHFFFAOYSA-N di-(2-ethylhexyl)phosphoric acid Chemical compound CCCCC(CC)COP(O)(=O)OCC(CC)CCCC SEGLCEQVOFDUPX-UHFFFAOYSA-N 0.000 claims description 2
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 239000010687 lubricating oil Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- 239000012047 saturated solution Substances 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- ZNCPFRVNHGOPAG-UHFFFAOYSA-L sodium oxalate Chemical compound [Na+].[Na+].[O-]C(=O)C([O-])=O ZNCPFRVNHGOPAG-UHFFFAOYSA-L 0.000 claims description 2
- 229940039790 sodium oxalate Drugs 0.000 claims description 2
- 229910052717 sulfur Inorganic materials 0.000 claims description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 5
- 229910052698 phosphorus Inorganic materials 0.000 claims 5
- 239000011574 phosphorus Substances 0.000 claims 5
- 125000000113 cyclohexyl group Chemical class [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims 2
- MUBVCQLLDIMUBV-UHFFFAOYSA-N N-[amino-[bis(6-methylheptoxy)amino]phosphoryl]-6-methylheptan-1-amine Chemical compound C(CCCCC(C)C)NP(=O)(N(OCCCCCC(C)C)OCCCCCC(C)C)N MUBVCQLLDIMUBV-UHFFFAOYSA-N 0.000 claims 1
- DIOQZVSQGTUSAI-NJFSPNSNSA-N decane Chemical compound CCCCCCCCC[14CH3] DIOQZVSQGTUSAI-NJFSPNSNSA-N 0.000 claims 1
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims 1
- 150000008300 phosphoramidites Chemical class 0.000 claims 1
- NSETWVJZUWGCKE-UHFFFAOYSA-N propylphosphonic acid Chemical compound CCCP(O)(O)=O NSETWVJZUWGCKE-UHFFFAOYSA-N 0.000 claims 1
- INIGCWGJTZDVRY-UHFFFAOYSA-N hafnium zirconium Chemical compound [Zr].[Hf] INIGCWGJTZDVRY-UHFFFAOYSA-N 0.000 abstract description 21
- 238000000746 purification Methods 0.000 abstract description 2
- 239000012074 organic phase Substances 0.000 description 51
- 239000000047 product Substances 0.000 description 26
- 238000002474 experimental method Methods 0.000 description 14
- 238000002360 preparation method Methods 0.000 description 14
- 239000002244 precipitate Substances 0.000 description 13
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 12
- IVORCBKUUYGUOL-UHFFFAOYSA-N 1-ethynyl-2,4-dimethoxybenzene Chemical compound COC1=CC=C(C#C)C(OC)=C1 IVORCBKUUYGUOL-UHFFFAOYSA-N 0.000 description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 8
- DFIPXJGORSQQQD-UHFFFAOYSA-N hafnium;tetrahydrate Chemical compound O.O.O.O.[Hf] DFIPXJGORSQQQD-UHFFFAOYSA-N 0.000 description 8
- HGJSMLMRKBXYJY-UHFFFAOYSA-N [N+](=O)([O-])[O-].[Zr+4].[Hf+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] Chemical compound [N+](=O)([O-])[O-].[Zr+4].[Hf+4].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-].[N+](=O)([O-])[O-] HGJSMLMRKBXYJY-UHFFFAOYSA-N 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- NXKAMHRHVYEHER-UHFFFAOYSA-J hafnium(4+);disulfate Chemical compound [Hf+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NXKAMHRHVYEHER-UHFFFAOYSA-J 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 4
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 4
- TZNXTUDMYCRCAP-UHFFFAOYSA-N hafnium(4+);tetranitrate Chemical compound [Hf+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O TZNXTUDMYCRCAP-UHFFFAOYSA-N 0.000 description 4
- 229910052761 rare earth metal Inorganic materials 0.000 description 4
- 150000002910 rare earth metals Chemical class 0.000 description 4
- ZXAUZSQITFJWPS-UHFFFAOYSA-J zirconium(4+);disulfate Chemical compound [Zr+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O ZXAUZSQITFJWPS-UHFFFAOYSA-J 0.000 description 4
- VYRDHRYMAZWQJH-UHFFFAOYSA-N [P].P Chemical compound [P].P VYRDHRYMAZWQJH-UHFFFAOYSA-N 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- BBMCTIGTTCKYKF-UHFFFAOYSA-N 1-heptanol Chemical compound CCCCCCCO BBMCTIGTTCKYKF-UHFFFAOYSA-N 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- ZQSGCHKRBHZTFF-UHFFFAOYSA-N N-[1-[bis(2-ethylhexoxy)phosphoryl]propyl]-2-ethylhexan-1-amine Chemical compound C(C)C(COP(OCC(CCCC)CC)(=O)C(CC)NCC(CCCC)CC)CCCC ZQSGCHKRBHZTFF-UHFFFAOYSA-N 0.000 description 2
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 125000003277 amino group Chemical group 0.000 description 2
- 150000001934 cyclohexanes Chemical class 0.000 description 2
- MWKFXSUHUHTGQN-UHFFFAOYSA-N decan-1-ol Chemical compound CCCCCCCCCCO MWKFXSUHUHTGQN-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- MLRVATMGALJBGQ-UHFFFAOYSA-N hafnium hydrochloride Chemical compound [Hf].Cl MLRVATMGALJBGQ-UHFFFAOYSA-N 0.000 description 2
- QXDNWIJGNPKDRX-UHFFFAOYSA-J hafnium(4+);oxalate Chemical compound [Hf+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O QXDNWIJGNPKDRX-UHFFFAOYSA-J 0.000 description 2
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 2
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- ZWRUINPWMLAQRD-UHFFFAOYSA-N nonan-1-ol Chemical compound CCCCCCCCCO ZWRUINPWMLAQRD-UHFFFAOYSA-N 0.000 description 2
- DAWBXZHBYOYVLB-UHFFFAOYSA-J oxalate;zirconium(4+) Chemical compound [Zr+4].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O DAWBXZHBYOYVLB-UHFFFAOYSA-J 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N thiocyanic acid Chemical compound SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 2
- 150000003738 xylenes Chemical class 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- YCSZNOZQTDJANW-UHFFFAOYSA-N [Zr+4].[Hf+4] Chemical compound [Zr+4].[Hf+4] YCSZNOZQTDJANW-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000002619 bicyclic group Chemical group 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 230000008602 contraction Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 150000001924 cycloalkanes Chemical class 0.000 description 1
- LMGZGXSXHCMSAA-UHFFFAOYSA-N cyclodecane Chemical compound C1CCCCCCCCC1 LMGZGXSXHCMSAA-UHFFFAOYSA-N 0.000 description 1
- GPTJTTCOVDDHER-UHFFFAOYSA-N cyclononane Chemical compound C1CCCCCCCC1 GPTJTTCOVDDHER-UHFFFAOYSA-N 0.000 description 1
- WJTCGQSWYFHTAC-UHFFFAOYSA-N cyclooctane Chemical compound C1CCCCCCC1 WJTCGQSWYFHTAC-UHFFFAOYSA-N 0.000 description 1
- 239000004914 cyclooctane Substances 0.000 description 1
- 150000001940 cyclopentanes Chemical class 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 125000002704 decyl 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])* 0.000 description 1
- 238000011161 development Methods 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
- 238000004945 emulsification Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 238000001640 fractional crystallisation Methods 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- HNNUVNCHWLBGRE-UHFFFAOYSA-F hafnium(4+) zirconium(4+) tetrasulfate Chemical compound S(=O)(=O)([O-])[O-].[Hf+4].[Zr+4].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-].S(=O)(=O)([O-])[O-] HNNUVNCHWLBGRE-UHFFFAOYSA-F 0.000 description 1
- SGPNITZHSOZEGX-UHFFFAOYSA-J hafnium(4+);dicarbonate Chemical compound [Hf+4].[O-]C([O-])=O.[O-]C([O-])=O SGPNITZHSOZEGX-UHFFFAOYSA-J 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009854 hydrometallurgy Methods 0.000 description 1
- KUYLHALFMPOMKK-UHFFFAOYSA-N hydroxy-sulfanylidene-bis(2,4,4-trimethylpentyl)-$l^{5}-phosphane Chemical compound CC(C)(C)CC(C)CP(O)(=S)CC(C)CC(C)(C)C KUYLHALFMPOMKK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 238000000622 liquid--liquid extraction Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 125000001421 myristyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- SJZRQLFXKRQEOT-UHFFFAOYSA-N n-[bis(2-ethylhexoxy)phosphorylmethyl]-2-ethylhexan-1-amine Chemical compound CCCCC(CC)CNCP(=O)(OCC(CC)CCCC)OCC(CC)CCCC SJZRQLFXKRQEOT-UHFFFAOYSA-N 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- KPSSIOMAKSHJJG-UHFFFAOYSA-N neopentyl alcohol Chemical compound CC(C)(C)CO KPSSIOMAKSHJJG-UHFFFAOYSA-N 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 125000001400 nonyl 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])C([H])([H])[H] 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
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 125000000913 palmityl 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])C([H])([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
- 125000002958 pentadecyl 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])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
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000000956 solid--liquid extraction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 125000002889 tridecyl 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])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000002948 undecyl 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])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052845 zircon Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 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
- C22B34/00—Obtaining refractory metals
- C22B34/10—Obtaining titanium, zirconium or hafnium
- C22B34/14—Obtaining zirconium or hafnium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
- C22B3/384—Pentavalent phosphorus oxyacids, esters thereof
- C22B3/3844—Phosphonic acid, e.g. H2P(O)(OH)2
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/408—Mixtures using a mixture of phosphorus-based acid derivatives of different types
-
- 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
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Extraction Or Liquid Replacement (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The phosphine of neutrality containing amino extractant the present invention relates to below formula I is used for the purposes and method of extracting and separating zirconium and/or hafnium,Wherein, R1And R2It is each independently selected from C1‑12Alkyl；R3And R4It is each independently selected from C1‑3Alkyl and hydrogen；R5And R6It is each independently selected from C1‑16Alkyl and hydrogen, and R5And R6At most one is hydrogen.After the neutral phosphine extraction system formed using the phosphine extractant of neutrality containing amino of above-mentioned general formula I as main extractant mixes extraction with the feed liquid containing zirconium (IV) and/or hafnium (IV), again through extract, be stripped and etc. after, respectively obtain solution or precipitation containing zirconium or hafnium.The result shows that the purity of final gained zirconium, more than 99.99%, the content of hafnium is less than 80ppm in zirconium, especially less than 10ppm, the purity of gained hafnium is more than 99.0%, and the content of zirconium is less than 0.1% in hafnium, the effective Separation ＆ Purification for realizing zirconium hafnium reach the use standard of atomic energy level zirconium hafnium.
Description
Technical Field
The invention belongs to the technical field of hydrometallurgy of zirconium and hafnium, and particularly relates to application and a method of an amino neutral phosphine extraction agent for extracting and separating zirconium and/or hafnium.
Background
Nuclear power is a technically mature clean energy source and is widely concerned by researchers in various countries, while zirconium and hafnium are key materials for constructing nuclear reactors and are listed as key research objects for strategic development of the countries. Zirconium and hafnium have distinct nuclear properties and are therefore used in different aspects of nuclear reactors. Zirconium has a small thermal neutron absorption cross-section (0.18 + -0.02 b,1 b-10)-28m2Atomic), is widely used for reactor cladding and structural materials, while hafnium has a large thermal neutron capture cross-section, and is an important material for controlling thermonuclear reactions. Atomic level zirconium (also known as nuclear grade zirconium) used in reactors requires less than 0.01% hafnium therein, while atomic level hafnium (also known as nuclear grade hafnium) requires less than 2% zirconium therein. Due to lanthanide contraction, the atomic radius and ionic radius of zirconium and hafnium are similar, and the physicochemical properties are also similar, making separation difficult. Therefore, zirconium hafnium separation is a key technology for preparing nuclear grade zirconium hafnium.
However, in nature, zirconium and hafnium are always associated, with no zirconium or hafnium present alone, and the hafnium content of zirconium is generally about 1% to 3%.In order to effectively separate zirconium and hafnium, different methods have been proposed by domestic and foreign scientists, mainly wet separation techniques including solvent extraction, fractional crystallization, and adsorptive separation. Among them, the solvent extraction method has advantages of large production capacity, simple equipment, convenient automation, low cost, etc., and thus is widely used in the production of nuclear grade zirconium hafnium. The current relatively mature solvent extraction separation systems for nuclear grade zirconium hafnium production are: methyl isobutyl ketone (MIBK) -hydrogen thiocyanate (HSCN) system, tributyl phosphate (TBP) -HCl-HNO3And (4) preparing the system. CN101643847A discloses tributyl phosphate extraction resin for zirconium hafnium separation and a preparation method thereof, which solve the problems of high system acidity, severe equipment corrosion, serious emulsification of tributyl phosphate and the like in liquid-liquid extraction separation of zirconium hafnium, but also face the problems that separation by a resin method cannot be continuously carried out, the separation treatment capacity is small and the like. CN1927725A discloses a process for preparing atomic-level zirconium oxide and hafnium oxide by a methyl isobutyl ketone double-solvent extraction method, but the method has the problems of serious MIBK and HSCN pollution and the like.
Therefore, the research on the efficient and green solvent extraction method is still a hot spot in the field of zirconium hafnium separation.
Disclosure of Invention
In order to solve the problems, the invention adopts a novel amino-containing neutral phosphine extraction agent to extract and separate zirconium and hafnium, unexpectedly obtains good extraction and separation effects, and the used extraction agent has stable properties and is easy to synthesize.
The present invention mainly relates to the following.
1. Use of an amino-containing neutral phosphine extractant of the general formula I below for the extractive separation of zirconium (IV) and/or hafnium (IV):
wherein,
R1and R2Each independently selected from C1-12An alkyl group;
R3and R4Each independently selected from C1-3Alkyl and hydrogen;
R5and R6Each independently selected from C1-16Alkyl and hydrogen, and R5And R6At most one is hydrogen.
2. Use according to item 1, wherein the amino-containing neutral phosphine extractant of the general formula I is used for separating zirconium (IV) from hafnium (IV) by extraction, wherein, in the general formula I, R3And R4Each independently selected from methyl, ethyl and hydrogen, and R3And R4At most one is ethyl, the amino-containing neutral phosphine extractant is preferentially complexed with zirconium.
3. Use according to item 1, wherein the amino-containing neutral phosphine extractant of the general formula I is used for separating zirconium (IV) from hafnium (IV) by extraction, wherein, in the general formula I, R3And R4Each independently selected from ethyl and propyl, said amino-containing neutral phosphine extractant being preferentially complexed with hafnium.
4. A method for extracting and separating zirconium and/or hafnium, which comprises the step of extracting zirconium (IV) and/or hafnium (IV) from a zirconium (IV) and/or hafnium (IV) -containing feed liquid by using an amino-containing neutral phosphine extractant of the general formula I described in the item 1.
5. The method of clause 4, wherein the method is performed using a solvent extraction process,
the method comprises the following steps: mixing a neutral phosphine extraction system containing an amino-containing neutral phosphine extraction agent with feed liquid containing zirconium (IV) and/or hafnium (IV) to extract to obtain zirconium-containing and/or hafnium-containing extract and raffinate.
6. The method of item 5, the method comprising: mixing a neutral phosphine extraction system containing an amino-containing neutral phosphine extraction agent with a feed liquid containing zirconium (IV) and hafnium (IV)Extracting to obtain zirconium-containing extract and hafnium-containing raffinate, wherein in the general formula I, R3And R4Each independently selected from methyl, ethyl and hydrogen, and R3And R4At most one is ethyl.
7. The method according to item 6, further comprising the step of extracting hafnium from the hafnium-containing raffinate separately as the hafnium-containing feed liquid, preferably by the method of extracting and separating hafnium as described in item 4 or 5, to obtain a hafnium-containing extract, more preferably by the neutral phosphine extraction system as described in item 6.
8. The method of item 5, the method comprising: mixing a neutral phosphine extraction system containing an amino neutral phosphine extraction agent with a feed liquid containing zirconium (IV) and hafnium (IV) to extract, thereby obtaining a hafnium-containing extract and a zirconium-containing raffinate, wherein in the formula I, R is3And R4Each independently selected from ethyl and propyl.
9. The method according to item 8, further comprising the step of extracting zirconium from the zirconium-containing feed solution by using zirconium-containing raffinate, preferably by using the method for separating zirconium by extraction as described in item 4 or 5, to obtain a zirconium-containing extract, and more preferably by using the neutral phosphine extraction system as described in item 8.
10. The method of any of clauses 5-9, further comprising:
optionally washing the zirconium-and/or hafnium-containing extract with a washing liquid;
and (3) stripping the zirconium and/or the hafnium in the zirconium-and/or hafnium-containing extract by using a stripping agent to obtain a stripping product containing the zirconium and/or the hafnium.
11. The method of item 10, further comprising: and (3) carrying out treatment selected from precipitation, filtration, calcination, acid dissolution and drying on the back extraction product containing zirconium or hafnium to obtain a zirconium or hafnium product.
12. The method of item 10, further comprising: separating zirconium and hafnium by the method according to item 6 or 8 using, as a feed liquid, a zirconium-and hafnium-containing solution obtained by subjecting a back-extraction product containing zirconium and hafnium or a back-extraction product containing zirconium and hafnium to a treatment selected from calcination and acid dissolution.
13. A method of separating zirconium (IV) from hafnium (IV), the method comprising:
mixing a neutral phosphine extraction system containing an amino neutral phosphine extraction agent with a feed liquid containing zirconium (IV) and hafnium (IV) to extract to obtain a zirconium-containing extract liquid and a hafnium-containing raffinate liquid, wherein in the formula I, R is3And R4Each independently selected from methyl, ethyl and hydrogen, and R3And R4At most one is ethyl;
optionally washing the zirconium-containing extract with a washing solution;
and (4) back-extracting the zirconium in the zirconium-containing extract liquor by using a back-extracting agent to obtain a zirconium-containing back-extracted product.
14. The method of item 13, further comprising:
mixing a neutral phosphine extraction system containing an amino-containing neutral phosphine extractant of the general formula I with a hafnium-containing raffinate to extract to obtain a hafnium-containing extract and a raffinate;
optionally washing the hafnium-containing extract with a washing solution;
and (3) back extracting hafnium in the hafnium-containing extract by using a back extractant to obtain a hafnium-containing back extraction product.
15. A method of separating zirconium (IV) from hafnium (IV), the method comprising:
mixing a neutral phosphine extraction system containing an amino neutral phosphine extraction agent with a feed liquid containing zirconium (IV) and hafnium (IV) to extract, thereby obtaining a hafnium-containing extract and a zirconium-containing raffinate, wherein in the formula I, R is3And R4Each independently selected from ethyl and propyl;
optionally washing the hafnium-containing extract with a washing solution;
and (3) back extracting hafnium in the hafnium-containing extract by using a back extractant to obtain a hafnium-containing back extraction product.
16. The method of item 15, further comprising:
mixing a neutral phosphine extraction system containing an amino-containing neutral phosphine extractant of the general formula I with a zirconium-containing raffinate to extract a hafnium-containing extract and a raffinate;
optionally washing the zirconium-containing extract with a washing solution;
and (4) back-extracting the zirconium in the zirconium-containing extract liquor by using a back-extracting agent to obtain a zirconium-containing back-extracted product.
17. A method for the extractive separation of zirconium and hafnium, the method comprising: mixing a neutral phosphine extraction system containing an amino-containing neutral phosphine extraction agent with a feed liquid containing zirconium (IV) and hafnium (IV) to extract to obtain zirconium-hafnium-containing extract liquid and raffinate;
optionally washing the zirconium-containing hafnium extract with a washing solution;
back extracting zirconium and hafnium in the zirconium and hafnium-containing extract liquor by using a back extractant to obtain a zirconium and hafnium-containing back extraction product;
preparing a zirconium-hafnium-containing solution from the zirconium-hafnium-containing back extraction product;
treating the hafnium-zirconium-containing solution by the method of item 13 to obtain a zirconium-containing back-extract product and a hafnium-containing raffinate; or treating the hafnium-zirconium containing solution by the method of item 15 to obtain a hafnium-containing strip product and a zirconium-containing raffinate.
The present invention is described in more detail below.
The invention relates to the use of an amino-containing neutral phosphine extractant of the general formula I:
wherein,
R1and R2Each independently selected from C1-12Alkyl, preferably C4-10Alkyl, more preferably C5-9Alkyl, most preferably C6-8An alkyl group;
R3and R4Each independently selected from C1-3Alkyl and hydrogen;
R5and R6Each independently selected from C1-16Alkyl and hydrogen, and R5And R6At most one is hydrogen.
In the general formula I, R1And R2The total number of carbon atoms of (a) is an integer between 8 and 20, preferably an integer between 10 and 18. Furthermore, R1And R2Preferably the same alkyl group, more preferably the same C5-9An alkyl group.
Preferably, R3And R4The total number of carbon atoms of (a) is an integer between 0 and 6.
Preferably, R5Is selected from C1-10Alkyl and hydrogen, preferably C1-8Alkyl and hydrogen, R6Is selected from C1-14Alkyl, preferably C1-12An alkyl group; preferably, R5And R6The total number of carbon atoms of (a) is an integer between 1 and 16, preferably an integer between 2 and 13.
Preferably, in the amino-containing neutral phosphine extraction agent of the general formula I of the invention, R1、R2、R3、R4、R5And R6The total number of carbon atoms of (a) is 10 to 46, including but not limited to 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45 and 46 carbon atoms, preferably 13 to 36, more preferably 15 to 34.
Preferably, the amino-containing neutral phosphine extractant of the general formula I is selected from the group consisting of bis (2-ethylhexyl) 1- (2-ethylhexylamino) methylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) ethylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) N-propylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) -1-methylethylphosphonate, bis (2-ethylhexyl) 1- (N, N-dibutylamino) ethylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) -1-ethyl-N-propylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) -1-N-propyl-propylphosphonate, 1- (2-ethylhexyl amino) -1-N-propyl-N-butyl phosphonic acid di (2-ethylhexyl) ester, 1- (N, N-dibutylamino) -1-ethyl-N-propyl phosphonic acid di (2-ethylhexyl) ester, 1- (dodecylamino) -1-ethyl-N-propyl phosphonic acid diethyl ester. The amino-containing neutral phosphine extractant of the general formula I in the invention can be a commercial product, and can also be prepared by referring to the method disclosed in CN201610227923. X.
In another aspect, the invention relates to a method for extracting and separating zirconium and/or hafnium, which comprises the step of extracting zirconium (IV) and/or hafnium (IV) from a zirconium (IV) and/or hafnium (IV) containing feed liquid by using an amino-containing neutral phosphine extracting agent with the general formula I. The method can adopt a solvent extraction method or a solid-liquid extraction method.
Furthermore, the inventors have surprisingly found that R in the amino-containing neutral phosphine extractant of the general formula I3And R4The chain length of (b) has a greater influence on the extraction of zirconium (IV) and hafnium (IV). Specifically, when R is3And R4Each independently selected from methyl, ethyl and hydrogen, and R3And R4When at most one is ethyl, the neutral phosphine extraction system prepared using the amino-containing neutral phosphine extractant of formula I is mixed with a feed solution containing zirconium (IV) and hafnium (IV), and it is found that the neutral extractant preferentially complexes with zirconium (IV) to form a zirconium extraction complex, while hafnium (IV) remains in the raffinate, thereby allowing efficient separation of zirconium from hafnium to obtain high purity zirconium. When R is3And R4When the neutral phosphine extraction system prepared by using the amino-containing neutral phosphine extractant of the general formula I is mixed with a feed solution containing zirconium (IV) and hafnium (IV) when each is independently selected from ethyl and propyl, it is found that the neutral extractant preferentially complexes with hafnium (IV) to form a hafnium extraction complex, while zirconium remains in the raffinateIn the liquid, zirconium and hafnium can be efficiently separated from each other, and high-purity hafnium can be obtained. Hafnium or zirconium in the raffinate can be extracted by further extraction.
The invention therefore also relates to the use or method of an amino-containing neutral phosphine extractant of the general formula I for the extractive separation of zirconium, wherein, in the general formula I, R3And R4Each independently selected from methyl, ethyl and hydrogen, and R3And R4At most one is ethyl and the other substituents are as defined. In this case, the amino-containing neutral phosphine extractant of the general formula I is preferably one or more selected from the group consisting of bis (2-ethylhexyl) 1- (2-ethylhexylamino) methylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) ethylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) N-propylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) 1-methylethylphosphonate, and bis (2-ethylhexyl) 1- (N, N-dibutylamino) ethylphosphonate.
The invention also relates to the use or method of the amino-containing neutral phosphine extraction agent of the general formula I for the extractive separation of hafnium, wherein in the general formula I, R3And R4Each independently selected from ethyl and propyl, with other substituents being as defined, and said amino-containing neutral phosphine extractant. In this case, the amino-containing neutral phosphine extractant of the general formula I is preferably one or more selected from the group consisting of bis (2-ethylhexyl) 1- (2-ethylhexylamino) -1-ethyl-N-propylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) -1-propyl-N-propylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) -1-N-propyl-N-butylphosphonate, bis (2-ethylhexyl) 1- (N, N-dibutylamino) -1-ethyl-N-propylphosphonate, and diethyl 1- (dodecylamino) -1-ethyl-N-propylphosphonate.
The invention also relates to the use or method of an amino-containing neutral phosphine extractant of the general formula I for separating zirconium (IV) from hafnium (IV) by extraction, wherein,
in the general formula I, R3And R4Each independently selected from methyl, ethyl and hydrogen, and R3And R4Up to one being ethyl, other substitutionThe definitions of the radicals are unchanged, and in this case, the zirconium-containing extract and the hafnium-containing raffinate can be obtained by mixing a neutral phosphine extraction system containing an amino-containing neutral phosphine extractant of the general formula I, preferably one or more selected from the group consisting of bis (2-ethylhexyl) 1- (2-ethylhexylamino) methylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) ethylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) N-propylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) 1-methylethylphosphonate, bis (2-ethylhexyl) 1- (N, N-dibutylamino) ethylphosphonate, and zirconium (IV) -and hafnium (IV) -containing feed liquid for extraction, or
In the general formula I, R3And R4Independently selected from ethyl and propyl, and the other substituents are not changed, wherein the hafnium-containing extract and the zirconium-containing raffinate can be obtained by mixing a neutral phosphine extraction system containing an amino neutral phosphine extractant of formula I, preferably selected from bis (2-ethylhexyl) 1- (2-ethylhexyl-amino) -1-ethyl-N-propylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexyl-amino) -1-propyl-N-propylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexyl-amino) -1-N-propyl-N-butylphosphonate, bis (2-ethylhexyl) 1- (N, N-dibutylamino) -1-ethyl-N-propylphosphonate, and, One or more of 1- (dodecylamino) -1-ethyl-n-propylphosphonic acid diethyl ester.
In one embodiment, the method for the extractive separation of zirconium and/or hafnium according to the invention may be carried out using a solvent extraction method, comprising: the neutral phosphine extraction system (hereinafter sometimes referred to as organic phase) containing the amino neutral phosphine extractant of the general formula I is mixed with feed liquid containing zirconium (IV) and/or hafnium (IV) to extract to obtain zirconium-containing and/or hafnium-containing extract liquid and raffinate. That is, the neutral phosphine extraction system formed by using the amino-containing neutral phosphine extraction agent of the general formula I as the main extraction agent is mixed with the feed liquid containing zirconium (IV) and/or hafnium (IV) for extraction, and then zirconium-containing extract, hafnium-containing extract or zirconium-hafnium-containing extract can be obtained.
In one embodiment, the method for separating zirconium by extraction of the present invention may be performed by a solvent extraction method, the method comprising: mixing a neutral phosphine extraction system containing an amino-containing neutral phosphine extraction agent with a feed liquid containing zirconium (IV) to extract to obtain zirconium-containing extract and raffinate.
In one embodiment, the method for the extractive separation of hafnium according to the present invention may be performed by a solvent extraction method, comprising: mixing a neutral phosphine extraction system containing an amino neutral phosphine extraction agent with a feed liquid containing hafnium (IV) to extract, thereby obtaining a hafnium-containing extract and a raffinate.
In one embodiment, the method for the extractive separation of zirconium and hafnium of the present invention may be performed using a solvent extraction method, the method comprising: mixing a neutral phosphine extraction system containing an amino-containing neutral phosphine extraction agent with feed liquid containing zirconium (IV) and hafnium (IV) to extract to obtain zirconium-hafnium-containing extract and raffinate.
In one embodiment, the method of separating zirconium (IV) from hafnium (IV) by extraction of the present invention may be performed using a solvent extraction method comprising:
mixing a neutral phosphine extraction system containing an amino neutral phosphine extraction agent with a feed liquid containing zirconium (IV) and hafnium (IV) to extract to obtain a zirconium-containing extract liquid and a hafnium-containing raffinate liquid, wherein in the formula I, R is3And R4Each independently selected from methyl, ethyl and hydrogen, and R3And R4Up to one being ethyl, the other substituents being defined unchanged, said amino-containing neutral phosphine extractant of formula I preferably being one or more selected from the group consisting of bis (2-ethylhexyl) 1- (2-ethylhexylamino) methylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) ethylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) N-propylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) 1-methylethylphosphonate, bis (2-ethylhexyl) 1- (N, N-dibutylamino) ethylphosphonate; or
Bag for packingMixing a neutral phosphine extraction system containing an amino neutral phosphine extractant of the general formula I with feed liquid containing zirconium (IV) and hafnium (IV) to extract to obtain hafnium-containing extract liquid and zirconium-containing raffinate liquid, wherein in the general formula I, R is3And R4Each independently selected from ethyl and propyl, the other substituents being as defined, said amino-containing neutral phosphine extractant of formula I preferably being one or more selected from the group consisting of di (2-ethylhexyl) 1- (2-ethylhexylamino) -1-ethyl-N-propylphosphonate, di (2-ethylhexyl) 1- (2-ethylhexylamino) -1-propyl-N-propylphosphonate, di (2-ethylhexyl) 1- (2-ethylhexylamino) -1-N-propyl-N-butylphosphonate, di (2-ethylhexyl) 1- (N, N-dibutylamino) -1-ethyl-N-propylphosphonate, diethyl 1- (dodecylamino) -1-ethyl-N-propylphosphonate.
The neutral phosphine extraction system comprises an amino-containing neutral phosphine extractant of the general formula I, an optional auxiliary extractant, an optional phase modifier and a diluent. Preferably, the neutral phosphine extraction system consists of the above ingredients.
The auxiliary extractant mainly plays a role in assisting extraction and can enhance the extraction performance of the amino-containing neutral phosphine extractant on zirconium and/or hafnium. The auxiliary extractant may be selected from phosphorus (phosphine) extractants of the following general formula II:
wherein,
z is O or S;
R7selected from hydrogen, C1-12Alkyl radical, C1-12Alkoxy, -SH and with a radical selected from C1-12-NH substituted by at least one substituent in the alkyl radical2Etc., preferably selected from hydrogen, C1-10Alkyl radical, C1-10Alkoxy, -SH and with a radical selected from C4-10-NH substituted by at least one substituent in the alkyl radical2Etc.; more preferably selected from C1-10Alkyl and C1-10An alkoxy group;
R8and R9Each independently selected from C4-12Alkyl radical, C4-12Alkoxy and with a radical selected from C4-12-NH substituted by at least one substituent in the alkyl radical2Etc., preferably selected from C4-10Alkyl radical, C4-10Alkoxy and with a radical selected from C4-10-NH substituted by at least one substituent in the alkyl radical2Etc., more preferably selected from C4-10Alkyl and C4-10An alkoxy group.
Suitable auxiliary extractants may be selected from: neutral phosphorus (phosphine) extractants such as linear trialkylphosphine oxide (Cyanex 923), branched trialkylphosphine oxide (Cyanex 925), trioctylphosphine oxide (TOPO), dimethylheptyl methylphosphonate (P350), di (-2-ethylhexyl) 2-ethylhexyl phosphonate, tributyl phosphate (TBP); acidic phosphorus (phosphine) extractants such as bis (2,4, 4-trimethylpentyl) dithiophosphinic acid (Cyanex 301), bis (2,4, 4-trimethylpentyl) thiophosphonic acid (Cyanex 302), bis (2-ethylhexyl) phosphoric acid (P204), mono-2-ethylhexyl 2-ethylhexylphosphonate (P507), bis (2,4, 4-trimethylpentyl) phosphonic acid (Cyanex 272), bis (2-ethylhexyl) phosphonic acid (P227 or P229); neutral phosphoramide extractants such as triisooctylphosphoramide, diisooctyl-isooctyloxyphosphoramide, isooctyl-diisooctyloxyphosphoramidate, tri (diisobutyl) phosphoramide, di (diisobutyl) -isooctyloxyphosphoramide, tridecylphosphamide, and dihexyl-decyloxyphosphamide and the like as disclosed in CN201410409451.0 and CN 201410040023.5; and the mixed extractant mixed with the extractant in any proportion.
The phase modifier, which mainly acts to modify the physical phenomena of extraction, may be selected from C4-10One or more of alkanol, preferably one or more selected from n-octanol, isooctanol, 2-methylheptanol, mixed alcohol of the three alcohols in any proportion, and tributyl phosphate; more preferably mixed alcohols or 2-methylheptanol.
The diluent is selected from: c5-16Alkanes, e.g. pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecaneEtc.; aviation kerosene; sulfonated kerosene, liquid paraffin, for example, light lubricating oil fraction at 250 to 400 ℃ and the like; c5-16Alicyclic alkanes, e.g. cyclopentane, C1-4Alkyl-substituted cyclopentanes, cyclohexanes, C1-4Alkyl-substituted cyclohexane, decahydronaphthalene, and the like; c6-10Aromatic hydrocarbons such as benzene, toluene, xylenes (including ortho-, meta-, para-xylene and mixed xylenes), and the like. Preferably, the diluent is one or more selected from the group consisting of jet fuel, sulfonated kerosene, heptane and xylene.
In the amino group-containing neutral phosphine extraction system, the volume ratio of the amino group-containing neutral phosphine extraction agent, the optional auxiliary extraction agent, the optional phase modifier and the diluent can be as follows: neutral phosphine extraction agent: auxiliary extracting agent: phase modifier: about 1 to 60% of a diluent: about 0 to 40: about 0 to 20: about 40-99, more preferably an amino-containing neutral phosphine extractant: auxiliary extracting agent: phase modifier: about 10-40% of diluent: about 0 to 20: about 0 to 20: about 50 to about 90; also preferred are amino-containing neutral phosphine extractants: auxiliary extracting agent: phase modifier: about 15 to 35% of a diluent: about 0 to 15: about 0 to 15: about 55 to about 85.
The feed liquid containing zirconium (IV) and/or hafnium (IV) comprises zirconium (IV) and/or hafnium (IV) and mineral acid, and can also comprise other elements. The concentration of zirconium (IV) or hafnium (IV) in the feed solution may be about 0.001 to 2 mol/L. When hafnium zirconium is present in the feed solution, the concentration of hafnium (IV) is generally less than the concentration of zirconium (IV), and may be 1/3 to 1/100 of the concentration of zirconium (IV). When the concentration of zirconium or hafnium in the feed liquid is too high, zirconium or hafnium is likely to be crystallized and precipitated, and the solution viscosity is high, which may affect the extraction.
The acidity of the feed liquid is about 0.1 to 10mol/L, preferably about 0.5 to 4mol/L, in terms of the molar concentration of hydrogen ions, of nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid, or a mixed solution of these acids in any proportion. In addition, the acidity of the feed liquid is too low or too high, which may reduce the extraction performance of the neutral phosphine extraction system on zirconium and hafnium.
There is no limitation on the raw materials for preparing the feed liquid as long as zirconium and/or hafnium are contained therein. Suitable materials for preparing the feed solution include various zirconium and/or hafnium-containing materials, such as zircon, hafnozostrite, anisolite, baddeleyite, and the like. The raw material can be pretreated by physical and chemical methods, and dissolved by sulfuric acid, hydrochloric acid, nitric acid, hydrofluoric acid or the mixed acid of the above acids to prepare the feed liquid suitable for the method of the invention.
In practical application, the feed liquid may also contain trivalent rare earth, alkali metal, alkaline earth metal, transition metal, non-metal elements and other elements. In this case, the method of the invention can be used for preferentially extracting zirconium and/or hafnium with high selectivity, and separating zirconium and hafnium from other elements.
In the extraction step, the number of extraction stages may be 1 to 50, for example, 3 to 40, preferably 5 to 20. Excessive extraction stages increase the amount of separation equipment and extractant used, thereby increasing the cost.
Preferably, the flow ratio of the neutral phosphine extraction system to the feed liquid can be about 0.05-20: 1, for example, about 0.1 to 20: 1, preferably about 0.2 to 10: 1. the flow ratio is changed mainly according to the concentration of zirconium and/or hafnium in the feed liquid, and when the concentration of zirconium and/or hafnium in the feed liquid is high, the flow of the neutral phosphine extraction system is properly increased to ensure that zirconium and/or hafnium can be sufficiently extracted into the organic phase.
In the process for separating zirconium (IV) from hafnium (IV) by extraction according to the invention, a zirconium-containing extract and a hafnium-containing raffinate, or a hafnium-containing extract and a zirconium-containing raffinate, are obtained. The hafnium-containing raffinate or the zirconium-containing raffinate can be further used as a hafnium-containing feed liquid or a zirconium-containing feed liquid to extract hafnium or zirconium therein, respectively, to obtain a hafnium-containing extract or a zirconium-containing extract, respectively. In this case, the method for separating hafnium (IV) or zirconium by extraction according to the present invention is preferably used, and more preferably, the same neutral phosphine extraction system as used in the method for separating zirconium (IV) from hafnium (IV) by extraction is used, so that the process can be simplified and the cost can be reduced.
Other valuable elements, such as rare earth elements, in the raffinate obtained after extraction of zirconium and/or hafnium can be separated and extracted by methods known in the art.
After obtaining the zirconium-and/or hafnium-containing extract, the zirconium-and/or hafnium-containing extract may be subjected to a subsequent treatment as follows.
The solvent extraction process according to the invention also comprises the step of optionally washing the zirconium-and/or hafnium-containing extract with a washing liquid (which may also be referred to as washing liquid, washing acid, washing agent). The washing process may further reduce the content of impurity elements in the zirconium-and/or hafnium-containing extract, thereby contributing to an increase in the purity of the final product.
The washing solution can be nitric acid, sulfuric acid, hydrochloric acid or a mixed solution of the above acids in any proportion. The acidity of the washing liquid is about 0.2 to 4mol/L in terms of the molar concentration of hydrogen ions.
The number of washing stages may be 0 to 20, preferably 0 to 10. Too long washing stages can affect the yield of zirconium and/or hafnium and waste energy and extractant.
The wash flow ratio may be the zirconium and/or hafnium containing extract: about 1: 0.1 to 5, preferably about 1: 0.2 to 2. Increasing the flow rate of the washing liquid, on the one hand, increases the product purity of zirconium and/or hafnium, but, on the other hand, also decreases the yield of the target element, and also consumes more washing acid and the amount of alkali needed to neutralize these washing acids, increasing the production costs.
The process according to the invention further comprises the step of stripping the zirconium and/or hafnium in the zirconium-and/or hafnium-containing extract with a stripping agent (which may also be referred to as a "stripping solution", a "stripping solution") to obtain a zirconium-and/or hafnium-containing strip product. The organic phase after the back extraction can be recycled and used for extracting and separating zirconium and/or hafnium from the zirconium and/or hafnium-containing feed liquid again.
The stripping solution is alkali solution such as ammonia water, sodium hydroxide, and sodium carbonate; oxalate solutions such as potassium oxalate, sodium oxalate, and the like. The concentration of hydroxide radical in the alkali solution is 0.001-6 mol/L; preferably 0.1-2 mol/L; the concentration of oxalate in the oxalate solution is from 0.01mol/L to saturated solution.
Preferably, in the solvent extraction method, the number of back extraction stages is 1-10, preferably 2-6; the flow ratio is the extraction liquid containing zirconium and/or hafnium: and (3) stripping solution is 1: 0.1 to 5, preferably 1: 0.2 to 2.
The resulting zirconium or hafnium-containing strip product may be further treated with a treatment selected from precipitation, filtration, calcination, acid dissolution, drying, etc., to obtain a zirconium or hafnium product.
The resultant zirconium-and hafnium-containing strip product is subjected to a treatment, for example, a treatment selected from precipitation, filtration, calcination, acid dissolution, etc., to prepare a zirconium-and hafnium-containing solution. The hafnium-zirconium-containing solution may be subjected to a method according to the invention for separating zirconium (IV) from hafnium (IV) by extraction to separate zirconium and hafnium to obtain a zirconium-containing strip product and a hafnium-containing raffinate; or a hafnium-containing strip product and a zirconium-containing raffinate. The zirconium-containing strip product and the hafnium-containing raffinate or the hafnium-containing strip product and the zirconium-containing raffinate can be further treated by a treatment selected from precipitation, filtration, calcination, acid dissolution, drying, etc., to obtain a zirconium or hafnium product.
In the solvent extraction process according to the present invention, the extraction, washing and back-extraction may be carried out using a separatory apparatus well known in the art, preferably in a series of separatory funnels, mixed-clarification extraction tanks, more preferably in a mixed-clarification extraction tank.
In the solvent extraction method according to the present invention, the above-mentioned extraction, washing and back-extraction may be carried out intermittently or continuously, preferably continuously.
The result shows that the purity of the obtained zirconium is more than 99.99 percent, the content of the hafnium in the zirconium is less than 80ppm, particularly less than 10ppm, the purity of the obtained hafnium is more than 99.0 percent, and the content of the zirconium in the hafnium is less than 0.1 percent through extraction separation, thereby effectively realizing the separation and purification of the hafnium and reaching the use standard of atomic level hafnium.
Term(s) for
Some of the terms used in the present invention are defined as follows.
"zirconium and/or hafnium" means "zirconium", "hafnium" or "zirconium and hafnium". For example, separating zirconium and/or hafnium means separating zirconium, separating hafnium or separating zirconium and hafnium, and the zirconium-and/or hafnium-containing extract means "zirconium-containing extract", "hafnium-containing extract" or "zirconium-and hafnium-containing extract".
C1-16Alkyl refers to a straight or branched chain alkyl group containing 1 to 16 carbon atoms, such as a straight or branched chain alkyl group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, or 16 carbon atoms, including, without limitation, methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, isobutyl, n-pentyl, neopentyl, isopentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, and the like. C1-5Alkyl radical, C1-10Alkyl radical, C4-12Alkyl radical, C4-10Alkyl radical, C5-9Alkyl and C6-8The meaning of alkyl is analogized.
C1-12Alkoxy means a straight or branched chain alkoxy group containing 1 to 12 carbon atoms, such as a straight or branched chain alkoxy group having 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11 or 12 carbon atoms, including, but not limited to, methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, t-butoxy, isobutoxy, n-pentoxy, neopentoxy, isopentoxy, hexoxy, heptoxy, octoxy, nonoxy, decyloxy, undecyloxy, dodecyloxy, and the like. C1-10Alkoxy and C4-10Alkoxy and the like are analogized in their meaning.
C4-10By alkanol is meant a straight or branched chain alkanol containing from 4 to 10 carbon atoms, such as straight or branched chain alkanols having 4, 5, 6, 7, 8, 9 or 10 carbon atoms, including without limitation n-butanol, t-butanol, isobutanol, n-pentanol, neopentanol, isopentanol, hexanol, heptanol, octanol, nonanol, decanol, and the like.
C5-16Alkane refers to a straight or branched alkane containing 5 to 16 carbon atoms, having 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15 or 16 carbon atoms, such as pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane, and the like.
C5-16Alicyclic alkane refers to saturated cyclic alkane containing 5 to 16 carbon atoms including the number of carbon atoms of the substituent which may be selected from C, which may be monocyclic or bicyclic, such as cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, decahydronaphthalene, etc1-C4One or more substituents of an alkyl group.
C6-10The aromatic hydrocarbon means an aromatic hydrocarbon containing 6 to 10 carbon atoms inclusive of the number of carbon atoms of the substituent, such as benzene and C1-4Benzene substituted with one or more substituents of alkyl, such as benzene, toluene, xylene, and the like.
Unless otherwise indicated, all numerical ranges recited herein include the endpoints thereof, and all values between the endpoints that are incremented or decremented by the minimum unit of the endpoint, and all subranges subsumed therein.
Advantageous effects
The amino-containing neutral phosphine extracting agent adopted by the invention can be used for extracting and separating zirconium and hafnium in different acid media (sulfuric acid, nitric acid and hydrochloric acid), and the synthesis method is simple, chemical raw materials used for synthesis are simple and easy to obtain, and the cost is low, so that the extraction and separation cost of zirconium and hafnium can be effectively reduced, and the amino-containing neutral phosphine extracting agent has high industrial application value.
Detailed Description
To further illustrate aspects of the present invention, specific examples of the present invention are provided to assist those skilled in the art in understanding and practicing the present invention, but the present invention is not limited to these examples.
Examples
Reagents and sources
The amino-containing neutral phosphine extractants used were prepared with reference to the procedure disclosed in cn201610227923.x, the names, structures and characterization data of which are given in the following table:
jet fuel and TBP were purchased from Shanghai Leiyeshi chemical Co.
Cyanex923 is available from Shanghai Cyanide speciality chemical Co.
The feed liquid, the washing liquid and the back extractant are self-made in a laboratory.
Other reagents (such as acids) were all commercially available analytical reagents.
The purity of the product was determined by means of ICP-OES (instrument model: Optical-8000, manufacturer: Perkin Elmer).
1H NMR measurements were performed on a Varian Mercury 400 or 600 NMR spectrometer.
Example 1:
preparation of organic phase: 3L of 1- (2-ethylhexyl amino) methyl phosphonic acid di (2-ethylhexyl) ester and 7L of aviation kerosene are mixed to prepare an organic phase.
The feed liquid is a mixed solution of zirconium sulfate, wherein the concentration of zirconium is 0.2 mol/L; the acidity is 1.5mol/L,
the washing solution is a 0.5mol/L sulfuric acid solution.
The stripping agent is 1.0mol/L ammonia solution.
The extraction separation experiment was performed using a 250ml mixing-clarifying extraction tank. Firstly, 20-stage countercurrent extraction is carried out, the flow ratio of an organic phase to a feed liquid is 10 mL/min: 15mL/min to obtain zirconium-containing extract. Then 5-stage countercurrent washing is carried out, the flow ratio of the zirconium-containing extract liquid to the washing liquid is 10 mL/min: 5 mL/min. Then, 5-stage countercurrent back extraction is carried out, wherein the flow ratio of the zirconium-containing extract to the back extractant is 10 mL/min: 13mL/min to obtain zirconium hydroxide precipitate. Wherein, the yield of the zirconium is 98.4 percent, and the purity of the zirconium is 99.993 percent.
Example 2:
preparation of organic phase: 3L of 1- (2-ethylhexyl amino) ethyl phosphonic acid di (2-ethylhexyl) ester, 1L of 2-methyl heptanol and 6L of aviation kerosene are mixed to prepare an organic phase.
The feed liquid is a mixed solution of zirconium sulfate and hafnium sulfate, wherein the concentration of zirconium is 0.2 mol/L; the concentration of hafnium is 0.004 mol/L; the acidity is 1.5mol/L,
the washing solution was 1.0mol/L hydrochloric acid solution.
The stripping agent is 1.0mol/L sodium hydroxide solution.
The extraction separation experiment was performed using a 250ml mixing-clarifying extraction tank. Firstly, 20-stage countercurrent extraction is carried out, the flow ratio of an organic phase to a feed liquid is 10 mL/min: 15mL/min to obtain zirconium-containing extract and hafnium-containing tail liquid. Then carrying out 7-stage countercurrent washing, wherein the flow ratio of the zirconium-containing extract liquid to the washing liquid is 10 mL/min: 5 mL/min. Then, 5-stage countercurrent back extraction is carried out, wherein the flow ratio of the zirconium-containing extract to the back extractant is 10 mL/min: 13mL/min to obtain zirconium hydroxide precipitate. Wherein the yield of zirconium was 96.6%, the purity of zirconium was 99.991%, and the hafnium content in zirconium was 80 ppm.
Example 3:
preparation of organic phase: 3L of 1- (2-ethylhexyl amino) 1-methylethyl phosphonic acid di (2-ethylhexyl) ester is mixed with 7L of aviation kerosene to prepare an organic phase.
The feed liquid is a mixed solution of zirconium and hafnium nitrate, wherein the concentration of zirconium is 0.5 mol/L; the concentration of hafnium is 0.04 mol/L; the acidity is 1.5mol/L,
the washing solution is a 1.0mol/L nitric acid solution.
The stripping agent is 4.0mol/L nitric acid solution.
The extraction separation experiment was performed using a 250ml mixing-clarifying extraction tank. Firstly, 20-stage countercurrent extraction is carried out, the flow ratio of an organic phase to a feed liquid is 20 mL/min: 10mL/min to obtain zirconium-containing extract and hafnium-containing tail liquid. Then carrying out 7-stage countercurrent washing, wherein the flow ratio of the zirconium-containing extract liquid to the washing liquid is 20 mL/min: 10 mL/min. Then, 5-stage countercurrent back extraction is carried out, wherein the flow ratio of the zirconium-containing extract to the back extractant is 20 mL/min: 11mL/min to obtain a zirconium nitrate solution. Wherein the yield of zirconium is 97.8%, the purity of zirconium is 99.995%, and the content of hafnium in zirconium is 30 ppm.
Mixing the hafnium-containing tail liquid serving as a feed liquid with an organic phase, and performing 15-stage countercurrent extraction, wherein the flow ratio of the organic phase to the feed liquid is 6 mL/min: 18mL/min to obtain hafnium-containing extract liquid; then 10 stages of countercurrent washing are carried out, and the flow ratio of the hafnium-containing extract liquid to the washing liquid is 6 mL/min: 3 mL/min. Then, 5-stage countercurrent back extraction is carried out, and the flow ratio of the hafnium-containing extraction liquid to the back extractant is 6 mL/min: 6mL/min to obtain a hafnium carbonate precipitate. Wherein the yield of hafnium is 96.8%, the purity of hafnium is 99.5%, and the zirconium content in hafnium is 0.4%.
Example 4:
preparation of organic phase: 3L of 1- (2-ethylhexyl amino) propyl phosphonic acid di (2-ethylhexyl) ester, 0.5L of LTBP, 1L of isooctyl alcohol and 5.5L of n-heptane are mixed to prepare a 10L organic phase.
The feed liquid is a mixed solution of zirconium and hafnium nitrate, wherein the concentration of zirconium is 0.5 mol/L; the concentration of hafnium is 0.1 mol/L; the acidity is 1.0mol/L,
the washing solution is a nitric acid solution of 0.5 mol/L.
The stripping agent is 2.0mol/L ammonia solution.
The extraction separation experiment was performed using a 250ml mixing-clarifying extraction tank. Firstly, 50-grade countercurrent extraction is carried out, the flow ratio of an organic phase to a feed liquid is 15 mL/min: 7.5mL/min to obtain zirconium-containing extract and hafnium-containing tail liquid. Then 5-stage countercurrent washing is carried out, and the flow ratio of the zirconium-containing extract liquid to the washing liquid is 15 mL/min: 7.5 mL/min. Then 10-stage countercurrent back extraction is carried out, the flow ratio of the zirconium-containing extract to the back extractant is 15 mL/min: 8.5mL/min, and the zirconium hydroxide precipitate is obtained. Wherein the yield of zirconium is 98.8%, the purity of zirconium is 99.998%, and the content of hafnium in zirconium is 10 ppm.
Example 5:
preparation of organic phase: 3L of di (2-ethylhexyl) 1- (N, N-dibutylamino) ethylphosphonate, 1L of LCyanex923 and 6L of aviation kerosene are mixed to prepare a 10L organic phase.
The feed liquid is a mixed solution of zirconium and hafnium hydrochloride, wherein the concentration of zirconium is 0.5 mol/L; the concentration of hafnium is 0.1 mol/L; the acidity is 1.0mol/L,
the washing solution was 0.5mol/L hydrochloric acid solution.
The stripping agent is 2.0mol/L ammonia solution.
The extraction separation experiment was performed using a 250ml mixing-clarifying extraction tank. Firstly, 50-grade countercurrent extraction is carried out, the flow ratio of an organic phase to a feed liquid is 15 mL/min: 7.5mL/min to obtain zirconium-containing extract and hafnium-containing tail liquid. Then 5-stage countercurrent washing is carried out, and the flow ratio of the zirconium-containing extract liquid to the washing liquid is 15 mL/min: 7.5 mL/min. Then 10-stage countercurrent back extraction is carried out, the flow ratio of the zirconium-containing extract to the back extractant is 15 mL/min: 8.5mL/min, and the zirconium hydroxide precipitate is obtained. Wherein the yield of zirconium is 96.8%, the purity of zirconium is 99.994%, and the hafnium content in zirconium is 60 ppm.
Example 6:
preparation of organic phase: 3L dimethyl 1- (dodecylamino) methylphosphonate, 1LCyanex923 and 6L aviation kerosene were mixed to prepare a 10L organic phase.
The feed liquid is a mixed solution of zirconium and hafnium hydrochloride, wherein the concentration of zirconium is 0.5 mol/L; the concentration of hafnium is 0.1 mol/L; the acidity is 1.0mol/L,
the washing solution was 0.5mol/L hydrochloric acid solution.
The stripping agent is 2.0mol/L ammonia solution.
The extraction separation experiment was performed using a 250ml mixing-clarifying extraction tank. Firstly, 50-stage countercurrent extraction is carried out, the flow ratio of an organic phase to a feed liquid is 17.5 mL/min: 7.0mL/min to obtain zirconium-containing hafnium extract; then 5-stage countercurrent washing is carried out, the flow ratio of the zirconium-containing hafnium extract to the washing liquid is 17.5 mL/min: 10 mL/min. Then 10-stage countercurrent back extraction is carried out, the flow ratio of the zirconium-containing hafnium extraction liquid to the back extractant is 17.5 mL/min: 10mL/min to obtain a mixture of zirconium hydroxide and hafnium hydroxide. The obtained mixture of zirconium hydroxide and hafnium hydroxide is dissolved with sulfuric acid to prepare a mixed solution of zirconium sulfate and hafnium sulfate.
Taking the prepared mixed solution of zirconium sulfate and hafnium sulfate as a feed liquid, extracting and separating by using an organic phase, and performing 20-grade countercurrent extraction, wherein the flow ratio of the organic phase to the feed liquid is 15 mL/min: 7.5mL/min to obtain zirconium-containing extract and hafnium-containing tail liquid; then carrying out 10-stage countercurrent washing on the zirconium-containing extract liquor, wherein the flow ratio of the zirconium-containing extract liquor to the washing liquor is 15 mL/min: 7.5 mL/min. Then 6-stage countercurrent back extraction is carried out, the flow ratio of the zirconium-containing extract to the back extractant is 15 mL/min: 7.5mL/min, and the zirconium hydroxide precipitate is obtained. Adding alkali into the tail liquid containing hafnium to precipitate so as to obtain the hafnium hydroxide precipitate. Wherein the total yield of zirconium is 96.3%, the purity of zirconium is 99.994%, and the content of hafnium in zirconium is 60 ppm. The overall yield of hafnium was 95.4%, the purity of hafnium was 99.03%, and the zirconium content of hafnium was 0.8%.
Example 7:
preparation of organic phase: 3L of 1- (2-ethylhexyl amino) ethyl propyl phosphonic acid di (2-ethylhexyl) ester and 7L of aviation kerosene are mixed to prepare an organic phase.
The feed liquid is a solution of hafnium sulfate, wherein the concentration of hafnium is 0.10 mol/L; the acidity is 1.5mol/L,
the washing solution is a 0.5mol/L sulfuric acid solution.
The stripping agent is 1.0mol/L ammonia solution.
The extraction separation experiment was performed using a 250ml mixing-clarifying extraction tank. Firstly, 20-stage countercurrent extraction is carried out, the flow ratio of an organic phase to a feed liquid is 10 mL/min: 15mL/min to obtain the hafnium-containing extract. Then 5-stage countercurrent washing is carried out, the flow ratio of the hafnium-containing extract liquid to the washing liquid is 10 mL/min: 5 mL/min. Then, 5-stage countercurrent back extraction is carried out, the flow ratio of the hafnium-containing extract to the back extractant is 10 mL/min: 13mL/min to obtain a hafnium hydroxide precipitate. Among them, the yield of hafnium was 98.4%, and the purity of hafnium was 99.3%.
Example 8:
preparation of organic phase: 2L of 1- (2-ethylhexyl amino) propyl phosphonic acid di (2-ethylhexyl) ester, 1LP507 and 7L of aviation kerosene are mixed to prepare an organic phase.
The feed liquid is a mixed solution of hafnium sulfate, wherein the concentration of zirconium is 0.2 mol/L; the concentration of hafnium is 0.004 mol/L; the acidity is 1.5mol/L,
the washing solution was 1.0mol/L hydrochloric acid solution.
The stripping agent is 1.0mol/L sodium hydroxide solution.
The extraction separation experiment was performed using a 250ml mixing-clarifying extraction tank. Firstly, 20-stage countercurrent extraction is carried out, the flow ratio of an organic phase to a feed liquid is 10 mL/min: 15mL/min to obtain zirconium-containing extract and hafnium-containing tail liquid. Then carrying out 7-stage countercurrent washing, wherein the flow ratio of the hafnium-containing extract liquid to the washing liquid is 10 mL/min: 5 mL/min. Then, 5-stage countercurrent back extraction is carried out, the flow ratio of the hafnium-containing extract to the back extractant is 10 mL/min: 13mL/min to obtain a hafnium hydroxide precipitate. Among them, the yield of hafnium was 96.6%, and the purity of hafnium was 99.1%.
Example 9:
preparation of organic phase: 3L of 1- (N, N-dibutylamino) -1-ethyl-N-propylphosphonic acid di (2-ethylhexyl) ester, 1L of TBP and 6L of aviation kerosene were mixed to prepare 10L of an organic phase.
The feed liquid is a mixed solution of hafnium and zirconium nitrate, wherein the concentration of hafnium is 0.25 mol/L; the concentration of zirconium is 0.15 mol/L; the acidity is 1.0mol/L,
the washing solution is a nitric acid solution of 0.5 mol/L.
The stripping agent is 2.0mol/L ammonia solution.
The extraction separation experiment was performed using a 250ml mixing-clarifying extraction tank. Firstly, 50-grade countercurrent extraction is carried out, the flow ratio of an organic phase to a feed liquid is 15 mL/min: 7.5mL/min to obtain a hafnium-containing extract and a zirconium-containing tail solution. Then 5-stage countercurrent washing is carried out, the flow ratio of the hafnium-containing extract liquid to the washing liquid is 15 mL/min: 7.5 mL/min. Then 10-stage countercurrent back extraction is carried out, the flow ratio of the hafnium-containing extract to the back extractant is 15 mL/min: 8.5mL/min, and obtaining the hafnium hydroxide precipitate. Wherein, the yield of the hafnium is 98.8 percent, the purity of the zirconium is 99.1 percent, and the content of the zirconium in the hafnium is 0.7 percent.
Example 10:
preparation of organic phase: 3L of 1- (dodecylamino) -1-ethyl-n-propylphosphonic acid diethyl ester, 1L of LCyanex923 and 6L of aviation kerosene were mixed to prepare a 10L organic phase.
The feed liquid is a mixed solution of hafnium zirconium hydrochloride and rare earth (III), wherein the concentration of hafnium is 0.3 mol/L; the concentration of zirconium is 0.1 mol/L; the concentration of the rare earth (III) is 0.1mol/L, the acidity is 1.0mol/L,
the washing solution was 0.5mol/L hydrochloric acid solution.
The stripping agent is 2.0mol/L ammonia solution.
The extraction separation experiment was performed using a 250ml mixing-clarifying extraction tank. Firstly, 50-grade countercurrent extraction is carried out, the flow ratio of an organic phase to a feed liquid is 15 mL/min: 7.5mL/min to obtain a hafnium-containing extract and a tail solution containing zirconium, RE and III. Then 5-stage countercurrent washing is carried out, the flow ratio of the hafnium-containing extract liquid to the washing liquid is 15 mL/min: 7.5 mL/min. Then 10-stage countercurrent back extraction is carried out, the flow ratio of the hafnium-containing extract to the back extractant is 15 mL/min: 8.5mL/min, and obtaining the hafnium hydroxide precipitate. Wherein the yield of hafnium is 96.8%, the purity of hafnium is 99.4%, and the zirconium content in hafnium is 0.4%.
Example 11:
preparation of organic phase: 3L of 1- (2-ethylhexyl amino) 1-methylethyl phosphonic acid di (2-ethylhexyl) ester is mixed with 7L of aviation kerosene to prepare an organic phase.
The feed liquid is a mixed solution of zirconium and hafnium nitrate, wherein the concentration of zirconium is 0.5 mol/L; the concentration of hafnium is 0.04 mol/L; the acidity is 1.5mol/L,
the washing solution is a 1.0mol/L nitric acid solution.
The stripping agent is 4.0mol/L nitric acid solution.
The extraction separation experiment was performed using a 250ml mixing-clarifying extraction tank. Firstly, carrying out 5-stage countercurrent extraction, wherein the flow ratio of an organic phase to a feed liquid is 20 mL/min: 8mL/min to obtain the zirconium-containing hafnium extract. Then, carrying out 3-stage countercurrent washing, wherein the flow ratio of the zirconium-containing hafnium extract to the washing liquid is 20 mL/min: 10 mL/min. And then 8-stage countercurrent back extraction is carried out, wherein the flow ratio of the zirconium-containing hafnium extraction liquid to the back extractant is 20 mL/min: 12mL/min to obtain the zirconium hafnium nitrate solution. Wherein, the yield of zirconium and hafnium is 99.8% and 99%, respectively.
Mixing the obtained zirconium hafnium nitrate solution with an organic phase, and performing 6-stage countercurrent extraction, wherein the flow ratio of the organic phase to the zirconium hafnium nitrate solution is 20 mL/min: 10mL/min to obtain zirconium-containing extract and hafnium-containing tail liquid; then carrying out 15-stage countercurrent washing, wherein the flow ratio of the zirconium-containing extract liquid to the washing liquid is 20 mL/min: 5 mL/min. Then, 5-stage countercurrent back extraction is carried out, wherein the flow ratio of the zirconium-containing extract to the back extractant is 20 mL/min: and (3) obtaining a zirconium nitrate solution at a rate of 10mL/min, and respectively carrying out oxalic acid precipitation on the obtained zirconium nitrate and the hafnium-containing tail solution to obtain zirconium oxalate and hafnium oxalate products. Wherein, the yield of the zirconium is 96.8 percent respectively, and the purity of the zirconium is 99.995 percent; the yield of hafnium was 95.8%, and the purity of hafnium was 99.5%.
Example 12:
preparation of organic phase: 3L of 1- (2-ethylhexyl amino) 1-methylethyl phosphonic acid di (2-ethylhexyl) ester is mixed with 7L of aviation kerosene to prepare an organic phase.
The feed liquid is a mixed solution of zirconium and hafnium nitrate, wherein the concentration of zirconium is 0.5 mol/L; the concentration of hafnium is 0.04 mol/L; the acidity is 1.5mol/L,
the washing solution is a 1.0mol/L nitric acid solution.
The stripping agent is 4.0mol/L nitric acid solution.
The extraction separation experiment was performed using a 250ml mixing-clarifying extraction tank. Firstly, carrying out 5-stage countercurrent extraction, wherein the flow ratio of an organic phase to a feed liquid is 20 mL/min: 8mL/min to obtain the zirconium-containing hafnium extract. Then, carrying out 3-stage countercurrent washing, wherein the flow ratio of the zirconium-containing hafnium extract to the washing liquid is 20 mL/min: 10 mL/min. And then 8-stage countercurrent back extraction is carried out, wherein the flow ratio of the zirconium-containing hafnium extraction liquid to the back extractant is 20 mL/min: 12mL/min to obtain the zirconium hafnium nitrate solution. Wherein, the yield of zirconium and hafnium is 99.8% and 99%, respectively.
Mixing the obtained zirconium hafnium nitrate solution with an organic phase, and performing 6-stage countercurrent extraction, wherein the flow ratio of the organic phase to the zirconium hafnium nitrate solution is 20 mL/min: 10mL/min to obtain zirconium-containing extract and hafnium-containing tail liquid; then carrying out 15-stage countercurrent washing, wherein the flow ratio of the zirconium-containing extract liquid to the washing liquid is 20 mL/min: 5 mL/min. Then, 5-stage countercurrent back extraction is carried out, wherein the flow ratio of the zirconium-containing extract to the back extractant is 20 mL/min: 10mL/min, and obtaining the zirconium nitrate solution. The obtained zirconium nitrate solution and the hafnium-containing tail solution are respectively subjected to oxalic acid precipitation to prepare zirconium oxalate and hafnium oxalate products. Wherein, the yield of the zirconium is 96.8 percent respectively, and the purity of the zirconium is 99.995 percent; the yield of hafnium was 95.8%, and the purity of hafnium was 99.5%.
Example 13:
preparation of organic phase: 3L of 1- (2-ethylhexyl amino) ethyl propyl phosphonic acid di (2-ethylhexyl) ester and 7L of aviation kerosene are mixed to prepare an organic phase.
The feed liquid is a solution of zirconium hafnium sulfate, wherein the concentration of zirconium is 0.5 mol/L; the concentration of hafnium is 0.04 mol/L; the acidity is 3.0mol/L,
the washing solution is a 0.5mol/L sulfuric acid solution.
The stripping agent is 1.0mol/L ammonia solution.
The extraction separation experiment was performed using a 250ml mixing-clarifying extraction tank. Firstly, 10-grade countercurrent extraction is carried out, the flow ratio of an organic phase to a feed liquid is 5 mL/min: 20mL/min to obtain the hafnium-containing extract and the zirconium-containing tail solution. Then 5-stage countercurrent washing is carried out, the flow ratio of the hafnium-containing extract liquid to the washing liquid is 5 mL/min: 5 mL/min. Then 5-stage countercurrent back extraction is carried out, the flow ratio of the hafnium-containing extract to the back extractant is 5 mL/min: 5mL/min to obtain a hafnium hydroxide precipitate. Among them, the yield of hafnium was 98.4%, and the purity of hafnium was 99.3%.
And taking the zirconium-containing tail liquid as feed liquid, and continuously adopting a 250ml mixing-clarifying extraction tank to perform an extraction separation experiment. Firstly, 10-stage countercurrent extraction is carried out, the flow ratio of an organic phase to a feed liquid is 18 mL/min: 10mL/min to obtain zirconium-containing extract. Then 8-stage countercurrent washing is carried out, and the flow ratio of the zirconium-containing extract liquid to the washing liquid is 18 mL/min: 6 mL/min. And then 8-stage countercurrent back extraction is carried out, wherein the flow ratio of the zirconium-containing extract to the back extractant is 18 mL/min: 20mL/min to obtain zirconium hydroxide precipitate. Wherein, the yield of zirconium is 95.8 percent, and the purity of zirconium is 99.993 percent.
Claims (69)
1. Use of an amino-containing neutral phosphine extractant of the general formula I below for the extractive separation of zirconium (IV) and/or hafnium (IV):
wherein,
R1and R2Each independently selected from C1-12An alkyl group;
R3and R4Each independently selected from C1-3Alkyl and hydrogen;
R5and R6Each independently selected from C1-16Alkyl and hydrogen, and R5And R6At most one is hydrogen.
2. Use according to claim 1, wherein R1And R2Each independently selected from C4-10An alkyl group.
3. Use according to claim 2, wherein R1And R2Each independently selected from C5-9An alkyl group.
4. Use according to claim 3, wherein R1And R2Each independently selected from C6-8An alkyl group.
5. Use according to claim 1, wherein R1And R2Is an integer between 8 and 20.
6. Use according to claim 5, wherein R1And R2The total number of carbon atoms of (a) is an integer between 10 and 18.
7. Use according to claim 1, wherein R1And R2Are the same alkyl groups.
8. Use according to claim 7, wherein R1And R2Is the same C5-9An alkyl group.
9. Use according to claim 1, wherein R3And R4The total number of carbon atoms of (a) is an integer between 0 and 6.
10. According to claim 1The use of, wherein R5Is selected from C1-10Alkyl and hydrogen, R6Is selected from C1-14An alkyl group.
11. Use according to claim 10, wherein R5Is selected from C1-8Alkyl and hydrogen, R6Is selected from C1-12An alkyl group.
12. Use according to claim 1, wherein R5And R6The total number of carbon atoms of (a) is an integer between 1 and 16.
13. Use according to claim 12, wherein R5And R6The total number of carbon atoms of (a) is an integer between 2 and 13.
14. Use according to claim 1, wherein R1、R2、R3、R4、R5And R6The total number of carbon atoms of (A) is 10 to 46.
15. Use according to claim 14, wherein R1、R2、R3、R4、R5And R6The total number of carbon atoms of (A) is 13 to 36.
16. Use according to claim 15, wherein R1、R2、R3、R4、R5And R6The total number of carbon atoms of (2) is 15 to 34.
17. Use according to claim 1, wherein the amino-containing neutral phosphine extractant of general formula I is selected from the group consisting of bis (2-ethylhexyl) 1- (2-ethylhexylamino) methylphosphonic acid, bis (2-ethylhexyl) 1- (2-ethylhexylamino) ethylphosphonic acid, bis (2-ethylhexyl) 1- (2-ethylhexylamino) N-propylphosphonic acid, bis (2-ethylhexyl) 1- (2-ethylhexylamino) -1-methylethylphosphonic acid, bis (2-ethylhexyl) 1- (N, N-dibutylamino) ethylphosphonic acid, bis (2-ethylhexyl) 1- (2-ethylhexylamino) -1-ethyl-N-propylphosphonic acid, bis (2-ethylhexyl) 1- (2-ethylhexylamino) -1-N-propyl-N-propylphosphonic acid -ethylhexyl) ester, di (2-ethylhexyl) 1- (2-ethylhexylamino) -1-N-propyl-N-butylphosphonic acid, di (2-ethylhexyl) 1- (N, N-dibutylamino) -1-ethyl-N-propylphosphonic acid, diethyl 1- (dodecylamino) -1-ethyl-N-propylphosphonic acid.
18. Use according to claim 1, wherein the amino-containing neutral phosphine extractant of the general formula I is used for separating zirconium (IV) from hafnium (IV) by extraction, wherein, in the general formula I, R3And R4Each independently selected from methyl, ethyl and hydrogen, and R3And R4At most one is ethyl, the amino-containing neutral phosphine extractant is preferentially complexed with zirconium.
19. Use according to claim 18, wherein the amino-containing neutral phosphine extractant of general formula I is one or more selected from the group consisting of bis (2-ethylhexyl) 1- (2-ethylhexylamino) methylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) ethylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) N-propylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) 1-methylethylphosphonate, bis (2-ethylhexyl) 1- (N, N-dibutylamino) ethylphosphonate.
20. Use according to claim 1, wherein the amino-containing neutral phosphine extractant of the general formula I is used for separating zirconium (IV) from hafnium (IV) by extraction, wherein, in the general formula I, R3And R4Each independently selected from ethyl and propyl, the amino-containing neutral phosphine extractant being preferentially complexed with hafnium.
21. Use according to claim 20, wherein the amino-containing neutral phosphine extractant of general formula I is one or more selected from the group consisting of di (2-ethylhexyl) 1- (2-ethylhexylamino) -1-ethyl-N-propylphosphonate, di (2-ethylhexyl) 1- (2-ethylhexylamino) -1-propyl-N-propylphosphonate, di (2-ethylhexyl) 1- (2-ethylhexylamino) -1-N-propyl-N-butylphosphonate, di (2-ethylhexyl) 1- (N, N-dibutylamino) -1-ethyl-N-propylphosphonate, diethyl 1- (dodecylamino) -1-ethyl-N-propylphosphonate.
22. A process for the extractive separation of zirconium and/or hafnium, comprising the step of extracting zirconium (IV) and/or hafnium (IV) from a zirconium (IV) and/or hafnium (IV) containing feed solution using an amino-containing neutral phosphine extractant of the general formula I as described in claims 1 to 21.
23. The process of claim 22, wherein the process is carried out using a solvent extraction process,
the method comprises the following steps: mixing a neutral phosphine extraction system containing an amino-containing neutral phosphine extraction agent with feed liquid containing zirconium (IV) and/or hafnium (IV) to extract to obtain zirconium-containing and/or hafnium-containing extract and raffinate.
24. The method of claim 23, wherein,
the method comprises the following steps: mixing a neutral phosphine extraction system containing an amino neutral phosphine extraction agent with a feed liquid containing zirconium (IV) and hafnium (IV) to extract to obtain a zirconium-containing extract liquid and a hafnium-containing raffinate liquid, wherein in the formula I, R is3And R4Each independently selected from methyl, ethyl and hydrogen, and R3And R4At most one is ethyl.
25. The process of claim 24, wherein the amino-containing neutral phosphine extractant of formula I is one or more selected from the group consisting of bis (2-ethylhexyl) 1- (2-ethylhexylamino) methylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) ethylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) N-propylphosphonate, bis (2-ethylhexyl) 1- (2-ethylhexylamino) 1-methylethylphosphonate, bis (2-ethylhexyl) 1- (N, N-dibutylamino) ethylphosphonate.
26. The method of claim 23, wherein the method comprises: mixing a neutral phosphine extraction system containing an amino neutral phosphine extraction agent with a feed liquid containing zirconium (IV) and hafnium (IV) to extract, thereby obtaining a hafnium-containing extract and a zirconium-containing raffinate, wherein in the formula I, R is3And R4Each independently selected from ethyl and propyl.
27. The process of claim 26, wherein the amino-containing neutral phosphine extractant of formula I is one or more selected from the group consisting of di (2-ethylhexyl) 1- (2-ethylhexylamino) -1-ethyl-N-propylphosphonate, di (2-ethylhexyl) 1- (2-ethylhexylamino) -1-propyl-N-propylphosphonate, di (2-ethylhexyl) 1- (2-ethylhexylamino) -1-N-propyl-N-butylphosphonate, di (2-ethylhexyl) 1- (N, N-dibutylamino) -1-ethyl-N-propylphosphonate, diethyl 1- (dodecylamino) -1-ethyl-N-propylphosphonate.
28. The method of claim 23, 24 or 26,
the neutral phosphine extraction system comprises an amino-containing neutral phosphine extractant of the general formula I, an optional auxiliary extractant, an optional phase modifier and a diluent.
29. The process of claim 28, wherein the co-extractant is selected from the group consisting of phosphorus or phosphine extractants of the following general formula II:
wherein,
z is O or S;
R7selected from hydrogen, C1-12Alkyl radical, C1-12Alkoxy, -SH and with a radical selected from C1-12-NH substituted by at least one substituent in the alkyl radical2；
R8And R9Each independently selected from C4-12Alkyl radical, C4-12Alkoxy and with a radical selected from C4-12-NH substituted by at least one substituent in the alkyl radical2。
30. The method of claim 29, wherein,
R7selected from hydrogen, C1-10Alkyl radical, C1-10Alkoxy, -SH and with a radical selected from C4-10-NH substituted by at least one substituent in the alkyl radical2；
R8And R9Each independently selected from C4-10Alkyl radical, C4-10Alkoxy and with a radical selected from C4-10-NH substituted by at least one substituent in the alkyl radical2。
31. The method of claim 30, wherein,
R7is selected from C1-10Alkyl and C1-10An alkoxy group;
R8and R9Each independently selected from C4-10Alkyl and C4-10An alkoxy group.
32. The process of claim 29, wherein the auxiliary extractant is selected from the group consisting of: a neutral phosphorus or phosphine extractant; an acidic phosphorus or phosphine extractant; a neutral phosphoramidite extractant; and the mixed extractant mixed with the extractant in any proportion.
33. The method of claim 32, wherein,
the neutral phosphorus or phosphine extractant is selected from: linear trialkylphosphine oxide, branched trialkylphosphine oxide, trioctylphosphine oxide, dimethylheptyl methylphosphonate, di (-2-ethylhexyl) 2-ethylhexyl phosphonate, tributyl phosphate;
the acidic phosphorus or phosphine extractant is selected from bis (2,4, 4-trimethylpentyl) dithiophosphinic acid, bis (2,4, 4-trimethylpentyl) thiophosphonic acid, bis (2-ethylhexyl) phosphoric acid, 2-ethylhexyl phosphonic acid mono-2-ethylhexyl ester, bis (2,4, 4-trimethylpentyl) phosphonic acid, bis (2-ethylhexyl) phosphonic acid;
the neutral phosphoramide extractant is selected from triisooctylphosphoramide, diisooctyl-isooctyloxyphosphoramide, isooctyl-diisooctyloxyphosphoramide, tri (diisobutyl) phosphoramide, di (diisobutyl) -isooctyloxyphosphoramide, tridecylphosphamide, and dihexyl-decyloxyphosphamide.
34. The method of claim 28, wherein said phase modifier is selected from C4-10One or more of alkanols.
35. The method of claim 28 wherein the phase modifier is one or more selected from the group consisting of n-octanol, iso-octanol, 2-methylheptanol, and mixed alcohols and tributyl phosphate in any proportion of the three.
36. The method of claim 35, wherein the phase modifier is a mixed alcohol or 2-methylheptanol.
37. The method of claim 28, wherein the diluent is selected from the group consisting of: c5-16Alkane, aviation kerosene, sulfonated kerosene, liquid paraffin, C5-16Alicyclic alkane, C6-10An aromatic hydrocarbon.
38. The method of claim 37, wherein,
said C is5-16The alkane is selected from pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane, pentadecane, hexadecane;
the liquid paraffin is a light lubricating oil fraction at 250-400 ℃;
said C is5-16The alicyclic alkane is selected from cyclopentane and C1-4Alkyl-substituted cyclopentanes, cyclohexanes, C1-4Alkyl substituted cyclohexane, decahydronaphthalene;
said C is6-10The aromatic hydrocarbon is selected from benzene, toluene and xylene.
39. The method of claim 37, wherein the diluent is one or more selected from jet fuel, sulfonated fuel, heptane, and xylene.
40. The process of claim 28, wherein the volume ratio of the amino-containing neutral phosphine extractant, optional co-extractant, optional phase modifier and diluent in the amino-containing neutral phosphine extraction system is: neutral phosphine extraction agent: auxiliary extracting agent: phase modifier: 1-60% of a diluent: 0-40: 0 to 20: 40 to 99.
41. The process of claim 40, wherein the amino-containing neutral phosphine extractant: auxiliary extracting agent: phase modifier: 10-40% of a diluent: 0 to 20: 0 to 20: 50-90.
42. The process of claim 41, wherein the amino-containing neutral phosphine extractant: auxiliary extracting agent: phase modifier: 15-35% of a diluent: 0-15: 0-15: 55-85.
43. The method according to claim 23, 24 or 26, wherein the concentration of zirconium (IV) or hafnium (IV) in the feed liquid is 0.001-2 mol/L;
the acidity of the feed liquid is 0.1 to 10mol/L in terms of the molar concentration of hydrogen ions.
44. The method according to claim 43, wherein the acidity of the feed liquid is 0.5 to 4mol/L of nitric acid, sulfuric acid, hydrochloric acid, hydrofluoric acid or a mixed solution of the above acids at an arbitrary ratio, as represented by the molar concentration of hydrogen ions.
45. The method as claimed in claim 23, 24 or 26, wherein the number of extraction stages in the extraction step is 1 to 50 stages.
46. The method of claim 45, wherein the number of extraction stages is 3 to 40 stages.
47. The method of claim 46, wherein the number of extraction stages is 5 to 20.
48. The method according to claim 23, 24 or 26, wherein the flow ratio of the neutral phosphine extraction system to the feed liquid is 0.05-20: 1.
49. a process as claimed in claim 48, wherein the flow ratio of neutral phosphine extraction system to feed liquid is 0.1-20: 1.
50. a process as claimed in claim 49, wherein the flow ratio of neutral phosphine extraction system to feed liquid is 0.2-10: 1.
51. the process of claim 24 or 26, further comprising the step of extracting hafnium or zirconium from the hafnium-containing raffinate or the zirconium-containing raffinate as the hafnium-containing feed or the zirconium-containing feed, respectively.
52. The method according to claim 51, wherein the method according to claim 22 or 23 is used to separate hafnium or zirconium by extraction to obtain a hafnium-containing extract or a zirconium-containing extract, respectively.
53. The process of claim 51 which employs the same neutral phosphine extraction system as employed in the process of claim 24 or 26 for separating zirconium (IV) from hafnium (IV) by extraction.
54. The method of claim 23, 24, or 26, further comprising:
optionally washing the zirconium-and/or hafnium-containing extract with a washing liquid;
and (3) stripping the zirconium and/or the hafnium in the zirconium-and/or hafnium-containing extract by using a stripping agent to obtain a stripping product containing the zirconium and/or the hafnium.
55. The method according to claim 54, wherein the washing solution is nitric acid, sulfuric acid, hydrochloric acid or a mixed solution of the above acids in any proportion; the acidity of the washing liquid is 0.2 to 4mol/L in terms of the molar concentration of hydrogen ions.
56. The method of claim 54, wherein the number of washing stages is 0 to 20.
57. The method of claim 54, wherein the number of washing stages is 0 to 10.
58. The method of claim 54, wherein the wash flow ratio is zirconium and/or hafnium containing extract: washing solution 1: 0.1 to 5.
59. The method of claim 58, wherein the wash flow ratio is zirconium-and/or hafnium-containing extract: washing solution 1: 0.2 to 2.
60. The process of claim 54, wherein said strip liquor is an acid solution; an alkali solution; or oxalate solutions.
61. The method of claim 60, wherein the acid solution is a hydrochloric acid or nitric acid solution; the alkali solution is ammonia water, sodium hydroxide or sodium carbonate solution; the oxalate solution is potassium oxalate or sodium oxalate solution.
62. The method according to claim 60, wherein the acid solution has a hydrogen ion concentration of 2 to 8 mol/L; the concentration of hydroxide radical in the alkali solution is 0.001-6 mol/L; the concentration of oxalate in the oxalate solution is from 0.1mol/L to saturated solution.
63. A process as claimed in claim 62, in which the alkali solution is present in an amount of 0.1 to 2mol/L expressed as hydroxide.
64. The method according to claim 54, wherein the number of stripping stages is 1-10; the flow ratio is the extraction liquid containing zirconium and/or hafnium: and (3) stripping solution is 1: 0.1 to 5.
65. The method of claim 64, wherein the number of stripping stages is 2-6; the flow ratio is the extraction liquid containing zirconium and/or hafnium: and (3) stripping solution is 1: 0.2 to 2.
66. The method of claim 54, further comprising:
carrying out treatment selected from precipitation, filtration, calcination, acid dissolution and drying on the back-extraction product containing zirconium or hafnium to obtain a zirconium or hafnium product; or
Separating zirconium and hafnium by the method according to claim 24 or 26 using a solution containing hafnium and zirconium obtained by subjecting the stripping product containing zirconium and hafnium to a treatment selected from calcination and acid dissolution as a feed solution.
67. The process of claim 54, wherein the extraction, washing and stripping are carried out in a series of separatory funnels, mixed clarification extraction cells.
68. The process of claim 67, wherein the extracting, washing and stripping are performed in a mixed clarification extraction tank.
69. The process of claim 54, wherein the extracting, washing and stripping are carried out batchwise or continuously.
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| CN108118150B (en) * | 2018-01-03 | 2021-04-16 | 中南民族大学 | Method for extracting and separating zirconium and hafnium from hydrochloric acid medium |
| CN108220597A (en) * | 2018-01-03 | 2018-06-29 | 中南民族大学 | The method of extracting and separating zirconium and hafnium in nitric acid medium |
| CN108822147B (en) * | 2018-05-25 | 2019-09-27 | 中南大学 | A kind of pyridyl group phosphamide compound and preparation method thereof and application as nickel cobalt extractant |
| CN110747357B (en) * | 2019-11-12 | 2021-06-25 | 济南大学 | Method for extracting and separating zirconium and hafnium by using biphosphoric acid extracting agent |
| CN112499679B (en) * | 2020-12-03 | 2023-04-25 | 广东先导微电子科技有限公司 | Method for removing hafnium tetrachloride from zirconium tetrachloride |
| CN112593079B (en) * | 2020-12-08 | 2022-05-31 | 中南民族大学 | Synergistic extraction agent and method for separating zirconium and hafnium |
| CN114807602B (en) * | 2022-05-19 | 2023-02-21 | 哈尔滨工业大学（威海） | Extraction solvent and extraction method for separating zirconium and hafnium |
| CN115679124B (en) * | 2022-11-07 | 2023-08-18 | 南通晶朋新材料科技有限公司 | Process for separating hafnium and zirconium |
| CN116732353A (en) * | 2023-06-16 | 2023-09-12 | 黄绍荣 | Method for separating zirconium and hafnium from industrial zirconium sulfate |
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