EP4355482A1 - Epoxydation catalyst systems and process for preparing epoxides - Google Patents
Epoxydation catalyst systems and process for preparing epoxidesInfo
- Publication number
- EP4355482A1 EP4355482A1 EP22733410.9A EP22733410A EP4355482A1 EP 4355482 A1 EP4355482 A1 EP 4355482A1 EP 22733410 A EP22733410 A EP 22733410A EP 4355482 A1 EP4355482 A1 EP 4355482A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- hydroxide
- catalyst system
- epoxidation catalyst
- group
- propene
- 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
- 150000002118 epoxides Chemical class 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 84
- 229910052751 metal Inorganic materials 0.000 claims abstract description 60
- 239000002184 metal Substances 0.000 claims abstract description 60
- 150000001875 compounds Chemical class 0.000 claims abstract description 58
- 150000003839 salts Chemical class 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 46
- 239000000203 mixture Substances 0.000 claims abstract description 45
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 claims abstract description 29
- 229910052740 iodine Inorganic materials 0.000 claims abstract description 26
- 239000011630 iodine Substances 0.000 claims abstract description 26
- 150000001336 alkenes Chemical class 0.000 claims abstract description 24
- 230000001590 oxidative effect Effects 0.000 claims abstract description 22
- 239000011133 lead Substances 0.000 claims abstract description 20
- 239000011651 chromium Substances 0.000 claims abstract description 15
- 150000002739 metals Chemical class 0.000 claims abstract description 8
- 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
- 238000006735 epoxidation reaction Methods 0.000 claims description 124
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 122
- 238000000034 method Methods 0.000 claims description 95
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 58
- 239000007789 gas Substances 0.000 claims description 57
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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 nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 39
- -1 Mo (acacE Chemical compound 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 28
- NDKBVBUGCNGSJJ-UHFFFAOYSA-M benzyltrimethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)CC1=CC=CC=C1 NDKBVBUGCNGSJJ-UHFFFAOYSA-M 0.000 claims description 27
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 27
- 125000005842 heteroatom Chemical group 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims description 23
- 125000004432 carbon atom Chemical group C* 0.000 claims description 21
- 239000007795 chemical reaction product Substances 0.000 claims description 20
- 239000011572 manganese Substances 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000002360 preparation method Methods 0.000 claims description 15
- 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
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 10
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 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
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 9
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 8
- 229910021591 Copper(I) chloride Inorganic materials 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
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 8
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 8
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-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
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052801 chlorine Inorganic materials 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
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 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
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 5
- 229910003206 NH4VO3 Inorganic materials 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
- ZFSLODLOARCGLH-UHFFFAOYSA-N isocyanuric acid Chemical compound OC1=NC(O)=NC(O)=N1 ZFSLODLOARCGLH-UHFFFAOYSA-N 0.000 claims description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 229940005561 1,4-benzoquinone Drugs 0.000 claims description 4
- FRASJONUBLZVQX-UHFFFAOYSA-N 1,4-naphthoquinone Chemical compound C1=CC=C2C(=O)C=CC(=O)C2=C1 FRASJONUBLZVQX-UHFFFAOYSA-N 0.000 claims description 4
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 claims description 4
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 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
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-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
- 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
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- 229930192474 thiophene Natural products 0.000 claims description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 claims description 3
- 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
- FHVRTMVXBVDWCK-UHFFFAOYSA-N 2-methyl-2-prop-2-enoxypropane Chemical compound CC(C)(C)OCC=C FHVRTMVXBVDWCK-UHFFFAOYSA-N 0.000 claims description 3
- 239000004805 Cyclohexane-1,2-dicarboxylic acid Substances 0.000 claims description 3
- QSAWQNUELGIYBC-UHFFFAOYSA-N cyclohexane-1,2-dicarboxylic acid Chemical compound OC(=O)C1CCCCC1C(O)=O QSAWQNUELGIYBC-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-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
- HPYNZHMRTTWQTB-UHFFFAOYSA-N dimethylpyridine Natural products CC1=CC=CN=C1C HPYNZHMRTTWQTB-UHFFFAOYSA-N 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 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
- 230000008569 process Effects 0.000 description 57
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 42
- 239000007788 liquid Substances 0.000 description 25
- 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
- 230000003647 oxidation Effects 0.000 description 23
- 238000007254 oxidation reaction Methods 0.000 description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 20
- 238000002474 experimental method Methods 0.000 description 20
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 16
- 229910001868 water Inorganic materials 0.000 description 15
- 229910001853 inorganic hydroxide Inorganic materials 0.000 description 14
- 239000000047 product Substances 0.000 description 13
- 239000010703 silicon Substances 0.000 description 12
- 229910052710 silicon Inorganic materials 0.000 description 12
- 238000012360 testing method Methods 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- 230000001681 protective effect Effects 0.000 description 10
- 239000000377 silicon dioxide Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 9
- 230000004913 activation Effects 0.000 description 9
- 239000006227 byproduct Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 8
- 238000001764 infiltration Methods 0.000 description 8
- 230000008595 infiltration Effects 0.000 description 8
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 238000004088 simulation Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000001816 cooling Methods 0.000 description 7
- 150000004820 halides Chemical class 0.000 description 7
- 229910001510 metal chloride Inorganic materials 0.000 description 7
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-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
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-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
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-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
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 6
- 230000033444 hydroxylation Effects 0.000 description 6
- 238000005805 hydroxylation reaction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 239000004408 titanium dioxide Substances 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-M toluene-4-sulfonate Chemical compound CC1=CC=C(S([O-])(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-M 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
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 5
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 239000000920 calcium hydroxide Substances 0.000 description 5
- 235000011116 calcium hydroxide Nutrition 0.000 description 5
- 229910002091 carbon monoxide Inorganic materials 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
- 229910010271 silicon carbide Inorganic materials 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 4
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- 229910021592 Copper(II) chloride Inorganic materials 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
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 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
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- 239000011591 potassium Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000003077 quantum chemistry computational method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 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
- 150000003626 triacylglycerols Chemical class 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/04—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen
- C07D301/06—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with air or molecular oxygen in the liquid phase
Definitions
- the invention relates to a first epoxidation catalyst system comprising a mixture of a metal salt of the metals chromium, manganese, molybdenum, lead and/or bismuth and a hydroxide and a redox-active compound.
- a further object of the invention is a further, second epoxidation catalyst system comprising a mixture of a further metal salt, iodine and a hydroxide.
- a process for preparing epoxides is comprised of oxidatively reacting an alkene in a reactor in the presence of the first epoxidation catalyst system or the second epoxidation catalyst system.
- propylene oxide by means of co-product-based processes (e.g. oxirane process) is relevant, in which ethylbenzene or isobutane is reacted in a 1st stage in the presence of oxygen to form the respective hydroperoxides, which are then reacted with propene to form propylene oxide and 1-Phenylethanol or tert-butanol can be implemented as further by-products.
- These by-products can then be further converted into styrene and isobutene or isobutane.
- a by-product is also formed, which has to be separated off and further processed in other plants.
- HPPO process is also of industrial relevance, in which propylene is reacted with hydrogen peroxide to form propylene oxide and water. Compared to the large-scale production processes mentioned above, it is advantageous that there are no by-products or salt loads in the product.
- hydrogen peroxide has to be produced in an upstream, technically complex catalytic process. The process is considered technically demanding and is usually only operated at network sites with other H2O2 consumers.
- This improved catalyst activity and selectivity should be reflected by the lowest possible activation energy E A for the reaction sequence or the reaction mechanism of the hydroxylation of propene, ie the addition of propene to the catalyst system, and the reductive elimination of the propylene oxide formed from the catalyst system.
- an epoxidation catalyst system (1) an epoxidation catalyst system (2) and a process for preparing epoxides comprising the oxidative reaction of an alkene in a reactor in the presence of the epoxidation catalyst system (1) or the epoxidation catalyst system (2) .
- the epoxidation catalyst system (1) comprises a) a mixture (1) or a reaction product (1) a-1) of a metal salt (A) of the metals chromium (Cr), manganese (Mn), molybdenum (Mo), lead (Pb) and/or bismuth (Bi) and a-2) a hydroxide (B) b) a redox-active compound (C).
- one or more metal salts (A) of the metals chromium (Cr), manganese (Mn), molybdenum (Mo), lead (Pb) and/or bismuth (Bi) are used.
- the metal salt (A) is a nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride.
- the metal salt (A) is one or more compounds and is selected from the group consisting of MoCE, MoOCE. MnCE, K 2 MnCE, CrOCE, PbCU and BiCE.
- the hydroxide (B) is an organic hydroxide (B-1) and/or inorganic hydroxide (B-2).
- the hydroxide (B) is an organic hydroxide (B-I) and the organic hydroxide (B-I) is one or more compound(s) and is selected from the group consisting of 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra- n-butylphosphonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide,
- the hydroxide (B) is an inorganic hydroxide (B-2) and the inorganic hydroxide (B-2) is one or more compounds and is selected from the group consisting of Lithium hydroxide, sodium hydroxide, potassium hydroxide and their crown ether complexes, cesium hydroxide, calcium hydroxide, barium hydroxide, potassium aluminate, sodium aluminate, potassium aluminate and sodium zincate, preferably lithium hydroxide, sodium hydroxide and potassium hydroxide.
- the redox-active compound (C) is one or more compound(s) and is selected from the group consisting of CuCF. Cu(BF )2.
- the calculated molar ratio of metal salt (A) to hydroxide groups of hydroxide (B) for epoxidation catalyst system (1) is from 1.000 moles to 1.000 moles to 6.000 moles to 1.000 moles.
- the calculated molar ratio of the metal salt (A) to the redox-active compound (C) for the epoxidation catalyst system (1) is from 0.100 mole to 1.000 mole to 10.000 mole to 1.000 mole.
- the calculated molar ratio of the hydroxide groups of the hydroxide (B) to that of the redox-active compound (C) for the epoxidation catalyst system (1) is from 0.100 mole to 1.000 mole to 50.000 mole to 1.000 mole.
- the epoxidation catalyst system (1) comprises the mixture (1) of the metal salt (A) and the hydroxide (B) in the calculated molar ratios described above.
- the epoxidation catalyst system (1) comprises the reaction product (1) of the metal salt (A) and the hydroxide (B), the metal salt (A) and the hydroxide (B) being prepared using a preparation process known to those skilled in the art, such as, for example Solid state syntheses, precipitation or co-precipitation methods or as in situ salt metathesis is produced.
- the reaction product (1) can be prepared by adding the organic hydroxide (B-1) and/or inorganic hydroxide (B-2) to a solution of the nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride of Metal salt (A) are synthesized in the above-described, calculated molar ratios, subsequent removal of the precipitate, drying and appropriate thermal treatment.
- a chloride of Metal salt (A) preferably a chloride of Metal salt (A) are synthesized in the above-described, calculated molar ratios, subsequent removal of the precipitate, drying and appropriate thermal treatment.
- reaction product (1) of the epoxidation catalyst system (1) has a structure of the formula (I), (II) and/or (III):
- Q nitrogen or phosphorus, preferably nitrogen
- Ri, R 2 , R 3 , R 4 independently selected from the group consisting of
- M(A) m+ Mo 5+ , Mn 4+ , Cr 4+ , Pb 4+ , Bi 5+ preferably Mo 5+ ;
- Hal Cl, Br or G, preferably Cl or Br, particularly preferably Cl;
- the reaction product (1) of the epoxidation catalyst system (1) is one or more compounds and is selected from the list consisting of [MO(Y)C1 2 (OH) 2 (THF) 2 ]C1, [Mn (IV)Cl(OH)3(THF) 2 ], [Cr(VI)Cl 2 (OH)2(THF) 2 ]Cl2, [Pb(IV)Cl 2 (OH) 2 (THF) 2 ] and [ Bi(V) Cl2 (OH)3THF] .
- the mixture (1) or the reaction product (1) can be mixed with the redox-active compound (C) to form the epoxidation catalyst system (1) using the mixing methods known to those skilled in the art, such as stirring in solutions or suitable mixing of solids.
- the epoxidation catalyst system (1) further contains iodine (I 2 ).
- the iodine (U) is used in a calculated mole fraction of 1 mol % to 2000 mol %, based on the amount of the metal salt (A).
- the epoxidation catalyst system (1) is supported on a catalyst support (D) to form a supported epoxidation catalyst system (1).
- the catalyst support (D) is one or more compound(s) and is selected from the group consisting of metal oxides, alkaline earth metal carbonates, silicates, silicon carbides, silicon oxy carbides, silicon nitrides, silicon oxynitrides and silicon dioxide, preferably aluminum oxide, aluminum dioxide, silica, Titanium dioxide, zirconia, calcium carbonate, phyllosilicates such as talc, kaolinites and pyrophyllites, and titanium dioxide.
- the catalyst support can be in the form of a shaped body or a powder.
- the epoxidation catalyst system (1) is applied to the catalyst support (D) in a calculated mass fraction of 1.0% by weight to 30.0% by weight.
- the epoxidation catalyst system (1) is applied to the catalyst support (D) using the wet infiltration method (wet infiltration) or the incipient wetness method.
- an epoxidation catalyst system (2) comprising c) a mixture (2) or a reaction product (2) c-1) a metal salt (E), c-2) iodine (E) and c-3) a hydroxide (F) d) optionally a redox-active compound (G).
- the metal salt (E) is a nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride.
- the metal salt (E) is one or more compound(s) and is selected from the group consisting of NiCk, MnCk. PbCk. SnCk. CrCk, VC1 3 , MoCU, FeCk and RuCk.
- the hydroxide (F) is an organic hydroxide (F-1) and/or inorganic hydroxide (F-2).
- the hydroxide (F) is an organic hydroxide (B-I) and the organic hydroxide (F-I) is one or more compound(s) and is selected from the group consisting of 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra- n-butylphosphonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide,
- the hydroxide (F) is an inorganic hydroxide (F-2) and the inorganic hydroxide (F-2) is one or more compound(s) and is selected from the group consisting of fithium hydroxide, Sodium hydroxide, potassium hydroxide and their crown ether complexes, cesium hydroxide, calcium hydroxide, barium hydroxide, potassium aluminate, sodium aluminate, potassium aluminate and sodium zincate, preferably fithium hydroxide, sodium hydroxide and potassium hydroxide.
- the redox-active compound (G) is one or more compound(s) and is selected from the group consisting of CuCk, Cu(BF4k, CuCl, VCk, VOCk, NH4VO3, 1,4-benzoquinones, 1,4 -Naphtoquinones, Se2Ck, TeCk, TeCk, Sb2C , Sb2Ck, CeCk, Co(salen), Co(OAc)2, SnSCk, Fe(acac)3, Mo(acac)3, K 2 Cr2Ck, Mn(OAc)3, Ni(CF3CO2H )2 and BiCk.
- the calculated molar ratio of metal salt (E) to hydroxide groups of hydroxide (F) for epoxidation catalyst system (2) is from 1.000 moles to 1.000 moles to 6.000 moles to 1.000 moles.
- the calculated molar ratio of the metal salt (E) to the redox-active compound (G) for the epoxidation catalyst system (2) is from 0.100 mole to 1.000 mole to 10.000 mole to 1.000 mole.
- the calculated molar ratio of the hydroxide groups of the hydroxide (F) to that of the redox-active compound (G) for the epoxidation catalyst system (2) is from 0.100 mole to 1.000 mole to 50.000 mole to 1.000 mole.
- the iodine (E) is used in a calculated amount of from 1 mol % to 2000 mol %, based on the amount of the metal salt (E).
- the epoxidation catalyst system (2) comprises the mixture (2) of the metal salt (E), iodine and the hydroxide (F) in the calculated molar ratios described above.
- the epoxidation catalyst system (2) comprises the reaction product (2) of the metal salt (E), iodine and the hydroxide (F), wherein the metal salt (E), the iodine and the hydroxide (F) with a for the Preparation methods known to those skilled in the art, such as solid-state syntheses, precipitation or co-precipitation methods, or as in situ salt metathesis.
- organic hydroxide (F-1) and/or inorganic hydroxide (F-2) to a solution of the nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride of the metal salt (E ) are synthesized in the above-described, calculated molar ratios, subsequent separation of the precipitation product, drying and suitable thermal treatment.
- reaction product (2) of the epoxidation catalyst system (2) has a structure of the formula (IV), (V) and/or (VI):
- Q nitrogen or phosphorus, preferably nitrogen
- R 1 , R 2 , R 1 . R 4 independently selected from the group consisting of
- Hal CI , Br or G preferably CI or Br particularly preferably CI ,
- X OTf,BF4 , Hai ; q>1 preferably 1 ⁇ q ⁇ 2000 particularly preferably 1 ⁇ q ⁇ 10.
- the epoxidation catalyst system (2) is supported on a catalyst support (H) to form a supported epoxidation catalyst system (2).
- the catalyst support (H) is one or more compound(s) and is selected from the group consisting of metal oxides, alkaline earth metal carbonates, silicates, silicon carbides, silicon oxycarbides, silicon nitrides, silicon oxynitrides and silicon dioxide, preferably aluminum oxide, aluminum dioxide, silica, Titanium dioxide, zirconia, calcium carbonate, phyllosilicates such as talc, kaolinites and pyrophyllites, and titanium dioxide.
- the catalyst support can be in the form of a shaped body or a powder.
- the epoxidation catalyst system (2) is applied to the catalyst support (H) in a calculated proportion by weight of from 1.0% by weight to 30.0% by weight.
- the epoxidation catalyst system (H) is applied to the catalyst support (H) using the wet infiltration method (wet infiltration) or the incipient wetness method.
- Another subject of the present invention is a process for preparing epoxides comprising the oxidative reaction of an alkene in a reactor in the presence of the epoxidation catalyst system (1) according to the invention or the epoxidation catalyst system according to the invention.
- the oxidative reaction takes place in the reactor in the presence of oxygen or an oxygen-containing gas mixture.
- the oxygen-containing gas mixture also includes dilution, carrier or inert gases such as hydrocarbons, noble gases, CO, CO 2 , N 2 .
- the oxygen or an oxygen-containing gas mixture are further additives such as water, CO, N-containing compounds such as hydrazine, ammonia (NH3), methylamine (MeMU), NOx, PH 3 , SO 2 and / or SO 3 is added in amounts from 10 ppm to 500 ppm, preferably from 30 ppm to 300 ppm and particularly preferably from 50 ppm to 200 ppm.
- CO 2 can be added in a proportion of 0.01% by volume to 50% by volume, preferably from 0.1% by volume to 20% by volume, and particularly preferably from 1% by volume to 10% by volume.
- organic halides such as ethylene dichloride, ethyl chloride, vinyl chloride, methyl chloride and/or methylene chloride can be added in amounts from 10 ppm to 500 ppm, preferably from 50 ppm to 400 ppm, and particularly preferably from 100 ppm to 300 ppm.
- the oxidative reaction takes place in the reactor in the presence of oxygen.
- the alkene is one or more compound(s) and is selected from the group consisting of ethene, propene, butene, 1-octene, butadiene, 1,4-butanediol diallyl ether, allyl chloride, allyl alcohol, styrene, cyclopentene, Cyclohexene, phenyl allyl ether, diallyl ether, n-butyl allyl ether, tert-butyl allyl ether, bisphenol A diallyl ether, resorcinol diallyl ether, triphenylolmethane triallyl ether, cyclohexane-1,2-dicarboxylic acid bis-
- alkenes preferably ethene, propene and allyl chloride and particularly preferably propene.
- the epoxide (alkylene oxide) according to the invention can be an epoxide having 2-45 carbon atoms.
- the epoxide is selected from at least one compound from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propylene oxide (isobutene oxide), 1,2 -pentylene oxide, 2,3-pentylene oxide, 2-methyl-1,2-butylene oxide, 3-methyl-1,2-butylene oxide, epoxides of C6-C22 a-olefins such as 1,2-hexylene oxide, 2,3-hexylene oxide , 3,4-hexylene oxide, 2-methyl-1,2-pentylene oxide, 4- Methyl-1,2-pentylene oxide, 2-ethyl-l,2-butylene oxide, 1,2-heptylene oxide, 1,2-octylene oxide, 1,2-nonylene oxide,
- Examples of derivatives of glycidol are phenyl glycidyl ether, cresyl glycidyl ether, methyl glycidyl ether, ethyl glycidyl ether and 2-ethylhexyl glycidyl ether.
- the epoxide is ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-pentylene oxide, 1,2-hexylene oxide, 1,2-heptylene oxide and/or 1,2-octylene oxide.
- the epoxide is ethylene oxide and/or propylene oxide.
- the epoxide is propylene oxide.
- epoxides are prepared in the presence of a solvent.
- the solvent is one or more compound(s) and is selected from the group consisting of CO 2 , water, perfluoromethyldecalin, perfluorodecalin, perfluoroperhydrophenanthrene,
- epoxides are prepared in the presence of a solvent, with the preparation being carried out at a temperature of from 20° C. to 200° C., preferably from 50° C. to 160° C. and particularly preferably from 100° C. to 150 °C
- epoxides are prepared in the presence of a solvent, with the preparation taking place at a pressure of from 1 bara to 200 bara, preferably from 1 bara to 35 bara and particularly preferably from 1 bara to 28 bara.
- epoxides are prepared in the presence of a solvent, the preparation taking place over a period of 6 minutes to 48 hours, preferably 6 minutes to 24 hours and particularly preferably 6 minutes to 3 hours.
- epoxides are prepared in the presence of a solvent, the molar ratio of the alkene to oxygen being from 1:100 to 100:1, preferably from 1:30 to 30:1.
- epoxides are prepared in the absence of a solvent.
- a solvent-free process means that solvent residues, for example as a result of the preparation of the starting materials, are present in an amount of up to 10% by volume, preferably up to 5% by volume and particularly preferably up to 2% by volume, based on the amount of propene used could be.
- epoxides are prepared in the absence of a solvent, the preparation being carried out using the supported epoxidation catalyst system (1) according to the invention or the supported epoxidation catalyst system (2) according to the invention.
- epoxides are prepared in the absence of a solvent, with the preparation being carried out at a temperature of from 20.degree. C. to 500.degree. C., preferably from 50.degree. C. to 400.degree. C. and particularly preferably from 50.degree. C. to 250.degree he follows.
- epoxides are prepared in the absence of a solvent, with the preparation taking place at a pressure of from 1 bara to 200 bara, preferably from 2 bara to 100 bara and particularly preferably from 2 bara to 50 bara.
- epoxides are produced in the absence of a solvent, the production being carried out with a space velocity (English Gas Houmly Space Velocity GHSV) as the quotient of the volume flow of the reactant gases used to the catalyst volume of 100 h-1 to 10000 h-1, preferably from 200 h-1 to 5000 h-1 and particularly preferably from 500 h-1 to 2000 h-1.
- a space velocity English Gas Houmly Space Velocity GHSV
- the catalyst volume corresponds to that of the supported catalyst epoxidation catalyst system (1) or (2) and/or the sum of the catalyst and diluent volume.
- epoxides are prepared in the absence of a solvent, the molar ratio of the alkene to oxygen being from 1.0:0.1 to 2:1, preferably from 1:0.5 to 2:1 and particularly preferably from is 1:0.8 to 2:1.
- the alkene is metered into the reactor continuously or in stages, preferably continuously.
- oxygen or the oxygen-containing gas mixture is metered into the reactor continuously or in stages, preferably continuously.
- the alkene and the oxygen or the oxygen-containing gas mixture are metered into the reactor continuously or in stages, preferably continuously.
- the epoxide is removed from the reactor continuously or in stages, preferably continuously.
- the epoxidation catalyst system (1) is metered continuously or stepwise, preferably continuously, into the reactor.
- epoxides can be prepared continuously by the oxidative reaction of alkenes in a continuous stirred tank reactor (CSTR) or a single- or double-column bubble reactor in the liquid phase in the presence of a solvent.
- CSTR continuous stirred tank reactor
- the continuous production of epoxides in the gas phase in the absence of a solvent can be carried out by means of a continuous gas phase reactor, such as a fixed bed reactor, also using ceramic packing materials.
- the epoxidation catalyst system (1) and/or epoxidation catalyst system (2) is used in a calculated amount of 10 ppm to 500,000 ppm, preferably 100 ppm to 200,000 ppm and particularly preferably 1000 ppm to 150,000 ppm by mass all reactants involved and optional solvents and possible other auxiliaries used.
- the invention relates to an epoxidation catalyst system (1) comprising a) a mixture, preferably a reaction product a-1) of a metal salt (A) of the metals chromium (Cr), manganese (Mn), molybdenum (Mo), lead (Pb) and/or bismuth (Bi) and a-2) a hydroxide (B) b) a redox-active compound (C).
- the invention relates to an epoxidation catalyst system (1) according to the first embodiment, wherein the metal salt (A) is a nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride.
- the metal salt (A) is a nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride.
- the 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 the group consisting of MoCE, MoOCE. MnCE, K 2 MnCE, CrOCE, PbCU and BiCE.
- the metal salt (A) is one or more compounds and is selected from the group consisting of MoCE, MoOCE. MnCE, K 2 MnCE, CrOCE, PbCU and BiCE.
- the invention relates to an epoxidation catalyst system (1) according to any one of the first to third embodiments, wherein the hydroxide (B) is an organic hydroxide (B-1) and/or inorganic hydroxide (B-2).
- the hydroxide (B) is an organic hydroxide (B-1) and/or inorganic hydroxide (B-2).
- the invention relates to an epoxidation catalyst system (1) according to the fourth embodiment, wherein the hydroxide (B) is an organic hydroxide (B-l) and the organic hydroxide (B-l) is one or more compound(s) 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.
- the hydroxide (B) is an organic hydroxide (B-l) and the organic hydroxide (B-l) is one or more compound(s) and is selected from The group consisting of 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, te
- the invention relates to an epoxidation catalyst system (1) according to the fourth embodiment, wherein the hydroxide (B) is an inorganic hydroxide (B-2) and the inorganic hydroxide (B-2) is one or more compound(s) and is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and their crown ether complexes, cesium hydroxide, calcium hydroxide, barium hydroxide, potassium aluminates, Sodium aluminate, potassium aluminate and sodium zincate, preferably lithium hydroxide, sodium hydroxide and potassium hydroxide.
- the hydroxide (B) is an inorganic hydroxide (B-2)
- the inorganic hydroxide (B-2) is one or more compound(s) and is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and their crown ether complexes, cesium hydroxide, calcium hydroxide, barium hydroxide, potassium aluminates, Sodium alumina
- the invention relates to an epoxidation catalyst system (1) according to one of the first to sixth embodiments, wherein the redox-active compound (C) is one or more compound(s) and is selected from the group consisting of copper dichloride, CuCl 2. Cu( BF4)2, CuCl, VCh.
- VOCE NH4VO3, 1,4-Benzoquinone, 1,4-Naphtoquinone, Se20s, Te02, TeCh, Sb2Ü3, Sb20s, CeCL, Co(salen), Co(OAc)2, SnS04, 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 .
- the invention relates to an epoxidation catalyst system (1) according to one of the first to seventh embodiments, wherein the calculated molar ratio of the metal salt (A) to the hydroxide groups of the hydroxide (B) is from 1.000 mol to 1.000 mol to 6.000 mol to 1.000 mol .
- the invention relates to an epoxidation catalyst system (1) according to one of the first to eighth embodiments, wherein the calculated molar ratio of the metal salt (A) to the redox-active compound (C) is from 0.100 mol to 1.000 mol to 10.000 mol to 1.000 mol.
- the invention relates to an epoxidation catalyst system (1) according to one of the first to ninth embodiments, the calculated molar ratio of the hydroxide groups of the hydroxide (B) to that of the redox-active compound (C) of 0.100 mol to 1.000 mol to 50.000 mol to 1,000 moles.
- the invention relates to an epoxidation catalyst system (1) according to one of the first to tenth embodiments, the epoxidation catalyst system (1) further comprising iodine (I2).
- the invention relates to an epoxidation catalyst system (1) according to the eleventh embodiment, the iodine (I2) being used in a calculated mole fraction of 1 mol % to 2000 mol % based on the amount of the metal salt (A).
- the invention relates to an epoxidation catalyst system (1) according to one of the first to twelfth embodiments, the epoxidation catalyst system (1) being applied to a catalyst support (D) to form a supported epoxidation catalyst system (1).
- the invention relates to an epoxidation catalyst system (1) according to the thirteenth embodiment, wherein the catalyst support (D) is one or more compound(s) and is selected from the group consisting of metal oxides, alkaline earth metal carbonates, silicates, silicon carbides, silicon oxy carbides, silicon nitrides,
- silicon oxynitrides and silica preferably alumina alumina, silica, titania, zirconia, calcium carbonate, phyllosilicates such as talc, kaolinites and pyrophyllites and titania.
- the invention relates to an epoxidation catalyst system (1) according to the thirteenth or fourteenth embodiment, the epoxidation catalyst system (1) being applied to the catalyst support in a calculated mass fraction of 1.0% by weight to 30.0% by weight (D) is applied.
- the invention features an epoxidation catalyst system
- the epoxidation catalyst system (1) is applied to the catalyst support (D) using the wet infiltration method (wet infiltration) or the incipient wetness method.
- the invention relates to an epoxidation catalyst system (2) comprising c) a mixture, preferably a reaction product of c-1) a metal salt (E), c-2) iodine (E) and c-3) a hydroxide (F) d) optionally a redox active compound (G).
- the invention relates to an epoxidation catalyst system (2) according to the seventeenth embodiment, wherein the metal salt (E) is a nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride.
- the metal salt (E) is a nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride.
- the invention features an epoxidation catalyst system
- the metal salt (E) is one or more compounds and is selected from the group consisting of NiCk, MnCE. PbCE. SnCl 2 , CrCk, VC1 3 , MoCU, FeCk and RuCk.
- the invention relates to an epoxidation catalyst system (2) according to one of the seventeenth to nineteenth embodiments, where the hydroxide (F) is an organic hydroxide (F1) and/or inorganic hydroxide (F-2).
- the invention relates to an epoxidation catalyst system (2) according to the twentieth embodiment, wherein the hydroxide (F) is an organic hydroxide (BI) and the organic hydroxide (FI) is one or more compound(s) 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.
- the invention relates to an epoxidation catalyst system (2) according to the twenty-first embodiment, wherein the hydroxide (F) is an inorganic hydroxide (F-2) and the inorganic hydroxide (F-2) is one or more compound(s) and is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and their crown ether complexes, cesium hydroxide, calcium hydroxide, barium hydroxide, potassium aluminate, sodium aluminate, potassium aluminate and sodium zincate, preferably lithium hydroxide, sodium hydroxide and potassium hydroxide.
- the hydroxide (F) is an inorganic hydroxide (F-2)
- the inorganic hydroxide (F-2) is one or more compound(s) and is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and their crown ether complexes, cesium hydroxide, calcium hydroxide, barium hydroxide, potassium aluminate, sodium
- the invention relates to a
- the invention relates to a
- Embodiment wherein the calculated molar ratio of the metal salt (E) to the hydroxide groups of the hydroxide (B) is from 1.000 moles to 1.000 moles to 6.000 moles to 1.000 moles.
- the invention relates to a
- Embodiment wherein the calculated molar ratio of the metal salt (E) to the redox-active compound (G) is from 0.100 mole to 1.000 mole to 10.000 mole to 1.000 mole.
- the invention relates to a
- Embodiment wherein the calculated molar ratio of the hydroxide groups of hydroxide (F) to that of the redox-active compound (G) is from 0.100 mol to 1.000 mol to 50.000 mol to 1.000 mol.
- the invention relates to a
- the epoxidation catalyst system (2) according to any one of the seventeenth to twenty-sixth embodiments, wherein the iodine (12) is used in a calculated mole fraction of 1 mol% to 2000 mol% based on the amount of the metal salt (A).
- the invention relates to a
- the epoxidation catalyst system (2) according to any one of the seventeenth to twenty-seventh embodiments, wherein the epoxidation catalyst system (2) is supported on a catalyst support (H) to form a supported epoxidation catalyst system (2).
- the invention relates to a
- the epoxidation catalyst system (2) according to the twenty-eighth embodiment, wherein the catalyst support (H) is one or more compound(s) and is selected from the group consisting of metal oxides, alkaline earth carbonates, silicates, silicon carbides, silicon oxy carbides, silicon nitrides, silicon oxynitrides and silicon dioxide, preferably alumina aluminum dioxide , silica, titanium dioxide, zirconia, calcium carbonate, phyllosilicates such as talc, kaolinites and pyrophyllites, and titanium dioxide.
- the catalyst support (H) is one or more compound(s) and is selected from the group consisting of metal oxides, alkaline earth carbonates, silicates, silicon carbides, silicon oxy carbides, silicon nitrides, silicon oxynitrides and silicon dioxide, preferably alumina aluminum dioxide , silica, titanium dioxide, zirconia, calcium carbonate, phyllosilicates such as talc, kaolinites and p
- the 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 support in a calculated mass fraction of from 1.0% to 30.0% by weight (H) is applied.
- the invention relates to an epoxidation catalyst system (2) according to one of the twenty-eighth to thirtieth embodiment, wherein the epoxidation catalyst system (2) is applied to the catalyst support (H) using the wet infiltration method (wet infiltration) or the incipient wetness method.
- the invention in a thirty-second embodiment, relates to a process for preparing epoxides comprising the oxidative reaction of an alkene in a reactor in the presence of the epoxidation catalyst system (1) according to one of the first to sixteenth embodiments or the epoxidation catalyst system (2) according to one of the seventeenth to thirty-first embodiments.
- the invention in a thirty-third embodiment, relates to a method according to the thirty-second embodiment, in which the oxidative reaction in the reactor takes place in the presence of oxygen or an oxygen-containing gas mixture.
- the invention relates to a process according to the thirty-second or thirty-third embodiment, wherein the alkene is one or more compound(s) and is selected from the group consisting of ethene, propene, butene, 1-octene, butadiene, 1,4 -Butanediol diallyl ether, allyl chloride, allyl alcohol, styrene, cyclopentene, cyclohexene, phenyl allyl ether, diallyl ether, n-butyl allyl ether, tert-butyl allyl ether, bisphenol-A diallyl ether, resorcinol diallyl ether, triphenylolmethane triallyl ether, cyclohexane-1,2- dicarboxylic acid bis(allyl ester), isocyanuric acid tris(prop-2,3-ene) ester and mixtures of these alkenes
- the alkene is one
- the invention relates to a method according to one of the thirty-second to thirty-fourth embodiments, the production being carried out in the presence of a solvent.
- the invention relates to a method according to one of the thirty-fifth embodiment, wherein the solvent is one or more compound(s) and is selected from the group consisting of CO 2 , water, perfluoromethyldecalin, perfluorodecalin, perfluoroperhydrophenanthrene,
- the invention relates to a method according to the thirty-fifth or thirty-sixth embodiment, wherein the production takes place at a temperature of 20°C to 200°C, preferably of 50°C to 160°C and particularly preferably of 100°C to 150°C he follows.
- the invention relates to a method according to one of the thirty-fifth to thirty-seventh embodiments, the production taking place at a pressure of 1 bara to 200 bara, preferably 1 bara to 35 bara and particularly preferably 1 bara to 28 bara.
- the invention relates to a method according to one of the thirty-fifth to thirty-eighth embodiments, the production taking place in a period of 6 minutes to 48 hours, preferably 6 minutes to 24 hours and particularly preferably 6 minutes to 3 hours.
- the invention relates to a process of one of the thirty-fifth to thirty-ninth embodiments, wherein the molar ratio of the alkene to the oxygen is from 1:100 to 100:1, preferably from 1:30 to 30:1.
- the invention relates to a method according to one of the thirty-second to thirty-fourth embodiments, wherein the preparation takes place in the absence of a solvent.
- the invention relates to a method according to the forty-first embodiment, wherein the preparation using the using the supported epoxidation catalyst system (1) according to one of the thirteenth to sixteenth embodiment or a supported epoxidation catalyst system (2) according to one of the twenty-eighth to thirty-first embodiment.
- the invention relates to a method according to the forty-first or forty-second embodiment, wherein the production takes place at a temperature of 20°C to 500°C, preferably of 50°C to 400°C and particularly preferably of 50°C to 250°C he follows.
- the invention relates to a method according to one of the forty-first to forty-third embodiments, the production taking place at a pressure of 1 bara to 200 bara, preferably 2 bara to 100 bara and particularly preferably 2 bara to 50 bara.
- the invention relates to a method according to one of the forty-first to forty-fourth embodiments, wherein the production takes place at a space velocity of 100 h-1 to 10000 h-1, preferably from 200 h-1 to 5000 h-1 and particularly preferably from 500 h-1 to 2000 h-1.
- the invention relates to a method according to one of the forty-first to forty-fifth embodiments, wherein the molar ratio of the alkene to the oxygen is from 1.0:0.1 to 2.0:1.0, preferably from 1.0:0.5 to is 2.0:1.0 and more preferably from 1.0:0.8 to 2.0:1.0.
- the invention relates to a process according to one of the thirty-second to forty-sixth embodiment, wherein the alkene is metered into the reactor continuously or in stages, preferably continuously.
- the invention relates to a method according to one of the thirty-third to forty-seventh embodiment, wherein the oxygen or the oxygen-containing gas mixture is metered into the reactor continuously or in stages, preferably continuously.
- the invention relates to a process according to one of the thirty-third to forty-eighth embodiments, the alkene and the oxygen or the oxygen-containing gas mixture being metered continuously or in stages, preferably continuously, into the reactor.
- the invention in a fiftieth embodiment, relates to a process according to one of the forty-seventh to forty-ninth embodiments, wherein the epoxide is removed from the reactor continuously or in stages, preferably continuously.
- the invention in a fifty-first embodiment, relates to a process of one of the forty-seventh to fiftieth embodiment, wherein the epoxidation catalyst system (1) and/or epoxidation catalyst system (2) is metered continuously or stepwise, preferably continuously, into the reactor.
- the invention relates to a method according to one of the thirty-second to fifty-first embodiment, wherein the
- Epoxidation catalyst system (1) and/or epoxidation catalyst system (2) in a calculated amount of 10 ppm to 500,000 ppm, preferably 100 ppm to 200,000 ppm and particularly preferably 1000 ppm to 150,000 ppm, based on the mass of all reactants involved and optionally solvents and possible others Auxiliaries is used.
- Metal chlorides and metal oxides All metal salts used are obtained directly from commercial sources and used without further processing as precursors for the active catalysts in the corresponding reactions:
- Tin(II) chloride from the manufacturer Sigma Aldrich Corporation with a purity of 98%.
- Molybdenum(VI) oxychloride was based on Vitzthumecker et al. in month Chem. 148, 629-633 (2017).
- Tetrahydrofuran from the manufacturer Sigma Aldrich Corporation with a purity of 99.9% (inhibitor-free).
- Triton B Benzyltrimethylammonium hydroxide
- Propylene was obtained from Sigma Aldrich Corporation at 99.9% purity and used as received.
- the chemicals are used for the synthesis without further purification.
- the gas chromatographic analysis (GC for short) of liquid and gas samples was based on "Determine Impurities in High-Purity Propylene Oxide with Agilent J&W PoraBOND U" by Dianli Ma, Ningbo ZRCC Lyondell Chemical Co., Ltd Zhejiang, China, and Yun Zou , Hua Wu, Agilent Technologies, Ine. carried out. Conversions of propenes, yields of propylene oxides and selectivities were determined on the basis of GC.
- Transition states were calculated using gradient based Monte Carlo as described in application WO 2020/079094A2.
- the activation energies for the catalytic reactions were calculated using quantum chemical simulations.
- a structure according to the transition states A TI - B T2 was drawn ( Figure 1).
- the bonds in bold were set to an atomic distance of 1.90 ⁇ (190 pm) each, in the case of A T2 to 1.30 ⁇ , and the resulting structures were translated into Cartesian coordinates.
- the atomic indices in the Cartesian coordinate set of the bonds drawn in bold in Figure 3 were set as a function space in the gradient-based Monte Carlo program and the Monte Carlo procedure was carried out until the corresponding transition states A TI - B T2 were obtained.
- Fig. 1 Three-step reaction mechanism for the oxidative hydroxylation of propene with hydroxide under metal catalysis.
- the epoxidation catalyst system (2) consisting of the metal salt (E), elemental iodine and the hydroxide (F) is used.
- This mixture (2) is loaded with propene, with the hydroxide first being added to the double bond of the propene.
- iodine is then inserted into the metal-carbon bond, releasing an iodohydrin. This decomposes in a slightly basic environment to form propylene oxide and iodide, which is oxidized back to elemental iodine by supplying oxygen.
- the metal catalyst ensures controlled addition of hydroxide and iodine to form intermediate iodohydrin without the formation of predominantly useless 1,2-diiodoalkanes.
- the iodine can be used here in catalytic or substoichiometric amounts. The oxidation can thus take place directly with oxygen.
- Fig. 2 Two-step reaction mechanism for the metal-catalyzed iodohydroxylation of propene.
- Fig. 3 Input geometries for the quantum chemical calculations of the transition states of the catalyzed oxidative hydroxylation A and iodohydroxylation B.
- the internal temperature of the reactor was regulated to 120° C. and oxygen was slowly forced in until a substance amount of 0.200 mol of oxygen was reached.
- the oxygen was added in such a way that the additional pressure rise was never more than 2 bar.
- the progress of the reaction and the end point were determined based on the pressure profile and/or by taking liquid and gas samples and analyzing them by GC.
- the reactor was cooled to 40° C. and then let down and the reaction product, propylene oxide, was distilled off via the degassing line into a cooled receiver.
- the yield of propylene oxide was 23.2 g for all five runs.
- the reaction vessel was then charged with 0.400 mol of propene (about 11 bar).
- the internal temperature of the reactor was regulated to 120° C. and oxygen was slowly forced in until a substance amount of 0.200 mol of oxygen was reached.
- the oxygen was added in such a way that the additional pressure rise was never more than 2 bar.
- the progress of the reaction and the end point of the reaction were determined based on the pressure profile and/or by taking liquid and gas samples and analyzing them by GC.
- the reactor was cooled to 40° C. and then let down and the reaction product, propylene oxide, was distilled off via the degassing line into a cooled receiver.
- the yield of propylene oxide was 23.2 g for all four experiments.
- the bubble column was then brought to the reaction temperature of 120° C. and a gas mixture of propene, oxygen and nitrogen (molar ratio of propene to oxygen 2:1) flowed therethrough, with a total volume flow of less than 10 L/min being regulated.
- the progress of the reaction or the stationary point was determined by taking liquid and gas samples at the upper sampling points and analyzing them by GC.
- the product gas mixture produced continuously was freed from propylene oxide by cascaded cooling and the resulting gas stream was again slightly compressed and mixed with propene, oxygen and nitrogen and flowed onto the gassing frit of the bubble column.
- N-benzyltrimethylammonium hydroxide (trade name Triton B) was added until a liquid sample taken in contact with a water-moist pH test strip showed a pH value of 10-11.
- the bubble column was then brought to the reaction temperature of 120° C. and a gas mixture of propene, oxygen and nitrogen (molar ratio of propene to oxygen 2:1) flowed therethrough, with a total volume flow of less than 10 L/min being regulated.
- the progress of the reaction or the stationary point was determined by taking liquid and gas samples at the upper sampling points and analyzing them by GC.
- the product gas mixture produced continuously was freed from propylene oxide by cascaded cooling and the resulting gas stream was again slightly compressed and mixed with propene, oxygen and nitrogen and flowed onto the gassing frit of the bubble column.
- N-benzyltrimethylammonium hydroxide (trade name Triton B) was added until a liquid sample taken in contact with a pH test strip moistened with water showed a pH value of 10-11.
- the second bubble column was prepared analogously. The bubble columns were then brought to the reaction temperature of 120.degree. A gas mixture of nitrogen and propene flowed against the first bubble column and a gas mixture of nitrogen and oxygen flowed against the second bubble column in both cases a total flow rate of less than 10 L/min was regulated. The molar ratio of propene to oxygen was 2:1.
- the liquid phase was continuously taken out from the first bubble column at the top point and added to the second bubble column at the bottom point, and from the second bubble column at the top point and added to the first bubble column at the bottom point.
- the volume flows were regulated in such a way that the levels in the two bubble columns did not change over the course of the test.
- the progress of the reaction or the stationary point was determined by taking liquid and gas samples from the upper sampling points of the two bubble columns and analyzing them by GC.
- the continuously generated product gas mixture from the first bubble column was freed from propylene oxide by cascaded cooling and the resulting gas stream was slightly compressed again and mixed with nitrogen and propene and flowed onto the gassing frit of the bubble column.
- the gas stream from the second bubble column was freed from propene by cascaded, cryogenic cooling and disposed of via the exhaust air.
- the propene recovered was reused by adding it at the lower gassing point of the first bubble column.
- Two pressure-resistant bubble columns (15 cm diameter), each equipped with gassing frit, overpressure protection, pressure sensor, upper and lower liquid withdrawal or addition, upper addition point for solids and inlet and outlet lines for gases are connected via the upper and lower liquid withdrawal via a pump.
- 3500 mL tetrahydrofuran were placed under inert conditions in one bubble column.
- 0.350 mol of the metal chloride of the corresponding oxidation state see Table 2, 9-12
- 0.700 mol (89.3 g) of elemental iodine were added to the solvent under protective gas countercurrent.
- N-benzyltrimethylammonium hydroxide (trade name Triton B) was added until a liquid sample taken in contact with a pH test strip moistened with water showed a pH value of 10-11.
- the second bubble column was prepared analogously.
- the Bubble columns were then brought to the reaction temperature of 120°C.
- a gas mixture of nitrogen and propene flowed against the first bubble column and a gas mixture of nitrogen and oxygen flowed against the second bubble column, with a total volume flow of less than 10 L/min being regulated in both cases.
- the molar ratio of propene to oxygen was 2:1.
- the liquid phase was continuously taken out from the first bubble column at the top point and added to the second bubble column at the bottom point, and from the second bubble column at the top point and added to the first bubble column at the bottom point.
- the volume flows were regulated in such a way that the levels in the two bubble columns did not change over the course of the test.
- the progress of the reaction or the stationary point was determined by taking liquid and gas samples from the upper sampling points of the two bubble columns and analyzing them by GC.
- the continuously generated product gas mixture from the first bubble column was freed from propylene oxide by cascaded cooling and the resulting gas stream was slightly compressed again and mixed with nitrogen and propene and flowed onto the gassing frit of the bubble column.
- the gas stream from the second bubble column was freed from propene by cascaded, cryogenic cooling and disposed of via the exhaust air.
- the propene recovered was reused by adding it at the lower gassing point of the first bubble column.
- a mixture of 200 mL tetrahydrofuran was placed under inert conditions in a pressure-resistant IL reactor with stirrer, overpressure protection, pressure sensor, riser pipe for liquid removal and gas-injection and degassing lines.
- 0.350 mol of the metal salt (A) of the corresponding oxidation state (see Table 1, Examples 1-5) and 0.350 mol of CuCl 2 were added to the solvent mixture under protective gas countercurrent.
- N-benzyltrimethylammonium hydroxide as hydroxide (F) (trade name Triton B) was stirred in until a liquid sample taken came into contact with a water-dampened pH test strip gave a pH of 10-11. The mixture obtained was then applied to silica as a carrier material.
- the solids were then introduced into an inerted, pressure-resistant and pressure-protected flow reactor. Nitrogen and oxygen were then passed through the flow reactor and the reaction temperature was brought to 180.degree. A quantity of propene was then added to the gas stream until a 2:1 molar ratio of propene to oxygen was achieved and continuously contacted with the solids. The flow conditions and contact time were chosen so that partial conversions were achieved.
- the continuously generated product gas mixture was in each case freed from propylene oxide by cascaded cooling, and the resulting gas stream was heated again, enriched with oxygen and propene, and the resulting mixture flowed back onto the solid.
- the gas analysis is carried out by taking gas samples and analyzing them by GC. The selectivities to propylene oxide were between 95 and 100% in all five experiments.
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Abstract
The invention relates to a first epoxydation catalyst system comprising a mixture of a metal salt of the metals chromium, manganese, molybdenum, lead and/or bismuth and a hydroxide as well as of a redox-active compound. The invention also relates to an additional second epoxydation catalyst system comprising a mixture of an additional metal salt, iodine and a hydroxide. Furthermore, the invention relates to a process for preparing epoxides comprising the oxidative reaction of an alkene in a reactor in the presence of the first epoxydation catalyst system or the second epoxydation catalyst system.
Description
Epoxidierungskatalvsatorsvsteme und Verfahren zur Herstellung von Epoxiden Epoxidation catalyst systems and processes for preparing epoxides
Gegenstand der Erfindung ist ein erstes Epoxidierungskatalysatorsystem umfassend ein Gemisch eines Metallsalz der Metalle Chrom, Mangan, Molybdän, Blei und/oder Bismut und eines Hydroxid sowie einer redoxaktiven Verbindung. Ein weiterer Gegenstand der Erfindung ist ein weiteres, zweites Epoxidierungskatalysatorsystem umfassend ein Gemisch eines weiteren Metallsalzes, Iod sowie eines Hydroxids. Außerdem ist ein Verfahren zur Herstellung von Epoxiden umfassend der oxidativen Umsetzung eines Alkens in einem Reaktor in Gegenwart des ersten Epoxidierungskatalysatorsystems oder des zweiten Epoxidierungskatalysatorsystems. The invention relates to a first epoxidation catalyst system comprising a mixture of a metal salt of the metals chromium, manganese, molybdenum, lead and/or bismuth and a hydroxide and a redox-active compound. A further object of the invention is a further, second epoxidation catalyst system comprising a mixture of a further metal salt, iodine and a hydroxide. Additionally, a process for preparing epoxides is comprised of oxidatively reacting an alkene in a reactor in the presence of the first epoxidation catalyst system or the second epoxidation catalyst system.
Im Stand der Technik sind zahlreiche Verfahren zur Herstellung von Alkyenoxiden, speziell Propylenoxid vorbeschrieben, wobei industriell vor allem das Chlorhydrin-Verfahren von Bedeutung ist, bei dem Propen mit unterchloriger Säure oder Chlor und Wasser einem Isomerengemisch aus 1- Chlor-2 -Propanol und 2 -Chlor- 1 -Propanol umgesetzt wird, welches im Anschluss mit Kalkmilch zu Propylenoxid und Calciumchlorid umgesetzt wird. Allerdings resultiert infolge der Bildung von CaC12-Salzfracht eine hohe Abwasserbelastung bzw. einen zusätzlichen Recylierungsschritt und die Einbindung in einen Chlor- Alkali-Betrieb. Diese Technologie wird als nachteilig bezüglich des Kohlenstofffußabdrucks (engl carbon footprint) und der Treibhausgasemissionen bewertet (Reduction of GHG Emissions in Propylene Oxide Production, Approved VCS Methodology VM0023 Version 1.0, 9 September 2013 Sectoral Scope 5, South Pole Carbon Asset Management Ltd.). Numerous processes for the production of alkylene oxides, especially propylene oxide, have been described in the prior art, with the chlorohydrin process being of particular importance industrially, in which propene is treated with hypochlorous acid or chlorine and water to form an isomer mixture of 1-chloro-2-propanol and 2 -Chlorine-1-propanol is reacted, which is then reacted with milk of lime to form propylene oxide and calcium chloride. However, as a result of the formation of CaC12 salt load, there is a high level of waste water pollution or an additional recycling step and the integration into a chlor-alkali plant. This technology is assessed as detrimental in terms of carbon footprint and greenhouse gas emissions (Reduction of GHG Emissions in Propylene Oxide Production, Approved VCS Methodology VM0023 Version 1.0, 9 September 2013 Sectoral Scope 5, South Pole Carbon Asset Management Ltd.).
Daneben ist die Herstellung von Proplyenoxid mittels Koppelprodukt-basierter Verfahren (z.B. Oxiranverfahren) von Relevanz, bei dem Ethylbenzol bzw. Iso-Butan in einer 1. Stufe in Gegenwart von Sauerstoff zu den jeweiligen Hydroperoxiden umgesetzt werden, welche im Anschluss mit Propen zu Propylenoxid und 1 -Phenylethanol bzw. tert-Butanol als weitere Koppelprodukte umgesetzt werden kann. Diese Koppelprodukte können in der Folge zu Styrol und Iso-Buten bzw. Isobutan weiter umgesetzt werden. Allerdings wird neben dem Propylenoxid ebenfalls ein Koppelprodukt gebildet, welches zusätzlich abgetrennt und in weiteren Anlagen weiter verarbeitet werden muss. Die Koppelprodukt-basierten Verfahren setzen immer einen Absatzmarkt für das Koppelprodukt voraus und machen die Ökonomie solcher Verfahren komplex und anfällig für adverse Effekte. Somit liegen neben den technischen anspruchsvollen Verfahren auch noch marktwirtschaftliche Risiken auf der Hand, so dass ein techno-ökonomische Betrachtung dieser Verfahren ein wenig vorteilhaftes Gesamtbild zeichnet. Zumal die Nachfrage- bzw. Absatzsituation beider Produkte, PO und das Koppelprodukt, i.d.R. regional unterschiedlich sind. D.h. es ist eine Femlogistik notwendig, die direkte Kosten und weitere Nachteile, wie C02/GHG-Emissionen, mit
sich bringt. Das industrielle MTBE-Verfahren benötigt eine Einbindung in einen Raffmeriebetrieb, um eine maximalen ökonomischen Beitrag zu erwirtschaften. In addition, the production of propylene oxide by means of co-product-based processes (e.g. oxirane process) is relevant, in which ethylbenzene or isobutane is reacted in a 1st stage in the presence of oxygen to form the respective hydroperoxides, which are then reacted with propene to form propylene oxide and 1-Phenylethanol or tert-butanol can be implemented as further by-products. These by-products can then be further converted into styrene and isobutene or isobutane. However, in addition to the propylene oxide, a by-product is also formed, which has to be separated off and further processed in other plants. The co-product-based processes always require a sales market for the co-product and make the economics of such processes complex and prone to adverse effects. Thus, in addition to the technically demanding processes, there are also market risks, so that a techno-economic view of these processes paints a less than favorable overall picture. Especially since the demand and sales situation of both products, PO and the by-product, usually differ from region to region. This means that long-distance logistics are necessary, which have direct costs and other disadvantages, such as CO2/GHG emissions brings. The industrial MTBE process requires integration into a refinery operation in order to generate a maximum economic contribution.
Auch das sogenannte HPPO-Verfahren hat großtechnische Relevanz, bei dem Propylen mit Wasserstoffperoxid zu Propylenoxid und Wasser umgesetzt wird. Vorteilhaft gegenüber den vorgenannten großtechnischen Herstellungsverfahren ist, dass kein Koppelprodukt oder Salzlasten im Produkt resultieren. Allerdings muss Wasserstoffperoxid in einem vorgeschalteten, technisch komplexen katalytischen Prozess hergestellt werden. Das Verfahren gilt als technisch anspruchsvoll und wird i.d.R. nur an Verbundstandorten mit anderen H202-Verbrauchem betrieben. The so-called HPPO process is also of industrial relevance, in which propylene is reacted with hydrogen peroxide to form propylene oxide and water. Compared to the large-scale production processes mentioned above, it is advantageous that there are no by-products or salt loads in the product. However, hydrogen peroxide has to be produced in an upstream, technically complex catalytic process. The process is considered technically demanding and is usually only operated at network sites with other H2O2 consumers.
Die Direktoxidation von Propen zu Propylenoxid gilt weiterhin als technisch nicht ausgereift und nach jetzigem Stand der Technik gibt es keinen Direktoxidationsprozess, der industriell ökonomisch durchführbar ist. Insbesondere die Reaktionsführung und besonders die Temperaturkontrolle in Gasphasen- und Salzschmelzenprozessen sind eine ungelöste Herausforderung, wobei jedoch eine hoher Propen-Umsatz in Verbindung mit einer hohen PO-Selektivität für ein effizientes technisches Verfahren maßgeblich ist. Bei der Direktoxidation treten eine Reihe von Neben- und Folgeprodukten, wie z.B. Methanol, Acetaldehyd, Kohlendioxid, Ethylen and Formaldehyd, in substantiellen Mengen auf (vgl. D. Kahlich et. al., Dow Deutschland in Ullmann’s Encyclopedia of Industrial Chemistry, Kapitel „Propylene Oxide“, Wiley VCH, 2012). Z.B. können als aktuelle Dokumente des Stands der Technik für die aerobe Oxidation von Alkene wie Propene US2018208569A1 und US2020346193A1 herangezogen werden. Lediglich 54,5 % bzw. 60 % Epoxid-Selektivität werden bei 8.6 % bzw. 5 % Umsatz erzielt. The direct oxidation of propene to propylene oxide is still considered to be technically immature and according to the current state of the art there is no direct oxidation process that can be carried out economically on an industrial scale. In particular, the conduct of the reaction and especially the temperature control in gas-phase and molten salt processes are an unsolved challenge, but a high propene conversion in connection with a high PO selectivity is decisive for an efficient technical process. A number of by-products and by-products, such as methanol, acetaldehyde, carbon dioxide, ethylene and formaldehyde, occur in substantial amounts during direct oxidation (cf. D. Kahlich et al., Dow Germany in Ullmann's Encyclopedia of Industrial Chemistry, Chapter " Propylene Oxides”, Wiley VCH, 2012). For example, as current prior art documents for the aerobic oxidation of alkenes such as propene, US2018208569A1 and US2020346193A1 can be referred to. Only 54.5% or 60% epoxide selectivity is achieved at 8.6% or 5% conversion.
Daher war es Aufgabe der vorliegenden Erfindung ein Katalysatorsystems für die direkte Herstellung von Epoxiden bevorzugt von Propylenoxid bereitzustellen, welches in der oxidativen Umsetzung von Alkenen bevorzugt mit Sauerstoff oder einem sauerstoff-haltigen Gasgemisch ein im Vergleich zu aus dem Stand der Technik bekannten Systemen mit verbessertem Epoxid- Umsatz sowie eine verbesserte Produktselektivität durch Reduktion der Bildung unerwünschter Nebenprodukte und die Vermeidung der Bildung von jeglichen Koppelprodukten aufweist. Diese verbesserte Katalysatoraktivität sowie Selektivität sollte sich durch eine möglichst geringe Aktivierungsenergie EA für die Reaktionssequenz bzw. den Reaktionsmechanismus der Hydroxylierung des Propens, d.h. der Anlagerung des Propens an das Katalysatorsystem, und der reduktiven Eliminierung des gebildeten Propylenoxids vom Katalysatorsystem widerspiegeln. It was therefore an object of the present invention to provide a catalyst system for the direct production of epoxides, preferably propylene oxide, which, in the oxidative reaction of alkenes, preferably with oxygen or an oxygen-containing gas mixture, has an improved epoxide compared to systems known from the prior art - Turnover and improved product selectivity by reducing the formation of unwanted by-products and avoiding the formation of any by-products. This improved catalyst activity and selectivity should be reflected by the lowest possible activation energy E A for the reaction sequence or the reaction mechanism of the hydroxylation of propene, ie the addition of propene to the catalyst system, and the reductive elimination of the propylene oxide formed from the catalyst system.
Überraschend wurde gefunden, dass die erfmdungsgemäße Aufgabe gelöst wird durch ein Epoxidierungskatalysatorsystem (1), ein Epoxidierungskatalysatorsystem (2) sowie Verfahren zur Herstellung von Epoxiden umfassend der oxidativen Umsetzung eines Alkens in einem Reaktor in Gegenwart des Epoxidierungskatalysatorsystems (1) oder des Epoxidierungskatalysatorsystems (2).
Das Epoxidierungskatalysatorsystem (1) umfasst hierbei a) ein Gemisch (1) oder ein Umsetzungsprodukt (1) a-1) eines Metallsalz (A) der Metalle Chrom (Cr), Mangan (Mn), Molybdän (Mo), Blei (Pb) und/oder Bismut (Bi) und a-2) eines Hydroxid (B) b) eine redoxaktive Verbindung (C). Surprisingly, it was found that the object of the invention is achieved by an epoxidation catalyst system (1), an epoxidation catalyst system (2) and a process for preparing epoxides comprising the oxidative reaction of an alkene in a reactor in the presence of the epoxidation catalyst system (1) or the epoxidation catalyst system (2) . The epoxidation catalyst system (1) comprises a) a mixture (1) or a reaction product (1) a-1) of a metal salt (A) of the metals chromium (Cr), manganese (Mn), molybdenum (Mo), lead (Pb) and/or bismuth (Bi) and a-2) a hydroxide (B) b) a redox-active compound (C).
Erfmdungsgemäß wird ein oder mehrere Metallsalze (A) der Metalle Chrom (Cr), Mangan (Mn), Molybdän (Mo), Blei (Pb) und/oder Bismut (Bi) verwendet. 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.
Die nachfolgenden Ausführungsformen können beliebig kombiniert werden, insofern sich aus dem technischen Kontext und dem allgemeinen Fachwissen nicht das Gegenteil ergibt. The following embodiments can be combined in any way, provided that the opposite does not result from the technical context and general specialist knowledge.
In einer Ausführungsform der Erfindung ist das Metallsalz (A) ein Nitrat, Halogenid, Tetrafluoroborat, Sulfat, Paratoluolsulfonat, Methansulfonat und/oder Triflat bevorzugt ein Chlorid.In one embodiment of the invention, the metal salt (A) is a nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride.
In einer bevorzugten Ausführungsform der Erfindung ist das Metallsalz (A) ein oder mehrere Verbindungen ist und ausgewählt wird aus der Gruppe bestehend aus MoCE, MoOCE. MnCE, K2MnCE, CrOCE, PbCU und BiCE. In a preferred embodiment of the invention, the metal salt (A) is one or more compounds and is selected from the group consisting of MoCE, MoOCE. MnCE, K 2 MnCE, CrOCE, PbCU and BiCE.
In einer Ausführungsform der Erfindung ist das Hydroxid (B) ein organisches Hydroxid (B-l) und/oder anorganisches Hydroxid (B-2). In one embodiment of the invention, the hydroxide (B) is an organic hydroxide (B-1) and/or inorganic hydroxide (B-2).
In einer bevorzugten Ausführungsform der Erfindung ist das Hydroxid (B) ein organisches Hydroxid (B-l) und das organische Hydroxid (B-l) ist eine oder mehrere Verbindung(en) und wird ausgewählt aus der Gruppe bestehend aus 3-(Trifluoromethyl)phenyltrimethylammoniumhydroxid, Tetra-n- butylphosphoniumhydroxid, Cholinhydroxid, Benzyltrimethylammoniumhydroxid,In a preferred embodiment of the invention, the hydroxide (B) is an organic hydroxide (B-I) and the organic hydroxide (B-I) is one or more compound(s) and is selected from the group consisting of 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra- n-butylphosphonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide,
Tetraethylammoniumhydroxid, Tetra-n-propylammoniumhydroxid, Tetrabutylammoniumhydroxid und Tetramethylammoniumhydroxid. tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetrabutylammonium hydroxide and tetramethylammonium hydroxide.
In einer weniger bevorzugten alternativen Ausführungsform der Erfindung ist das Hydroxid (B) ein anorganisches Hydroxid (B-2) und das das anorganische Hydroxid (B-2) ist eine oder mehrere Verbindung(en) und wird ausgewählt aus der Gruppe bestehend aus bestehend aus Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid sowie deren Kronenetherkomplexen, Caesiumhydroxid, Calciumhydroxid, Bariumhydroxid, Kaliumaluminate, Natriumaluminat, Kaliumaluminat und Natriumzinkat bevorzugt Lithiumhydroxid, Natriumhydroxid und Kaliumhydroxid.
In einer Ausführungsform der Erfindung ist die redoxaktive Verbindung (C) eine oder mehrere Verbindung(en) und wird ausgewählt aus der Gruppe bestehend aus CuCF. Cu(BF )2. CuCl, VCE, VOCI3, NH4VO3, 1,4-Benzochinone, 1,4-Naphtochinone, SC2O5. Te02, Te02, SÜ203, SbiOs. CeCfi, Co(salen), Co(OAc)2, SnS04, Fe(acac)3, Mo(acac)3, K2Cr207, Mn(OAc)3, Ni(CF3C02H)2 und Bi CI,.In a less preferred alternative embodiment of the invention, the hydroxide (B) is an inorganic hydroxide (B-2) and the inorganic hydroxide (B-2) is one or more compounds and is selected from the group consisting of Lithium hydroxide, sodium hydroxide, potassium hydroxide and their crown ether complexes, 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 compound(s) and is selected from the group consisting of CuCF. Cu(BF )2. CuCl, VCE, VOCI3, NH4VO3, 1,4-Benzoquinone, 1,4-Naphtoquinone, SC2O5. Te02, Te02, SÜ203, SbiOs. CeCfi, Co(salen), Co(OAc)2, SnS0 4 , Fe(acac)3, Mo(acac)3, K 2 Cr2O7, Mn(OAc)3, Ni(CF3C0 2 H) 2 and Bi CI,.
In einer Ausführungsform der Erfindung beträgt das berechnete Stoffmengenverhältnis des Metallsalzes (A) zu den Hydroxidgruppen des Hydroxids (B) für das Epoxidierungskatalysatorsystem (1) von 1,000 mol zu 1,000 mol bis 6,000 mol zu 1,000 mol.In one embodiment of the invention, the calculated molar ratio of metal salt (A) to hydroxide groups of hydroxide (B) for epoxidation catalyst system (1) is from 1.000 moles to 1.000 moles to 6.000 moles to 1.000 moles.
In einer Ausführungsform der Erfindung beträgt das berechnete Stoffmengenverhältnis des Metallsalz (A) zu der redoxaktiven Verbindung (C) für das Epoxidierungskatalysatorsystem (1) von 0,100 mol zu 1,000 mol bis 10,000 mol zu 1,000 mol. In one embodiment of the invention, the calculated molar ratio of the metal salt (A) to the redox-active compound (C) for the epoxidation catalyst system (1) is from 0.100 mole to 1.000 mole to 10.000 mole to 1.000 mole.
In einer Ausführungsform der Erfindung beträgt das berechnete Stoffmengenverhältnis der Hydroxidgruppen des Hydroxids (B) zu dem der redoxaktiven Verbindung (C) für das Epoxidierungskatalysatorsystem (1) von 0,100 mol zu 1,000 mol bis 50,000 mol zu 1,000 mol.In one embodiment of the invention, the calculated molar ratio of the hydroxide groups of the hydroxide (B) to that of the redox-active compound (C) for the epoxidation catalyst system (1) is from 0.100 mole to 1.000 mole to 50.000 mole to 1.000 mole.
In einer weniger bevorzugten Ausführungsform der Erfindung umfasst das Epoxidierungskatalysatorsystem (1) die Mischung (1) des Metallsalzes (A) und des Hydroxids (B) in den oben beschriebenen, berechneten Stoffmengenverhältnissen. In a less preferred embodiment of the invention, the epoxidation catalyst system (1) comprises the mixture (1) of the metal salt (A) and the hydroxide (B) in the calculated molar ratios described above.
In einer bevorzugten Ausführungsform der Erfindung umfasst das Epoxidierungskatalysatorsystem (1) das Umsetzungsprodukt (1) des Metallsalzes (A) und des Hydroxids (B), wobei das Metallsalz (A) und das Hydroxid (B) mit einem für den Fachmann bekannten Herstellungsverfahren wie beispielsweise Festkörpersynthesen, Fällungs- oder Co-Fällungsmethoden oder als in Situ- Salzmetathese hergestellt wird. So kann das Umsetzungsprodukt (1) zum Beispiel durch Zugabe des organischen Hydroxids (B-l) und/oder anorganischen Hydroxids (B-2) zu einer Lösung des Nitrats, Halogenids, Tetrafluoroborats, Sulfats, Paratoluolsulfonats, Methansulfonats und/oder Triflats bevorzugt eines Chlorids des Metallsalzes (A) in den oben beschriebenen, berechneten Stoffmengenverhältnissen, anschließender Abtrennung des Fällungsproduktes, Trocknung und geeigneter thermische Behandlung synthetisiert werden. In a preferred embodiment of the invention, the epoxidation catalyst system (1) comprises the reaction product (1) of the metal salt (A) and the hydroxide (B), the metal salt (A) and the hydroxide (B) being prepared using a preparation process known to those skilled in the art, such as, for example Solid state syntheses, precipitation or co-precipitation methods or as in situ salt metathesis is produced. For example, the reaction product (1) can be prepared by adding the organic hydroxide (B-1) and/or inorganic hydroxide (B-2) to a solution of the nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride of Metal salt (A) are synthesized in the above-described, calculated molar ratios, subsequent removal of the precipitate, drying and appropriate thermal treatment.
In einer bevorzugten Ausführungsform der Erfindung weist das Umsetzungsprodukt (1) des Epoxidierungskatalysatorsystems (1) eine Struktur gemäß Formel (I), (II) und/oder (III) aufweist: In a preferred embodiment of the invention, the reaction product (1) of the epoxidation catalyst system (1) has a structure of the formula (I), (II) and/or (III):
(Q RiR2R3R4)+„+o-m[M(A)m+(Hal)„(OH)0(S)p] im-n-o (Q RiR 2 R3R4) + n + om[M(A) m+ (Hal)n(OH) 0 (S)p] im-no
(I) für den Fall m < n + o(I) for the case m < n + o
[M(A)m+(Hal)„(OH)0(S)p] (P) für den Fall m = n + o[M(A) m+ (Hal)„(OH) 0 (S)p] (P) for the case m = n + o
[M(A)m+(Hal)n(OH)o(S)p](m n o) [X] n+o-m (III) für den Fall m > n + o
mit [M(A) m+ (Hal) n (OH)o(S)p] (mno) [X] n+om (III) for the case m > n + o with
Q = Stickstoff oder Phosphor bevorzugt Stickstoff Q = nitrogen or phosphorus, preferably nitrogen
Ri, R2, R3, R4 unabhängig voneinander ausgewählt aus der Gruppe bestehend aus Ri, R 2 , R 3 , R 4 independently selected from the group consisting of
(i) linearen oder verzweigten Alkylgruppen enthaltend 1 bis 22 C Atome, optional substituiert mit Heteroatomen und/oder Heteroatom enthaltenden Substituenten; (i) linear or branched alkyl groups containing 1 to 22 C atoms optionally substituted with heteroatoms and/or heteroatom containing substituents;
(ii) cycloaliphatische Gruppen enthaltend 3 bis 22 C Atome mit 1 bis 3 verbrückenden C Atomen, optional substituiert mit Heteroatomen und/oder Heteroatom enthaltenden Substituenten und/oder (ii) cycloaliphatic groups containing 3 to 22 C atoms with 1 to 3 bridging C atoms optionally substituted with heteroatoms and/or heteroatom containing substituents and/or
(iii) Arylgruppen enthaltend 6 bis 18 C Atome, optional substituiert mit 1 bis 10 C Atomen und/oder optional substituiert mit Heteroatomen und/oder Heteroatom enthaltenden Substituenten; bevorzugt Ri, R2, R3 und R4 unabhängig voneinander ausgewählt aus der Gruppe bestehend aus Methyl, Ethyl, iso-Propyl, n-Propyl, iso-Butyl, t-Bu, n-Butyl, Phenyl, Benzyl, (Trifluoromethyl)phenyl (iii) aryl groups containing 6 to 18 C atoms optionally substituted with 1 to 10 C atoms and/or optionally substituted with heteroatoms and/or heteroatom containing substituents; preferably R1, R2, R3 and R4 are independently selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, isobutyl, t-Bu, n-butyl, phenyl, benzyl, (trifluoromethyl)phenyl
M(A)m+ = Mo5+,Mn4+, Cr4+, Pb4+, Bi5+ bevorzugt Mo5+; M(A) m+ = Mo 5+ , Mn 4+ , Cr 4+ , Pb 4+ , Bi 5+ preferably Mo 5+ ;
Hai = CI , Br oder G bevorzugt CI oder Br besonders bevorzugt CI ; Hal=Cl, Br or G, preferably Cl or Br, particularly preferably Cl;
S = H2O, THF (Tetrahydrofuran), oder Dioxan, Bis(2methoxyethyl)ether (Diglyme), Methoxyethanol, Polyethylenglykole, Pyridin, Lutidin, 2,2‘-Bipyridin, Acetonitril, Dimethylsulfoxid, Sulfolan, Thiophen, bevorzugt THF; n+o+p = 6 n > 1; bevorzugt n > 2; besonders bevorzugt n = 2 o > 1; bevorzugt o > 1; besonders bevorzugt o = 1; 2; 3 oder 4 X = OTf,BF4 , Hai S = H2O, THF (tetrahydrofuran), or dioxane, bis(2-methoxyethyl)ether (diglyme), methoxyethanol, polyethylene glycols, pyridine, lutidine, 2,2'-bipyridine, acetonitrile, dimethyl sulfoxide, sulfolane, thiophene, preferably THF; n+o+p = 6n > 1; preferably n > 2; particularly preferably n = 2 o > 1; preferably o > 1; particularly preferably o=1; 2; 3 or 4 X = OTf,BF4 , Hai
In einer besonders bevorzugten Ausführungsform der Erfindung ist das Umsetzungsprodukt (1) des Epoxidierungskatalysatorsystems (1) eine oder mehrere Verbindungen und wird ausgewählt aus der Liste bestehend aus [MO(Y)C12(OH)2(THF)2]C1, [Mn(IV)Cl(OH)3(THF)2], [Cr(VI)Cl2(OH)2(THF)2]Cl2, [Pb(IV)Cl2(OH)2(THF)2] und [Bi(V)Cl2(OH)3THF] .
Die Vermengung des Gemisches (1) oder des Umsetzungproduktes (1) mit der redoxaktiven Verbindung (C) zu dem Epoxidierungskatalysatorsystem (1) ist mit den für den Fachmann bekannten Mischmethoden wie beispielsweise Einrühren von Lösungen oder geeigneten Vermengen von Feststoffen möglich. 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 list consisting of [MO(Y)C1 2 (OH) 2 (THF) 2 ]C1, [Mn (IV)Cl(OH)3(THF) 2 ], [Cr(VI)Cl 2 (OH)2(THF) 2 ]Cl2, [Pb(IV)Cl 2 (OH) 2 (THF) 2 ] and [ Bi(V) Cl2 (OH)3THF] . The mixture (1) or the reaction product (1) can be mixed with the redox-active compound (C) to form the epoxidation catalyst system (1) using the mixing methods known to those skilled in the art, such as stirring in solutions or suitable mixing of solids.
In einer Ausführungsform der Erfindung enthält das Epoxidierungskatalysatorsystem (1) weiterhin Iod (I2). In one embodiment of the invention, the epoxidation catalyst system (1) further contains iodine (I 2 ).
In einer bevorzugten Ausführungsform der Erfindung wird das Iod (U) in einem berechneten Stoffmengenanteil von 1 mol-% bis 2000 mol-% bezogen auf die Menge des Metallsalzes (A) eingesetzt. In a preferred embodiment of the invention, the iodine (U) is used in a calculated mole fraction of 1 mol % to 2000 mol %, based on the amount of the metal salt (A).
In einer Ausführungsform der Erfindung wird das Epoxidierungskatalysatorsystem (1) auf einem Katalysatorträger (D) aufgebracht unter Bildung eines geträgerten Epoxidierungskatalysatorsystem (1). In one embodiment of the invention, the epoxidation catalyst system (1) is supported on a catalyst support (D) to form a supported epoxidation catalyst system (1).
In einer bevorzugten Ausführungsform der Erfindung ist der Katalysatorträger (D) eine oder mehrere Verbindung(en) und wird ausgewählt aus der Gruppe bestehend aus Metalloxide, Erdalkalicarbonate, Silicate, Siliciumcarbide, Siliciumoxy Carbide, Siliciumnitride, Siliciumoxynitride und Siliciumdioxid, bevorzugt Aluminiumoxid Aluminiumdioxid, Silica, Titandioxid, Zircondioxid, Calciumcarbonat, Phyllosilikate, wie Talkum, Kaolinite und Pyrophyllite, und Titandioxid. In a preferred embodiment of the invention, the catalyst support (D) is one or more compound(s) and is selected from the group consisting of metal oxides, alkaline earth metal carbonates, silicates, silicon carbides, silicon oxy carbides, silicon nitrides, silicon oxynitrides and silicon dioxide, preferably aluminum oxide, aluminum dioxide, silica, Titanium dioxide, zirconia, calcium carbonate, phyllosilicates such as talc, kaolinites and pyrophyllites, and titanium dioxide.
Erfindungsgemäß kann der Katalysatorträger als Formkörper oder als Pulver vorliegen. According to the invention, the catalyst support can be in the form of a shaped body or a powder.
In einer Ausführungsform der Erfindung wird das Epoxidierungskatalysatorsystem (1) in einem berechneten Massenanteil von 1,0 Gew.-% bis 30,0 Gew.-% auf den Katalysatorträger (D) aufgebracht. In one embodiment of the invention, the epoxidation catalyst system (1) is applied to the catalyst support (D) in a calculated mass fraction of 1.0% by weight to 30.0% by weight.
In einer Ausführungsform der Erfindung wird das Epoxidierungskatalysatorsystem (1) mithilfe der Nassinfiltrationsmethode (wet-infiltration) oder der incipient-wetness Methode auf den Katalysatorträger (D) aufgebracht wird. In one embodiment of the invention, the epoxidation catalyst system (1) is applied to the catalyst support (D) using the wet infiltration method (wet infiltration) or the incipient wetness method.
Ein weiterer Gegenstand der Erfindung ist ein Epoxidierungskatalysatorsystem (2) umfassend c) ein Gemisch (2) oder ein Umsetzungsprodukt (2) c-1) eines Metallsalzes (E), c-2) Iod (E) sowie c-3) eines Hydroxid (F) d) optional eine redoxaktive Verbindung (G).
In einer Ausführungsform der Erfindung ist das Metallsalz (E) ein Nitrat, Halogenid, Tetrafluoroborat, Sulfat, Paratoluolsulfonat, Methansulfonat und/oder Triflat bevorzugt ein Chlorid.Another subject of the invention is an epoxidation catalyst system (2) comprising c) a mixture (2) or a reaction product (2) c-1) a metal salt (E), c-2) iodine (E) and c-3) a hydroxide (F) d) optionally a redox-active compound (G). In one embodiment of the invention, the metal salt (E) is a nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride.
In einer bevorzugten Ausführungsform der Erfindung ist das Metallsalz (E) eine oder mehrere Verbindung(en) und wird ausgewählt aus der Gruppe bestehend aus NiCk, MnCk. PbCk. SnCk. CrCk, VC13, MoCU, FeCk und RuCk. In a preferred embodiment of the invention, the metal salt (E) is one or more compound(s) and is selected from the group consisting of NiCk, MnCk. PbCk. SnCk. CrCk, VC1 3 , MoCU, FeCk and RuCk.
In einer Ausführungsform der Erfindung ist das Hydroxid (F) ein organisches Hydroxid (F-l) und/oder anorganisches Hydroxid (F-2). In one embodiment of the invention, the hydroxide (F) is an organic hydroxide (F-1) and/or inorganic hydroxide (F-2).
In einer bevorzugten Ausführungsform der Erfindung ist das Hydroxid (F) ein organisches Hydroxid (B-l) und das organische Hydroxid (F-l) ist eine oder mehrere Verbindung(en) und wird ausgewählt aus der Gruppe bestehend aus 3-(Trifluoromethyl)phenyltrimethylammoniumhydroxid, Tetra-n- butylphosphoniumhydroxid, Cholinhydroxid, Benzyltrimethylammoniumhydroxid,In a preferred embodiment of the invention, the hydroxide (F) is an organic hydroxide (B-I) and the organic hydroxide (F-I) is one or more compound(s) and is selected from the group consisting of 3-(trifluoromethyl)phenyltrimethylammonium hydroxide, tetra- n-butylphosphonium hydroxide, choline hydroxide, benzyltrimethylammonium hydroxide,
Tetraethylammoniumhydroxid, Tetra-n-propylammoniumhydroxid, Tetrabutylammoniumhydroxid und Tetramethylammoniumhydroxid. tetraethylammonium hydroxide, tetra-n-propylammonium hydroxide, tetrabutylammonium hydroxide and tetramethylammonium hydroxide.
In einer weniger bevorzugten alternativen Ausführungsform der Erfindung ist das Hydroxid (F) ein anorganisches Hydroxid (F-2) und das das anorganische Hydroxid (F-2) ist eine oder mehrere Verbindung(en) und wird ausgewählt aus der Gruppe bestehend aus Fithiumhydroxid, Natriumhydroxid, Kaliumhydroxid sowie deren Kronenetherkomplexen, Caesiumhydroxid, Calciumhydroxid, Bariumhydroxid, Kaliumaluminate, Natriumaluminat, Kaliumaluminat und Natriumzinkat bevorzugt Fithiumhydroxid, Natriumhydroxid und Kaliumhydroxid. In a less preferred alternative embodiment of the invention, the hydroxide (F) is an inorganic hydroxide (F-2) and the inorganic hydroxide (F-2) is one or more compound(s) and is selected from the group consisting of fithium hydroxide, Sodium hydroxide, potassium hydroxide and their crown ether complexes, cesium hydroxide, calcium hydroxide, barium hydroxide, potassium aluminate, sodium aluminate, potassium aluminate and sodium zincate, preferably fithium hydroxide, sodium hydroxide and potassium hydroxide.
In einer Ausführungsform der Erfindung ist die redoxaktive Verbindung (G) eine oder mehrere Verbindung(en) und wird ausgewählt aus der Gruppe bestehend aus CuCk, Cu(BF4k, CuCl, VCk, VOCk, NH4VO3, 1,4-Benzochinone, 1,4-Naphtochinone, Se2Ck, TeCk, TeCk, Sb2C , Sb2Ck, CeCk, Co(salen), Co(OAc)2, SnSCk, Fe(acac)3, Mo(acac)3, K2Cr2Ck, Mn(OAc)3, Ni(CF3C02H)2 und BiCk.In one embodiment of the invention, the redox-active compound (G) is one or more compound(s) and is selected from the group consisting of CuCk, Cu(BF4k, CuCl, VCk, VOCk, NH4VO3, 1,4-benzoquinones, 1,4 -Naphtoquinones, Se2Ck, TeCk, TeCk, Sb2C , Sb2Ck, CeCk, Co(salen), Co(OAc)2, SnSCk, Fe(acac)3, Mo(acac)3, K 2 Cr2Ck, Mn(OAc)3, Ni(CF3CO2H )2 and BiCk.
In einer Ausführungsform der Erfindung beträgt das berechnete Stoffmengenverhältnis des Metallsalz (E) zu den Hydroxidgruppen des Hydroxids (F) für das Epoxidierungskatalysatorsystem (2) von 1,000 mol zu 1,000 mol bis 6,000 mol zu 1,000 mol. In one embodiment of the invention, the calculated molar ratio of metal salt (E) to hydroxide groups of hydroxide (F) for epoxidation catalyst system (2) is from 1.000 moles to 1.000 moles to 6.000 moles to 1.000 moles.
In einer Ausführungsform der Erfindung beträgt das berechnete Stoffmengenverhältnis des Metallsalz (E) zu der redoxaktiven Verbindung (G) für das Epoxidierungskatalysatorsystem (2) von 0,100 mol zu 1,000 mol bis 10,000 mol zu 1,000 mol. In one embodiment of the invention, the calculated molar ratio of the metal salt (E) to the redox-active compound (G) for the epoxidation catalyst system (2) is from 0.100 mole to 1.000 mole to 10.000 mole to 1.000 mole.
In einer Ausführungsform der Erfindung beträgt das berechnete Stoffmengenverhältnis der Hydroxidgruppen des Hydroxids (F) zu dem der redoxaktiven Verbindung (G) für das Epoxidierungskatalysatorsystem (2) von 0,100 mol zu 1,000 mol bis 50,000 mol zu 1,000 mol.
In einer bevorzugten Ausführungsform der Erfindung wird das Iod (E) in einem berechneten Stofftnengenanteil von 1 mol-% bis 2000 mol-% bezogen auf die Menge des Metallsalzes (E) eingesetzt. In one embodiment of the invention, the calculated molar ratio of the hydroxide groups of the hydroxide (F) to that of the redox-active compound (G) for the epoxidation catalyst system (2) is from 0.100 mole to 1.000 mole to 50.000 mole to 1.000 mole. In a preferred embodiment of the invention, the iodine (E) is used in a calculated amount of from 1 mol % to 2000 mol %, based on the amount of the metal salt (E).
In einer weniger bevorzugten Ausführungsform der Erfindung umfasst das Epoxidierungskatalysatorsystem (2) die Mischung (2) des Metallsalzes (E), Iod und des Hydroxids (F) in den oben beschriebenen, berechneten Stoffmengenverhältnissen. In a less preferred embodiment of the invention, the epoxidation catalyst system (2) comprises the mixture (2) of the metal salt (E), iodine and the hydroxide (F) in the calculated molar ratios described above.
In einer bevorzugten Ausführungsform der Erfindung umfasst das Epoxidierungskatalysatorsystem (2) das Umsetzungsprodukt (2) des Metallsalzes (E),Iod und des Hydroxids (F), wobei das Metallsalz (E), das Iod und das Hydroxid (F) mit einem für den Fachmann bekannten Herstellungsverfahren wie beispielsweise Festkörpersynthesen, Fällungs- oder Co-Fällungsmethoden oder als in Situ- Salzmetathese hergestellt wird. So kann das Umsetzungsprodukt zum Beispiel durch Zugabe des organischen Hydroxids (F-l) und/oder anorganischen Hydroxids (F-2) zu einer Lösung des Nitrats, Halogenids, Tetrafluoroborats, Sulfats, Paratoluolsulfonats, Methansulfonats und/oder Triflats bevorzugt eines Chlorids des Metallsalzes (E) in den oben beschriebenen, berechneten Stoffmengenverhältnissen, anschließender Abtrennung des Fällungsproduktes, Trocknung und geeigneter thermische Behandlung synthetisiert werden. In a preferred embodiment of the invention, the epoxidation catalyst system (2) comprises the reaction product (2) of the metal salt (E), iodine and the hydroxide (F), wherein the metal salt (E), the iodine and the hydroxide (F) with a for the Preparation methods known to those skilled in the art, such as solid-state syntheses, precipitation or co-precipitation methods, or as in situ salt metathesis. For example, by adding the organic hydroxide (F-1) and/or inorganic hydroxide (F-2) to a solution of the nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride of the metal salt (E ) are synthesized in the above-described, calculated molar ratios, subsequent separation of the precipitation product, drying and suitable thermal treatment.
In einer bevorzugten Ausführungsform der Erfindung weist das Umsetzungsprodukt (2) des Epoxidierungskatalysatorsystems (2) eine Struktur gemäß Formel (IV), (V) und/oder (VI) auf: In a preferred embodiment of the invention, the reaction product (2) of the epoxidation catalyst system (2) has a structure of the formula (IV), (V) and/or (VI):
(Q RiR2R3R4)+im-o-pi [M(E)m+(Hal)n(OH)o(S)p]m n ° · q T2 (IV) für den Fall m < n + o,(Q RiR 2 R 3 R 4 ) + im-o-pi [M(E) m+ (Hal)n(OH)o(S)p] mn ° q T 2 (IV) for the case m < n + O,
[M(E)m+(Hal)n(OH)0(S)p] qT2 (V) für den Fall m = n + o[M(E) m+ (Hal)n(OH) 0 (S) p ] qT 2 (V) for the case m = n + o
[M(E)m+(Hal)„(OH)o(S)p]m n ° · q T2 [X] „+0-m (VI) für den Fall m > n + o mit [M(E) m+ (Hal)„(OH)o(S) p ] mn ° q T 2 [X] „ +0 -m (VI) for the case m > n + o with
Q = Stickstoff oder Phosphor bevorzugt Stickstoff Q = nitrogen or phosphorus, preferably nitrogen
Ri, R2, R,. R4 unabhängig voneinander ausgewählt aus der Gruppe bestehend aus R 1 , R 2 , R 1 . R 4 independently selected from the group consisting of
(i) linearen oder verzweigten Alkylgruppen enthaltend 1 bis 22 C Atome, optional substituiert mit Heteroatomen und/oder Heteroatom enthaltenden Substituenten; (i) linear or branched alkyl groups containing 1 to 22 C atoms optionally substituted with heteroatoms and/or heteroatom containing substituents;
(ii) cycloaliphatische Gruppen enthaltend 3 bis 22 C Atome mit 1 bis 3 verbrückenden C Atomen, optional substituiert mit Heteroatomen und/oder Heteroatom enthaltenden Substituenten und/oder (ii) cycloaliphatic groups containing 3 to 22 C atoms with 1 to 3 bridging C atoms optionally substituted with heteroatoms and/or heteroatom containing substituents and/or
(iii) Arylgruppen enthaltend 6 bis 18 C Atome, optional substituiert mit 1 bis 10 C Atomen und/oder optional substituiert mit Heteroatomen und/oder Heteroatom enthaltenden Substituenten; bevorzugt Ri, R2, R, und R4 unabhängig voneinander ausgewählt aus der Gruppe bestehend aus Methyl, Ethyl, iso-Propyl, n-Propyl, iso-Butyl, t-Bu, n-Butyl, Phenyl, Benzyl, (Trifluoromethyl)phenyl besonders bevorzugt Methyl, Benzyl und n-Butyl;
M(E)m+ = Ni2+, Mn2+, Pb2+, Sn2+, Cr' . V3+, Mo4+, Fe2+ oder Ru3+ bevorzugt Ni2+, Mn2+, Pb2+,(iii) aryl groups containing 6 to 18 C atoms optionally substituted with 1 to 10 C atoms and/or optionally substituted with heteroatoms and/or heteroatom containing substituents; preferably Ri, R 2 , R and R 4 independently selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, isobutyl, t-Bu, n-butyl, phenyl, benzyl, (trifluoromethyl) phenyl particularly preferably methyl, benzyl and n-butyl; M(E) m+ = Ni 2+ , Mn 2+ , Pb 2+ , Sn 2+ , Cr' . V 3+ , Mo 4+ , Fe 2+ or Ru 3+ preferably Ni 2+ , Mn 2+ , Pb 2+ ,
Sn2+; Sn 2+ ;
Hai = CI , Br oder G bevorzugt CI oder Br besonders bevorzugt CI , Hal = CI , Br or G preferably CI or Br particularly preferably CI ,
S = H2O, THF (Tetrahydrofuran), oder Dioxan, Bis(2methoxyethyl)ether (Diglyme), Methoxyethanol, Polyethylenglykole, Pyridin, Futidin, 2,2‘-Bipyridin, Acetonitril, Dimethylsulfoxid, Sulfolan, Thiophen, bevorzugt THF; n+o+p = 6; n > 1; bevorzugt n > 2; besonders bevorzugt n = 2; o > 1; bevorzugt o > 1; besonders bevorzugt o = 1; 2; 3 oder 4; S = H2O, THF (tetrahydrofuran), or dioxane, bis(2-methoxyethyl)ether (diglyme), methoxyethanol, polyethylene glycols, pyridine, futidine, 2,2'-bipyridine, acetonitrile, dimethyl sulfoxide, sulfolane, thiophene, preferably THF; n+o+p = 6; n > 1; preferably n > 2; particularly preferably n=2; o > 1; preferably o > 1; particularly preferably o=1; 2; 3 or 4;
X = OTf,BF4 , Hai ; q > 1 bevorzugt 1< q < 2000 besonders bevorzugt 1< q < 10. X = OTf,BF4 , Hai ; q>1 preferably 1<q<2000 particularly preferably 1<q<10.
In einer besonders bevorzugten Ausführungsform der Erfindung ist das Umsetzungsprodukt (2) des Epoxidierungskatalysatorsystems (2) eine oder mehrere Verbindungen und wird ausgewählt aus der Fiste bestehend aus (Q RiR2R3R4)[Ni(II)Cl2(OH)(THF)3] I2, (Q RiR2R3R4)[Mn(II)Cl2(OH)(THF)3] I2, (Q RiR2R3R4)[Pb(II)Cl2(OH)(THF)3] I2 und (Q RiR2R3R4)[Sn(II)Cl2(OH)(THF)3] I2 mit Q = Stickstoff und Ri, R2, R3 und R4 unabhängig voneinander ausgewählt aus der Gruppe bestehend Methyl, Benzyl und n-Butyl. 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 the list consisting of (Q RiR 2 R 3 R4)[Ni(II)Cl2(OH)(THF) 3] I 2, (Q RiR 2 R3R4)[Mn(II)Cl 2 (OH)(THF)3] I 2, (Q RiR 2 R3R 4 )[Pb(II)Cl 2 (OH)(THF) 3 ] I 2 and (Q RiR 2 R3R 4 )[Sn(II)Cl 2 (OH)(THF) 3 ] I 2 with Q = nitrogen and Ri, R 2 , R3 and R4 independently selected from the group consisting of methyl, benzyl and n-butyl.
In einer Ausführungsform der Erfindung wird das Epoxidierungskatalysatorsystem (2) auf einem Katalysatorträger (H) aufgebracht unter Bildung eines geträgerten Epoxidierungskatalysatorsystem (2). In one embodiment of the invention, the epoxidation catalyst system (2) is supported on a catalyst support (H) to form a supported epoxidation catalyst system (2).
In einer bevorzugten Ausführungsform der Erfindung ist der Katalysatorträger (H) eine oder mehrere Verbindung(en) und wird ausgewählt aus der Gruppe bestehend aus Metalloxide, Erdalkalicarbonate, Silicate, Siliciumcarbide, Siliciumoxy Carbide, Siliciumnitride, Siliciumoxynitride und Siliciumdioxid, bevorzugt Aluminiumoxid Aluminiumdioxid, Silica, Titandioxid, Zircondioxid, Calciumcarbonat, Phyllosilikate, wie Talkum, Kaolinite und Pyrophyllite, und Titandioxid. In a preferred embodiment of the invention, the catalyst support (H) is one or more compound(s) and is selected from the group consisting of metal oxides, alkaline earth metal carbonates, silicates, silicon carbides, silicon oxycarbides, silicon nitrides, silicon oxynitrides and silicon dioxide, preferably aluminum oxide, aluminum dioxide, silica, Titanium dioxide, zirconia, calcium carbonate, phyllosilicates such as talc, kaolinites and pyrophyllites, and titanium dioxide.
Erfindungsgemäß kann der Katalysatorträger als Formkörper oder als Pulver vorliegen. According to the invention, the catalyst support can be in the form of a shaped body or a powder.
In einer Ausführungsform der Erfindung wird das Epoxidierungskatalysatorsystem (2) in einem berechneten Massenanteil von 1,0 Gew.-% bis 30,0 Gew.-% auf den Katalysatorträger (H) aufgebracht. In one embodiment of the invention, the epoxidation catalyst system (2) is applied to the catalyst support (H) in a calculated proportion by weight of from 1.0% by weight to 30.0% by weight.
In einer Ausführungsform der Erfindung wird das Epoxidierungskatalysatorsystem (H) mithilfe der Nassinfiltrationsmethode (wet-infiltration) oder der incipient-wetness Methode auf den Katalysatorträger (H) aufgebracht wird.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von Epoxiden umfassend der oxidativen Umsetzung eines Alkens in einem Reaktor in Gegenwart des erfindungsgemäßen Epoxidierungskatalysatorsystems (1) oder des erfindungsgemäßen Epoxidierungskatalysatorsystems . In one embodiment of the invention, the epoxidation catalyst system (H) is applied to the catalyst support (H) using the wet infiltration method (wet infiltration) or the incipient wetness method. Another subject of the present invention is a process for preparing epoxides comprising the oxidative reaction of an alkene in a reactor in the presence of the epoxidation catalyst system (1) according to the invention or the epoxidation catalyst system according to the invention.
In einer Ausführungsform des erfmdungsgemäßen Verfahrens erfolgt die oxidative Umsetzung im Reaktor in Gegenwart von Sauerstoff oder einem Sauerstoff-haltigen Gasgemisch. In one embodiment of the process according to the invention, the oxidative reaction takes place in the reactor in the presence of oxygen or an oxygen-containing gas mixture.
Das sauerstoff-haltige Gasgemisch umfasst neben Sauerstoff auch Verdünnungs-, Träger- oder Inert- Gase wie Kohlenwasserstoffe, Edelgase, CO, C02, N2. In addition to oxygen, the oxygen-containing gas mixture also includes dilution, carrier or inert gases such as hydrocarbons, noble gases, CO, CO 2 , N 2 .
In einer Ausführungsform des erfmdungsgemäßen Verfahrens werden dem Sauerstoff oder einem Sauerstoff-haltigen Gasgemisch weitere Additive wie Wasser, CO, N-haltige Verbindungen wie beispielsweise Hydrazin, Ammoniak (NH3), Methylamin (MeMU), NOx, PH3, SO2 und/oder SO3 in Mengen von 10 ppm bis 500 ppm, bevorzugt von 30 ppm bis 300 ppm und besonders bevorzugt von 50 ppm bis 200 ppm zugefügt. Zudem kann C02 in einem Anteil von 0,01 Vol-% bis 50 Vol- %, bevorzugt von 0, 1 Vol-% bis 20 Vol-%, und besonders bevorzugt von 1 Vol-% bis 10 Vol-% zugesetzt werden. Außerdem können organische Halogenide wie Ethylendichlorid, Ethylchlorid, Vinylchlorid, Methylchlorid und/oder Methylenchlorid in Mengen von 10 ppm bis 500 ppm, bevorzugt von 50 ppm bis 400 ppm, und besonders bevorzugt von 100 ppm bis 300 ppm ppm zugestzt werden. In one embodiment of the inventive method, the oxygen or an oxygen-containing gas mixture are further additives such as water, CO, N-containing compounds such as hydrazine, ammonia (NH3), methylamine (MeMU), NOx, PH 3 , SO 2 and / or SO 3 is added in amounts from 10 ppm to 500 ppm, preferably from 30 ppm to 300 ppm and particularly preferably from 50 ppm to 200 ppm. In addition, CO 2 can be added in a proportion of 0.01% by volume to 50% by volume, preferably from 0.1% by volume to 20% by volume, and particularly preferably from 1% by volume to 10% by volume. In addition, organic halides such as ethylene dichloride, ethyl chloride, vinyl chloride, methyl chloride and/or methylene chloride can be added in amounts from 10 ppm to 500 ppm, preferably from 50 ppm to 400 ppm, and particularly preferably from 100 ppm to 300 ppm.
In einer bevorzugten Ausführungsform des erfmdungsgemäßen Verfahrens erfolgt die oxidative Umsetzung im Reaktor in Gegenwart von Sauerstoff. In a preferred embodiment of the process according to the invention, the oxidative reaction takes place in the reactor in the presence of oxygen.
In einer Ausführungsform des erfmdungsgemäßen Verfahrens ist das Alken eine oder mehrere Verbindung(en) und wird ausgewählt aus der Gruppe bestehend aus Ethen, Propen, Buten, 1-Okten, Butadien, 1,4-Butandioldiallylether, Allylchlorid, Allylalcohol, Styrol, Cyclopenten, Cyclohexen, Phenyl-allylether, Diallylether, n-Butyl-allylether, tert-Butyl-allylether, Bisphenol-A diallyl ether, Resorcindiallylether, Triphenylolmethan-triallylether, Cy clohexan- 1 ,2-dicarbonsäure-bis-In one embodiment of the process according to the invention, the alkene is one or more compound(s) and is selected from the group consisting of ethene, propene, butene, 1-octene, butadiene, 1,4-butanediol diallyl ether, allyl chloride, allyl alcohol, styrene, cyclopentene, Cyclohexene, phenyl allyl ether, diallyl ether, n-butyl allyl ether, tert-butyl allyl ether, bisphenol A diallyl ether, resorcinol diallyl ether, triphenylolmethane triallyl ether, cyclohexane-1,2-dicarboxylic acid bis-
(allylester), Isocyanursäuretris-(prop-2,3-en)-ester und Gemische dieser Alkene bevorzugt Ethen, Propen und Allylchlorid und besonders bevorzugt Propen. (allyl ester), tris-(2,3-propene) isocyanurate and mixtures of these alkenes, preferably ethene, propene and allyl chloride and particularly preferably propene.
Das erfmdungsgemäße Epoxid (Alkylenoxid) kann ein Epoxid mit 2-45 Kohlenstoffatomen sein. In einer Ausführungsform des erfmdungsgemäßen Verfahrens wird das Epoxid ausgewählt aus mindestens einer Verbindung der Gruppe bestehend aus Ethylenoxid, Propylenoxid, 1,2- Butylenoxid, 2,3-Butylenoxid, 2-Methyl-l,2-propylenoxid (Isobutenoxid), 1,2-Pentylenoxid, 2,3- Pentylenoxid, 2-Methyl-l,2-butylenoxid, 3 -Methyl- 1,2-butylenoxid, Epoxide von C6-C22 a- Olefinen, wie 1,2-Hexylenoxid, 2,3-Hexylenoxid, 3,4-Hexylenoxid, 2-Methyl-l,2-pentylenoxid, 4-
Methyl- 1,2-pentylenoxid, 2-Ethyl-l,2-butylenoxid, 1,2-Heptylenoxid, 1,2-Octylenoxid, 1,2- Nonylenoxid, 1,2-Decylenoxid, 1,2-Undecylenoxid, 1,2-Dodecylenoxid, 4-Methyl- 1,2- pentylenoxid, Cyclopentylenoxid, Cyclohexylenoxid, Cycloheptylenoxid, Cyclooctylenoxid, Styroloxid, Methylstyroloxid, Pinenoxid, Allylglycedylether, Vinylcyclohexylenoxid, Cyclooctadienmonoepoxid, Cyclododecatrienmono-epoxid, Butadienmonoepoxid,The epoxide (alkylene oxide) according to the invention can be an epoxide having 2-45 carbon atoms. In one embodiment of the process according to the invention, the epoxide is selected from at least one compound from the group consisting of ethylene oxide, propylene oxide, 1,2-butylene oxide, 2,3-butylene oxide, 2-methyl-1,2-propylene oxide (isobutene oxide), 1,2 -pentylene oxide, 2,3-pentylene oxide, 2-methyl-1,2-butylene oxide, 3-methyl-1,2-butylene oxide, epoxides of C6-C22 a-olefins such as 1,2-hexylene oxide, 2,3-hexylene oxide , 3,4-hexylene oxide, 2-methyl-1,2-pentylene oxide, 4- Methyl-1,2-pentylene oxide, 2-ethyl-l,2-butylene oxide, 1,2-heptylene oxide, 1,2-octylene oxide, 1,2-nonylene oxide, 1,2-decylene oxide, 1,2-undecylene oxide, 1, 2-dodecylene oxide, 4-methyl- 1,2-pentylene oxide, cyclopentylene oxide, cyclohexylene oxide, cycloheptylene oxide, cyclooctylene oxide, styrene oxide, methylstyrene oxide, pinene oxide, allyl glycedyl ether, vinylcyclohexylene oxide, cyclooctadiene monoepoxide, cyclododecatriene monoepoxide, butadiene monoepoxide,
Isoprenmonoepoxid, Limonenoxid, 1,4-Divinylbenzolmonoepoxid, 1,3-Divinylbenzolmonoepoxid, Glycidylacrylat und Glycidylmethacrylat ein- oder mehrfach epoxidierte Fette als Mono-, Di- und Triglyceride, epoxidierte Fettsäuren, Cl-C24-Ester epoxidierter Fettsäuren, Epichlorhydrin, Glycidol, und Derivate des Glycidols wie beispielsweise Glycidylether von C1-C22 Alkanolen, Glycidylester von C1-C22 Alkancarbonsäuren. Beispiele für Derivate des Glycidols sind Phenylglycidylether, Kresylglycidylether, Methylglycidylether, Ethylglycidylether und 2- Ethylhexylglycidylether. Isoprene monoepoxide, limonene oxide, 1,4-divinylbenzene monoepoxide, 1,3-divinylbenzene monoepoxide, glycidyl acrylate and glycidyl methacrylate, one or more times epoxidized fats as mono-, di- and triglycerides, epoxidized fatty acids, Cl-C24 esters of epoxidized fatty acids, epichlorohydrin, glycidol, and Glycidol derivatives such as glycidyl ethers of C1-C22 alkanols, glycidyl esters of C1-C22 alkanecarboxylic acids. Examples of derivatives of glycidol are phenyl glycidyl ether, cresyl glycidyl ether, methyl glycidyl ether, ethyl glycidyl ether and 2-ethylhexyl glycidyl ether.
In einer bevorzugten Ausführungsform des Verfahrens ist das Epoxid Ethylenoxid, Propylenoxid, 1,2-Butylenoxid, 1,2-Pentylenoxid, 1,2-Hexylenoxid, 1,2-Heptylenoxid und/oder 1,2-Octylenoxid. In einer besonders bevorzugten Ausführungsform des Verfahrens ist das Epoxid Ethylenoxid und/oder Propylenoxid. In einer ganz besonders bevorzugten Ausführungsform des Verfahrens ist das Epoxid Propylenoxid. In a preferred embodiment of the process, the epoxide is ethylene oxide, propylene oxide, 1,2-butylene oxide, 1,2-pentylene oxide, 1,2-hexylene oxide, 1,2-heptylene oxide and/or 1,2-octylene oxide. In a particularly preferred embodiment of the process, the epoxide is ethylene oxide and/or propylene oxide. In a most preferred embodiment of the process, the epoxide is propylene oxide.
In einer Ausführungsform des erfmdungsgemäßen Verfahrens erfolgt die Herstellung von Epoxiden in Gegenwart eines Lösungsmittels. In one embodiment of the process according to the invention, epoxides are prepared in the presence of a solvent.
In einer Ausführungsform des erfmdungsgemäßen Verfahrens ist das Lösungsmittel eine oder mehrere Verbindung(en) und wird ausgewählt aus der Gruppe bestehend aus C02, Wasser , Perfluoromethyldecalin, Perfluorodecalin, Perfluoroperhydrophenanthren,In one embodiment of the method according to the invention, the solvent is one or more compound(s) and is selected from the group consisting of CO 2 , water, perfluoromethyldecalin, perfluorodecalin, perfluoroperhydrophenanthrene,
Perfluoro(butyltetrahydrofüran), Tetrahydrofüran, 2-Methyl-THF, Essigsäure, Acetonitril, Dimethylsulfoxid, Sulfolan, Aceton, Ethylmethylketon, Dimethylformamid, Dichlormethan, Chloroform, Tetrachlormethan, N-methyl-2-pyrrolidinon, Methyl-t-butylether (MTBE), Dimrthylsulxid (DMSO), Hexamethylphosphoramid, Dichlorbenzol, 1,2-Dichloroethylen, 1,1,1,3,3,3-Hexafluoroisopropanol, Perfluoro-tert-butylalkohol, 1,1,2,3,3-Pentafluoropropan, 1- Brom-2-chlor- 1 , 1 ,2-trifluoroethan, 1 ,2-Dichloro- 1 , 1 ,2,3 ,3 ,3 -hexafluorpropan, Ethylenglycol, Glycerin, und Phenol. Perfluoro(butyltetrahydrofuran), tetrahydrofuran, 2-methyl-THF, acetic acid, acetonitrile, dimethyl sulfoxide, sulfolane, acetone, ethyl methyl ketone, dimethylformamide, dichloromethane, chloroform, tetrachloromethane, N-methyl-2-pyrrolidinone, methyl t-butyl ether (MTBE), Dimethyl Sulfide (DMSO), Hexamethylphosphoramide, Dichlorobenzene, 1,2-Dichloroethylene, 1,1,1,3,3,3-Hexafluoroisopropanol, Perfluoro-tert-butyl Alcohol, 1,1,2,3,3-Pentafluoropropane, 1-Bromo -2-chloro-1,1,2-trifluoroethane, 1,2-dichloro-1,1,2,3,3,3-hexafluoropropane, ethylene glycol, glycerine, and phenol.
In einer Ausführungsform des erfmdungsgemäßen Verfahrens erfolgt die Herstellung von Epoxiden in Gegenwart eines Lösungsmittels, wobei die Herstellung bei einer Temperatur von Temperatur von 20 °C bis 200 °C bevorzugt von 50 °C bis 160 °C und besonders bevorzugt von 100 °C bis 150 °C.
In einer Ausführungsform des erfmdungsgemäßen Verfahrens erfolgt die Herstellung von Epoxiden in Gegenwart eines Lösungsmittels, wobei die Herstellung bei einem Druck von 1 bara bis 200 bara bevorzugt von 1 bara bis 35 bara und besonders bevorzugt von 1 bara bis 28 bara erfolgt. In one embodiment of the process according to the invention, epoxides are prepared in the presence of a solvent, with the preparation being carried out at a temperature of from 20° C. to 200° C., preferably from 50° C. to 160° C. and particularly preferably from 100° C. to 150 °C In one embodiment of the process according to the invention, epoxides are prepared in the presence of a solvent, with the preparation taking place at a pressure of from 1 bara to 200 bara, preferably from 1 bara to 35 bara and particularly preferably from 1 bara to 28 bara.
In einer Ausführungsform des erfmdungsgemäßen Verfahrens erfolgt die Herstellung von Epoxiden in Gegenwart eines Lösungsmittels, wobei die Herstellung in einem Zeitraum von 6 min bis 48 h, bevorzugt von 6 min bis 24 h und besonders bevorzugt von 6 min bis 3 h erfolgt. In one embodiment of the process according to the invention, epoxides are prepared in the presence of a solvent, the preparation taking place over a period of 6 minutes to 48 hours, preferably 6 minutes to 24 hours and particularly preferably 6 minutes to 3 hours.
In einer Ausführungsform des erfmdungsgemäßen Verfahrens erfolgt die Herstellung von Epoxiden in Gegenwart eines Lösungsmittels, wobei das Stoffmengenverhältnis des Alkens zum Sauerstoff von 1: 100 bis 100: 1 bevorzugt von 1:30 bis 30: 1 beträgt. In one embodiment of the process according to the invention, epoxides are prepared in the presence of a solvent, the molar ratio of the alkene to oxygen being from 1:100 to 100:1, preferably from 1:30 to 30:1.
In einer alternativen Ausführungsform des erfmdungsgemäßen Verfahrens erfolgt die Herstellung von Epoxiden in Abwesenheit eines Lösungsmittels. In an alternative embodiment of the process according to the invention, epoxides are prepared in the absence of a solvent.
Hierbei bedeutet erfindungsgemäß ein lösungsmittelfreies Verfahren, dass Lösungsmittelreste beispielsweise infolge der Herstellung der Einsatzstoffe von bis zu 10 Vol.-% bevorzugt von bis zu 5 Vol.-% und besonders bevorzugt von bis 2 Vol.-% bezogen auf die Menge an eingesetztem Propen zugegen sein können. According to the invention, a solvent-free process means that solvent residues, for example as a result of the preparation of the starting materials, are present in an amount of up to 10% by volume, preferably up to 5% by volume and particularly preferably up to 2% by volume, based on the amount of propene used could be.
In einer Ausführungsform des erfmdungsgemäßen Verfahrens erfolgt die Herstellung von Epoxiden in Abwesenheit eines Lösungsmittels, wobei die Herstellung unter Verwendung des erfmdungsgemäßen, geträgerten Epoxidierungskatalysatorsystems (1) oder des erfmdungsgemäßen, geträgerten Epoxidierungskatalysatorsystems (2) erfolgt. In one embodiment of the process according to the invention, epoxides are prepared in the absence of a solvent, the preparation being carried out using the supported epoxidation catalyst system (1) according to the invention or the supported epoxidation catalyst system (2) according to the invention.
In einer Ausführungsform des erfmdungsgemäßen Verfahrens erfolgt die Herstellung von Epoxiden in Abwesenheit eines Lösungsmittels, wobei die Herstellung bei einer Temperatur von 20 °C bis 500 °C bevorzugt von 50 °C bis 400 °C und besonders bevorzugt von 50 °C bis 250 °C erfolgt.In one embodiment of the process according to the invention, epoxides are prepared in the absence of a solvent, with the preparation being carried out at a temperature of from 20.degree. C. to 500.degree. C., preferably from 50.degree. C. to 400.degree. C. and particularly preferably from 50.degree. C. to 250.degree he follows.
In einer Ausführungsform des erfmdungsgemäßen Verfahrens erfolgt die Herstellung von Epoxiden in Abwesenheit eines Lösungsmittels, wobei die Herstellung bei einem Druck von 1 bara bis 200 bara bevorzugt von 2 bara bis 100 bara und besonders bevorzugt von 2 bara bis 50 bara erfolgt.In one embodiment of the process according to the invention, epoxides are prepared in the absence of a solvent, with the preparation taking place at a pressure of from 1 bara to 200 bara, preferably from 2 bara to 100 bara and particularly preferably from 2 bara to 50 bara.
In einer Ausführungsform des erfmdungsgemäßen Verfahrens erfolgt die Herstellung von Epoxiden in Abwesenheit eines Lösungsmittels, wobei die Herstellung mit einer Raumgeschwindigkeit (englisch Gas Houmly Space Velocity GHSV) als Quotient des Volumenstroms der eingesetzten Eduktgase zum Katalysatorvolumen von 100 h-1 bis 10000 h-1, bevorzugt von 200 h-1 bis 5000 h- 1 und besonders bevorzugt von 500 h-1 bis 2000 h-1 erfolgt. Das Katalysatorvolumen entspricht hierbei bei geträgerten und/oder mittels inerten Verdünnungsmittels (beispielsweise Aluminiumoxid, Silica, Siliciumcarbid) verdünnten Katalysators denen des geträgerten
Epoxidierungskatalysatorsystems (1) bzw. (2) und/oder der Summe des Katalysator- und V erdünnungsmittelvolumens . In one embodiment of the process according to the invention, epoxides are produced in the absence of a solvent, the production being carried out with a space velocity (English Gas Houmly Space Velocity GHSV) as the quotient of the volume flow of the reactant gases used to the catalyst volume of 100 h-1 to 10000 h-1, preferably from 200 h-1 to 5000 h-1 and particularly preferably from 500 h-1 to 2000 h-1. In the case of a supported catalyst and/or a catalyst diluted by means of an inert diluent (for example aluminum oxide, silica, silicon carbide), the catalyst volume corresponds to that of the supported catalyst epoxidation catalyst system (1) or (2) and/or the sum of the catalyst and diluent volume.
In einer Ausführungsform des erfindungsgemäßen Verfahrens erfolgt die Herstellung von Epoxiden in Abwesenheit eines Lösungsmittels, wobei das Stoffmengenverhältnis des Alkens zum Sauerstoff von 1,0:0, 1 bis 2: 1 bevorzugt von 1:0,5 bis 2: 1 und besonders bevorzugt von 1:0,8 bis 2: 1 beträgt.In one embodiment of the process according to the invention, epoxides are prepared in the absence of a solvent, the molar ratio of the alkene to oxygen being from 1.0:0.1 to 2:1, preferably from 1:0.5 to 2:1 and particularly preferably from is 1:0.8 to 2:1.
In einer Ausführungsform des erfindungsgemäßen Verfahrens wird das Alken kontinuierlich oder stufenweise bevorzugt kontinuierlich in den Reaktor dosiert. In one embodiment of the process according to the invention, the alkene is metered into the reactor continuously or in stages, preferably continuously.
In einer Ausführungsform des erfindungsgemäßen Verfahrens wird Sauerstoff oder das Sauerstoff haltige Gasgemisch kontinuierlich oder stufenweise bevorzugt kontinuierlich in den Reaktor dosiert.In one embodiment of the process according to the invention, oxygen or the oxygen-containing gas mixture is metered into the reactor continuously or in stages, preferably continuously.
In einer Ausführungsform des erfindungsgemäßen Verfahrens wird das Alken und der Sauerstoff oder das Sauerstoff-haltige Gasgemisch kontinuierlich oder stufenweise bevorzugt kontinuierlich in den Reaktor dosiert. In one embodiment of the process according to the invention, the alkene and the oxygen or the oxygen-containing gas mixture are metered into the reactor continuously or in stages, preferably continuously.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird das Epoxid kontinuierlich oder stufenweise bevorzugt kontinuierlich aus dem Reaktor entnommen. In a preferred embodiment of the process according to the invention, the epoxide is removed from the reactor continuously or in stages, preferably continuously.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird das Epoxidierungskatalysatorsystem (1) kontinuierlich oder stufenweise bevorzugt kontinuierlich in den Reaktor dosiert wird. 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.
Das erfindungsgemäße Verfahren kann im batch-Verfahren, im semi-batch Verfahren oder in kontinuierlicher Fahrweise durchgeführt werden, wobei hierzu für den Fachmann bekannte Reaktortypen verwendet werden. So kann die kontinuierliche Herstellung von Epoxiden durch oxidative Umsetzung von Alkenen in einem kontinuierlich rückvermischten Rührkessel (engl. Continuous Stirred Tank Reactor CSTR) oder einem Ein- oder Zweisäulenblasenreaktor in der Flüssigphase in Gegenwart eines Lösungsmittels erfolgen. Die kontinuierliche Herstellung von Epoxiden in der Gasphase in Abwesenheit eines Lösungsmittels kann mittels eines kontinuierlichen Gasphasenreaktors, wie beispielsweise eines Festbettreaktors auch unter Verwendung von keramischen Füllmaterialien erfolgen. The process according to the invention can be carried out in a batch process, in a semi-batch process or in a continuous procedure, reactor types known to those skilled in the art being used for this purpose. Thus, epoxides can be prepared continuously by the oxidative reaction of alkenes in a continuous stirred tank reactor (CSTR) or a single- or double-column bubble reactor in the liquid phase in the presence of a solvent. The continuous production of epoxides in the gas phase in the absence of a solvent can be carried out by means of a continuous gas phase reactor, such as a fixed bed reactor, also using ceramic packing materials.
In einer bevorzugten Ausführungsform des erfindungsgemäßen Verfahrens wird das Epoxidierungskatalysatorsystem (1) und/oder Epoxidierungskatalysatorsystem (2) in einer berechneten Menge von lO ppm bis 500.000 ppm bevorzugt von 100 ppm bis 200.000 ppm und besonders bevorzugt von 1000 ppm bis 150.000 ppm bezogen auf die Masse aller beteiligter Reaktanden und optional Lösungsmittel und mögliche weitere Hilfsstoffe eingesetzt.
In einer ersten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) umfassend a) ein Gemisch bevorzugt ein Umsetzungsprodukt a-1) eines Metallsalz (A) der Metalle Chrom (Cr), Mangan (Mn), Molybdän (Mo), Blei (Pb) und/oder Bismut (Bi) und a-2) eines Hydroxid (B) b) eine redoxaktive Verbindung (C). In a preferred embodiment of the process according to the invention, the epoxidation catalyst system (1) and/or epoxidation catalyst system (2) is used in a calculated amount of 10 ppm to 500,000 ppm, preferably 100 ppm to 200,000 ppm and particularly preferably 1000 ppm to 150,000 ppm by mass all reactants involved and optional solvents and possible other auxiliaries used. In a first embodiment, the invention relates to an epoxidation catalyst system (1) comprising a) a mixture, preferably a reaction product a-1) of a metal salt (A) of the metals chromium (Cr), manganese (Mn), molybdenum (Mo), lead (Pb) and/or bismuth (Bi) and a-2) a hydroxide (B) b) a redox-active compound (C).
In einer zweiten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß der ersten Ausführungsform, wobei das Metallsalz (A) ein Nitrat, Halogenid, Tetrafluoroborat, Sulfat, Paratoluolsulfonat, Methansulfonat und/oder Triflat bevorzugt ein Chlorid ist. In a second embodiment, the invention relates to an epoxidation catalyst system (1) according to the first embodiment, wherein the metal salt (A) is a nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride.
In einer dritten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß der ersten oder zweiten Ausführungsform, wobei das Metallsalz (A) ein oder mehrere Verbindungen ist und ausgewählt wird aus der Gruppe bestehend aus MoCE, MoOCE. MnCE, K2MnCE, CrOCE, PbCU und BiCE. In a third embodiment, the 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 the group consisting of MoCE, MoOCE. MnCE, K 2 MnCE, CrOCE, PbCU and BiCE.
In einer vierten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß einer der ersten bis dritten Ausführungsform, wobei das Hydroxid (B) ein organisches Hydroxid (B-l) und/oder anorganisches Hydroxid (B-2) ist. In a fourth embodiment, the invention relates to an epoxidation catalyst system (1) according to any one of the first to third embodiments, wherein the hydroxide (B) is an organic hydroxide (B-1) and/or inorganic hydroxide (B-2).
In einer fünften Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß der vierten Ausführungsform, wobei das Hydroxid (B) ein organisches Hydroxid (B-l) ist und das organische Hydroxid (B-l) eine oder mehrere Verbindung(en) ist und ausgewählt wird aus der Gruppe bestehend aus 3-(Trifluoromethyl)phenyltrimethylammoniumhydroxid, Tetra-n- butylphosphonium hydroxid, Cholinhydroxid, Benzyltrimethylammoniumhydroxid, Tetraethylammoniumhydroxid, Tetra-n-propylammoniumhydroxid, Tetrabutylammoniumhydroxid und Tetramethylammoniumhydroxid. In a fifth embodiment, the invention relates to an epoxidation catalyst system (1) according to the fourth embodiment, wherein the hydroxide (B) is an organic hydroxide (B-l) and the organic hydroxide (B-l) is one or more compound(s) 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 einer sechsten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß der vierten Ausführungsform, wobei das Hydroxid (B) ein anorganisches Hydroxid (B-2) ist und das anorganische Hydroxid (B-2) eine oder mehrere Verbindung(en) ist und ausgewählt wird aus der Gruppe bestehend aus Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid sowie deren Kronenetherkomplexen, Caesiumhydroxid, Calciumhydroxid, Bariumhydroxid, Kaliumaluminate,
Natriumaliminat, Kaliumaluminat und Natriumzinkat bevorzugt Lithiumhydroxid, Natriumhydroxid und Kaliumhydroxid. In a sixth embodiment, the invention relates to an epoxidation catalyst system (1) according to the fourth embodiment, wherein the hydroxide (B) is an inorganic hydroxide (B-2) and the inorganic hydroxide (B-2) is one or more compound(s) and is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and their crown ether complexes, cesium hydroxide, calcium hydroxide, barium hydroxide, potassium aluminates, Sodium aluminate, potassium aluminate and sodium zincate, preferably lithium hydroxide, sodium hydroxide and potassium hydroxide.
In einer siebten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß einer der ersten bis sechsten Ausführungsform, wobei die redoxaktive Verbindung (C) eine oder mehrere Verbindung(en) ist und ausgewählt wird aus der Gruppe bestehend aus Kupferdichlorid, CuCl 2. Cu(BF4)2, CuCl, VCh. VOCE, NH4VO3, 1,4-Benzochinone, 1,4- Naphtochinone, Se20s, Te02, TeCh, Sb2Ü3, Sb20s, CeCL, Co(salen), Co(OAc)2, SnS04, Fe(acac)3, Mo(acac)3, K2Cr207, Mn(OAc)3, Ni(CF3C02H)2 und BiCl3. In a seventh embodiment, the invention relates to an epoxidation catalyst system (1) according to one of the first to sixth embodiments, wherein the redox-active compound (C) is one or more compound(s) and is selected from the group consisting of copper dichloride, CuCl 2. Cu( BF4)2, CuCl, VCh. VOCE, NH4VO3, 1,4-Benzoquinone, 1,4-Naphtoquinone, Se20s, Te02, TeCh, Sb2Ü3, Sb20s, CeCL, Co(salen), Co(OAc)2, SnS04, 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 einer achten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß einer der ersten bis siebten Ausführungsform, wobei das berechnete Stoffmengenverhältnis des Metallsalz (A) zu den Hydroxidgruppen des Hydroxids (B) von 1,000 mol zu 1,000 mol bis 6,000 mol zu 1,000 mol beträgt. In an eighth embodiment, the invention relates to an epoxidation catalyst system (1) according to one of the first to seventh embodiments, wherein the calculated molar ratio of the metal salt (A) to the hydroxide groups of the hydroxide (B) is from 1.000 mol to 1.000 mol to 6.000 mol to 1.000 mol .
In einer neunten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß einer der ersten bis achten Ausführungsform, wobei das berechnete Stoffmengenverhältnis des Metallsalz (A) zu der redoxaktiven Verbindung (C) von 0,100 mol zu 1,000 mol bis 10,000 mol zu 1,000 mol beträgt. In a ninth embodiment, the invention relates to an epoxidation catalyst system (1) according to one of the first to eighth embodiments, wherein the calculated molar ratio of the metal salt (A) to the redox-active compound (C) is from 0.100 mol to 1.000 mol to 10.000 mol to 1.000 mol.
In einer zehnten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß einer der ersten bis neunten Ausführungsform, wobei das berechnete Stoffmengenverhältnis der Hydroxidgruppen des Hydroxids (B) zu dem der redoxaktiven Verbindung (C) von 0, 100 mol zu 1,000 mol bis 50,000 mol zu 1,000 mol beträgt. In a tenth embodiment, the invention relates to an epoxidation catalyst system (1) according to one of the first to ninth embodiments, the calculated molar ratio of the hydroxide groups of the hydroxide (B) to that of the redox-active compound (C) of 0.100 mol to 1.000 mol to 50.000 mol to 1,000 moles.
In einer elften Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß einer der ersten bis zehnten Ausführungsform, wobei das Epoxidierungskatalysatorsystem (1) weiterhin Iod (I2) enthält. In an eleventh embodiment, the invention relates to an epoxidation catalyst system (1) according to one of the first to tenth embodiments, the epoxidation catalyst system (1) further comprising iodine (I2).
In einer zwölften Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß der elften Ausführungsform, wobei das das Iod (I2) in einem berechneten Stoffmengenanteil von 1 mol-% bis 2000 mol-% bezogen auf die Menge des Metallsalzes (A) eingesetzt wird. In a twelfth embodiment, the invention relates to an epoxidation catalyst system (1) according to the eleventh embodiment, the iodine (I2) being used in a calculated mole fraction of 1 mol % to 2000 mol % based on the amount of the metal salt (A).
In einer dreizehnten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß einer der ersten bis zwölften Ausführungsform, wobei das Epoxidierungskatalysatorsystem (1) auf einem Katalysatorträger (D) aufgebracht wird unter Bildung eines geträgerten Epoxidierungskatalysatorsystem ( 1 ) . In a thirteenth embodiment, the invention relates to an epoxidation catalyst system (1) according to one of the first to twelfth embodiments, the epoxidation catalyst system (1) being applied to a catalyst support (D) to form a supported epoxidation catalyst system (1).
In einer vierzehnten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß der dreizehnten Ausführungsform, wobei der Katalysatorträger (D) eine oder mehrere
Verbindung(en) ist und ausgewählt wird aus der Gruppe bestehend aus Metalloxide, Erdalkalicarbonate, Silicate, Siliciumcarbide, Siliciumoxy Carbide, Siliciumnitride,In a fourteenth embodiment, the invention relates to an epoxidation catalyst system (1) according to the thirteenth embodiment, wherein the catalyst support (D) is one or more compound(s) and is selected from the group consisting of metal oxides, alkaline earth metal carbonates, silicates, silicon carbides, silicon oxy carbides, silicon nitrides,
Siliciumoxynitride und Siliciumdioxid, bevorzugt Aluminiumoxid Aluminiumdioxid, Silica, Titandioxid, Zircondioxid, Calciumcarbonat, Phyllosilikate, wie Talkum, Kaolinite und Pyrophyllite und Titandioxid. silicon oxynitrides and silica, preferably alumina alumina, silica, titania, zirconia, calcium carbonate, phyllosilicates such as talc, kaolinites and pyrophyllites and titania.
In einer fünfzehnten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (1) gemäß der dreizehnten oder vierzehnten Ausführungsform, wobei das Epoxidierungskatalysatorsystem (1) in einem berechneten Massenanteil von 1,0 -Gew.-% bis 30,0- Gew.-% auf den Katalysatorträger (D) aufgebracht wird. In a fifteenth embodiment, the invention relates to an epoxidation catalyst system (1) according to the thirteenth or fourteenth embodiment, the epoxidation catalyst system (1) being applied to the catalyst support in a calculated mass fraction of 1.0% by weight to 30.0% by weight (D) is applied.
In einer sechzehnten Ausführungsform betrifft die Erfindung ein EpoxidierungskatalysatorsystemIn a sixteenth embodiment, the invention features an epoxidation catalyst system
(1) gemäß einer der dreizehnten bis fünfzehnten Ausführungsform, wobei das(1) according to any one of the thirteenth to fifteenth embodiments, wherein the
Epoxidierungskatalysatorsystem (1) mithilfe der Nassinfiltrationsmethode (wet-infiltration) oder der incipient-wetness Methode auf den Katalysatorträger (D) aufgebracht wird. The epoxidation catalyst system (1) is applied to the catalyst support (D) using the wet infiltration method (wet infiltration) or the incipient wetness method.
In einer siebzehnten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (2) umfassend c) ein Gemisch bevorzugt ein Umsetzungsprodukt c-1) eines Metallsalzes (E), c-2) Iod (E) sowie c-3) eines Hydroxid (F) d) optional eine redoxaktive Verbindung (G). In a seventeenth embodiment, the invention relates to an epoxidation catalyst system (2) comprising c) a mixture, preferably a reaction product of c-1) a metal salt (E), c-2) iodine (E) and c-3) a hydroxide (F) d) optionally a redox active compound (G).
In einer achtzehnten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (2) gemäß der siebzehnten Ausführungsform, wobei das Metallsalz (E) ein Nitrat, Halogenid, Tetrafluoroborat, Sulfat, Paratoluolsulfonat, Methansulfonat und/oder Triflat bevorzugt ein Chlorid ist. In an eighteenth embodiment, the invention relates to an epoxidation catalyst system (2) according to the seventeenth embodiment, wherein the metal salt (E) is a nitrate, halide, tetrafluoroborate, sulfate, paratoluenesulfonate, methanesulfonate and/or triflate, preferably a chloride.
In einer neunzehnten Ausführungsform betrifft die Erfindung ein EpoxidierungskatalysatorsystemIn a nineteenth embodiment, the invention features an epoxidation catalyst system
(2) gemäß der siebzehnten oder achtzehnten Ausführungsform, wobei das Metallsalz (E) ein oder mehrere Verbindungen ist und ausgewählt wird aus der Gruppe bestehend aus NiCk, MnCE. PbCE. SnCl2, CrCk, VC13, MoCU, FeCk und RuCk. (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 NiCk, MnCE. PbCE. SnCl 2 , CrCk, VC1 3 , MoCU, FeCk and RuCk.
In einer zwanzigsten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (2) gemäß einer der siebzehnten bis neunzehnten Ausführungsform, wobei das Hydroxid (F) ein organisches Hydroxid (F-l) und/oder anorganisches Hydroxid (F-2) ist.
In einer einundzwanzigsten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (2) gemäß zwanzigsten Ausführungsform, wobei das Hydroxid (F) ein organisches Hydroxid (B-l) ist und das organische Hydroxid (F-l) eine oder mehrere Verbindung(en) ist und ausgewählt wird aus der Gruppe bestehend aus 3- (Trifluoromethyl)phenyltrimethylammoniumhydroxid, Tetra-n-butylphosphonium hydroxid, Cholinhydroxid, Benzyltrimethylammoniumhydroxid, Tetraethylammoniumhydroxid, Tetra-n- propylammoniumhydroxid, Tetrabutylammoniumhydroxid und Tetramethylammoniumhydroxid.In a twentieth embodiment, the invention relates to an epoxidation catalyst system (2) according to one of the seventeenth to nineteenth embodiments, where the hydroxide (F) is an organic hydroxide (F1) and/or inorganic hydroxide (F-2). In a twenty-first embodiment, the invention relates to an epoxidation catalyst system (2) according to the twentieth embodiment, wherein the hydroxide (F) is an organic hydroxide (BI) and the organic hydroxide (FI) is one or more compound(s) 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 einer zweiundzwanzigsten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (2) gemäß der einundzwanzigsten Ausführungsform, wobei das Hydroxid (F) ein anorganisches Hydroxid (F-2) ist und das anorganische Hydroxid (F-2) eine oder mehrere Verbindung(en) ist und ausgewählt wird aus der Gruppe bestehend aus Lithiumhydroxid, Natriumhydroxid, Kaliumhydroxid sowie deren Kronenetherkomplexen, Caesiumhydroxid, Calciumhydroxid, Bariumhydroxid, Kaliumaluminate, Natriumaliminat, Kaliumaluminat und Natriumzinkat bevorzugt Lithiumhydroxid, Natriumhydroxid und Kaliumhydroxid. In a twenty-second embodiment, the invention relates to an epoxidation catalyst system (2) according to the twenty-first embodiment, wherein the hydroxide (F) is an inorganic hydroxide (F-2) and the inorganic hydroxide (F-2) is one or more compound(s) and is selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide and their crown ether complexes, cesium hydroxide, calcium hydroxide, barium hydroxide, potassium aluminate, sodium aluminate, potassium aluminate and sodium zincate, preferably lithium hydroxide, sodium hydroxide and potassium hydroxide.
In einer dreiundzwanzigsten Ausführungsform betrifft die Erfindung einIn a twenty-third embodiment, the invention relates to a
Epoxidierungskatalysatorsystem (2) gemäß einer der siebzehnten bis zweiundzwanzigstenThe epoxidation catalyst system (2) according to any one of the seventeenth to twenty-second
Ausführungsform, wobei die redoxaktive Verbindung (G) zugegen ist, und die redoxaktive Verbindung (G) ein oder mehrere Verbindungen ist und ausgewählt wird aus der Gruppe bestehend aus CuCE. CU(BF4)2, CuCl, VC’k VOCE, NH4VO3, 1,4-Benzochinone, 1,4-Naphtochinone, SC2O5. Te02, Te02, Sb203, Sb20s, CeCE, Co(salen), Co(OAc)2, SnS04, Fe(acac)3, Mo(acac)3, K2Cr207, Mn(OAc)3, Ni(CF3C02H)2 und BiCE. Embodiment wherein the redox active compound (G) is present and the redox active compound (G) is one or more compounds and is selected from the group consisting of CuCE. CU(BF4)2, CuCl, VC'k VOCE , NH4VO3, 1,4-Benzoquinone, 1,4-Naphtoquinone, SC2O5. Te02, Te02, Sb203, Sb20s, CeCE, Co(salen), Co(OAc)2, SnS04, Fe(acac)3, Mo(acac)3, K2Cr207, Mn(OAc) 3 , Ni(CF 3 C02H) 2 and BiCE.
In einer vierundzwanzigsten Ausführungsform betrifft die Erfindung einIn a twenty-fourth embodiment, the invention relates to a
Epoxidierungskatalysatorsystem (2) gemäß einer der siebzehnten bis dreiundzwanzigstenThe epoxidation catalyst system (2) according to any one of the seventeenth to twenty-third
Ausführungsform, wobei das berechnete Stoffmengenverhältnis des Metallsalz (E) zu den Hydroxidgruppen des Hydroxids (B) von 1,000 mol zu 1,000 mol bis 6,000 mol zu 1,000 mol beträgt.Embodiment wherein the calculated molar ratio of the metal salt (E) to the hydroxide groups of the hydroxide (B) is from 1.000 moles to 1.000 moles to 6.000 moles to 1.000 moles.
In einer fünfündzwanzigsten Ausführungsform betrifft die Erfindung einIn a twenty-fifth embodiment, the invention relates to a
Epoxidierungskatalysatorsystem (2) gemäß einer der siebzehnten bis vierundzwanzigstenThe epoxidation catalyst system (2) according to any one of the seventeenth to twenty-fourth
Ausführungsform, wobei das berechnete Stoffmengenverhältnis des Metallsalz (E) zu der redoxaktiven Verbindung (G) von 0,100 mol zu 1,000 mol bis 10,000 mol zu 1,000 mol beträgt.Embodiment wherein the calculated molar ratio of the metal salt (E) to the redox-active compound (G) is from 0.100 mole to 1.000 mole to 10.000 mole to 1.000 mole.
In einer sechsundzwanzigsten Ausführungsform betrifft die Erfindung einIn a twenty-sixth embodiment, the invention relates to a
Epoxidierungskatalysatorsystem (2) gemäß einer der siebzehnten bis fünfündzwanzigstenThe epoxidation catalyst system (2) according to any one of the seventeenth to twenty-fifth
Ausführungsform, wobei das berechnete Stoffmengenverhältnis der Hydroxidgruppen des
Hydroxids (F) zu dem der redoxaktiven Verbindung (G) von 0,100 mol zu 1,000 mol bis 50,000 mol zu 1,000 mol beträgt. Embodiment, wherein the calculated molar ratio of the hydroxide groups of hydroxide (F) to that of the redox-active compound (G) is from 0.100 mol to 1.000 mol to 50.000 mol to 1.000 mol.
In einer siebenundzwanzigsten Ausführungsform betrifft die Erfindung einIn a twenty-seventh embodiment, the invention relates to a
Epoxidierungskatalysatorsystem (2) gemäß einer der siebzehnten bis sechsundzwanzigsten Ausführungsform, wobei das das Iod (12) in einem berechneten Stoffmengenanteil von 1 mol-% bis 2000 mol-% bezogen auf die Menge des Metallsalzes (A) eingesetzt wird. The epoxidation catalyst system (2) according to any one of the seventeenth to twenty-sixth embodiments, wherein the iodine (12) is used in a calculated mole fraction of 1 mol% to 2000 mol% based on the amount of the metal salt (A).
In einer achtundzwanzigsten Ausführungsform betrifft die Erfindung einIn a twenty-eighth embodiment, the invention relates to a
Epoxidierungskatalysatorsystem (2) gemäß einer der siebzehnten bis siebenundzwanzigsten Ausführungsform, wobei das Epoxidierungskatalysatorsystem (2) auf einem Katalysatorträger (H) aufgebracht wird unter Bildung eines geträgerten Epoxidierungskatalysatorsystem (2). The epoxidation catalyst system (2) according to any one of the seventeenth to twenty-seventh embodiments, wherein the epoxidation catalyst system (2) is supported on a catalyst support (H) to form a supported epoxidation catalyst system (2).
In einer neunundzwanzigsten Ausführungsform betrifft die Erfindung einIn a twenty-ninth embodiment, the invention relates to a
Epoxidierungskatalysatorsystem (2) gemäß der achtundzwanzigsten Ausführungsform, wobei der Katalysatorträger (H) eine oder mehrere Verbindung(en) ist und ausgewählt wird aus der Gruppe bestehend aus Metalloxide, Erdalkalicarbonate, Silicate Siliciumcarbide, Siliciumoxy Carbide, Siliciumnitride, Siliciumoxynitride und Siliciumdioxid, bevorzugt Aluminiumoxid Aluminiumdioxid, Silica, Titandioxid, Zircondioxid, Calciumcarbonat, Phyllo Silikate, wie Talkum, Kaolinite und Pyrophyllite, und Titandioxid. The epoxidation catalyst system (2) according to the twenty-eighth embodiment, wherein the catalyst support (H) is one or more compound(s) and is selected from the group consisting of metal oxides, alkaline earth carbonates, silicates, silicon carbides, silicon oxy carbides, silicon nitrides, silicon oxynitrides and silicon dioxide, preferably alumina aluminum dioxide , silica, titanium dioxide, zirconia, calcium carbonate, phyllosilicates such as talc, kaolinites and pyrophyllites, and titanium dioxide.
In einer dreißigsten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (2) gemäß der achtundzwanzigsten oder neunundzwanzigsten Ausführungsform, wobei das Epoxidierungskatalysatorsystem (2) in einem berechneten Massenanteil von 1,0 -Gew.-% bis 30,0- Gew.-% auf den Katalysatorträger (H) aufgebracht wird. In a thirtieth embodiment, the 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 support in a calculated mass fraction of from 1.0% to 30.0% by weight (H) is applied.
In einer einunddreißigsten Ausführungsform betrifft die Erfindung ein Epoxidierungskatalysatorsystem (2) gemäß einer der achtundzwanzigsten bis dreißigsten Ausführungsform, wobei das Epoxidierungskatalysatorsystem (2) mithilfe der Nassinfiltrationsmethode (wet-infiltration) oder der incipient-wetness Methode auf den Katalysatorträger (H) aufgebracht wird. In a thirty-first embodiment, the invention relates to an epoxidation catalyst system (2) according to one of the twenty-eighth to thirtieth embodiment, wherein the epoxidation catalyst system (2) is applied to the catalyst support (H) using the wet infiltration method (wet infiltration) or the incipient wetness method.
In einer zweiunddreißigsten Ausführungsform betrifft die Erfindung ein Verfahren zur Herstellung von Epoxiden umfassend der oxidativen Umsetzung eines Alkens in einem Reaktor in Gegenwart des Epoxidierungskatalysatorsystems (1) gemäß einer der ersten bis sechzehnten Ausführungsform oder des Epoxidierungskatalysatorsystems (2) gemäß einer der siebzehnten bis einunddreißigsten Ausführungsform.
In einer dreiunddreißigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß der zweiunddreißigsten Ausführungsform, wobei die oxidative Umsetzung im Reaktor in Gegenwart von Sauerstoff oder einem Sauerstoff-haltigen Gasgemisch erfolgt. In a thirty-second embodiment, the invention relates to a process for preparing epoxides comprising the oxidative reaction of an alkene in a reactor in the presence of the epoxidation catalyst system (1) according to one of the first to sixteenth embodiments or the epoxidation catalyst system (2) according to one of the seventeenth to thirty-first embodiments. In a thirty-third embodiment, the invention relates to a method according to the thirty-second embodiment, in which the oxidative reaction in the reactor takes place in the presence of oxygen or an oxygen-containing gas mixture.
In einer vierunddreißigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß der zweiunddreißigsten oder dreiunddreißigsten Ausführungsform, wobei das Alken eine oder mehrere Verbindung(en) ist und ausgewählt wird aus der Gruppe bestehend aus Ethen, Propen, Buten, 1- Okten, Butadien, 1,4-Butandioldiallylether, Allylchlorid, Allylalcohol, Styrol, Cyclopenten, Cyclohexen, Phenyl-allylether, Diallylether, n-Butyl-allylether, tert-Butyl-allylether, Bisphenol-A diallyl ether, Resorcindiallylether, Triphenylolmethan-triallylether, Cy clohexan- 1,2-dicarbonsäure- bis-(allylester), Isocyanursäuretris-(prop-2,3-en)-ester und Gemische dieser Alkene bevorzugt Ethen, Propen und Allylchlorid und besonders bevorzugt Propen. In a thirty-fourth embodiment, the invention relates to a process according to the thirty-second or thirty-third embodiment, wherein the alkene is one or more compound(s) and is selected from the group consisting of ethene, propene, butene, 1-octene, butadiene, 1,4 -Butanediol diallyl ether, allyl chloride, allyl alcohol, styrene, cyclopentene, cyclohexene, phenyl allyl ether, diallyl ether, n-butyl allyl ether, tert-butyl allyl ether, bisphenol-A diallyl ether, resorcinol diallyl ether, triphenylolmethane triallyl ether, cyclohexane-1,2- dicarboxylic acid bis(allyl ester), isocyanuric acid tris(prop-2,3-ene) ester and mixtures of these alkenes, preferably ethene, propene and allyl chloride and particularly preferably propene.
In einer fünfünddreißigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß einer der zweiunddreißigsten bis vierunddreißigsten Ausführungsform, wobei die Herstellung in Gegenwart eines Lösungsmittels erfolgt. In a thirty-fifth embodiment, the invention relates to a method according to one of the thirty-second to thirty-fourth embodiments, the production being carried out in the presence of a solvent.
In einer sechsunddreißigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß einem der fünfünddreißigsten Ausführungsform, wobei das Lösungsmittel eine oder mehrere Verbindung(en) und wird ausgewählt aus der Gruppe bestehend aus C02, Wasser , Perfluoromethyldecalin, Perfluorodecalin, Perfluoroperhydrophenanthren,In a thirty-sixth embodiment, the invention relates to a method according to one of the thirty-fifth embodiment, wherein the solvent is one or more compound(s) and is selected from the group consisting of CO 2 , water, perfluoromethyldecalin, perfluorodecalin, perfluoroperhydrophenanthrene,
Perfluoro(butyltetrahydrofüran), Tetrahydrofüran, 2-Methyl-THF, Essigsäure, Acetonitril, Dimethylsulfoxid, Sulfolan, Aceton, Ethylmethylketon, Dimethylformamid, Dichlormethan, Chloroform, Tetrachlormethan, N-methyl-2-pyrrolidinon, Methyl-t-butylether (MTBE), Dimrthylsulxid (DMSO), Hexamethylphosphoramid, Dichlorbenzol, 1,2-Dichloroethylen, 1,1,1,3,3,3-Hexafluoroisopropanol, Perfluoro-tert-butylalkohol, 1,1,2,3,3-Pentafluoropropan, 1- Brom-2-chlor- 1 , 1 ,2-trifluoroethan, 1 ,2-Dichloro- 1 , 1 ,2,3 ,3 ,3 -hexafluorpropan, Ethylenglycol, Glycerin, und Phenol. Perfluoro(butyltetrahydrofuran), tetrahydrofuran, 2-methyl-THF, acetic acid, acetonitrile, dimethyl sulfoxide, sulfolane, acetone, ethyl methyl ketone, dimethylformamide, dichloromethane, chloroform, tetrachloromethane, N-methyl-2-pyrrolidinone, methyl t-butyl ether (MTBE), Dimethyl Sulfide (DMSO), Hexamethylphosphoramide, Dichlorobenzene, 1,2-Dichloroethylene, 1,1,1,3,3,3-Hexafluoroisopropanol, Perfluoro-tert-butyl Alcohol, 1,1,2,3,3-Pentafluoropropane, 1-Bromo -2-chloro-1,1,2-trifluoroethane, 1,2-dichloro-1,1,2,3,3,3-hexafluoropropane, ethylene glycol, glycerine, and phenol.
In einer siebenunddreißigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß der fünfünddreißigsten oder sechsunddreißigsten Ausführungsform, wobei die Herstellung bei einer Temperatur von 20 °C bis 200 °C bevorzugt von 50 °C bis 160 °C und besonders bevorzugt von 100 °C bis 150 °C erfolgt. In a thirty-seventh embodiment, the invention relates to a method according to the thirty-fifth or thirty-sixth embodiment, wherein the production takes place at a temperature of 20°C to 200°C, preferably of 50°C to 160°C and particularly preferably of 100°C to 150°C he follows.
In einer achtunddreißigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß einer der fünfünddreißigsten bis siebenunddreißigsten Ausführungsform, wobei die Herstellung bei einem Druck von 1 bara bis 200 bara bevorzugt von 1 bara bis 35 bara und besonders bevorzugt von 1 bara bis 28 bara erfolgt.
In einer neununddreißigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß einer der fünfimddreißigsten bis achtunddreißigsten Ausführungsform, wobei die Herstellung in einem Zeitraum von 6 min bis 48 h, bevorzugt von 6 min bis 24 h und besonders bevorzugt von 6 min bis 3 h erfolgt. In a thirty-eighth embodiment, the invention relates to a method according to one of the thirty-fifth to thirty-seventh embodiments, the production taking place at a pressure of 1 bara to 200 bara, preferably 1 bara to 35 bara and particularly preferably 1 bara to 28 bara. In a thirty-ninth embodiment, the invention relates to a method according to one of the thirty-fifth to thirty-eighth embodiments, the production taking place in a period of 6 minutes to 48 hours, preferably 6 minutes to 24 hours and particularly preferably 6 minutes to 3 hours.
In einer vierzigsten Ausführungsform betrifft die Erfindung ein Verfahren einer der fünfimddreißigsten bis neununddreißigsten Ausführungsform, wobei das Stoffmengenverhältnis des Alkens zum Sauerstoff von 1: 100 bis 100: 1 bevorzugt von 1:30 bis 30: 1 beträgt. In a fortieth embodiment, the invention relates to a process of one of the thirty-fifth to thirty-ninth embodiments, wherein the molar ratio of the alkene to the oxygen is from 1:100 to 100:1, preferably from 1:30 to 30:1.
In einer einundvierzigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß einer der zweiunddreißigsten bis vierunddreißigsten Ausführungsform, wobei die Herstellung in Abwesenheit eines Lösungsmittels erfolgt. In a forty-first embodiment, the invention relates to a method according to one of the thirty-second to thirty-fourth embodiments, wherein the preparation takes place in the absence of a solvent.
In einer zweiundvierzigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß der einundvierzigsten Ausführungsform, wobei die Herstellung unter Verwendung des unter Verwendung des geträgerten Epoxidierungskatalysatorsystem (1) gemäß einer der dreizehnten bis sechzehnten Ausführungsform oder eines geträgerten Epoxidierungskatalysatorsystem (2) gemäß einer der achtundzwanzigsten bis einunddreißigsten Ausführungsform. In a forty-second embodiment, the invention relates to a method according to the forty-first embodiment, wherein the preparation using the using the supported epoxidation catalyst system (1) according to one of the thirteenth to sixteenth embodiment or a supported epoxidation catalyst system (2) according to one of the twenty-eighth to thirty-first embodiment.
In einer dreiundvierzigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß der einundvierzigsten oder zweiundvierzigsten Ausführungsform, wobei die Herstellung bei einer Temperatur von 20 °C bis 500 °C bevorzugt von 50 °C bis 400 °C und besonders bevorzugt von 50 °C bis 250 °C erfolgt. In a forty-third embodiment, the invention relates to a method according to the forty-first or forty-second embodiment, wherein the production takes place at a temperature of 20°C to 500°C, preferably of 50°C to 400°C and particularly preferably of 50°C to 250°C he follows.
In einer vierundvierzigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß einer der einundvierzigsten bis dreiundvierzigsten Ausführungsform, wobei die Herstellung bei einem Druck von 1 bara bis 200 bara bevorzugt von 2 bara bis 100 bara und besonders bevorzugt von 2 bara bis 50 bara erfolgt. In a forty-fourth embodiment, the invention relates to a method according to one of the forty-first to forty-third embodiments, the production taking place at a pressure of 1 bara to 200 bara, preferably 2 bara to 100 bara and particularly preferably 2 bara to 50 bara.
In einer fünfündvierzigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß einer der einundvierzigsten bis vierundvierzigsten Ausführungsform, wobei die Herstellung mit einer Raumgeschwindigkeit von 100 h-1 bis 10000 h-1, bevorzugt von 200 h-1 bis 5000 h-1 und besonders bevorzugt von 500 h-1 bis 2000 h-1 erfolgt. In a forty-fifth embodiment, the invention relates to a method according to one of the forty-first to forty-fourth embodiments, wherein the production takes place at a space velocity of 100 h-1 to 10000 h-1, preferably from 200 h-1 to 5000 h-1 and particularly preferably from 500 h-1 to 2000 h-1.
In einer sechsundvierzigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß einer der einundvierzigsten bis fünfündvierzigsten Ausführungsform, wobei das Stoffmengenverhältnis des Alkens zum Sauerstoff von 1,0:0, 1 bis 2,0: 1,0 bevorzugt von 1,0:0, 5 bis 2,0: 1,0 und besonders bevorzugt von 1,0:0, 8 bis 2,0: 1,0 beträgt.
In einer siebenundvierzigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß einer der zweiunddreißgsten bis sechsundvierzigsten Ausführungsform, wobei das Alken kontinuierlich oder stufenweise bevorzugt kontinuierlich in den Reaktor dosiert wird. In a forty-sixth embodiment, the invention relates to a method according to one of the forty-first to forty-fifth embodiments, wherein the molar ratio of the alkene to the oxygen is from 1.0:0.1 to 2.0:1.0, preferably from 1.0:0.5 to is 2.0:1.0 and more preferably from 1.0:0.8 to 2.0:1.0. In a forty-seventh embodiment, the invention relates to a process according to one of the thirty-second to forty-sixth embodiment, wherein the alkene is metered into the reactor continuously or in stages, preferably continuously.
In einer achtundvierzigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß einer der dreiunddreißigsten bis siebenundvierzigsten Ausführungsform, wobei der Sauerstoff oder das Sauerstoff-haltige Gasgemisch kontinuierlich oder stufenweise bevorzugt kontinuierlich in den Reaktor dosiert wird. In a forty-eighth embodiment, the invention relates to a method according to one of the thirty-third to forty-seventh embodiment, wherein the oxygen or the oxygen-containing gas mixture is metered into the reactor continuously or in stages, preferably continuously.
In einer neunundvierzigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß einer der dreiunddreißigsten bis achtundvierzigsten Ausführungsform, wobei das Alken und der Sauerstoff oder das Sauerstoff-haltige Gasgemisch kontinuierlich oder stufenweise bevorzugt kontinuierlich in den Reaktor dosiert wird. In a forty-ninth embodiment, the invention relates to a process according to one of the thirty-third to forty-eighth embodiments, the alkene and the oxygen or the oxygen-containing gas mixture being metered continuously or in stages, preferably continuously, into the reactor.
In einer fünfzigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß einer der siebenundvierzigsten bis neunundvierzigsten Ausführungsform, wobei das Epoxid kontinuierlich oder stufenweise bevorzugt kontinuierlich aus dem Reaktor entnommen wird. In einer einundfünfzigsten Ausführungsform betrifft die Erfindung ein Verfahren einer der siebenundvierzigsten bis fünfzigsten Ausführungsform, wobei das Epoxidierungskatalysatorsystem (1) und/oder Epoxidierungskatalysatorsystem (2) kontinuierlich oder stufenweise bevorzugt kontinuierlich in den Reaktor dosiert wird. In a fiftieth embodiment, the invention relates to a process according to one of the forty-seventh to forty-ninth embodiments, wherein the epoxide is removed from the reactor continuously or in stages, preferably continuously. In a fifty-first embodiment, the invention relates to a process of one of the forty-seventh to fiftieth embodiment, wherein the epoxidation catalyst system (1) and/or epoxidation catalyst system (2) is metered continuously or stepwise, preferably continuously, into the reactor.
In einer zweiundfünfzigsten Ausführungsform betrifft die Erfindung ein Verfahren gemäß einer der zweiunddreißigsten bis einundfünfzigsten Ausführungsform, wobei dasIn a fifty-second embodiment, the invention relates to a method according to one of the thirty-second to fifty-first embodiment, wherein the
Epoxidierungskatalysatorsystem (1) und/oder Epoxidierungskatalysatorsystem (2) in einer berechneten Menge von lO ppm bis 500.000 ppm bevorzugt von 100 ppm bis 200.000 ppm und besonders bevorzugt von 1000 ppm bis 150.000 ppm bezogen auf die Masse aller beteiligter Reaktanden und optional Lösungsmittel und möglicher weiterer Hilfsstoffe eingesetzt wird.
Epoxidation catalyst system (1) and/or epoxidation catalyst system (2) in a calculated amount of 10 ppm to 500,000 ppm, preferably 100 ppm to 200,000 ppm and particularly preferably 1000 ppm to 150,000 ppm, based on the mass of all reactants involved and optionally solvents and possible others Auxiliaries is used.
Beispiele examples
Verwendete Ausgangsstoffe: Raw materials used:
Metallchloride und Metalloxide: Alle eingesetzten Metallsalze werden direkt aus kommerziellen Quellen bezogen und ohne weitere Aufarbeitung als Vorstufen für die aktiven Katalysatoren in die entsprechenden Reaktionen eingesetzt: Metal chlorides and metal oxides: All metal salts used are obtained directly from commercial sources and used without further processing as precursors for the active catalysts in the corresponding reactions:
Molybdän-(V)-chlorid des Herstellers Sigma Aldrich Corporation in einer Reinheit von 95%. Mangan-(II) -chlorid des Herstellers Sigma Aldrich Corporation in einer Reinheit von 99%. Chrom-(VI)-oxychlorid des Herstellers Sigma Aldrich Corporation in einer Reinheit von 99%. Blei-(II)-chlorid des Herstellers Sigma Aldrich Corporation in einer Reinheit von 98%. Bismuth-(III)-chlorid des Herstellers Sigma Aldrich Corporation in einer Reinheit von 98%. Kupfer-(II)-chlorid des Herstellers Sigma Aldrich Corporation in einer Reinheit von 97%. Nickel-(II)-chlorid des Herstellers Sigma Aldrich Corporation in einer Reinheit von 98%. Zinn-(II)-chlorid des Herstellers Sigma Aldrich Corporation in einer Reinheit von 98%. Molybdän-(VI)-oxychlorid wurde in Anlehnung an Vitzthumecker et al. in Monatsh. Chem. 148, 629-633 (2017) hergestellt. Molybdenum (V) chloride from the manufacturer Sigma Aldrich Corporation in a purity of 95%. Manganese (II) chloride from the manufacturer Sigma Aldrich Corporation in a purity of 99%. Chromium (VI) oxychloride from the manufacturer Sigma Aldrich Corporation in a purity of 99%. Lead (II) chloride from the manufacturer Sigma Aldrich Corporation with a purity of 98%. Bismuth (III) chloride from the manufacturer Sigma Aldrich Corporation in a purity of 98%. Copper (II) chloride from the manufacturer Sigma Aldrich Corporation in a purity of 97%. Nickel(II) chloride from the manufacturer Sigma Aldrich Corporation with a purity of 98%. Tin(II) chloride from the manufacturer Sigma Aldrich Corporation with a purity of 98%. Molybdenum(VI) oxychloride was based on Vitzthumecker et al. in month Chem. 148, 629-633 (2017).
Elementares Iod, Triton B und alle verwendeten Lösungsmittel wurden ebenfalls wurden ebenfalls ohne weitere Aufarbeitung in die Reaktionsführung eingesetzt: Elemental iodine, Triton B and all solvents used were also used in the reaction without further processing:
Iod des Herstellers Sigma Aldrich Corporation in einer Reinheit von 99,8%. Iodine from the manufacturer Sigma Aldrich Corporation in a purity of 99.8%.
Tetrathydrofüran (THF) des Herstellers Sigma Aldrich Corporation in einer Reinheit von 99,9% (Inhibitorfrei). Tetrahydrofuran (THF) from the manufacturer Sigma Aldrich Corporation with a purity of 99.9% (inhibitor-free).
Benzyltrimethylammoniumhydroxid (Triton B) des Herstellers Sigma Aldrich Corporation als 40%-ige Lösung in Methanol. Benzyltrimethylammonium hydroxide (Triton B) from Sigma Aldrich Corporation as a 40% solution in methanol.
Propylen wurde vom Hersteller Sigma Aldrich Corporation in einer Reinheit von 99,9% bezogen und wie erhältlich eingesetzt. Propylene was obtained from Sigma Aldrich Corporation at 99.9% purity and used as received.
Die Chemikalien werden ohne weitere Aufreinigung für die Synthese eingesetzt. The chemicals are used for the synthesis without further purification.
Gaschromatographie- Analytik Gas chromatography analysis
Die gaschromatographische Analyse (kurz GC) von Flüssig- und Gasproben wurde in Anlehnung an „Determine Impurities in High-Purity Propylene Oxide with Agilent J&W PoraBOND U“ von Dianli Ma, Ningbo ZRCC Lyondell Chemical Co., Ltd Zhejiang, China, und Yun Zou, Hua Wu, Agilent
Technologies, Ine. durchgeführt. Auf Basis von GC wurden Umsätze an Propene, Ausbeuten an Propylenoxide und Selektivitäten ermittelt. The gas chromatographic analysis (GC for short) of liquid and gas samples was based on "Determine Impurities in High-Purity Propylene Oxide with Agilent J&W PoraBOND U" by Dianli Ma, Ningbo ZRCC Lyondell Chemical Co., Ltd Zhejiang, China, and Yun Zou , Hua Wu, Agilent Technologies, Ine. carried out. Conversions of propenes, yields of propylene oxides and selectivities were determined on the basis of GC.
Simulationsmethode simulation method
Alle quantenmechanischen Berechnungen wurden dabei mit dem Programmpaket TURBOMOLE Version 7.4.1 der Firma Cosmologic GmbH & Co. KG durchgeführt. Die verwendete Dichtefünktionaltheoretische Methode war das TPSS-Dichtefünktional, ausgeführt als unrestricted- DFT für Spincontamination offenschaliger Systeme, mit einem def2-SVP-Basissatz, so wie standardmäßig im Turbomole-Programmpaket implementiert. Die erhaltenen Energien wurden mit der beschrieben DFT-Methode und einem Basissatz der Qualität def2-TZVP verfeinert. All quantum mechanical calculations were carried out with the program package TURBOMOLE Version 7.4.1 from Cosmologic GmbH & Co. KG. The density functional theory method used was the TPSS density functional, executed as an unrestricted-DFT for spin contamination of open-shell systems, with a def2-SVP basis set, as implemented by default in the Turbomole program package. The energies obtained were refined using the described DFT method and a basis set of quality def2-TZVP.
Übergangszustände wurden mittels Gradient basiertem Monte Carlo berechnet, wie in Anmeldung WO 2020/079094A2 beschrieben. Transition states were calculated using gradient based Monte Carlo as described in application WO 2020/079094A2.
Herstellung des Epoxidierungskatalysatorsystems (1). Preparation of the epoxidation catalyst system (1).
Die in den Tabellen 1 und 2 aufgeführten Epoxidierungskatalysatorsysteme wurden wie in den allgemeinen Versuchsvorschriften beschrieben hergestellt und eingesetzt. The epoxidation catalyst systems listed in Tables 1 and 2 were prepared and used as described in the general experimental specifications.
Allgemeine Arbeitsvorschrift für die in Situ-Svnthese des Epoxidierungskatalvsatorsvstem (1) General working instructions for the in situ synthesis of the epoxidation catalyst system (1)
In einem Reaktionsgefäß mit Rührvorrichtung und Schutzgasbegasung wurden 200 mL Tetrahydrofüran unter Inertbedingungen vorgelegt. Dem Lösemittel wurden in jedem Versuch 0,020 mol des Metall(oxy)chlorids der entsprechenden Oxidationstufe (siehe Tabelle 1, 1-5) und 0,020 mol CuCh als redoxaktive Verbindung (C) unter Schutzgasgegenstrom zugesetzt. Unter kräftigem Rühren wurde jeweils so lange N-Benzyltrimethylammoniumhydroxid (Handelsname Triton B) eingerührt bis eine entnommene Flüssigprobe in Kontakt mit einem Wasser-feuchtem pH- Teststreifen einen pH-Wert von 10-11 ergab. 200 mL of tetrahydrofuran were placed under inert conditions in a reaction vessel with a stirrer and protective gas aeration. In each experiment, 0.020 mol of the metal (oxy)chloride of the corresponding oxidation state (see Table 1, 1-5) and 0.020 mol of CuCh as the redox-active compound (C) were added to the solvent under protective gas countercurrent. With vigorous stirring, N-benzyltrimethylammonium hydroxide (trade name Triton B) was stirred in until a liquid sample taken in contact with a pH test strip moistened with water showed a pH value of 10-11.
Die so erzeugte Suspension wurde ohne weitere Aufreinigung für die Oxidation von Propen eingesetzt.
Tabelle 1: Übersicht über die eingesetzten Epoxidierungskatalysatorsysteme (1) zur oxidativen Umsetzung von Propen
The suspension produced in this way was used for the oxidation of propene without further purification. Table 1: Overview of the epoxidation catalyst systems (1) used for the oxidative conversion of propene
(Vgl.) Vergleichsbeispiel Herstellung des Epoxidierungskatalysatorsystems (2). (Ref.) Comparative Example Preparation of Epoxidation Catalyst System (2).
Allgemeine Arbeitsvorschrift für die in Situ-Synthese des Epoxidierungskatalysatorsystem (2) General Procedure for the In Situ Synthesis of the Epoxidation Catalyst System (2)
In einem Reaktionsgefaß mit Rührvorrichtung und Schutzgasbegasung wurden ein Gemisch aus 180 mL Tetrahydrofuran und 20 mL Wasser unter Inertbedingungen vorgelegt. Dem Lösemittelgemisch wurden 0,020 mol des Metall(oxy)chlorids der entsprechenden Oxidationstufe (siehe Tabelle 2, 9-12) und 0,040 mol (5,1 g) elementares Iod unter Schutzgasgegenstrom zugesetzt. Unter kräftigem Rühren wurde so lange N-Benzyltrimethylammoniumhydroxid (Handelsname Triton B) eingerührt bis eine entnommene Flüssigprobe in Kontakt mit einem Wasser-feuchtem pH- Teststreifen einen pH-Wert von 10-11 ergab. Die so erzeugte Suspension wurde ohne weitere Aufreinigung für die Oxidation von Propen eingesetzt.
Tabelle 2: Übersicht über die eingesetzten Epoxidierungskatalysatorsysteme (2) zur oxidativen Umsetzung von Propen
A mixture of 180 mL of tetrahydrofuran and 20 mL of water was placed under inert conditions in a reaction vessel with a stirrer and inert gas aeration. 0.020 mol of the metal (oxy)chloride of the corresponding oxidation state (see Table 2, 9-12) and 0.040 mol (5.1 g) of elementary iodine were added to the solvent mixture under protective gas countercurrent. With vigorous stirring, N-benzyltrimethylammonium hydroxide (trade name Triton B) was stirred in until a liquid sample taken in contact with a pH test strip moistened with water showed a pH value of 10-11. The suspension produced in this way was used for the oxidation of propene without further purification. Table 2: Overview of the epoxidation catalyst systems (2) used for the oxidative conversion of propene
R2=R3=R4=Methyl R2 = R3 = R4 =methyl
Simulationsergebnisse für das Verfahren zur Herstellung von Propylenoxid durch Oxidation von Propen in Gegenwart des Epoxidierungskatalysatorsystems (1). Simulation results for the process of producing propylene oxide by oxidation of propene in the presence of the epoxidation catalyst system (1).
Im Folgenden wurden die Aktivierungsenergien für die katalytischen Reaktionen mittels quantenchemischer Simulationen berechnet. Dazu wurde jeweils eine Struktur gemäß der Übergangszustände A TI - B T2 gezeichnet (Abbildung 1). Die fett eingezeichneten Bindungen wurden auf einen Atomabstand von jeweils 1,90 Ä (190 pm) gesetzt, im Fall von A T2 auf 1,30 Ä und die so erhaltenen Strukturen in kartesische Koordinaten übersetzt. Die Atomindices im kartesischen Koordinatensatz der in Abbildung 3 fett eingezeichneten Bindungen wurden in dem Gradient basierten Monte Carlo Programm als Funktionsraum gesetzt und die Monte Carlo Prozedur so lange ausgeführt bis die entsprechenden Übergangszustände A TI - B T2 erhalten wurden. Danach wurden die so erhaltenen Kartesischen Koordinaten der Strukturen A TI - B T2 manipuliert um die dazugehörigen Edukt-katalysatorkomplexe bzw. die dazugehörigen Katalysator- Produktkomplexe zu erhalten. Dazu wurde jeweils eine der fett gezeichneten Bindungen (Abbildung 3) um DC=0,20 Ä (20 pm) i) verlängert und ii) verkürzt. Die so erhaltenen Strukturen i) und ii) wurden in Form kartesischer Koordinaten gebracht, einer Geometrieoptimierung mit der beschriebenen DFT-Methode unterworfen und die erhaltenen Geometrien für die Berechnung der Aktivierungsenergien verwendet. Die jeweils ausgewählten Bindungen sind in Tabelle 3 zusammengestellt.
Tab. 3: Auswahl der Bindungen zur Manipulation zum Erhalt der Gleichgewichtsstrukturen.
In the following, the activation energies for the catalytic reactions were calculated using quantum chemical simulations. For this purpose, a structure according to the transition states A TI - B T2 was drawn (Figure 1). The bonds in bold were set to an atomic distance of 1.90 Å (190 pm) each, in the case of A T2 to 1.30 Å, and the resulting structures were translated into Cartesian coordinates. The atomic indices in the Cartesian coordinate set of the bonds drawn in bold in Figure 3 were set as a function space in the gradient-based Monte Carlo program and the Monte Carlo procedure was carried out until the corresponding transition states A TI - B T2 were obtained. The Cartesian coordinates of the structures A TI - B T2 obtained in this way were then manipulated in order to obtain the associated educt-catalyst complexes or the associated catalyst-product complexes. For this purpose, one of the bonds drawn in bold (Figure 3) was i) lengthened and ii) shortened by DC=0.20 Å (20 pm). The structures i) and ii) obtained in this way were brought into the form of Cartesian coordinates, subjected to geometry optimization using the DFT method described, and the geometries obtained were used to calculate the activation energies. The bonds selected in each case are compiled in Table 3. Table 3: Selection of the bonds for manipulation to obtain the equilibrium structures.
Abb. 1: Dreistufiger Reaktionsmechanismus der oxidativen Hydroxylierung von Propen mit Hydroxid unter Metallkatalyse.
Fig. 1: Three-step reaction mechanism for the oxidative hydroxylation of propene with hydroxide under metal catalysis.
Der in Abbildung 1 beschriebene Dreistufenmechanismus wurde durch quantenchemische Simulation für verschiedene Katalysatoren berechnet und die Aktivierungsenergien aus der jeweiligen Reaktionssequenz bestimmt. Die so erhaltene Abschätzung der Aktivierungsenergien wurde zur Bewertung verschiedener Metallverbindungen als potenzielle Katalysatoren für die oxidative Hydroxylierung heran gezogen. Die Ergebnisse der Simulationen sind in Tabelle 4 zusammengefasst.
Tab. 4: Vergleich der quantenchemisch simulierten Aktivierungsenergien für die oxidative Umsetzung von Propen mit verschiedenen Epoxidierungskatalysatorsystemen (1).
The three-step mechanism described in Figure 1 was calculated by quantum chemical simulation for different catalysts and the activation energies were determined from the respective reaction sequence. The obtained activation energy estimate was used to evaluate different metal compounds as potential catalysts for the oxidative hydroxylation. The results of the simulations are summarized in Table 4. Tab. 4: Comparison of the quantum chemically simulated activation energies for the oxidative conversion of propene with different epoxidation catalyst systems (1).
(Vgl.) Vergleichsbeispiel; Q(l) = Benzyltrimethylammonium mit Q = N; Ri = Benzyl, R2=R3=R4=Methyl a) Annahme das der THF Ligand vor der oxidativen Umsetzung aus dem komplexen Epoxidierungskatalysatorsystemen (1) mindestens teilweise durch Propen verdrängt wird. (Comp.) Comparative Example; Q(l) = benzyltrimethylammonium with Q = N; R 1 =benzyl, R 2 =R 3 =R 4 =methyl a) Assumption that the THF ligand is at least partially displaced by propene from the complex epoxidation catalyst system (1) before the oxidative conversion.
Die in Tabelle 4 zusammengestellten Ergebnisse zeigen dass insbesondere die Aktivierungsenergien der Hydroxylierung des Propens und der reduktiven Eliminierung des gebildeten Propylenoxids stark von dem jeweiligen als Katalysator füngierenden Metall abhängen. Dadurch ist die mögliche Auswahl der untersuchten Metallverbindungen als Katalysatoren für die oxidative Hydroxylierung auf bestimmte Metalle beschränkt. Geeignete Metalle sind vor allem Mo(V), Mn(IV), Cr(VI), Bi(V) und Pb(IV).
Simulationsergebnisse für das Verfahren zur Herstellung von Propylenoxid durch Oxidation von Propen in Gegenwart des Epoxidierungskatalysatorsystems (2). The results summarized in Table 4 show that in particular the activation energies of the hydroxylation of the propene and the reductive elimination of the propylene oxide formed depend strongly on the particular metal functioning as a catalyst. As a result, the possible selection of the investigated metal compounds as catalysts for the oxidative hydroxylation is limited to certain metals. Suitable metals are, above all, Mo(V), Mn(IV), Cr(VI), Bi(V) and Pb(IV). Simulation results for the process of producing propylene oxide by oxidation of propene in the presence of the epoxidation catalyst system (2).
In einer weiteren Ausführung B des Verfahrens wird das Epoxidierungskatalysatorsystem (2), bestehend aus dem Metallsalz (E), elementarem Iod und dem Hydroxid (F) verwendet. Diese Mischung (2) wird mit Propen beladen, wobei zuerst das Hydroxid an die Doppelbindung des Propens angelagert wird. In einem zweiten Schritt wird dann Iod in die Metall -Kohlenstoffbindung insertiert, wobei ein Iodhydrin freigesetzt wird. Dieses zerfallt im leicht basischen Milieu zu Propylenoxid und Iodid, welches durch Zuführung von Sauerstoff zu elementarem Iod zurück oxidiert wird. Der Metallkatalysator stellt dabei eine kontrollierte Anlagerung von Hydroxid und Iod zu intermediärem Iodhydrin sicher, ohne dass überwiegend unbrauchbare 1,2-Diiodalkane gebildet werden. Verglichen mit der bekannten Chlorhydroxylierung kann das Iod hier in katalytischen oder substöchiometrischen Mengen eingesetzt werden. So kann die Oxidation direkt mit Sauerstoff erfolgen. In a further embodiment B of the process, the epoxidation catalyst system (2) consisting of the metal salt (E), elemental iodine and the hydroxide (F) is used. This mixture (2) is loaded with propene, with the hydroxide first being added to the double bond of the propene. In a second step, iodine is then inserted into the metal-carbon bond, releasing an iodohydrin. This decomposes in a slightly basic environment to form propylene oxide and iodide, which is oxidized back to elemental iodine by supplying oxygen. The metal catalyst ensures controlled addition of hydroxide and iodine to form intermediate iodohydrin without the formation of predominantly useless 1,2-diiodoalkanes. Compared to the known chlorohydroxylation, the iodine can be used here in catalytic or substoichiometric amounts. The oxidation can thus take place directly with oxygen.
Hierzu wurden quantenchemische Simulationen durchgeführt um geeignete Metallkatalysatoren zu identifizieren. For this purpose, quantum chemical simulations were carried out to identify suitable metal catalysts.
Tab. 5: Vergleich der quantenchemisch simulierten Aktivierungsenergien für die Iodhydroxylierung von Propen mit verschiedenen Metallkatalysatoren.
Tab. 5: Comparison of the quantum chemically simulated activation energies for the iodohydroxylation of propene with different metal catalysts.
(Vgl.) Vergleichsbeispiel; Q(l) = Benzyltrimethylammonium mit Q = N; Ri = Benzyl, R2=R3=R4=Methyl; a) Annahme das der THF Ligand vor der oxidativen Umsetzung aus dem komplexen Epoxidierungskatalysatorsystemen (1) mindestens teilweise durch Propen und Iod verdrängt wird. (Comp.) Comparative Example; Q(l) = benzyltrimethylammonium with Q = N; Ri=benzyl, R2=R3=R4=methyl; a) Assumption that the THF ligand is at least partially displaced by propene and iodine before the oxidative conversion from the complex epoxidation catalyst system (1).
Die in Tabelle 5 zusammengefassten Simulationsergebnisse zeigen dass die Aktivierungsenergie der Iodinsertion wesentlich von den eingesetzten Metallkatalysatoren abhängt. Insbesondere Mn(II), Sn(II) und Pb(II), aber auch Ni(II) werden hierdurch für die Reaktion als Katalysatoren als geeignet identifiziert. The simulation results summarized in Table 5 show that the activation energy of the iodine insertion essentially depends on the metal catalysts used. Mn(II), Sn(II) and Pb(II) in particular, but also Ni(II) are thereby identified as suitable catalysts for the reaction.
Abb. 2: zweistufiger Reaktionsmechanismus für die metallkatalysierte Iodhydroxylierung von Propen.
Fig. 2: Two-step reaction mechanism for the metal-catalyzed iodohydroxylation of propene.
Abb. 3: Input-Geometrien für die quantenchemischen Berechnungen der Übergangszustände der katalysierten oxidativen Hydroxylierungen A und Jodhydroxylierungen B.
Fig. 3: Input geometries for the quantum chemical calculations of the transition states of the catalyzed oxidative hydroxylation A and iodohydroxylation B.
B T1 B T2 B T1 B T2
Allgemeine Versuchsvorschrift für das Verfahren zur Herstellung von Propylenoxid durch Oxidation von Propen in Gegenwart des Epoxidierungskatalysatorsystems (1) in einem diskontinuierlichem Rührkessel. General experimental procedure for the process for preparing propylene oxide by oxidizing propene in the presence of the epoxidation catalyst system (1) in a discontinuous stirred tank.
In einem druckfesten lL-Reaktor mit Rührwerk, Überdruckabsicherung, Druckaufnehmer, Steigrohr zur Flüssigkeitsentnahme sowie Be- und Entgasungsleitungen wurden 200 mL Tetrahydrofuran unter Inertbedingungen vorgelegt. Dem Lösemittel wurden in jedem Versuch 0,020 mol des Metallchlorid der entsprechenden Oxidationstufe (siehe Tabelle 1, 1-5) und 0,020 mol CuC12 unter Schutzgasgegenstrom zugesetzt. Unter kräftigem Rühren wurde jeweils so lange N-Benzyltrimethylammoniumhydroxid (Handelsname Triton B)
eingerührt bis eine entnommene Flüssigprobe in Kontakt mit einem Wasser-feuchtem pH- Teststreifen einen pH-Wert von 10-11 ergab. Das Reaktionsgefäß wurde anschließend mit 0,400 mol Propen beaufschlagt (ca. 11 bar). Die Reaktorinnentemperatur wurde auf 120°C eingeregelt und es wurde langsam so lange Sauerstoff aufgepresst bis eine Stoffmenge von 0,200 mol Sauerstoff erreicht wurde. Die Zugabe des Sauerstoffs wurde so durchgeführt, dass der zusätzliche Druckanstieg nie mehr als 2 bar betrug. Der Reaktionsfortschritt und - Endpunkt wurde anhand des Druckverlaufs und/oder durch Entnahme von Flüssig- und Gasproben und Analyse per GC analysiert ermittelt. Nach Beendigung der Reaktion wurde der Reaktor auf 40 °C abgekühlt, anschließend entspannt und das Reaktionsprodukt Propylenoxid über die Entgasungsleitung in eine gekühlte Vorlage abdestilliert. 200 mL of tetrahydrofuran were placed under inert conditions in a pressure-resistant IL reactor with stirrer, overpressure protection, pressure sensor, riser pipe for removing liquid and gassing and degassing lines. In each experiment, 0.020 mol of the metal chloride of the appropriate oxidation state (see Table 1, 1-5) and 0.020 mol of CuCl2 were added to the solvent under protective gas countercurrent. With vigorous stirring, N-benzyltrimethylammonium hydroxide (trade name Triton B) stirred until a liquid sample taken in contact with a water-moist pH test strip showed a pH value of 10-11. The reaction vessel was then charged with 0.400 mol of propene (about 11 bar). The internal temperature of the reactor was regulated to 120° C. and oxygen was slowly forced in until a substance amount of 0.200 mol of oxygen was reached. The oxygen was added in such a way that the additional pressure rise was never more than 2 bar. The progress of the reaction and the end point were determined based on the pressure profile and/or by taking liquid and gas samples and analyzing them by GC. After the reaction had ended, the reactor was cooled to 40° C. and then let down and the reaction product, propylene oxide, was distilled off via the degassing line into a cooled receiver.
Die Ausbeute an Propylenoxid betrugen dabei 23,2 g für alle fünf Versuche. The yield of propylene oxide was 23.2 g for all five runs.
Allgemeine Versuchsvorschrift für das Verfahren zur Herstellung von Propylenoxid durch Oxidation von Propen in Gegenwart des Epoxidierungskatalysatorsystems (2) in einem diskontinuierlichem Rührkessel. General experimental procedure for the process for preparing propylene oxide by oxidizing propene in the presence of the epoxidation catalyst system (2) in a discontinuous stirred tank.
In einem druckfesten lL-Reaktor mit Rührwerk, Überdruckabsicherung, Druckaufnehmer, Steigrohr zur Flüssigkeitsentnahme sowie Be- und Entgasungsleitungen wurden ein Gemisch aus 180 mL Tetrahydrofuran und 20 mL Wasser unter Inertbedingungen vorgelegt. Dem Lösemittelgemisch wurden 0,020 mol des Metallchlorid der entsprechenden Oxidationstufe (siehe Tabelle 2, 9-12) und 0,040 mol (5,1 g) elementares Iod unter Schutzgasgegenstrom zugesetzt. Unter kräftigem Rühren wurde so lange N- Benzyltrimethylammoniumhydroxid (Handelsname Triton B) eingerührt bis eine entnommene Flüssigprobe in Kontakt mit einem Wasser-feuchtem pH-Teststreifen einen pH-Wert von 10-11 ergab. Das Reaktionsgefäß wurde anschließend mit 0,400 mol Propen beaufschlagt (ca. 11 bar). Die Reaktorinnentemperatur wurde auf 120°C eingeregelt und es wurde langsam so lange Sauerstoff aufgepresst, bis eine Stoffmenge von 0,200 mol Sauerstoff erreicht wurde. Die Zugabe des Sauerstoffs wurde so durchgeführt, dass der zusätzliche Druckanstieg nie mehr als 2 bar betrug. Der Reaktionsfortschritt und -Endpunkt wurde anhand des Druckverlaufs und/oder durch Entnahme von Flüssig- und Gasproben und Analyse per GC analysiert ermittelt. Nach Beendigung der Reaktion wurde der Reaktor auf 40 °C abgekühlt, anschließend entspannt und das Reaktionsprodukt Propylenoxid über die Entgasungsleitung in eine gekühlte Vorlage abdestilliert. A mixture of 180 mL of tetrahydrofuran and 20 mL of water was placed under inert conditions in a pressure-resistant IL reactor with a stirrer, overpressure protection, pressure sensor, riser pipe for taking off liquid and gassing and degassing lines. 0.020 mol of the metal chloride of the corresponding oxidation state (see Table 2, 9-12) and 0.040 mol (5.1 g) of elementary iodine were added to the solvent mixture under protective gas countercurrent. With vigorous stirring, N-benzyltrimethylammonium hydroxide (trade name Triton B) was stirred in until a liquid sample taken in contact with a pH test strip moistened with water showed a pH value of 10-11. The reaction vessel was then charged with 0.400 mol of propene (about 11 bar). The internal temperature of the reactor was regulated to 120° C. and oxygen was slowly forced in until a substance amount of 0.200 mol of oxygen was reached. The oxygen was added in such a way that the additional pressure rise was never more than 2 bar. The progress of the reaction and the end point of the reaction were determined based on the pressure profile and/or by taking liquid and gas samples and analyzing them by GC. After the reaction had ended, the reactor was cooled to 40° C. and then let down and the reaction product, propylene oxide, was distilled off via the degassing line into a cooled receiver.
Die Ausbeute an Propylenoxid betrugen dabei 23,2 g für alle vier Versuche.
Allgemeine Versuchsvorschrift für das Verfahren zur Herstellung von Propylenoxid durch Oxidation von Propen in Gegenwart des Epoxidierungskatalysatorsystems (1) in einem einer kontinuierlichen Ein-Blasensäulenreaktor. The yield of propylene oxide was 23.2 g for all four experiments. General experimental procedure for the process for the production of propylene oxide by the oxidation of propene in the presence of the epoxidation catalyst system (1) in a continuous single-bubble column reactor.
In eine druckfeste Blasensäule (15 cm Durchmesser) mit Begasungsfritte, Überdruckabsicherung, Druckaufnehmer, obere und untere Flüssigkeitsentnahme, oberen Zugabepunkt für Feststoffe sowie Zu- und Ableitungen für Gase wurden 3500 mL Tetrahydrofuran unter Inertbedingungen vorgelegt. Dem Lösemittel wurden in jedem Versuch 0,350 mol des Metallchlorid der entsprechenden Oxidationstufe (siehe Tabelle 1, 1-5) und 0,350 mol CuC12 unter Schutzgasgegenstrom zugesetzt. Unter Begasen mit N2 mit 10 L/min wurde so lange N-Benzyltrimethylammoniumhydroxid (Handelsname Triton B) zugegeben bis eine entnommene Flüssigprobe in Kontakt mit einem Wasser-feuchtem pH- Teststreifen einen pH-Wert von 10-11 ergab. Die Blasensäule wurde anschließend auf Reaktionstemperatur gebracht 120 °C und mit einem Gasgemisch aus Propen, Sauerstoff und Stickstoff (Stoffmengenverhältnis Propen zu Sauerstoff 2:1) angeströmt wobei ein Gesamtvolumenstrom von weniger als 10 L/min eingeregelt wurde. Der Reaktionsfortschritt bzw. -stationärpunkt wurde durch Entnahme von Flüssig- und Gasproben an den oberen Entnahmepunkten und deren Analyse per GC ermittelt. Das kontinuierlich erzeugte Produktgasgemisch wurde durch kaskadiertes Auskühlen von Propylenoxid befreit und der resultierende Gasstrom erneut leicht verdichtet und in Abmischung mit Propen, Sauerstoff und Stickstoff die Begasungsfritte der Blasensäule angeströmt. 3500 mL tetrahydrofuran were placed under inert conditions in a pressure-resistant bubble column (15 cm diameter) with gassing frit, overpressure protection, pressure sensor, upper and lower liquid outlet, upper addition point for solids and inlet and outlet lines for gases. In each experiment, 0.350 mol of the metal chloride of the corresponding oxidation state (see Table 1, 1-5) and 0.350 mol of CuCl2 were added to the solvent under protective gas countercurrent. While gassing with N2 at 10 L/min, N-benzyltrimethylammonium hydroxide (trade name Triton B) was added until a liquid sample taken in contact with a water-moist pH test strip showed a pH value of 10-11. The bubble column was then brought to the reaction temperature of 120° C. and a gas mixture of propene, oxygen and nitrogen (molar ratio of propene to oxygen 2:1) flowed therethrough, with a total volume flow of less than 10 L/min being regulated. The progress of the reaction or the stationary point was determined by taking liquid and gas samples at the upper sampling points and analyzing them by GC. The product gas mixture produced continuously was freed from propylene oxide by cascaded cooling and the resulting gas stream was again slightly compressed and mixed with propene, oxygen and nitrogen and flowed onto the gassing frit of the bubble column.
Die Selektivitäten zu Propylenoxid betrugen dabei zwischen 95 und 100% in allen fünf Versuchen). The selectivities to propylene oxide were between 95 and 100% in all five experiments.
Allgemeine Versuchsvorschrift für das Verfahren zur Herstellung von Propylenoxid durch Oxidation von Propen in Gegenwart des Epoxidierungskatalysatorsystems (2) in einem kontinuierlichen Ein-Blasensäulenreaktor. General experimental procedure for the process for the production of propylene oxide by the oxidation of propene in the presence of the epoxidation catalyst system (2) in a continuous single-bubble column reactor.
In eine druckfeste Blasensäule (15 cm Durchmesser) mit Begasungsfritte, Überdruckabsicherung, Druckaufnehmer, obere und untere Flüssigkeitsentnahme, oberer Zugabepunkt für Feststoffe sowie Zu- und Ableitungen für Gase wurden 3150 mL Tetrahydrofuran und 350 mL Wasser unter Inertbedingungen vorgelegt. Dem Lösemittelgemisch wurden in jedem Versuch 0,350 mol des Metallchlorid der
entsprechenden Oxidationstufe (siehe Tabelle 2, 9-12) und 0,700 mol (89,3 g) elementares Iod unter Schutzgasgegenstrom zugesetzt. Unter Begasen mit N2 mit 10 L/min wurde so lange N-Benzyltrimethylammoniumhydroxid (Handelsname Triton B) zugegeben bis eine entnommene Flüssigprobe in Kontakt mit einem Wasser-feuchtem pH-Teststreifen einen pH-Wert von 10-11 ergab. Die Blasensäule wurde anschließend auf Reaktionstemperatur gebracht 120 °C und mit einem Gasgemisch aus Propen, Sauerstoff und Stickstoff (Stoffmengenverhältnis Propen zu Sauerstoff 2:1) angeströmt wobei ein Gesamtvolumenstrom von weniger als 10 L/min eingeregelt wurde. Der Reaktionsfortschritt bzw. -stationärpunkt wurde durch Entnahme von Flüssig- und Gasproben an den oberen Entnahmepunkten und deren Analyse per GC ermittelt. Das kontinuierlich erzeugte Produktgasgemisch wurde durch kaskadiertes Auskühlen von Propylenoxid befreit und der resultierende Gasstrom erneut leicht verdichtet und in Abmischung mit Propen, Sauerstoff und Stickstoff die Begasungsfritte der Blasensäule angeströmt. 3150 mL tetrahydrofuran and 350 mL water were placed under inert conditions in a pressure-resistant bubble column (15 cm diameter) with gassing frit, overpressure protection, pressure sensor, upper and lower liquid outlet, upper addition point for solids and inlet and outlet lines for gases. In each experiment, 0.350 mol of the metal chloride were added to the solvent mixture corresponding oxidation state (see Table 2, 9-12) and 0.700 mol (89.3 g) of elemental iodine were added under protective gas countercurrent. While gassing with N2 at 10 L/min, N-benzyltrimethylammonium hydroxide (trade name Triton B) was added until a liquid sample taken in contact with a water-moist pH test strip showed a pH value of 10-11. The bubble column was then brought to the reaction temperature of 120° C. and a gas mixture of propene, oxygen and nitrogen (molar ratio of propene to oxygen 2:1) flowed therethrough, with a total volume flow of less than 10 L/min being regulated. The progress of the reaction or the stationary point was determined by taking liquid and gas samples at the upper sampling points and analyzing them by GC. The product gas mixture produced continuously was freed from propylene oxide by cascaded cooling and the resulting gas stream was again slightly compressed and mixed with propene, oxygen and nitrogen and flowed onto the gassing frit of the bubble column.
Die Selektivitäten zu Propylenoxid betrugen dabei zwischen 95 und 100% in allen vier Versuchen. The selectivities to propylene oxide were between 95 and 100% in all four experiments.
Allgemeine Versuchsvorschrift für das Verfahren zur Herstellung von Propylenoxid durch Oxidation von Propen in Gegenwart des Epoxidierungskatalysatorsystems (1) in einem einer kontinuierlichen Zwei-Blasensäulenreaktor. General experimental procedure for the process for the production of propylene oxide by the oxidation of propene in the presence of the epoxidation catalyst system (1) in a continuous two-bubble column reactor.
Zwei druckfeste Blasensäulen (15 cm Durchmesser) je ausgestattet mit Begasungsfritte, Überdruckabsicherung, Druckaufnehmer, obere und untere Flüssigkeitsentnahme bzw. - zugabe, oberer Zugabepunkt für Feststoffe sowie Zu- und Ableitungen für Gase sind über die obere und untere Flüssigkeitsentnahme über eine Pumpe verbunden. In die eine Blasensäule wurden 3500 mL Tetrahydrofuran unter Inertbedingungen vorgelegt. Dem Lösemittel wurden in jedem Versuch 0,350 mol des Metallchlorid der entsprechenden Oxidationstufe (siehe Tabelle 1, 1-5) und 0,350 mol CuC12 unter Schutzgasgegenstrom zugesetzt. Unter Begasen mit Stickstoff mit 10 L/min wurde so lange N- Benzyltrimethylammoniumhydroxid (Handelsname Triton B) zugegeben bis eine entnommene Flüssigprobe in Kontakt mit einem Wasser-feuchtem pH-Teststreifen einen pH-Wert von 10-11 ergab. Die zweite Blasensäule wurde analog vorbereitet. Die Blasensäulen wurden anschließend auf Reaktionstemperatur gebracht 120 °C. Die erste Blasensäule wurde mit einem Gasgemisch aus Stickstoff und Propen angeströmt und die zweite Blasensäule wurde mit einem Gasgemisch aus Stickstoff und Sauerstoff angeströmt
wobei in beiden Fällen ein Gesamtvolumenstrom von weniger als 10 L/min eingeregelt wurde. Das Stoffmengenverhältnis von Propen zu Sauerstoff betrug 2:1. Gleichzeit wurde die Flüssigphase aus der ersten Blasensäule am oberen Punkt kontinuierlich entnommen und der zweiten Blasensäule am unteren Punkt zugegeben und aus der zweiten Blasensäule am oberen Punkt kontinuierlich entnommen und der ersten Blasensäule am unteren Punkt zugegeben. Die Volumenströme wurden dabei so eingeregelt, dass sich die Füllstände der beiden Blasensäulen über die Versuchsdauer nicht veränderten. Der Reaktionsfortschritt bzw. -Stationärpunkt wurde durch Entnahme von Flüssig- und Gasproben an den oberen Entnahmepunkten der beiden Blasensäulen und deren Analyse per GC ermittelt. Das kontinuierlich erzeugte Produktgasgemisch aus der ersten Blasensäule wurde durch kaskadiertes Auskühlen von Propylenoxid befreit und der resultierende Gasstrom erneut leicht verdichtet und in Abmischung mit Stickstoff und Propen die Begasungsfritte der Blasensäule angeströmt. Der Gasstrom aus der zweiten Blasensäule wurde durch kaskadiertes, tiefkaltes Auskühlen von Propen befreit über die Abluft entsorgt. Das zurückgewonnene Propen wurde durch die Zugabe am unteren Begasungspunkt der ersten Blasensäule wieder eingesetzt. Two pressure-resistant bubble columns (15 cm diameter), each equipped with gassing frit, overpressure protection, pressure sensor, upper and lower liquid withdrawal or addition, upper addition point for solids and inlet and outlet lines for gases are connected via the upper and lower liquid withdrawal via a pump. 3500 mL tetrahydrofuran were placed under inert conditions in one bubble column. In each experiment, 0.350 mol of the metal chloride of the corresponding oxidation state (see Table 1, 1-5) and 0.350 mol of CuCl2 were added to the solvent under protective gas countercurrent. While gassing with nitrogen at 10 L/min, N-benzyltrimethylammonium hydroxide (trade name Triton B) was added until a liquid sample taken in contact with a pH test strip moistened with water showed a pH value of 10-11. The second bubble column was prepared analogously. The bubble columns were then brought to the reaction temperature of 120.degree. A gas mixture of nitrogen and propene flowed against the first bubble column and a gas mixture of nitrogen and oxygen flowed against the second bubble column in both cases a total flow rate of less than 10 L/min was regulated. The molar ratio of propene to oxygen was 2:1. At the same time, the liquid phase was continuously taken out from the first bubble column at the top point and added to the second bubble column at the bottom point, and from the second bubble column at the top point and added to the first bubble column at the bottom point. The volume flows were regulated in such a way that the levels in the two bubble columns did not change over the course of the test. The progress of the reaction or the stationary point was determined by taking liquid and gas samples from the upper sampling points of the two bubble columns and analyzing them by GC. The continuously generated product gas mixture from the first bubble column was freed from propylene oxide by cascaded cooling and the resulting gas stream was slightly compressed again and mixed with nitrogen and propene and flowed onto the gassing frit of the bubble column. The gas stream from the second bubble column was freed from propene by cascaded, cryogenic cooling and disposed of via the exhaust air. The propene recovered was reused by adding it at the lower gassing point of the first bubble column.
Die Selektivitäten zu Propylenoxid betrugen dabei zwischen 95 und 100% in allen fünf Versuchen. The selectivities to propylene oxide were between 95 and 100% in all five experiments.
Allgemeine Versuchsvorschrift für das Verfahren zur Herstellung von Propylenoxid durch Oxidation von Propen in Gegenwart des Epoxidierungskatalysatorsystems (2) in einem einer kontinuierlichen Zwei-Blasensäulenreaktor. General experimental procedure for the process for the production of propylene oxide by the oxidation of propene in the presence of the epoxidation catalyst system (2) in a continuous two-bubble column reactor.
Zwei druckfeste Blasensäulen (15 cm Durchmesser) je ausgestattet mit Begasungsfritte, Überdruckabsicherung, Druckaufnehmer, obere und untere Flüssigkeitsentnahme bzw. - zugabe, oberer Zugabepunkt für Feststoffe sowie Zu- und Ableitungen für Gase sind über die obere und untere Flüssigkeitsentnahme über eine Pumpe verbunden. In die eine Blasensäule wurden 3500 mL Tetrahydrofuran unter Inertbedingungen vorgelegt. Dem Lösemittel wurden in jedem Versuch 0,350 mol des Metallchlorid der entsprechenden Oxidationstufe (siehe Tabelle 2, 9-12) und 0,700 mol (89,3 g) elementares Iod unter Schutzgasgegenstrom zugesetzt. Unter Begasen mit Stickstoff mit 10 L/min wurde so lange N-Benzyltrimethylammoniumhydroxid (Handelsname Triton B) zugegeben bis eine entnommene Flüssigprobe in Kontakt mit einem Wasser-feuchtem pH-Teststreifen einen pH-Wert von 10-11 ergab. Die zweite Blasensäule wurde analog vorbereitet. Die
Blasensäulen wurden anschließend auf Reaktionstemperatur gebracht 120 °C. Die erste Blasensäule wurde mit einem Gasgemisch aus Stickstoff und Propen angeströmt und die zweite Blasensäule wurde mit einem Gasgemisch aus Stickstoff und Sauerstoff angeströmt wobei in beiden Fällen ein Gesamtvolumenstrom von weniger als 10 L/min eingeregelt wurde. Das Stoffmengenverhältnis von Propen zu Sauerstoff betrug 2:1. Gleichzeit wurde die Flüssigphase aus der ersten Blasensäule am oberen Punkt kontinuierlich entnommen und der zweiten Blasensäule am unteren Punkt zugegeben und aus der zweiten Blasensäule am oberen Punkt kontinuierlich entnommen und der ersten Blasensäule am unteren Punkt zugegeben. Die Volumenströme wurden dabei so eingeregelt, dass sich die Füllstände der beiden Blasensäulen über die Versuchsdauer nicht veränderten. Der Reaktionsfortschritt bzw. -Stationärpunkt wurde durch Entnahme von Flüssig- und Gasproben an den oberen Entnahmepunkten der beiden Blasensäulen und deren Analyse per GC ermittelt. Das kontinuierlich erzeugte Produktgasgemisch aus der ersten Blasensäule wurde durch kaskadiertes Auskühlen von Propylenoxid befreit und der resultierende Gasstrom erneut leicht verdichtet und in Abmischung mit Stickstoff und Propen die Begasungsfritte der Blasensäule angeströmt. Der Gasstrom aus der zweiten Blasensäule wurde durch kaskadiertes, tiefkaltes Auskühlen von Propen befreit über die Abluft entsorgt. Das zurückgewonnene Propen wurde durch die Zugabe am unteren Begasungspunkt der ersten Blasensäule wieder eingesetzt. Two pressure-resistant bubble columns (15 cm diameter), each equipped with gassing frit, overpressure protection, pressure sensor, upper and lower liquid withdrawal or addition, upper addition point for solids and inlet and outlet lines for gases are connected via the upper and lower liquid withdrawal via a pump. 3500 mL tetrahydrofuran were placed under inert conditions in one bubble column. In each experiment, 0.350 mol of the metal chloride of the corresponding oxidation state (see Table 2, 9-12) and 0.700 mol (89.3 g) of elemental iodine were added to the solvent under protective gas countercurrent. While gassing with nitrogen at 10 L/min, N-benzyltrimethylammonium hydroxide (trade name Triton B) was added until a liquid sample taken in contact with a pH test strip moistened with water showed a pH value of 10-11. The second bubble column was prepared analogously. the Bubble columns were then brought to the reaction temperature of 120°C. A gas mixture of nitrogen and propene flowed against the first bubble column and a gas mixture of nitrogen and oxygen flowed against the second bubble column, with a total volume flow of less than 10 L/min being regulated in both cases. The molar ratio of propene to oxygen was 2:1. At the same time, the liquid phase was continuously taken out from the first bubble column at the top point and added to the second bubble column at the bottom point, and from the second bubble column at the top point and added to the first bubble column at the bottom point. The volume flows were regulated in such a way that the levels in the two bubble columns did not change over the course of the test. The progress of the reaction or the stationary point was determined by taking liquid and gas samples from the upper sampling points of the two bubble columns and analyzing them by GC. The continuously generated product gas mixture from the first bubble column was freed from propylene oxide by cascaded cooling and the resulting gas stream was slightly compressed again and mixed with nitrogen and propene and flowed onto the gassing frit of the bubble column. The gas stream from the second bubble column was freed from propene by cascaded, cryogenic cooling and disposed of via the exhaust air. The propene recovered was reused by adding it at the lower gassing point of the first bubble column.
Die Selektivitäten zu Propylenoxid betrugen dabei zwischen 95 und 100% in allen vier Versuchen. The selectivities to propylene oxide were between 95 and 100% in all four experiments.
Allgemeine Versuchsvorschrift für das Verfahren zur Herstellung von Propylenoxid durch Oxidation von Propen in Gegenwart des geträgerten Epoxidierungskatalysatorsystems (1) in einem kontinuierlichen Gasphasenreaktor: General experimental procedure for the process for the production of propylene oxide by oxidation of propene in the presence of the supported epoxidation catalyst system (1) in a continuous gas-phase reactor:
In einem druckfesten lL-Reaktor mit Rührwerk, Überdruckabsicherung, Druckaufnehmer, Steigrohr zur Flüssigkeitsentnahme sowie Be- und Entgasungsleitungen wurden ein Gemisch aus 200 mL Tetrahydrofuran unter Inertbedingungen vorgelegt. Dem Lösemittelgemisch wurden je Versuch 0,350 mol des Metall salzes (A) der entsprechenden Oxidationstufe (siehe Tabelle 1, Beispiel 1-5) und 0,350 mol CuC12 unter Schutzgasgegenstrom zugesetzt. Unter kräftigem Rühren wurde so lange N- Benzyltrimethylammoniumhydroxid als Hydroxid (F) (Handelsname Triton B) eingerührt bis eine entnommene Flüssigprobe in Kontakt mit einem Wasser-feuchtem pH-Teststreifen
einen pH-Wert von 10-11 ergab. Anschließend wurde die gewonnenen Gemisch auf Silica als Trägermaterial aufgebracht. Die Feststoffe wurden anschließend in einen inertisierten, druckfesten und druckabgesicherten Strömungsreaktor eingebracht. Nun wurde der Strömungsreaktor mit Stickstoff und Sauerstoff durchströmt und auf 180 °C Reaktionstemperatur gebracht. Anschließend wurde dem Gasstrom eine gewissen Menge Propen zugesetzt, bis ein Stoffmengenverhältnis Propen zu Sauerstoff von 2:1 erreicht wurde, und mit den Feststoffen in kontinuierlich in Kontakt gebracht. Dabei wurde die Strömungsbedingungen und Kontaktzeit so gewählt, das Teilumsätze erzielt wurden. Das kontinuierlich erzeugte Produktgasgemisch wurde jeweils durch kaskadiertes Auskühlen von Propylenoxid befreit und der resultierende Gasstrom erneut erhitzt, mit Sauerstoff und Propen angereichert und mit dem resultierenden Gemisch wieder der Feststoff angeströmt. Die Gasanalytik erfolgt dabei durch Entnahme von Gasproben und deren Analyse per GC. Die Selektivitäten zu Propylenoxid betrugen dabei zwischen 95 und 100% in allen fünf Versuchen.
A mixture of 200 mL tetrahydrofuran was placed under inert conditions in a pressure-resistant IL reactor with stirrer, overpressure protection, pressure sensor, riser pipe for liquid removal and gas-injection and degassing lines. For each experiment, 0.350 mol of the metal salt (A) of the corresponding oxidation state (see Table 1, Examples 1-5) and 0.350 mol of CuCl 2 were added to the solvent mixture under protective gas countercurrent. With vigorous stirring, N-benzyltrimethylammonium hydroxide as hydroxide (F) (trade name Triton B) was stirred in until a liquid sample taken came into contact with a water-dampened pH test strip gave a pH of 10-11. The mixture obtained was then applied to silica as a carrier material. The solids were then introduced into an inerted, pressure-resistant and pressure-protected flow reactor. Nitrogen and oxygen were then passed through the flow reactor and the reaction temperature was brought to 180.degree. A quantity of propene was then added to the gas stream until a 2:1 molar ratio of propene to oxygen was achieved and continuously contacted with the solids. The flow conditions and contact time were chosen so that partial conversions were achieved. The continuously generated product gas mixture was in each case freed from propylene oxide by cascaded cooling, and the resulting gas stream was heated again, enriched with oxygen and propene, and the resulting mixture flowed back onto the solid. The gas analysis is carried out by taking gas samples and analyzing them by GC. The selectivities to propylene oxide were between 95 and 100% in all five experiments.
Claims
1. Epoxidierungskatalysatorsystem ( 1 ) umfassend a) ein Gemisch (1) oder ein Umsetzungsprodukt (1) a-1) eines Metallsalz (A) der Metalle Chrom (Cr), Mangan (Mn), Molybdän (Mo), Blei (Pb) und/oder Bismut (Bi) und a-2) eines Hydroxid (B) b) eine redoxaktive Verbindung (C). 1. epoxidation catalyst system (1) comprising a) a mixture (1) or a reaction product (1) a-1) of a metal salt (A) of the metals 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. Epoxidierungskatalysatorsystem (1) gemäß Anspruch 1, wobei das Metallsalz (A) ein oder mehrere Verbindungen ist und ausgewählt wird aus der Gruppe bestehend aus M0CI5, M0OCI3, MnCE, K2MnCl6, CrOCl2, PbCE und BiCE. 2. The epoxidation catalyst system (1) according to claim 1, wherein the metal salt (A) is one or more compounds and is selected from the group consisting of MOCI 5 , MOOCI 3 , MnCE, K 2 MnCl 6 , CrOCl 2 , PbCE and BiCE.
3. Epoxidierungskatalysatorsystem (1) gemäß Anspruch 1 oder 2, wobei das Hydroxid (B) ein organisches Hydroxid (B-l) ist und das organische Hydroxid (B-l) eine oder mehrere Verbindung(en) ist und ausgewählt wird aus der Gruppe bestehend aus 3- (Trifluoromethyl)phenyltrimethylammoniumhydroxid, Tetra-n-butylphosphoniumhydroxid, Cholinhydroxid, Benzyltrimethylammoniumhydroxid, Tetraethylammoniumhydroxid, Tetra-n- propylammoniumhydroxid, Tetrabutylammoniumhydroxid und Tetramethylammonium hydroxid. 3. The epoxidation catalyst system (1) according to claim 1 or 2, wherein the hydroxide (B) is an organic hydroxide (B-I) and the organic hydroxide (B-I) is one or more compound(s) 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. Epoxidierungskatalysatorsystem (1) gemäß einem der Ansprüche 1 bis 3, wobei die redoxaktive Verbindung (C) eine oder mehrere Verbindung(en) ist und ausgewählt wird aus der Gruppe bestehend aus CuCl2, Cu(BF4)2, CuCl, VCE, VOCI3, NH4VO3, 1,4-Benzochinone, 1,4- Naphtochinone, Se20s, TeCh, TeC>2, Sb2Ü3, Sb20s, CeCE, Co(salen), Co(OAc)2, SnSCE, Fe(acac)3, Mo(acacE, K2Cr207, Mn(OAc)3, Ni(CF3C02H)2 und BiCE. 4. epoxidation catalyst system (1) according to any one of claims 1 to 3, wherein the redox-active compound (C) is one or more compound (s) and is selected from the group consisting of CuCl 2 , Cu (BF4) 2 , CuCl, VCE, VOCI3, NH4VO3, 1,4-Benzoquinone, 1,4-Naphtoquinone, Se20s, TeCh, TeC>2, Sb2Ü3, Sb20s, CeCE, Co(salen), Co(OAc) 2 , SnSCE, Fe(acac)3, Mo (acacE, K 2 Cr2O7, Mn(OAc)3, Ni(CF3CO 2 H) 2 and BiCE.
5. Epoxidierungskatalysatorsystem (1) gemäß einem der Ansprüche 1 bis 4, wobei das Epoxidierungskatalysatorsystem (1) das Umsetzungsprodukt (1) umfasst und das Umsetzungsprodukt (1) eine Struktur gemäß Formel (I), (II) und/oder (III) aufweist: 5. epoxidation catalyst system (1) according to any one of claims 1 to 4, wherein the epoxidation catalyst system (1) comprises the reaction product (1) and the reaction product (1) has a structure according to formula (I), (II) and / or (III). :
(Q RiR2R3R4)+„+o-m[M(A)m+(Hal)„(OH)o(S)p]m n o (I) für den Fall m < n + o(Q RiR 2 R 3 R 4 ) + „ +om [M(A) m+ (Hal)„(OH) o (S) p ] mno (I) for the case m < n + o
[M(A)m+(Hal)n(OH)0(S)p] (II) für den Fall m = n + o[M(A) m+ (Hal) n (OH) 0 (S) p ] (II) for the case m = n + o
[M(A)m+(Hal)„(OH)0(S)p](m n o) [X] „+0-m (III) für den Fall m > n + o mit
Q = Stickstoff oder Phosphor bevorzugt Stickstoff [M(A) m+ (Hal)„(OH) 0 (S) p ] (mno) [X] „ +0-m (III) for the case m > n + o with Q = nitrogen or phosphorus, preferably nitrogen
Ri, R2, R3, R4 unabhängig voneinander ausgewählt aus der Gruppe bestehend aus Ri, R2, R3, R4 independently selected from the group consisting of
(iv) linearen oder verzweigten Alkylgruppen enthaltend 1 bis 22 C Atome, optional substituiert mit Heteroatomen und/oder Heteroatom enthaltenden Substituenten; (iv) linear or branched alkyl groups containing 1 to 22 C atoms optionally substituted with heteroatoms and/or heteroatom containing substituents;
(v) cycloaliphatische Gruppen enthaltend 3 bis 22 C Atome mit 1 bis 3 verbrückenden C Atomen, optional substituiert mit Heteroatomen und/oder Heteroatom enthaltenden Substituenten und/oder (v) cycloaliphatic groups containing 3 to 22 C atoms with 1 to 3 bridging C atoms optionally substituted with heteroatoms and/or heteroatom containing substituents and/or
(vi) Arylgruppen enthaltend 6 bis 18 C Atome, optional substituiert mit 1 bis 10 C Atomen und/oder optional substituiert mit Heteroatomen und/oder Heteroatom enthaltenden Substituenten; bevorzugt Ri, R2, R3 und R4 unabhängig voneinander ausgewählt aus der Gruppe bestehend aus Methyl, Ethyl, iso-Propyl, n-Propyl, iso-Butyl, t-Bu, n-Butyl, Phenyl, Benzyl, (Trifluoromethyl)phenyl (vi) aryl groups containing 6 to 18 C atoms optionally substituted with 1 to 10 C atoms and/or optionally substituted with heteroatoms and/or heteroatom containing substituents; preferably R1, R2, R3 and R4 are independently selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, isobutyl, t-Bu, n-butyl, phenyl, benzyl, (trifluoromethyl)phenyl
M(A)m+ = Mo5+,Mn4+, Cr4+, Pb4+, Bi5+ bevorzugt Mo5+ M(A) m+ = Mo 5+ , Mn 4+ , Cr 4+ , Pb 4+ , Bi 5+ preferably Mo 5+
Hai = CI , Br oder G bevorzugt CI oder Br besonders bevorzugt CI Hal=CI, Br or G, preferably CI or Br, particularly preferably CI
S = H20, THF (Tetrahydrofuran), oder Dioxan, Bis(2methoxyethyl)ether (Diglyme), Methoxyethanol, Polyethylenglykole, Pyridin, Lutidin, 2,2‘-Bipyridin, Acetonitril, Dimethylsulfoxid, Sulfolan, Thiophen, bevorzugt THF; n+o+p = 6 n > 1 ; bevorzugt n > 2; besonders bevorzugt n = 2 o > 1; bevorzugt o > 1; besonders bevorzugt o = 1; 2; 3 oder 4 X = OTf,BF4 , Hai . S=H2O, THF (tetrahydrofuran), or dioxane, bis(2-methoxyethyl)ether (diglyme), methoxyethanol, polyethylene glycols, pyridine, lutidine, 2,2'-bipyridine, acetonitrile, dimethyl sulfoxide, sulfolane, thiophene, preferably THF; n+o+p = 6n > 1 ; preferably n > 2; particularly preferably n = 2 o > 1; preferably o > 1; particularly preferably o=1; 2; 3 or 4 X = OTf,BF4 , Hai .
6. Epoxidierungskatalysatorsystem (2) umfassend c) ein Gemisch (2) oder ein Umsetzungsprodukt (2) c-1) eines Metallsalzes (E), c-2) Iod (I2) sowie c-3) eines Hydroxid (F) d) optional eine redoxaktive Verbindung (G). 6. epoxidation catalyst system (2) comprising c) a mixture (2) or a reaction product (2) c-1) a metal salt (E), c-2) iodine (I2) and c-3) a hydroxide (F) d) optionally a redox active compound (G).
7. Epoxidierungskatalysatorsystem (2) gemäß Anspruch 6, wobei das Metallsalz (E) ein oder mehrere Verbindungen ist und ausgewählt wird aus der Gruppe bestehend aus NiCT. MnCE. PbCl2, SnCl2, CrCl3, VC13, MoCU, FeCl2 und RUC13. 7. The epoxidation catalyst system (2) according to claim 6, wherein the metal salt (E) is one or more compounds and is selected from the group consisting of NiCT. MnCE. PbCl 2 , SnCl 2 , CrCl 3 , VC1 3 , MoCU, FeCl 2 and RUC1 3 .
8. Epoxidierungskatalysatorsystem (2) gemäß Anspruch 6 oder 7, wobei das Hydroxid (F) ein organisches Hydroxid (B-l) ist und das organische Hydroxid (F-l) eine oder mehrere Verbindung(en) ist und ausgewählt wird aus der Gruppe bestehend aus 3-
(Trifluoromethyl)phenyltrimethylammoniumhydroxid, Tetra-n-butylphosphonium hydroxid, Cholinhydroxid, Benzyltrimethylammoniumhydroxid, Tetraethylammoniumhydroxid, Tetra-n- propylammoniumhydroxid, Tetrabutylammoniumhydroxid und8. epoxidation catalyst system (2) according to claim 6 or 7, wherein the hydroxide (F) is an organic hydroxide (Bl) and the organic hydroxide (Fl) is one or more compound (s) 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
Tetramethylammoniumhydroxid. tetramethylammonium hydroxide.
9. Epoxidierungskatalysatorsystem (2) gemäß einem der Ansprüche 6 bis 8, wobei das Epoxidierungskatalysatorsystem (2) das Umsetzungsprodukt (2) umfasst und das Umsetzungsprodukt (2) eine Struktur gemäß Formel (IV), (V) und/oder (VI) aufweist: 9. epoxidation catalyst system (2) according to any one of claims 6 to 8, wherein the epoxidation catalyst system (2) comprises the reaction product (2) and the reaction product (2) has a structure according to formula (IV), (V) and / or (VI). :
(Q RiR2R3R4)+im-o-pi [M(E)m+(Hal)n(OH)o(S)p]m n ° · q T2 (IV) für den Fall m < n + o,(Q RiR 2 R 3 R 4 ) + im- o -pi [M(E) m+ (Hal) n (OH) o (S)p] mn ° q T 2 (IV) for the case m < n + O,
[M(E)m+(Hal)n(OH)0(S)p] qT2 (V) für den Fall m = n + o[M(E) m+ (Hal) n (OH) 0 (S) p ] qT 2 (V) for the case m = n + o
[M(E)m+(Hal)„(OH)o(S)p]m n ° · q T2 [X] „+0-m (VI) für den Fall m > n + o mit [M(E) m+ (Hal)„(OH) o (S) p ] mn ° q T 2 [X] „ +0-m (VI) for the case m > n + o with
Q = Stickstoff oder Phosphor bevorzugt Stickstoff Q = nitrogen or phosphorus, preferably nitrogen
Ri, R2, R,. R4 unabhängig voneinander ausgewählt aus der Gruppe bestehend aus R 1 , R 2 , R 1 . R 4 independently selected from the group consisting of
(iv) linearen oder verzweigten Alkylgruppen enthaltend 1 bis 22 C Atome, optional substituiert mit Heteroatomen und/oder Heteroatom enthaltenden Substituenten; (iv) linear or branched alkyl groups containing 1 to 22 C atoms optionally substituted with heteroatoms and/or heteroatom containing substituents;
(v) cycloaliphatische Gruppen enthaltend 3 bis 22 C Atome mit 1 bis 3 verbrückenden C Atomen, optional substituiert mit Heteroatomen und/oder Heteroatom enthaltenden Substituenten und/oder(v) cycloaliphatic groups containing 3 to 22 C atoms with 1 to 3 bridging C atoms optionally substituted with heteroatoms and/or heteroatom containing substituents and/or
(vi) Arylgruppen enthaltend 6 bis 18 C Atome, optional substituiert mit 1 bis IO C Atomen und/oder optional substituiert mit Heteroatomen und/oder Heteroatom enthaltenden Substituenten; bevorzugt Ri, R2, R, und R4 unabhängig voneinander ausgewählt aus der Gruppe bestehend aus Methyl, Ethyl, iso-Propyl, n-Propyl, iso-Butyl, t-Bu, n-Butyl, Phenyl, Benzyl, (Trifluoromethyl)phenyl besonders bevorzugt Methyl, Benzyl und n-Butyl; (vi) aryl groups containing 6 to 18 C atoms, optionally substituted with 1 to 10 C atoms and/or optionally substituted with heteroatoms and/or heteroatom-containing substituents; preferably Ri, R 2 , R and R 4 independently selected from the group consisting of methyl, ethyl, isopropyl, n-propyl, isobutyl, t-Bu, n-butyl, phenyl, benzyl, (trifluoromethyl) phenyl particularly preferably methyl, benzyl and n-butyl;
M(E)m+ = Ni2+, Mn2+, Pb2+, Sn2+, Cr' . V3+, Mo4+, Fe2+ oder Ru3+ bevorzugt Ni2+, Mn2+, Pb2+,M(E) m+ = Ni 2+ , Mn 2+ , Pb 2+ , Sn 2+ , Cr' . V 3+ , Mo 4+ , Fe 2+ or Ru 3+ preferably Ni 2+ , Mn 2+ , Pb 2+ ,
Sn2+; Sn 2+ ;
Hai = CI , Br oder T bevorzugt CI oder Br besonders bevorzugt CI , n+o+p = 6; Hal = Cl , Br or T, preferably Cl or Br, particularly preferably Cl , n+o+p = 6;
S = H20, THF (Tetrahydrofuran), oder Dioxan, Bis(2methoxyethyl)ether (Diglyme), Methoxyethanol, Polyethylenglykole, Pyridin, Futidin, 2,2‘-Bipyridin, Acetonitril, Dimethylsulfoxid, Sulfolan, Thiophen, bevorzugt THF; n > 1; bevorzugt n > 2; besonders bevorzugt n = 2; o > 1; bevorzugt o > 1; besonders bevorzugt o = 1; 2; 3 oder 4; S=H 2 0, THF (tetrahydrofuran), or dioxane, bis(2-methoxyethyl)ether (diglyme), methoxyethanol, polyethylene glycols, pyridine, futidine, 2,2'-bipyridine, acetonitrile, dimethyl sulfoxide, sulfolane, thiophene, preferably THF; n >1; preferably n >2; particularly preferably n=2; o >1; preferably o >1; particularly preferably o=1; 2; 3 or 4;
X = OTf,BF4 , Hai ; q > 1 bevorzugt 1< q < 2000 besonders bevorzugt 1< q < 10.
X = OTf,BF4 , Hai ; q>1 preferably 1<q<2000 particularly preferably 1<q<10.
10. Verfahren zur Herstellung von Epoxiden umfassend der oxidativen Umsetzung eines Alkens in einem Reaktor in Gegenwart des Epoxidierungskatalysatorsystems (1) gemäß einem der Ansprüche 1 bis 5 oder des Epoxidierungskatalysatorsystems (2) gemäß einem der Ansprüche 6 bis 9. 10. A process for preparing epoxides comprising the oxidative reaction of an alkene in a reactor in the presence of the epoxidation catalyst system (1) according to any one of claims 1 to 5 or the epoxidation catalyst system (2) according to any one of claims 6 to 9.
11. Verfahren gemäß Anspruch 10, wobei die oxidative Umsetzung im Reaktor in Gegenwart von Sauerstoff oder einem Sauerstoff-haltigen Gasgemisch erfolgt. 11. The method according to claim 10, wherein the oxidative reaction in the reactor takes place in the presence of oxygen or an oxygen-containing gas mixture.
12. Verfahren gemäß Anspruch 10 oder 11, wobei das Alken eine oder mehrere Verbindung(en) ist und ausgewählt wird aus der Gruppe bestehend aus Ethen, Propen, Buten, 1-Okten, Butadien, 1,4-Butandioldiallylether, Allylchlorid, Allylalcohol, Styrol, Cyclopenten, Cy clohexen, Phenyl-allylether, Diallylether, n-Butyl-allylether, tert-Butyl-allylether, Bisphenol-A diallyl ether, Resorcindiallylether, Triphenylolmethan-triallylether, Cy clohexan- 1,2-dicarbonsäure- bis-(allylester), Isocyanursäuretris-(prop-2,3-en)-ester und Gemische dieser Alkene bevorzugt Ethen, Propen und Allylchlorid und besonders bevorzugt Propen. 12. The method according to claim 10 or 11, wherein the alkene is one or more compound (s) and is selected from the group consisting of ethene, propene, butene, 1-octene, butadiene, 1,4-butanediol diallyl ether, allyl chloride, allyl alcohol, Styrene, cyclopentene, cyclohexene, phenyl allyl ether, diallyl ether, n-butyl allyl ether, tert-butyl allyl ether, bisphenol A diallyl ether, resorcinol diallyl ether, triphenylolmethane triallyl ether, cyclohexane-1,2-dicarboxylic acid bis(allyl ester). ), isocyanuric acid tris-(2,3-propene) ester and mixtures of these alkenes, preferably ethene, propene and allyl chloride and particularly preferably propene.
13. Verfahren gemäß einem der Ansprüche 10 bis 12, wobei die Herstellung in Gegenwart eines Lösungsmittels erfolgt. 13. The method according to any one of claims 10 to 12, wherein the preparation takes place in the presence of a solvent.
14. Verfahren gemäß einem der Ansprüche 10 bis 13, wobei die Herstellung in Abwesenheit eines Lösungsmittels erfolgt. 14. The method according to any one of claims 10 to 13, wherein the preparation takes place in the absence of a solvent.
15. Verfahren gemäß einem der Ansprüche 10 bis 14, wobei das das Alken und das Sauerstoff haltige Gasgemisch kontinuierlich oder stufenweise bevorzugt kontinuierlich in den Reaktor dosiert wird.
15. The method according to any one of claims 10 to 14, wherein the gas mixture containing the alkene and the oxygen is metered continuously or in stages, preferably continuously, into the reactor.
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