CN105413701B - For producing the catalyst of ethylidene diacetate - Google Patents
For producing the catalyst of ethylidene diacetate Download PDFInfo
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- CN105413701B CN105413701B CN201410474738.1A CN201410474738A CN105413701B CN 105413701 B CN105413701 B CN 105413701B CN 201410474738 A CN201410474738 A CN 201410474738A CN 105413701 B CN105413701 B CN 105413701B
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- Prior art keywords
- catalyst
- ethylidene diacetate
- reaction
- selectivity
- yield
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- 239000003054 catalyst Substances 0.000 title claims abstract description 128
- GOKCJCODOLGYQD-UHFFFAOYSA-N 4,6-dichloro-2-imidazol-1-ylpyrimidine Chemical compound ClC1=CC(Cl)=NC(N2C=NC=C2)=N1 GOKCJCODOLGYQD-UHFFFAOYSA-N 0.000 title claims abstract description 82
- 239000000203 mixture Substances 0.000 claims abstract description 22
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 15
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 14
- 150000002505 iron Chemical class 0.000 claims abstract description 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052593 corundum Inorganic materials 0.000 claims abstract description 4
- 229910001845 yogo sapphire Inorganic materials 0.000 claims abstract description 4
- 238000006243 chemical reaction Methods 0.000 claims description 93
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 87
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 39
- 229910052739 hydrogen Inorganic materials 0.000 claims description 39
- 239000001257 hydrogen Substances 0.000 claims description 39
- 238000002360 preparation method Methods 0.000 claims description 38
- XBDQKXXYIPTUBI-UHFFFAOYSA-M Propionate Chemical compound CCC([O-])=O XBDQKXXYIPTUBI-UHFFFAOYSA-M 0.000 claims description 25
- KXKVLQRXCPHEJC-UHFFFAOYSA-N acetic acid trimethyl ester Natural products COC(C)=O KXKVLQRXCPHEJC-UHFFFAOYSA-N 0.000 claims description 25
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 23
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 22
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 21
- 229910052681 coesite Inorganic materials 0.000 claims description 18
- 229910052906 cristobalite Inorganic materials 0.000 claims description 18
- 239000000377 silicon dioxide Substances 0.000 claims description 18
- 229910052682 stishovite Inorganic materials 0.000 claims description 18
- 229910052905 tridymite Inorganic materials 0.000 claims description 18
- 239000010955 niobium Substances 0.000 claims description 16
- 229910052700 potassium Inorganic materials 0.000 claims description 11
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 9
- 239000002184 metal Substances 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229910052744 lithium Inorganic materials 0.000 claims description 7
- 229910052758 niobium Inorganic materials 0.000 claims description 7
- 229910052787 antimony Inorganic materials 0.000 claims description 6
- 229910052759 nickel Inorganic materials 0.000 claims description 6
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 239000011591 potassium Substances 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 238000010189 synthetic method Methods 0.000 claims description 5
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 150000002739 metals Chemical class 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 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 claims description 2
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000003426 co-catalyst Substances 0.000 claims description 2
- 229910052701 rubidium Inorganic materials 0.000 claims description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052715 tantalum Inorganic materials 0.000 claims description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 claims description 2
- -1 solves the problems Chemical compound 0.000 abstract description 19
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 abstract description 12
- 230000000694 effects Effects 0.000 abstract description 6
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000004458 analytical method Methods 0.000 description 37
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 34
- 239000000284 extract Substances 0.000 description 33
- 238000002803 maceration Methods 0.000 description 33
- 230000015572 biosynthetic process Effects 0.000 description 23
- 238000003786 synthesis reaction Methods 0.000 description 23
- 239000007789 gas Substances 0.000 description 21
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 20
- OKJPEAGHQZHRQV-UHFFFAOYSA-N Triiodomethane Chemical group IC(I)I OKJPEAGHQZHRQV-UHFFFAOYSA-N 0.000 description 19
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical group IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 description 19
- 238000001816 cooling Methods 0.000 description 18
- 239000000463 material Substances 0.000 description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 17
- 229910052786 argon Inorganic materials 0.000 description 17
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 17
- 230000006837 decompression Effects 0.000 description 17
- 238000010438 heat treatment Methods 0.000 description 17
- 238000005470 impregnation Methods 0.000 description 17
- 239000007791 liquid phase Substances 0.000 description 17
- 238000002156 mixing Methods 0.000 description 17
- 239000001301 oxygen Substances 0.000 description 17
- 229910052760 oxygen Inorganic materials 0.000 description 17
- 239000000376 reactant Substances 0.000 description 17
- 238000000926 separation method Methods 0.000 description 17
- 230000002459 sustained effect Effects 0.000 description 17
- 239000010936 titanium Substances 0.000 description 17
- 229910052719 titanium Inorganic materials 0.000 description 17
- 238000010792 warming Methods 0.000 description 17
- 239000011148 porous material Substances 0.000 description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 14
- 238000001035 drying Methods 0.000 description 14
- 206010013786 Dry skin Diseases 0.000 description 11
- 238000000034 method Methods 0.000 description 11
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical compound [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 description 8
- 229910019804 NbCl5 Inorganic materials 0.000 description 6
- 229910021012 Co2(CO)8 Inorganic materials 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- YHBDIEWMOMLKOO-UHFFFAOYSA-I pentachloroniobium Chemical compound Cl[Nb](Cl)(Cl)(Cl)Cl YHBDIEWMOMLKOO-UHFFFAOYSA-I 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 241001614291 Anoplistes Species 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 229910021551 Vanadium(III) chloride Inorganic materials 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- FAWGZAFXDJGWBB-UHFFFAOYSA-N antimony(3+) Chemical compound [Sb+3] FAWGZAFXDJGWBB-UHFFFAOYSA-N 0.000 description 2
- 229910000380 bismuth sulfate Inorganic materials 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 239000002798 polar solvent Substances 0.000 description 2
- 239000000052 vinegar Substances 0.000 description 2
- 235000021419 vinegar Nutrition 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- DHKHKXVYLBGOIT-UHFFFAOYSA-N 1,1-Diethoxyethane Chemical compound CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 description 1
- ITQTTZVARXURQS-UHFFFAOYSA-N 3-methylpyridine Chemical group CC1=CC=CN=C1 ITQTTZVARXURQS-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 229910000014 Bismuth subcarbonate Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 241001292396 Cirrhitidae Species 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 229910013594 LiOAc Inorganic materials 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 229910021604 Rhodium(III) chloride Inorganic materials 0.000 description 1
- 229910004537 TaCl5 Inorganic materials 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000011354 acetal resin Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 229910052936 alkali metal sulfate Inorganic materials 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 229910000379 antimony sulfate Inorganic materials 0.000 description 1
- FAPDDOBMIUGHIN-UHFFFAOYSA-K antimony trichloride Chemical compound Cl[Sb](Cl)Cl FAPDDOBMIUGHIN-UHFFFAOYSA-K 0.000 description 1
- MVMLTMBYNXHXFI-UHFFFAOYSA-H antimony(3+);trisulfate Chemical compound [Sb+3].[Sb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MVMLTMBYNXHXFI-UHFFFAOYSA-H 0.000 description 1
- 229940036348 bismuth carbonate Drugs 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Inorganic materials [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 description 1
- 230000006315 carbonylation Effects 0.000 description 1
- 238000005810 carbonylation reaction Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229940011182 cobalt acetate Drugs 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- UMYVESYOFCWRIW-UHFFFAOYSA-N cobalt;methanone Chemical compound O=C=[Co] UMYVESYOFCWRIW-UHFFFAOYSA-N 0.000 description 1
- 235000009508 confectionery Nutrition 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- GMZOPRQQINFLPQ-UHFFFAOYSA-H dibismuth;tricarbonate Chemical compound [Bi+3].[Bi+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GMZOPRQQINFLPQ-UHFFFAOYSA-H 0.000 description 1
- BEQZMQXCOWIHRY-UHFFFAOYSA-H dibismuth;trisulfate Chemical compound [Bi+3].[Bi+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BEQZMQXCOWIHRY-UHFFFAOYSA-H 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 239000009322 erkang Substances 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 238000007037 hydroformylation reaction Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 229910001510 metal chloride Inorganic materials 0.000 description 1
- ZYTNDGXGVOZJBT-UHFFFAOYSA-N niobium Chemical compound [Nb].[Nb].[Nb] ZYTNDGXGVOZJBT-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920006324 polyoxymethylene Polymers 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 150000003284 rhodium compounds Chemical class 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- RTHYXYOJKHGZJT-UHFFFAOYSA-N rubidium nitrate Inorganic materials [Rb+].[O-][N+]([O-])=O RTHYXYOJKHGZJT-UHFFFAOYSA-N 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- OEIMLTQPLAGXMX-UHFFFAOYSA-I tantalum(v) chloride Chemical compound Cl[Ta](Cl)(Cl)(Cl)Cl OEIMLTQPLAGXMX-UHFFFAOYSA-I 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- HQYCOEXWFMFWLR-UHFFFAOYSA-K vanadium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[V+3] HQYCOEXWFMFWLR-UHFFFAOYSA-K 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 229920006163 vinyl copolymer Polymers 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to the catalyst for producing ethylidene diacetate, mainly solves the problems, such as that ethylidene diacetate catalyst activity and selectivity is relatively low in the prior art, and SiO is used by using for ethylidene diacetate catalyst, the catalyst2、Al2O3Or its mixture is carrier, active component includes at least one, alkali metal and the technical scheme selected from least one of VB and VA metallic element selected from iron series element, the technical problem is preferably resolved, available in the industrial production of vinyl acetate.
Description
Technical field
The present invention relates to the catalyst for producing ethylidene diacetate, ethylidene diacetate method for preparing catalyst and
The synthetic method of ethylidene diacetate.
Background technology
Vinyl acetate, i.e. vinyl acetate (vinyl acetate, abbreviation VAC or VAM), are water white transparency at room temperature
Inflammable liquid, the ether fragrance with sweet tea.It is one of Organic Chemicals that yield is larger in the world, and it is poly- to be widely used in production
Vinyl acetate (PVAc), polyvinyl alcohol, coating, slurry, adhesive, polyvinyl, film, vinyl copolymer resin, acetal resin etc.
A series of chemical industry and fiber product, are widely used in all trades and professions.
Ethene vapor phase method and acetylene in gas phase method technique are used inside and outside the producing country of vinyl acetate, belongs to petrochemical process
Route, from after rising C1 chemistry, in the 1980s, U.S. Ha Erkang (Halcon) companies and BP (BP) company are successively
It is proposed is prepared new technology-carbonyl process synthesizing vinyl acetate of vinyl acetate by methanol and synthesis gas.The technique is independent of oil
Work raw material, but by methyl acetate and the carbonylation of synthesis gas, synthetic intermediate ethylidene diacetate (EDDA), then pass through
Cross thermal cracking production vinyl acetate and acetic acid.The novel part of whole technique is the hydroformylation reaction of methyl acetate, is catalyzed
Agent radium chloride is simultaneously modified with beta-picoline and iodomethane, and carbon monoxide intercalation reaction is the key point of whole technology.
It is (entitled via US4,429,150 by the preparation method of methyl acetate synthesis ethylidene diacetate：
Manufacture of ethylidene diacetate) it is disclosed, i.e., with methyl acetate or methyl ether, carbon monoxide and hydrogen
For raw material, catalyst is using the double acetic acid Asias second of synthesis in the presence of VIII halide or acetate and phosphorous polar solvent
Ester.US5,354,886 is (entitled：Catalysts on inorganic carriers for producing
Ethylidene diacetate) mention RhCl3Or rhodium compound is supported on diatomite, titanium oxide, magnesia, aluminum oxide
With loaded catalyst is made on zinc oxide.Using methyl acetate, carbon monoxide and hydrogen as raw material, under polar solvent conditions,
The reaction synthesis ethylidene diacetate under above-mentioned catalyst.Double vinegar during ethylidene diacetate is prepared be present in the above method
The problem of sour ethyl yield is low and selective not high.
The content of the invention
The problem of one of technical problems to be solved by the invention are that ethylidene diacetate yield is low and selectivity is low, there is provided
A kind of catalyst for being used to produce ethylidene diacetate, the catalyst have ethylidene diacetate high income to ethylidene diacetate
The characteristics of selectivity is high.
The two of the technical problems to be solved by the invention are the preparation sides using one of the above-mentioned technical problem catalyst
Method.
The three of the technical problems to be solved by the invention are double acetic acid using one of the above-mentioned technical problem catalyst
The synthetic method of ethyl.
One of in order to solve the above-mentioned technical problem, the technical solution adopted by the present invention is as follows：For producing double acetic acid Asias second
The catalyst of ester, the catalyst use SiO2、Al2O3Or its mixture is carrier, active component includes being selected from iron series element
At least one, alkali metal and selected from least one of VB and VA metallic element.It is preferred that the active component includes iron simultaneously
Series elements, alkali metal, selected from least one of VB metallic elements and selected from least one of VA metallic elements.Now VB
There is synergy in terms of EDDA selectivity and yield is improved between metallic element and VA metallic element.
In above-mentioned technical proposal, the iron series element preferably is selected from least one of iron, cobalt and nickel.
In above-mentioned technical proposal, the alkali metal preferably is selected from least one of lithium, sodium, potassium, rubidium and caesium.
In above-mentioned technical proposal, the VB metals preferably are selected from least one of vanadium, niobium and tantalum.
In above-mentioned technical proposal, the VA metals preferably are selected from least one of antimony and bismuth.
In above-mentioned technical proposal, as most preferred technical scheme, the active component is simultaneously including iron series element, alkali gold
Category, niobium element and antimony element；Such as the active component is made up of cobalt, lithium, potassium, niobium and antimony, or by nickel, lithium, potassium, niobium and antimony
When forming, or being made up of cobalt, nickel, lithium, potassium, niobium and antimony element.
In above-mentioned technical proposal, the content of iron series element is preferably 3.00~15.00g/L in the catalyst, more preferably
For 7.00~12.00g/L；The content of alkali metal is preferably 0.10~5.00g/L in the catalyst, more preferably 1.00~
3.00g/L；At least one content of metal is preferably 0.50~8.00g/L in VB and VA in the catalyst, more preferably
For 1.00~5.00g/L.Load surface area per unit volume used in the catalyst is preferably 50~300m2/ g, more preferably 150~
200m2/ g, pore volume are preferably 0.80~1.20, and more preferably 0.90~1.00.
To solve the two of above-mentioned technical problem, technical scheme is as follows：The technical side of one of above-mentioned technical problem
The preparation method of catalyst described in case, comprises the following steps：
1. by the composition of catalyst by the chemical combination of metal in the compound of iron series element, the compound of alkali metal, VB and VA
The solution of thing mixes with carrier；
2. dry.
In above-mentioned technical proposal, the compound of the step 1. iron series element preferably be selected from ferrocene, carbonyl cobalt, cobalt acetate,
At least one of cobalt chloride, carbonyl nickel and nickel chloride.1. the alkali metal compound preferably is selected from alkali metal oxide, alkali to step
At least one of metal chloride, alkali nitrates, alkali metal sulfates and alkali metal acetate.1. the VB is golden for step
Belong at least one of compound preferred vanadium trichloride, vanadic anhydride, columbium pentachloride and tantalic chloride.Step is 1. in the VA
Metallic compound preferably is selected from least one of basic bismuth carbonate, bismuth sulfate, bismuth chloride, antimony sulfate and antimony chloride.Step 2. institute
It is preferably 80~120 DEG C to state drying temperature, more preferably 100~120 DEG C.
To solve the three of above-mentioned technical problem, technical scheme is as follows：The synthetic method of ethylidene diacetate, with
Methyl acetate, carbon monoxide and hydrogen are raw material, using acetic acid as solvent, are reacted in the presence of catalyst and co-catalyst iodide
Generate ethylidene diacetate.The preferred iodomethane of iodide.
The key of the present invention is the selection of catalyst, and skilled person will know how suitable according to determination is actually needed
Reaction temperature, the reaction time, the proportioning of reaction pressure and material.But the temperature reacted in above-mentioned technical proposal is preferably
130~200 DEG C；The pressure of reaction is preferably 3.0~10.0MPa；The time of reaction is preferably 3.0~10.0h.Carbon monoxide with
The mol ratio of hydrogen is preferably 0.1~10.0.
Product of the present invention is analyzed after cooling down, depressurize, separate using gas chromatograph-mass spectrometer (GC-MS) (GC-MASS), is pressed
Row formula calculates the conversion ratio of methyl acetate and the yield and selectivity of ethylidene diacetate：
Compared with prior art, key of the invention be catalyst active component include a certain amount of iron series element,
Alkali metal and selected from least one of VB and VA metallic element, is advantageous to improve the activity and stability of catalyst, so as to carry
The high yield and selectivity of ethylidene diacetate.
Test result indicates that the ethylidene diacetate yield prepared by the present invention selectively reaches up to 59.65%
86.12%, achieve active component in preferable technique effect, especially catalyst while include iron series element, alkali metal, choosing
During from least one of VB metallic elements and selected from least one of VA metallic elements, more prominent technology effect is achieved
Fruit, it can be used in the synthesis of vinyl acetate.Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
The preparation of catalyst：By Co containing 8.60g, K containing 2.40g and the Nb containing 3.48g Co2(CO)8, KOAc and NbCl5
It is sufficiently mixed and is dissolved in ethanol, obtain maceration extract 400ml, than surface is 167m by 1.0L2/ g, pore volume 0.95 are a diameter of
5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through analysis
The Co contents of the catalyst are 8.60g/L, K contents 2.40g/L, Nb content 3.48g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 59.65%, and selectivity is 86.12%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 2】
The preparation of catalyst：By Co containing 8.60g, K containing 2.40g and the Sb containing 3.48g Co2(CO)8, KOAc and Cl3Sb
It is sufficiently mixed and is dissolved in the acetic acid that concentration is 10wt%, obtain maceration extract 400ml, than surface is 167m by 1.0L2/ g, pore volume
For 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtained described in above-mentioned maceration extract
Catalyst.Co contents through analyzing the catalyst are 8.60g/L, K contents 2.40g/L, Sb content 3.48g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 59.73%, and selectivity is 86.41%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Comparative example 1】
For【Embodiment 1】With【Embodiment 2】Comparative example.
The preparation of catalyst：By Co containing the 8.60g and K containing 2.40g Co2(CO)8It is sufficiently mixed with KOAc and is dissolved in concentration
Than surface it is 167m by 1.0L in 10wt% acetic acid, to obtain maceration extract 400ml2/ g, pore volume 0.95, a diameter of 5.6mm
Spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Urged through analyzing this
The Co contents of agent are 8.60g/L, K contents 2.40g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 50.23%, and selectivity is 73.79%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
The catalyst used by can be seen that the present invention compared with embodiment 1~2, using simultaneously containing Co, K and Nb work
Property component while catalyst performance ratio containing Co, K and Sb active component will be more containing only the performance of Co, K active constituent catalyst
Excellent, the selectivity and yield of ethylidene diacetate will be high.
【Embodiment 3】
The preparation of catalyst：By Co containing 7.00g, Rb containing 1.00g and the V containing 1.00g Co (OAc)2·4H2O、RbNO3
And VCl3It is sufficiently mixed and is dissolved in the acetic acid that concentration is 10wt%, obtain maceration extract 400ml, than surface is 150m by 1.0L2/
G, pore volume 0.90, a diameter of 5.6mm spherical Al2O3Carrier impregnation stands 2h in 80 DEG C of dryings, obtained in above-mentioned maceration extract
To the catalyst.Co contents through analyzing the catalyst are 7.00g/L, Rb content 1.00g/L, V content 1.00g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 58.97%, and selectivity is 86.93%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 4】
The preparation of catalyst：By Fe containing 12.00g, Na containing 3.00g and the V containing 5.00g ferrocene (Fe (C5H5)2)、
Na2O and V2O5It is sufficiently mixed and is dissolved in the nitric acid that concentration is 8wt%, obtains maceration extract 400ml, be than surface by 1.0L
200m2/ g, pore volume 1.00, a diameter of 5.6mm spherical SiO2It is dry in 120 DEG C to stand 2h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.Fe contents through analyzing the catalyst are 12.00g/L, Na content 3.00g/L, V content 5.00g/
L。
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 59.81%, and selectivity is 86.05%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 5】
The preparation of catalyst：By Ni containing 8.60g, Li containing 2.40g and the Ta containing 3.48g Ni (CO)4, LiOAc and TaCl5
It is sufficiently mixed and is dissolved in ethanol, obtain maceration extract 400ml, than surface is 167m by 1.0L2/ g, pore volume 0.95 are a diameter of
5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through analysis
The Ni contents of the catalyst are 8.60g/L, Li contents 2.40g/L, Ta content 3.48g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 59.46%, and selectivity is 86.32%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 6】
The preparation of catalyst：By Ni containing 8.60g, Cs containing 2.40g and the Bi containing 3.48g NiCl2·6H2O、Cs2SO4With
(BiO)2CO3·0.5H2O, which is sufficiently mixed, to be dissolved in pure water, obtains maceration extract 400ml, than surface is 167m by 1.0L2/ g, hole
Hold for 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.Ni contents through analyzing the catalyst are 8.60g/L, Cs contents 2.40g/L, Bi content 3.48g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 59.22%, and selectivity is 86.43%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 7】
The preparation of catalyst：By Co containing 8.60g, Li containing 2.40g and the Bi containing 3.48g Co (NO3)2·6H2O、LiCl
And Bi2(SO4)3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, 1.0L is compared into table
Face is 167m2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.Co contents through analyzing the catalyst are 8.60g/L, Li contents 2.40g/L, Bi content
3.48g/L。
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 3.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 130 DEG C, and the mol ratio of carbon monoxide and hydrogen is 1：After 10, sustained response 3.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 52.45%, and selectivity is 78.09%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 8】
The preparation of catalyst：By Co containing 8.60g, Li containing 2.40g and the Bi containing 3.48g Co (NO3)2·6H2O、LiCl
And BiCl3It is sufficiently mixed and is dissolved in the aqueous hydrochloric acid solution that concentration is 8wt%, obtains maceration extract 400ml, be than surface by 1.0L
167m2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 2h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.Co contents through analyzing the catalyst are 8.60g/L, Li contents 2.40g/L, Bi content 3.48g/
L。
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 10.0MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 200 DEG C, and the mol ratio of carbon monoxide and hydrogen is 10：After 1, sustained response 10.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 60.03%, and selectivity is 85.89%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 9】
The preparation of catalyst：By Co containing 8.60g, the Co containing the 2.40gLi and Sb containing 3.48g2(CO)8, LiCl and Cl3Sb
It is sufficiently mixed and is dissolved in the acetic acid that concentration is 10wt%, obtain maceration extract 400ml, than surface is 167m by 1.0L2/ g, pore volume
For 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtained described in above-mentioned maceration extract
Catalyst.Co contents through analyzing the catalyst are 8.60g/L, Li contents 2.40g/L, Sb content 3.48g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 59.37%, and selectivity is 86.53%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 10】
The preparation of catalyst：By Co containing 8.60g, the Co containing the 2.40gLi and Sb containing 3.48g2(CO)8, LiCl and Sb2
(SO4)3It is sufficiently mixed and is dissolved in the acetic acid that concentration is 10wt%, obtain maceration extract 400ml, than surface is 167m by 1.0L2/
G, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtained in above-mentioned maceration extract
To the catalyst.Co contents through analyzing the catalyst are 8.60g/L, Li contents 2.40g/L, Sb content 3.48g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 59.21%, and selectivity is 86.17%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 11】
The preparation of catalyst：By Co containing 8.60g, the Co containing the 2.40gLi and Nb containing 3.48g2(CO)8, LiCl and NbCl5
It is sufficiently mixed and is dissolved in ethanol, obtain maceration extract 400ml, than surface is 167m by 1.0L2/ g, pore volume 0.95 are a diameter of
5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains the catalyst in above-mentioned maceration extract.Through analysis
The Co contents of the catalyst are 8.60g/L, Li contents 2.40g/L, Nb content 3.48g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 59.82%, and selectivity is 86.71%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 12】
The preparation of catalyst：By Co containing 8.60g, K containing 1.26g, the Co containing the 1.14gLi and Nb containing 3.48g2(CO)8、
KOAc, LiCl and NbCl5It is sufficiently mixed and is dissolved in ethanol, obtain maceration extract 400ml, than surface is 167m by 1.0L2/ g, hole
Hold for 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 DEG C of dryings, obtains institute in above-mentioned maceration extract
State catalyst.Co contents through analyzing the catalyst are 8.60g/L, K contents 1.26g/L, Li content 1.14g/L, Nb content
3.48g/L。
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 62.28%, and selectivity is 88.78%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
The present embodiment is compared with embodiment 1, embodiment 11 as can be seen that alkali metal Li and K is improving ethylidene diacetate
The activity and selectivity of catalyst has preferably synergy.
【Embodiment 13】
The preparation of catalyst：By Co containing 8.60g, K containing 1.26g, the Co containing the 1.14gLi and Sb containing 3.48g2(CO)8、
KOAc, LiCl and Cl3Sb is sufficiently mixed in the acetic acid that concentration is 10wt%, is obtained maceration extract 400ml, is than surface by 1.0L
167m2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 2h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.Co contents through analyzing the catalyst are 8.60g/L, K contents 1.26g/L, Li content 1.14g/L,
Sb contents 3.48g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 62.35%, and selectivity is 88.49%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 14】
The preparation of catalyst：By Co containing 8.60g, K containing 1.26g, containing 1.14gLi, Sb containing 1.91g and containing 1.57gNb's
Co2(CO)8、KOAc、LiCl、Cl3Sb and NbCl5It is sufficiently mixed in ethanol, obtains maceration extract 400ml, is than surface by 1.0L
167m2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2It is dry in 100 DEG C to stand 2h in above-mentioned maceration extract for carrier impregnation
It is dry, obtain the catalyst.Co contents through analyzing the catalyst are 8.60g/L, K contents 1.26g/L, Li content 1.14g/L,
Sb contents 1.91g/L, Nb content 1.57g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 65.14%, and selectivity is 89.94%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
The present embodiment is compared with embodiment 12, embodiment 13 as can be seen that alkali metal Li and K and the metal selected from VB and VA
Element has preferably synergy in the activity and selectivity for improving ethylidene diacetate catalyst.
【Embodiment 15】
The preparation of catalyst：By Ni containing 8.60g, K containing 1.26g, containing 1.14gLi, Sb containing 1.91g and containing 1.57gNb's
Ni(CO)4、KOAc、LiCl、Cl3Sb and NbCl5It is sufficiently mixed and is dissolved in ethanol, obtain maceration extract 400ml, 1.0L is compared into table
Face is 167m2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation stands 2h in 100 in above-mentioned maceration extract
DEG C drying, obtains the catalyst.Ni contents through analyzing the catalyst are 8.60g/L, K contents 1.26g/L, Li content
1.14g/L, Sb content 1.91g/L, Nb content 1.57g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 65.20%, and selectivity is 89.72%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
【Embodiment 16】
The preparation of catalyst：To contain 5.73g Co, Ni containing 2.87g, K containing 1.26g, containing 1.14gLi, Sb containing 1.91g and
Co containing 1.57gNb2(CO)8、Ni(CO)4、KOAc、LiCl、Cl3Sb and NbCl5It is sufficiently mixed in ethanol, obtains maceration extract
400ml, than surface it is 167m by 1.0L2/ g, pore volume 0.95, a diameter of 5.6mm spherical SiO2Carrier impregnation is in above-mentioned dipping
In liquid, 2h is stood in 100 DEG C of dryings, obtains the catalyst.Co contents through analyzing the catalyst are 5.73g/L, Ni contents
2.87g/L, K content 1.26g/L, Li content 1.14g/L, Sb content 1.91g/L, Nb content 1.57g/L.
The synthesis of ethylidene diacetate：By 1.0mol acetic acid, 0.05mol catalyst, 0.10mol iodomethane and 0.45mol
Methyl acetate is added in 500ml titanium reactors, first with 2.0MPa is pressurized to after air in argon gas discharge kettle, then passes to an oxygen
Change carbon and hydrogen until pressure 7.8MPa, improves mixing speed to 1200rpm, while agitating and heating is warming up to reaction temperature, control
Reaction temperature processed is 174 DEG C, and the mol ratio of carbon monoxide and hydrogen is 2：After 1, sustained response 8.0h, stop reaction.
Product analysis：Reactant mixture cooling, decompression, the separation that above-mentioned reaction is obtained, liquid phase use gas-chromatography-matter
Compose combined instrument (GC-MASS) analysis.
The yield for being computed ethylidene diacetate is 68.01%, and selectivity is 91.57%, for convenience of description and is compared,
The preparation condition of catalyst, reaction condition, material inlet amount, the yield of ethylidene diacetate and selectivity are listed in table 1 respectively
With table 2.
The present embodiment is compared with embodiment 14, embodiment 15 as can be seen that iron series element is simultaneously selected from double vinegar when Co, Ni
The selectivity and yield of sour ethyl will be high, illustrate exist very well between six kinds of active components of Co, Ni, Li, K, Nb and Sb
Synergy.
Table 1
Table 2
Claims (8)
1. the catalyst for producing ethylidene diacetate, the catalyst use SiO2、Al2O3Or its mixture is carrier,
Active component includes at least one selected from iron series element, alkali metal and selected from least one of VB and VA metallic element, urges
The content of iron series element is 3.00~15.00g/L in agent, and the content of alkali metal is 0.10~5.00g/L, described in catalyst
At least one content of metal is 0.50~8.00g/L in VB and VA.
2. catalyst according to claim 1, it is characterised in that the iron series element in iron, cobalt and nickel at least one
Kind.
3. catalyst according to claim 1, it is characterised in that the alkali metal in lithium, sodium, potassium, rubidium and caesium at least
It is a kind of.
4. catalyst according to claim 1, it is characterised in that the VB metals are selected from least one of vanadium, niobium and tantalum.
5. catalyst according to claim 1, it is characterised in that the VA metals are selected from least one of antimony and bismuth.
6. as the preparation method of the catalyst described in claim 1, comprise the following steps：
1. by the composition of catalyst by the compound of metal in the compound of iron series element, the compound of alkali metal, VB and VA
Solution mixes with carrier；
2. dry.
7. the synthetic method of ethylidene diacetate, using methyl acetate, carbon monoxide and hydrogen as raw material, using acetic acid as solvent,
Ethylidene diacetate is synthesized in the presence of catalyst any one of Claims 1 to 5 and co-catalyst iodide.
8. synthetic method according to claim 7, it is characterized in that the temperature of reaction is 130~200 DEG C.
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