CN111346664B - Modified vanadium-silicon molecular sieve, preparation method thereof and thioether oxidation method - Google Patents
Modified vanadium-silicon molecular sieve, preparation method thereof and thioether oxidation method Download PDFInfo
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- CN111346664B CN111346664B CN201811584264.0A CN201811584264A CN111346664B CN 111346664 B CN111346664 B CN 111346664B CN 201811584264 A CN201811584264 A CN 201811584264A CN 111346664 B CN111346664 B CN 111346664B
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- molecular sieve
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- 239000002808 molecular sieve Substances 0.000 title claims abstract description 300
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 title claims abstract description 300
- MANBDHUBXBMZNV-UHFFFAOYSA-N [V]=[Si] Chemical class [V]=[Si] MANBDHUBXBMZNV-UHFFFAOYSA-N 0.000 title claims abstract description 185
- 238000000034 method Methods 0.000 title claims abstract description 63
- 150000003568 thioethers Chemical class 0.000 title claims abstract description 49
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 25
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 238000002360 preparation method Methods 0.000 title abstract description 11
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 106
- 239000010703 silicon Substances 0.000 claims abstract description 106
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 84
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 79
- 239000011148 porous material Substances 0.000 claims abstract description 39
- 238000009826 distribution Methods 0.000 claims abstract description 32
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001301 oxygen Substances 0.000 claims abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 5
- 239000002253 acid Substances 0.000 claims description 48
- 238000002156 mixing Methods 0.000 claims description 48
- 239000003513 alkali Substances 0.000 claims description 45
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 44
- 238000010438 heat treatment Methods 0.000 claims description 43
- 239000007788 liquid Substances 0.000 claims description 35
- 239000000203 mixture Substances 0.000 claims description 28
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical group CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 claims description 24
- 150000003681 vanadium Chemical class 0.000 claims description 23
- 239000007800 oxidant agent Substances 0.000 claims description 22
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- 230000007062 hydrolysis Effects 0.000 claims description 21
- 238000006460 hydrolysis reaction Methods 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 20
- 239000002585 base Substances 0.000 claims description 18
- 230000001590 oxidative effect Effects 0.000 claims description 18
- 238000000926 separation method Methods 0.000 claims description 18
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000002904 solvent Substances 0.000 claims description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 16
- -1 aliphatic alcohol amine Chemical class 0.000 claims description 16
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 11
- 238000000862 absorption spectrum Methods 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 8
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 7
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical group N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 claims description 6
- 150000002978 peroxides Chemical group 0.000 claims description 6
- 230000000630 rising effect Effects 0.000 claims description 6
- 229910001935 vanadium oxide Inorganic materials 0.000 claims description 6
- 150000007522 mineralic acids Chemical class 0.000 claims description 5
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 4
- QKDGGEBMABOMMW-UHFFFAOYSA-I [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[V+5] QKDGGEBMABOMMW-UHFFFAOYSA-I 0.000 claims description 4
- AZFUOHYXCLYSQJ-UHFFFAOYSA-N [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [V+5].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O AZFUOHYXCLYSQJ-UHFFFAOYSA-N 0.000 claims description 4
- WAVVREKFUSALRV-UHFFFAOYSA-D [V+5].[V+5].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O Chemical compound [V+5].[V+5].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O WAVVREKFUSALRV-UHFFFAOYSA-D 0.000 claims description 4
- GLMOMDXKLRBTDY-UHFFFAOYSA-A [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O Chemical compound [V+5].[V+5].[V+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O GLMOMDXKLRBTDY-UHFFFAOYSA-A 0.000 claims description 4
- 150000007524 organic acids Chemical class 0.000 claims description 4
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 claims description 4
- 239000012002 vanadium phosphate Substances 0.000 claims description 4
- VLOPEOIIELCUML-UHFFFAOYSA-L vanadium(2+);sulfate Chemical compound [V+2].[O-]S([O-])(=O)=O VLOPEOIIELCUML-UHFFFAOYSA-L 0.000 claims description 4
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 150000002576 ketones Chemical class 0.000 claims description 3
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- 229910052814 silicon oxide Inorganic materials 0.000 claims description 3
- 239000002210 silicon-based material Substances 0.000 claims description 3
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 2
- 150000002894 organic compounds Chemical class 0.000 claims description 2
- 239000000377 silicon dioxide Substances 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 33
- 150000003457 sulfones Chemical class 0.000 abstract description 13
- 230000002349 favourable effect Effects 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 33
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 31
- 239000007864 aqueous solution Substances 0.000 description 28
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 26
- 238000002441 X-ray diffraction Methods 0.000 description 22
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 17
- 238000001035 drying Methods 0.000 description 16
- 229910001220 stainless steel Inorganic materials 0.000 description 16
- 239000010935 stainless steel Substances 0.000 description 16
- 238000005406 washing Methods 0.000 description 16
- 238000001914 filtration Methods 0.000 description 15
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 14
- 238000010587 phase diagram Methods 0.000 description 14
- 238000004537 pulping Methods 0.000 description 14
- 238000003756 stirring Methods 0.000 description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 238000010335 hydrothermal treatment Methods 0.000 description 10
- 125000000217 alkyl group Chemical group 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 6
- 238000007796 conventional method Methods 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 239000000741 silica gel Substances 0.000 description 6
- 229910002027 silica gel Inorganic materials 0.000 description 6
- HHVIBTZHLRERCL-UHFFFAOYSA-N sulfonyldimethane Chemical compound CS(C)(=O)=O HHVIBTZHLRERCL-UHFFFAOYSA-N 0.000 description 6
- 125000002947 alkylene group Chemical group 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
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- KFSLWBXXFJQRDL-UHFFFAOYSA-N Peracetic acid Chemical compound CC(=O)OO KFSLWBXXFJQRDL-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- 230000003068 static effect Effects 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
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- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 3
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- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 3
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 3
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical group CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
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- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910021552 Vanadium(IV) chloride Inorganic materials 0.000 description 2
- 125000001931 aliphatic group Chemical group 0.000 description 2
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- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
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- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 102000004877 Insulin Human genes 0.000 description 1
- 108090001061 Insulin Proteins 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- LUFPJJNWMYZRQE-UHFFFAOYSA-N benzylsulfanylmethylbenzene Chemical compound C=1C=CC=CC=1CSCC1=CC=CC=C1 LUFPJJNWMYZRQE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 238000010812 external standard method Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- SYECJBOWSGTPLU-UHFFFAOYSA-N hexane-1,1-diamine Chemical compound CCCCCC(N)N SYECJBOWSGTPLU-UHFFFAOYSA-N 0.000 description 1
- FGGJBCRKSVGDPO-UHFFFAOYSA-N hydroperoxycyclohexane Chemical compound OOC1CCCCC1 FGGJBCRKSVGDPO-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229940125396 insulin Drugs 0.000 description 1
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- CZPZWMPYEINMCF-UHFFFAOYSA-N propaneperoxoic acid Chemical compound CCC(=O)OO CZPZWMPYEINMCF-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- CMZUMMUJMWNLFH-UHFFFAOYSA-N sodium metavanadate Chemical compound [Na+].[O-][V](=O)=O CMZUMMUJMWNLFH-UHFFFAOYSA-N 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 description 1
- ZQZCOBSUOFHDEE-UHFFFAOYSA-N tetrapropyl silicate Chemical compound CCCO[Si](OCCC)(OCCC)OCCC ZQZCOBSUOFHDEE-UHFFFAOYSA-N 0.000 description 1
- HNKJADCVZUBCPG-UHFFFAOYSA-N thioanisole Chemical compound CSC1=CC=CC=C1 HNKJADCVZUBCPG-UHFFFAOYSA-N 0.000 description 1
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 description 1
- JBIQAPKSNFTACH-UHFFFAOYSA-K vanadium oxytrichloride Chemical compound Cl[V](Cl)(Cl)=O JBIQAPKSNFTACH-UHFFFAOYSA-K 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229940041260 vanadyl sulfate Drugs 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 229910000166 zirconium phosphate Inorganic materials 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C315/00—Preparation of sulfones; Preparation of sulfoxides
- C07C315/02—Preparation of sulfones; Preparation of sulfoxides by formation of sulfone or sulfoxide groups by oxidation of sulfides, or by formation of sulfone groups by oxidation of sulfoxides
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present disclosure relates to a modified vanadium silicon molecular sieve, a preparation method thereof and a thioether oxidation method, wherein the modified vanadium silicon molecular sieve comprises: vanadium element, silicon element and oxygen element, wherein the modified vanadium silicon molecular sieve satisfies X 1‑1.8 /X 0.4‑0.9 ＝A，0.2<A<0.5, preferably 0.25<A<0.45，X 1‑1.8 The ratio of the micropore diameter of the molecular sieve in the range of 1-1.8nm to the total micropore diameter distribution quantity, X 0.4‑0.9 Is the proportion of the pore diameter of the micropores of the molecular sieve in the range of 0.4-0.9nm in the total pore diameter distribution. The modified vanadium-silicon molecular sieve provided by the disclosure has a special physicochemical characteristic structure, is used for thioether oxidation reaction, is favorable for improving thioether conversion rate, and is favorable for modulating the selectivity of a target product sulfone.
Description
Technical Field
The disclosure relates to the field of molecular sieves, in particular to a modified vanadium-silicon molecular sieve, a preparation method thereof and a thioether oxidation method.
Background
The vanadium-silicon molecular sieve is a molecular sieve with a framework composed of silicon, vanadium and oxygen elements. The vanadium-silicon molecular sieve has wide application prospect in petroleum refining and petrochemical industry.
CN1500729A discloses a vanadium-siliconThe preparation method of the molecular sieve comprises the following steps: (SiO) 4 )n·(VO 4 ) m and n/m are 30-200, ammonium vanadate is used as a vanadium source, silica sol is used as a silicon source, tetraethylammonium hydroxide or tetrapropylammonium hydroxide is used as a template agent, wherein the molar ratio of the materials in the molecular sieve precursor is as follows: siO 2 2 ∶VO 3 ∶OH-∶H 2 O = 1: x: y: 10-100, wherein the value range of x is 0.005-0.05, and the value range of y is 0.1-0.6; the reaction mixture is firstly aged for 1 to 48 hours at the temperature of between 50 and 110 ℃, then hydrothermal crystallization is carried out for 20 to 120 hours under the conditions that the crystallization reaction temperature is between 150 and 200 ℃ and the normal pressure is between 0.05MPa, then a crystallization product is separated, and the vanadium-silicon molecular sieve is prepared by washing, drying and roasting.
CN104512900A discloses a method for preparing a vanadium-silicon molecular sieve, which is characterized by comprising the following steps: (1) Contacting a vanadium source with a template to obtain a mixture containing the vanadium source and the template; (2) Mixing and contacting the mixture containing the vanadium source and the template agent in the step (1) with a silicon molecular sieve to obtain a mixture; (3) And (3) carrying out hydrothermal treatment on the mixture obtained in the step (2) under the hydrothermal crystallization condition, and then obtaining the vanadium-silicon molecular sieve from the recovered product.
Although the vanadium-silicon molecular sieve can be prepared by the prior art, the catalytic performance of the vanadium-silicon molecular sieve is poor, so that the application of the vanadium-silicon molecular sieve is limited.
Sulfones are important sulfur-containing compounds, such as dimethyl sulfone, which is a white crystalline powder, readily soluble in water, ethanol, benzene, methanol and acetone, and slightly soluble in ethers. Dimethyl sulfone is industrially used as a high-temperature solvent and raw material for organic synthesis, a gas chromatography stationary liquid, an analytical reagent, a food additive, and a drug. Dimethyl sulfone, as an organic sulfide, has the functions of enhancing the human body's ability to produce insulin, and promoting the metabolism of saccharides, and is an essential substance for the synthesis of human collagen.
At present, the sulfone can be prepared by a thioether oxidation method, and when the thioether is oxidized by an oxidizing agent (especially peroxide), the oxidation product is mainly a mixture of sulfoxide and sulfone. Therefore, modulating the selectivity of the target product according to the production needs is an important research content in the thioether oxidation process.
Disclosure of Invention
The purpose of the disclosure is to provide a modified vanadium silicalite molecular sieve, a preparation method thereof and a thioether oxidation method, wherein the modified vanadium silicalite molecular sieve is used for catalyzing thioether oxidation reaction and can effectively improve the selectivity of sulfone.
To achieve the above object, a first aspect of the present disclosure: providing a modified vanadium silicalite molecular sieve, the modified vanadium silicalite molecular sieve comprising: vanadium element, silicon element and oxygen element, wherein the modified vanadium silicon molecular sieve satisfies X 1-1.8 /X 0.4-0.9 ＝A，0.2<A<0.5, preferably 0.25<A<0.45，X 1-1.8 The ratio of the micropore diameter of the molecular sieve in the range of 1-1.8nm to the total micropore diameter distribution quantity, X 0.4-0.9 Is the ratio of the pore diameter of the micropores of the molecular sieve in the range of 0.4-0.9nm to the distribution quantity of the total pore diameter.
Optionally, the modified vanadium silicon molecular sieve satisfies I 960 /I 800 ＝B，0.2<B<0.6，I 960 The infrared absorption spectrum of the molecular sieve is 960cm -1 Absorption intensity in the vicinity, I 800 The infrared absorption spectrum of the molecular sieve is 800cm -1 Absorption intensity in the vicinity, preferably, 0.25<B<0.55。
Optionally, the modified vanadium silicon molecular sieve satisfies T w /T k ＝C，0.5<C<0.9，T w Is the micropore volume of the molecular sieve, T k Is the total pore volume of the molecular sieve, preferably, 0.55<C<0.85。
Optionally, the molar ratio of the silicon element to the vanadium element of the modified vanadium-silicon molecular sieve is 100: (0.1-10), preferably 100: (0.2-5).
Optionally, the surface silicon-vanadium ratio of the modified vanadium-silicon molecular sieve is not lower than the bulk silicon-vanadium ratio, wherein the silicon-vanadium ratio refers to the molar ratio of silicon oxide to vanadium oxide;
preferably, the ratio of the surface silicon-vanadium ratio to the bulk silicon-vanadium ratio is 1.1-2;
further preferably, the ratio of the surface silicon-vanadium ratio to the bulk silicon-vanadium ratio is 1.2-1.8.
Optionally, the modified vanadium silicon molecular sieve is a molecular sieve of MFI structure, a molecular sieve of BEA structure, a molecular sieve of MEL structure, or a molecular sieve of MOR structure.
In a second aspect of the present disclosure: there is provided a process for preparing a modified vanadium silicalite molecular sieve according to the first aspect of the disclosure, the process comprising:
(1) Mixing the vanadium-silicon molecular sieve with first heat treatment liquid, carrying out first heat treatment for 0.5-360h at 40-200 ℃, and then carrying out solid-liquid separation on the obtained mixture to obtain a first solid, wherein the first heat treatment liquid is an acid solution with the concentration of 0.1-10 mol/L;
(2) Mixing the first solid with a second heat treatment liquid, and carrying out second heat treatment at 100-200 ℃ for 0.5-96h, wherein the second heat treatment liquid contains a silicon source, a vanadium source, an alkali source and water;
wherein, siO is used 2 And (3) calculating the molar ratio of the vanadium-silicon molecular sieve in the step (1) to the silicon source in the step (2) to be 100: (5-80), preferably 100: (10-50).
Optionally, the second heat treatment sequentially goes through a stage (1), a stage (2) and a stage (3), wherein the stage (1) is maintained at 100-140 ℃ for 2-24 hours, the stage (2) is heated to 180-200 ℃ for 0.1-12 hours, and the stage (3) is cooled to 140-180 ℃ for 4-24 hours; preferably, the temperature difference between stage (3) and stage (2) is at least 20 ℃, preferably 25-60 ℃; preferably, the temperature rising rate from room temperature to the stage (1) is 0.1-20 ℃/min, the temperature rising rate from the stage (1) to the stage (2) is 1-50 ℃/min, and the temperature falling rate from the stage (2) to the stage (3) is 1-20 ℃/min.
Alternatively, the vanadium-silicon molecular sieve: a vanadium source: acid: alkali source: the molar ratio of water is 100: (0.1-10): (0.005-50): (0.5-50): (20-1000), wherein the vanadium-silicon molecular sieve is SiO 2 In terms of H, the acid is + The alkali source is counted as N when containing nitrogen element, and the alkali source is counted as OH when not containing nitrogen element - Counting;
preferably, the vanadium-silicon molecular sieve is a molecular sieve with MFI structure, a molecular sieve with BEA structure, a molecular sieve with MEL structure or a molecular sieve with MOR structure; the acid is organic acid and/or inorganic acid; the alkali source is ammonia, aliphatic amine, aliphatic alcohol amine or quaternary ammonium base; the vanadium source is vanadium oxide, vanadium acid, vanadate, vanadium halide, vanadium carbonate, vanadium nitrate, vanadium sulfate, vanadium phosphate, vanadium hydroxide or organic compound, or the combination of two or three of the above.
Optionally, the silicon source is one or more selected from silicon-containing compounds shown in formula I;
in the formula I, R 1 、R 2 、R 3 And R 4 Each is a C1-C4 alkyl group;
preferably, the hydrolysis rate of the silicon source is 60-90%.
A third aspect of the disclosure: a method for oxidizing a thioether is provided, the method comprising: under the condition of thioether oxidation, enabling thioether, an oxidant and an optional solvent to contact with a catalyst to react, wherein the catalyst contains the modified vanadium silicalite molecular sieve of the first aspect of the disclosure;
preferably, the thioether is dimethyl sulfide and/or thioanisole, the oxidant is peroxide, and the solvent is water, C1-C6 alcohol, C3-C8 ketone or C2-C6 nitrile; the molar ratio of the thioether to the oxidant is 1: (0.1-10), the weight ratio of the thioether to the catalyst is 100: (0.2-50); the thioether oxidation conditions include: the temperature is 0-120 ℃, and the pressure is 0-5MPa in gauge pressure.
Through the technical scheme, the modified vanadium silicalite molecular sieve obtained by modifying the vanadium silicalite molecular sieve through specific modification steps (the steps of sequentially treating by using acid and alkali and combining with heat treatment and the like) has a special physicochemical characteristic structure, is favorable for the diffusion of reactant and product molecules in a catalytic reaction, has a better catalytic effect when used for a thioether oxidation reaction, and can effectively modulate the selectivity of a target product.
Additional features and advantages of the present disclosure will be set forth in the detailed description which follows.
Detailed Description
Specific embodiments of the present disclosure are described in detail below. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the disclosure: providing a modified vanadium silicalite molecular sieve, the modified vanadium silicalite molecular sieve comprising: vanadium element, silicon element and oxygen element, wherein the modified vanadium silicon molecular sieve satisfies X 1-1.8 /X 0.4-0.9 ＝A，0.2<A<0.5, preferably 0.25<A<0.45，X 1-1.8 The ratio of the micropore diameter of the molecular sieve in the range of 1-1.8nm to the total micropore diameter distribution quantity, X 0.4-0.9 Is the proportion of the pore diameter of the micropores of the molecular sieve in the range of 0.4-0.9nm in the total pore diameter distribution.
The modified vanadium-silicon molecular sieve provided by the disclosure has pore size distribution within the range of 0.4-0.9nm and also has distribution within the range of 1-1.8nm, the ratio of the proportion of the pore size distribution of micropores within the range of 1-1.8nm to the proportion of the pore size distribution of micropores within the range of 0.4-0.9nm to the pore size distribution of micropores within the range of 0.2 is A, and the ratio of the pore size distribution of vanadium-silicon molecular sieve to the pore size distribution of micropores within the range of 0.4-0.9nm is C<A<0.5, preferably, 0.25<A<0.45. When the modified vanadium-silicon molecular sieve adopting the preferable technical scheme disclosed by the disclosure is used for thioether oxidation reaction, the stable proceeding of catalytic reaction is facilitated, the diffusion of reactant and product molecules in the process is more gradual, and the catalytic selectivity of the catalyst is facilitated to play. Not only can further improve the conversion rate of raw materials, but also can more effectively modulate the selectivity of target products. In the present disclosure, the method for measuring the pore diameter of the micropores can be performed according to a conventional method, and the present disclosure has no special requirement and is well known to those skilled in the art, for example, using N 2 Static adsorption and the like.
It is to be noted here that, if the ratio of the pore size distribution of micropores to the total pore size distribution of micropores is in the range of 1 to 1.8nm, the ratio is<At 1%, the pore distribution of the micropores is negligible, i.e. no micropore distribution in the range of 1-1.8nm is considered, as known to the person skilled in the art. Thus, the disclosure is said to be in N 2 The pore diameter of the micropores in the range of 1-1.8nm in the static adsorption test means that the pore diameter distribution of the micropores in the range of 1-1.8nm accounts for the total pore diameterProportion of the distribution amount>1 percent. The microporous molecular sieve prepared by conventional direct hydrothermal synthesis has the ratio of the micropore size distribution to the total micropore size distribution in the range of 1-1.8nm<1 percent, the microporous molecular sieve which is treated and modified by a common treatment and modification method has lower proportion of the micropore size distribution in the total micropore size distribution within the range of 1-1.8nm, and is generally the microporous molecular sieve<1％。
Further, the modified vanadium-silicon molecular sieve can meet I 960 /I 800 ＝B，0.2<B<0.6，I 960 The infrared absorption spectrum of the molecular sieve is 960cm -1 Absorption intensity in the vicinity, I 800 The infrared absorption spectrum of the molecular sieve is 800cm -1 Absorption intensity in the vicinity, preferably, 0.25<B<0.55. Therefore, the method is more favorable for the diffusion of reactant and product molecules in the catalytic oxidation reaction, not only can further improve the conversion rate of raw materials, but also can more effectively modulate the selectivity of a target product. For example, when the catalyst is used in a thioether oxidation reaction, the conversion rate of thioether can be further improved, and the selectivity of the target product sulfone can be more effectively modulated.
In the present disclosure, the absorption intensity of the infrared absorption spectrum of the molecular sieve at a specific wave number and the pore size of the molecular sieve refer to the absorption intensity of the fourier transform infrared absorption spectrum of the molecular sieve at a specific wave number and the pore size in the molecular sieve, respectively, which are well known to those skilled in the art and are not described herein again.
In the present disclosure, the absorption intensity of the infrared absorption spectrum of the molecular sieve at a specific wave number is measured by using an infrared spectroscopy (IR), and the measurement method can be performed according to a conventional method, and the present disclosure has no special requirement, and is well known to those skilled in the art, and is not described herein in detail.
Further, the modified vanadium-silicon molecular sieve can meet T w /T k ＝C，0.5<C<0.9, preferably, 0.55<C<0.85, wherein, T w Is the micropore volume of the molecular sieve, T k Is the total pore volume of the molecular sieve. In the present disclosure, the pore volume can be measured by conventional methods, and the present disclosure is not particularly limited and is well known to those skilled in the art, e.g., by using N 2 Static adsorption and the like.
Further, the molar ratio of the silicon element to the vanadium element of the modified vanadium-silicon molecular sieve can be 100: (0.1-10), preferably 100: (0.2-5), more preferably 100: (0.5-4), more preferably 100: (1-4). In the present disclosure, the content of silicon and vanadium in the molecular sieve is measured by X-ray fluorescence spectroscopy (XRF). The test methods are performed according to conventional methods without special requirements, which are well known to those skilled in the art and will not be described herein.
Further, the surface silicon-vanadium ratio of the modified vanadium-silicon molecular sieve is not lower than the bulk silicon-vanadium ratio, wherein the silicon-vanadium ratio refers to the molar ratio of silicon oxide to vanadium oxide; preferably, the ratio of the surface silicon-vanadium ratio to the bulk silicon-vanadium ratio is 1.1-2; further preferably, the ratio of the surface silicon-vanadium ratio to the bulk silicon-vanadium ratio is 1.2-1.8. In the disclosure, the surface silicon-vanadium ratio is determined by an X-ray photoelectron spectroscopy method, and the bulk silicon-vanadium ratio is determined by an X-ray fluorescence spectroscopy method.
According to the present disclosure, the modified vanadium-silicon molecular sieve may be a molecular sieve of MFI structure, a molecular sieve of BEA structure, a molecular sieve of MEL structure, or a molecular sieve of MOR structure, etc.
In a second aspect of the present disclosure: there is provided a process for preparing a modified vanadium silicalite molecular sieve according to the first aspect of the disclosure, the process comprising:
(1) Mixing the vanadium-silicon molecular sieve with first heat treatment liquid, carrying out first heat treatment for 0.5-360h at 40-200 ℃, and then carrying out solid-liquid separation on the obtained mixture to obtain a first solid, wherein the first heat treatment liquid is an acid solution with the concentration of 0.1-10 mol/L;
(2) Mixing the first solid with a second heat treatment liquid, and carrying out second heat treatment at 100-200 ℃ for 0.5-96h, wherein the second heat treatment liquid contains a silicon source, a vanadium source, an alkali source and water;
wherein, siO is used 2 And (3) calculating the molar ratio of the vanadium-silicon molecular sieve in the step (1) to the silicon source in the step (2) to be 100: (5-80).
In the preparation method of the modified vanadium-silicon molecular sieve provided by the disclosure, the prepared modified vanadium-silicon molecular sieve can be adjusted by adjusting the adding amount of the silicon source in the step (2)The prepared modified vanadium-silicon molecular sieve has the micropore diameter distribution when being made of SiO 2 And (3) calculating the molar ratio of the vanadium-silicon molecular sieve in the step (1) to the silicon source in the step (2) to be 100: (10-50), the modified V-Si molecular sieve can satisfy X 1-1.8 /X 0.4-0.9 ＝A，0.2<A<0.5。
According to the disclosure, the type of the prepared modified vanadium-silicon molecular sieve is determined by the variety of the initial vanadium-silicon molecular sieve, the variety of the alkali source, the material ratio and other factors. The vanadium-silicon molecular sieve refers to an unmodified vanadium-silicon molecular sieve, which can be a fresh vanadium-silicon molecular sieve or an inactivated vanadium-silicon molecular sieve, and can be obtained by commercial purchase or self-synthesis. The vanadium-silicon molecular sieve is not particularly limited in the present disclosure, and can be common vanadium-silicon molecular sieves with various topologies, such as: the silicon molecular sieve can be selected from one or more of a vanadium silicon molecular sieve with an MFI structure, a vanadium silicon molecular sieve with an MEL structure, a vanadium silicon molecular sieve with a BEA structure, a vanadium silicon molecular sieve with an MWW structure, a vanadium silicon molecular sieve with a hexagonal structure, a vanadium silicon molecular sieve with an MOR structure, a vanadium silicon molecular sieve with a TUN structure and vanadium silicon molecular sieves with other structures. Preferably, the vanadium-silicon molecular sieve is selected from one or more of a vanadium-silicon molecular sieve of an MFI structure, a vanadium-silicon molecular sieve of an MEL structure and a vanadium-silicon molecular sieve of a BEA structure. More preferably, the vanadium silicalite molecular sieve is a vanadium silicalite molecular sieve of MFI structure, such as S-1 molecular sieve.
According to the present disclosure, the first heat treatment of step (1) and the second heat treatment of step (2) are generally performed under autogenous pressure in a sealed condition without specific description.
According to the present disclosure, it is preferred that the temperature of the first heat treatment is 40 to 200 ℃, more preferably 50 to 180 ℃, and still more preferably 60 to 180 ℃. The time of the first heat treatment is preferably 1 to 240 hours, more preferably 2 to 120 hours.
According to the present disclosure, it is preferred that the temperature of the second heat treatment is 120 to 180 ℃, more preferably 140 to 170 ℃. The time of the second heat treatment is preferably 2 to 48 hours, more preferably 6 to 24 hours.
In the preferred case of the present disclosure, in the second heat treatment process, the specific stages (1), (2) and (3) are adopted, and the obtained modified vanadium silicalite molecular sieve is used for the reaction of thioether oxidation, which is more beneficial to effectively modulating the selectivity of the target product.
Thus, according to a preferred embodiment of the present disclosure, the second heat treatment is carried out in succession in stages (1), (2) and (3), stage (1) being carried out at 100-140 ℃, preferably at 125-140 ℃, stage (2) being carried out at elevated temperature to 180-200 ℃ and stage (3) being carried out at reduced temperature to 140-180 ℃, preferably 140-170 ℃.
Further, the temperature difference between stage (3) and stage (2) is at least 20 ℃, preferably 25-60 ℃.
Further, the temperature rising rate from the room temperature to the stage (1) is 0.1-20 ℃/min, preferably 2-10 ℃/min; the temperature rising rate from the stage (1) to the stage (2) is 1-50 ℃/min, preferably 15-20 ℃/min; the cooling rate from the stage (2) to the stage (3) is 1-20 ℃/min, more preferably 10-20 ℃/min.
Further, it is preferable that the maintenance time of the stage (1) is 2 to 24 hours, preferably 4 to 16 hours; the maintenance time of stage (2) is 0.1 to 12 hours, preferably 2 to 6 hours; the holding time of stage (3) is 4 to 24 hours, preferably 4 to 12 hours.
According to the present disclosure, preferably, in SiO 2 And (3) calculating the molar ratio of the vanadium-silicon molecular sieve in the step (1) to the silicon source in the step (2) to be 100: (10-50). The adoption of the preferred embodiment of the disclosure is more beneficial to adjusting the micropore size distribution of the prepared modified vanadium silicalite molecular sieve, and the prepared modified vanadium silicalite molecular sieve can obtain a more stable catalytic effect when being used in a thioether oxidation reaction process.
Preferably, according to the disclosure, the vanadium silicalite molecular sieve: a vanadium source: acid: alkali source: the molar ratio of water is 100: (0.1-10): (0.005-50): (0.5-50): (20-1000), further preferably the vanadium silicalite molecular sieve: a vanadium source: acid: alkali source: the molar ratio of water is 100: (0.5-2.0): (1-15): (1-20): (100-800), wherein the vanadium-silicon molecular sieve is SiO 2 In terms of H, the acid is + The alkali source is counted as N when containing nitrogen element, and the alkali source is counted as OH when not containing nitrogen element - And (6) counting.
According to the present disclosure, the acid may be selected from a wide range of species, which may be organic and/or inorganic acids, preferably inorganic acids; wherein, the inorganic acid can be one or more of hydrochloric acid, sulfuric acid, perchloric acid, nitric acid and phosphoric acid, and is preferably phosphoric acid; the organic acid can be C1-C10 organic carboxylic acid, preferably one or more of formic acid, acetic acid, propionic acid, naphthenic acid peroxyacetic acid and peroxypropionic acid. The concentration of the acid solution is 0.1 to 10mol/L, preferably 1 to 8mol/L, and more preferably 1 to 5mol/L. In the present disclosure, the main solvent of the acid solution is water, and other solvents may be added as needed. The pore volume and the micropore distribution characteristics of the modified vanadium-silicon molecular sieve prepared in the way are more obvious in 1-1.8 nm.
The silicon source is not particularly limited in the present disclosure, and may be any substance capable of providing silicon element in the art, for example, the silicon source may be an organic silicon source and/or an inorganic silicon source.
Specifically, the organic silicon source may be one or more selected from silicon-containing compounds represented by formula I,
in the formula I, R 1 、R 2 、R 3 And R 4 Each C1-C4 alkyl, including C1-C4 straight chain alkyls and C3-C4 branched chain alkyls, such as: r 1 、R 2 、R 3 And R 4 Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl. Specifically, the organic silicon source may be tetramethyl orthosilicate, tetraethyl orthosilicate, tetra-n-propyl orthosilicate, or tetra-n-butyl orthosilicate.
The optional range of the types of the inorganic silicon source is wide, and for the present disclosure, the inorganic silicon source is preferably silica sol and/or silica gel, and the silica gel or silica sol in the present disclosure may be silica gel or silica sol obtained by various production methods in various forms.
According to the present disclosure, preferably the silicon source is an organic silicon source; further, the hydrolysis rate of the organic silicon source is 60-90%. Thus, the catalytic performance of the prepared modified vanadium-silicon molecular sieve can be further improved.
According to the present disclosure, the alkali source may be an organic alkali source and/or an inorganic alkali source, wherein the inorganic alkali source may be ammonia, an alkali whose cation is an alkali metal, or an alkali whose cation is an alkaline earth metal, such as sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate, barium hydroxide, etc., and the organic alkali source may be urea, an aliphatic amine compound, an aliphatic alcohol amine compound, or a quaternary ammonium alkali compound.
In the present disclosure, the quaternary ammonium base can be various organic quaternary ammonium bases and the aliphatic amine can be various NH 3 In which at least one hydrogen is substituted with an aliphatic hydrocarbon group (preferably an alkyl group), which may be a variety of NH 3 In which at least one hydrogen is substituted with a hydroxyl-containing aliphatic hydrocarbon group (preferably an alkyl group).
Specifically, the quaternary ammonium base may be a quaternary ammonium base represented by formula II, the aliphatic amine may be an aliphatic amine represented by formula III, and the aliphatic alcohol amine may be an aliphatic alcohol amine represented by formula IV:
in the formula II, R 5 、R 6 、R 7 And R 8 Each C1-C4 alkyl, including C1-C4 straight chain alkyls and C3-C4 branched chain alkyls, such as: r 5 、R 6 、R 7 And R 8 Each may be methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl or tert-butyl.
R 9 (NH 2 ) n (formula III)
In the formula III, n is an integer of 1 or 2. When n is 1, R 9 Is C1-C6 alkyl, including C1-C6 straight-chain alkyl and C3-C6 branched-chain alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutylAlkyl, tert-butyl, n-pentyl, neopentyl, isopentyl, tert-pentyl and n-hexyl. When n is 2, R 9 Is C1-C6 alkylene, including C1-C6 linear alkylene and C3-C6 branched alkylene, such as methylene, ethylene, n-propylene, n-butylene, n-pentylene, or n-hexylene. More preferably, the aliphatic amine compound is ethylamine, n-butylamine, butanediamine or hexamethylenediamine, or a combination of two or three thereof.
(HOR 10 ) m NH (3-m) (formula IV)
In the formula IV, m are R 10 Identical or different, are each C1-C4 alkylene, including C1-C4 linear alkylene and C3-C4 branched alkylene, such as methylene, ethylene, n-propylene and n-butylene; m is 1, 2 or 3. More preferably, the aliphatic alcohol amine compound is monoethanolamine, diethanolamine or triethanolamine, or a combination of two or three thereof.
According to the disclosure, in order to further improve the pore channel order of the synthesized modified vanadium-silicon molecular sieve, the alkali source is preferably selected from sodium hydroxide, ammonia water, ethylenediamine, n-butylamine, butanediamine, hexanediamine, monoethanolamine, diethanolamine, triethanolamine, tetraethylammonium hydroxide or tetrapropylammonium hydroxide, or a combination of two or three of them. The alkali source is preferably provided in the form of an alkali solution, more preferably an alkali solution having a pH >9.
According to the present disclosure, the vanadium source is a compound of various vanadium, for example, can be an oxide of vanadium, vanadic acid (HVO) 3 ) Orthovanadic acid (H) 3 VO 4 ) Pyrovanadic acid (H) 4 V 2 O 7 、H 3 V 3 O 9 ) Vanadate (corresponding salts of the aforementioned vanadic acid), vanadium halide, vanadium carbonate, vanadium nitrate, vanadium sulfate, vanadium phosphate, and vanadium hydroxide, including but not limited to sodium vanadate, ammonium metavanadate, vanadium pentoxide, vanadium oxytrichloride, potassium metavanadate, vanadyl sulfate, vanadium acetylacetonate, vanadium tetrachloride, and the like.
According to the present disclosure, preferably, the method of the present disclosure further comprises a step of recovering the product (i.e., the modified vanadium silicalite) from the material obtained in step (2). The step of recovering the product is a conventional method, is familiar to those skilled in the art, and is not particularly required herein, and generally refers to a process of filtering, washing, drying and calcining the product. Wherein, the drying process can be carried out at the temperature of between room temperature and 200 ℃, and the roasting process can be carried out at the temperature of between 300 and 800 ℃ in a nitrogen atmosphere for 0.5 to 6 hours and then in an air atmosphere for 3 to 12 hours.
A third aspect of the disclosure: a method for oxidizing a thioether is provided, the method comprising: under the condition of thioether oxidation, a thioether, an oxidant and an optional solvent are contacted with a catalyst to react, wherein the catalyst contains the modified vanadium silicalite molecular sieve disclosed by the first aspect of the disclosure.
In accordance with the present disclosure, the thioether can be a variety of compounds containing an-S-bond. The methods of the present disclosure can oxidize various thioethers to yield the corresponding sulfoxides and/or sulfones. Specifically, the thioether is preferably a thioether having 2 to 18 carbon atoms, such as dimethyl sulfide and/or benzyl sulfide.
In accordance with the present disclosure, the oxidizing agent may be any of a variety of substances commonly available that are capable of oxidizing thioethers. The method disclosed by the invention is particularly suitable for the occasion of oxidizing thioether by taking peroxide as an oxidizing agent, so that the effective utilization rate of the peroxide can be obviously improved. The peroxide is a compound containing an-O-O-bond in the molecular structure, and can be selected from hydrogen peroxide, organic peroxide and peracid. The organic peroxide is a substance obtained by substituting one or two hydrogen atoms in a hydrogen peroxide molecule with an organic group. The peracid refers to an organic oxyacid having an-O-O-bond in the molecular structure. Specific examples of the oxidizing agent in the present disclosure may include, but are not limited to: hydrogen peroxide, tert-butyl hydroperoxide, cumene peroxide, cyclohexyl hydroperoxide, peracetic acid and propionic acid. Preferably, the oxidizing agent is hydrogen peroxide, which further reduces the separation cost.
The hydrogen peroxide may be hydrogen peroxide in various forms commonly used in the art. From the viewpoint of further improving the safety of the method according to the present disclosure, the method according to the present disclosure preferably uses hydrogen peroxide in the form of an aqueous solution. In accordance with the methods of the present disclosure, when the hydrogen peroxide is provided as an aqueous solution, the concentration of the aqueous hydrogen peroxide solution may be a concentration conventional in the art, for example: 20-80 wt%. Aqueous solutions of hydrogen peroxide at concentrations meeting the above requirements may be prepared by conventional methods or may be obtained commercially, for example: can be 30 percent by weight of hydrogen peroxide, 50 percent by weight of hydrogen peroxide or 70 percent by weight of hydrogen peroxide which can be obtained commercially.
The amount of the oxidizing agent used may be conventionally selected according to the present disclosure, and is not particularly limited. Generally, the molar ratio of thioether to oxidant may be 1: (0.1-10), preferably 1: (0.2-5).
According to the method, the reaction speed can be adjusted through the content of the solvent, so that the reaction is more stable. The solvent may be various liquid substances capable of dissolving or promoting mixing of the thioether and the oxidizing agent and dissolving the target product. In general, the solvent may be selected from water, C1-C6 alcohols, C3-C8 ketones, and C2-C6 nitriles. Specific examples of the solvent may include, but are not limited to: water, methanol, ethanol, n-propanol, isopropanol, tert-butanol, isobutanol, acetone, butanone and acetonitrile. Preferably, the solvent is water. When water is used as a solvent, the selectivity of the target product sulfone can be effectively adjusted. The amount of the solvent to be used may be appropriately selected depending on the amounts of the thioether and the oxidizing agent to be used. Generally, the molar ratio of the solvent to the thioether may be (0.1-100): 1, preferably (0.2-80): 1.
according to the present disclosure, the amount of the catalyst may be appropriately selected according to the amounts of the thioether and the oxidant, for example, the weight ratio of the thioether to the catalyst may be 100: (0.2-50).
In accordance with the present disclosure, the thioether oxidation reaction conditions are dependent on the target product. In general, the thioether oxidation reaction can be carried out at a temperature of from 0 to 120 ℃ and preferably at a temperature of from 20 to 80 ℃; the pressure in the reactor may be in the range of 0 to 5MPa, preferably 0.1 to 3MPa, in terms of gauge pressure.
The method according to the present disclosure may further include separating the reaction mixture output from the fixed bed reactor to obtain the target product and unreacted reactants. The method for separating the reaction mixture may be a method conventionally selected in the art, and is not particularly limited. The separated unreacted reactant can be recycled.
The present disclosure is described in detail below with reference to examples, but the scope of the present disclosure is not limited thereby.
In the following examples and comparative examples, all reagents used were commercially available analytical grade reagents, and the pressures were measured by gauge pressure.
The pore volume and pore size distribution of the molecular sieve samples were measured on a Micromeritics company ASAP2405 static nitrogen adsorption apparatus; the composition of vanadium and silicon elements is measured on a 3271E type X-ray fluorescence spectrometer of Japan science and electronics Co., ltd; the surface silicon-vanadium ratio is measured by an ESCALB 250 type X-ray photoelectron spectrometer of Thermo Scientific company, and the bulk silicon-vanadium ratio is measured by a 3271E type X-ray fluorescence spectrometer of Japan science and electronics Co; fourier transform infrared absorption spectrum is measured on a Nicolet 8210 type Fourier infrared spectrometer, KBr tablets (the sample accounts for 1 wt%) are adopted under vacuum, and the test range is 400-1400cm -1 (ii) a X-ray diffraction (XRD) crystallographic phase diagram measurements were carried out on a Siemens D5005X-ray diffractometer. Specific data are shown in table 1.
The hydrolysis amount of the organic silicon source is measured by gas chromatography. The gas chromatograph used was an Agilent 6890N, equipped with thermal conductivity detectors TCD and a capillary column of HP-5 (30 m.times.320. Mu.m.times.25 μm). Wherein the injection port temperature is 180 ℃, the column temperature is 150 ℃, nitrogen is used as carrier gas, and the flow rate of the carrier gas is 25mL/min. The specific method comprises the following steps: and (3) taking a certain amount of mixture to be injected from an injection port of a gas chromatograph, flowing through a chromatographic column, detecting by using TCD (trichloroacetic acid) and quantifying by using an external standard method. Calculating the hydrolysis rate of the organic silicon source by adopting the following formula:
X organic silicon source ％＝[(m o Organic silicon source －m Organic silicon source )/m o Organic silicon source ]×100％
In the formula, X Organic silicon source The hydrolysis rate of the organic silicon source is shown; m is o Organic silicon source Represents the weight of the added organic silicon source; m is Organic silicon source The weight of the unhydrolyzed organic silicon source is indicated.
The v-si molecular sieve used in the examples was the MFI structure v-si molecular sieve prepared according to example 3 of CN1840477 a. The unmodified v-si molecular sieves used in the examples were used as reference.
Example 1
Mixing and pulping the vanadium-silicon molecular sieve and 1mol/L hydrochloric acid aqueous solution at normal temperature (20 ℃, the same in other examples and comparative examples) and normal pressure (0.1 MPa, the same in other examples and comparative examples), and then mixing and stirring the mixed pulp at 80 ℃ for 12 hours; after solid-liquid separation, mixing solid, vanadium source ammonium metavanadate, organic silicon source tetraethyl orthosilicate and sodium hydroxide aqueous solution (pH is 12), transferring the mixture into a stainless steel sealed reaction kettle after tetraethyl orthosilicate is hydrolyzed (hydrolysis rate is 80%), and treating for 12 hours at 170 ℃, wherein the vanadium-silicon molecular sieve: a vanadium source: an organic silicon source: acid: alkali: the molar ratio of water is 100:0.5:15:10:15:450, vanadium-silicon molecular sieve and organic silicon source are made of SiO 2 Measured as H, acid + Calculated as OH, base - And (6) counting. And filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and then roasting at 550 ℃ for 3h to obtain the modified vanadium-silicon molecular sieve S-1, wherein an XRD (X-ray diffraction) crystalline phase diagram of the modified vanadium-silicon molecular sieve S-1 shows that the modified vanadium-silicon molecular sieve is an MFI (melt flow index) structure molecular sieve.
Example 2
Mixing and pulping the vanadium-silicon molecular sieve and 5mol/L hydrochloric acid solution at normal temperature and normal pressure, and then mixing and stirring the mixed slurry at 60 ℃ for 2 hours; after solid-liquid separation, mixing solid, vanadium tetrachloride as a vanadium source, organic silicon source methyl orthosilicate and tetrapropyl ammonium hydroxide aqueous solution (pH is 10), transferring the mixture into a stainless steel sealed reaction kettle after methyl orthosilicate is hydrolyzed (hydrolysis rate is 90%), and treating for 12 hours at 150 ℃, wherein the vanadium-silicon molecular sieve: a vanadium source: an organic silicon source: acid: alkali: the molar ratio of water is 100:1:10:15:25:600 vanadium-silicon molecular sieve and organic silicon source made of SiO 2 Measured as H, acid + The base is calculated as N. Filtering the obtained product, washing with water, oven drying at 110 deg.C for 120min, and calcining at 550 deg.C for 3h to obtain the final productThe XRD crystal phase diagram of the vanadium-silicon molecular sieve S-2 shows that the vanadium-silicon molecular sieve is an MFI structure molecular sieve.
Example 3
Mixing and pulping a vanadium-silicon molecular sieve and 5mol/L aqueous solution of nitric acid at normal temperature and normal pressure, and then mixing and stirring the mixed pulp at 100 ℃ for 2 hours; after solid-liquid separation, mixing solid, vanadium source ammonium metavanadate, organic silicon source tetraethyl orthosilicate and sodium hydroxide aqueous solution (pH is 14), transferring the mixture into a stainless steel sealed reaction kettle after tetraethyl orthosilicate is hydrolyzed (hydrolysis rate is 70 percent), and carrying out hydrothermal treatment for 18h at 140 ℃, wherein the vanadium-silicon molecular sieve: a vanadium source: an organic silicon source: acid: alkali: the molar ratio of water is 100:2:15:10:15:200, vanadium-silicon molecular sieve and organic silicon source are made of SiO 2 Measured as H, acid + Calculated as OH, base - And (6) counting. And filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and then roasting at 550 ℃ for 3h to obtain the modified vanadium-silicon molecular sieve S-3, wherein an XRD (X-ray diffraction) crystalline phase diagram of the modified vanadium-silicon molecular sieve S-3 shows that the modified vanadium-silicon molecular sieve is an MFI (melt flow index) structure molecular sieve.
Example 4
Mixing and pulping a vanadium-silicon molecular sieve and 5mol/L sulfuric acid aqueous solution at normal temperature and normal pressure, and then mixing and stirring the mixed pulp at 120 ℃ for 2 hours; after solid-liquid separation, mixing solid, vanadium source ammonium metavanadate, organic silicon source tetraethyl orthosilicate and n-butylamine aqueous solution (pH is 12), transferring the mixture into a stainless steel sealed reaction kettle after the tetraethyl orthosilicate is hydrolyzed (the hydrolysis rate is 85%), and treating for 12 hours at 170 ℃, wherein the vanadium-silicon molecular sieve: a vanadium source: an organic silicon source: acid: alkali: the molar ratio of water is 100:1:25:2:12:120, vanadium-silicon molecular sieve and organic silicon source are made of SiO 2 Measured as H, acid + The base is calculated as N. And then filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and then roasting at 550 ℃ for 3h to obtain the modified vanadium-silicon molecular sieve S-4, wherein an XRD (X-ray diffraction) crystalline phase diagram of the modified vanadium-silicon molecular sieve S-4 shows that the modified vanadium-silicon molecular sieve is an MFI (melt flow index) structure molecular sieve.
Example 5
Mixing and pulping a vanadium-silicon molecular sieve and 2mol/L perchloric acid aqueous solution at normal temperature and normal pressure, and then mixing and stirring the mixed pulp at 70 ℃ for 5 hours; after solid-liquid separation, solid and vanadium source are metavanadiumMixing ammonium silicate, tetraethyl orthosilicate containing an organic silicon source and ammonia water (pH is 11), transferring the mixture into a stainless steel sealed reaction kettle after the tetraethyl orthosilicate is hydrolyzed (the hydrolysis rate is 65%), and treating at 170 ℃ for 12 hours, wherein the vanadium-silicon molecular sieve: a vanadium source: an organic silicon source: acid: alkali: the molar ratio of water is 100:1:50:5:10:150, vanadium-silicon molecular sieve and organic silicon source are made of SiO 2 Measured as H, acid + The alkali is counted as N. And filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and then roasting at 550 ℃ for 3h to obtain the modified vanadium-silicon molecular sieve S-5, wherein an XRD (X-ray diffraction) crystalline phase diagram of the modified vanadium-silicon molecular sieve S-5 shows that the modified vanadium-silicon molecular sieve is an MFI structure molecular sieve.
Example 6
Mixing and pulping a vanadium-silicon molecular sieve and 15mol/L phosphoric acid aqueous solution at normal temperature and normal pressure, and then mixing and stirring the mixed pulp at 180 ℃ for 3 hours; after solid-liquid separation, mixing solid, vanadium source potassium metavanadate, organic silicon source tetraethyl orthosilicate and sodium hydroxide aqueous solution (pH is 14), transferring the mixture into a stainless steel sealed reaction kettle after tetraethyl orthosilicate is hydrolyzed (hydrolysis rate is 70 percent), and treating for 6 hours at 150 ℃, wherein the vanadium-silicon molecular sieve: a vanadium source: an organic silicon source: acid: alkali: the molar ratio of water is 100:1:20:10:15:100, vanadium-silicon molecular sieve and organic silicon source are made of SiO 2 Measured as H, acid + Calculated as OH, base - And (6) counting. And filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and then roasting at 550 ℃ for 3h to obtain the modified vanadium-silicon molecular sieve S-6, wherein an XRD (X-ray diffraction) crystalline phase diagram of the modified vanadium-silicon molecular sieve S-6 shows that the modified vanadium-silicon molecular sieve is an MFI structure molecular sieve.
Example 7
A molecular sieve was prepared according to the method of example 1, except that SiO 2 The organic silicon source tetraethyl orthosilicate was replaced with an equimolar amount of inorganic silicon source silica gel (purchased from Qingdao silica gel factory, siO) 2 Has a mass fraction of more than 95%, an average pore diameter of 2.6nm and a specific surface area of 680m 2 The pore volume is 0.38 ml/g), and the specific steps are as follows: mixing and pulping a silicon molecular sieve and 1mol/L hydrochloric acid aqueous solution at normal temperature and normal pressure, and then mixing and stirring the mixed pulp at 80 ℃ for 12 hours; after solid-liquid separation, solid, vanadium source ammonium metavanadate, inorganic silicon source silica gel and sodium hydroxideMixing the aqueous solution (pH is 12), transferring the mixture into a stainless steel sealed reaction kettle, and treating for 12 hours at 170 ℃, wherein the ratio of the vanadium-silicon molecular sieve: a vanadium source: inorganic silicon source: acid: alkali: the molar ratio of water is 100:0.5:15:10:15:450, vanadium-silicon molecular sieve and inorganic silicon source are SiO 2 Measured as H, acid + Calculated as OH as base - And (6) counting. And filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and then roasting at 550 ℃ for 3h to obtain the modified vanadium-silicon molecular sieve S-7, wherein an XRD (X-ray diffraction) crystalline phase diagram of the modified vanadium-silicon molecular sieve S-7 shows that the modified vanadium-silicon molecular sieve is an MFI (melt flow index) structure molecular sieve.
Example 8
A molecular sieve was prepared as in example 1, except that the material composition was SiO 2 In terms of the vanadium-silicon molecular sieve: the molar ratio of the organic silicon source is 100:60. obtaining the modified V-Si molecular sieve S-8, wherein the XRD crystal phase diagram shows that the modified V-Si molecular sieve is an MFI structure molecular sieve.
Example 9
A molecular sieve was prepared according to the method of example 1, except that after tetraethyl orthosilicate was hydrolyzed (hydrolysis rate: 50%), the mixture was transferred to a stainless steel sealed reaction vessel to obtain a modified vanadium-silicon molecular sieve S-9, which is an MFI structure molecular sieve as shown by the XRD crystal phase diagram.
Example 10
A molecular sieve was prepared according to the method of example 1, except that after the hydrolysis of tetraethyl orthosilicate (hydrolysis ratio of 100%), the mixture was transferred to a stainless steel sealed reaction vessel to obtain a modified V-Si molecular sieve S-10, which has an XRD crystal phase diagram showing that it is a MFI structure molecular sieve.
Example 11
A molecular sieve was prepared according to the method of example 1, except that the second heat treatment employed a specific treatment procedure, comprising the specific steps of:
mixing and pulping a vanadium-silicon molecular sieve and 1mol/L hydrochloric acid aqueous solution at normal temperature and normal pressure, and then mixing and stirring the mixed pulp at 80 ℃ for 12 hours; after solid-liquid separation, mixing the solid, vanadium source ammonium metavanadate, organic silicon source tetraethyl orthosilicate and sodium hydroxide aqueous solution (pH is 12), transferring the mixture into a stainless steel sealed reaction kettle after the tetraethyl orthosilicate is hydrolyzed (hydrolysis rate is 40%),treatment at a temperature of 125 ℃ and autogenous pressure for 6 hours in succession (stage (1)); hydrothermal treatment at 180 ℃ and autogenous pressure for 2 hours (stage (2)); carrying out hydrothermal treatment at 150 ℃ and autogenous pressure for 4 hours (stage (3)), wherein the heating rate from room temperature to stage (1) is 2 ℃/min, the heating rate from stage (1) to stage (2) is 15 ℃/min, the cooling rate from stage (2) to stage (3) is 10 ℃/min, and the ratio of the vanadium-silicon molecular sieve: a vanadium source: an organic silicon source: acid: alkali: the molar ratio of water is 100:0.5:15:10:15:450, vanadium-silicon molecular sieve and organic silicon source are made of SiO 2 Measured as H, acid + Calculated as OH, base - And (6) counting. And filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and then roasting at 550 ℃ for 3h to obtain the modified vanadium-silicon molecular sieve S-11, wherein an XRD (X-ray diffraction) crystalline phase diagram of the modified vanadium-silicon molecular sieve S-11 shows that the modified vanadium-silicon molecular sieve is an MFI (melt flow index) structure molecular sieve.
Example 12
A molecular sieve was prepared according to the method of example 1 except that the second heat treatment employed a specific treatment procedure, comprising the specific steps of:
mixing and pulping a vanadium-silicon molecular sieve and 1mol/L hydrochloric acid aqueous solution at normal temperature and normal pressure, and then mixing and stirring the mixed pulp at 80 ℃ for 12 hours; after solid-liquid separation, mixing solid, vanadium source ammonium metavanadate, organic silicon source tetraethyl orthosilicate and sodium hydroxide aqueous solution (pH is 12), transferring the mixture into a stainless steel sealed reaction kettle after tetraethyl orthosilicate is hydrolyzed (hydrolysis rate is 80%), and performing hydrothermal treatment for 4 hours at 130 ℃ and autogenous pressure in sequence (stage (1)); hydrothermal treatment at 200 ℃ and autogenous pressure for 4 hours (stage (2)); carrying out hydrothermal treatment at 140 ℃ and autogenous pressure for 12 hours (stage (3)), wherein the heating rate from room temperature to stage (1) is 10 ℃/min, the heating rate from stage (1) to stage (2) is 20 ℃/min, and the cooling rate from stage (2) to stage (3) is 10 ℃/min, wherein the vanadium-silicon molecular sieve: a vanadium source: an organic silicon source: acid: alkali: the molar ratio of water is 100:0.5:15:10:15:450, vanadium-silicon molecular sieve and organic silicon source are made of SiO 2 Measured as H, acid + Calculated as OH as base - And (6) counting. Filtering the obtained product, washing with water, oven drying at 110 deg.C for 120min, and calcining at 550 deg.C for 3h to obtainThe XRD crystal phase diagram of the modified vanadium-silicon molecular sieve S-12 shows that the modified vanadium-silicon molecular sieve is an MFI structure molecular sieve.
Example 13
A molecular sieve was prepared according to the method of example 1, except that the second heat treatment employed a specific treatment procedure, comprising the specific steps of:
mixing and pulping a vanadium-silicon molecular sieve and 1mol/L hydrochloric acid aqueous solution at normal temperature and normal pressure, and then mixing and stirring the mixed pulp at 80 ℃ for 12 hours; after solid-liquid separation, mixing the solid, ammonium metavanadate as a vanadium source, tetraethyl orthosilicate as an organic silicon source and an aqueous solution of sodium hydroxide (pH is 12), transferring the mixture into a stainless steel sealed reaction kettle after the tetraethyl orthosilicate is hydrolyzed (the hydrolysis rate is 80 percent), and performing hydrothermal treatment for 18 hours at the temperature of 120 ℃ and the autogenous pressure in sequence (stage (1)); hydrothermal treatment at 190 ℃ and autogenous pressure for 8 hours (stage (2)); carrying out hydrothermal treatment for 14 hours at the temperature of 180 ℃ and the autogenous pressure (stage (3)), wherein the heating rate from the room temperature to the stage (1) is 10 ℃/min, the heating rate from the stage (1) to the stage (2) is 20 ℃/min, and the cooling rate from the stage (2) to the stage (3) is 10 ℃/min, wherein the vanadium-silicon molecular sieve: a vanadium source: an organic silicon source: acid: alkali: the molar ratio of water is 100:0.5:15:10:15:450, vanadium-silicon molecular sieve and organic silicon source are made of SiO 2 Measured as H, acid + Calculated as OH, base - And (6) counting. And filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and then roasting at 550 ℃ for 3h to obtain the modified vanadium-silicon molecular sieve S-13, wherein an XRD (X-ray diffraction) crystalline phase diagram of the modified vanadium-silicon molecular sieve S-13 shows that the modified vanadium-silicon molecular sieve is an MFI (melt flow index) structure molecular sieve.
Comparative example 1
A molecular sieve was prepared according to the method of example 1, except that no alkali source was added during the molecular sieve preparation, the specific steps were:
mixing and pulping a vanadium-silicon molecular sieve and 1mol/L hydrochloric acid aqueous solution at normal temperature and normal pressure, and then mixing and stirring the mixed pulp at 80 ℃ for 12 hours; after solid-liquid separation, mixing the solid, vanadium source ammonium metavanadate and organic silicon source tetraethyl orthosilicate, transferring the mixture into a stainless steel sealed reaction kettle after the tetraethyl orthosilicate is hydrolyzed (the hydrolysis rate is 80 percent), and treating for 12 hours at 170 ℃, wherein vanadium-silicon moleculesScreening: a vanadium source: an organic silicon source: acid: the molar ratio of water is 100:0.5:15:10:450, vanadium-silicon molecular sieve and organic silicon source are made of SiO 2 Measured as H, acid + And (6) counting. And filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and roasting at 550 ℃ for 3h to obtain the modified vanadium-silicon molecular sieve D-1.
Comparative example 2
A molecular sieve was prepared according to the method of example 1, except that no organic silicon source was added during the molecular sieve preparation, which specifically comprises the steps of: mixing and pulping a vanadium-silicon molecular sieve and 1mol/L hydrochloric acid aqueous solution at normal temperature and normal pressure, and then mixing and stirring the mixed pulp at 80 ℃ for 12 hours; after solid-liquid separation, mixing the solid, vanadium source ammonium metavanadate and sodium hydroxide aqueous solution (pH is 12), then transferring the mixture into a stainless steel sealed reaction kettle, and treating for 12 hours at 170 ℃, wherein the vanadium-silicon molecular sieve: a vanadium source: acid: alkali: the molar ratio of water is 100:0.5:10:15:450, vanadium-silicon molecular sieve is made of SiO 2 Measured as H, acid + Calculated as OH, base - And (6) counting. And filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and roasting at 550 ℃ for 3h to obtain the modified vanadium-silicon molecular sieve D-2.
Comparative example 3
The molecular sieve was prepared according to the method of example 1, except that no ammonium metavanadate as vanadium source was added during the molecular sieve preparation, and the specific steps were: mixing and pulping a vanadium-silicon molecular sieve and 1mol/L hydrochloric acid aqueous solution at normal temperature and normal pressure, and then mixing and stirring the mixed pulp at 80 ℃ for 12 hours; after solid-liquid separation, mixing solid, organic silicon source tetraethyl orthosilicate and sodium hydroxide aqueous solution (pH is 12), transferring the mixture into a stainless steel sealed reaction kettle after tetraethyl orthosilicate is hydrolyzed (hydrolysis rate is 80%), and treating for 12 hours at 170 ℃, wherein the vanadium-silicon molecular sieve: an organic silicon source: acid: alkali: the molar ratio of water is 100:15:10:15:450, vanadium-silicon molecular sieve and organic silicon source are made of SiO 2 Measured as H, acid + Calculated as OH, base - And (6) counting. And filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and roasting at 550 ℃ for 3h to obtain the modified vanadium-silicon molecular sieve D-3.
Comparative example 4
The vanadium-silicon molecular sieve is impregnated and loaded with vanadium, and the method comprises the following specific steps: firstly, mixing and pulping a vanadium-silicon molecular sieve and 1mol/L ammonium metavanadate aqueous solution, and then mixing and stirring the mixed slurry at 80 ℃ for 12 hours; and after solid-liquid separation, drying and roasting the solid to obtain the modified vanadium-silicon molecular sieve D-4 impregnated with the supported vanadium.
Comparative example 5
A molecular sieve was prepared according to the method of example 1, except that the vanadium silicalite molecular sieve was not subjected to the first heat treatment during the molecular sieve preparation, and the specific steps were as follows:
mixing a vanadium-silicon molecular sieve, a vanadium source ammonium metavanadate, an organic silicon source tetraethyl orthosilicate and a sodium hydroxide aqueous solution (pH is 12) at normal temperature and normal pressure, transferring the mixture into a stainless steel sealed reaction kettle after the tetraethyl orthosilicate is hydrolyzed (the hydrolysis rate is 80 percent), and treating for 12 hours at 170 ℃, wherein the vanadium-silicon molecular sieve: a vanadium source: an organic silicon source: alkali: the molar ratio of water is 100:0.5:15:15:450, vanadium-silicon molecular sieve and organic silicon source are made of SiO 2 Measured as H, acid + Calculated as OH as base - And (6) counting. And filtering the obtained product, washing with water, drying at 110 ℃ for 120min, and roasting at 550 ℃ for 3h to obtain the modified vanadium-silicon molecular sieve D-5.
TABLE 1
In table 1:
A＝X 1-1.8 /X 0.4-0.9 ，X 0.4-0.9 the ratio of the pore diameter of the micropores of the molecular sieve in the range of 0.4-0.9nm to the distribution quantity of the total pore diameter, X 1-1.8 The proportion of the micropore diameter of the molecular sieve in the range of 1-1.8nm to the total micropore diameter distribution amount is adopted;
B＝I 960 /I 800 ，I 960 the infrared absorption spectrum of the molecular sieve is 960cm -1 Absorption intensity in the vicinity, I 800 The infrared absorption spectrum of the molecular sieve is 800cm -1 Absorption strength in the vicinity;
C＝T w /T k ，T w is the micropore volume of the molecular sieve, T k Is the total pore volume of the molecular sieve;
silicon: vanadium refers to the silicon element: molar ratio of vanadium element.
As can be seen from the results of table 1: the modified vanadium-silicon molecular sieve prepared by the method has the following characteristics of pore size distribution, proportion of micropore pore volume to total pore volume, silicon element: the molar ratio of vanadium element, the ratio of surface silicon-vanadium ratio to bulk silicon-vanadium ratio and other data completely satisfy all the characteristics of the product disclosed by the invention. In contrast, the molecular sieve obtained in the second heat treatment liquid in comparative example 1 without an alkali, the molecular sieve obtained in the second heat treatment liquid in comparative example 2 without a silicon source, the molecular sieve obtained in the second heat treatment liquid in comparative example 3 without a vanadium source, the modified vanadium-silicon molecular sieve obtained in comparative example 4 by loading vanadium on the vanadium-silicon molecular sieve, or the modified vanadium-silicon molecular sieve obtained in comparative example 5 without the first heat treatment cannot satisfy all the characteristics of the product disclosed in the present disclosure.
Test examples
This test example is intended to illustrate the reaction effect of the modified vanadium-silicon molecular sieve obtained by the method provided in the present disclosure and the molecular sieve obtained by the method of the comparative example for the thioether oxidation reaction.
The catalyst (the molecular sieve prepared in the embodiment and the comparative example is tableted and formed, the particle size is 10-20 meshes) is filled in a fixed bed reactor to form a catalyst bed layer, and the height-diameter ratio of the catalyst bed layer is 10.
Dimethyl sulfide, hydrogen peroxide (provided as 30 wt.% hydrogen peroxide) as an oxidant and methanol as a solvent were mixed to form a liquid mixture, which was fed from the bottom of the fixed bed reactor and passed through the catalyst bed. Wherein the molar ratio of dimethyl sulfide to hydrogen peroxide is 1:1, the molar ratio of dimethyl sulfide to methanol is 1:5, the weight hourly space velocity of dimethyl sulfide is 1.5h -1 The reaction temperature is 40 ℃, water is used as a heat exchange medium to exchange heat with a catalyst bed layer in the reaction process so as to remove reaction heat, and the reaction is carried outThe pressure in the fixed bed reactor was controlled to 2MPa during the process.
The contents of the respective components in the obtained reaction liquid were analyzed by gas chromatography, and on the basis of which the following formulas were used to calculate the relative amounts of the conversion of the oxidizing agent and the increase in the selectivity of sulfone in the product, respectively, and the results obtained after 0.5 hour and 200 hours of the reaction are shown in Table 2.
Oxidant conversion (%) = (moles of oxidant participating in the reaction/moles of oxidant added) × 100%;
the relative amount (%) of increase in selectivity to sulfone in the product (%) = (number of moles of sulfone in the reaction mixture obtained in test example-number of moles of sulfone in the reaction mixture obtained in test comparative example 5)/number of moles of sulfone in the reaction mixture obtained in test comparative example 5 × 100%.
TABLE 2
It can be seen from the data in table 2 that the modified vanadium silicalite molecular sieve disclosed by the present disclosure is used for the reaction of thioether oxidation, which is beneficial to modulating the selectivity of a target product, and has good stability and can obtain a good catalytic effect.
The preferred embodiments of the present disclosure have been described in detail above, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all fall within the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.
Claims (21)
1. A modified vanadium silicalite molecular sieve, comprising: vanadium element, silicon element and oxygen element, wherein the modified vanadium silicon molecular sieve satisfies X 1-1.8 /X 0.4-0.9 ＝A，0.2<A<0.5，X 1-1.8 The ratio of the micropore diameter of the molecular sieve in the range of 1-1.8nm to the total micropore diameter distribution quantity, X 0.4-0.9 Is the proportion of the pore diameter of the micropores of the molecular sieve in the range of 0.4-0.9nm in the total pore diameter distribution.
2. The modified vanadium silicon molecular sieve of claim 1, wherein the modified vanadium silicon molecular sieve satisfies I 960 /I 800 ＝B，0.2<B<0.6，I 960 The infrared absorption spectrum of the molecular sieve is 960cm -1 Absorption intensity in the vicinity, I 800 The infrared absorption spectrum of the molecular sieve is 800cm -1 Absorption intensity in the vicinity.
3. The modified v-si molecular sieve of claim 1, wherein the modified v-si molecular sieve satisfies T w /T k ＝C，0.5<C<0.9，T w Is the micropore volume of the molecular sieve, T k Is the total pore volume of the molecular sieve.
4. The modified vanadium silicon molecular sieve of claim 1, wherein the modified vanadium silicon molecular sieve satisfies 0.25-a-straw-0.45.
5. The modified vanadium silicon molecular sieve of claim 2, wherein the modified vanadium silicon molecular sieve satisfies 0.25-b-t-0.55.
6. The modified vanadium silicon molecular sieve of claim 3, wherein the modified vanadium silicon molecular sieve satisfies 0.55-c-t-0.85.
7. The modified vanadium-silicon molecular sieve of claim 1, wherein the molar ratio of silicon to vanadium of the modified vanadium-silicon molecular sieve is 100: (0.1-10).
8. The modified vanadium silicalite molecular sieve of claim 7, wherein the molar ratio of silicon to vanadium of the modified vanadium silicalite molecular sieve is 100: (0.2-5).
9. The modified vanadia molecular sieve of claim 1, wherein the modified vanadia molecular sieve has a surface silicon to vanadium ratio of no less than a bulk silicon to vanadium ratio, the silicon to vanadium ratio being the molar ratio of silicon oxide to vanadium oxide; the ratio of the surface silicon-vanadium ratio to the bulk silicon-vanadium ratio is 1.1-2.
10. The modified vanadia sieve of claim 9, wherein the ratio of the surface silicon to vanadium ratio to the bulk silicon to vanadium ratio is 1.2-1.8.
11. The modified vanadium silica molecular sieve of claim 1, wherein the modified vanadium silica molecular sieve is a molecular sieve of MFI structure, a molecular sieve of BEA structure, a molecular sieve of MEL structure or a molecular sieve of MOR structure.
12. A method of preparing the modified vanadium silicalite molecular sieve of any one of claims 1 to 11, comprising:
(1) Mixing the vanadium-silicon molecular sieve with first heat treatment liquid, carrying out first heat treatment for 0.5-360h at 40-200 ℃, and then carrying out solid-liquid separation on the obtained mixture to obtain a first solid, wherein the first heat treatment liquid is an acid solution with the concentration of 0.1-10 mol/L;
(2) Mixing the first solid with a second heat treatment liquid, and carrying out second heat treatment at 100-200 ℃ for 0.5-96h, wherein the second heat treatment liquid contains a silicon source, a vanadium source, an alkali source and water;
wherein, siO is used 2 Measuring the vanadium content and the silicon content in the step (1)The molar ratio of the subsieve to the silicon source in the step (2) is 100: (5-80).
13. The method of claim 12, wherein the molar ratio of the vanadium-silicon molecular sieve in step (1) to the silicon source in step (2) is 100: (10-50).
14. The method of claim 12, wherein the second heat treatment is sequentially subjected to stage (1), stage (2), and stage (3), stage (1) being maintained at 100-140 ℃ for 2-24 hours, stage (2) being warmed to 180-200 ℃ for 0.1-12 hours, stage (3) being cooled to 140-180 ℃ for 4-24 hours; the temperature difference between stage (3) and stage (2) is at least 20 ℃; the temperature rising rate from the room temperature to the stage (1) is 0.1-20 ℃/min, the temperature rising rate from the stage (1) to the stage (2) is 1-50 ℃/min, and the temperature falling rate from the stage (2) to the stage (3) is 1-20 ℃/min.
15. The method of claim 14, wherein the temperature difference between stage (3) and stage (2) is 25-60 ℃.
16. The method of claim 12, wherein the vanadium silicalite molecular sieve: a vanadium source: acid: alkali source: the molar ratio of water is 100: (0.1-10): (0.005-50): (0.5-50): (20-1000), wherein the vanadium-silicon molecular sieve is SiO 2 In terms of H, the acid is + The alkali source is counted as N when containing nitrogen element, and the alkali source is counted as OH when not containing nitrogen element - And (6) counting.
17. The process of claim 12, wherein the vanadium silicalite molecular sieve is a molecular sieve of MFI structure, a molecular sieve of BEA structure, a molecular sieve of MEL structure, or a molecular sieve of MOR structure; the acid is organic acid and/or inorganic acid; the alkali source is ammonia, aliphatic amine, aliphatic alcohol amine or quaternary ammonium base; the vanadium source is vanadium oxide, vanadium acid, vanadate, vanadium halide, vanadium carbonate, vanadium nitrate, vanadium sulfate, vanadium phosphate, vanadium hydroxide or organic compound of vanadium, or the combination of two or three of the vanadium oxide, vanadium acid, vanadate, vanadium halide, vanadium carbonate, vanadium nitrate, vanadium sulfate, vanadium phosphate, vanadium hydroxide or vanadium organic compound.
18. The method according to claim 12, wherein the silicon source is one or more selected from silicon-containing compounds represented by formula I;
in the formula I, R 1 、R 2 、R 3 And R 4 Each is a C1-C4 alkyl group.
19. The method as claimed in claim 12, wherein the silicon source has a hydrolysis rate of 60-90%.
20. A method of oxidizing a thioether, the method comprising: a thioether, an oxidant and an optional solvent are contacted with a catalyst to react under thioether oxidation conditions, wherein the catalyst contains the modified vanadium silicalite molecular sieve of any one of claims 1 to 11.
21. The method of claim 20, wherein the sulfide is dimethyl sulfide and/or dimethyl sulfide, the oxidant is a peroxide, and the solvent is water, a C1-C6 alcohol, a C3-C8 ketone, or a C2-C6 nitrile; the molar ratio of the thioether to the oxidant is 1: (0.1-10), the weight ratio of the thioether to the catalyst is 100: (0.2-50); the thioether oxidation conditions include: the temperature is 0-120 ℃, and the pressure is 0-5MPa in gauge pressure.
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