CN1089934A - The method for preparing 3-pentenoic acid and 4-pentenoic acid with acidity, alkalescence or amphoteric catalyst isomerization 2-pentenoic acid - Google Patents
The method for preparing 3-pentenoic acid and 4-pentenoic acid with acidity, alkalescence or amphoteric catalyst isomerization 2-pentenoic acid Download PDFInfo
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- CN1089934A CN1089934A CN93118205A CN93118205A CN1089934A CN 1089934 A CN1089934 A CN 1089934A CN 93118205 A CN93118205 A CN 93118205A CN 93118205 A CN93118205 A CN 93118205A CN 1089934 A CN1089934 A CN 1089934A
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- metal
- zeolite
- zsm
- acid
- pentenoic acid
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- 238000000034 method Methods 0.000 title claims abstract description 69
- YIYBQIKDCADOSF-UHFFFAOYSA-N alpha-Butylen-alpha-carbonsaeure Natural products CCC=CC(O)=O YIYBQIKDCADOSF-UHFFFAOYSA-N 0.000 title claims abstract description 48
- YIYBQIKDCADOSF-ONEGZZNKSA-N trans-pent-2-enoic acid Chemical compound CC\C=C\C(O)=O YIYBQIKDCADOSF-ONEGZZNKSA-N 0.000 title claims abstract description 46
- HVAMZGADVCBITI-UHFFFAOYSA-N pent-4-enoic acid Chemical compound OC(=O)CCC=C HVAMZGADVCBITI-UHFFFAOYSA-N 0.000 title claims abstract description 14
- UIUWNILCHFBLEQ-NSCUHMNNSA-N trans-pent-3-enoic acid Chemical compound C\C=C\CC(O)=O UIUWNILCHFBLEQ-NSCUHMNNSA-N 0.000 title claims abstract description 14
- 238000006317 isomerization reaction Methods 0.000 title claims abstract description 9
- 239000003054 catalyst Substances 0.000 title description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 26
- -1 basic metal phosphoric acid salt Chemical class 0.000 claims abstract description 24
- 239000004927 clay Substances 0.000 claims abstract description 23
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 20
- 229910052728 basic metal Inorganic materials 0.000 claims abstract description 18
- 239000002808 molecular sieve Substances 0.000 claims abstract description 18
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000011949 solid catalyst Substances 0.000 claims abstract description 16
- 230000002378 acidificating effect Effects 0.000 claims abstract description 13
- 239000003513 alkali Substances 0.000 claims abstract description 7
- YYRMJZQKEFZXMX-UHFFFAOYSA-N calcium;phosphoric acid Chemical compound [Ca+2].OP(O)(O)=O.OP(O)(O)=O YYRMJZQKEFZXMX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002426 superphosphate Substances 0.000 claims abstract description 5
- 239000010457 zeolite Substances 0.000 claims description 53
- 229910021536 Zeolite Inorganic materials 0.000 claims description 51
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims description 47
- 150000001875 compounds Chemical class 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 25
- 239000000203 mixture Substances 0.000 claims description 21
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 20
- 239000001257 hydrogen Substances 0.000 claims description 18
- 229910052739 hydrogen Inorganic materials 0.000 claims description 18
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- 229910052751 metal Inorganic materials 0.000 claims description 18
- 239000002184 metal Substances 0.000 claims description 18
- 229910052792 caesium Inorganic materials 0.000 claims description 16
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 15
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 13
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 12
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 150000003112 potassium compounds Chemical class 0.000 claims description 12
- 229910052701 rubidium Inorganic materials 0.000 claims description 12
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 150000003818 basic metals Chemical class 0.000 claims description 10
- 229910052796 boron Inorganic materials 0.000 claims description 10
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 229910052784 alkaline earth metal Inorganic materials 0.000 claims description 9
- 150000001342 alkaline earth metals Chemical class 0.000 claims description 9
- 229910052680 mordenite Inorganic materials 0.000 claims description 9
- 239000000377 silicon dioxide Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052733 gallium Inorganic materials 0.000 claims description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 8
- 235000012239 silicon dioxide Nutrition 0.000 claims description 8
- 229960001866 silicon dioxide Drugs 0.000 claims description 8
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 7
- 238000002360 preparation method Methods 0.000 claims description 7
- 230000008569 process Effects 0.000 claims description 7
- 239000007787 solid Substances 0.000 claims description 7
- 229910019142 PO4 Inorganic materials 0.000 claims description 6
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 6
- 239000004411 aluminium Substances 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- LQFNMFDUAPEJRY-UHFFFAOYSA-K lanthanum(3+);phosphate Chemical compound [La+3].[O-]P([O-])([O-])=O LQFNMFDUAPEJRY-UHFFFAOYSA-K 0.000 claims description 6
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 6
- 239000010452 phosphate Substances 0.000 claims description 6
- 150000003016 phosphoric acids Chemical class 0.000 claims description 6
- 229910052726 zirconium Inorganic materials 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical class O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 5
- 229910052783 alkali metal Inorganic materials 0.000 claims description 5
- 150000001340 alkali metals Chemical class 0.000 claims description 5
- VNSBYDPZHCQWNB-UHFFFAOYSA-N calcium;aluminum;dioxido(oxo)silane;sodium;hydrate Chemical compound O.[Na].[Al].[Ca+2].[O-][Si]([O-])=O VNSBYDPZHCQWNB-UHFFFAOYSA-N 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 5
- 229910001657 ferrierite group Inorganic materials 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- 230000004048 modification Effects 0.000 claims description 5
- 238000012986 modification Methods 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 4
- 125000004429 atom Chemical group 0.000 claims description 4
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 4
- 239000000460 chlorine Substances 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- 239000011737 fluorine Substances 0.000 claims description 4
- 229910052736 halogen Inorganic materials 0.000 claims description 4
- 150000002367 halogens Chemical class 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- 150000002596 lactones Chemical class 0.000 claims description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 4
- 229910000484 niobium oxide Inorganic materials 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 3
- 239000002585 base Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- FUFJGUQYACFECW-UHFFFAOYSA-L calcium hydrogenphosphate Chemical compound [Ca+2].OP([O-])([O-])=O FUFJGUQYACFECW-UHFFFAOYSA-L 0.000 claims description 3
- TYAVIWGEVOBWDZ-UHFFFAOYSA-K cerium(3+);phosphate Chemical compound [Ce+3].[O-]P([O-])([O-])=O TYAVIWGEVOBWDZ-UHFFFAOYSA-K 0.000 claims description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- WVUYYXUATWMVIT-UHFFFAOYSA-N 1-bromo-4-ethoxybenzene Chemical compound CCOC1=CC=C(Br)C=C1 WVUYYXUATWMVIT-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- 229940126062 Compound A Drugs 0.000 claims description 2
- QGLBZNZGBLRJGS-UHFFFAOYSA-N Dihydro-3-methyl-2(3H)-furanone Chemical compound CC1CCOC1=O QGLBZNZGBLRJGS-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- NLDMNSXOCDLTTB-UHFFFAOYSA-N Heterophylliin A Natural products O1C2COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC2C(OC(=O)C=2C=C(O)C(O)=C(O)C=2)C(O)C1OC(=O)C1=CC(O)=C(O)C(O)=C1 NLDMNSXOCDLTTB-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical group [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- FPAFDBFIGPHWGO-UHFFFAOYSA-N dioxosilane;oxomagnesium;hydrate Chemical compound O.[Mg]=O.[Mg]=O.[Mg]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O FPAFDBFIGPHWGO-UHFFFAOYSA-N 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- KWLMIXQRALPRBC-UHFFFAOYSA-L hectorite Chemical compound [Li+].[OH-].[OH-].[Na+].[Mg+2].O1[Si]2([O-])O[Si]1([O-])O[Si]([O-])(O1)O[Si]1([O-])O2 KWLMIXQRALPRBC-UHFFFAOYSA-L 0.000 claims description 2
- 229910000271 hectorite Inorganic materials 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 150000004679 hydroxides Chemical class 0.000 claims description 2
- 238000005470 impregnation Methods 0.000 claims description 2
- 238000012423 maintenance Methods 0.000 claims description 2
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum Substances 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000273 nontronite Inorganic materials 0.000 claims description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 claims description 2
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 239000000725 suspension 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
- 235000012976 tarts Nutrition 0.000 claims description 2
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910001930 tungsten oxide Inorganic materials 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
- 230000026030 halogenation Effects 0.000 claims 1
- 238000005658 halogenation reaction Methods 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims 1
- 230000007704 transition Effects 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- JQZGUQIEPRIDMR-UHFFFAOYSA-N 3-methylbut-1-yn-1-ol Chemical compound CC(C)C#CO JQZGUQIEPRIDMR-UHFFFAOYSA-N 0.000 description 6
- 150000002431 hydrogen Chemical class 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 235000011121 sodium hydroxide Nutrition 0.000 description 3
- 229940083608 sodium hydroxide Drugs 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- BNDRWEVUODOUDW-UHFFFAOYSA-N 3-Hydroxy-3-methylbutan-2-one Chemical compound CC(=O)C(C)(C)O BNDRWEVUODOUDW-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000005660 chlorination reaction Methods 0.000 description 2
- ORTFAQDWJHRMNX-UHFFFAOYSA-N hydroxidooxidocarbon(.) Chemical group O[C]=O ORTFAQDWJHRMNX-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 208000037656 Respiratory Sounds Diseases 0.000 description 1
- 239000003570 air Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
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- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 1
- 239000001506 calcium phosphate Substances 0.000 description 1
- 229910000389 calcium phosphate Inorganic materials 0.000 description 1
- 235000011010 calcium phosphates Nutrition 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-M dihydrogenphosphate Chemical compound OP(O)([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-M 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000003822 preparative gas chromatography Methods 0.000 description 1
- 206010037833 rales Diseases 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C57/00—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms
- C07C57/02—Unsaturated compounds having carboxyl groups bound to acyclic carbon atoms with only carbon-to-carbon double bonds as unsaturation
- C07C57/03—Monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/347—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups
- C07C51/353—Preparation of carboxylic acids or their salts, halides or anhydrides by reactions not involving formation of carboxyl groups by isomerisation; by change of size of the carbon skeleton
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The present invention relates to the method that isomerization 2-pentenoic acid prepares 3-pentenoic acid and 4-pentenoic acid.
Method of the present invention mainly is a kind of by 2-pentenoic acid isomery being turned to other pentenoic acid, it is characterized in that the described 2-pentenoic acid that is gas phase is arranged and is selected from the acidic solid catalyst of acidic molecular sieve, clay, bridging clay (or pillared clays), soild oxide and superphosphate, the both sexes solid catalyst that is selected from the alkali solid catalyst of basic metal phosphoric acid salt, alkaline metal oxide and alkaline molecular sieve or is selected from the amphoteric metal oxide compound contacts.
Description
With acid, alkalescence or amphoteric catalyst isomerization 2-pentenoic acid preparation 3 method of olefin(e) acid and 4-pentenoic acid intentionally.
The present invention relates to the method that isomerization 2-pentenoic acid prepares 3-pentenoic acid and 4-pentenoic acid.
The hydroxy carbonyl divinyl prepares pentenoic acid and usually causes generating all places isomer: 2-pentenoic acid, 3-pentenoic acid and 4-pentenoic acid.
3-pentenoic acid and 4-pentenoic acid can so that hydroxy carbonyl generate hexanodioic acid, and the 2-pentenoic acid can not so transform.
Therefore,, take dual hydroxy carbonyl divinyl method in order to improve the overall yield of preparation hexanodioic acid process, with 2-pentenoic acid isomery turn to 3-pentenoic acid and/or 4-pentenoic acid industrial be practical.
If recognize that the required investment of this method is very high, so, any improvement that the raising overall yield is done all will demonstrate great importance.
At patent EP-A-0, in 291,033, introduced and a kind ofly make its isomery turn to the method for 4-pentenoic acid or derivatives thereof by fluoridized acidic ion exchange resin 3-pentenoic acid or derivatives thereof (mainly being the 3-amylene-4 acid methyl ester).
This method is not suitable for the 2-pentenoic acid, and the not anti-higher temperature of the resin of used the above-mentioned type, therefore, must operate in liquid phase, and in addition, this method also can generate the very high lactone of ratio by the 3-pentenoic acid, and this does not wish to take place.
Thereby the problem for preparing 3-pentenoic acid and/or 4-pentenoic acid raising 2-pentenoic acid use value by the isomerization of 2-pentenoic acid still fails to achieve a solution.
The present invention proposes solution to this problem, that is, by the 2-pentenoic acid being converted into other pentenoic acid, the latter generates hexanodioic acid through hydroxy carbonyl again.
This method comprises that isomerization 2-pentenoic acid generates the process of 3-pentenoic acid and/or 4-pentenoic acid, it is characterized in that the above-mentioned 2-pentenoic acid that is gas phase is arranged to contact with tart, alkaline or amphoteric solid catalyst.
In this manual, acidic solid catalyst is meant some solid chemical compound (in most of the cases being metal oxide or metal-salt), and these compounds can make the methylbutynol dehydration be methyl butene alkynes (" methylbutynol " test) by following reaction:
Alkali solid catalyst is meant some solid chemical compound (in most of the cases being metal oxide or metal-salt), and these compounds can make methylbutynol be degraded to acetylene and acetone (" methylbutynol " test) by following reaction:
The both sexes solid catalyst is meant some solid chemical compound, in most of the cases be metal oxide, these compounds can make methylbutynol be converted into 3-hydroxy-3-methyl-2-butanone and 3-methyl-3-butene-2-ketone (" methylbutynol " test) by following reaction:
The both sexes solid
The details of relevant this test can be with reference to the paper in " Applied Catalysis, 78(1991), p.213-225 ".
The 2-pentenoic acid that adopts in the method for the present invention can result from any source.
As mentioned above, in most of the cases it can result from the hydroxy carbonyl divinyl, and still, method of the present invention is not limited to only adopt the product in this source.For example, it can result from: in the presence of following acidity or basic catalyst, lactone (mainly the being γ-Wu Neizhi) isomery that will contain 5 carbon atoms turns to the mixture of several pentenoic acids.
The 2-pentenoic acid can be used alone, and still, other compound that also can contain different ratios is for example γ-Wu Neizhi, δ-Wu Neizhi or 2-methyl butyrolactone, hexanodioic acid, 2-methylglutaric acid or 2-ethyl succsinic acid of other pentenoic acid, lactone for example.2-pentenoic acid component usually greater than this mixture weight half, but suitably the time, also can adopt less ratio.Hereinafter, term 2-pentenoic acid also comprises the mixture with above-mentioned one or more compounds.
In acidic solid catalyst, can list acidic molecular sieve, acid clay, bridging clay (or pillared clays), soild oxide and superphosphate.
Acidic molecular sieve mainly is the zeolite of pentasil structure, for example the zeolite of the zeolite of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-48, ferrierite structure, mordenite structure and faujusite structure, for example X zeolite or zeolite Y.
The zeolite of pentasil structure or mordenite structure mainly is the zeolite of ZSM-5, ZSM-11, ZSM-22, ZSM-23 and ZSM-48 and mordenite type, and they have with the logical formula I of oxidation than expression:
In the formula:
-M represents to be selected from hydrogen, NH
4With one, two, three and a kind of element of tetravalent metal,
-X represents to be selected from a kind of trivalent element of Al, Ga, Fe and B,
-n represents from 1 to 4 number,
-m represents to be equal to or greater than 10 number,
-p represent from
Number to 40.
The zeolite of faujusite type mainly has with the logical formula II of oxidation than expression:
In the formula:
-M represents to be selected from hydrogen, NH
4With one, two, three and a kind of element of tetravalent metal, M at least a portion is a hydrogen atom
-Z represents to be selected from a kind of trivalent element of Al, Ga, Fe and B,
-n represents from 1 to 4 number,
-d represents to be equal to or greater than 2 number,
-x represents from 5 to 100 number.
The acid zeolite of Cai Yonging mainly is that to be used in its general formula with silicon-dioxide bonded oxide compound be those zeolites of trivalent metal oxide within the scope of the invention.
Usually preferred zeolite is that M is selected from hydrogen, NH in its logical formula I or (II)
4, basic metal Na, K, Li, Rb or Cs, alkaline-earth metal Be, Mg, Ca, Sr or Ba, rare earth metal La or Ce and transition metal Fe for example for example for example for example.
But the detailed introduction referenced patent FR-A-2 of relevant acid clay, 622,575(incorporates this paper into as the reference data).
In the method for the invention, preferably adopt terre verte for example montmorillonite, beidellite, nontronite, hectorite, rich magnesium montmorillonite and talcum powder.
Can be between its thallus, to have introduced the bridge shape at maintenance base portion interval or the clay of column in the method for the invention as the bridging clay of catalyzer.This base portion is the thickness sum at interval between clay thallus and the thallus at interval.
The preparation of above-mentioned bridging clay is at patent FR-A-2, is described specially in 543,446 and patent FR-A-2,618,143.
Beidellite is preferably raw clay usually.
The bridging of clay especially can realize by the oxyhydroxide of aluminium, vanadium, molybdenum, zirconium, iron, niobium, tantalum, chromium, lanthanum, cerium, titanium or gallium or by the mixed hydroxides of above-mentioned some metal.
Above-mentioned bridging clay can be modified, particularly by dihalo, ammonium halide or certain
Above-mentioned bridging clay can be modified, particularly by dihalo, ammonium halide or certain acid for example the effect of sulfuric acid or haloid acid carry out modification.Can select preferred chlorine of halogen or the fluorine introduced.
Clay, particularly the beidellite by the aluminium hydroxide bridging preferably adopts in the method for the invention.
Soild oxide is the mixture of metal oxide, metal oxide or the metal oxide of modification, particularly by dihalo, ammonium halide or certain acid metal oxide of the effect modification of sulfuric acid or haloid acid for example.Can select preferred chlorine of halogen or the fluorine introduced.
As unrestriced example, the mixture that can mention is SiO
2/ Al
2O
3, SiO
2/ Ga
2O
3, SiO
2/ Fe
2O
3And SiO
2/ B
2O
3, halogenated alumina for example chlorating alumina and fluorizated alumina, sulfonated zirconium white, niobium oxides or Tungsten oxide 99.999.
The superphosphate that can adopt mainly is that the phosphoric acid salt of boron (is introduced separately into or by different H as an example in the method for the invention
3BO
3/ H
3PO
4Mol ratio and alumina or silicon-dioxide mix the back to be introduced in building-up process), the phosphoric acid salt of lanthanum orthophosphate, aluminium (is equivalent to different Al
2O
3/ H
PO
4Mol ratio is introduced in building-up process), Vanadium Pentoxide in FLAKES/-mixture (being commonly referred to the UOP catalyzer) of silicon-dioxide, have zeolite structured aluminate or phosphate (AlPO) and have zeolite structured aluminosilicophosphate (SAPO).
The alkali solid catalyst that can adopt mainly is basic metal phosphoric acid salt, alkaline metal oxide, metal carbonate and alkaline molecular sieve in the method for the invention.
Basic metal phosphoric acid salt mainly is phosphoric acid salt, hydrophosphate and the dihydrogen phosphate of logical formula III:
In the formula:
-A represents that a kind of atoms metal, one group of atoms metal or a part are hydrogen atoms;
-y represents from 3/4 to 3 integer or mark (valency that depends on elements A);
-Imp represents alkaline impregnation compound, and its contained metal (be used for oppositely negatively charged ion chemical combination to guarantee charge neutrality) is selected from alkaline-earth metal, basic metal and composition thereof;
-coefficient z represents soaker and macerate (A
yPO
4) weight ratio, its value is for 0%-20%, preferred 2%-10%.
The compound of the alkaline phosphate preferred formula (III) that can adopt in the method for the invention, in the formula:
-A represents that calcium, zirconium, lanthanum, cerium, samarium, aluminium, boron, iron and a part are hydrogen;
-y represents from 3/4 to 3 integer or mark (valency that depends on elements A);
-Imp represents oppositely negatively charged ion of basic metal or alkali-metal mixture and alkalescence;
The value of-coefficient z is 2%-10%.
Example as indefiniteness, the alkaline phosphate that can mention is a lanthanum orthophosphate, combination with caesium, rubidium or potassium compound, the combination of Cerium monophosphate and caesium, rubidium or potassium compound, the combination of samaric orthophosphate and caesium, rubidium or potassium compound, the combination of calcium phosphate and caesium, rubidium or potassium compound, the combination of the combination of secondary calcium phosphate and caesium, rubidium or potassium compound or phosphoric acid hydrogen zirconium and caesium, rubidium or potassium compound.
The alkaline phosphate of logical formula III can be with the Imp suspension in a kind of solution or the volatile solvent, preferably water for example, and dipping leads to formula IV (A
' yPO
4) compound be prepared, in the general formula, A' is identical with the implication of A.
If Imp can dissolve and A
' yPO
4Be just to prepare, then the gained result is better.
Therefore, the logical phosphatic best method of formula III of preparation comprises:
A) synthetic compound A
' yPO
4; Preferably from reaction mixture, do not separate A
' yPO
4,
B) soaker Imp is introduced in the reaction mixture,
C) raffinate in the separating reaction solid,
D) dry and calcining in case of necessity.
If (particularly p.821-823 and " Gmelins Handbuch der anorganischen Chemie " the 8th edition at " P.Pascal Nouveau trait é de chimie min é rale " X volume (1956) with reference to the phosphatic current techique of preparation, 16 volumes (C) are p.202-206(1965) in describe), can discern two kinds and main utilize phosphatic technological line.A kind of is to precipitate soluble metallic salt (muriate, nitrate) and use the ammoniacal liquor aftertreatment with ammonium hydrogen phosphate, neutralizes in case of necessity subsequently.Another kind of route is with phosphoric acid and reactive metal oxide, then, to do aftertreatment with alkali metal hydroxide in case of necessity under heating.
The alkaline metal oxide that can adopt is the oxide compound of alkalescence or by for example can become the oxide compound of alkalescence after the hydroxide treatment of basic metal or alkaline-earth metal with alkali in the method for the invention.
The alkaline metal oxide that can mention (not containing any restrictive sense) is the oxide compound that III a family alkali-metal, alkaline-earth metal, the period of element table sort is metal, transition metal or rare earth metal, pass through or do not handle through alkali metal hydroxide.
What can mention as an example, mainly is alumina, zinc oxide and the calcium oxide of crossing with sodium-hydroxide treatment.
The alkaline molecular sieve that can adopt mainly is the zeolite of pentasil structure in the method for the invention, the zeolite of for example ZSM-5, ZSM-11, ZSM-22, ZSM-23 or ZSM-48, mordenite structure, the ferrierite structure or faujusite structure, for example zeolite of X zeolite or zeolite Y, the general formula (V) represented with oxide compound:
In the formula:
-E represents basic metal or alkaline-earth metal, and whole or small portion is a hydrogen,
-T represents to be selected from the trivalent metal of Al, Ga, Fe and B,
-a represents from 1 to 2 number,
-b represents to be equal to or greater than 2 number,
-r represents from 0 to 100 number.
In general formula (V), the meaning of " small portion hydrogen " that symbol E expresses is meant that the proton that can exist in the molecular sieve must not cause molecular sieve to have acid-reaction in above-mentioned test.
In the alkaline molecular sieve of general formula (V), what preferably adopt is that those E represent alkali-metal molecular sieve.
As unrestriced example, the alkaline molecular sieve that can mention is zeolite NaZSM-5, zeolite NaMOR, zeolite 13XCs, zeolite NaY, zeolite KY and zeolite CsY.
Can adopt the both sexes solid catalyst in the method for the invention mainly is the amphoteric metal oxide compound.
Can adopt the amphoteric metal oxide compound in the method for the invention is amphoteric oxide compound or by its preparation method or through becoming the amphoteric oxide compound after the aftertreatment.
As unrestriced example, the amphoteric metal oxide compound that can mention is thorium dioxide (ThO
2), zirconium dioxide (ZrO
2), titanium dioxide (TiO
2), cerium dioxide (CeO
2), silicon-dioxide (SiO
2), alumina (Al
2O
3) and some above-mentioned hopcalites.
This method adopts operate continuously.
Used catalyzer can maybe can be operated by fluidized-bed by fixed bed.In order to increase contact area, this catalyzer can mix use with inert solid.
Isomerization process is to carry out under 200 ℃-500 ℃ in temperature normally, preferred 250 ℃-400 ℃.
Be defined as the ratio of catalyst volume and total gas flow rate (2-pentenoic acid+suitable carrier gas) duration of contact, under chosen temperature, between 0.1-50sec, change usually, and in most cases be 1-10sec.
Pressure is not crucial.Usually being in normal atmosphere clings to 10MPa(100) between, preferably cling to from normal atmosphere to 1.5MPa(15).
The 2-pentenoic acid can enter in the reactor that catalyzer is housed individually.
The 2-pentenoic acid also can be introduced reactor together with inert carrier gas; The mode of associating introducing can be taked the form of mixture or two kinds of gases are introduced respectively simultaneously.
Inert carrier gas can be made up of the mixture of a kind of gas or some gases, and they are inert under reaction conditions, for example nitrogen, argon gas, air, water vapor and be the carboxylic acid of gas under the temperature of operation.
The content of 2-pentenoic acid is the 10%-100%(weight of the gas gross weight of introducing reactor), preferred 40%-100%.
Method of the present invention can produce the mixture of 3-pentenoic acid and 4-pentenoic acid usually, and as mentioned above, these two kinds of acid can be by turning to hexanodioic acid with carbon monoxide and water reaction hydroxycarbonyl group.Can observe simultaneously the generation of γ-Wu Neizhi.
Following examples will further be illustrated the present invention.
Except as otherwise noted, following working method will adopt in an embodiment.
Vertically arranged reactor (silica tube, length=15cm, the diameter=2cm) 2cm that packs into continuously
3Quartz, 2cm
3Catalyzer and 10cm
3Quartzy mixture closely refills 5cm then
3Quartz.Granulated glass sphere (diameter: 2-3mm) as the last filler of reactor.
In that (300 ℃, unless otherwise indicated) down logical nitrogen two hours (under normal pressure and temperature condition per hour 2 liters) is regulated catalyzer for the selected temperature of reaction.
Then, with syringe the 2-pentenoic acid is injected.
In each embodiment, will the rate of injection of 2-pentenoic acid be explained: with the cm of the 2-pentenoic acid of liquid state
3Expression.
After about 15 minutes, promptly set up steady state, test continues 1 hour usually.The product that leaves reactor is collected in 10cm is housed
3In the collector of acetonitrile.
With vapor-phase chromatography (GC) analytical reaction product and unreacted 2-pentenoic acid.
And the following is calculated in each test:
-hour weight yield (HWE): with respect to the weight of catalyzer with per hour (with h
-1Expression) the 2-pentenoic acid weight of introducing;
The transforming degree of-2-pentenoic acid (DC); 2-pentenoic acid transformation efficiency % with respect to the 2-pentenoic acid of introducing;
The productive rate (RY) of-various pentenoic acids and γ-Wu Neizhi: each pentenoic acid that is generated with respect to the 2-pentenoic acid of introducing or the mole % of γ-Wu Neizhi.
Embodiment 1-3
The test of the different zeolites of the ZSM-5 type of logical formula I, this zeolite has different Si/Al mol ratios:
-zeolite 1:Si/Al=30
75% element M is a hydrogen in the logical formula I,
-zeolite 2:Si/Al=52
75% element M is a hydrogen in the logical formula I,
-zeolite 3:Si/Al=120
75% element M is a hydrogen in the logical formula I,
What provide in operational condition and the above-mentioned total working method is identical.
The duration of contact of each embodiment, (tc) was about 1.4sec.
Gained is the result be organized in the following table 1.
Abbreviation P2, the P3, P4 and the VAL that adopt have following meaning:
The P2=2-pentenoic acid
The P3=3-pentenoic acid
The P4=4-pentenoic acid
The VAL=γ-Wu Neizhi
Embodiment 4-11
The test of different an acidic catalysts:
-SiO
2/ Al
2O
3(Degussa sale)
Contain 16%(weight) Al
2O
3,
-SiO
2/ Al
2O
3Than the zeolite Y that is 5, and and Fe
3+Exchange,
- LaPO
4，
-montmorillonite Volclay clay (Montmo),
-montmorillonite Volclay bridging clay (Montmo-P),
-chlorating Al
2O
3,
-sulfonated ZrO
2,
-niobium oxides.
Operational condition as mentioned above.Be 1 hour reaction time, and except the embodiment 9 of chlorination alumina, be 0.5 hour its reaction time, and temperature can be different from 300 ℃, and the flow of nitrogen can be different from 2L/h, and the introducing speed of 2-pentenoic acid can be different from 3.2mL liquid/h.
Table 2 has been listed the test-results of some different parameter values and gained.
Table 2
| Embodiment | Catalyzer | Temperature | N 2Flow L/h | P2 flow mL/h | DC P2% | PY% | tc (s) | HWE (h -1) | ||
| P4 | P3 | VAL | ||||||||
| Embodiment 4 | SiO 2/Al 2O 3(2cm 3) | 300 | 2 | 3.2 | 38 | 1 | 30 | 6 | 1.4 | 4.9 |
| Embodiment 5 | Zeolite Y (1.5cm 3) | 300 | 3 | 3.2 | 40 | 0 | 30 | 2 | 0.7 | 5.9 |
| Embodiment 6 | LaPO 4(2cm 3) | 300 | 2 | 3.2 | 88 | 2 | 15 | 45 | 1.4 | 1.9 |
| Embodiment 7 | MONTMO (2cm 3) | 320 | 2 | 3.2 | 35 | 0 | 25 | 2 | 1.3 | 2.0 |
| Embodiment 8 | MONTMO-P (4cm 3) | 280 | 2 | 6.4 | 81 | 1 | 10 | 32 | 5.5 | 0.4 |
| Embodiment 9 | Chlorination Al 2O 3(2cm 3) | 380 | 0.5 | 9.6 | 76 | 2 | 40 | 6 | 1.2 | 8.6 |
| Embodiment 10 | Sulfonation ZrO 2(4cm 3) | 300 | 0.5 | 0.96 | 69 | 2 | 40 | 7 | 10.2 | 0.4 |
| Embodiment 11 | Niobium oxides (2cm 3) | 380 | 2 | 3.2 | 79 | 25 | 30 | 9 | 1.2 | 1.9 |
Embodiment 12-21
The test of different alkali solid catalysts:
The Cerium monophosphate of-3% phosphoric acid hydrogen the caesium that mixes
-secondary calcium phosphate (hydroxylapatite)
-zeolite 13XCs
The alumina of-usefulness sodium-hydroxide treatment (10% sodium hydroxide is in the heavy weight of per unit alumina)
The lanthanum orthophosphate of-3% phosphoric acid hydrogen the caesium that mixes
The aluminum phosphate of-3% phosphoric acid hydrogen the caesium that mixes
The lanthanum orthophosphate of-3% potassium primary phosphate that mixes
-magnesium oxide
-zinc oxide
-cerium dioxide (C é rine).
Operational condition is existing narration in above-mentioned total working method.
Gained result and the parameter value that parameter in total working method has been done to change put in order in table 3.
Embodiment 22-25
The test of different both sexes solid catalysts:
-zirconium dioxide (ZrO
2)
-thorium dioxide (ThO
2)
-titanium dioxide (TiO
2)
-Condea alumina (Al
2O
3)
Operational condition is existing narration in above-mentioned total working method.
Gained result and the parameter value that parameter in total working method has been done to change put in order in table 4.
Claims (29)
1, isomerization 2-pentenoic acid generates the method for 3-pentenoic acid and/or 4-pentenoic acid, it is characterized in that the described 2-pentenoic acid that is gas phase is arranged to contact with tart, alkaline or amphoteric solid catalyst.
2, according to the method for claim 1, it is characterized in that the 2-pentenoic acid can be used alone, or other compound that contains different ratios for example γ-Wu Neizhi, δ-Wu Neizhi or 2-methyl butyrolactone, hexanodioic acid, 2-methylglutaric acid or 2-ethyl succsinic acid of other pentenoic acid, lactone for example.
3,, it is characterized in that this catalyzer is the acidic solid catalyst that is selected from acidic molecular sieve, acid clay, bridging clay (or pillared clays), soild oxide and superphosphate according to the method for one of claim 1 and 2.
4, according to the method for claim 3, it is characterized in that acidic molecular sieve is the zeolite of pentasil structure, the for example zeolite of ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-48, ferrierite, mordenite and faujusite structure, for example X zeolite or zeolite Y.
5, according to the method for one of claim 3 and 4, the acid zeolite that it is characterized in that pentasil structure or mordenite structure is the zeolite of ZSM-5, ZSM-11, ZSM-22, ZSM-23 and ZSM-48 or the zeolite of mordenite type, and they have with the logical formula I of oxidation than expression:
In the formula:
-M represents to be selected from hydrogen, NH
4With one, two, three and a kind of element of tetravalent metal,
-X represents to be selected from a kind of trivalent element of Al, Ga, Fe and B,
-n represents from 1 to 4 number,
-m represents to be equal to or greater than 10 number,
-p represents from 0 to 40 number.
6, according to the method for claim 3, it is characterized in that this acidic molecular sieve is the zeolite of the faujusite structure of X zeolite or zeolite Y type, they have with the logical formula II of oxidation than expression:
In the formula:
-M represents to be selected from hydrogen, NH
4With one, two, three and a kind of element of tetravalent metal, M to small part be hydrogen atom,
-Z represents to be selected from a kind of trivalent element of Al, Ga, Fe and B,
-n represents from 1 to 4 number,
-d represents to be equal to or greater than 2 number,
-x represents from 5 to 100 number.
7, according to each method among the claim 3-6, it is characterized in that this acidic molecular sieve be in its general formula, be used for silicon-dioxide bonded oxide compound be the acid zeolite of trivalent metal oxide.
8,, it is characterized in that the clay that adopts is for example montmorillonite, beidellite, nontronite, hectorite, rich magnesium montmorillonite and a talcum powder of terre verte according to the method for claim 3.
9, according to the method for claim 3, it is characterized in that the bridging clay that adopts is to have introduced the bridge shape at maintenance base portion interval or the clay of column between its thallus, the bridging of clay can be by the oxyhydroxide of aluminium, vanadium, molybdenum, zirconium, iron, niobium, tantalum, chromium, lanthanum, cerium, titanium or gallium or by the mixed hydroxides of above-mentioned some metal, preferably by the beidellite of aluminium hydroxide bridging.
10,, it is characterized in that the bridging clay that adopts is by for example effect modification of sulfuric acid or haloid acid of dihalo, ammonium halide or certain acid, can select preferred chlorine of halogen or the fluorine introduced according to the method for one of claim 3 and 9.
11, according to the method for claim 3, it is characterized in that the soild oxide that is adopted is the mixture of metal oxide, metal oxide or by dihalo, ammonium halide or certain acid metal oxide of the effect modification of sulfuric acid or halogenation hydracid for example, can select preferred chlorine of halogen or the fluorine introduced.
12,, it is characterized in that the soild oxide that is adopted is to be selected from mixture SiO according to the method for one of claim 3 and 11
2/ Al
2O
3, SiO
2/ Ga
2O
3, SiO
2/ Fe
2O
3, SiO
2/ B
2O
3, halogenated alumina for example chlorating alumina and fluorizated alumina, sulfonated zirconium white, niobium oxides or Tungsten oxide 99.999.
13,, it is characterized in that this superphosphate is selected from the phosphoric acid salt of boron and (is introduced separately into or by different H according to the method for claim 3
3BO
3/ H
3PO
4Mol ratio (is equivalent to different Al with the phosphoric acid salt that alumina or silicon-dioxide mix back introducing in building-up process, lanthanum orthophosphate, aluminium
2O
3/ H
3PO
4Mol ratio is introduced in building-up process), Vanadium Pentoxide in FLAKES/-mixture (being commonly referred to the UOP catalyzer) of silicon-dioxide, have zeolite structured aluminate or phosphate (AlPO) and have zeolite structured aluminosilicophosphate (SAPO).
14,, it is characterized in that this catalyzer is the alkali solid catalyst that is selected from basic metal phosphoric acid salt, alkaline metal oxide, metal carbonate and alkaline molecular sieve according to the method for one of claim 1 and 2.
15,, it is characterized in that this basic metal phosphoric acid salt mainly is the various phosphoric acid salt of logical formula III according to the method for claim 14:
In the formula:
-A represents that an atoms metal, one group of atoms metal or a part are hydrogen atoms;
-y represents from 3/4 to 3 integer or mark (valency that depends on elements A);
-Imp represents alkaline impregnation compound, and its contained metal (be used for oppositely negatively charged ion chemical combination to guarantee electric neutrality) is selected from alkaline-earth metal, basic metal and composition thereof;
-coefficient z represents soaker and macerate (A
yPO
4) weight ratio, its value is for 0%-20%, preferred 2%-10%.
16,, it is characterized in that basic metal phosphoric acid salt mainly is the various phosphoric acid salt of logical formula III according to the method for one of claim 14 and 15:
In the formula:
-A represents that calcium, zirconium, lanthanum, cerium, samarium, aluminium, boron, iron and a part are hydrogen;
-y represents from 3/4 to 3 integer or mark (valency that depends on elements A);
-Imp represents oppositely negatively charged ion of basic metal or alkali-metal mixture and alkalescence;
The value of-coefficient z is 2%-10%.
17, according to each method among the claim 14-16, it is characterized in that basic metal phosphoric acid salt mainly is the combination of lanthanum orthophosphate and caesium, rubidium or potassium compound, the combination of Cerium monophosphate and caesium, rubidium or potassium compound, the combination of samaric orthophosphate and caesium, rubidium or potassium compound, the combination of secondary calcium phosphate and caesium, rubidium or potassium compound, the combination of the combination of secondary calcium phosphate and caesium, rubidium or potassium compound or phosphoric acid hydrogen zirconium and caesium, rubidium or potassium compound.
18,, it is characterized in that this basic metal phosphoric acid salt can be with the Imp suspension in a kind of solution or the volatile solvent, preferably water for example, the logical formula IV (A of dipping according to each method among the claim 14-17
' yPO
4) compound be prepared, in the general formula, A' is identical with the implication of A.
19, according to each method among the claim 14-18, it is characterized in that this basic metal method for production of phosphate salt comprises:
A) synthetic compound A
' yPO
4; Preferably from reaction mixture, do not separate A
' yPO
4;
B) soaker Imp is introduced in the reaction mixture;
C) raffinate in the separating reaction solid;
D) dry and calcining in case of necessity.
20,, it is characterized in that this alkaline metal oxide mainly is the oxide compound of alkalescence or by for example can become the oxide compound of alkalescence after the hydroxide treatment of basic metal or alkaline-earth metal with alkali according to the method for claim 14.
21,, it is characterized in that this alkaline metal oxide is to be selected from the oxide compound that III a family alkali-metal, alkaline-earth metal, the period of element table sort is metal, transition element or rare earth metal, pass through or do not handle through alkali metal hydroxide according to the method for one of claim 14 and 20.
22, according to the method for claim 14, it is characterized in that this alkaline molecular sieve mainly is the zeolite of pentasil structure, the zeolite of for example ZSM-5, ZSM-11, ZSM-22, ZSM-23 or ZSM-48, mordenite structure, the ferrierite structure or faujusite structure, for example zeolite of X zeolite or zeolite Y, the general formula (V) represented with oxide compound:
In the formula:
-E represents basic metal or alkaline-earth metal, and whole or small portion is a hydrogen,
-T represents to be selected from the trivalent metal of Al, Ga, Fe and B,
-a represents from 1 to 2 number,
-b represents to be equal to or greater than 2 number,
-r represents from 0 to 100 number.
23,, it is characterized in that this alkaline molecular sieve mainly is zeolite ZSM-5, ZSM-11, ZSM-22, ZSM-23 and ZSM-48, mordenite, ferrierite, faujusite for example X zeolite or zeolite Y according to the method for claim 14.
24,, it is characterized in that this catalyzer is the both sexes solid catalyst that is selected from the amphoteric metal oxide compound according to the method for one of claim 1 and 2.
25,, it is characterized in that this amphoteric metal oxide compound is an amphoteric oxide compound or by its preparation method or through becoming the amphoteric oxide compound after the aftertreatment, for example thorium dioxide (ThO according to the method for claim 24
2), zirconium dioxide (ZrO
2), titanium dioxide (TiO
2), cerium dioxide (CeO
2), silicon-dioxide (SiO
2), alumina (Al
2O
3) and some above-mentioned hopcalites.
26, according to each method among the claim 1-25, it is characterized in that the temperature that is adopted is 200 ℃-500 ℃, preferred 250 ℃-400 ℃.
27, according to each method among the claim 1-26, it is characterized in that the 2-pentenoic acid can enter in the reactor that catalyzer is housed individually.
28, according to each method among the claim 1-24, it is characterized in that the 2-pentenoic acid can introduce reactor together with inert carrier gas, this inert carrier gas is made up of the mixture of a kind of gas or some gases, they are inert under reaction conditions, for example nitrogen, argon gas, air, steam and be the carboxylic acid of gas under the service temperature of reaction.
29,, it is characterized in that the 10%-100%(weight of the content of 2-pentenoic acid for the gas gross weight of introducing reactor according to the method for one of claim 27 and 28), preferred 40%-100%.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| FR9212184A FR2696451B1 (en) | 1992-10-02 | 1992-10-02 | Process for the isomerization of pentene-2-oic acid into pentene-3-oic and pentene-4-oic acids by basic catalysis. |
| FR9212183 | 1992-10-02 | ||
| FR9212185A FR2696452B1 (en) | 1992-10-02 | 1992-10-02 | Process for the isomerization of pentene-2-oic acid into pentene-3-oic and pentene-4-oic acids by amphoteric catalysis. |
| FR9212183A FR2696450B1 (en) | 1992-10-02 | 1992-10-02 | Process for the isomerization of pentene-2-oic acid into pentene-3-oic and pentene-4-oic acids by acid catalysis. |
| FR9212184 | 1992-10-02 | ||
| FR9212185 | 1992-10-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1089934A true CN1089934A (en) | 1994-07-27 |
Family
ID=27252668
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93118205A Pending CN1089934A (en) | 1992-10-02 | 1993-09-28 | The method for preparing 3-pentenoic acid and 4-pentenoic acid with acidity, alkalescence or amphoteric catalyst isomerization 2-pentenoic acid |
Country Status (13)
| Country | Link |
|---|---|
| EP (1) | EP0662945A1 (en) |
| JP (1) | JPH08500839A (en) |
| KR (1) | KR950703509A (en) |
| CN (1) | CN1089934A (en) |
| BR (1) | BR9307160A (en) |
| CA (1) | CA2146154A1 (en) |
| CZ (1) | CZ79695A3 (en) |
| MX (1) | MX9306075A (en) |
| PL (1) | PL308209A1 (en) |
| SG (1) | SG43041A1 (en) |
| SK (1) | SK41795A3 (en) |
| TW (1) | TW272979B (en) |
| WO (1) | WO1994007836A1 (en) |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2382464A (en) * | 1942-01-30 | 1945-08-14 | Carbide & Carbon Chem Corp | Production of unsaturated carboxylic acids |
| US3090807A (en) * | 1958-07-31 | 1963-05-21 | Basf Ag | Isomerization of saturated aliphatic carboxylic acids |
| US3389156A (en) * | 1965-03-22 | 1968-06-18 | Ashland Oil Inc | Process for isomerizing unsaturated fatty acids or derivatives thereof |
| US3470214A (en) * | 1968-04-23 | 1969-09-30 | Air Prod & Chem | Isomerization of tetrahydrophthalic anhydride |
| GB1454751A (en) * | 1973-04-11 | 1976-11-03 | Laporte Industries Ltd | Production of ypsilon lactones |
| DE3317163A1 (en) * | 1983-05-11 | 1984-11-15 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING 4-PENTENIC ACID ESTERS |
| DE3521381A1 (en) * | 1985-06-14 | 1986-12-18 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING 4-PENTENIC ACID ESTERS |
| DE3638011A1 (en) * | 1986-11-07 | 1988-05-11 | Basf Ag | METHOD FOR PRODUCING 4-PENTENIC ACID ESTERS |
| DE3640597A1 (en) * | 1986-11-27 | 1988-06-01 | Basf Ag | METHOD FOR ISOMERIZING 2-PENTENIC ACID ESTERS TO 3-PENTENSIC ACID ESTERS |
-
1993
- 1993-09-14 TW TW082107534A patent/TW272979B/zh active
- 1993-09-23 EP EP93920925A patent/EP0662945A1/en not_active Ceased
- 1993-09-23 SG SG1996002905A patent/SG43041A1/en unknown
- 1993-09-23 JP JP6508768A patent/JPH08500839A/en not_active Ceased
- 1993-09-23 KR KR1019950701254A patent/KR950703509A/en not_active Ceased
- 1993-09-23 CZ CZ95796A patent/CZ79695A3/en unknown
- 1993-09-23 SK SK417-95A patent/SK41795A3/en unknown
- 1993-09-23 CA CA002146154A patent/CA2146154A1/en not_active Abandoned
- 1993-09-23 BR BR9307160A patent/BR9307160A/en not_active Application Discontinuation
- 1993-09-23 WO PCT/FR1993/000929 patent/WO1994007836A1/en not_active Ceased
- 1993-09-23 PL PL93308209A patent/PL308209A1/en unknown
- 1993-09-28 CN CN93118205A patent/CN1089934A/en active Pending
- 1993-09-30 MX MX9306075A patent/MX9306075A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CZ79695A3 (en) | 1995-09-13 |
| EP0662945A1 (en) | 1995-07-19 |
| JPH08500839A (en) | 1996-01-30 |
| SG43041A1 (en) | 1997-10-17 |
| TW272979B (en) | 1996-03-21 |
| SK41795A3 (en) | 1995-08-09 |
| MX9306075A (en) | 1994-06-30 |
| KR950703509A (en) | 1995-09-20 |
| WO1994007836A1 (en) | 1994-04-14 |
| PL308209A1 (en) | 1995-07-24 |
| BR9307160A (en) | 1999-03-30 |
| CA2146154A1 (en) | 1994-04-14 |
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