CN117551015A - Method for co-production of xanthates, thiourethanes and trithiocarbonate carboxylates and use thereof - Google Patents
Method for co-production of xanthates, thiourethanes and trithiocarbonate carboxylates and use thereof Download PDFInfo
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- CN117551015A CN117551015A CN202311513579.7A CN202311513579A CN117551015A CN 117551015 A CN117551015 A CN 117551015A CN 202311513579 A CN202311513579 A CN 202311513579A CN 117551015 A CN117551015 A CN 117551015A
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- CN
- China
- Prior art keywords
- reaction
- trithiocarbonate
- xanthate
- potassium
- purity
- Prior art date
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- 239000012989 trithiocarbonate Substances 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 47
- 239000012991 xanthate Substances 0.000 title claims abstract description 37
- -1 trithiocarbonate carboxylates Chemical class 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title abstract description 14
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 81
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims abstract description 75
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims abstract description 36
- 238000005188 flotation Methods 0.000 claims abstract description 30
- 239000012267 brine Substances 0.000 claims abstract description 29
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011591 potassium Substances 0.000 claims abstract description 28
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 28
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000002360 preparation method Methods 0.000 claims abstract description 23
- 238000000926 separation method Methods 0.000 claims abstract description 20
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 14
- HIZCIEIDIFGZSS-UHFFFAOYSA-L trithiocarbonate Chemical compound [S-]C([S-])=S HIZCIEIDIFGZSS-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000005886 esterification reaction Methods 0.000 claims abstract description 9
- 150000002191 fatty alcohols Chemical class 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 150000007942 carboxylates Chemical class 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 8
- 150000004820 halides Chemical class 0.000 claims abstract description 5
- 239000007788 liquid Substances 0.000 claims abstract description 4
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 150000001735 carboxylic acids Chemical class 0.000 claims abstract 3
- 239000000203 mixture Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 12
- 238000005915 ammonolysis reaction Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 8
- 150000001875 compounds Chemical class 0.000 claims description 8
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- 239000003518 caustics Substances 0.000 claims description 7
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 239000003513 alkali Substances 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- PFRUBEOIWWEFOL-UHFFFAOYSA-N [N].[S] Chemical compound [N].[S] PFRUBEOIWWEFOL-UHFFFAOYSA-N 0.000 claims description 2
- 150000003977 halocarboxylic acids Chemical class 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 claims 4
- 239000005083 Zinc sulfide Substances 0.000 claims 1
- 229910052981 lead sulfide Inorganic materials 0.000 claims 1
- 229940056932 lead sulfide Drugs 0.000 claims 1
- 229910052984 zinc sulfide Inorganic materials 0.000 claims 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 claims 1
- 208000012839 conversion disease Diseases 0.000 abstract description 3
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000003153 chemical reaction reagent Substances 0.000 abstract 1
- 239000000047 product Substances 0.000 description 30
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 23
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 18
- KIACEOHPIRTHMI-UHFFFAOYSA-N o-propan-2-yl n-ethylcarbamothioate Chemical compound CCNC(=S)OC(C)C KIACEOHPIRTHMI-UHFFFAOYSA-N 0.000 description 17
- 239000012071 phase Substances 0.000 description 17
- 238000004064 recycling Methods 0.000 description 15
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 14
- ZMWBGRXFDPJFGC-UHFFFAOYSA-M potassium;propan-2-yloxymethanedithioate Chemical compound [K+].CC(C)OC([S-])=S ZMWBGRXFDPJFGC-UHFFFAOYSA-M 0.000 description 11
- 230000015572 biosynthetic process Effects 0.000 description 10
- 235000011056 potassium acetate Nutrition 0.000 description 9
- 238000003786 synthesis reaction Methods 0.000 description 9
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- IRZFQKXEKAODTJ-UHFFFAOYSA-M sodium;propan-2-yloxymethanedithioate Chemical compound [Na+].CC(C)OC([S-])=S IRZFQKXEKAODTJ-UHFFFAOYSA-M 0.000 description 8
- 239000000706 filtrate Substances 0.000 description 7
- CMGLSTYFWSQNEC-UHFFFAOYSA-N o-ethyl n-ethylcarbamothioate Chemical compound CCNC(=S)OCC CMGLSTYFWSQNEC-UHFFFAOYSA-N 0.000 description 7
- 239000001103 potassium chloride Substances 0.000 description 7
- 235000011164 potassium chloride Nutrition 0.000 description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 6
- 229940106681 chloroacetic acid Drugs 0.000 description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 description 6
- 238000011084 recovery Methods 0.000 description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 239000003814 drug Substances 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 description 4
- 150000002540 isothiocyanates Chemical class 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- JCBJVAJGLKENNC-UHFFFAOYSA-M potassium ethyl xanthate Chemical compound [K+].CCOC([S-])=S JCBJVAJGLKENNC-UHFFFAOYSA-M 0.000 description 4
- CRAXZMAICBMTCW-UHFFFAOYSA-M potassium;2-methylpropoxymethanedithioate Chemical compound [K+].CC(C)COC([S-])=S CRAXZMAICBMTCW-UHFFFAOYSA-M 0.000 description 4
- OMKVZYFAGQKILB-UHFFFAOYSA-M potassium;butoxymethanedithioate Chemical compound [K+].CCCCOC([S-])=S OMKVZYFAGQKILB-UHFFFAOYSA-M 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- 125000003396 thiol group Chemical class [H]S* 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- WIKSRXFQIZQFEH-UHFFFAOYSA-N [Cu].[Pb] Chemical compound [Cu].[Pb] WIKSRXFQIZQFEH-UHFFFAOYSA-N 0.000 description 3
- 238000006136 alcoholysis reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- FPIIKJRRXOPKIB-UHFFFAOYSA-N copper;sulfanylidenelead Chemical compound [Cu].[Pb]=S FPIIKJRRXOPKIB-UHFFFAOYSA-N 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 2
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 description 2
- QCXYRIKNUUVLLG-UHFFFAOYSA-N 3-dithiocarboxysulfanylpropanoic acid Chemical compound OC(=O)CCSC(S)=S QCXYRIKNUUVLLG-UHFFFAOYSA-N 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-M Butyrate Chemical compound CCCC([O-])=O FERIUCNNQQJTOY-UHFFFAOYSA-M 0.000 description 2
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Natural products CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 description 2
- 238000004566 IR spectroscopy Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 2
- 229940079593 drug Drugs 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001819 mass spectrum Methods 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 description 1
- DSCFFEYYQKSRSV-UHFFFAOYSA-N 1L-O1-methyl-muco-inositol Natural products COC1C(O)C(O)C(O)C(O)C1O DSCFFEYYQKSRSV-UHFFFAOYSA-N 0.000 description 1
- GAWAYYRQGQZKCR-UHFFFAOYSA-N 2-chloropropionic acid Chemical compound CC(Cl)C(O)=O GAWAYYRQGQZKCR-UHFFFAOYSA-N 0.000 description 1
- IPLKGJHGWCVSOG-UHFFFAOYSA-N 4-chlorobutanoic acid Chemical compound OC(=O)CCCCl IPLKGJHGWCVSOG-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- VJXUJFAZXQOXMJ-UHFFFAOYSA-N D-1-O-Methyl-muco-inositol Natural products CC12C(OC)(C)OC(C)(C)C2CC(=O)C(C23OC2C(=O)O2)(C)C1CCC3(C)C2C=1C=COC=1 VJXUJFAZXQOXMJ-UHFFFAOYSA-N 0.000 description 1
- DSCFFEYYQKSRSV-KLJZZCKASA-N D-pinitol Chemical compound CO[C@@H]1[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@H]1O DSCFFEYYQKSRSV-KLJZZCKASA-N 0.000 description 1
- AEMRFAOFKBGASW-UHFFFAOYSA-M Glycolate Chemical compound OCC([O-])=O AEMRFAOFKBGASW-UHFFFAOYSA-M 0.000 description 1
- GGLZPLKKBSSKCX-YFKPBYRVSA-N L-ethionine Chemical compound CCSCC[C@H](N)C(O)=O GGLZPLKKBSSKCX-YFKPBYRVSA-N 0.000 description 1
- JQGGYOXTWZQQLY-UHFFFAOYSA-N Lyaline Natural products COC(=O)C1=CNC=C(C=C)C1CC1=NC=CC2=C1NC1=CC=CC=C12 JQGGYOXTWZQQLY-UHFFFAOYSA-N 0.000 description 1
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007036 catalytic synthesis reaction Methods 0.000 description 1
- DVRDHUBQLOKMHZ-UHFFFAOYSA-N chalcopyrite Chemical compound [S-2].[S-2].[Fe+2].[Cu+2] DVRDHUBQLOKMHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052951 chalcopyrite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- RQPRTOROWUUIIX-UHFFFAOYSA-L dipotassium;carbonotrithioate Chemical compound [K+].[K+].[S-]C([S-])=S RQPRTOROWUUIIX-UHFFFAOYSA-L 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 229910052949 galena Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- XCAUINMIESBTBL-UHFFFAOYSA-N lead(ii) sulfide Chemical compound [Pb]=S XCAUINMIESBTBL-UHFFFAOYSA-N 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 150000002815 nickel Chemical class 0.000 description 1
- 230000005311 nuclear magnetism Effects 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 150000002905 orthoesters Chemical class 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- KPFSGNRRZMYZPH-UHFFFAOYSA-M potassium;2-chloroacetate Chemical compound [K+].[O-]C(=O)CCl KPFSGNRRZMYZPH-UHFFFAOYSA-M 0.000 description 1
- RWMKSKOZLCXHOK-UHFFFAOYSA-M potassium;butanoate Chemical compound [K+].CCCC([O-])=O RWMKSKOZLCXHOK-UHFFFAOYSA-M 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- FVSKHRXBFJPNKK-UHFFFAOYSA-N propionitrile Chemical group CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 230000002000 scavenging effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 description 1
- VGTPCRGMBIAPIM-UHFFFAOYSA-M sodium thiocyanate Chemical compound [Na+].[S-]C#N VGTPCRGMBIAPIM-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 150000003558 thiocarbamic acid derivatives Chemical class 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Abstract
The invention belongs to the field of preparation of flotation reagents, and particularly discloses a method for circularly preparing xanthate by using brine, which comprises the following steps: step (1): carrying out xanthation reaction on a raw material solution containing fatty alcohol, potassium hydroxide, carbon disulfide and water; step (2): adding halogenated carboxylic acid into the reaction system of the step (1) for esterification reaction, and then separating oil from water to obtain xanthate and potassium halide brine; step (3): the potassium halide water is directly recycled to the step (1) or is recycled to the preparation of xanthate after solid-liquid separation. The invention also includes the co-production preparation and use of further thiourethane and trithiocarbonate-based carboxylates. The preparation process is simple to operate, high in reaction conversion rate, low in production cost, energy-saving and environment-friendly, and easy to realize industrial production, and the obtained trithiocarbonate carboxylate can assist in selective flotation of copper sulfide.
Description
Technical Field
The invention belongs to the field of mineral medicament preparation, and particularly relates to the fields of preparation and application of xanthate, thiourethane and trithiocarbonate carboxylate.
Background
The thiourethane has the chemical name of O-alkyl-N-alkyl thiocarbamate, is widely applied to the floatation of sulphide ores, has the advantages of good floatation selectivity and strong collection capacity, has certain foaming capacity, and can realize the floatation separation of minerals such as gold ores, copper ores, lead zinc ores and the like under the low-alkalinity condition. At present, the synthesis of thiourethane mainly comprises an isothiocyanate alcoholysis method, a one-step catalytic synthesis method, an electrochemical synthesis method, a xanthate oxidative ammonolysis method, a xanthate esterification-ammonolysis method and the like. The isothiocyanate alcoholysis method is to synthesize an isothiocyanate intermediate first and then react with alcohol to obtain thiourethane, and U.S. Pat. No. 3,182 discloses that the phase transfer isothiocyanate alcoholysis method is adopted to successfully synthesize N-allyl basic-O-alkylthio carbamate by taking sodium thiocyanate and chloropropene as raw materials, but the process is complex, the reaction steps are more, the process is discontinuous, and the yield is lower. The one-step catalysis method is to directly react xanthate with fatty amine by using a catalyst to prepare the thiourethane. US patent 3975264 discloses the formation of isopropyl esters by reaction using soluble palladium and nickel salts as catalysts. U.S. patent No. 5041599 discloses that palladium, rhodium, platinum and ruthenium are used as catalysts for reaction to generate thiourethane, and the one-step catalytic method has the advantages of simple process, few reaction steps and the like, but has the disadvantages of low yield, low byproduct recycling value, difficult catalyst recovery, difficult subsequent wastewater treatment, serious environmental pollution and the like. The electrochemical synthesis method mainly uses xanthate, methylamine and sodium chloride as raw materials to synthesize (LYALIN B V, PETROSYAN VA. Electrochemical synthesis ofthiocarbamates [ J ]. Russian Journal ofElectrochemistry,2000,36 (2): 164-169), and the electrochemical synthesis method has the problem of low current efficiency and is still in the laboratory stage at present. The xanthate oxidation-ammonolysis method is to oxidize xanthate by using oxidant to obtain double xanthate, and then ammonolysis the double xanthate to obtain thiourethane and sulfur. (Li Hua, liu Anyi. New Process for preparation of thiocarbamates [ J ]. Fine chemical intermediate, 2022,52 (01): 56-61.). The yellow drug esterification-ammonolysis method is a main method for industrial production of the thiourethane at present, the yellow original acid salt and sodium chloroacetate are adopted for esterification reaction, then the obtained alkyl sulfonic orthoester and fatty amine are subjected to ammonolysis reaction to obtain a mixture of the thiourethane and thiol compounds, chinese patent CN106380434B discloses a method for preparing the thiourethane and combining the trithiocarbonate.
In the production process of copper sulfide ores, agents such as dichromate and Nox are commonly used for matching with a collector, and because the dichromate and the Nox have toxicity, the operation environment of workers is deteriorated in the production and use processes, and the green production of mines is influenced, so that the agent needs to be found, the selectivity of copper sulfide ores and other sulfide ores is improved under the mild condition of low alkalinity, the production cost is reduced, the resources are saved, and the development of green mines is promoted.
Disclosure of Invention
Aiming at the problems that brine in the existing alkyl xanthate production stage is difficult to treat and is easy to cause reaction degradation by recycling, the first aim of the invention is to provide a method for circularly preparing xanthate by brine, which aims at solving the problems that byproduct brine is difficult to recycle and the reaction degradation is caused by recycling.
The second object of the present invention is to provide a process for the preparation of a thiourethane based on said brine cycle.
The third object of the invention is to provide a method for preparing the thiourethane and combining the trithiocarbonate carboxylate based on the brine circulation thought.
The fourth object of the invention is to provide the application of the trithiocarbonate carboxylate prepared by the preparation method in the selective flotation of copper sulphide ores.
Aiming at the preparation of alkyl xanthate, most of the prior methods are to carry out xanthation reaction on alcohol, carbon disulfide and sodium hydroxide, then carry out esterification reaction on the xanthate and then carry out acidification and oil-water separation to obtain xanthate. Although recycling is a good brine treatment idea, previous researches of the inventor show that the conversion efficiency of the recycling reaction is greatly affected by recycling the brine obtained by the method. In view of this problem, the present invention has been made by intensive studies to provide the following improvements:
a method for preparing xanthate by brine circulation, comprising the steps of:
step (1):
carrying out xanthation reaction on a raw material solution containing fatty alcohol, potassium hydroxide, carbon disulfide and water;
step (2):
adding halogenated carboxylic acid into the reaction system of the step (1) for esterification reaction, and then separating oil from water to obtain xanthate and potassium halide brine;
step (3):
the potassium halide water is directly recycled to the step (1) or is recycled to the preparation of xanthate after solid-liquid separation.
The innovative research of the invention shows that the aliphatic alcohol, potassium hydroxide and carbon disulfide are innovatively subjected to xanthogenic acid reaction and then are subjected to esterification reaction with halogenated carboxylic acid, the reaction conversion rate is high, and excellent xanthate yield can be obtained; more importantly, based on the preparation process of the present invention, the potassium halide brine by-produced can be recycled for the xanthogenic acid reaction and subsequent esterification reaction, and can unexpectedly exhibit excellent recycling reaction stability, for example, it can also obtain a reaction yield of 80% or more at 4 times and above. Therefore, the invention can realize zero discharge of wastewater in the preparation process and can recover potassium salt crystals in the brine circulation stage.
In the present invention, the fatty alcohol is not particularly requiredFor example, it has the formula R 1 OH, wherein said R 1 Is C 1 ～C 8 Alkyl of (a);
the reaction formula of step 1 of the present invention is, for example:
preferably, the amount of the substances of the fatty alcohol, the potassium hydroxide and the carbon disulfide is 1:1-2:1-2, preferably 1:1-1.2:1-1.2;
preferably, in the raw material solution, the initial concentration of potassium hydroxide is 20% -50%;
preferably, the reaction temperature is 10-50 ℃, preferably 20-30 ℃ and the reaction time is 0.5-5 h.
In the present invention, in the step (2), the halogenated carboxylic acid is not particularly limited, and the chemical formula thereof may be XR in view of the preparation cost and the effect of recycling brine 2 COOH；
Preferably, said R 2 Is C 1 ～C 8 X is halogen, preferably Cl, br, I, etc., which may be further Cl in view of material cost;
in the present invention, the reaction formula of step (2) is, for example:
preferably, the halocarboxylic acid is 1 to 1.5 times, preferably 1 to 1.2 times the amount of fatty alcohol material;
preferably, in the step (2), the reaction temperature is 50-100 ℃;
preferably, in the step (2), the reaction time is 1-8 hours;
in the invention, after the reaction in the step (2) is finished, the xanthate can be obtained by directly extracting without additional regulation and control. Excellent xanthate yield can be obtained, and in addition, the recycling reaction stability of the by-product brine can be improved.
In the present invention, the extraction stage may be carried out using a conventional hydrophobic solvent, for example, diethyl ether, ethyl acetate, etc., or the thiourethane obtained in the present process may be used.
In the present invention, the number of brine cycles is 2 or more, and in addition, the number of cycles may be 3 or more, and further 3 to 6, from the viewpoint of maximizing the economic value of the treatment process, thanks to the excellent cycle reactivity of the brine.
In the invention, when the salt concentration reaches saturation in the salt water circulation stage, the separated salt crystallization product can be separated by means of a conventional solid-liquid separation mode, has excellent purity and can be used as a potassium salt product.
The invention also provides a method for preparing the thiourethane by brine circulation, which is characterized in that the circulating xanthate is recycled by adopting the brine circulation preparation method, and is subjected to ammonolysis reaction with fatty amine, and then oil-water separation is carried out, so that the aqueous solution of the thiourethane and the mercapto acid compound is obtained.
In the present invention, the fatty amine may be any primary or secondary amine, for example, having the formula R 3 -NH 2 Wherein R is 3 Is C 1 ～C 8 Alkyl, C of (2) 2 ～C 6 Alkenyl, benzyl or propionitrile groups, etc., preferably C 1 ～C 8 Alkyl of (a); further, the aliphatic amine may be methylamine, ethylamine, propylamine or butylamine.
In the present invention, the ammonolysis reaction formula is, for example:
preferably, the fatty amine is 1 to 1.2 times the amount of xanthate material.
Preferably, the ammonolysis reaction temperature is 30-100 ℃, and the reaction time is preferably 1-5 h.
The invention also provides a method for preparing the thiourethane and co-producing the trithiocarbonate carboxylate by brine circulation, which is adopted to prepare the thiourethane and obtain the aqueous solution of the mercapto acid compound;
caustic alkali and carbon disulfide are added into the aqueous solution of the mercapto acid compound to carry out the second stage xanthation reaction, and the solution containing the trithiocarbonate carboxylate is obtained in a co-production way.
The reaction formula of the second stage xanthogen reaction according to the present invention is, for example (caustic exemplified by KOH):
preferably, the amount of the mercapto acid compound, caustic alkali and carbon disulfide is 1:1-2:1-2, preferably 1:1-1.2:1-1.2;
preferably, the caustic is sodium hydroxide and or potassium hydroxide;
preferably, the second stage xanthation reaction temperature is 5-80 ℃, and the reaction time is preferably 2-8 h.
The method can realize the recycling of the brine, and based on the preparation method, the reaction stability of the preparation stage can be unexpectedly improved. The method realizes the high-value recycling of the brine and overcomes the problem of unsatisfactory wastewater discharge and recycling reaction stability.
The invention also provides application of the trithiocarbonate-based carboxylate prepared by the preparation method, and the trithiocarbonate-based carboxylate and a collector are combined for selective flotation recovery of copper sulfide ores.
The study of the present invention also found that the trithiocarbonate-based carboxylate salt was able to unexpectedly assist in the selective flotation of copper sulphide ores.
The further preferred application scheme of the invention combines the copper sulphide ore with a collector for selectively floating copper sulphide ores from mixed ores of copper sulphide ores and other sulphide ores;
the study of the invention shows that the trithiocarbonate-based carboxylate can be used for selectively floating copper sulfide ores from a system containing copper sulfide ores and other sulfide ores unexpectedly, and has excellent floatation selectivity.
Preferably, the other sulphide ore is at least one sulphide ore of lead and zinc.
In the invention, the trithiocarbonate carboxylate can be prepared by the preparation method directly and the solution thereof;
in the present invention, the collector is not particularly limited, and may be any collector capable of collecting copper sulfide, and may be at least one of a xanthate collector, a sulfur-nitrogen collector, a black-drug collector, a thiourethane collector, and MAC-12;
preferably, in the flotation stage, the amount of the trithiocarbonate carboxylate is 20-300 g/t, preferably 20-50 g/t, and the amount of the collector is 10-200 g/t, preferably 10-30 g/t;
preferably, the pH of the flotation stage is between 4 and 11; preferably 6 to 10, more preferably 7 to 10.
The study of the invention also shows that the flotation selectivity of copper sulfide ores and other sulfide ores can be unexpectedly further improved by further matching with the combined control of the pH value in the flotation stage with the assistance of the trithiocarbonate carboxylate.
Compared with the prior art, the technical scheme of the invention has the following beneficial effects:
(1) The innovative research of the invention shows that the aliphatic alcohol, potassium hydroxide and carbon disulfide are subjected to the xanthation reaction innovatively and then are subjected to the esterification reaction with halogenated carboxylic acid, the reaction conversion rate is high, and the excellent xanthate yield can be obtained by direct extraction without additional auxiliary treatment; more importantly, based on the preparation process, the potassium halide brine obtained as a byproduct can be recycled for the xanthogenic acid reaction and the subsequent esterification reaction, and can unexpectedly show excellent recycling reaction stability. In addition, the invention can be based on the thought of brine circulation, can co-produce a plurality of components such as xanthate, thiourethane, trithiocarbonate carboxylate and the like, and can realize zero discharge of wastewater in the preparation process.
(2) The technical scheme of the invention adopts a one-pot method for production, and can realize the efficient separation of various products through extraction, filtration and separation, thereby simplifying the process operation, avoiding the loss of raw materials and intermediate products and reducing the cost.
(3) The invention also co-produces the trithiocarbonate carboxylate, and further researches find that the trithiocarbonate carboxylate can assist the floatation of copper sulfide ores, and is beneficial to improving the floatation selectivity of copper sulfide ores and other sulfide ores. On the basis, the pH value of the flotation stage is further controlled, the flotation separation selectivity of copper sulfide ores and other sulfide ores is further synergistically improved by being combined with a medicament.
Drawings
FIG. 1 is a synthetic flow chart of the present invention;
FIG. 2 is an infrared spectrum of carboxyethyl trithiocarbonate synthesized in example 1
FIG. 3 is a mass spectrum of carboxyethyl trithiocarbonate synthesized in example 1
FIG. 4 is an infrared spectrum of O-isopropyl-N-ethylthiocarbamate synthesized in example 1
FIG. 5 is a nuclear magnetic resonance spectrum of O-tert-butyl-N-ethylthiocarbamate synthesized in example 4
FIG. 6 is a nuclear magnetic resonance spectrum of O-tert-butyl-N-ethylthiocarbamate synthesized in example 4
FIG. 7 is a flow chart of a flotation process according to example 8
FIG. 8 is a test result of copper-lead flotation separation in example 8
FIG. 9 is a flow chart of a copper lead ore flotation process in example 9
Detailed Description
The invention is further illustrated by, but not limited by, the following examples. All parts and percentages in the examples refer to mass unless otherwise specified.
In the present invention, the production scale is not particularly limited, and may be, for example, a laboratory scale, a pilot scale or a process scale, and examples of the embodiment include laboratory scale, that is, the "parts" are, for example, 10 to 100g by weight unless otherwise specified.
Example 1: synthesis of O-isopropyl-N-ethylthiocarbamate (Z-200) with co-production of Potassium 2-trithiocarbonate-based acetate
Step (1):
30.05 parts of isopropyl alcohol with the purity of 99%, 66.00 parts of KOH with the concentration of 50% (with the purity of 85%), 39.97 parts of carbon disulfide with the purity of 99%, fully stirring, controlling the reaction temperature to be 30 ℃, cooling to room temperature after 3 hours of reaction, adding 68.87 parts of chloroacetic acid with the concentration of 70% (with the purity of 98%) into a constant-pressure dropping funnel, heating to 80 ℃, cooling to room temperature after 2 hours of reaction, filtering to remove potassium chloride, and extracting filtrate by adopting ethionine to obtain an oil phase and a water phase;
step (2)
Transferring the oil phase in the step (1) to a reactor, adding 32.2 parts of ethylamine aqueous solution (with the purity of 65% -70%) into the reactor, heating to 70 ℃, cooling to room temperature after reacting for 1h, and obtaining O-isopropyl-N-ethyl thiocarbamate and an aqueous phase after oil-water separation;
step (3)
Transferring the water phase in the step (2) to a reactor, adding 41.88 parts of carbon disulfide with the purity of 99% and 36.31 parts of KOH (with the purity of 85%), heating to 30 ℃, and after 2 hours of reaction, obtaining the 2-potassium trithiocarbonate acetate.
Analysis showed that the O-isopropyl-N-ethylthiocarbamate product had a purity of 92.05%, a yield of 96.96% based on potassium isopropyl xanthate, a purity of 90.77% based on potassium 2-trithiocarbonate glycolate, and a product yield of 86.93% based on potassium isopropyl xanthate.
The water phase in the step (1) is used as alkali liquor, recycled to the step (1) and reused for the step (1) and subsequent reactions, and the reaction conditions in the recycling treatment process are the same as those in the step (1) and the step (2).
After one cycle, the purity of the O-isopropyl-N-ethyl thiocarbamate product was 90.11%, the yield based on potassium isopropyl xanthate was 92.32%, the purity of the potassium 2-trithiocarbonate-based acetate was 89.27%, and the yield based on potassium isopropyl xanthate was 85.74%.
After two cycles, the O-isopropyl-N-ethylthiocarbamate product had a purity of 91.45%, a yield of 93.66% based on potassium isopropylxanthate, and a potassium 2-trithiocarbonate-based acetate purity of 89.91%, and a product yield of 86.69% based on potassium isopropylxanthate.
After three cycles, the O-isopropyl-N-ethyl thiocarbamate product had a purity of 90.33%, a yield of 90.36% based on potassium isopropyl xanthate, and a purity of 88.98% based on potassium 2-trithiocarbonate-based acetate, and a product yield of 86.65% based on potassium isopropyl xanthate.
After four cycles, the O-isopropyl-N-ethylthiocarbamate product had a purity of 90.07%, a yield of 87.29% based on potassium isopropylxanthate, a potassium 2-trithiocarbonate-based acetate purity of 86.41%, and a product yield of 82.07% based on potassium isopropylxanthate.
The potassium 2-trithiocarbonate acetate is characterized by recrystallization, the infrared spectrum is shown in figure 2, and the mass spectrum is shown in figure 3. The O-isopropyl-N-ethyl thiocarbamate product is characterized by washing with saturated saline, distilling, separating and purifying, and the infrared spectrum is shown in figure 4.
TABLE 1 Infrared Spectrometry for O-isopropyl-N-ethylthiocarbamate
Table 22 Infrared Spectrometry of Potassium trithiocarbonate based acetate
Comparative example 1
The only difference compared to example 1 is that in step (1) the KOH was replaced with an equimolar amount of NaOH, and other operations and parameters were the same as in example 1 and based on the same verification of its recycling properties.
The results showed that the O-isopropyl-N-ethylthiocarbamate product had a purity of 90.33%, a yield of 89.35% based on sodium isopropyl xanthate, a purity of 88.05% of sodium 3-trithiocarbonate based acetate, and a product yield of 89.15% based on sodium isopropyl xanthate.
After one cycle, the purity of the O-isopropyl-N-ethyl thiocarbamate product was 57.13%, the yield based on sodium isopropyl xanthate was 42.02%, the purity of sodium 3-trithiocarbonate-based acetate was 50.06%, and the yield based on sodium isopropyl xanthate was 49.77%.
After two cycles, the purity of the O-isopropyl-N-ethyl thiocarbamate product was 28.12%, the yield based on sodium isopropyl xanthate was 20.05%, the purity of the sodium 3-trithiocarbonate group acetate was 30.03%, and the yield based on sodium isopropyl xanthate was 19.55%.
After three cycles, the purity of the O-isopropyl-N-ethyl thiocarbamate product was 15.46%, the yield based on sodium isopropyl xanthate was 12.63%, the purity of sodium 3-trithiocarbonate-based acetate was 10.05%, and the yield based on sodium isopropyl xanthate was 9.79%.
As can be seen from the above, sodium hydroxide is adopted to participate in the type-changing reaction, and the water circulation preparation performance is not ideal.
Comparative example 2
The only difference compared to example 1 is that in step 1, the chloroacetic acid is replaced with an equimolar amount of potassium chloroacetate. Wherein the operation and parameters are the same as in example 1.
Analysis showed that the O-isopropyl-N-ethylthiocarbamate product purity was 81.33% with a yield of 82.45% based on potassium isopropyl xanthate. It can be seen that the effect of the reaction is not as good as the present invention.
Example 2: synthesis of O-ethyl-N-ethylthiocarbamate with coproduction of potassium 4-trithiocarbonate butyrate
24.25 parts of ethanol with the purity of 95%, 66.00 parts of KOH with the concentration of 50% (with the purity of 85%), 39.97 parts of carbon disulfide with the purity of 99% are fully stirred, the reaction temperature is controlled to be 30 ℃, the reaction is carried out for 2 hours and then cooled to room temperature, then 85.79 parts of 4-chlorobutyric acid with the concentration of 70% (with the purity of 98%) are added into a constant pressure dropping funnel, the temperature is raised to 80 ℃, the reaction is carried out for 2.5 hours and then cooled to room temperature, potassium chloride is removed by filtration, the filtrate is extracted by adopting ethyl thiourethane, the oil phase is transferred into a reactor, 37.19 parts of ethylamine aqueous solution (with the purity of 65% -70%) is added into the reactor, the temperature is raised to 75 ℃, the reaction is carried out for 1 hour and then cooled to room temperature, after oil-water separation, O-ethyl-N-ethylthiocarbamic acid is obtained, the water phase is transferred into the reactor, 41.88 parts of 4-trithiocarbonate potassium butyrate is obtained after the reaction is completed by adding 36.31 parts of flaky KOH with the purity of 99% (with the purity of 85%) and the temperature raised to 30 ℃ for 2 hours. Analysis showed that the O-ethyl-N-ethylthiocarbamate product had a purity of 90.33%, a yield of 88.18% based on potassium ethylxanthate, a purity of 85.66% of potassium 4-trithiocarbonate-based butyrate, and a product yield of 89.49% based on potassium ethylxanthate.
Example 3: synthesis of O-ethyl-N-isopropyl thiocarbamate with coproduction of potassium 2-trithiocarbonate-based acetate
24.25 parts of ethanol with the purity of 95%, 66.00 parts of KOH with the concentration of 50% (with the purity of 85%), 39.97 parts of carbon disulfide with the purity of 99% are fully stirred, the reaction temperature is controlled to be 25 ℃, the mixture is cooled to room temperature after being reacted for 3 hours, 68.87 parts of chloroacetic acid with the concentration of 70% (with the purity of 98%) is added into a constant pressure dropping funnel, the mixture is heated to 80 ℃, the mixture is cooled to room temperature after being reacted for 2.5 hours, potassium chloride is removed by filtration, the filtrate is extracted by adopting ethyl thiourethane, an oil phase is transferred into a reactor, 30.16 parts of isopropylamine (with the purity of 98%) is added into the reactor, the mixture is heated to 85 ℃, the mixture is cooled to room temperature after being reacted for 2 hours, O-ethyl-N-isopropyl thiocarbamate is obtained after being separated from oil and water, the water phase is transferred into the reactor, 41.88 parts of carbon disulfide with the purity of 99% and 36.31 parts of KOH (with the purity of 85%) are added, the mixture is heated to 40 ℃, the reaction is finished after 2 hours, and the reaction is finished to obtain 2-trithiocarbonate potassium acetate. Analysis showed 92.19% purity of the O-ethyl-N-isopropylthiocarbamate product, 96.11% yield based on potassium ethylxanthate, 89.08% purity of the 2-trithiocarbonate potassium acetate, and 90.80% yield based on potassium ethylxanthate.
Example 4: synthesis of O-tert-butyl-N-ethylthiocarbamate with coproduction of potassium 2-trithiocarbonate-based acetate
37.06 parts of tertiary butanol with the purity of 99 percent, 66.00 parts of KOH with the concentration of 50 percent (with the purity of 85 percent), 39.97 parts of carbon disulfide with the purity of 99 percent are fully stirred, the reaction temperature is controlled to be 30 ℃, the reaction is carried out for 3 hours and then cooled to room temperature, then 68.87 parts of chloroacetic acid with the concentration of 70 percent (with the purity of 98 percent) is added by a constant pressure dropping funnel, the temperature is raised to 75 ℃, the reaction is cooled to the room temperature after 2.5 hours, the potassium chloride is removed by filtration, the filtrate is extracted by adopting ethyl thiourethane, the oil phase is transferred to a reactor, 32.2 parts of ethylamine aqueous solution (with the purity of 65-70 percent) is added into the reactor, the temperature is raised to 80 ℃ for 2.5 hours, the reaction is cooled to the room temperature after the reaction is carried out, the O-tertiary butyl-N-ethyl thiocarbamate is obtained after the oil-water separation, 41.88 parts of carbon disulfide with the purity of 99 percent and 36.31 parts of KOH (with the purity of 85 percent) are heated to 40 ℃, and the reaction is finished after 2 hours of reaction, so as to obtain the 2-trithiocarbonate potassium acetate. Analysis showed that the O-butyl-N-butylthiocarbamate product had a purity of 91.86%, a yield of 90.65% based on potassium butylxanthate, and a potassium 2-trithiocarbonate-based acetate purity of 91.05%, and a product yield of 89.78% based on potassium butylxanthate. Washing O-tert-butyl-N-ethyl thiocarbamate product with saturated saline solution, distilling, separating and purifying, and characterizing the nuclear magnetism 1 H、 13 The C spectrum is shown in FIG. 5.
TABLE 3 Nuclear magnetic resonance Spectrometry
Example 5: synthesis of O-butyl-N-propyl thiocarbamate with co-production of potassium 2-trithiocarbonate-based acetate
37.06 parts of N-butanol with the purity of 99%, 66.00 parts of KOH with the concentration of 50% (with the purity of 85%), 38.15 parts of carbon disulfide with the purity of 99% are fully stirred, the reaction temperature is controlled to be 30 ℃, the mixture is cooled to room temperature after being reacted for 3 hours, 68.87 parts of chloroacetic acid with the concentration of 70% (with the purity of 98%) is added into the mixture by a constant pressure dropping funnel, the mixture is heated to 75 ℃, the mixture is cooled to room temperature after being reacted for 2.5 hours, potassium chloride is removed by filtration, the filtrate is extracted by using ethyl thiourethane, an oil phase is transferred into a reactor, 30.16 parts of N-propylamine (with the purity of 98%) is added into the reactor, the mixture is heated to 70 ℃, the mixture is cooled to the room temperature after being reacted for 3 hours, O-butyl-N-propylthiocarbamate is obtained after being separated from oil and water, the water phase is transferred into the reactor, 41.88 parts of carbon disulfide with the purity of 99% and 36.31 parts of KOH (with the purity of 85%) are heated to 35 ℃, the mixture is heated to 35 ℃, the reaction is finished after 2 hours, and the reaction is finished, so that 2-trithiocarbonate potassium acetate is obtained. Analysis showed that the purity of the O-butyl-N-propylthiocarbamate product was 89.95%, the yield based on potassium butylxanthate was 93.22%, the purity of the potassium 2-trithiocarbonate-based acetate was 90.14%, and the yield based on potassium butylxanthate was 85.18%.
Example 6: synthesis of O-isobutyl-N-propylthiocarbamate with coproduction of potassium 2-trithiocarbonate-based acetate
37.06 parts of isobutanol with the purity of 99 percent, 66.00 parts of KOH with the concentration of 50 percent (with the purity of 85 percent), 39.97 parts of carbon disulfide with the purity of 99 percent are fully stirred, the reaction temperature is controlled to be 30 ℃, the reaction is carried out for 3 hours and then cooled to room temperature, then 68.87 parts of chloroacetic acid with the concentration of 70 percent (with the purity of 98 percent) is added by a constant pressure dropping funnel, the temperature is raised to 80 ℃, the reaction is carried out for 3 hours and then cooled to room temperature, potassium chloride is removed by filtration, the ethyl thiourethane extraction filtrate is adopted, the oil phase is transferred to a reactor, 36.94 parts of N-propylamine (with the purity of 99 percent) is added to the reactor, the temperature is raised to 80 ℃, the reaction is carried out for 3 hours and then cooled to the room temperature, O-isobutyl-N-propyl thiocarbamate is obtained after oil-water separation, the water phase is transferred to the reactor, 41.88 parts of carbon disulfide with the purity of 99 percent and 36.31 parts of KOH (with the purity of 85 percent) are added, the temperature is raised to 30 ℃, and the reaction is finished after 3 hours, and the reaction is finished to obtain the 2-trithiocarbonate potassium acetate. Analysis showed 91.07% purity of O-isobutyl-N-propylthiocarbamate product, 92.97% yield based on potassium isobutyl xanthate, 90.55% purity of potassium 2-trithiocarbonate-based acetate, 86.63% yield based on potassium isobutyl xanthate.
Example 7: synthesis of O-isobutyl-N-isobutyl thiocarbamate with coproduction of potassium 2-trithiocarbonate-based acetate
37.06 parts of isobutanol with the purity of 99 percent, 66.00 parts of KOH with the concentration of 50 percent (with the purity of 85 percent), 38.15 parts of carbon disulfide with the purity of 99 percent are fully stirred, the reaction temperature is controlled to be 30 ℃, the reaction is carried out for 2 hours and then cooled to room temperature, then 69.21 parts of 2-chloropropionic acid with the concentration of 80 percent (with the purity of 98 percent) is added by a constant pressure dropping funnel, the temperature is raised to 90 ℃, the reaction is carried out for 3 hours and then cooled to room temperature, potassium chloride is removed by filtration, the filtrate is extracted by adopting ethyl thiourethane, the oil phase is transferred to a reactor, 36.94 parts of isobutylamine with the purity of 99 percent is added to the reactor, the temperature is raised to 90 ℃, the reaction is carried out for 3 hours and then cooled to the room temperature, O-isobutyl-N-isopropyl thiocarbamate is obtained after oil-water separation, the water phase is transferred to the reactor, 41.88 parts of carbon disulfide with the purity of 99 percent and 36.31 parts of flaky KOH with the purity of 85 percent are added, the temperature is raised to 30 ℃, and the reaction is finished after 3 hours, and the reaction is finished to obtain the potassium 2-trithiocarbonate acetate. Analysis showed that the O-isobutyl-N-isopropylthiocarbamate product had a purity of 90.05%, a yield of 93.32% based on potassium isobutyl xanthate, a purity of 87.28% based on potassium 2-trithiocarbonate-based acetate, and a product yield of 84.71% based on potassium isobutyl xanthate.
Example 8: flotation separation of copper sulfide lead ore by 2-trithiocarbonate potassium acetate
The rotation speed of the flotation machine is 1650r/min, copper sulfide lead ore with the granularity of 0.074mm to 0.038mm is subjected to flotation, and the flotation process flow is shown in figure 7. The dosage of the 2-trithiocarbonate potassium acetate is 30mg/L, the dosage of the Z-200 is 20mg/L, the dosage of the pinitol oil is 10mg/L, the mixture is stirred for 30 seconds and then aerated for 30 seconds, the floatation time is 3 minutes, the pH of ore pulp is changed, the recovery rate of each mineral component is calculated when the pH of different ore pulp is calculated, and the result is shown in figure 8. As shown in FIG. 8, the potassium 2-trithiocarbonate-based acetate has a strong inhibiting effect on lead ores at a pH > 4. When the pH of the ore pulp is 8.2, the chalcopyrite flotation recovery rate in the foam product is 85.65%, and the galena recovery rate is 9.35%. The flotation separation of two minerals under the low alkalinity condition is realized.
Example 9: flotation separation of copper sulfide lead ore by 2-trithiocarbonate potassium acetate
The grade of copper in the ore is 0.55% and the grade of lead is 2.21% in a copper-lead ore sample in Jiangxi province. The experimental procedure is as follows: the fineness of the ground ore is 65% of-200 meshes, the ore dressing flow of one roughing and one scavenging is carried out, the lime consumption is 1200g/t, the flotation process flow chart is shown in figure 9, and the flotation result is shown in table 4. From the table, the actual copper-lead ore is selected by using the 2-trithiocarbonate potassium acetate, and the flotation index is better than that of the traditional inhibitor.
Table 4 example 11 flotation test results
In conclusion, the trithiocarbonate-based carboxylate provided by the invention can assist a collector to selectively collect copper sulfide ores and improve the flotation selectivity of copper sulfide ores and other sulfide ores.
Claims (10)
1. A method for preparing xanthate by brine circulation, which is characterized by comprising the following steps:
step (1):
carrying out xanthation reaction on a raw material solution containing fatty alcohol, potassium hydroxide, carbon disulfide and water;
step (2):
adding halogenated carboxylic acid into the reaction system of the step (1) for esterification reaction, and then separating oil from water to obtain xanthate and potassium halide brine;
step (3):
the potassium halide water is directly recycled to the step (1) or is recycled to the preparation of xanthate after solid-liquid separation.
2. The method of claim 1, wherein the fatty alcohol has the formula R 1 OH, wherein said R 1 Is C 1 ～C 8 Alkyl of (a);
preferably, the amount of the substances of the fatty alcohol, the potassium hydroxide and the carbon disulfide is 1:1-2:1-2, preferably 1:1-1.2:1-1.2;
preferably, in the raw material solution, the initial concentration of potassium hydroxide is 20% -50%;
preferably, the reaction temperature is 10-50 ℃, preferably 20-30 ℃ and the reaction time is 0.5-5 h.
3. The process of claim 1 wherein in step (2), the halogenated carboxylic acid has the formula XR 2 COOH；
Preferably, said R 2 Is C 1 ～C 8 X is halogen, preferably Cl;
preferably, the halocarboxylic acid is 1 to 1.5 times, preferably 1 to 1.2 times the amount of fatty alcohol material;
preferably, in the step (2), the reaction temperature is 50-100 ℃;
preferably, in step (2), the reaction time is 1 to 8 hours.
4. The method according to claim 1, wherein the number of brine cycles is more than 2, preferably more than 3, further 3-6.
5. A method for preparing thiourethane by brine circulation, which is characterized in that xanthate is prepared by adopting the method of any one of claims 1-4 in a circulating way, and then the xanthate and fatty amine are subjected to ammonolysis reaction, and oil-water separation is carried out, so as to obtain the thiourethane and mercapto acid compound aqueous solution.
6. The method of claim 5, wherein the fatty amine has the formula R 3 -NH 2 Wherein R is 3 Is C 1 ～C 8 Alkyl of (a);
preferably, the fatty amine is 1 to 1.5 times, preferably 1 to 1.2 times the amount of xanthate material;
preferably, the ammonolysis reaction temperature is 30-100 ℃, and the reaction time is preferably 1-5 h.
7. A method for preparing thiourethane and co-producing trithiocarbonate carboxylate by brine circulation, which is characterized in that the method of any one of claims 5-6 is adopted to prepare the thiourethane and obtain an aqueous solution of a mercapto acid compound;
adding caustic alkali and carbon disulfide into the aqueous solution of the mercapto acid compound to perform a second stage of xanthation reaction, and coproducing a solution containing trithiocarbonate carboxylate;
preferably, the mass ratio of the mercapto acid compound, caustic alkali and carbon disulfide is 1:1-2:1-2, preferably 1:1-1.2:1-1.2;
preferably, the caustic is sodium hydroxide and or potassium hydroxide;
preferably, the second stage xanthation reaction temperature is 5-80 ℃, and the reaction time is preferably 2-8 h.
8. Use of a trithiocarbonate-based carboxylate in combination with a collector for the selective flotation of copper sulphide ores.
9. Use of the trithiocarbonate-based carboxylate salt according to claim 8 in combination with a collector for selective flotation of copper sulphide ores from a mixture of copper sulphide ores and other sulphide ores;
preferably, the other sulfide ore is at least one ore of lead sulfide and zinc sulfide.
10. Use of a trithiocarbonate-based carboxylate according to claim 8 or 9, wherein the trithiocarbonate-based carboxylate is prepared according to claim 7 and solutions thereof;
preferably, the collector is a collector capable of collecting copper sulfide, preferably at least one of xanthate collector, sulfur-nitrogen collector, black agent collector, thiourethane collector and MAC-12;
preferably, in the flotation stage, the consumption of the trithiocarbonate carboxylate is 20-300 g/t, and the consumption of the collector is 10-200 g/t;
preferably, the pH of the flotation stage is between 4 and 11; preferably 6 to 10, more preferably 7 to 10.
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