CN117529365A - Epoxidation catalyst system and process for preparing epoxide - Google Patents
Epoxidation catalyst system and process for preparing epoxide Download PDFInfo
- Publication number
- CN117529365A CN117529365A CN202280043467.7A CN202280043467A CN117529365A CN 117529365 A CN117529365 A CN 117529365A CN 202280043467 A CN202280043467 A CN 202280043467A CN 117529365 A CN117529365 A CN 117529365A
- Authority
- CN
- China
- Prior art keywords
- hydroxide
- catalyst system
- epoxidation catalyst
- equal
- propylene
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 168
- 238000006735 epoxidation reaction Methods 0.000 title claims abstract description 129
- 150000002118 epoxides Chemical class 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title description 34
- 238000000034 method Methods 0.000 claims abstract description 94
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 80
- 230000008569 process Effects 0.000 claims abstract description 58
- 150000001875 compounds Chemical class 0.000 claims abstract description 57
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- 239000000203 mixture Substances 0.000 claims abstract description 45
- 150000003839 salts Chemical class 0.000 claims abstract description 45
- 150000001336 alkenes Chemical class 0.000 claims abstract description 24
- 239000011133 lead Substances 0.000 claims abstract description 20
- 239000011651 chromium Substances 0.000 claims abstract description 19
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims abstract description 18
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 6
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052804 chromium Inorganic materials 0.000 claims abstract description 6
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 6
- 239000011733 molybdenum Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 63
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 58
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 57
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 57
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 48
- 238000006243 chemical reaction Methods 0.000 claims description 48
- 229910052760 oxygen Inorganic materials 0.000 claims description 48
- 239000001301 oxygen Substances 0.000 claims description 48
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical group N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 42
- -1 (trifluoromethyl) phenyl Chemical group 0.000 claims description 34
- 239000002904 solvent Substances 0.000 claims description 28
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 27
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 26
- 125000005842 heteroatom Chemical group 0.000 claims description 24
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000007795 chemical reaction product Substances 0.000 claims description 21
- 229910052757 nitrogen Inorganic materials 0.000 claims description 21
- 239000011572 manganese Substances 0.000 claims description 20
- 230000001590 oxidative effect Effects 0.000 claims description 19
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 12
- 125000001424 substituent group Chemical group 0.000 claims description 12
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 12
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 12
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 10
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 10
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 10
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 10
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 10
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 10
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 claims description 9
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 9
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 8
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 claims description 8
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 8
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 7
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 claims description 6
- HMBHAQMOBKLWRX-UHFFFAOYSA-N 2,3-dihydro-1,4-benzodioxine-3-carboxylic acid Chemical compound C1=CC=C2OC(C(=O)O)COC2=C1 HMBHAQMOBKLWRX-UHFFFAOYSA-N 0.000 claims description 6
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 claims description 6
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 claims description 6
- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 claims description 6
- 229940075419 choline hydroxide Drugs 0.000 claims description 6
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 claims description 6
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 claims description 6
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 6
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 6
- BJQWBACJIAKDTJ-UHFFFAOYSA-N tetrabutylphosphanium Chemical compound CCCC[P+](CCCC)(CCCC)CCCC BJQWBACJIAKDTJ-UHFFFAOYSA-N 0.000 claims description 6
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 6
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 6
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 6
- BFPOZPZYPNVMHU-UHFFFAOYSA-M trimethyl-[3-(trifluoromethyl)phenyl]azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)C1=CC=CC(C(F)(F)F)=C1 BFPOZPZYPNVMHU-UHFFFAOYSA-M 0.000 claims description 6
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 claims description 5
- VZHHNBNSMNNUAD-UHFFFAOYSA-N cobalt 2-[2-[(2-hydroxyphenyl)methylideneamino]ethyliminomethyl]phenol Chemical compound [Co].OC1=CC=CC=C1C=NCCN=CC1=CC=CC=C1O VZHHNBNSMNNUAD-UHFFFAOYSA-N 0.000 claims description 5
- LZKLAOYSENRNKR-LNTINUHCSA-N iron;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LZKLAOYSENRNKR-LNTINUHCSA-N 0.000 claims description 5
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 125000002723 alicyclic group Chemical group 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 4
- 229910052698 phosphorus Chemical group 0.000 claims description 4
- 239000011574 phosphorus Chemical group 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- SCZZNWQQCGSWSZ-UHFFFAOYSA-N 1-prop-2-enoxy-4-[2-(4-prop-2-enoxyphenyl)propan-2-yl]benzene Chemical compound C=1C=C(OCC=C)C=CC=1C(C)(C)C1=CC=C(OCC=C)C=C1 SCZZNWQQCGSWSZ-UHFFFAOYSA-N 0.000 claims description 3
- 239000007983 Tris buffer Substances 0.000 claims description 3
- OCVXZQOKBHXGRU-UHFFFAOYSA-N iodine(1+) Chemical compound [I+] OCVXZQOKBHXGRU-UHFFFAOYSA-N 0.000 claims description 3
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- POSICDHOUBKJKP-UHFFFAOYSA-N prop-2-enoxybenzene Chemical compound C=CCOC1=CC=CC=C1 POSICDHOUBKJKP-UHFFFAOYSA-N 0.000 claims description 3
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 claims description 2
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 27
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052740 iodine Inorganic materials 0.000 abstract description 23
- 239000011630 iodine Substances 0.000 abstract description 23
- 150000002739 metals Chemical class 0.000 abstract description 5
- 150000004679 hydroxides Chemical class 0.000 abstract description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 abstract description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 42
- 230000003647 oxidation Effects 0.000 description 26
- 239000007788 liquid Substances 0.000 description 25
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 239000000047 product Substances 0.000 description 20
- 239000000460 chlorine Substances 0.000 description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 230000005587 bubbling Effects 0.000 description 16
- 238000002474 experimental method Methods 0.000 description 16
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 14
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 12
- 230000015572 biosynthetic process Effects 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- 239000007787 solid Substances 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 230000004913 activation Effects 0.000 description 9
- 238000012360 testing method Methods 0.000 description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 238000004088 simulation Methods 0.000 description 8
- 229910001868 water Inorganic materials 0.000 description 8
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 7
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 7
- 230000033444 hydroxylation Effects 0.000 description 7
- 238000005805 hydroxylation reaction Methods 0.000 description 7
- 229910001510 metal chloride Inorganic materials 0.000 description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 6
- 229910002651 NO3 Inorganic materials 0.000 description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 6
- 229910002092 carbon dioxide Inorganic materials 0.000 description 6
- 238000001816 cooling Methods 0.000 description 6
- 235000012239 silicon dioxide Nutrition 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 description 6
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 5
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 5
- 238000007872 degassing Methods 0.000 description 5
- 229910044991 metal oxide Inorganic materials 0.000 description 5
- 150000004706 metal oxides Chemical class 0.000 description 5
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 5
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 4
- 238000003775 Density Functional Theory Methods 0.000 description 4
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 229910052581 Si3N4 Inorganic materials 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 4
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 4
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 4
- 229910001863 barium hydroxide Inorganic materials 0.000 description 4
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 4
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 4
- 239000000920 calcium hydroxide Substances 0.000 description 4
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000005470 impregnation Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 4
- 229910052622 kaolinite Inorganic materials 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 229910052615 phyllosilicate Inorganic materials 0.000 description 4
- 229910052903 pyrophyllite Inorganic materials 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 150000004760 silicates Chemical class 0.000 description 4
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 4
- 238000009751 slip forming Methods 0.000 description 4
- 229910001388 sodium aluminate Inorganic materials 0.000 description 4
- HVTHJRMZXBWFNE-UHFFFAOYSA-J sodium zincate Chemical compound [OH-].[OH-].[OH-].[OH-].[Na+].[Na+].[Zn+2] HVTHJRMZXBWFNE-UHFFFAOYSA-J 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000011877 solvent mixture Substances 0.000 description 4
- 239000000454 talc Substances 0.000 description 4
- 229910052623 talc Inorganic materials 0.000 description 4
- 230000007704 transition Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- YOUGRGFIHBUKRS-UHFFFAOYSA-N benzyl(trimethyl)azanium Chemical compound C[N+](C)(C)CC1=CC=CC=C1 YOUGRGFIHBUKRS-UHFFFAOYSA-N 0.000 description 3
- 238000007599 discharging Methods 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 238000000746 purification Methods 0.000 description 3
- LWRNQOBXRHWPGE-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4a,5,5,6,6,7,7,8,8a-heptadecafluoro-8-(trifluoromethyl)naphthalene Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)C2(F)C(C(F)(F)F)(F)C(F)(F)C(F)(F)C(F)(F)C21F LWRNQOBXRHWPGE-UHFFFAOYSA-N 0.000 description 2
- RBACIKXCRWGCBB-UHFFFAOYSA-N 1,2-Epoxybutane Chemical compound CCC1CO1 RBACIKXCRWGCBB-UHFFFAOYSA-N 0.000 description 2
- GELKGHVAFRCJNA-UHFFFAOYSA-N 2,2-Dimethyloxirane Chemical compound CC1(C)CO1 GELKGHVAFRCJNA-UHFFFAOYSA-N 0.000 description 2
- YXIOECOAAMLHPG-UHFFFAOYSA-N 2-(2-methylpropyl)oxirane Chemical compound CC(C)CC1CO1 YXIOECOAAMLHPG-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 description 2
- 125000002947 alkylene group Chemical group 0.000 description 2
- 238000005284 basis set Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229950005499 carbon tetrachloride Drugs 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 150000003983 crown ethers Chemical class 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- RCJVRSBWZCNNQT-UHFFFAOYSA-N dichloridooxygen Chemical compound ClOCl RCJVRSBWZCNNQT-UHFFFAOYSA-N 0.000 description 2
- 239000003085 diluting agent Substances 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 125000003055 glycidyl group Chemical group C(C1CO1)* 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000026045 iodination Effects 0.000 description 2
- 238000006192 iodination reaction Methods 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 238000005649 metathesis reaction Methods 0.000 description 2
- 229950011087 perflunafene Drugs 0.000 description 2
- UWEYRJFJVCLAGH-IJWZVTFUSA-N perfluorodecalin Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)[C@@]2(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)[C@@]21F UWEYRJFJVCLAGH-IJWZVTFUSA-N 0.000 description 2
- QKENRHXGDUPTEM-UHFFFAOYSA-N perfluorophenanthrene Chemical compound FC1(F)C(F)(F)C(F)(F)C(F)(F)C2(F)C3(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C3(F)C(F)(F)C(F)(F)C21F QKENRHXGDUPTEM-UHFFFAOYSA-N 0.000 description 2
- XOKSLPVRUOBDEW-UHFFFAOYSA-N pinane Chemical compound CC1CCC2C(C)(C)C1C2 XOKSLPVRUOBDEW-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 description 2
- RRKODOZNUZCUBN-CCAGOZQPSA-N (1z,3z)-cycloocta-1,3-diene Chemical compound C1CC\C=C/C=C\C1 RRKODOZNUZCUBN-CCAGOZQPSA-N 0.000 description 1
- UKDOTCFNLHHKOF-FGRDZWBJSA-N (z)-1-chloroprop-1-ene;(z)-1,2-dichloroethene Chemical group C\C=C/Cl.Cl\C=C/Cl UKDOTCFNLHHKOF-FGRDZWBJSA-N 0.000 description 1
- XZNOAVNRSFURIR-UHFFFAOYSA-N 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)propan-2-ol Chemical compound FC(F)(F)C(O)(C(F)(F)F)C(F)(F)F XZNOAVNRSFURIR-UHFFFAOYSA-N 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- PRJNEUBECVAVAG-UHFFFAOYSA-N 1,3-bis(ethenyl)benzene Chemical compound C=CC1=CC=CC(C=C)=C1 PRJNEUBECVAVAG-UHFFFAOYSA-N 0.000 description 1
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- KFTODZKBBUMDQB-UHFFFAOYSA-N 1-bromo-2-chloro-1,1,2-trifluoroethane Chemical compound FC(Cl)C(F)(F)Br KFTODZKBBUMDQB-UHFFFAOYSA-N 0.000 description 1
- YYTSGNJTASLUOY-UHFFFAOYSA-N 1-chloropropan-2-ol Chemical compound CC(O)CCl YYTSGNJTASLUOY-UHFFFAOYSA-N 0.000 description 1
- WAPNOHKVXSQRPX-UHFFFAOYSA-N 1-phenylethanol Chemical compound CC(O)C1=CC=CC=C1 WAPNOHKVXSQRPX-UHFFFAOYSA-N 0.000 description 1
- OVKYVUFYOFPYNK-UHFFFAOYSA-N 2,2-diethyloxirane Chemical compound CCC1(CC)CO1 OVKYVUFYOFPYNK-UHFFFAOYSA-N 0.000 description 1
- PCGTXZMDZGOMJG-UHFFFAOYSA-N 2,3-diethyloxirane Chemical compound CCC1OC1CC PCGTXZMDZGOMJG-UHFFFAOYSA-N 0.000 description 1
- PQXKWPLDPFFDJP-UHFFFAOYSA-N 2,3-dimethyloxirane Chemical compound CC1OC1C PQXKWPLDPFFDJP-UHFFFAOYSA-N 0.000 description 1
- STMDPCBYJCIZOD-UHFFFAOYSA-N 2-(2,4-dinitroanilino)-4-methylpentanoic acid Chemical compound CC(C)CC(C(O)=O)NC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O STMDPCBYJCIZOD-UHFFFAOYSA-N 0.000 description 1
- BBBUAWSVILPJLL-UHFFFAOYSA-N 2-(2-ethylhexoxymethyl)oxirane Chemical compound CCCCC(CC)COCC1CO1 BBBUAWSVILPJLL-UHFFFAOYSA-N 0.000 description 1
- LKMJVFRMDSNFRT-UHFFFAOYSA-N 2-(methoxymethyl)oxirane Chemical compound COCC1CO1 LKMJVFRMDSNFRT-UHFFFAOYSA-N 0.000 description 1
- WHNBDXQTMPYBAT-UHFFFAOYSA-N 2-butyloxirane Chemical compound CCCCC1CO1 WHNBDXQTMPYBAT-UHFFFAOYSA-N 0.000 description 1
- GBOMEIMCQWMHGB-UHFFFAOYSA-N 2-butyltetrahydrofuran Chemical compound CCCCC1CCCO1 GBOMEIMCQWMHGB-UHFFFAOYSA-N 0.000 description 1
- VZIQXGLTRZLBEX-UHFFFAOYSA-N 2-chloro-1-propanol Chemical class CC(Cl)CO VZIQXGLTRZLBEX-UHFFFAOYSA-N 0.000 description 1
- MPGABYXKKCLIRW-UHFFFAOYSA-N 2-decyloxirane Chemical compound CCCCCCCCCCC1CO1 MPGABYXKKCLIRW-UHFFFAOYSA-N 0.000 description 1
- QZXUQPKFNQQQAJ-UHFFFAOYSA-N 2-ethyl-2-methyloxirane Chemical compound CCC1(C)CO1 QZXUQPKFNQQQAJ-UHFFFAOYSA-N 0.000 description 1
- GXOYTMXAKFMIRK-UHFFFAOYSA-N 2-heptyloxirane Chemical compound CCCCCCCC1CO1 GXOYTMXAKFMIRK-UHFFFAOYSA-N 0.000 description 1
- NJWSNNWLBMSXQR-UHFFFAOYSA-N 2-hexyloxirane Chemical compound CCCCCCC1CO1 NJWSNNWLBMSXQR-UHFFFAOYSA-N 0.000 description 1
- FFXMEOKFDOVSGT-UHFFFAOYSA-N 2-methyl-2-propyloxirane Chemical compound CCCC1(C)CO1 FFXMEOKFDOVSGT-UHFFFAOYSA-N 0.000 description 1
- YVCOJTATJWDGEU-UHFFFAOYSA-N 2-methyl-3-phenyloxirane Chemical compound CC1OC1C1=CC=CC=C1 YVCOJTATJWDGEU-UHFFFAOYSA-N 0.000 description 1
- LIESJAYIOKBLIL-UHFFFAOYSA-N 2-methyl-3-propyloxirane Chemical compound CCCC1OC1C LIESJAYIOKBLIL-UHFFFAOYSA-N 0.000 description 1
- LXVAZSIZYQIZCR-UHFFFAOYSA-N 2-nonyloxirane Chemical compound CCCCCCCCCC1CO1 LXVAZSIZYQIZCR-UHFFFAOYSA-N 0.000 description 1
- AAMHBRRZYSORSH-UHFFFAOYSA-N 2-octyloxirane Chemical compound CCCCCCCCC1CO1 AAMHBRRZYSORSH-UHFFFAOYSA-N 0.000 description 1
- NMOFYYYCFRVWBK-UHFFFAOYSA-N 2-pentyloxirane Chemical compound CCCCCC1CO1 NMOFYYYCFRVWBK-UHFFFAOYSA-N 0.000 description 1
- REYZXWIIUPKFTI-UHFFFAOYSA-N 2-propan-2-yloxirane Chemical compound CC(C)C1CO1 REYZXWIIUPKFTI-UHFFFAOYSA-N 0.000 description 1
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 description 1
- HWOWEGAQDKKHDR-UHFFFAOYSA-N 4-hydroxy-6-(pyridin-3-yl)-2H-pyran-2-one Chemical compound O1C(=O)C=C(O)C=C1C1=CC=CN=C1 HWOWEGAQDKKHDR-UHFFFAOYSA-N 0.000 description 1
- MLOZFLXCWGERSM-UHFFFAOYSA-N 8-oxabicyclo[5.1.0]octane Chemical compound C1CCCCC2OC21 MLOZFLXCWGERSM-UHFFFAOYSA-N 0.000 description 1
- MELPJGOMEMRMPL-UHFFFAOYSA-N 9-oxabicyclo[6.1.0]nonane Chemical compound C1CCCCCC2OC21 MELPJGOMEMRMPL-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- GXBYFVGCMPJVJX-UHFFFAOYSA-N Epoxybutene Chemical compound C=CC1CO1 GXBYFVGCMPJVJX-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- CTKINSOISVBQLD-UHFFFAOYSA-N Glycidol Chemical class OCC1CO1 CTKINSOISVBQLD-UHFFFAOYSA-N 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 229910002089 NOx Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- FQYUMYWMJTYZTK-UHFFFAOYSA-N Phenyl glycidyl ether Chemical compound C1OC1COC1=CC=CC=C1 FQYUMYWMJTYZTK-UHFFFAOYSA-N 0.000 description 1
- AWMVMTVKBNGEAK-UHFFFAOYSA-N Styrene oxide Chemical compound C1OC1C1=CC=CC=C1 AWMVMTVKBNGEAK-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- 229910021626 Tin(II) chloride Inorganic materials 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- YPQXZQGMHZHWAU-UHFFFAOYSA-N [Mo+6].ClOCl Chemical compound [Mo+6].ClOCl YPQXZQGMHZHWAU-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N alpha-methylbenzylalcohol Natural products CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 description 1
- GMGLYSIINJPYLI-UHFFFAOYSA-N butan-2-one;propan-2-one Chemical compound CC(C)=O.CCC(C)=O GMGLYSIINJPYLI-UHFFFAOYSA-N 0.000 description 1
- 239000001110 calcium chloride Substances 0.000 description 1
- 229910001628 calcium chloride Inorganic materials 0.000 description 1
- 235000011148 calcium chloride Nutrition 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 239000012084 conversion product Substances 0.000 description 1
- 229960003280 cupric chloride Drugs 0.000 description 1
- HYPABJGVBDSCIT-UPHRSURJSA-N cyclododecene Chemical compound C1CCCCC\C=C/CCCC1 HYPABJGVBDSCIT-UPHRSURJSA-N 0.000 description 1
- QSAWQNUELGIYBC-UHFFFAOYSA-L cyclohexane-1,2-dicarboxylate Chemical compound [O-]C(=O)C1CCCCC1C([O-])=O QSAWQNUELGIYBC-UHFFFAOYSA-L 0.000 description 1
- ZWAJLVLEBYIOTI-UHFFFAOYSA-N cyclohexene oxide Chemical compound C1CCCC2OC21 ZWAJLVLEBYIOTI-UHFFFAOYSA-N 0.000 description 1
- 229940117389 dichlorobenzene Drugs 0.000 description 1
- GYZLOYUZLJXAJU-UHFFFAOYSA-N diglycidyl ether Chemical class C1OC1COCC1CO1 GYZLOYUZLJXAJU-UHFFFAOYSA-N 0.000 description 1
- 238000011234 economic evaluation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 229960003750 ethyl chloride Drugs 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000012812 general test Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- GNOIPBMMFNIUFM-UHFFFAOYSA-N hexamethylphosphoric triamide Chemical compound CN(C)P(=O)(N(C)C)N(C)C GNOIPBMMFNIUFM-UHFFFAOYSA-N 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N hexane Substances CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 239000003701 inert diluent Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- HWSZZLVAJGOAAY-UHFFFAOYSA-L lead(II) chloride Chemical compound Cl[Pb]Cl HWSZZLVAJGOAAY-UHFFFAOYSA-L 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940050176 methyl chloride Drugs 0.000 description 1
- 239000008267 milk Substances 0.000 description 1
- 210000004080 milk Anatomy 0.000 description 1
- 235000013336 milk Nutrition 0.000 description 1
- GICWIDZXWJGTCI-UHFFFAOYSA-I molybdenum pentachloride Chemical compound Cl[Mo](Cl)(Cl)(Cl)Cl GICWIDZXWJGTCI-UHFFFAOYSA-I 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- RPQRDASANLAFCM-UHFFFAOYSA-N oxiran-2-ylmethyl prop-2-enoate Chemical compound C=CC(=O)OCC1CO1 RPQRDASANLAFCM-UHFFFAOYSA-N 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- ZGSXCGTUPZOUPE-UHFFFAOYSA-N oxolane;tetrachloromethane Chemical compound C1CCOC1.ClC(Cl)(Cl)Cl ZGSXCGTUPZOUPE-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229930006728 pinane Natural products 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000006894 reductive elimination reaction Methods 0.000 description 1
- 235000011150 stannous chloride Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- ADXGNEYLLLSOAR-UHFFFAOYSA-N tasosartan Chemical compound C12=NC(C)=NC(C)=C2CCC(=O)N1CC(C=C1)=CC=C1C1=CC=CC=C1C=1N=NNN=1 ADXGNEYLLLSOAR-UHFFFAOYSA-N 0.000 description 1
- AXZWODMDQAVCJE-UHFFFAOYSA-L tin(II) chloride (anhydrous) Chemical compound [Cl-].[Cl-].[Sn+2] AXZWODMDQAVCJE-UHFFFAOYSA-L 0.000 description 1
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Landscapes
- Epoxy Compounds (AREA)
Abstract
The subject of the present invention is a first epoxidation catalyst system comprising a mixture of metallic salts and hydroxides of the metals chromium, manganese, molybdenum, lead and/or bismuth, and a redox-active compound. Another subject of the invention is a further second epoxidation catalyst system comprising a mixture of a further metal salt, iodine and hydroxide. Also, a process for producing an epoxide comprising the oxidation reaction of an olefin in a reactor in the presence of a first epoxidation catalyst system or a second epoxidation catalyst system.
Description
The subject of the present invention is a first epoxidation catalyst system comprising a mixture of metallic salts and hydroxides of the metals chromium, manganese, molybdenum, lead and/or bismuth, and a redox-active compound. Another subject of the invention is a further second epoxidation catalyst system comprising a mixture of a further metal salt, iodine and hydroxide. Also a process for producing an epoxide comprising the oxidative conversion of an olefin in a reactor in the presence of a first epoxidation catalyst system or a second epoxidation catalyst system.
The prior art has described a number of processes for the production of alkylene oxides, in particular propylene oxide, of particular industrial interest in which propylene is reacted with hypochlorous acid or with chlorine and water, 1-chloro-2-propanol and 2-chloro-1-propanol isomer mixtures, followed by reaction with lime milk to produce propylene oxide and calcium chloride. However, the formation of CaCl2 salt load results in high wastewater pollution or additional recycling steps and incorporation into chlor-alkali operation. This technology is considered disadvantageous in terms of carbon footprint (english carbon print) and greenhouse gas emissions (Reduction of GHG Emissions in Propylene Oxide Production, approved VCS Methodology VM version 0023, 1.0,2013, 9-solar Scope 5,South Pole Carbon Asset Management Ltd).
It is furthermore relevant to produce propylene oxide by means of a co-product based process, such as an ethylene oxide process, wherein ethylbenzene or isobutane is converted in a first stage in the presence of oxygen to the respective hydroperoxide, which can then be reacted with propylene to produce propylene oxide and 1-phenylethanol or tert-butanol as further co-products. These co-products can then be further converted into styrene and isobutene or isobutane. However, in addition to propylene oxide, co-products are likewise formed which have to be separated off additionally and processed further in other units. Co-product based processes continue to require the co-product market and make these processes economically complex and susceptible to adverse effects. Thus, in addition to the technically demanding methods, there is also a significant market economic risk, so that technical and economic evaluations of these methods represent a less favorable overall view. This is especially because the demand and sales of the two products, namely PO and co-product, often have regional differences. In other words, a remote stream is required, which brings direct costs and other drawbacks, such as CO2/GHG emissions. Industrial MTBE processes need to be incorporated into refinery operations to make the greatest economic contribution.
Also relevant at industrial scale is the so-called HPPO process, in which propylene is reacted with hydrogen peroxide to produce propylene oxide and water. It is advantageous in comparison with the above-described industrial-scale production process that there is no co-product or salt burden in the product. However, hydrogen peroxide must be produced in an upstream, technically complex catalytic process. This method is considered technically demanding and is usually only run at the integration site with other H2O2 consumers.
The direct oxidation of propylene to propylene oxide is additionally considered to be technically immature and, according to the state of the art, there is no direct oxidation process which can be economically carried out on an industrial scale. In particular, reaction management, especially temperature control, in gas phase and salt melt processes is an unresolved challenge, but where high propylene conversion and high PO selectivity are critical to efficient industrial processes. In the case of direct oxidation, there are numerous byproducts and conversion products in large amounts, such as methanol, acetaldehyde, carbon dioxide, ethylene, and formaldehyde (see d.kahlich et al Dow Deutschland in Ullmann's Encyclopedia of Industrial Chemistry, section entitled "Propylene Oxide", wiley VCH, 2012). For example, the prior art documents which may be cited in connection with the aerobic oxidation of olefins such as propylene are US2018208569A1 and US2020346193A1. At 8.6% and 5% conversion, the epoxy selectivity was only 54.5% and 60% respectively.
It is therefore an object of the present invention to provide a catalyst system for the direct production of epoxides, preferably propylene oxide, which has an improved epoxide conversion in the oxidative conversion of olefins, preferably with oxygen or oxygen-containing gas mixtures, compared to the systems known in the prior art, and an improved product selectivity by reducing the formation of unwanted by-products and avoiding the formation of various co-products. The improved catalyst activity and selectivity should be manifested in the hydroxylation of propylene, i.e. the addition of propylene to the catalyst system, and the formation of propylene oxide from the catalyst bodyThe activation energy E of the reaction sequence or reaction mechanism of the reduction elimination is as small as possible A 。
It has surprisingly been found that the object of the present invention is achieved by an epoxidation catalyst system (1), an epoxidation catalyst system (2) and a process for producing epoxide, which process comprises the oxidative conversion of an olefin in a reactor in the presence of the epoxidation catalyst system (1) or the epoxidation catalyst system (2).
The epoxidation catalyst system (1) here comprises
a) A mixture (1) or reaction product (1) of
a-1) metallic chromium (Cr), manganese (Mn), molybdenum (Mo), lead (Pb) and/or bismuth (Bi), and
a-2) a hydroxide (B),
b) A redox-active compound (C).
According to the invention, one or more metal salts (A) of the metals chromium (Cr), manganese (Mn), molybdenum (Mo), lead (Pb) and/or bismuth (Bi) are used.
The following embodiments may be arbitrarily combined unless otherwise apparent from the technical background and general expert knowledge.
In one embodiment of the invention, the metal salt (a) is a nitrate, a halide, a tetrafluoroborate, a sulfate, a p-toluenesulfonate, a methanesulfonate and/or a trifluoromethanesulfonate, preferably a chloride.
In a preferred embodiment of the invention, the metal salt (A) is one or more compounds and is selected from MoCl 5 、MoOCl 3 、MnCl 2 、K 2 MnCl 6 、CrOCl 2 、PbCl 4 And BiCl 3 。
In one embodiment of the present invention, hydroxide (B) is an organic hydroxide (B-1) and/or an inorganic hydroxide (B-2).
In a preferred embodiment of the present invention, hydroxide (B) is an organic hydroxide (B-1), and organic hydroxide (B-1) is one or more compounds selected from the group consisting of 3- (trifluoromethyl) phenyltrimethylammonium hydroxide, tetra-n-butylphosphonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetrabutylammonium hydroxide, and tetramethylammonium hydroxide.
In a less preferred alternative embodiment of the invention, hydroxide (B) is an inorganic hydroxide (B-2) and inorganic hydroxide (B-2) is one or more compounds and is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide and crown complexes thereof, cesium hydroxide, calcium hydroxide, barium hydroxide, potassium aluminate, sodium aluminate, potassium aluminate and sodium zincate, preferably lithium hydroxide, sodium hydroxide and potassium hydroxide.
In one embodiment of the invention, the redox-active compound (C) is one or more compounds and is selected from CuCl 2 、Cu(BF 4 ) 2 、CuCl、VCl 3 、VOCl 3 、NH 4 VO 3 1, 4-benzoquinone, 1, 4-naphthoquinone, and Se 2 O 5 、TeO 2 、TeO 2 、Sb 2 O 3 、Sb 2 O 5 、CeCl 3 、Co(salen)、Co(OAc) 2 、SnSO 4 、Fe(acac) 3 、Mo(acac) 3 、K 2 Cr 2 O 7 、Mn(OAc) 3 、Ni(CF 3 CO 2 H) 2 And BiCl 3 。
In one embodiment of the invention, the calculated molar ratio of hydroxyl groups of the metal salt (A) to hydroxide (B) of the epoxidation catalyst system (1) is from 1.000mol:1.000mol to 6.000mol:1.000mol.
In one embodiment of the invention, the calculated molar ratio of metal salt (A) to redox-active compound (C) of epoxidation catalyst system (1) is from 0.100mol:1.000mol to 10.000mol:1.000mol.
In one embodiment of the invention, the calculated molar ratio of hydroxyl groups of hydroxide (B) to redox active compound (C) of epoxidation catalyst system (1) is from 0.100mol:1.000mol to 50.000mol:1.000mol.
In a less preferred embodiment of the invention, the epoxidation catalyst system (1) comprises a mixture (1) of metal salt (A) and hydroxide (B) in the above calculated molar ratio.
In a preferred embodiment of the present invention, the epoxidation catalyst system (1) comprises the reaction product (1) of a metal salt (a) and a hydroxide (B), wherein the metal salt (a) and the hydroxide (B) are produced by production methods known to the person skilled in the art, such as solid state synthesis, precipitation or co-precipitation methods, or in situ salt metathesis. Thus, the reaction product (1) can be synthesized, for example, by adding the organic hydroxide (B-1) and/or the inorganic hydroxide (B-2) to a solution of the nitrate, halide, tetrafluoroborate, sulfate, p-toluenesulfonate, methanesulfonate and/or trifluoromethanesulfonate, preferably chloride, of the metal salt (A) in the above-described calculated molar ratio, followed by separating out the precipitated product, drying and suitable heat treatment.
In a preferred embodiment of the present invention, the reaction product (1) of the epoxidation catalyst system (1) has the structure of the formulae (I), (II) and/or (III):
if m is<n+o，(Q R 1 R 2 R 3 R 4 ) + n+o-m [M(A) m+ (Hal) n (OH) o (S) p ] m-n-o (I)
If m=n+o, [ M (A) m+ (Hal) n (OH) o (S) p ] (II)
If m is>n+o，[M(A) m+ (Hal) n (OH) o (S) p ] (m-n-o) [X] - n+o-m (III)
Wherein the method comprises the steps of
Q=nitrogen or phosphorus, preferably nitrogen,
R 1 、R 2 、R 3 、R 4 independently of one another selected from
(i) A linear or branched alkyl group containing 1 to 22 carbon atoms, optionally substituted with heteroatoms and/or heteroatom-containing substituents;
(ii) Alicyclic groups containing 3 to 22 carbon atoms having 1 to 3 bridging carbon atoms, optionally substituted with heteroatoms and/or heteroatom-containing substituents, and/or
(iii) Aryl groups containing 6 to 18 carbon atoms, optionally substituted with 1 to 10 carbon atoms and/or optionally substituted with heteroatoms and/or heteroatom-containing substituents;
R 1 、R 2 、R 3 and R is 4 Preferably independently of one another selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, isobutyl, t-Bu, n-butyl, phenyl, benzyl, (trifluoromethyl) phenyl, M (A) m+ ＝Mo 5+ 、Mn 4+ 、Cr 4+ 、Pb 4+ 、Bi 5+ Mo is preferred 5+ ；
Hal＝Cl - 、Br - Or I - Preferably Cl - Or Br (Br) - More preferably Cl - ；
S＝H 2 O, THF (tetrahydrofuran) or dioxane, bis (2-methoxyethyl) ether (diethylene glycol dimethyl ether), methoxyethanol, polyethylene glycol, pyridine, lutidine, 2' -bipyridine, acetonitrile, dimethyl sulfoxide, sulfolane, thiophene, preferably THF;
n+o+p＝6
n is more than or equal to 1; preferably n is greater than or equal to 2; more preferably n=2
o is more than or equal to 1; preferably o is greater than or equal to 1; more preferably o=1; 2;3 or 4
X＝OTf - 、BF 4 - 、Hal - 。
In a particularly preferred embodiment of the invention, the reaction product (1) of the epoxidation catalyst system (1) is one or more compounds and is selected from the group consisting of [ Mo (V) Cl ] 2 (OH) 2 (THF) 2 ]Cl、[Mn(IV)Cl(OH) 3 (THF) 2 ]、[Cr(VI)Cl 2 (OH) 2 (THF) 2 ]Cl 2 、[Pb(IV)Cl 2 (OH) 2 (THF) 2 ]And [ Bi (V) Cl 2 (OH) 3 THF]。
Blending of mixture (1) or reaction product (1) with redox active compound (C) to produce epoxidation catalyst system (1) may be accomplished by mixing methods known to those skilled in the art, such as stirred addition of solutions or suitable blending of solids.
In one embodiment of the invention, the epoxidation catalyst system (1) also contains iodine (I 2 )。
In a preferred embodiment of the invention, iodine (I 2 ) The molar ratio is used in a calculated amount of 1 to 2000 mol% based on the amount of the metal salt (A).
In one embodiment of the invention, the epoxidation catalyst system (1) is applied to a catalyst support (D) to form a supported epoxidation catalyst system (1).
In a preferred embodiment of the invention, the catalyst support (D) is one or more compounds and is selected from the group consisting of metal oxides, alkaline earth metal carbonates, silicates, silicon carbide, silicon oxycarbide, silicon nitride, silicon oxynitride and silicon dioxide, preferably alumina, aluminum dioxide, silicon dioxide, titanium dioxide, zirconium dioxide, calcium carbonate, phyllosilicates, such as talc, kaolinite and pyrophyllite, and titanium dioxide.
According to the invention, the catalyst support may be in the form of a shaped body or a powder.
In one embodiment of the invention, the epoxidation catalyst system (1) may be applied to the catalyst support (D) in a calculated mass proportion of from 1.0 to 30.0% by weight.
In one embodiment of the invention, the epoxidation catalyst system (1) is applied to the catalyst support (D) by wet-impregnation or incipient wetness.
Another subject matter of the invention is an epoxidation catalyst system (2) comprising
c) A mixture (2) or reaction product (2) of
c-1) a metal salt (E),
c-2) iodine (I) 2 ) A kind of electronic device
c-3) hydroxide (F)
d) Optionally, a redox-active compound (G).
In one embodiment of the invention, the metal salt (E) is a nitrate, a halide, a tetrafluoroborate, a sulfate, a p-toluenesulfonate, a methanesulfonate and/or a trifluoromethanesulfonate, preferably a chloride.
In a preferred embodiment of the invention, the metal salt (E) is one or more ofThe compound is selected from NiCl 2 、MnCl 2 、PbCl 2 、SnCl 2 、CrCl 3 、VCl 3 、MoCl 4 、FeCl 2 And RuCl 3 。
In one embodiment of the present invention, hydroxide (F) is an organic hydroxide (F-1) and/or an inorganic hydroxide (F-2).
In a preferred embodiment of the present invention, hydroxide (F) is an organic hydroxide (B-1), and organic hydroxide (F-1) is one or more compounds selected from the group consisting of 3- (trifluoromethyl) phenyltrimethylammonium hydroxide, tetra-n-butylphosphonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetrabutylammonium hydroxide, and tetramethylammonium hydroxide.
In a less preferred alternative embodiment of the invention, hydroxide (F) is an inorganic hydroxide (F-2), and inorganic hydroxide (F-2) is one or more compounds and is selected from lithium hydroxide, sodium hydroxide, potassium hydroxide and crown complexes thereof, cesium hydroxide, calcium hydroxide, barium hydroxide, potassium aluminate, sodium aluminate, potassium aluminate and sodium zincate, preferably lithium hydroxide, sodium hydroxide and potassium hydroxide.
In one embodiment of the invention, the redox-active compound (G) is one or more compounds and is selected from CuCl 2 、Cu(BF 4 ) 2 、CuCl、VCl 3 、VOCl 3 、NH 4 VO 3 1, 4-benzoquinone, 1, 4-naphthoquinone, and Se 2 O 5 、TeO 2 、TeO 2 、Sb 2 O 3 、Sb 2 O 5 、CeCl 3 、Co(salen)、Co(OAc) 2 、SnSO 4 、Fe(acac) 3 、Mo(acac) 3 、K 2 Cr 2 O 7 、Mn(OAc) 3 、Ni(CF 3 CO 2 H) 2 And BiCl 3 。
In one embodiment of the invention, the calculated molar ratio of the hydroxyl groups of the metal salt (E) to the hydroxide (F) of the epoxidation catalyst system (2) is from 1.000mol:1.000mol to 6.000mol:1.000mol.
In one embodiment of the invention, the calculated molar ratio of metal salt (E) to redox active compound (G) of epoxidation catalyst system (2) is from 0.100mol:1.000mol to 10.000mol:1.000mol.
In one embodiment of the invention, the calculated molar ratio of hydroxyl groups of hydroxide (F) of epoxidation catalyst system (2) to redox active compound (G) is from 0.100mol:1.000mol to 50.000mol:1.000mol.
In a preferred embodiment of the invention, iodine (I 2 ) The molar ratio is used in a calculated amount of 1 mol% to 2000 mol% based on the amount of the metal salt (E).
In a less preferred embodiment of the invention, the epoxidation catalyst system (2) comprises a mixture (2) of the above calculated molar ratios of metal salt (E), iodine and hydroxide (F).
In a preferred embodiment of the present invention, the epoxidation catalyst system (2) comprises the reaction product (2) of a metal salt (E), iodine and a hydroxide (F), wherein the metal salt (E), iodine and hydroxide (F) are produced by production methods known to the person skilled in the art, such as solid state synthesis, precipitation or co-precipitation methods, or in situ salt metathesis. Thus, the reaction product can be synthesized, for example, by adding the organic hydroxide (F-1) and/or the inorganic hydroxide (F-2) to a solution of the nitrate, halide, tetrafluoroborate, sulfate, p-toluenesulfonate, methanesulfonate and/or trifluoromethanesulfonate, preferably chloride, of the metal salt (E) in the above-described calculated molar ratio, followed by separating out the precipitated product, drying and suitable heat treatment.
In a preferred embodiment of the present invention, the reaction product (2) of the epoxidation catalyst system (2) has the structure of formula (IV), (V) and/or (VI):
If m is<n+o，(Q R 1 R 2 R 3 R 4 ) + Im-o-pI [M(E) m+ (Hal) n (OH) o (S) p ] m-n-o ·q·I 2 (IV)
If m=n+o, [ M (E) m+ (Hal) n (OH) o (S) p ]·q·I 2 (V)
If m is>n+o，[M(E) m+ (Hal) n (OH) o (S) p ] m-n-o ·q·I 2 [X] - n+o-m (VI)
Wherein the method comprises the steps of
Q=nitrogen or phosphorus, preferably nitrogen,
R 1 、R 2 、R 3 、R 4 independently of one another selected from
(i) A linear or branched alkyl group containing 1 to 22 carbon atoms, optionally substituted with heteroatoms and/or heteroatom-containing substituents;
(ii) Alicyclic groups containing 3 to 22 carbon atoms having 1 to 3 bridging carbon atoms, optionally substituted with heteroatoms and/or heteroatom-containing substituents, and/or
(iii) Aryl groups containing 6 to 18 carbon atoms, optionally substituted with 1 to 10 carbon atoms and/or optionally substituted with heteroatoms and/or heteroatom-containing substituents;
R 1 、R 2 、R 3 and R is 4 Preferably independently of each other selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, isobutyl, t-Bu, n-butyl, phenyl, benzyl, (trifluoromethyl) phenyl, more preferably methyl, benzyl and n-butyl;
M(E) m+ ＝Ni 2+ 、Mn 2+ 、Pb 2+ 、Sn 2+ 、Cr 3+ 、V 3+ 、Mo 4+ 、Fe 2+ or Ru (Rust) 3+ Preferably Ni 2+ 、Mn 2+ 、Pb 2+ 、Sn 2+ ；
Hal＝Cl - 、Br - Or I - Preferably Cl - Or Br (Br) - More preferably Cl - ，
S＝H 2 O, THF (tetrahydrofuran) or dioxane, bis (2-methoxyethyl) ether (diethylene glycol dimethyl ether), methoxyethanol, polyethylene glycol, pyridine, lutidine, 2' -bipyridine, acetonitrile, dimethyl sulfoxide, sulfolane, thiophene, preferably THF;
n+o+p＝6；
n is more than or equal to 1; preferably n is greater than or equal to 2; more preferably n=2;
o is more than or equal to 1; preferably o is greater than or equal to 1; more preferably o=1; 2;3 or 4;
X＝OTf - 、BF 4 - 、Hal - ；
q is more than or equal to 1, preferably more than or equal to 1 and less than or equal to 2000, and more preferably more than or equal to 1 and less than or equal to 10.
In a particularly preferred embodiment of the invention, the reaction product (2) of the epoxidation catalyst system (2) is one or more compounds and is selected from (Q R) 1 R 2 R 3 R 4 )[Ni(II)Cl 2 (OH)(THF) 3 ]I 2 、(Q R 1 R 2 R 3 R 4 )[Mn(II)Cl 2 (OH)(THF) 3 ]I 2 、(Q R 1 R 2 R 3 R 4 )[Pb(II)Cl 2 (OH)(THF) 3 ]I 2 Sum (Q R) 1 R 2 R 3 R 4 )[Sn(II)Cl 2 (OH)(THF) 3 ]I 2 Wherein q=nitrogen, and R 1 、R 2 、R 3 And R is 4 Independently of each other selected from methyl, benzyl and n-butyl.
In one embodiment of the invention, the epoxidation catalyst system (2) is applied to a catalyst support (H) to form a supported epoxidation catalyst system (2).
In a preferred embodiment of the invention, the catalyst support (H) is one or more compounds and is selected from the group consisting of metal oxides, alkaline earth metal carbonates, silicates, silicon carbide, silicon oxycarbide, silicon nitride, silicon oxynitride and silicon dioxide, preferably alumina, aluminum dioxide, silicon dioxide, titanium dioxide, zirconium dioxide, calcium carbonate, phyllosilicates, such as talc, kaolinite and pyrophyllite, and titanium dioxide.
According to the invention, the catalyst support may be in the form of a shaped body or a powder.
In one embodiment of the invention, the epoxidation catalyst system (2) is applied to the catalyst support (H) in a calculated mass proportion of from 1.0 to 30.0% by weight.
In one embodiment of the invention, the epoxidation catalyst system (H) is applied to the catalyst support (H) by wet-impregnation or incipient wetness.
Another subject of the invention is a process for producing epoxides which comprises the oxidative conversion of an olefin in a reactor in the presence of the epoxidation catalyst system (1) according to the invention or of the epoxidation catalyst system according to the invention.
In one embodiment of the process of the invention, the oxidative conversion in the reactor is carried out in the presence of oxygen or an oxygen-containing gas mixture.
The oxygen-containing gas mixture contains, in addition to oxygen, a diluent gas, carrier gas or inert gas, such as hydrocarbons, noble gases, CO2, N2.
In one embodiment of the process of the invention, further additives, such as water, CO, N-containing compounds, for example hydrazine, ammonia (NH 3), methylamine (MeNH) 2 )、NOx、PH 3 、SO 2 And/or SO 3 Is added to the oxygen or oxygen-containing gas mixture in an amount of 10ppm to 500ppm, preferably 30ppm to 300ppm, more preferably 50ppm to 200 ppm. Furthermore, CO2 may be added in a proportion of 0.01 to 50% by volume, preferably 0.1 to 20% by volume, more preferably 1 to 10% by volume. Organic halides such as dichloroethane, ethyl chloride, vinyl chloride, methyl chloride and/or methylene chloride may also be added in amounts of from 10ppm to 500ppm, preferably from 50ppm to 400ppm, more preferably from 100ppm to 300 ppm.
In a preferred embodiment of the process of the invention, the oxidative conversion in the reactor is carried out in the presence of oxygen.
In one embodiment of the process of the present invention the olefin is one or more compounds and is selected from the group consisting of ethylene, propylene, butene, 1-octene, butadiene, but-1, 4-diol diallyl ether, allyl chloride, allyl alcohol, styrene, cyclopentene, cyclohexene, phenylallyl ether, diallyl ether, n-butylallyl ether, t-butylallyl ether, bisphenol a diallyl ether, resorcinol diallyl ether, triphenylolmethane triallyl ether, bis (allyl) cyclohexane-1, 2-dicarboxylate, tris (prop-2, 3-enyl) isocyanurate and mixtures of these olefins, preferably ethylene, propylene and allyl chloride, more preferably propylene.
The epoxide (alkylene oxide) of the present invention may be an epoxide having 2 to 45 carbon atoms. In one embodiment of the method of the invention, the epoxide is selected from at least one of the following compounds: ethylene oxide, propylene oxide, 1, 2-butylene oxide, 2, 3-butylene oxide, 2-methyl-1, 2-propylene oxide (isobutylene oxide), 1, 2-pentane oxide, 2, 3-pentane oxide, 2-methyl-1, 2-butylene oxide, 3-methyl-1, 2-butylene oxide, epoxides of C6-C22 alpha-olefins, such as 1, 2-epoxyhexane, 2, 3-epoxyhexane, 3, 4-epoxyhexane, 2-methyl-1, 2-epoxypentane, 4-methyl-1, 2-epoxypentane, 2-ethyl-1, 2-epoxybutane, 1, 2-epoxyheptane, 1, 2-epoxyoctane, 1, 2-epoxynonane, 1, 2-epoxydecane, 1, 2-epoxyundecane, 1, 2-epoxydodecane, 4-methyl-1, 2-epoxypentane, cyclopentane, epoxycyclohexane, epoxycycloheptane, epoxycyclooctane, styrene oxide, methyl styrene oxide, pinane, allyl glycidyl ether, vinyl epoxycyclohexane, cyclooctadiene monoepoxide, cyclododecene monoepoxide, butadiene monoepoxide, isoprene monoepoxide, epoxylimonene, 1, 4-divinylbenzene monoepoxide, 1, 3-divinylbenzene monoepoxide, glycidyl acrylate and methacrylate, mono-or poly-epoxidized fats such as mono-, di-and tri-glycidyl esters, epoxy, C1-glycidyl esters, glycidyl esters and aliphatic derivatives, such as glycidyl ethers of C1-C22 alkanols, glycidyl esters of C1-C22 alkane carboxylic acids. Examples of derivatives of glycidol are phenyl glycidyl ether, tolyl glycidyl ether, methyl glycidyl ether, ethyl glycidyl ether and 2-ethylhexyl glycidyl ether.
In a preferred embodiment of the process, the epoxide is ethylene oxide, propylene oxide, 1, 2-butylene oxide, 1, 2-pentane oxide, 1, 2-hexane oxide, 1, 2-heptane oxide and/or 1, 2-octane oxide. In a particularly preferred embodiment of the process, the epoxide is ethylene oxide and/or propylene oxide. In a very particularly preferred embodiment of the process, the epoxide is propylene oxide.
In one embodiment of the process of the present invention, the epoxide is produced in the presence of a solvent.
In one embodiment of the method of the present invention, the solvent is one or more compounds selected from the group consisting of CO2, water, perfluoromethyl decalin, perfluorodecalin, perfluoroperhydrophenanthrene, perfluoro (butyltetrahydrofuran), tetrahydrofuran, 2-methyl-THF, acetic acid, acetonitrile, dimethyl sulfoxide, sulfolane, acetone, methyl ethyl ketone, dimethylformamide, methylene chloride, chloroform, tetrachloromethane, N-methyl-2-pyrrolidone, methyl tert-butyl ether (MTBE), dimethyl sulfoxide (DMSO), hexamethylphosphoramide, dichlorobenzene, 1, 2-dichloroethylene, 1, 3-hexafluoroisopropanol perfluoro-tert-butanol, 1,2, 3-pentafluoropropane, 1-bromo-2-chloro-1, 2-trifluoroethane, 1, 2-dichloro-1, 2, 3-hexafluoropropane, ethylene glycol, glycerol and phenol.
In one embodiment of the process of the present invention, the epoxide is produced in the presence of a solvent, wherein the production is carried out at a temperature of from 20 ℃ to 200 ℃, preferably from 50 ℃ to 160 ℃, more preferably from 100 ℃ to 150 ℃.
In one embodiment of the process of the present invention, the epoxide is produced in the presence of a solvent, wherein the production is carried out at a pressure of from 1 to 200bara, preferably from 1 to 35bara, more preferably from 1 to 28 bara.
In one embodiment of the process of the present invention, the epoxide is produced in the presence of a solvent, wherein the production is carried out over a period of from 6 minutes to 48 hours, preferably from 6 minutes to 24 hours, more preferably from 6 minutes to 3 hours.
In one embodiment of the process of the present invention, the epoxide is produced in the presence of a solvent, wherein the molar ratio of olefin to oxygen is from 1:100 to 100:1, preferably from 1:30 to 30:1.
In an alternative embodiment of the process of the present invention, the epoxide is produced in the absence of a solvent.
By solvent-free process is meant herein according to the invention that solvent residues, for example due to the production of the starting material, may be present in an amount of at most 10% by volume, preferably at most 5% by volume, more preferably at most 2% by volume, based on the amount of propylene used.
In one embodiment of the process of the present invention, the epoxide is produced in the absence of a solvent, wherein the production is carried out using the supported epoxidation catalyst system (1) of the present invention or the supported epoxidation catalyst system (2) of the present invention.
In one embodiment of the process of the present invention, the epoxide is produced in the absence of a solvent, wherein the production is carried out at a temperature of from 20 ℃ to 500 ℃, preferably from 50 ℃ to 400 ℃, more preferably from 50 ℃ to 250 ℃.
In one embodiment of the process of the present invention, the epoxide is produced in the absence of solvent, wherein the production is carried out at a pressure of from 1 to 200bara, preferably from 2 to 100bara, more preferably from 2 to 50 bara.
In one embodiment of the process of the present invention, the epoxide is produced in the absence of solvent, wherein the production is carried out at a gas hourly space velocity (English Gas Hournly Space Velocity GHSV) of from 100h-1 to 10000h-1, preferably from 200h-1 to 5000h-1, more preferably from 500h-1 to 2000h-1, as quotient of the volumetric flow of reactant gas used and the catalyst volume. The catalyst volume here corresponds to the volume of the supported epoxidation catalyst system (1) or (2) and/or to the sum of the volumes of catalyst and diluent in the case of supported catalysts and/or catalysts diluted with inert diluents (e.g. alumina, silica, silicon carbide).
In one embodiment of the process of the present invention, the epoxide is produced in the absence of a solvent, wherein the molar ratio of olefin to oxygen is from 1.0:0.1 to 2:1, preferably from 1:0.5 to 2:1, more preferably from 1:0.8 to 2:1.
In one embodiment of the process of the invention, the olefin is metered continuously or stepwise, preferably continuously, into the reactor.
In one embodiment of the process according to the invention, oxygen or an oxygen-containing gas mixture is metered continuously or stepwise, preferably continuously, into the reactor.
In one embodiment of the process of the invention, the olefin and oxygen or oxygen-containing gas mixture are metered continuously or stepwise, preferably continuously, into the reactor.
In a preferred embodiment of the process of the invention, the epoxide is continuously or stepwise, preferably continuously, withdrawn from the reactor.
In a preferred embodiment of the process according to the invention, the epoxidation catalyst system (1) is metered continuously or stepwise, preferably continuously, into the reactor.
The process of the invention can be carried out in batch, semi-batch or continuous mode, wherein reactor types known to the person skilled in the art are used for this purpose. Thus, the continuous production of epoxides may be carried out by the oxidative conversion of olefins in the presence of solvents in the liquid phase in a continuous back-mixing stirred tank (english Continuous StirredTankReactor CSTR) or in a single-column or double-column bubble reactor. The continuous production of epoxides in the gas phase in the absence of solvent can be carried out by means of continuous gas phase reactors, for example fixed bed reactors, in which case ceramic packing materials can also be used.
In a preferred embodiment of the process of the invention, the epoxidation catalyst system (1) and/or the epoxidation catalyst system (2) is used in a calculated amount of from 10ppm to 500000ppm, preferably from 100ppm to 200000ppm, more preferably from 1000ppm to 150000ppm, based on the mass of all reactants involved and optional solvents and possible other auxiliaries.
In a first embodiment, the present invention relates to an epoxidation catalyst system (1) comprising
a) Mixtures of the following components, preferably reaction products
a-1) metallic chromium (Cr), manganese (Mn), molybdenum (Mo), lead (Pb) and/or bismuth (Bi), and
a-2) hydroxide (B)
b) A redox-active compound (C).
In a second embodiment, the present invention relates to an epoxidation catalyst system (1) according to the first embodiment, wherein the metal salt (a) is a nitrate, a halide, a tetrafluoroborate, a sulfate, a p-toluenesulfonate, a methanesulfonate and/or a trifluoromethanesulfonate, preferably a chloride.
In a third embodiment, the present invention relates to an epoxidation catalyst system (1) according to the first or second embodiment, wherein the metal salt (A) is one or more compounds and is selected from MoCl 5 、MoOCl 3 、MnCl 2 、K 2 MnCl 6 、CrOCl 2 、PbCl 4 And BiCl 3 。
In a fourth embodiment, the present invention relates to an epoxidation catalyst system (1) according to any of the first to third embodiments, wherein hydroxide (B) is an organic hydroxide (B-1) and/or an inorganic hydroxide (B-2).
In a fifth embodiment, the present invention relates to an epoxidation catalyst system (1) according to the fourth embodiment, wherein hydroxide (B) is an organic hydroxide (B-1) and organic hydroxide (B-1) is one or more compounds and is selected from the group consisting of 3- (trifluoromethyl) phenyltrimethylammonium hydroxide, tetra-n-butylphosphonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetrabutylammonium hydroxide and tetramethylammonium hydroxide.
In a sixth embodiment, the present invention relates to an epoxidation catalyst system (1) according to the fourth embodiment, wherein hydroxide (B) is an inorganic hydroxide (B-2) and inorganic hydroxide (B-2) is one or more compounds and is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and crown ether complexes thereof, cesium hydroxide, calcium hydroxide, barium hydroxide, potassium aluminate, sodium aluminate, potassium aluminate and sodium zincate, preferably lithium hydroxide, sodium hydroxide and potassium hydroxide.
In a seventh embodiment, the present invention relates to an epoxidation catalyst system (1) according to any of the first to sixth embodiments, wherein the redox-active compound (C) is one or more compounds and is selected from copper dichloride, cuCl 2 、Cu(BF 4 ) 2 、CuCl、VCl 3 、VOCl 3 、NH 4 VO 3 1, 4-benzoquinone, 1, 4-naphthoquinone, and Se 2 O 5 、TeO 2 、TeO 2 、Sb 2 O 3 、Sb 2 O 5 、CeCl 3 、Co(salen)、Co(OAc) 2 、SnSO 4 、Fe(acac) 3 、Mo(acac) 3 、K 2 Cr 2 O 7 、Mn(OAc) 3 、Ni(CF 3 CO 2 H) 2 And BiCl 3 。
In an eighth embodiment, the present invention relates to an epoxidation catalyst system (1) according to any of the first to seventh embodiments, wherein the calculated molar ratio of the metal salt (a) to the hydroxide groups of hydroxide (B) is from 1.000mol:1.000mol to 6.000mol:1.000mol.
In a ninth embodiment, the present invention relates to an epoxidation catalyst system (1) according to any of the first to eighth embodiments, wherein the calculated molar ratio of metal salt (a) to redox-active compound (C) is from 0.100mol:1.000mol to 10.000mol:1.000mol.
In a tenth embodiment, the present invention relates to an epoxidation catalyst system (1) according to any of the first to ninth embodiments, wherein the calculated molar ratio of hydroxyl groups of hydroxide (B) to redox active compound (C) is from 0.100mol:1.000mol to 50.000mol:1.000mol.
In an eleventh embodiment, the present invention relates to an epoxidation catalyst system (1) according to any of the first to tenth embodiments, wherein the epoxidation catalyst (1) further comprises iodine (I 2 )。
In a twelfth embodiment, the present invention relates to an epoxidation catalyst system (1) according to the eleventh embodiment, wherein iodine (I 2 ) The molar ratio is used in a calculated amount of 1 to 2000 mol% based on the amount of the metal salt (A).
In a thirteenth embodiment, the present invention relates to an epoxidation catalyst system (1) according to any of the first to twelfth embodiments, wherein the epoxidation catalyst system (1) is applied onto a catalyst carrier (D) to form a supported epoxidation catalyst system (1).
In a fourteenth embodiment, the present invention relates to an epoxidation catalyst system (1) according to the thirteenth embodiment, wherein the catalyst support (D) is one or more compounds and is selected from the group consisting of metal oxides, alkaline earth metal carbonates, silicates, silicon carbide, silicon oxycarbide, silicon nitride, silicon oxynitride and silica, preferably alumina, aluminum dioxide, silica, titania, zirconia, calcium carbonate, phyllosilicates, such as talc, kaolinite and pyrophyllite, and titania.
In a fifteenth embodiment, the present invention relates to an epoxidation catalyst system (1) according to the thirteenth or fourteenth embodiment, wherein the epoxidation catalyst system (1) is applied to the catalyst carrier (D) in a calculated mass proportion of from 1.0 to 30.0% by weight.
In a sixteenth embodiment, the present invention relates to an epoxidation catalyst system (1) according to any of the thirteenth to fifteenth embodiments, wherein the epoxidation catalyst system (1) is applied to the catalyst carrier (D) by wet-impregnation or incipient wetness.
In a seventeenth embodiment, the present invention relates to an epoxidation catalyst system (2) comprising
c) Mixtures of the following components, preferably reaction products
c-1) a metal salt (E),
c-2) iodine (I) 2 ) And
c-3) hydroxide (F)
d) Optionally, a redox-active compound (G).
In an eighteenth embodiment, the present invention relates to an epoxidation catalyst system (2) according to the seventeenth embodiment, wherein the metal salt (E) is a nitrate, a halide, a tetrafluoroborate, a sulfate, a p-toluenesulfonate, a methanesulfonate and/or a trifluoromethanesulfonate, preferably a chloride.
In a nineteenth embodiment, the present invention relates to an epoxidation catalyst system (2) according to the seventeenth or eighteenth embodiment, wherein the metal salt (E) is one or more compounds and is selected from the group consisting of NiCl 2 、MnCl 2 、PbCl 2 、SnCl 2 、CrCl 3 、VCl 3 、MoCl 4 、FeCl 2 And RuCl 3 。
In a twentieth embodiment, the present invention relates to an epoxidation catalyst system (2) according to any of the seventeenth to nineteenth embodiments, wherein hydroxide (F) is an organic hydroxide (F-1) and/or an inorganic hydroxide (F-2).
In a twenty-first embodiment, the present invention relates to an epoxidation catalyst system (2) according to the twentieth embodiment, wherein hydroxide (F) is an organic hydroxide (B-1) and organic hydroxide (F-1) is one or more compounds and is selected from the group consisting of 3- (trifluoromethyl) phenyltrimethylammonium hydroxide, tetra-n-butylphosphonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetrabutylammonium hydroxide, and tetramethylammonium hydroxide.
In a twenty-second embodiment, the present invention relates to an epoxidation catalyst system (2) according to the twenty-first embodiment, wherein hydroxide (F) is an inorganic hydroxide (F-2) and inorganic hydroxide (F-2) is one or more compounds and is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and crown ether complexes thereof, cesium hydroxide, calcium hydroxide, barium hydroxide, potassium aluminate, sodium aluminate, potassium aluminate and sodium zincate, preferably lithium hydroxide, sodium hydroxide and potassium hydroxide.
In a twenty-third embodiment, the present invention relates to an epoxidation catalyst system (2) according to any of the seventeenth to twenty-second embodiments, wherein a redox-active compound (G) is present and is one or more compounds selected from CuCl 2 、Cu(BF 4 ) 2 、CuCl、VCl 3 、VOCl 3 、NH 4 VO 3 1, 4-benzoquinone, 1, 4-naphthoquinone, and Se 2 O 5 、TeO 2 、TeO 2 、Sb 2 O 3 、Sb 2 O 5 、CeCl 3 、Co(salen)、Co(OAc) 2 、SnSO 4 、Fe(acac) 3 、Mo(acac) 3 、K 2 Cr 2 O 7 、Mn(OAc) 3 、Ni(CF 3 CO 2 H) 2 And BiCl 3 。
In a twenty-fourth embodiment, the present disclosure is directed to an epoxidation catalyst system (2) according to any of the seventeenth to twenty-third embodiments, wherein the calculated molar ratio of the metal salt (E) to the hydroxyl groups of hydroxide (B) is from 1.000mol:1.000mol to 6.000mol:1.000mol.
In a twenty-fifth embodiment, the present disclosure is directed to an epoxidation catalyst system (2) according to any of the seventeenth to twenty-fourth embodiments, wherein the calculated molar ratio of metal salt (E) to redox-active compound (G) is from 0.100mol:1.000mol to 10.000mol:1.000mol.
In a twenty-sixth embodiment, the present disclosure is directed to an epoxidation catalyst system (2) according to any of the seventeenth to twenty-fifth embodiments, wherein the calculated molar ratio of hydroxyl groups of hydroxide (F) to redox active compound (G) is from 0.100mol:1.000mol to 50.000mol:1.000mol.
In a twenty-seventh embodiment, the present invention relates to an epoxidation catalyst system (2) according to any of the seventeenth to twenty-sixth embodiments, wherein iodine (I2) is used in a calculated molar ratio of from 1 mol% to 2000 mol% based on the amount of metal salt (a).
In a twenty-eighth embodiment, the present disclosure is directed to an epoxidation catalyst system (2) according to any of the seventeenth to twenty-seventh embodiments, wherein the epoxidation catalyst system (2) is applied to a catalyst carrier (H) to form a supported epoxidation catalyst system (2).
In a twenty-ninth embodiment, the present invention relates to an epoxidation catalyst system (2) according to the twenty-eighth embodiment, wherein the catalyst support (H) is one or more compounds and is selected from the group consisting of metal oxides, alkaline earth metal carbonates, silicates, silicon carbide, silicon oxycarbide, silicon nitride, silicon oxynitride and silicon dioxide, preferably aluminum oxide, aluminum dioxide, silicon dioxide, titanium dioxide, zirconium dioxide, calcium carbonate, phyllosilicates, such as talc, kaolinite and pyrophyllite, and titanium dioxide.
In a thirty-first embodiment, the present invention relates to an epoxidation catalyst system (2) according to the twenty-eighth or twenty-ninth embodiment, wherein the epoxidation catalyst system (2) is applied to the catalyst carrier (H) in a calculated mass proportion of from 1.0 to 30.0% by weight.
In a thirty-first embodiment, the present invention relates to an epoxidation catalyst system (2) according to any of the twenty-eighth to thirty-first embodiments, wherein the epoxidation catalyst system (2) is applied to the catalyst carrier (H) by wet-impregnation or incipient wetness.
In a thirty-second embodiment, the present invention relates to a process for producing an epoxide comprising the oxidative conversion of an olefin in a reactor in the presence of an epoxidation catalyst system (1) according to any of the first to sixteenth embodiments or an epoxidation catalyst system (2) according to any of the seventeenth to thirty-first embodiments.
In a thirty-third embodiment, the present invention relates to a process according to the thirty-second embodiment, wherein the oxidative conversion in the reactor is performed in the presence of oxygen or an oxygen-containing gas mixture.
In a thirty-fourth embodiment, the present invention is directed to the method according to the thirty-third or thirty-third embodiment, wherein the olefin is one or more compounds and is selected from the group consisting of ethylene, propylene, butene, 1-octene, butadiene, but-1, 4-diol diallyl ether, allyl chloride, allyl alcohol, styrene, cyclopentene, cyclohexene, phenyl allyl ether, diallyl ether, n-butyl allyl ether, t-butyl allyl ether, bisphenol a diallyl ether, resorcinol diallyl ether, triphenylol methane triallyl ether, cyclohexane-1, 2-dicarboxylic acid bis (allyl ester), tris (prop-2, 3-enyl) isocyanurate, and mixtures of these olefins, preferably ethylene, propylene, and allyl chloride, more preferably propylene.
In a thirty-fifth embodiment, the present disclosure is directed to the method according to any one of the thirty-second to thirty-fourth embodiments, wherein the producing is performed in the presence of a solvent.
In a thirty-sixth embodiment, the present invention is directed to a method according to the thirty-fifth embodiment, wherein the solvent is one or more compounds and is selected from the group consisting of CO2, water, perfluoromethyl decalin, perfluorodecalin, perfluoroperhydrophenanthrene, perfluoro (butyl tetrahydrofuran) tetrahydrofuran, 2-methyl-THF, acetic acid, acetonitrile, dimethyl sulfoxide, sulfolane, acetone, methyl ethyl ketone, dimethylformamide, methylene chloride, chloroform, tetrachloromethane tetrahydrofuran, 2-methyl-THF, acetic acid, acetonitrile, dimethyl sulfoxide, sulfolane, acetone methyl ethyl ketone, dimethylformamide, methylene chloride, chloroform, tetrachloromethane.
In a thirty-seventh embodiment, the present invention relates to the method according to the thirty-fifth or thirty-sixth embodiment, wherein the production is performed at a temperature of 20 ℃ to 200 ℃, preferably 50 ℃ to 160 ℃, more preferably 100 ℃ to 150 ℃.
In a thirty-eighth embodiment, the present invention relates to a process according to any one of the thirty-fifth to thirty-seventh embodiments, wherein the production is carried out at a pressure of from 1 to 200bara, preferably from 1 to 35bara, more preferably from 1 to 28 bara.
In a thirty-ninth embodiment, the present disclosure is directed to the method according to any one of the thirty-fifth to thirty-eighth embodiments, wherein the producing is performed over a period of 6 minutes to 48 hours, preferably 6 minutes to 24 hours, more preferably 6 minutes to 3 hours.
In a fortieth embodiment, the present disclosure is directed to the method according to any one of the thirty-fifth to thirty-ninth embodiments, wherein the molar ratio of olefin to oxygen is from 1:100 to 100:1, preferably from 1:30 to 30:1.
In a forty-first embodiment, the present disclosure is directed to the method according to any one of the thirty-second to thirty-fourth embodiments, wherein the producing is performed in the absence of a solvent.
In a forty-second embodiment, the present invention relates to a method according to the forty-first embodiment, wherein the production is performed using the supported epoxidation catalyst system (1) according to any of the thirteenth to sixteenth embodiments or the supported epoxidation catalyst system (2) according to any of the twenty-eighth to thirty-first embodiments.
In a forty-third embodiment, the present invention relates to a method according to the forty-first or forty-second embodiment, wherein the production is performed at a temperature of 20 ℃ to 500 ℃, preferably 50 ℃ to 400 ℃, more preferably 50 ℃ to 250 ℃.
In a forty-fourth embodiment, the present invention relates to a process according to any one of the forty-first to forty-third embodiments, wherein the production is performed at a pressure of from 1 to 200bara, preferably from 2 to 100bara, more preferably from 2 to 50 bara.
In a forty-fifth embodiment, the present invention relates to a method according to any one of the forty-first to forty-fourth embodiments, wherein the production is performed at a gas hourly space of 100h "1 to 10000 h" 1, preferably 200h "1 to 5000 h" 1, more preferably 500h "1 to 2000 h" 1.
In a forty-sixth embodiment, the present invention is directed to the method according to any one of the forty-first to forty-fifth embodiments, wherein the molar ratio of olefin to oxygen is from 1.0:0.1 to 2.0:1.0, preferably from 1.0:0.5 to 2.0:1.0, more preferably from 1.0:0.8 to 2.0:1.0.
In a forty-seventh embodiment, the present invention relates to a process according to any one of the thirty-second to forty-sixth embodiments, wherein the olefin is continuously or stepwise, preferably continuously metered into the reactor.
In a forty-eighth embodiment, the present invention relates to a process according to any one of the thirty-third to forty-seventh embodiments, wherein oxygen or an oxygen-containing gas mixture is metered continuously or stepwise, preferably continuously, into the reactor.
In a forty-ninth embodiment, the present invention relates to a process according to any one of the thirty-third to forty-eighth embodiments, wherein the olefin and the oxygen or oxygen-containing gas mixture are metered continuously or stepwise, preferably continuously, into the reactor.
In a fifty-first embodiment, the present disclosure is directed to the process according to any one of the forty-seventh to forty-ninth embodiments, wherein the epoxide is continuously or stepwise, preferably continuously, withdrawn from the reactor.
In a fifty-first embodiment, the present invention relates to a process according to any one of the fortieth to fifty-seventh embodiments, wherein the epoxidation catalyst system (1) and/or the epoxidation catalyst system (2) is metered continuously or stepwise, preferably continuously, into the reactor.
In a fifty-second embodiment, the present invention relates to the process according to any one of the thirty-second to fifty-first embodiments, wherein the epoxidation catalyst system (1) and/or the epoxidation catalyst system (2) is used in a calculated amount of from 10ppm to 500000ppm, preferably from 100ppm to 200000ppm, more preferably from 1000ppm to 150000ppm, based on the mass of all reactants involved and optional solvents and possibly other auxiliaries.
Examples
The raw materials used are as follows:
metal chloride and metal oxide: all metal salts used were obtained directly from commercial sources and were used as precursors of the active catalysts for the corresponding reactions without further processing:
molybdenum (V) chloride was from manufacturer Sigma Aldrich Corporation at 95% purity.
Manganese (II) chloride was from manufacturer Sigma Aldrich Corporation at 99% purity.
Chromium (VI) oxychloride was from manufacturer SigmaAldrich Corporation in 99% purity.
Lead (II) chloride was from manufacturer Sigma Aldrich Corporation at 98% purity.
Bismuth (III) chloride was from manufacturer Sigma Aldrich Corporation at 98% purity.
Copper (II) chloride was from manufacturer Sigma Aldrich Corporation at 97% purity.
Nickel (II) chloride was from manufacturer Sigma Aldrich Corporation at 98% purity.
Tin (II) chloride was from manufacturer Sigma Aldrich Corporation at 98% purity.
Molybdenum (VI) oxychloride was produced according to Vitzthumb et al Monatsh. Chem.148,629-633 (2017).
Elemental iodine, triton B and all solvents used were also introduced into the reaction without further processing:
iodine was from manufacturer Sigma Aldrich Corporation at 99.8% purity.
Tetrahydrofuran (THF) was from manufacturer Sigma Aldrich Corporation in 99.9% purity (no inhibitor).
Benzyltrimethylammonium hydroxide (triton b) was from manufacturer Sigma Aldrich Corporation as a 40% solution in methanol.
Propylene was obtained from manufacturer Sigma Aldrich Corporation in 99.9% purity and used in the available manner.
The chemicals were used for synthesis without further purification.
Gas chromatography analysis
Gas chromatography of liquid and gas samples (GC for short) was performed according to "Determine Impurities in High-Purity Propylene Oxide with Agilent J & W PoraBOND U", dianli Ma, ningbo ZRCC Lyondell Chemical co., ltd Zhejiang, china and Yun Zou, hua Wu, agilent Technologies, inc. Propylene conversion, propylene oxide yield and selectivity were determined based on GC.
Simulation method
All quantum mechanical calculations were performed using the software package turbloole version 7.4.1 from the company cooling GmbH & co.kg. The density functional theory method used is the TPSS density functional, which is implemented as an unrestricted DFT for spin contamination of the open-shell system, with the def2-SVP basis set, as implemented as a standard in the Turboole software package. The resulting energy is refined by the DFT method and with the def2-TZVP quality basis set.
Transition states were calculated by gradient-based Monte Carlo as described in application WO 2020/079094A 2.
Production of epoxidation catalyst System (1)
The epoxidation catalyst systems listed in tables 1 and 2 were produced and used as described in the general test methods.
General procedure for in situ Synthesis of epoxidation catalyst System (1)
200 ml of tetrahydrofuran was initially charged under inert conditions in a reaction vessel with stirring and bubbling of shielding gas. In each experiment 0.020 mole of metal (oxy) chloride in the corresponding oxidation state was reacted under the reverse flow of the shielding gasSee tables 1, 1-5) and 0.020 moles of CuCl as redox active compound (C) 2 Added to the solvent. While stirring vigorously, N-benzyltrimethylammonium hydroxide (trade name: triton B) was added with stirring in each case until the liquid sample withdrawn gave a pH of 10-11 when contacted with a water-wet pH test strip.
The suspension thus produced was used for the oxidation of propylene without further purification.
TABLE 1 overview of epoxidation catalyst systems (1) for the oxidative conversion of propylene
(vgl.) comparative examples
Production of epoxidation catalyst System (2)
General procedure for in situ Synthesis of epoxidation catalyst System (2)
A mixture of 180 ml of tetrahydrofuran and 20 ml of water was initially charged under inert conditions in a reaction vessel with stirring and sparging with a shielding gas. To this solvent mixture was added 0.020 moles of the corresponding oxidation state metal (oxy) chloride (see tables 2, 9-12) and 0.040 moles (5.1 grams) of elemental iodine under a reverse flow of shielding gas. While vigorously stirring, N-benzyltrimethylammonium hydroxide (trade name: triton B) was added with stirring until the withdrawn liquid sample gave a pH of 10-11 upon contact with a water-wet pH test strip.
The suspension thus produced was used for the oxidation of propylene without further purification.
TABLE 2 overview of epoxidation catalyst System (2) for the oxidative conversion of propylene
(vgl.) comparative example; q (1) =benzyltrimethylammonium, where q=n; r is R 1 =benzyl, R 2 ＝R 3 ＝R 4 Methyl group =methyl group
Simulation results of the method for producing propylene oxide by propylene oxidation in the presence of the epoxidation catalyst system (1)
The activation energy for the catalytic reaction is calculated by quantum chemical simulation. To this end, the structure is in each case drawn according to the transition states A T1-B T2 (fig. 1). The key drawn in bold is set to be in each case(190 pm) atomic spacing, set to +. A T2 >And converts the structure thus obtained into cartesian coordinates. The atomic index of the keys in the Cartesian coordinate system, shown in bold in FIG. 3, is set as a function space in the gradient-based Monte Carlo program and the Monte Carlo program is executed until the corresponding transition states AT1-B T2 are obtained. Thereafter, the cartesian coordinates of the structures A T1-B T2 thus obtained are manipulated to obtain the corresponding reactant catalyst complex or related catalyst product complex. For this purpose, one of the bonds (FIG. 3) in bold in each case is i) lengthened and ii) shortened +.>(20 pm). The structures i) and ii) thus obtained are represented in the form of cartesian coordinates and geometrically optimized by the DFT method, the resulting geometry being used for calculating the activation energy. The keys selected in each case are compiled in table 3.
Table 3: selection of keys for manipulation to obtain a balanced structure
FIG. 1 three-stage reaction mechanism of oxidative hydroxylation of propylene with hydroxides under metal catalysis
The three-stage mechanism depicted in fig. 1 was calculated for each catalyst by quantum chemical simulation and the activation energy from the respective reaction sequence was determined. The activation energy estimates thus obtained were used to evaluate various metal compounds as potential catalysts for oxidative hydroxylation. The simulation results are summarized in table 4.
Table 4: comparison of Quantum chemical simulated activation energy of propylene Oxidation conversion at various epoxidation catalyst systems (1)
(vgl.) comparative example; q (1) =benzyltrimethylammonium, where q=n; r is R 1 =benzyl, R 2 ＝R 3 ＝R 4 Methyl group =methyl group
a) It is assumed that the THF ligand is at least partially displaced by propylene from the complex epoxidation catalyst system (1) prior to oxidative conversion.
The results compiled in Table 4 show that, in particular, the activation energy for the hydroxylation of propylene and the reductive elimination of the propylene oxide formed is greatly dependent on the respective metal acting as catalyst. Thus, the possible choices of metal compounds investigated as oxidative hydroxylation catalysts are limited to specific metals. Suitable metals are in particular Mo (V), mn (IV), cr (VI), bi (V) and Pb (IV).
Simulation results of the method for producing propylene oxide by propylene oxidation in the presence of the epoxidation catalyst system (2)
In another embodiment B of the process, an epoxidation catalyst system (2) consisting of a metal salt (E), elemental iodine and hydroxide (F) is used. This mixture (2) is loaded with propylene, wherein the hydroxide is first added to the double bond of propylene. In the second step, iodine is then inserted into the metal-carbon bond to release the iodic alcohol. Which in a weakly alkaline medium is decomposed into propylene oxide and iodide, which is oxidized back to elemental iodine by the supply of oxygen. The metal catalyst ensures controlled addition of hydroxide and iodine to produce the intermediate iodic alcohol without formation of the predominantly unusable 1, 2-diiodoalkane. In contrast to known chlorohydroxylations, iodine can be used here in catalytic or sub-stoichiometric amounts. Thus, the oxidation may be performed directly with oxygen.
For this purpose, quantum chemical simulations were performed to confirm a suitable metal catalyst.
TABLE 5 comparison of the Quantum chemical modeling activation energies for the iodination of propylene with various Metal catalysts
(vgl.) comparative example; q (1) =benzyltrimethylammonium, where q=n; r is R 1 =benzyl, R 2 ＝R 3 ＝R 4 Methyl group; a) it is assumed that the THF ligand is at least partially displaced by propylene and iodine from the complex epoxidation catalyst system (1) prior to oxidative conversion.
The simulation results compiled in table 5 show that the activation energy of the iodine insertion is greatly dependent on the metal catalyst used. In particular Mn (II), sn (II) and Pb (II), and Ni (II) were thus identified as suitable catalysts for this reaction.
FIG. 2 two-stage reaction mechanism of metal-catalyzed iodination of propylene
FIG. 3 input geometry for quantum chemistry of transition states of catalyzed oxidative hydroxylation A and iodinated hydroxylation B
General procedure for the production of propylene oxide by the oxidation of propylene in the Presence of an epoxidation catalyst System (1) in a discontinuous stirred tank
200 ml of tetrahydrofuran was initially charged under inert conditions in a pressure-resistant 1 liter reactor having a stirrer system, pressure-reducing valve, pressure sensor, riser for discharging liquid and bubbling and degassing conduits. In each experiment 0.020 moles of the corresponding oxidation state metal chloride (see tables 1, 1-5) and 0.020 moles of CuCl2 were added to the solvent under reverse flow of the shielding gas. While stirring vigorously, N-benzyltrimethylammonium hydroxide (trade name: triton B) was added in each case with stirring until the liquid sample withdrawn gave a pH of 10-11 when contacted with a water-wet pH test strip. Then 0.400 mol of propylene was injected into the reaction vessel (about 11 bar). The reactor internal temperature was maintained at 120 ℃ by closed loop control and oxygen was slowly injected until a molar amount of 0.200 moles of oxygen was reached. The addition of oxygen is performed such that the additional pressure rise is never greater than 2 bar. The progress and endpoint of the reaction were determined from the pressure profile and/or by taking liquid and gas samples and analyzing by GC. After the reaction was completed, the reactor was cooled to 40 ℃, then expanded, and the reaction product propylene oxide was distilled via a degassing line into a cooled receiver.
For all five experiments, the propylene oxide yield was 23.2 grams.
General procedure for the production of propylene oxide by the oxidation of propylene in the Presence of an epoxidation catalyst System (2) in a discontinuous stirred tank
A pressure-resistant 1 liter reactor with a stirrer system, pressure-reducing valve, pressure sensor, riser for discharging liquid and bubbling and degassing conduits was initially charged with a mixture of 180 ml of tetrahydrofuran and 20 ml of water under inert conditions. To this solvent mixture, 0.020 moles of the corresponding oxidation state metal chloride (see tables 2, 9-12) and 0.040 moles (5.1 grams) of elemental iodine were added under a reverse flow of shielding gas. While vigorously stirring, N-benzyltrimethylammonium hydroxide (trade name: triton B) was added with stirring until the withdrawn liquid sample gave a pH of 10-11 upon contact with a water-wet pH test strip. Then 0.400 mol of propylene was injected into the reaction vessel (about 11 bar). The reactor internal temperature was maintained at 120 ℃ by closed loop control and oxygen was slowly injected until a molar amount of 0.200 moles of oxygen was reached. The addition of oxygen is performed such that the additional pressure rise is never greater than 2 bar. The progress and endpoint of the reaction were determined from the pressure profile and/or by taking liquid and gas samples and analyzing by GC. After the reaction was completed, the reactor was cooled to 40 ℃, then expanded, and the reaction product propylene oxide was distilled via a degassing line into a cooled receiver.
For all four experiments, the propylene oxide yield was 23.2 grams.
General procedure for the production of propylene oxide by the oxidation of propylene in the Presence of the epoxidation catalyst System (1) in a continuous Single bubble column reactor
3500 ml of tetrahydrofuran was initially charged under inert conditions in a pressure-resistant bubble column (diameter 15 cm) having a bubble frit, pressure relief valves, pressure sensors, upper and lower liquid take-off ports, upper solid addition points, and gas inlet and outlet ports. In each experiment 0.350 moles of the corresponding oxidation state metal chloride (see tables 1, 1-5) and 0.350 moles of CuCl2 were added to the solvent under reverse flow of the shielding gas. N-benzyltrimethylammonium hydroxide (trade name: triton B) was added while bubbling N2 at 10l/min until the liquid sample withdrawn gave a pH of 10-11 when contacted with a water-wet pH test strip. The bubble column was then brought to a reaction temperature of 120℃and a mixture of propylene, oxygen and nitrogen (molar ratio propylene/oxygen 2:1) was introduced, wherein a total volumetric flow of less than 10l/min was established by closed loop control. The progress of the reaction and its steady state point were determined by taking liquid and gas samples at the upper take-off point and analyzing them by GC. The continuously formed product gas mixture was freed from propylene oxide by cascade cooling, the resulting gas stream was again slightly compressed and mixed with propylene, oxygen and nitrogen and fed to the bubbling frit of the bubbling column.
The selectivity to propylene oxide was between 95% and 100% in all five experiments.
General procedure for the production of propylene oxide by the oxidation of propylene in the Presence of an epoxidation catalyst System (2) in a continuous Single bubble column reactor
3150 ml of tetrahydrofuran and 350 ml of water were initially charged under inert conditions in a pressure-resistant bubble column (diameter 15 cm) having a bubble frit, pressure relief valves, pressure sensors, upper and lower liquid take-off ports, upper solid addition points, and gas inlet and outlet. In each experiment 0.350 mol of the corresponding oxidation state of the metal chloride (see tables 2, 9-12) and 0.700 mol (89.3 g) of elemental iodine were added to the solvent mixture under a reverse flow of shielding gas. N-benzyltrimethylammonium hydroxide (trade name: triton B) was added while bubbling N2 at 10l/min until the liquid sample withdrawn gave a pH of 10-11 when contacted with a water-wet pH test strip. The bubble column was then brought to a reaction temperature of 120℃and a gas mixture of propylene, oxygen and nitrogen (molar ratio propylene/oxygen 2:1) was introduced, wherein a total volumetric flow of less than 10l/min was established by closed loop control. The progress of the reaction and its steady state point were determined by taking liquid and gas samples at the upper take-off point and analyzing them by GC. The continuously formed product gas mixture was freed from propylene oxide by cascade cooling, the resulting gas stream was again slightly compressed and mixed with propylene, oxygen and nitrogen and fed to the bubbling frit of the bubbling column.
The selectivity to propylene oxide was between 95% and 100% in all four experiments.
General procedure for the production of propylene oxide by the oxidation of propylene in the Presence of the epoxidation catalyst System (1) in a continuous double bubble column reactor
Two pressure-resistant bubble columns (15 cm in diameter) each equipped with a bubble frit, a pressure reducing valve, a pressure sensor, upper and lower liquid take-off/addition ports, an upper solid addition point, and a gas inlet and outlet were connected via pumps via the upper and lower liquid take-off points. A bubble column was initially loaded with 3500 ml of tetrahydrofuran under inert conditions. In each experiment 0.350 moles of the corresponding oxidation state metal chloride (see tables 1, 1-5) and 0.350 moles of CuCl2 were added to the solvent under reverse flow of the shielding gas. N-benzyltrimethylammonium hydroxide (trade name: triton B) was added while bubbling nitrogen gas at 10l/min until the liquid sample withdrawn gave a pH of 10-11 when contacted with a water-wet pH test strip. A second bubble column was similarly prepared. The bubble column was then brought to a reaction temperature of 120 ℃. A gas mixture of nitrogen and propylene was fed to the first bubble column and a gas mixture of nitrogen and oxygen was fed to the second bubble column, wherein in both cases a total volumetric flow of less than 10l/min was established by closed loop control. The molar ratio of propylene to oxygen was 2:1. At the same time, the liquid phase is continuously withdrawn from the first bubble column at the upper point and added to the second bubble column at the lower point, and continuously withdrawn from the second bubble column at the upper point and added to the first bubble column at the lower point. The volumetric flow is regulated by closed loop control so that the filling level of the two bubble columns does not change during the duration of the experiment. The progress of the reaction and its steady state point were determined by taking liquid and gas samples at the take-off points on the two bubble columns and analyzing them by GC. The continuously formed product gas mixture from the first bubble column was freed from propylene oxide by cascade cooling, the resulting gas stream was again slightly compressed and mixed with nitrogen and propylene and fed into the bubble frit of the bubble column. The gas stream from the second bubble column is freed from propylene by cascade subcooling and discarded by vent gas. The recovered propylene was reused by addition at the lower bubbling point of the first bubbling column.
The selectivity to propylene oxide was between 95% and 100% in all five experiments.
General procedure for the production of propylene oxide by the oxidation of propylene in the Presence of an epoxidation catalyst System (2) in a continuous double bubble column reactor
Two pressure-resistant bubble columns (15 cm in diameter) each equipped with a bubble frit, a pressure reducing valve, a pressure sensor, upper and lower liquid take-off/addition ports, an upper solid addition point, and a gas inlet and outlet were connected via pumps via the upper and lower liquid take-off points. A bubble column was initially loaded with 3500 ml of tetrahydrofuran under inert conditions. In each experiment 0.350 mol of the corresponding oxidation state of the metal chloride (see tables 2, 9-12) and 0.700 mol (89.3 g) of elemental iodine were added to the solvent under a reverse flow of shielding gas. N-benzyltrimethylammonium hydroxide (trade name: triton B) was added while bubbling nitrogen gas at 10l/min until the liquid sample withdrawn gave a pH of 10-11 when contacted with a water-wet pH test strip. A second bubble column was similarly prepared. The bubble column was then brought to a reaction temperature of 120 ℃. A gas mixture of nitrogen and propylene was fed to the first bubble column and a gas mixture of nitrogen and oxygen was fed to the second bubble column, in both cases establishing a total volumetric flow of less than 10l/min by closed loop control. The molar ratio of propylene to oxygen was 2:1. At the same time, the liquid phase is continuously withdrawn from the first bubble column at the upper point and added to the second bubble column at the lower point, and continuously withdrawn from the second bubble column at the upper point and added to the first bubble column at the lower point. The volumetric flow is regulated by closed loop control so that the filling level of the two bubble columns does not change during the duration of the experiment. The progress of the reaction and its steady state point were determined by taking liquid and gas samples at the take-off points on the two bubble columns and analyzing them by GC. The continuously formed product gas mixture from the first bubble column was freed from propylene oxide by cascade cooling, the resulting gas stream was again slightly compressed and mixed with nitrogen and propylene and fed into the bubble frit of the bubble column. The gas stream from the second bubble column is freed from propylene by cascade subcooling and discarded by vent gas. The recovered propylene was reused by addition at the lower bubbling point of the first bubbling column.
The selectivity to propylene oxide was between 95% and 100% in all four experiments.
General procedure for the production of propylene oxide by the oxidation of propylene in the continuous gas phase reactor in the presence of a supported epoxidation catalyst system (1)
A pressure-resistant 1 liter reactor with a stirrer system, pressure-reducing valve, pressure sensor, riser for discharging liquid and bubbling and degassing conduits was initially charged with 200 ml of a mixture of tetrahydrofuran under inert conditions. In each experiment 0.350 mol of the corresponding oxidation state of the metal salt (A) (see Table 1, examples 1-5) and 0.350 mol of CuCl2 were added to the solvent mixture under a reverse flow of shielding gas. While vigorously stirring, N-benzyltrimethylammonium hydroxide was added as hydroxide (F) (trade name: triton B) with stirring until the liquid sample withdrawn gave a pH of 10-11 upon contact with a water-wet pH test strip. Subsequently, the resulting mixture is applied to silica as support material. The solids are then introduced into an inerted pressure-resistant and pressure-protected flow reactor. Nitrogen and oxygen were now passed through the flow reactor to reach a reaction temperature of 180 ℃. Subsequently, an amount of propylene was added to the gas stream until a molar ratio of propylene to oxygen of 2:1 was reached and was continuously contacted with the solid. The flow conditions and contact time are selected here to achieve partial conversion. The continuously produced product gas mixture is in each case freed from propylene oxide by cascade cooling, the resulting gas stream is heated again, enriched in oxygen and propylene, and the resulting mixture is reintroduced into the solid. The gas was analyzed by taking a sample of the gas and analyzing it by GC.
The selectivity to propylene oxide was between 95% and 100% in all five experiments.
Claims (15)
1. Epoxidation catalyst system (1) comprising
a) A mixture (1) or reaction product (1) of
a-1) metallic chromium (Cr), manganese (Mn), molybdenum (Mo), lead (Pb) and/or bismuth (Bi), and
a-2) a hydroxide (B),
b) A redox-active compound (C).
2. An epoxidation catalyst system (1) as claimed in claim 1 wherein the metal salt (a) is one or more compounds and is selected from MoCl 5 、MoOCl 3 、MnCl 2 、K 2 MnCl 6 、CrOCl 2 、PbCl 4 And BiCl 3 。
3. The epoxidation catalyst system (1) as claimed in claim 1 or 2, wherein the hydroxide (B) is an organic hydroxide (B-1) and the organic hydroxide (B-1) is one or more compounds and is selected from the group consisting of 3- (trifluoromethyl) phenyltrimethylammonium hydroxide, tetra-n-butylphosphonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetrabutylammonium hydroxide and tetramethylammonium hydroxide.
4. An epoxidation catalyst system (1) as claimed in any of claims 1 to 3 wherein the redox-active compound (C) is one or more compounds and is selected from CuCl 2 、Cu(BF 4 ) 2 、CuCl、VCl 3 、VOCl 3 、NH 4 VO 3 1, 4-benzoquinone, 1, 4-naphthoquinone, and Se 2 O 5 、TeO 2 、TeO 2 、Sb 2 O 3 、Sb 2 O 5 、CeCl 3 、Co(salen)、Co(OAc) 2 、SnSO 4 、Fe(acac) 3 、Mo(acac) 3 、K 2 Cr 2 O 7 、Mn(OAc) 3 、Ni(CF 3 CO 2 H) 2 And BiCl 3 。
5. The epoxidation catalyst system (1) as claimed in any of claims 1 to 4, wherein the epoxidation catalyst system (1) comprises a reaction product (1), and the reaction product (1) has the structure of formula (I), (II) and/or (III):
if m is<n+o，(Q R 1 R 2 R 3 R 4 ) + n+o-m [M(A) m+ (Hal) n (OH) o (S) p ] m-n-o (I)
If m=n+o, [ M (A) m+ (Hal) n (OH) o (S) p ] (II)
If m is>n+o，[M(A) m+ (Hal) n (OH) o (S) p ] (m-n-o) [X] - n+o-m (III)
Wherein the method comprises the steps of
Q=nitrogen or phosphorus, preferably nitrogen,
R 1 、R 2 、R 3 、R 4 independently of one another selected from
(iv) A linear or branched alkyl group containing 1 to 22 carbon atoms, optionally substituted with heteroatoms and/or heteroatom-containing substituents;
(v) Alicyclic groups containing 3 to 22 carbon atoms having 1 to 3 bridging carbon atoms, optionally substituted with heteroatoms and/or heteroatom-containing substituents, and/or
(vi) Aryl groups containing 6 to 18 carbon atoms, optionally substituted with 1 to 10 carbon atoms and/or optionally substituted with heteroatoms and/or heteroatom-containing substituents;
R 1 、R 2 、R 3 and R is 4 Preferably independently of one another selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, isobutyl, t-Bu, n-butyl, phenyl, benzyl, (trifluoromethyl) phenyl,
M(A) m+ ＝Mo 5+ 、Mn 4+ 、Cr 4+ 、Pb 4+ 、Bi 5+ mo is preferred 5+ ，
Hal＝Cl - 、Br - Or I - Preferably Cl - Or Br (Br) - More preferably Cl - ，
S＝H 2 O, THF (tetrahydrofuran) or dioxane, bis (2-methoxyethyl) ether (diethylene glycol dimethyl ether), methoxyethanol, polyethylene glycol, pyridine, lutidine, 2' -bipyridine, acetonitrile, dimethyl sulfoxide, sulfolane, thiophene, preferably THF;
n+o+p＝6
n is more than or equal to 1; preferably n is greater than or equal to 2; more preferably n=2
o is more than or equal to 1; preferably o is greater than or equal to 1; more preferably o=1; 2;3 or 4
X＝OTf - 、BF4 - 、Hal - 。
6. Epoxidation catalyst system (2) comprising
c) A mixture (2) or reaction product (2) of
c-1) a metal salt (E),
c-2) iodine (I) 2 ) A kind of electronic device
c-3) hydroxide (F)
d) Optionally, a redox-active compound (G).
7. An epoxidation catalyst system (2) as claimed in claim 6 wherein said metal salt (E) is one or more compounds selected from the group consisting of NiCl 2 、MnCl 2 、PbCl 2 、SnCl 2 、CrCl 3 、VCl 3 、MoCl 4 、FeCl 2 And RuCl 3 。
8. An epoxidation catalyst system (2) as claimed in claim 6 or 7 wherein the hydroxide (F) is an organic hydroxide (B-1) and the organic hydroxide (F-1) is one or more compounds and is selected from the group consisting of 3- (trifluoromethyl) phenyltrimethylammonium hydroxide, tetra-n-butylphosphonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide, tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetrabutylammonium hydroxide and tetramethylammonium hydroxide.
9. The epoxidation catalyst system (2) as claimed in any of claims 6 to 8, wherein the epoxidation catalyst system (2) comprises a reaction product (2), and the reaction product (2) has the structure of formula (IV), (V) and/or (VI):
If m is<n+o，(Q R 1 R 2 R 3 R 4 ) + Im-o-pI [M(E) m+ (Hal) n (OH) o (S) p ] m-n-o ·q·I 2 (IV)
If m=n+o, [ M (E) m+ (Hal) n (OH) o (S) p ]·q·I 2 (V)
If m is>n+o，[M(E) m+ (Hal) n (OH) o (S) p ] m-n-o ·q·I 2 [X] - n+o-m (VI)
Wherein the method comprises the steps of
Q=nitrogen or phosphorus, preferably nitrogen,
R 1 、R 2 、R 3 、R 4 independently of one another selected from
(iv) A linear or branched alkyl group containing 1 to 22 carbon atoms, optionally substituted with heteroatoms and/or heteroatom-containing substituents;
(v) Alicyclic groups containing 3 to 22 carbon atoms having 1 to 3 bridging carbon atoms, optionally substituted with heteroatoms and/or heteroatom-containing substituents, and/or
(vi) Aryl groups containing 6 to 18 carbon atoms, optionally substituted with 1 to 10 carbon atoms and/or optionally substituted with heteroatoms and/or heteroatom-containing substituents;
R 1 、R 2 、R 3 and R is 4 Preferably independently of each other selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, isobutyl, t-Bu, n-butyl, phenyl, benzyl, (trifluoromethyl) phenyl, more preferably methyl, benzyl and n-butyl;
M(E) m+ ＝Ni 2+ 、Mn 2+ 、Pb 2+ 、Sn 2+ 、Cr 3+ 、V 3+ 、Mo 4+ 、Fe 2+ or Ru (Rust) 3+ Preferably Ni 2+ 、Mn 2+ 、Pb 2+ 、Sn 2+ ；
Hal＝Cl - 、Br - Or I - Preferably Cl - Or Br (Br) - More preferably Cl - ，
n+o+p＝6；
S＝H 2 O, THF (tetrahydrofuran) or dioxane, bis (2-methoxyethyl) ether (diethylene glycol dimethyl ether), methoxyethanol, polyethylene glycol, pyridine, lutidine, 2' -bipyridine, acetonitrile, dimethyl sulfoxide, sulfolane, thiophene, preferably THF;
n is more than or equal to 1; preferably n is greater than or equal to 2; more preferably n=2;
o is more than or equal to 1; preferably o is greater than or equal to 1; more preferably o=1; 2;3 or 4;
X＝OTf - 、BF 4 - 、Hal - ；
q is more than or equal to 1, preferably more than or equal to 1 and less than or equal to 2000, and more preferably more than or equal to 1 and less than or equal to 10.
10. A process for producing an epoxide comprising the oxidative conversion of an olefin in a reactor in the presence of an epoxidation catalyst system (1) as claimed in any of claims 1 to 5 or an epoxidation catalyst system (2) as claimed in any of claims 6 to 9.
11. The process as claimed in claim 10, wherein the oxidative conversion in the reactor is carried out in the presence of oxygen or an oxygen-containing gas mixture.
12. The process as claimed in claim 10 or 11, wherein the olefin is one or more compounds and is selected from the group consisting of ethylene, propylene, butene, 1-octene, butadiene, but-1, 4-diol diallyl ether, allyl chloride, allyl alcohol, styrene, cyclopentene, cyclohexene, phenyl allyl ether, diallyl ether, n-butyl allyl ether, t-butyl allyl ether, bisphenol a diallyl ether, resorcinol diallyl ether, triphenylol methane triallyl ether, cyclohexane-1, 2-dicarboxylic acid bis (allyl ester), tris (prop-2, 3-enyl) isocyanurate and mixtures of these olefins, preferably ethylene, propylene and allyl chloride, more preferably propylene.
13. A process as claimed in any one of claims 10 to 12 wherein the preparation is carried out in the presence of a solvent.
14. A process as claimed in any one of claims 10 to 13 wherein the preparation is carried out in the absence of solvent.
15. A process as claimed in any one of claims 10 to 14, wherein the olefin and oxygen-containing gas mixture is metered continuously or stepwise, preferably continuously, into the reactor.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP21180223.6 | 2021-06-18 | ||
| EP22164095 | 2022-03-24 | ||
| EP22164095.6 | 2022-03-24 | ||
| PCT/EP2022/065954 WO2022263343A1 (en) | 2021-06-18 | 2022-06-13 | Epoxydation catalyst systems and process for preparing epoxides |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117529365A true CN117529365A (en) | 2024-02-06 |
Family
ID=81384900
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202280043467.7A Pending CN117529365A (en) | 2021-06-18 | 2022-06-13 | Epoxidation catalyst system and process for preparing epoxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117529365A (en) |
-
2022
- 2022-06-13 CN CN202280043467.7A patent/CN117529365A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Song et al. | Synthesis of cyclic carbonates from epoxides and CO 2 catalyzed by potassium halide in the presence of β-cyclodextrin | |
| JP2004131505A (en) | Method for epoxidation of cyclic alkene | |
| JP2004131504A (en) | Use of cyclic alkane as settling accelerator in epoxidation of cyclic alkene | |
| JP2009503030A (en) | Method for preparing alkylene carbonate | |
| Liu et al. | Syntheses of new peroxo-polyoxometalates intercalated layered double hydroxides for propene epoxidation by molecular oxygen in methanol | |
| CN117529365A (en) | Epoxidation catalyst system and process for preparing epoxide | |
| CN106582879A (en) | Epoxidation catalyst and preparation method thereof, epoxidation catalyst system and preparation method of epoxidation catalyst system | |
| JPH11501250A (en) | Epoxides produced by oxidizing olefins with air or oxygen | |
| Zhang et al. | Oxidation reactions catalyzed by polyoxomolybdate salts | |
| CN106478387A (en) | A kind of preparation method of naphthyl containing α two arone compound | |
| JP4315800B2 (en) | One-step production of 1,3-propanediol from ethylene oxide and synthesis gas using catalyst with phosphoranoalkane ligand | |
| EP2602251B1 (en) | Method for producing epoxy compound by oxidation | |
| JPS6134431B2 (en) | ||
| EP4355482A1 (en) | Epoxydation catalyst systems and process for preparing epoxides | |
| JP6080858B2 (en) | Process for preparing divinylarene dioxide | |
| WO2021066756A2 (en) | Catalyst composition for cyclic carbonate production from co2 and olefins | |
| JP2005254068A (en) | Catalyst for cyclic carbonate, manufacturing method therefor and manufacturing method for cyclic carbonate using the catalyst | |
| JPH0480909B2 (en) | ||
| CN106117157B (en) | A kind of process for catalytic synthesis of heterocycle nitrile compounds | |
| EP0188912B1 (en) | Epoxidation of propylene | |
| CN110950822A (en) | Method for catalyzing olefin epoxidation | |
| KR102724472B1 (en) | Direct method for the preparation of glycols | |
| CN111377951A (en) | Rare earth metal compound, preparation method, composition and method for catalyzing olefin epoxidation | |
| CN105315240B (en) | The method for producing epoxychloropropane | |
| JP2004099541A (en) | Method for producing epoxy compound |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |