CN113578390A - Preparation method of low-noble metal catalyst for acetylene hydrochlorination - Google Patents
Preparation method of low-noble metal catalyst for acetylene hydrochlorination Download PDFInfo
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- CN113578390A CN113578390A CN202110900481.1A CN202110900481A CN113578390A CN 113578390 A CN113578390 A CN 113578390A CN 202110900481 A CN202110900481 A CN 202110900481A CN 113578390 A CN113578390 A CN 113578390A
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- noble metal
- low
- metal catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 147
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 130
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 title claims abstract description 71
- 238000002360 preparation method Methods 0.000 title claims abstract description 66
- 238000007038 hydrochlorination reaction Methods 0.000 title claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 121
- 239000005048 methyldichlorosilane Substances 0.000 claims abstract description 40
- -1 fluoroalkyl methyl dichlorosilane Chemical compound 0.000 claims abstract description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 60
- 239000013110 organic ligand Substances 0.000 claims description 57
- 229910001507 metal halide Inorganic materials 0.000 claims description 50
- 150000005309 metal halides Chemical class 0.000 claims description 50
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- KTQYJQFGNYHXMB-UHFFFAOYSA-N dichloro(methyl)silicon Chemical compound C[Si](Cl)Cl KTQYJQFGNYHXMB-UHFFFAOYSA-N 0.000 claims description 27
- 150000003839 salts Chemical class 0.000 claims description 24
- 229910002651 NO3 Inorganic materials 0.000 claims description 23
- 239000007789 gas Substances 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 23
- RADPGJBZLCMARV-GSVOUGTGSA-N (4r)-4-sulfanylpyrrolidin-2-one Chemical compound S[C@H]1CNC(=O)C1 RADPGJBZLCMARV-GSVOUGTGSA-N 0.000 claims description 21
- HQLVRJJDJGNYQW-UHFFFAOYSA-N 1-prop-1-enylimidazole Chemical compound CC=CN1C=CN=C1 HQLVRJJDJGNYQW-UHFFFAOYSA-N 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 21
- 238000003756 stirring Methods 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 20
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 claims description 20
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 20
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 19
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 19
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 12
- 238000006845 Michael addition reaction Methods 0.000 claims description 11
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 11
- 238000006459 hydrosilylation reaction Methods 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 150000002736 metal compounds Chemical class 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000003960 organic solvent Substances 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- VBDMVWQNRXVEGC-UHFFFAOYSA-N dichloro-methyl-(3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl)silane Chemical compound C[Si](Cl)(Cl)CCC(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F VBDMVWQNRXVEGC-UHFFFAOYSA-N 0.000 claims description 4
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229960001701 chloroform Drugs 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 10
- 238000005516 engineering process Methods 0.000 abstract description 3
- 125000002883 imidazolyl group Chemical group 0.000 abstract description 3
- 125000000168 pyrrolyl group Chemical group 0.000 abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 abstract description 2
- 230000003213 activating effect Effects 0.000 abstract 1
- 239000002131 composite material Substances 0.000 abstract 1
- 230000002035 prolonged effect Effects 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 8
- 125000000217 alkyl group Chemical group 0.000 description 8
- 238000004458 analytical method Methods 0.000 description 8
- 229910052731 fluorine Inorganic materials 0.000 description 8
- 239000011737 fluorine Substances 0.000 description 8
- 238000004817 gas chromatography Methods 0.000 description 8
- 229910001510 metal chloride Inorganic materials 0.000 description 5
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 4
- 229910052797 bismuth Inorganic materials 0.000 description 4
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 4
- 239000002608 ionic liquid Substances 0.000 description 4
- 229910052698 phosphorus Inorganic materials 0.000 description 4
- 239000011574 phosphorus Substances 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 229920000915 polyvinyl chloride Polymers 0.000 description 4
- 239000005997 Calcium carbide Substances 0.000 description 3
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 3
- 239000005977 Ethylene Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 3
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical group [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 3
- 229910010271 silicon carbide Inorganic materials 0.000 description 3
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 2
- 229910017053 inorganic salt Inorganic materials 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical group Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 239000000178 monomer Substances 0.000 description 2
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical group Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 description 2
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical group Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 description 2
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- DANYXEHCMQHDNX-UHFFFAOYSA-K trichloroiridium Chemical compound Cl[Ir](Cl)Cl DANYXEHCMQHDNX-UHFFFAOYSA-K 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 229910003803 Gold(III) chloride Inorganic materials 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 229910019029 PtCl4 Inorganic materials 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
- 229910019891 RuCl3 Inorganic materials 0.000 description 1
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical group Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RJHLTVSLYWWTEF-UHFFFAOYSA-K gold trichloride Chemical compound Cl[Au](Cl)Cl RJHLTVSLYWWTEF-UHFFFAOYSA-K 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 229910052809 inorganic oxide Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- FBEIPJNQGITEBL-UHFFFAOYSA-J tetrachloroplatinum Chemical compound Cl[Pt](Cl)(Cl)Cl FBEIPJNQGITEBL-UHFFFAOYSA-J 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C17/00—Preparation of halogenated hydrocarbons
- C07C17/07—Preparation of halogenated hydrocarbons by addition of hydrogen halides
- C07C17/08—Preparation of halogenated hydrocarbons by addition of hydrogen halides to unsaturated hydrocarbons
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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- C07F15/004—Iridium compounds without a metal-carbon linkage
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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- C07F15/0053—Ruthenium compounds without a metal-carbon linkage
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- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
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- C07F15/0066—Palladium compounds without a metal-carbon linkage
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- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
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- C07F7/0803—Compounds with Si-C or Si-Si linkages
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- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/0825—Preparations of compounds not comprising Si-Si or Si-cyano linkages
- C07F7/083—Syntheses without formation of a Si-C bond
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- B01J2231/30—Addition reactions at carbon centres, i.e. to either C-C or C-X multiple bonds
- B01J2231/32—Addition reactions to C=C or C-C triple bonds
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Abstract
The invention belongs to the technical field of catalysts for acetylene hydrochlorination and preparation technologies and reaction processes thereof, and particularly relates to a preparation method of a low-noble metal catalyst for acetylene hydrochlorination; according to the preparation method of the low-noble-metal catalyst for hydrochlorination of acetylene, through the composite action of the fluoroalkyl methyl dichlorosilane, the imidazolyl group, the pyrrolyl group and the like, and the complex formed by the fluoroalkyl methyl dichlorosilane, the imidazolyl group, the pyrrolyl group and the like and the metal ions, the thermal stability of the catalyst can be improved, the effect of effectively activating products can be achieved, and meanwhile, the service life of the catalyst is greatly prolonged.
Description
Technical Field
The invention belongs to the technical field of catalysts for acetylene hydrochlorination and preparation technologies and reaction processes thereof, and particularly relates to a preparation method of a low-noble metal catalyst for acetylene hydrochlorination.
Background
Vinyl chloride also known as vinyl chloride (C)2H3Cl), is an important chemical raw material for synthesizing polyvinyl chloride. The common preparation methods mainly comprise a calcium carbide acetylene method, an ethane method and an ethylene oxychlorination method, wherein the ethylene oxychlorination method is the most main method for producing vinyl chloride in the world at present; meanwhile, vinyl chloride is a monomer for preparing polyvinyl chloride and copolymers thereof, also commonly referred to as vinyl chloride monomer, and is one of the most important chemical products in parallel with ethylene, sodium hydroxide and the like worldwide.
With the development of social economy, the yield of polyvinyl chloride plastics is continuously increased, and the consumption of the catalyst is also continuously increased. Mercury is a toxic substance and causes serious environmental pollution. Therefore, the reaction process for synthesizing chloroethylene from acetylene has double pressure of mercury resource and environmental protection. Aiming at the current industrial situation of preparing chloroethylene by a calcium carbide method in China, in order to realize green sustainable development of the polyethylene industry, research and development of mercury-free catalysts are imperative.
Application number CN200910000950.3 discloses a mercury-free catalyst for hydrochlorination of acetylene and a preparation method and application thereof. The catalyst contains bismuth element and phosphorus element, and the balance is promoter metal element and carrier. The bismuth element exists in the form of bismuth oxide, bismuth inorganic salt or bismuth organic salt; the phosphorus element exists in the mixture of one or more of inorganic acid containing phosphorus, inorganic salt and oxide containing phosphorus. The preparation method comprises the process steps of preparing impregnation mother liquor, adding a catalyst carrier, impregnating in equal volume, drying, roasting and the like, and can be used for acetylene hydrochlorination reaction in the production of polyvinyl chloride by a calcium carbide method.
Application number CN202110079145.5 discloses a catalyst for acetylene hydrochlorination and a preparation method thereof. The catalyst comprises a carrier and a metal chloride active component loaded on the carrier; the carrier is silicon carbide, and the specific surface area of the silicon carbide is not less than 20 square meters per gram; the metal chloride active components comprise noble metal chlorides and common metal chlorides; the noble metal chloride is selected from any one of AuCl3, RuCl3, PtCl4 or PdCl 2; the common metal chloride is selected from any one of SnCl4, CsCl, CuCl2 or CeCl 3. Preparation: (1) dissolving a noble metal chloride to obtain a solution A; (2) adding common metal chloride into the solution A to obtain a solution B; (3) adding a solvent into the solution B to obtain a solution C; (4) adding silicon carbide into the solution C, performing ultrasonic treatment, and removing the solvent to obtain a pre-product; (4) and drying the pre-product to obtain the catalyst for the hydrochlorination of acetylene.
However, the mercury-free catalyst system reported in the literature and the patent at present is mainly characterized in that the catalyst disperses metal in an ionic liquid layer in a metal-based catalyst system loaded with the ionic liquid, the metal caused by the metal agglomeration anchors the metal on the surface of a carbon carrier, and the influence of metal dispersion and mass transfer caused by loading the ionic liquid layer again causes poor catalytic life in the metal-based catalyst system loaded with the ionic liquid.
Disclosure of Invention
The invention aims at the defects in the prior art, discloses a preparation method of a low-noble metal catalyst for acetylene hydrochlorination, and belongs to the technical field of catalysts for acetylene hydrochlorination, preparation technologies and reaction processes thereof.
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluoro-alkyl methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 1-4.0.
Further, the preparation method of the intermediate 1 comprises the following steps:
adding 5-10 parts by weight of (R) -4-mercapto-2-pyrrolidone, 2.6-4.2 parts by weight of 1-allyl-3-vinyl imidazole nitrate and 100 parts by weight of ethanol into a closed high-pressure reaction kettle, adding 2.2-5.14 parts by weight of sodium methoxide, heating and stirring to 48-68 ℃, reacting for 100-200min, and evaporating to remove the ethanol to obtain an intermediate 1.
The fluorocarbon methyl dichlorosilane is one of (1H,1H,2H, 2H-perfluorohexyl) methyl dichlorosilane, (1H,1H,2H, 2H-perfluorooctyl) methyl dichlorosilane and (1H,1H,2H, 2H-perfluorodecyl) methyl dichlorosilane.
Further, the preparation method of the organic ligand comprises the following steps:
adding 12-18 parts by mass of intermediate 1, 18-23 parts by mass of fluoro-alkyl methyl dichlorosilane, 0.01-0.3 part by mass of N-propenyl imidazole and 100-120 parts by mass of N, N-dimethylformamide into a reaction kettle, dropwise adding 0.5-1.2 parts by mass of a chloroplatinic acid isopropanol solution with the mass percent of 3-7% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature to be 60-70 ℃, stirring for 1-3h, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
Furthermore, the metal halide is lanthanide halide.
Furthermore, the lanthanide is one or more of lanthanum, cerium, praseodymium, neodymium and the like.
Further, the mass content of the noble metal may be 0.001 to 0.1% by mass of the low noble metal catalyst.
Further, the mass content of the noble metal may be 0.005 to 0.01% of the mass of the low noble metal catalyst.
Further, the noble metal compound may be a soluble salt thereof, preferably a chloride, sulfate, phosphate, nitrate, etc., more preferably a chloride.
Further, the noble metal is selected from gold, palladium, ruthenium, platinum and iridium.
Further, the preparation method of the low noble metal catalyst comprises the following steps:
according to the weight portion, 20-30 portions of organic ligand and 15-22 portions of metal halide are stirred for 12-24 hours at 35-45 ℃ by taking alkane as a solvent at 60-120 ℃, and the alkane is evaporated after the reaction is finished, so that the low-noble metal catalyst is prepared.
Further, the organic solvent is selected from one of methanol, ethanol, diethyl ether, acetone, ethyl acetate, benzene, toluene, chloroform or carbon tetrachloride.
Furthermore, the molar ratio of the organic ligand to the metal halide is optimized to be 1: 1-2.0.
Further: the preparation of the low noble metal catalyst is utilized to catalyze the hydrochlorination of acetylene to prepare chloroethylene, the low noble metal catalyst is used as the catalyst in a bubble reactor, the reaction temperature is 120-: the volume ratio of hydrogen chloride/acetylene is 0.5-1.5, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 70-120h-1。
Furthermore, the volume ratio of the hydrogen chloride/acetylene is 0.8-1.2, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 90-100h-1。
The reaction mechanism is as follows:
(R) -4-mercapto-2-pyrrolidone, 2.6-4.2 parts of 1-allyl-3-vinyl imidazole nitrate are subjected to Michael addition reaction to obtain an intermediate product 1 with double bonds, and then the intermediate product 1 is subjected to hydrosilylation reaction with fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, and the organic ligand and metal halide are stirred and mixed to obtain the fluorine-containing catalyst for acetylene hydrochlorination.
The technical effects are as follows:
(1) the thioether functional group of the organic ligand can improve the interaction between the organic ligand and the metal halide and stabilize the valence state of the metal, and the pyridine functional group can play a certain role in catalysis and plays an auxiliary role in the main active component.
(2) The complex formed by the fluorocarbon alkyl methyl dichlorosilane, the imidazolyl group, the pyrrolyl group and the like and metal ions has stronger thermal stability, is beneficial to acetylene hydrochlorination, and can effectively activate products, thereby achieving better reaction conversion rate and selectivity. The service life of the catalyst is long.
Drawings
FIG. 1: a is the conversion of the acetylene of example 5; b is the selectivity of vinyl chloride.
Detailed Description
Catalyst preparation example 1
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1:1.
The preparation method of the intermediate 1 comprises the following steps:
adding 5g of (R) -4-mercapto-2-pyrrolidone, 2.6g of 1-allyl-3-vinyl imidazole nitrate and 100g of ethanol into a sealed high-pressure reaction kettle, adding 2.2g of sodium methoxide, heating and stirring to 48 ℃, reacting for 100min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorohexyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
adding 12g of intermediate 1, 18g of fluoro-alkyl methyl dichlorosilane, 0.01g of N-propenyl imidazole, 100g N, N-dimethylformamide into a reaction kettle, dropwise adding 0.5g of chloroplatinic acid isopropanol solution with the mass percent content of 3% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature at 60 ℃, stirring for 1h, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The metal halide is lanthanum chloride.
The mass content of the noble metal is 0.001% of the mass of the low noble metal catalyst.
The noble metal compound is palladium chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
20g of organic ligand and 15g of metal halide are stirred at 35 ℃ for 12 hours at 60 ℃ by using alkane as a solvent, and the alkane is evaporated after the reaction is finished to prepare the low-noble metal catalyst.
The organic solvent is methanol.
The catalyst was evaluated by reaction example 1.
Catalyst preparation example 2
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 1.5.
The preparation method of the intermediate 1 comprises the following steps:
adding 6g of (R) -4-mercapto-2-pyrrolidone, 3g of 1-allyl-3-vinyl imidazole nitrate and 110g of ethanol into a sealed high-pressure reaction kettle, adding 2.6g of sodium methoxide, heating and stirring to 50 ℃, reacting for 120min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorohexyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
14g of intermediate 1, 19g of fluoro-alkyl methyl dichlorosilane, 0.015g of N-propenyl imidazole, 100g N, N-dimethylformamide are added into a reaction kettle, 0.6g of chloroplatinic acid isopropanol solution with the mass percent content of 4% is dropwise added into the reaction kettle under the protection of high-purity nitrogen, the temperature is controlled at 60 ℃, stirring is carried out for 1h, and the N, N-dimethylformamide is evaporated to obtain the organic ligand.
The metal halide is cerium chloride.
The mass content of the noble metal is 0.005% of the mass of the low noble metal catalyst.
The noble metal compound is palladium chloride.
Further, the preparation method of the low noble metal catalyst comprises the following steps:
under 80 ℃, 22g of organic ligand and 16g of metal halide are stirred for 14 hours at 40 ℃ by using alkane as a solvent, and the alkane is evaporated after the reaction is finished, so that the low-noble metal catalyst is prepared.
The organic solvent is methanol.
The catalyst was evaluated by reaction example 2.
Catalyst preparation example 3
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1:2.
The preparation method of the intermediate 1 comprises the following steps:
adding 8g of (R) -4-mercapto-2-pyrrolidone, 3.2g of 1-allyl-3-vinyl imidazole nitrate and 125g of ethanol into a sealed high-pressure reaction kettle, adding 2.8g of sodium methoxide, heating and stirring to 55 ℃, reacting for 160min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorooctyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
adding 15g of intermediate 1,20g of fluoro-alkyl methyl dichlorosilane, 0.2g of N-propenyl imidazole, 110g N, N-dimethylformamide into a reaction kettle, dropwise adding 0.8g of chloroplatinic acid isopropanol solution with the mass percent of 5% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature to be 65 ℃, stirring for 2 hours, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The metal halide is praseodymium chloride.
The mass content of the noble metal is 0.008 percent of the mass of the low noble metal catalyst.
The noble metal compound is iridium chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
at 90 ℃, 24g of organic ligand and 18g of metal halide are stirred for 16 hours at 40 ℃ by taking alkane as a solvent, and the alkane is evaporated after the reaction is finished, so that the low-noble metal catalyst is prepared.
The organic solvent is ethanol.
The catalyst was evaluated by reaction example 3.
Catalyst preparation example 4
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 3.
The preparation method of the intermediate 1 comprises the following steps:
adding 8g of (R) -4-mercapto-2-pyrrolidone, 3.6g of 1-allyl-3-vinyl imidazole nitrate and 135g of ethanol into a sealed high-pressure reaction kettle, adding 3.5g of sodium methoxide, heating and stirring to 65 ℃, reacting for 180min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorooctyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
adding 16g of intermediate 1,21g of fluoro-alkyl methyl dichlorosilane, 0.25g of N-propenyl imidazole, 120g N, N-dimethylformamide into a reaction kettle according to the mass parts, dropwise adding 0.8g of chloroplatinic acid isopropanol solution with the mass percent content of 5% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature to be 70 ℃, stirring for 3 hours, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The metal halide is neodymium chloride.
The mass content of the noble metal is 0.001% of the mass of the low noble metal catalyst.
The noble metal compound is ruthenium chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
at 100 ℃, 28g of organic ligand and 20g of metal halide are stirred for 20 hours at 40 ℃ by using alkane as a solvent, and the alkane is evaporated after the reaction is finished to prepare the low-noble metal catalyst.
The organic solvent is ethyl acetate.
The catalyst was evaluated by reaction example 4.
Catalyst preparation example 5
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 4.
The preparation method of the intermediate 1 comprises the following steps:
adding 10g of (R) -4-mercapto-2-pyrrolidone, 4.2g of 1-allyl-3-vinyl imidazole nitrate and 150g of ethanol into a sealed high-pressure reaction kettle, adding 5.14g of sodium methoxide, heating and stirring to 68 ℃, reacting for 200min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorodecyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
adding 18g of intermediate 1, 23g of fluoro-alkyl methyl dichlorosilane, 0.3g of N-propenyl imidazole, 120g N, N-dimethylformamide into a reaction kettle, dropwise adding 1.2g of chloroplatinic acid isopropanol solution with the mass percent of 7% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature to be 70 ℃, stirring for 3 hours, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The metal halide is neodymium chloride.
The mass content of the noble metal is 0.1 percent of the mass of the low noble metal catalyst.
The noble metal compound is gold chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
at 120 ℃, 30g of organic ligand and 22g of metal halide are stirred for 24 hours at 45 ℃ by using alkane as a solvent, and the alkane is evaporated after the reaction is finished, so that the low-noble metal catalyst is prepared.
The organic solvent is carbon tetrachloride.
The catalyst was evaluated by reaction example 5.
Catalyst preparation comparative example 1
Carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1:1.
The preparation method of the intermediate 1 comprises the following steps:
adding 5g of (R) -4-mercapto-2-pyrrolidone, 2.6g of 1-allyl-3-vinyl imidazole nitrate and 100g of ethanol into a closed high-pressure reaction kettle in parts by weight, adding 2.2g of sodium methoxide, heating and stirring to 48 ℃, reacting for 100min, and evaporating to remove ethanol to obtain an intermediate 1.
The preparation method of the organic ligand comprises the following steps:
adding 12g of intermediate 1, 18g of fluoro-alkyl methyl dichlorosilane, 0.01g of N-propenyl imidazole, 100g N, N-dimethylformamide into a reaction kettle, dropwise adding 0.5g of chloroplatinic acid isopropanol solution with the mass percent content of 3% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature at 60 ℃, stirring for 1h, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The metal halide is lanthanum chloride.
The mass content of the noble metal is 0.001% of the mass of the low noble metal catalyst.
The noble metal compound is gold chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
20g of organic ligand and 15g of metal halide are stirred at 35 ℃ for 12 hours at 60 ℃ by using alkane as a solvent, and the alkane is evaporated after the reaction is finished to prepare the low-noble metal catalyst.
The organic solvent is methanol.
The catalyst was evaluated by comparative reaction example 1.
Catalyst preparation comparative example 2
A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding noble metal salt, and reacting the organic ligand and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 2.5.
The preparation method of the intermediate 1 comprises the following steps:
adding 8g of (R) -4-mercapto-2-pyrrolidone, 3.5g of 1-allyl-3-vinyl imidazole nitrate and 120g of ethanol into a sealed high-pressure reaction kettle, adding 4g of sodium methoxide, heating and stirring to 55 ℃, reacting for 150min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorohexyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
adding 15g of intermediate 1,20g of fluoro-alkyl methyl dichlorosilane, 0.15g of N-propenyl imidazole, 110g N, N-dimethylformamide into a reaction kettle, dropwise adding 0.8g of chloroplatinic acid isopropanol solution with the mass percent of 5% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature to be 65 ℃, stirring for 2 hours, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The mass content of the noble metal is 0.01 percent of the mass of the low noble metal catalyst.
The noble metal compound is palladium chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
at 90 ℃, stirring 25g of organic ligand and noble metal salt at 40 ℃ for 18 hours by using alkane as a solvent, and evaporating the alkane after the reaction is finished to prepare the low-noble metal catalyst.
The organic solvent is acetone.
The catalyst was evaluated by comparative reaction example 2.
Catalyst preparation comparative example 3
Carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluorocarbon methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 4.
The preparation method of the intermediate 1 comprises the following steps:
adding 10g of (R) -4-mercapto-2-pyrrolidone, 4.2g of 1-allyl-3-vinyl imidazole nitrate and 150g of ethanol into a sealed high-pressure reaction kettle, adding 5.14g of sodium methoxide, heating and stirring to 68 ℃, reacting for 200min, and evaporating to remove ethanol to obtain an intermediate 1.
The fluorine alkyl methyl dichlorosilane is (1H,1H,2H, 2H-perfluorohexyl) methyl dichlorosilane.
The preparation method of the organic ligand comprises the following steps:
adding 12-18 parts of intermediate 1, 0.3g of N-propenyl imidazole and 100 parts of N, N-dimethylformamide into a reaction kettle, dropwise adding 1.2g of chloroplatinic acid isopropanol solution with the mass percentage content of 7% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature at 70 ℃, stirring for 3 hours, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
The metal halide is praseodymium chloride.
The mass content of the noble metal is 0.1 percent of the mass of the low noble metal catalyst.
The noble metal compound is iridium chloride.
The preparation method of the low-noble metal catalyst comprises the following steps:
at 120 ℃, 30g of organic ligand and 22g of metal halide are stirred for 24 hours at 45 ℃ by using alkane as a solvent, and the alkane is evaporated after the reaction is finished, so that the low-noble metal catalyst is prepared.
The organic solvent is trichloromethane.
The catalyst was evaluated by comparative reaction example 3.
Reaction example 1:
using 10ml of the low noble metal catalyst in catalyst preparation example 1 to catalyze the hydrochlorination of acetylene to prepare vinyl chloride, introducing reaction raw material gases, namely hydrogen chloride and acetylene, into a bubble reactor at the reaction temperature of 120 ℃, wherein the reaction raw material gases comprise the following components in percentage by weight: the volume ratio of hydrogen chloride/acetylene is 0.5, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 70h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion is 80.47%, and the vinyl chloride selectivity is 99.10%. After 96 hours of reaction, the activity and selectivity of the catalyst are unchanged.
Reaction example 2:
using 10ml of the low noble metal catalyst in catalyst preparation example 2 to catalyze the hydrochlorination of acetylene to prepare vinyl chloride, introducing reaction raw material gases, namely hydrogen chloride and acetylene, into a bubble reactor at the reaction temperature of 140 ℃, wherein the reaction raw material gases comprise the following components in percentage by weight: the volume ratio of hydrogen chloride/acetylene is 0.8, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 80h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion was 85.41%, and the vinyl chloride selectivity was 99.55%. After 96 hours of reaction, the activity and selectivity of the catalyst are unchanged.
Reaction example 3:
the catalyst was used to prepare 10ml of the low noble metal catalyst of example 3, and reaction raw material gases, hydrogen chloride and acetylene, were introduced into a bubble reactor at a reaction temperature of 160 ℃ in the following proportions: the volume ratio of the hydrogen chloride to the acetylene is 1, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 90h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion rate is 83.71 percent, and the vinyl chloride selectivity is 99.42 percent. After 96 hours of reaction, the activity and selectivity of the catalyst are unchanged.
Reaction example 4:
the catalyst was used to prepare 10ml of the low noble metal catalyst of example 4, and the reaction raw material gases, hydrogen chloride and acetylene, were fed into a bubble reactor at a reaction temperature of 200 ℃ in the following proportions: the volume ratio of hydrogen chloride/acetylene is 1.2, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 110h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion rate is 89.14 percent, and the vinyl chloride selectivity is 99.87 percent. After 96 hours of reaction, the activity and selectivity of the catalyst are unchanged.
Reaction example 5:
the catalyst was used to prepare 10ml of the low noble metal catalyst of example 5, and the reaction raw material gases, hydrogen chloride and acetylene, were introduced into a bubble reactor at a reaction temperature of 220 ℃ in the following proportions: the volume ratio of hydrogen chloride/acetylene is 1.5, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 120h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion rate was 91.78% and the vinyl chloride selectivity was 99.93%. After 96 hours of reaction, the activity and selectivity of the catalyst are unchanged.
Comparative reaction example 1:
10ml of the low noble metal catalyst in comparative example 1 was prepared using a catalyst, and in a bubble reactor, reaction temperature was 120 ℃ and reaction raw material gases of hydrogen chloride and acetylene were introduced in the following proportions: the volume ratio of hydrogen chloride/acetylene is 0.5, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 70h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion was 54.89% and the vinyl chloride selectivity was 74.41%. After 96 hours of reaction, the activity and selectivity of the catalyst are reduced.
Comparative reaction example 2:
the catalyst was used to prepare 10ml of the low noble metal catalyst of comparative example 2, and the reaction was carried out in a bubble reactor at a reaction temperature of 180 ℃ by introducing a reaction raw material gas for chlorinationHydrogen and acetylene, wherein the reaction raw material gas ratio is as follows: the volume ratio of the hydrogen chloride/acetylene is 1, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 90h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion rate is 70.12 percent, and the vinyl chloride selectivity is 80.09 percent. After 96 hours of reaction, the activity and selectivity of the catalyst are reduced.
Comparative reaction example 3:
10ml of the low noble metal catalyst in comparative example 3 was prepared using a catalyst, and in a bubble reactor, reaction temperature was 220 ℃ and reaction raw material gases of hydrogen chloride and acetylene were introduced in the following proportions: the volume ratio of hydrogen chloride/acetylene is 1.5, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 120h-1。
The analysis result of the product after the reaction by gas chromatography is as follows: the acetylene conversion is 74.87%, and the vinyl chloride selectivity is 86.41%. After 96 hours of reaction, the activity and selectivity of the catalyst are slightly reduced.
Claims (15)
1. A preparation method of a low noble metal catalyst for acetylene hydrochlorination reaction comprises the following steps:
carrying out Michael addition reaction on (R) -4-mercapto-2-pyrrolidone and 1-allyl-3-vinyl imidazole nitrate to obtain an intermediate 1 with double bonds, carrying out hydrosilylation reaction on the intermediate 1 and fluoro-alkyl methyl dichlorosilane and N-propenyl imidazole to obtain an organic ligand, adding common metal halide and noble metal salt, and reacting the common metal halide and the noble metal salt to generate a low-noble metal catalyst, wherein the molar ratio of the organic ligand to the metal halide is 1: 1-4.0.
2. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the preparation method of the intermediate 1 comprises the following steps:
adding 5-10 parts by weight of (R) -4-mercapto-2-pyrrolidone, 2.6-4.2 parts by weight of 1-allyl-3-vinyl imidazole nitrate and 100 parts by weight of ethanol into a closed high-pressure reaction kettle, adding 2.2-5.14 parts by weight of sodium methoxide, heating and stirring to 48-68 ℃, reacting for 100-200min, and evaporating to remove the ethanol to obtain an intermediate 1.
3. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the fluorocarbon methyl dichlorosilane is one of (1H,1H,2H, 2H-perfluorohexyl) methyl dichlorosilane, (1H,1H,2H, 2H-perfluorooctyl) methyl dichlorosilane and (1H,1H,2H, 2H-perfluorodecyl) methyl dichlorosilane.
4. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the preparation method of the organic ligand comprises the following steps:
adding 12-18 parts by mass of intermediate 1, 18-23 parts by mass of fluoro-alkyl methyl dichlorosilane, 0.01-0.3 part by mass of N-propenyl imidazole and 100-120 parts by mass of N, N-dimethylformamide into a reaction kettle, dropwise adding 0.5-1.2 parts by mass of a chloroplatinic acid isopropanol solution with the mass percent of 3-7% into the reaction kettle under the protection of high-purity nitrogen, controlling the temperature to be 60-70 ℃, stirring for 1-3h, and evaporating to remove the N, N-dimethylformamide to obtain the organic ligand.
5. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the metal halide is lanthanide halide.
6. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 5, wherein: the lanthanide is one or more of lanthanum, cerium, praseodymium, neodymium and the like.
7. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the mass content of the noble metal may be 0.001 to 0.1% by mass of the low noble metal catalyst.
8. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the mass content of the noble metal can be optimized to be 0.005-0.01% of the mass of the low noble metal catalyst.
9. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the noble metal compound may be a soluble salt thereof, preferably a chloride, sulfate, phosphate, nitrate, etc., more preferably a chloride.
10. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the noble metal is selected from gold, palladium, ruthenium, platinum and iridium.
11. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 1, wherein: the preparation method of the low-noble metal catalyst comprises the following steps:
according to the weight portion, 20-30 portions of organic ligand and 15-22 portions of metal halide are stirred for 12-24 hours at 35-45 ℃ by taking alkane as a solvent at 60-120 ℃, and the alkane is evaporated after the reaction is finished, so that the low-noble metal catalyst is prepared.
12. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 11, wherein: the organic solvent is selected from one of methanol, ethanol, diethyl ether, acetone, ethyl acetate, benzene, toluene, trichloromethane or carbon tetrachloride.
13. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 12, wherein: the molar ratio of the organic ligand to the metal halide is optimized to be 1: 1-2.0.
14. A process for the preparation of acetylene, hydrochlorocarbon, according to claim 1The preparation method of the low-noble metal catalyst for the chemical reaction is characterized by comprising the following steps: the preparation of the low noble metal catalyst is utilized to catalyze the hydrochlorination of acetylene to prepare chloroethylene, the low noble metal catalyst is used as the catalyst in a bubble reactor, the reaction temperature is 120-: the volume ratio of hydrogen chloride/acetylene is 0.5-1.5, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 70-120h-1。
15. The method for preparing a low noble metal catalyst for hydrochlorination of acetylene according to claim 14, wherein: the volume ratio of hydrogen chloride/acetylene is 0.8-1.2, and the volume ratio of the flow rate of the reaction raw material gas to the catalyst is 90-100h-1。
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101716528A (en) * | 2009-10-30 | 2010-06-02 | 于志勇 | Catalyst system of chloroethylene prepared by hydrochlorinating acetylene and preparation method and application thereof |
CN101879464A (en) * | 2010-05-28 | 2010-11-10 | 于志勇 | Catalyst system for preparing vinyl chloride by hydrochlorinating acetylene and preparation and application thereof |
CN103894208A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Low noble metal mercury-free catalyst for acetylene hydrochlorination reaction, preparation method and application thereof |
US20140228602A1 (en) * | 2011-07-11 | 2014-08-14 | Johnson Matthey Public Limited Company | Catalyst and method for its preparation |
CN107715914A (en) * | 2017-09-29 | 2018-02-23 | 浙江工业大学 | The ruthenium catalyst and its application in unsaturated hydrocarbons hydrogenates halogenation that a kind of supported sulfided ionic liquid promotes |
WO2018049820A1 (en) * | 2016-09-18 | 2018-03-22 | 天津大学 | Use of catalyst supporting quaternary phosphonium salt and metal chloride for acetylene hydrochlorination |
CN109158126A (en) * | 2018-07-12 | 2019-01-08 | 天津大学 | A kind of metal halo acid ion liquid and its application method for catalyzing acetylene hydrochlorination |
CN110963883A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Method for hydrochlorinating acetylene |
CN111203278A (en) * | 2020-03-05 | 2020-05-29 | 石河子大学 | Metal complex catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof |
CN112237945A (en) * | 2019-07-18 | 2021-01-19 | 中国科学院大连化学物理研究所 | Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination |
CN112892568A (en) * | 2021-01-21 | 2021-06-04 | 常州永蓁材料科技有限公司 | Catalyst for acetylene hydrochlorination and preparation method thereof |
-
2021
- 2021-08-06 CN CN202110900481.1A patent/CN113578390B/en active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN101716528A (en) * | 2009-10-30 | 2010-06-02 | 于志勇 | Catalyst system of chloroethylene prepared by hydrochlorinating acetylene and preparation method and application thereof |
CN101879464A (en) * | 2010-05-28 | 2010-11-10 | 于志勇 | Catalyst system for preparing vinyl chloride by hydrochlorinating acetylene and preparation and application thereof |
US20140228602A1 (en) * | 2011-07-11 | 2014-08-14 | Johnson Matthey Public Limited Company | Catalyst and method for its preparation |
CN103894208A (en) * | 2012-12-25 | 2014-07-02 | 中国科学院大连化学物理研究所 | Low noble metal mercury-free catalyst for acetylene hydrochlorination reaction, preparation method and application thereof |
WO2018049820A1 (en) * | 2016-09-18 | 2018-03-22 | 天津大学 | Use of catalyst supporting quaternary phosphonium salt and metal chloride for acetylene hydrochlorination |
CN107715914A (en) * | 2017-09-29 | 2018-02-23 | 浙江工业大学 | The ruthenium catalyst and its application in unsaturated hydrocarbons hydrogenates halogenation that a kind of supported sulfided ionic liquid promotes |
CN109158126A (en) * | 2018-07-12 | 2019-01-08 | 天津大学 | A kind of metal halo acid ion liquid and its application method for catalyzing acetylene hydrochlorination |
CN110963883A (en) * | 2018-09-28 | 2020-04-07 | 中国石油化工股份有限公司 | Method for hydrochlorinating acetylene |
CN112237945A (en) * | 2019-07-18 | 2021-01-19 | 中国科学院大连化学物理研究所 | Preparation and application of noble metal cluster catalyst for acetylene hydrochlorination |
CN111203278A (en) * | 2020-03-05 | 2020-05-29 | 石河子大学 | Metal complex catalyst for catalyzing hydrochlorination of acetylene and preparation method and application thereof |
CN112892568A (en) * | 2021-01-21 | 2021-06-04 | 常州永蓁材料科技有限公司 | Catalyst for acetylene hydrochlorination and preparation method thereof |
Non-Patent Citations (4)
Title |
---|
JIA ZHAO等: "Supported ionic liquid-palladium catalyst for the highly effective hydrochlorination of acetylene", 《CHEMICAL ENGINEERING JOURNAL》 * |
JIN ZUOHONG等: "Design and control of n-butyl acetate synthetic process", 《HEHEI JOURNAL OF INDUSTRIAL SCIENCE & THECHNOLOGY》 * |
王小龙: "钌炭催化剂的调控合成及乙炔氢氯化性能研究", 《中国博士学位论文全文数据库工程科技Ⅰ辑》 * |
王录等: "乙炔氯氧化反应无汞催化剂的研究进展", 《化工进展》 * |
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