WO2021042814A1 - 一种烷基硫醚基乙基羟肟酸选矿药剂及其制备方法与应用 - Google Patents
一种烷基硫醚基乙基羟肟酸选矿药剂及其制备方法与应用 Download PDFInfo
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- WO2021042814A1 WO2021042814A1 PCT/CN2020/096986 CN2020096986W WO2021042814A1 WO 2021042814 A1 WO2021042814 A1 WO 2021042814A1 CN 2020096986 W CN2020096986 W CN 2020096986W WO 2021042814 A1 WO2021042814 A1 WO 2021042814A1
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- WIPO (PCT)
- Prior art keywords
- alkyl sulfide
- hydroxamic acid
- group
- acid
- ethyl hydroxamic
- Prior art date
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- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 125000005012 alkyl thioether group Chemical group 0.000 title abstract 5
- RSIPQHOWTCNEBI-UHFFFAOYSA-N n-hydroxypropanamide Chemical compound CCC(=O)NO RSIPQHOWTCNEBI-UHFFFAOYSA-N 0.000 title abstract 4
- 239000002253 acid Substances 0.000 claims abstract description 83
- 238000005188 flotation Methods 0.000 claims abstract description 43
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052500 inorganic mineral Inorganic materials 0.000 claims abstract description 17
- 239000011707 mineral Substances 0.000 claims abstract description 17
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000005886 esterification reaction Methods 0.000 claims abstract description 7
- 239000003513 alkali Substances 0.000 claims abstract description 4
- NEAQRZUHTPSBBM-UHFFFAOYSA-N 2-hydroxy-3,3-dimethyl-7-nitro-4h-isoquinolin-1-one Chemical compound C1=C([N+]([O-])=O)C=C2C(=O)N(O)C(C)(C)CC2=C1 NEAQRZUHTPSBBM-UHFFFAOYSA-N 0.000 claims description 73
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 64
- 125000000217 alkyl group Chemical group 0.000 claims description 42
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 39
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical group [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- -1 sec-hexyl Chemical group 0.000 claims description 26
- WTDHULULXKLSOZ-UHFFFAOYSA-N Hydroxylamine hydrochloride Chemical group Cl.ON WTDHULULXKLSOZ-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 239000002184 metal Substances 0.000 claims description 19
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 13
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 12
- 229910001570 bauxite Inorganic materials 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- KXKVLQRXCPHEJC-UHFFFAOYSA-N methyl acetate Chemical compound COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 8
- 239000002002 slurry Substances 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 8
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 6
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 6
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 6
- 125000003118 aryl group Chemical group 0.000 claims description 5
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims description 4
- 239000005751 Copper oxide Substances 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 229910000431 copper oxide Inorganic materials 0.000 claims description 4
- 125000003438 dodecyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 239000012266 salt solution Substances 0.000 claims description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052721 tungsten Inorganic materials 0.000 claims description 4
- 239000010937 tungsten Substances 0.000 claims description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N Dodecane Natural products CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 claims description 3
- 238000009291 froth flotation Methods 0.000 claims description 3
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 claims description 3
- ZNBNBTIDJSKEAM-UHFFFAOYSA-N 4-[7-hydroxy-2-[5-[5-[6-hydroxy-6-(hydroxymethyl)-3,5-dimethyloxan-2-yl]-3-methyloxolan-2-yl]-5-methyloxolan-2-yl]-2,8-dimethyl-1,10-dioxaspiro[4.5]decan-9-yl]-2-methyl-3-propanoyloxypentanoic acid Chemical compound C1C(O)C(C)C(C(C)C(OC(=O)CC)C(C)C(O)=O)OC11OC(C)(C2OC(C)(CC2)C2C(CC(O2)C2C(CC(C)C(O)(CO)O2)C)C)CC1 ZNBNBTIDJSKEAM-UHFFFAOYSA-N 0.000 claims description 2
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 claims description 2
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 claims description 2
- 125000000640 cyclooctyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C([H])([H])C1([H])[H] 0.000 claims description 2
- 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 claims description 2
- 229910000378 hydroxylammonium sulfate Inorganic materials 0.000 claims description 2
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 2
- 125000004491 isohexyl group Chemical group C(CCC(C)C)* 0.000 claims description 2
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 claims description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 claims description 2
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 2
- 125000002914 sec-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000003548 sec-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 2
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims 1
- 125000000101 thioether group Chemical group 0.000 abstract description 6
- 125000000524 functional group Chemical group 0.000 abstract description 4
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000032050 esterification Effects 0.000 abstract 1
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 description 32
- VDEUYMSGMPQMIK-UHFFFAOYSA-N benzhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1 VDEUYMSGMPQMIK-UHFFFAOYSA-N 0.000 description 16
- 235000010755 mineral Nutrition 0.000 description 15
- 238000011084 recovery Methods 0.000 description 13
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 12
- ZXOKVTWPEIAYAB-UHFFFAOYSA-N dioxido(oxo)tungsten Chemical compound [O-][W]([O-])=O ZXOKVTWPEIAYAB-UHFFFAOYSA-N 0.000 description 7
- 229910021645 metal ion Inorganic materials 0.000 description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- 239000012153 distilled water Substances 0.000 description 6
- 238000004768 lowest unoccupied molecular orbital Methods 0.000 description 6
- UPYPTOCXMIWHSG-UHFFFAOYSA-N 1-dodecylsulfanyldodecane Chemical compound CCCCCCCCCCCCSCCCCCCCCCCCC UPYPTOCXMIWHSG-UHFFFAOYSA-N 0.000 description 5
- FPOQLQZHRCEVOT-UHFFFAOYSA-N N-hydroxy-2-phenylacetamide Chemical compound ONC(=O)CC1=CC=CC=C1 FPOQLQZHRCEVOT-UHFFFAOYSA-N 0.000 description 5
- 241000907663 Siproeta stelenes Species 0.000 description 5
- 238000004770 highest occupied molecular orbital Methods 0.000 description 5
- WVYWICLMDOOCFB-UHFFFAOYSA-N 4-methyl-2-pentanol Chemical compound CC(C)CC(C)O WVYWICLMDOOCFB-UHFFFAOYSA-N 0.000 description 4
- SMWZHEUHWLCWGN-UHFFFAOYSA-N CC(=O)O.C1=CC=C(C=C1)CSCC2=CC=CC=C2 Chemical compound CC(=O)O.C1=CC=C(C=C1)CSCC2=CC=CC=C2 SMWZHEUHWLCWGN-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000004088 foaming agent Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- CWERGRDVMFNCDR-UHFFFAOYSA-N thioglycolic acid Chemical compound OC(=O)CS CWERGRDVMFNCDR-UHFFFAOYSA-N 0.000 description 4
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 230000002209 hydrophobic effect Effects 0.000 description 3
- 238000002329 infrared spectrum Methods 0.000 description 3
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ROKCSPWHXSXFAU-UHFFFAOYSA-N C(C)(=O)O.C(CCCCCCCCCCC)SCCCCCCCCCCCC Chemical compound C(C)(=O)O.C(CCCCCCCCCCC)SCCCCCCCCCCCC ROKCSPWHXSXFAU-UHFFFAOYSA-N 0.000 description 2
- NOJWAEBWOCWOPM-UHFFFAOYSA-N C(C)(=O)[O-].C(CCCCCCCCCCC)[SH+]C Chemical compound C(C)(=O)[O-].C(CCCCCCCCCCC)[SH+]C NOJWAEBWOCWOPM-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- TUVYSBJZBYRDHP-UHFFFAOYSA-N acetic acid;methoxymethane Chemical compound COC.CC(O)=O TUVYSBJZBYRDHP-UHFFFAOYSA-N 0.000 description 2
- RRUDCFGSUDOHDG-UHFFFAOYSA-N acetohydroxamic acid Chemical compound CC(O)=NO RRUDCFGSUDOHDG-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- 239000013522 chelant Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005421 electrostatic potential Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 125000004430 oxygen atom Chemical group O* 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- JFALSRSLKYAFGM-UHFFFAOYSA-N uranium(0) Chemical compound [U] JFALSRSLKYAFGM-UHFFFAOYSA-N 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- QCDFXUMPKFFJNG-UHFFFAOYSA-N C(C)(=O)OC.C(C1=CC=CC=C1)SCC1=CC=CC=C1 Chemical compound C(C)(=O)OC.C(C1=CC=CC=C1)SCC1=CC=CC=C1 QCDFXUMPKFFJNG-UHFFFAOYSA-N 0.000 description 1
- ZUNYYESGTMPQBI-UHFFFAOYSA-N CC(=O)O.CSCC1=CC=CC=C1 Chemical compound CC(=O)O.CSCC1=CC=CC=C1 ZUNYYESGTMPQBI-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 241000692870 Inachis io Species 0.000 description 1
- 206010028980 Neoplasm Diseases 0.000 description 1
- 229910052778 Plutonium Inorganic materials 0.000 description 1
- 229960001171 acetohydroxamic acid Drugs 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 201000011510 cancer Diseases 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 230000009920 chelation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- YMVRAWQSGGANMM-UHFFFAOYSA-N dimethylsulfanium acetate Chemical compound C[SH+]C.CC([O-])=O YMVRAWQSGGANMM-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000008396 flotation agent Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002068 genetic effect Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 208000014951 hematologic disease Diseases 0.000 description 1
- 229940121372 histone deacetylase inhibitor Drugs 0.000 description 1
- 239000003276 histone deacetylase inhibitor Substances 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 208000030159 metabolic disease Diseases 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000004776 molecular orbital Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- OYEHPCDNVJXUIW-UHFFFAOYSA-N plutonium atom Chemical compound [Pu] OYEHPCDNVJXUIW-UHFFFAOYSA-N 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- HBROZNQEVUILML-UHFFFAOYSA-N salicylhydroxamic acid Chemical compound ONC(=O)C1=CC=CC=C1O HBROZNQEVUILML-UHFFFAOYSA-N 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/012—Organic compounds containing sulfur
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/008—Organic compounds containing oxygen
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D1/00—Flotation
- B03D1/001—Flotation agents
- B03D1/004—Organic compounds
- B03D1/01—Organic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C323/00—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups
- C07C323/50—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton
- C07C323/51—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton
- C07C323/60—Thiols, sulfides, hydropolysulfides or polysulfides substituted by halogen, oxygen or nitrogen atoms, or by sulfur atoms not being part of thio groups containing thio groups and carboxyl groups bound to the same carbon skeleton having the sulfur atoms of the thio groups bound to acyclic carbon atoms of the carbon skeleton with the carbon atom of at least one of the carboxyl groups bound to nitrogen atoms
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2201/00—Specified effects produced by the flotation agents
- B03D2201/02—Collectors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
- B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
- B03D2203/00—Specified materials treated by the flotation agents; specified applications
- B03D2203/02—Ores
- B03D2203/04—Non-sulfide ores
Definitions
- the invention belongs to the field of beneficiation agents, and specifically relates to a novel alkyl sulfide-based ethyl hydroxamic acid beneficiation agent and a preparation method and application thereof.
- Hydroxamic acid compounds are a class of typical chelating agents with high efficiency and selectivity to metal ions. Because its molecular structure contains oxygen and nitrogen with a lone pair of electrons and their positions are close to each other, it can chelate with metal ions to form a stable chelate, which is formed by combining two O atoms in the carbonyl group and the hydroxyl group with the metal cation. Five-membered ring structure. With such a special structure, hydroxamic acid compounds have been widely used in the fields of metal oxide ore flotation, solvent extraction, wastewater treatment, and medicine.
- hydroxamic acid collectors in the flotation industry are mainly short-carbon chain hydroxamic acids such as alkyl hydroxamic acid, benzyl hydroxamic acid and salicylic hydroxamic acid. These short-chain hydroxamic acids generally have good selectivity, but their collection ability is weak. There is no report about the use of alkyl sulfide ethyl hydroxamic acid as a collector for mineral flotation.
- the purpose of the present invention is to provide a novel structure of alkyl sulfide-based ethyl hydroxamic acid beneficiation agent in view of the defects of the existing oxide ore collectors.
- Another object of the present invention is to provide a preparation method of the alkyl sulfide ethyl hydroxamic acid beneficiation agent.
- the third object of the present invention is to provide the application of the alkyl sulfide-based ethyl hydroxamic acid beneficiation agent, which can be widely used in bauxite, tungsten ore, copper oxide ore, tin ore, etc. Flotation of oxide ore. Compared with the commonly used hydroxamic acid collectors in industry, it has better selectivity to target minerals and higher flotation efficiency.
- the invention discloses an alkyl sulfide-based ethyl hydroxamic acid beneficiation agent, which has a structure shown in formula I:
- R 1 in formula I is C 1 ⁇ C 12 alkane group; C 5 ⁇ C 12 cycloalkyl group; C 6 ⁇ C 12 aromatic group; C 1 ⁇ C 12 alkane group substituted with at least one substituent.
- R 1 is a C 1 -C 12 alkane group, for example, a linear alkane group or a branched alkyl group.
- R 1 can also be a C 5 ⁇ C 12 cycloalkyl group, preferably a five-membered or six-membered cycloalkane group.
- the cycloalkane group may have a substituent, and the substituent may be at least one of halogen and alkyl. .
- the C 6 -C 12 aromatic group for example, a phenyl group, a benzyl group, or a benzene ring containing at least one of an alkane group or a halogen.
- the C 1 -C 12 alkane group substituted with at least one substituent may be at least one of phenyl, benzyl, and p-tert-butylbenzyl.
- R 1 is methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, sec-pentyl, neopentyl, ring Pentyl, n-hexyl, isohexyl, sec-hexyl, cyclohexyl, heptyl, cycloheptyl, n-octyl, isooctyl, sec-octyl, cyclooctyl, benzyl, phenyl, p-tert-butylbenzyl And one of dodecyl.
- R 1 is one of benzyl and dodecyl.
- the invention also provides a preparation method of the alkyl sulfide ethyl hydroxamic acid beneficiation agent, which comprises the following steps:
- Esterification reaction the alkyl sulfide acetic acid of the formula II structure and methanol are subjected to an esterification reaction under the catalysis of concentrated sulfuric acid to obtain the methyl sulfide acetate of the formula III structure;
- R 1 is a C 1 ⁇ C 12 alkane group; a C 5 ⁇ C 12 cycloalkyl group; a C 6 ⁇ C 12 aromatic group; a C 1 ⁇ C 12 alkane group substituted with at least one substituent.
- the esterification reaction temperature is 50-100°C
- the reaction time is 1-6h
- the molar ratio of alkylsulfide acetic acid to methanol is 1:1-8
- the mass fraction of concentrated sulfuric acid is 25-50g/mol
- the addition amount is 2.5-5g/0.1mol alkyl sulfide acetic acid.
- the hydrooximation reaction temperature is 10-60°C
- the reaction time is 2.5-6h
- the hydroxylamine is hydroxylamine hydrochloride or hydroxylamine sulfate
- the base is sodium hydroxide or potassium hydroxide
- the alkyl sulfide group The molar ratio of methyl acetate, hydroxylamine and alkali is 1:1 to 1.5:1 to 1.5, and the amount of water is 10 to 100 mL of water/0.1 mol of alkyl sulfide methyl acetate.
- the invention also provides the application of the alkyl sulfide ethyl hydroxamic acid beneficiation agent, which is used as a collector for the flotation of metal ore.
- the metal ore is at least one of bauxite, tungsten ore, copper oxide ore and tin ore.
- the alkyl sulfide ethyl hydroxamic acid beneficiation agent of the present invention is used as a flotation collector to efficiently recover valuable metals from metal ore.
- the thioether group and the hydroxamic acid group in the flotation collector have the effect of synergistically chelating metal ions, strengthen the effect of the collector and the metal ions on the mineral surface, and promote the efficient recovery of the mineral.
- the alkyl sulfide-based ethyl hydroxamic acid collector is added, and the metal mineral is floated by the foam flotation method.
- the basic process of alkyl sulfide ethyl hydroxamic acid as a collector is: (1) flotation of metal ore after grinding; (2) the alkyl sulfide ethyl hydroxamic acid of formula I Mixed with sodium hydroxide or potassium hydroxide in water to form a salt solution of alkyl sulfide ethyl hydroxamic acid as a flotation agent; (3) Add hydrochloric acid or sodium hydroxide during the flotation process to adjust the pH of the slurry to 7 ⁇ 9. Under weakly alkaline conditions, add 25-400 mg/L of the salt solution of alkyl sulfide ethyl hydroxamic acid; (4) Flotation of useful metal minerals by froth flotation.
- the alkyl sulfide ethyl hydroxamic acid collector used in the present invention has a strong collection capacity for bauxite, malachite, tin ore, wolframite and other minerals, and can improve bauxite, peacock Flotation recovery rate of minerals such as stone, tin ore and wolframite.
- the alkyl sulfide ethyl hydroxamic acid of the present invention is used as a collector, the dosage of the alkyl sulfide ethyl hydroxamic acid is 25-400 mg/L, and hydrochloric acid or sodium hydroxide is added during the flotation process to adjust The pH of the slurry is 7-9.
- the flotation recovery rate of oxide ore can be increased, and the flotation separation of valuable minerals and gangue minerals can be realized. Increase by about 30%.
- the collector is a compound with a complex functional group, which has a complex functional group of -S- and a hydroxime group.
- the synergistic chelation between the two functional groups is strong, the collection effect is good, and it has a strong chelating ability to some metal ions.
- the sulfide group-containing hydroxamic acid collector of the structure of the present invention has good collection performance.
- the length of the hydrophobic hydrocarbon chain of the present invention is relatively longer, which can improve the hydrophobic foaming performance of the collector and increase the froth flotation efficiency.
- the non-ferrous metal recycling process is simple, efficient, and feasible, and meets the requirements of industrial applications.
- thiourethane wastewater contains a large amount of thioglycolic acid in the industry, and the raw material of the present invention is derived from thioglycolic acid, which improves the recovery of valuable substances in the wastewater and turns waste into treasure.
- Figure 1 is a hydrogen nuclear magnetic resonance spectrum of benzyl sulfide ethyl hydroxamic acid
- Figure 2 is a carbon nuclear magnetic resonance spectrum of benzyl sulfide ethyl hydroxamic acid
- Figure 3 is the infrared spectrum of benzyl sulfide ethyl hydroxamic acid
- Figure 4 The proton nuclear magnetic resonance spectrum of dodecyl sulfide ethyl hydroxamic acid
- Figure 6 shows the optimal configuration of benzyl sulfide ethyl hydroxamic acid at the level of DFT/B2LYP6-311G(d);
- Figure 7 shows the optimal configuration of benzhydroxamic acid at the level of DFT/B2LYP6-311G(d);
- Figure 8 shows the highest occupied orbital (HOMO) and lowest occupied orbital (LUMO) of benzyl sulfide ethyl hydroxamic acid at the DFT/B2LYP6-311G(d) level;
- Figure 9 shows the highest occupied orbital (HOMO) and lowest occupied orbital (LUMO) of benzhydroxamic acid at the DFT/B2LYP6-311G(d) level;
- Figure 10 shows the molecular electrostatic potential of benzyl sulfide ethyl hydroxamic acid at the level of DFT/B2LYP6-311G(d);
- Figure 11 shows the molecular electrostatic potential of benzhydroxamic acid at the level of DFT/B2LYP6-311G(d);
- Figure 12 is a schematic diagram of the molecular structure and atomic numbers of benzhydroxamic acid and benzyl sulfide ethyl hydroxamic acid;
- Fig. 13 is a flow chart of the flotation process of wolframite in Example 6 of the present invention.
- Quantum chemistry calculation results show that the hydrophobic constant ClogP of benzyl sulfide ethyl hydroxamic acid is 0.9626, and the energy values of the highest occupied orbital (HOMO) and lowest occupied orbital (LUMO) of the molecule are -0.24699 and -0.03267, respectively, the highest The energy gap between the occupied molecular orbital and the lowest unoccupied molecular orbital can be used as a stability index of organic matter.
- the energy gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital of benzyl sulfide ethyl hydroxamic acid is 0.21432, which is close to the energy gap of the currently used benzhydroxamic acid (see Table 3), so it has a strong collection capacity and good selectivity, and is especially suitable for copper oxide ore, bauxite ore, and tungsten ore Flotation of oxidized minerals such as tin ore.
- benzyl sulfide ethyl hydroxamic acid is more likely to interact with metal cations.
- the dihedral angle data show that the dihedral angle composed of benzyl sulfide ethyl hydroxamic acid O4-C3-N2-O1 is closer to 0 than benzyl hydroxamic acid, which is conducive to the formation of conjugated ⁇ bonds. Improving the ability to interact with mineral metal ions is also conducive to forming a more stable chelating ring after interacting with metal ions.
- the concentration of benzyl sulfide ethyl hydroxamic acid and benzhydroxamic acid is 400 mg/L
- the pH of the slurry is 8
- the concentration of foaming agent (MIBC) is 30 mg/L
- the rotation speed is 1650r/min
- the particle size The flotation of malachite with a diameter of -0.076mm ⁇ +0.038mm is 5 minutes respectively.
- the flotation recovery rate of malachite can reach 96.26%
- benzyl hydroxamic acid is used as a collector, the flotation recovery rate of malachite is only 30.88. %.
- the concentration of benzyl sulfide ethyl hydroxamic acid and benzhydroxamic acid is 150 mg/L
- the pH of the slurry is 8
- the concentration of foaming agent (MIBC) is 30 mg/L
- the rotation speed is 1650r/min
- the particle size Flotation of bauxite with a diameter of -0.076mm ⁇ +0.038mm for 5 minutes.
- the concentration of benzyl sulfide ethyl hydroxamic acid and benzhydroxamic acid is 25 mg/L
- the pH of the slurry is 8
- the concentration of activator (Pb 2+ ) is 30 mg/L
- the concentration of foaming agent (MIBC) is 30 mg /L
- the rotation speed is 1650r/min
- the wolframite with a particle size of -0.076mm ⁇ +0.038mm is flotated for 5 minutes respectively.
- the flotation process flow chart is shown in Figure 10.
- the flotation recovery rate of wolframite can reach 95.89%, while when benzyl hydroxamic acid is used as a collector, the flotation recovery rate of wolframite is only It is 46.86%.
- the concentration of benzyl sulfide ethyl hydroxamic acid and benzhydroxamic acid is 400 mg/L
- the pH of the slurry is 8
- the concentration of foaming agent (MIBC) is 30 mg/L
- the rotation speed is 1650r/min
- the particle size The cassiterite with a diameter of -0.076mm ⁇ +0.038mm is floated for 5 minutes respectively.
- the flotation recovery rate of cassiterite can reach 79.41%, while when benzhydroxamic acid is used as a collector, the flotation recovery rate of cassiterite is only 42.83. %.
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Abstract
一种烷基硫醚基乙基羟肟酸选矿药剂及其制备方法与应用，烷基硫醚基乙基羟肟酸分子同时具有硫醚基和羟肟基两种功能基，其采用烷基硫醚基乙酸与甲醇进行酯化，再采用羟胺和碱进行羟肟化得到。烷基硫醚基乙基羟肟酸选矿药剂可以用作矿物浮选的捕收剂，制备方法简单，收率高，其分子中的硫醚基和羟肟酸基团具有协同作用，可有效提高其捕收性能。
Description
本发明属于选矿药剂领域，具体涉及一种新型的烷基硫醚基乙基羟肟酸选矿药剂及其制备方法与应用。
羟肟酸类化合物是一类对金属离子具有高效选择性的典型螯合剂。由于其分子结构中具有含孤对电子的氧和氮并且位置相互靠近，使它能与金属离子螯合生成稳定的螯合物，其通过羰基和羟基中的两个O原子与金属阳离子结合形成五元环结构。这样的特殊结构，使得羟肟酸类化合物已被广泛用于金属氧化矿的浮选、溶剂萃取、废水处理以及医药等领域。
Wang等报道了烷基羟肟酸对细粒锡石的浮选及其溶液化学性质(结构式a，Peipei Wang，Wenqing Qin，Liuyi Ren，et al.Solution chemistry and utilization of alkyl hydroxamic acid in flotation of fine cassiterite[J].Transactions of Nonferrous Metals Society ofChina,2013，23(6):1789-1796.)。Zuo等经多次实验研究证实，经还原萃取后的铀燃料，用含乙酰羟肟酸的有机萃取相处理，能够很好的实现铀与钚的分离和净化(结构b,Chen Zuo,Taihong Yan,Weifang Zheng,et al.Kinetics and mechanism of stripping ofNp(Ⅳ)by acetohyroxamic acid using a Lewis cell[J].Journal of Radioanalytical and Nuclear Chemistry,2010,283(1):83-87.)。US20020143052A1报道了芳基脂肪酸和羟肟酸作为组蛋白去乙酰化酶抑制剂，用于治疗癌症、血液病和遗传相关代谢疾病(结构c)。
目前，浮选工业上常用的羟肟酸捕收剂还是以烷基羟肟酸、苯甲羟肟酸和水杨羟肟酸等短碳链的羟肟酸为主。这些短碳链结构的羟肟酸一般选择性好，但捕收能力弱。目前还没有烷基硫醚基乙基羟肟酸药剂用作矿物浮选捕收剂的有关报道。
发明内容
本发明的目的是针对现有氧化矿捕收剂存在的缺陷，提供一种新的结构的烷基硫醚基乙基羟肟酸选矿药剂。
本发明的另一目的在于提供所述的烷基硫醚基乙基羟肟酸选矿药剂的制备方法。
本发明的第三目的在于提供所述的烷基硫醚基乙基羟肟酸选矿药剂的应用，该化合物作捕收剂可广泛应用于铝土矿、钨矿、氧化铜矿、锡矿等氧化矿的浮选。与工业上常用的羟肟酸捕收剂相比，其对目标矿物选择性更好，浮选效率更高。
本发明公开了一种烷基硫醚基乙基羟肟酸选矿药剂，具有式I所示的结构:
其中式I中R
1为C
1～C
12烷烃基；C
5～C
12环烷基；C
6～C
12芳香基；至少含一个取代基取代的C
1～C
12烷烃基。
本发明中，R
1为C
1～C
12烷烃基，例如为直链烷烃基或带支链的烷基。
R
1还可以为C
5～C
12环烷基，优选为五元或者六元的环烷烃基，所述的环烷烃基可以有取代基，取代基可以为卤素、烷基中的至少一种。
所述的C
6～C
12芳香基，例如苯基、苄基、或者苯环上含有烷烃基或者卤素中至少一种。
所述的至少含一个取代基取代的C
1～C
12烷烃基，取代基可以为苯基、苄基、对叔丁苄基中的至少一种。
作为优选，R
1为甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、异戊基、仲戊基、新戊基、环戊基、正己基、异己基、仲己基、环己基、庚基、环庚基、正辛基、异辛基、仲辛基、环辛基、苄基、苯基、对叔丁基苄基和十二烷基中的一种。
较优选的，R
1为苄基和十二烷基中的一种。
本发明还提供了所述的烷基硫醚基乙基羟肟酸选矿药剂的制备方法，包括如下步骤：
(1)酯化反应：将式II结构的烷基硫醚基乙酸与甲醇在浓硫酸催化作用下进行酯化反应得到具有式III结构的烷基硫醚基乙酸甲酯；
(2)羟肟化反应：将式III结构的烷基硫醚基乙酸甲酯与羟胺、碱在水溶液中进行羟肟化反应，制得烷基硫醚基乙基羟肟酸选矿药剂；
其中，R
1为C
1～C
12烷烃基；C
5～C
12环烷基；C
6～C
12芳香基；至少含一个取代基取代的C
1～C
12烷烃基。
作为优选，步骤(1)中，酯化反应温度为50～100℃，反应时间为1～6h，烷基硫醚基乙酸与甲醇的摩尔比为1：1～8，浓硫酸的质量分数为25～50g/mol，添加量为2.5～5g/0.1mol烷基硫醚基乙酸。
作为优选，步骤(2)中，羟肟化反应温度为10～60℃，反应时间为2.5～6h，羟胺为盐酸羟胺或硫酸羟胺，碱为氢氧化钠或氢氧化钾，烷基硫醚基乙酸甲酯、羟胺和碱地摩尔比为1：1～1.5：1～1.5，水的用量为10～100mL水/0.1mol烷基硫醚基乙酸甲酯。
本发明还提供了所述的烷基硫醚基乙基羟肟酸选矿药剂的应用，将其作为捕收剂用于金属矿石的浮选。
作为优选，所述金属矿石为铝土矿、钨矿、氧化铜矿和锡矿中的至少一种。
本发明的的烷基硫醚基乙基羟肟酸选矿药剂作为浮选捕收剂，从金属矿石中高效回收有价金属。该浮选捕收剂中硫醚基和羟肟酸基团之间具有协同螯合金属离子的作用，增强捕收剂与矿物表面金属离子的作用，促进矿物的高效回收。
本发明中，在金属矿石浮选过程中，调浆后，加入所述的烷基硫醚基乙基羟肟酸捕收剂，通过泡沫浮选法浮选出金属矿物。
作为优选，烷基硫醚基乙基羟肟酸作为捕收剂的基本流程为：(1)金属矿石磨细后浮选；(2)将式Ⅰ的烷基硫醚基乙基羟肟酸与氢氧化钠或者氢氧化钾在水中配成烷基硫醚基乙基羟肟酸的盐溶液作浮选药剂；(3)在浮选过程中加入盐酸或者氢氧化钠调节矿浆pH为7～9，弱碱性条件下，添加烷基硫醚基乙基羟肟酸的盐溶液25～400mg/L；(4)通过泡沫浮选法浮选有用金属矿物。
本发明所使用的烷基硫醚基乙基羟肟酸捕收剂，对铝土矿、孔雀石、锡矿、黑钨矿等矿物具有较强的捕收能力，可以提高铝土矿、孔雀石、锡矿、黑钨矿等矿物的浮选回收率。采用本发明所述的烷基硫醚基乙基羟肟酸作为捕收剂，烷基硫醚基乙基羟肟酸药剂用量25～400mg/L，浮选过程中加入盐酸或者氢氧化钠调节矿浆pH为7～9，弱碱性条件下，与苯甲羟肟酸相比，可以使氧化矿的浮选回收率提高，实现有价矿物与脉石矿物的浮选分离，浮选回收率提高30％左右。
相对于现有技术，本发明的有益效果是：
1、首次将含硫醚基和羟肟酸基团的化合物应用于有色金属矿物的浮选分离，实现有色金属矿物高效回收。
2、该捕收剂是具有复合官能团的化合物，它具有-S-和羟肟基团复合官能团。两种官能团之间的协同螯合作用较强，捕收效果好，对一些金属离子具有较强的螯合能力。
3、与目前工业上常用的的浮选捕收剂相比，本发明所述结构的含硫醚基的羟肟酸捕收剂具有良好的捕收性能。与苯甲羟肟酸相比，本发明的疏水基烃链的长度相对较长，可改善捕收剂的疏水起泡性能，提高泡沫浮选效率。有色金属回收过程简单、高效、切实可行，满足工业应用要求。
4、目前工业上硫氨酯废水中含有大量的巯基乙酸，而本发明的原料来源于巯基乙酸，提高了废水中有价物质的回收，变废为宝。
图1为苄基硫醚基乙基羟肟酸的核磁共振氢谱图；
图2为苄基硫醚基乙基羟肟酸的核磁共振碳谱图；
图3为苄基硫醚基乙基羟肟酸的红外光谱图；
图4十二烷基硫醚基乙基羟肟酸的核磁共振氢谱图；
图5十二烷基硫醚基乙基羟肟酸的核磁共振碳谱图；
图6为在DFT/B2LYP6-311G(d)水平下苄基硫醚基乙基羟肟酸的最优构型；
图7为在DFT/B2LYP6-311G(d)水平下苯甲羟肟酸的最优构型；
图8为在DFT/B2LYP6-311G(d)水平下苄基硫醚基乙基羟肟酸的最高占据轨道(HOMO)和最低占据轨道(LUMO)；
图9为在DFT/B2LYP6-311G(d)水平下苯甲羟肟酸的最高占据轨道(HOMO) 和最低占据轨道(LUMO)；
图10为在DFT/B2LYP6-311G(d)水平下苄基硫醚基乙基羟肟酸的分子静电势；
图11为在DFT/B2LYP6-311G(d)水平下苯甲羟肟酸的分子静电势；
图12为苯甲羟肟酸与苄基硫醚基乙基羟肟酸分子结构示意图与原子序号；
图13为本发明实施例6的黑钨矿浮选工艺流程图。
本发明由下列实施例进一步说明，但不受这些实施例的限制。
实施例1
苄基硫醚基乙基羟肟酸的制备：
将18.93g 96.15％的苄基硫醚基乙酸、16.16g 99％的甲醇和2.5g 98％的浓硫酸加入到150mL三口烧瓶中，升温至75℃反应5h，冷却至室温后，加入4.2g 98.5％的碳酸氢钠固体，待无气泡放出后，过滤，减压蒸馏除去甲醇得到苄基硫醚基乙酸甲酯。将7.76g 99.5％的盐酸羟胺加入容积为150mL的三口烧瓶中，并加入30mL蒸馏水使盐酸羟胺溶解。称取8.33g 96％的氢氧化钠，用20mL蒸馏水使之溶解，然后将氢氧化钠的水溶液在冰浴下滴加至盐酸羟胺的水溶液中，滴加完后，向混合物中加入苄基硫醚基乙酸甲酯，升温至40℃反应4h，反应完后用硫酸酸化得苄基硫醚基乙基羟肟酸产品16.81g，基于苄基硫醚基乙酸的收率为91.86％。苄基硫醚基乙基羟肟酸经提纯后进行表征，
1HNMR、
13CNMR和红外光谱图分别如图1～3所示.
表1 核磁共振氢谱和碳谱分析结果
表2 红外光谱分析结果
量子化学计算结果表明，苄基硫醚基乙基羟肟酸的疏水常数ClogP值为0.9626，分子最高占据轨道(HOMO)和最低占据轨道(LUMO)的能量值分别为-0.24699和-0.03267，最高占据分子轨道与最低未占据分子轨道之间的能隙可以作为有机物的一种稳定性指数，苄基硫醚基乙基羟肟酸最高占据分子轨道与最低未占据分子轨道之间的能隙为0.21432，与现用的苯甲羟肟酸的能隙比较接近(见表3)，因此具有较强的捕收能力和较好的选择性，特别适用于氧化铜矿、铝土矿、钨矿、锡矿等氧化矿物的浮选。
由表4结合图10可知，苄基硫醚基乙基羟肟酸N-O键长与苯甲羟肟酸相近，但C＝O双键长比苯甲羟肟酸长，说明苄基硫醚基乙基羟肟酸电子在C＝O双键之间的分布少，导致C＝O双键的强度较苯甲羟肟酸弱，因此活性更高。而羟肟酸与矿物作用是通过羰基和羟基中的两个O原子与金属阳离子结合形成五元环结构。因此，苄基硫醚基乙基羟肟酸更易与金属阳离子作用。二面角的数据表明，苄基硫醚基乙基羟肟酸O4-C3-N2-O1组成的二面角比苯甲羟肟酸更接近于0，有利于共轭п键的形成，能提高与矿物金属离子的作用能力，也有利于与金属离子作用后形成更加稳定的螯合环。
表3 在DFT/B3LYP6-311G(d)水平下羟肟酸捕收剂的单点能、HOMO与LUMO能量值及CLogP值
表4 在DFT/B3LYP6-311G(d)水平下苄羟肟酸捕收剂的结构参数
实施例2
苄基硫醚基乙基羟肟酸的制备：
将9.47g 96.15％的苄基硫醚基乙酸、8.08g 99％的甲醇和1.3g 98％的浓硫酸加入到容积为100mL三口烧瓶中，升温至75℃反应5h，冷却至室温后，加入2.1g 98.5％的碳酸氢钠固体，待无气泡放出后，过滤，减压蒸馏除去甲醇得到苄基硫醚基乙酸甲酯。将3.88g 99.5％的盐酸羟胺加入容积为100mL的三口烧瓶中，并加入30mL蒸馏水使盐酸羟胺溶解。称取6.59g 85.0％的氢氧化钾，用20mL蒸馏水使之溶解，然后将氢氧化钾的水溶液在冰浴下滴加至盐酸羟胺的水溶液中，滴加完后，向混合物中加入苄基硫醚基乙酸甲酯，升温至40℃反应4.5h，反应完后用硫酸酸化得苄基硫醚基乙基羟肟酸产品8.92g，基于苄基硫醚基乙酸的收率为90.56％。
实施例3
十二烷基硫醚基乙基羟肟酸的制备：
称取18.71g 97.30％的十二烷基硫醚基乙酸、16.16g 99％的甲醇和2.5g 98％的浓硫酸加入到容积为150mL三口烧瓶中，加热至75℃反应4.5h，冷却至室温后，加入4.2g 98.5％的碳酸氢钠固体，待无气泡放出后，过滤，减压蒸馏得到十二烷基硫醚基乙酸甲酯。将7.76g 99.5％的盐酸羟胺和30mL蒸馏水加入150mL的三口烧瓶中，将8.33g 96％的氢氧化钠和20mL蒸馏水混合，然后将氢氧化钠的水溶液在冰浴下滴加至盐酸羟胺的水溶液中，滴加完后，向混合物中加入十二烷基硫醚基乙酸甲酯，升温至40℃反应4h，反应完后用硫酸酸化得十二烷基硫醚基乙基羟肟酸产品17.20g，基于十二烷基硫醚基乙酸的收率为89.30％。十二烷基硫醚基乙基羟肟酸经提纯后进行表征，
1H NMR和
13C NMR分别如图4～5所示。
表5 核磁共振氢谱和碳谱分析结果
实施例4
苄基硫醚基乙基羟肟酸浮选孔雀石：
当苄基硫醚基乙基羟肟酸和苯甲羟肟酸浓度为400mg/L，矿浆pH为8，起泡剂(MIBC)浓度为30mg/L，转速为1650r/min时，对粒径为-0.076mm～+0.038mm的孔雀石分别浮选5分钟。苄基硫醚基乙基羟肟酸做捕收剂时，孔雀石的浮选回收率可达96.26％，而苯甲羟肟酸做捕收剂时，孔雀石的浮选回收率仅为30.88％。
实施例5
苄基硫醚基乙基羟肟酸浮选铝土矿：
当苄基硫醚基乙基羟肟酸和苯甲羟肟酸浓度为150mg/L，矿浆pH为8，起泡剂(MIBC)浓度为30mg/L，转速为1650r/min时，对粒径为-0.076mm～+0.038mm的铝土矿分别浮选5分钟。苄基硫醚基乙基羟肟酸做捕收剂时，铝土矿的浮选回收率可达95.91％，而苯甲羟肟酸做捕收剂时，铝土矿的浮选回收率仅为19.88％。
实施例6
苄基硫醚基乙基羟肟酸浮选黑钨矿：
当苄基硫醚基乙基羟肟酸和苯甲羟肟酸浓度为25mg/L，矿浆pH为8，活化剂(Pb
2+)浓度为30mg/L，起泡剂(MIBC)浓度为30mg/L，转速为1650r/min时，对粒径为-0.076mm～+0.038mm的黑钨矿分别浮选5分钟，浮选工艺流程图见图10。苄基硫醚基乙基羟肟酸做捕收剂时，黑钨矿的浮选回收率可达95.89％，而苯甲羟肟酸做捕收剂时，黑钨矿的浮选回收率仅为46.86％。
实施例7
苄基硫醚基乙基羟肟酸浮选锡石：
当苄基硫醚基乙基羟肟酸和苯甲羟肟酸浓度为400mg/L，矿浆pH为8，起泡剂(MIBC)浓度为30mg/L，转速为1650r/min时，对粒径为-0.076mm～+0.038mm的锡石分别浮选5分钟。苄基硫醚基乙基羟肟酸做捕收剂时，锡石的浮选回收率可达79.41％，而苯甲羟肟酸做捕收剂时，锡石的浮选回收率仅为42.83％。
Claims (9)
- 一种烷基硫醚基乙基羟肟酸选矿药剂，其特征在于，具有式I所示结构：
其中式I中R 1为C 1～C 12烷烃基；C 5～C 12环烷基；C 6～C 12芳香基；至少含一个取代基取代的C 1～C 12烷烃基。 - 根据权利要求1所述的烷基硫醚基乙基羟肟酸选矿药剂，其特征在于：R 1选自甲基、乙基、丙基、异丙基、丁基、异丁基、仲丁基、叔丁基、戊基、异戊基、仲戊基、新戊基、环戊基、正己基、异己基、仲己基、环己基、庚基、环庚基、正辛基、异辛基、仲辛基、环辛基、苄基、苯基、对叔丁基苄基和十二烷基中的一种。
- 根据权利要求2所述的烷基硫醚基乙基羟肟酸选矿药剂，其特征在于：R 1选自苄基和十二烷基中的一种。
- 权利要求1-3任一项所述的烷基硫醚基乙基羟肟酸选矿药剂的制备方法，其特征在于，包括如下步骤：(1)酯化反应：将式II结构的烷基硫醚基乙酸与甲醇在浓硫酸催化作用下进行酯化反应得到具有式III结构的烷基硫醚基乙酸甲酯；(2)羟肟化反应：将式III结构的烷基硫醚基乙酸甲酯与羟胺、碱在水溶液中进行羟肟化反应，制得烷基硫醚基乙基羟肟酸选矿药剂；
其中，R 1为C 1～C 12烷烃基；C 5～C 12环烷基；C 6～C 12芳香基；至少含一个取代基取代的C 1～C 12烷烃基。 - 根据权利要求4所述的烷基硫醚基乙基羟肟酸选矿药剂的制备方法，其特征在于：步骤(1)中，酯化反应温度为50～100℃，反应时间为1～6h，烷基硫醚基乙酸与甲醇的摩尔比为1：1～8，浓硫酸的质量分数为25～50g/mol，添加量为2.5～5g/0.1mol烷基硫醚基乙酸。
- 根据权利要求4所述的烷基硫醚基乙基羟肟酸选矿药剂的制备方法，其特征在于：步骤(2)中，羟肟化反应温度为10～60℃，反应时间为2.5～6h，羟胺为盐酸羟胺或硫酸羟胺，碱为氢氧化钠或氢氧化钾，烷基硫醚基乙酸甲酯、羟胺和碱地摩尔比为1：1～1.5：1～1.5，水的用量为10～100mL水/0.1mol烷基硫醚基乙酸甲酯。
- 权利要求1-3任一项所述的烷基硫醚基乙基羟肟酸选矿药剂或权利要求4-6任一项所述的制备方法制得的烷基硫醚基乙基羟肟酸选矿药剂的应用，其特征在于：将其作为捕收剂用于金属矿石的浮选。
- 根据权利要求7所述的烷基硫醚基乙基羟肟酸选矿药剂的应用，其特征在于：所述金属矿石为铝土矿、钨矿、氧化铜矿和锡矿中的至少一种。
- 根据权利要求7或8所述的烷基硫醚基乙基羟肟酸选矿药剂的应用，其特征在于：烷基硫醚基乙基羟肟酸作为捕收剂的基本流程为：(1)金属矿石磨细后浮选；(2)将式Ⅰ的烷基硫醚基乙基羟肟酸与氢氧化钠或者氢氧化钾在水中配成烷基硫醚基乙基羟肟酸的盐溶液作浮选药剂；(3)在浮选过程中加入盐酸或者氢氧化钠调节矿浆pH为7～9，弱碱性条件下，添加烷基硫醚基乙基羟肟酸的盐溶液25～400mg/L；(4)通过泡沫浮选法浮选有用金属矿物。
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