WO2012140617A1 - Catalyseur pour la production d'oxyde d'éthylène - Google Patents
Catalyseur pour la production d'oxyde d'éthylène Download PDFInfo
- Publication number
- WO2012140617A1 WO2012140617A1 PCT/IB2012/051837 IB2012051837W WO2012140617A1 WO 2012140617 A1 WO2012140617 A1 WO 2012140617A1 IB 2012051837 W IB2012051837 W IB 2012051837W WO 2012140617 A1 WO2012140617 A1 WO 2012140617A1
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- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- range
- support
- carrier
- ppm
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 139
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 229910052709 silver Inorganic materials 0.000 claims abstract description 51
- 239000004332 silver Substances 0.000 claims abstract description 51
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims description 49
- 239000011148 porous material Substances 0.000 claims description 35
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 27
- 239000005977 Ethylene Substances 0.000 claims description 25
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 24
- 229910052792 caesium Inorganic materials 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 23
- 229910052702 rhenium Inorganic materials 0.000 claims description 23
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 21
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 19
- 229910052721 tungsten Inorganic materials 0.000 claims description 19
- 239000010937 tungsten Substances 0.000 claims description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 17
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- 229910052744 lithium Inorganic materials 0.000 claims description 17
- 229910052717 sulfur Inorganic materials 0.000 claims description 17
- 239000011593 sulfur Substances 0.000 claims description 17
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 13
- 230000003647 oxidation Effects 0.000 claims description 13
- 238000007254 oxidation reaction Methods 0.000 claims description 13
- 229910052700 potassium Inorganic materials 0.000 claims description 13
- 239000011591 potassium Substances 0.000 claims description 13
- 230000002902 bimodal effect Effects 0.000 claims description 12
- 238000009826 distribution Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052804 chromium Inorganic materials 0.000 claims description 7
- 239000011651 chromium Substances 0.000 claims description 7
- 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 claims description 7
- 238000002459 porosimetry Methods 0.000 claims description 5
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 239000011733 molybdenum Substances 0.000 claims description 4
- 239000000243 solution Substances 0.000 description 33
- 239000007789 gas Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000001354 calcination Methods 0.000 description 16
- 238000005470 impregnation Methods 0.000 description 13
- 239000011734 sodium Substances 0.000 description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- 229910052708 sodium Inorganic materials 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 10
- -1 polyethylenes Polymers 0.000 description 10
- 239000011575 calcium Substances 0.000 description 9
- 238000006735 epoxidation reaction Methods 0.000 description 9
- 239000011777 magnesium Substances 0.000 description 9
- 239000012495 reaction gas Substances 0.000 description 9
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 8
- 229910052791 calcium Inorganic materials 0.000 description 8
- 239000000470 constituent Substances 0.000 description 8
- 229910052749 magnesium Inorganic materials 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 239000000969 carrier Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 6
- 150000001342 alkaline earth metals Chemical class 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 229910052783 alkali metal Inorganic materials 0.000 description 5
- 238000001125 extrusion Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- 229940100890 silver compound Drugs 0.000 description 5
- 150000003379 silver compounds Chemical class 0.000 description 5
- 238000009489 vacuum treatment Methods 0.000 description 5
- 150000001340 alkali metals Chemical class 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000001913 cellulose Substances 0.000 description 3
- 229920002678 cellulose Polymers 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- MFGOFGRYDNHJTA-UHFFFAOYSA-N 2-amino-1-(2-fluorophenyl)ethanol Chemical compound NCC(O)C1=CC=CC=C1F MFGOFGRYDNHJTA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000001856 Ethyl cellulose Substances 0.000 description 2
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical compound CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N Propene Chemical compound CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 229910052788 barium Inorganic materials 0.000 description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 2
- 229910052790 beryllium Inorganic materials 0.000 description 2
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229920001249 ethyl cellulose Polymers 0.000 description 2
- 235000019325 ethyl cellulose Nutrition 0.000 description 2
- 229960003750 ethyl chloride Drugs 0.000 description 2
- MVLVMROFTAUDAG-UHFFFAOYSA-N ethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCC MVLVMROFTAUDAG-UHFFFAOYSA-N 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
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- 150000002642 lithium compounds Chemical class 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
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- 239000000047 product Substances 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- XZQYTGKSBZGQMO-UHFFFAOYSA-I rhenium pentachloride Chemical compound Cl[Re](Cl)(Cl)(Cl)Cl XZQYTGKSBZGQMO-UHFFFAOYSA-I 0.000 description 2
- 229910052701 rubidium Inorganic materials 0.000 description 2
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052712 strontium Inorganic materials 0.000 description 2
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 2
- 150000003464 sulfur compounds Chemical class 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- 150000003658 tungsten compounds Chemical class 0.000 description 2
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 2
- 239000001993 wax Substances 0.000 description 2
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- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- YPFNIPKMNMDDDB-UHFFFAOYSA-K 2-[2-[bis(carboxylatomethyl)amino]ethyl-(2-hydroxyethyl)amino]acetate;iron(3+) Chemical compound [Fe+3].OCCN(CC([O-])=O)CCN(CC([O-])=O)CC([O-])=O YPFNIPKMNMDDDB-UHFFFAOYSA-K 0.000 description 1
- UNANDJIJRBQOOF-UHFFFAOYSA-N 5-(dimethoxymethyl)-1,3-benzodioxole Chemical compound COC(OC)C1=CC=C2OCOC2=C1 UNANDJIJRBQOOF-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
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- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
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- 229910021634 Rhenium(III) chloride Inorganic materials 0.000 description 1
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- 150000001339 alkali metal compounds Chemical class 0.000 description 1
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- 150000003842 bromide salts Chemical class 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
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- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
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- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- CAMHHLOGFDZBBG-UHFFFAOYSA-N epoxidized methyl oleate Natural products CCCCCCCCC1OC1CCCCCCCC(=O)OC CAMHHLOGFDZBBG-UHFFFAOYSA-N 0.000 description 1
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- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
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- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- 150000002823 nitrates Chemical class 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 229910052756 noble gas Inorganic materials 0.000 description 1
- 150000002835 noble gases Chemical class 0.000 description 1
- HPEUJPJOZXNMSJ-UHFFFAOYSA-N octadecanoic acid methyl ester Natural products CCCCCCCCCCCCCCCCCC(=O)OC HPEUJPJOZXNMSJ-UHFFFAOYSA-N 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- UKUWGTWCIFEMQK-UHFFFAOYSA-I pentafluororhenium Chemical compound F[Re](F)(F)(F)F UKUWGTWCIFEMQK-UHFFFAOYSA-I 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000004375 physisorption Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229910052573 porcelain Inorganic materials 0.000 description 1
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 description 1
- 238000012216 screening Methods 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
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- VFWRGKJLLYDFBY-UHFFFAOYSA-N silver;hydrate Chemical compound O.[Ag].[Ag] VFWRGKJLLYDFBY-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000013179 statistical model Methods 0.000 description 1
- 150000004763 sulfides Chemical class 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 description 1
- LOIHSHVELSAXQN-UHFFFAOYSA-K trirhenium nonachloride Chemical compound Cl[Re](Cl)Cl LOIHSHVELSAXQN-UHFFFAOYSA-K 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 235000020234 walnut Nutrition 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000010626 work up procedure Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- 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
- C07D301/08—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 gaseous phase
- C07D301/10—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 gaseous phase with catalysts containing silver or gold
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/58—Platinum group metals with alkali- or alkaline earth metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6522—Chromium
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6525—Molybdenum
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/656—Manganese, technetium or rhenium
- B01J23/6567—Rhenium
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
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- 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
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
- B01J35/69—Pore distribution bimodal
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0027—Powdering
- B01J37/0036—Grinding
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Definitions
- the present invention relates to a catalyst for the preparation of ethylene oxide, at least comprising silver, supported on a support, wherein the support has a BET constant C in the range of 0 to 800 and wherein the constant is determined according to DIN ISO 9277. Furthermore, the present invention relates to this cata- carrier in itself. Moreover, the present invention relates to a process for the preparation of the catalyst and the catalyst, which can be prepared by this process and the use of the catalyst for the oxidation of ethene to ethylene oxide. Moreover, the present invention relates to a process for the production of ethylene oxide from ethylene, comprising an oxidation of ethylene in the presence of said catalyst.
- Ethylene oxide is an important basic chemical and is often produced industrially by direct oxidation of ethylene with oxygen in the presence of silver-containing catalysts. Frequently, supported catalysts are used to which the catalytically active metallic silver has been applied by a suitable method.
- a carrier material can in principle different porous materials such. As activated carbon, titanium, zirconium or silica or ceramic compositions or mixtures of these materials can be used. As a rule, alpha-alumina is used as the carrier.
- Exemplary of the direct oxidation of ethene are DE-A-2300512, DE-A 2521906, EP-A-0014457, DE-A-2454972, EP-A-0172565, EP-A-0357293, EP-A-0266015, EP -A-001 1356, EP-A-0085237, DE 2560684 or DE-A-2753359.
- these catalysts In addition to silver as an active component, these catalysts often contain promoters to improve the catalytic properties.
- alkali metal and / or alkaline earth metal compounds may be mentioned as promoters.
- Some writings teach the use of transition metals such as tungsten or molybdenum.
- a particularly preferred promoter for influencing the activity and selectivity of catalysts is rhenium.
- Catalysts containing rhenium and / or other transition metal promoters in combination with alkali and / or alkaline earth metal compounds are preferably used industrially because of their high selectivity.
- selectivity is meant the molar percentage of ethylene that reacts to ethylene oxide.
- the activity is characterized by the ethylene oxide concentration in the reactor outlet under otherwise constant conditions, such as temperature, pressure, gas quantity, amount of catalyst, etc.
- Another object of the present invention was to provide suitable supports for the preparation of catalysts which have particularly advantageous property profiles for the epoxidation of ethylene.
- this object is achieved by a catalyst for the production of ethylene oxide, comprising silver, applied to a support, the support having a BET constant C in the range from 0 to 800, determined in accordance with DIN ISO 9277.
- a catalyst for the production of ethylene oxide comprising silver, applied to a support, the support having a BET constant C in the range from 0 to 800, determined in accordance with DIN ISO 9277.
- the invention relates to a catalyst for the production of ethylene oxide, comprising silver, applied to a support, wherein the support has a BET constant C in the range of 0 to 800, determined in accordance with DIN ISO 9277.
- the invention relates to the carrier per se, ie a catalyst support for a catalyst for the production of ethylene oxide, wherein the support has a BET constant C in the range of 0 to 800, determined according to DIN ISO 9277.
- the invention relates to a process for the preparation of a catalyst for the production of ethylene oxide, and to the catalyst preparable by this process, the process comprising the steps
- the invention relates to the use of the catalyst or catalyst according to the invention, which can be prepared by the process according to the invention for the epoxidation of ethylene.
- silver is suitably applied to the carrier.
- at least one mixture containing silver for example, by impregnation or Spray or mixing method on the support, as described in more detail below, applied.
- the carrier it is characterized by a BET constant C in the range of 0 to 800, preferably in the range of 0 to 700, more preferably in the range of 0 to 600, further preferably in the range of 25 to 500 and more preferably ranging from 50 to 450.
- the BET constant C (also the C value) is determined according to DIN ISO 9277 ( May 2003).
- the C-value determination is based on the method of Brunnauer, Emmet and Teller for determining the total specific surface area of porous solids by measuring the physisorbed amount of gas (BET) as in Journal of the American Chemical Society, Vol. 60, pp. 301-319 (1938).
- BET physisorbed amount of gas
- V M is the volume of gas required to form a monolayer
- p r p / p 0 , ie the relative pressure
- p is the equilibrium pressure
- p 0 is the saturation vapor pressure of the gas at the measurement temperature.
- C is the BET constant to which the relationship applies: where E- ⁇ is the adsorption energy when forming the first layer, E L is the adsorption energy of the second and higher layers, A is the kinetic factor, and R is the gas constant. T stands for the respective temperature in Kelvin.
- the C value contains information about the interaction energy of the adsorbate with the carrier and gives information about the polarity of the carrier surface. Small C values are characteristic of non-polar areas, whereas large C values are indicative of highly polar or microporous areas.
- the C value depends, for example, on the composition of the support, the acidity of the surface and the porosity and the shape of the pores.
- the calcination conditions used in the preparation of the carrier or the addition of polar compounds (silicon additives) or nonpolar compounds (eg waxes) to the carrier material have an influence on the C value.
- Suitable supports according to the invention can be prepared by processes known from the prior art. Examples include US 2009/0198076 A1, WO 2006/133187, WO 03/072244, US 2005/0096219 A1, or EP 0 496 386 B2.
- the present invention accordingly relates to a catalyst as described above or a support as described above, wherein the support is an alumina support. Furthermore, the present invention also relates to a catalyst as described above, preparable by the method described above, wherein the carrier is an alumina carrier.
- alumina as used herein, includes all conceivable structures such as alpha, gamma or tetha alumina.
- the carrier is an alpha alumina carrier.
- the present invention also relates to a process as described above and to a catalyst or carrier preparable by the process, wherein the support is an alpha-alumina.
- the present invention also relates to a catalyst as described above, wherein the carrier is an alpha-alumina carrier.
- the alpha-alumina has a purity of at least 75%, preferably a purity of at least 80%, more preferably a purity of at least 85%, more preferably a purity of at least 90%, more preferably a purity of at least 98 %, more preferably a purity of at least 98.5%, and most preferably a purity of at least 99%.
- alpha-alumina therefore also includes alpha-aluminas containing further constituents, for example elements selected from the group consisting of zirconium, alkali metals, alkaline earth metals, silicon, zinc, gallium, hafnium, boron, fluorine, copper, nickel, manganese, iron , Cerium, titanium, chromium and mixtures of two or more of these elements.
- elements selected from the group consisting of zirconium, alkali metals, alkaline earth metals, silicon, zinc, gallium, hafnium, boron, fluorine, copper, nickel, manganese, iron , Cerium, titanium, chromium and mixtures of two or more of these elements.
- a suitable catalyst support for the present invention can be prepared by mixing the alumina with water or other suitable liquid with a burnout material or a pore former and at least one binder.
- Suitable pore formers are, for example, cellulose and cellulose derivatives, such as, for example, methylcellulose, ethylcellulose, carboxymethylcellulose. loose, or polyolefins, such as polyethylenes and polypropylenes, or natural burnout materials, such as walnut shell meal.
- the pore formers are selected to be completely burned out of the alumina to the final alpha alumina support at the selected kiln temperatures of the calcination.
- Suitable binders or extrusion and extrusion aids are described, for example, in EP 0 496 386 B2.
- Examples are alumina gels with nitric acid or acetic acid, cellulose, for example methyl, ethyl cellulose, or carboxyethyl cellulose, or methyl or ethyl stearate, polyolefin oxides, waxes and the like.
- the paste formed by mixing can be made into the desired shape by extrusion.
- Extrusion aids may be used to assist in the extrusion process.
- the molded article obtained as described above is optionally dried following the molding and calcined to obtain the alumina support according to (i).
- the calcination is usually carried out at temperatures in the range of 1200 ° C to 1600 ° C. It is common to wash the alumina carrier after calcining to remove soluble ingredients.
- the alpha-alumina may contain the constituents in any suitable form, for example as an element and / or in the form of one or more compounds. If the alpha-alumina contains one or more constituents in the form of a compound, it contains this, for example, as oxide or mixed oxide.
- the present invention also describes an alpha alumina containing at least one further constituent selected from the group consisting of silica, sodium oxide, potassium oxide, calcium oxide and magnesium oxide, nickel oxide, gallium oxide, hafnium oxide, copper oxide, iron oxide and mixed oxides thereof.
- the total content of the further constituents is preferably in a range of less than 25% by weight, more preferably less than 20% by weight, more preferably less than 15% by weight, more preferably less than 10% by weight, more preferably less than 5% by weight, more preferably less than 2% by weight, more preferably less than 1.5% by weight and particularly preferably less than 1% by weight, based on the total weight of the carrier.
- the carrier when the carrier contains silicon, it preferably contains it in an amount in the range of 50 to 10,000 ppm, more preferably in an amount of 50 to 5,000 ppm, further preferably in an amount of 50 to 800 ppm based on the total weight of the carrier and calculated as an element.
- the carrier if the carrier contains alkali metals, it preferably contains them in a total amount in the range of 10 to 2500 ppm, more preferably in an amount of 10 to 1000 ppm, further preferably in an amount of 50 to 850 ppm based on the total weight of the carrier and calculated as an element.
- the carrier contains at least one alkali metal selected from the group consisting of sodium and potassium.
- the carrier when the carrier contains sodium, it preferably contains it in an amount in the range of 10 to 1500 ppm, more preferably in an amount of 10 to 800 ppm, further preferably in an amount of 10 to 500 ppm based on the total weight of the carrier and calculated as an element.
- the carrier if the carrier contains potassium, it preferably contains it in an amount in the range of 10 to 1000 ppm, more preferably in an amount of 10 to 500 ppm, further preferably in an amount of 10 to 300 ppm based on the total weight of the carrier and calculated as an element.
- the carrier contains sodium in an amount of 10 to 1500 ppm and potassium in an amount of 10 to 1000 ppm.
- the present invention also describes a process for preparing a catalyst and a catalyst as described above, preparable by this process, wherein the carrier sodium in an amount of 10 to 1500 ppm, potassium in an amount of 10 to 1000 ppm and cesium in a Amount of 0 to 1000 ppm, more preferably wherein the carrier sodium in an amount of 10 to 500 ppm, potassium in an amount of 10 to 300 ppm and cesium in an amount of 0 to 100 ppm, based on the total weight of the carrier and calculated as Element comprising. Furthermore, the invention describes a catalyst preparable by this method and the carrier itself.
- the present invention also relates to a catalyst as described above and a carrier as described above, wherein the carrier sodium in an amount of 10 to 1500 ppm, potassium in an amount of 10 to 1000 ppm and cesium in an amount of 0 to 100 ppm, more preferably sodium in an amount of 10 to 500 ppm, potassium in an amount of 10 to 300 ppm and cesium in an amount of 0 to 100 ppm, each based on the total weight of the carrier and calculated as element comprises.
- the carrier contains, for example, alkaline earth metals, it preferably contains these in a total amount in the range of at most 2500 ppm, for example in the range from 10 to 2500 ppm, more preferably in an amount of from 10 to 1200 ppm, more preferably in an amount of from 10 to 700 ppm, based on the total weight of the carrier and calculated as element.
- the carrier comprises at least one alkaline earth metal selected from the group consisting of calcium and magnesium.
- the carrier when the carrier contains calcium, it preferably contains it in an amount in the range of 10 to 1500 ppm, more preferably in an amount of 10 to 1000 ppm, further preferably in an amount of 10 to 500 ppm, based on the Total weight of the carrier and calculated as an element.
- the carrier when the carrier contains magnesium, it preferably contains it in an amount in the range of 10 to 800 ppm, more preferably in an amount of 10 to 500 ppm, further preferably in an amount of 10 to 250 ppm based on the total weight of the carrier and calculated as an element.
- the present invention also describes a process for producing a catalyst and a catalyst prepared by this process as described above, wherein the carrier contains magnesium in an amount of 10 to 800 ppm, and calcium in an amount of 10 to 1500 ppm, respectively on the total weight of the carrier and calculated as an element that includes.
- the present invention also relates to a catalyst as described above and a carrier as described above, wherein the carrier magnesium in an amount of 10 to 800 ppm, and calcium in an amount of 10 to 1500 ppm, each based on the total weight of Carrier and calculated as an element, includes.
- the carrier comprises, for example, sodium in an amount of 10 to 1500 ppm, potassium in an amount of 10 to 1000 ppm, magnesium in an amount of 10 to 800 ppm, and calcium in an amount of 10 to 1500 ppm, based on the total weight of the carrier and calculated as an element.
- the carrier when it contains silicon, it preferably contains it in an amount in the range of 50 to 10,000 ppm, more preferably in an amount of 50 to 5,000 ppm, further preferably in an amount of 50 to 600 ppm based on the total weight of the carrier and calculated as an element.
- a support preferred according to the present invention is, for example, an alpha-alumina in a purity of at least 90%, which calculates 50 to 10,000 ppm of silicon, 10 to 1500 ppm of sodium and 10 to 2500 ppm of total alkaline earth metals, respectively Element and based on the total weight of the carrier.
- the support preferably comprises calcium and / or magnesium as the alkaline earth metal.
- Particularly preferred is an alpha-alumina in a purity of at least 98 wt .-%, which 50 to 5000 ppm silicon, 10 to 800 ppm of sodium and 10 to 700 ppm of alkaline earth metals in total, each calculated as an element and based on the total weight of the carrier , includes.
- the carriers used according to the invention preferably have a BET surface area, determined in accordance with DIN ISO 9277, of 0.1 to 5 m 2 / g, more preferably in the range of 0.1 to 2 m 2 / g, more preferably in the range of 0 , 5 to 1, 5 m 2 / g, more preferably in the range of 0.6 to 1, 3 m 2 / g, and particularly preferably in the range of 0.6 to 1, 0 m 2 / g, determined according to DIN ISO 9277th
- the supports according to the invention preferably have pores with diameters in the range from 0.1 to 100 ⁇ m, it being possible for the pore distribution to be monomodal or polymodal, for example bimodal, trimodal or tetramodal.
- the carriers have a bimodal pore distribution.
- the supports furthermore preferably have a bimodal pore distribution with peak maxima in the range from 0.1 to 10 ⁇ m and 15 to 100 ⁇ m, preferably in the range from 0.1 to 5 ⁇ m and 17 to 80 ⁇ m, more preferably in the range from 0.1 to 3 ⁇ and 20 to 50 ⁇ , more preferably in the range of 0.1 to 1, 5 ⁇ and 20 to 40 ⁇ on.
- the pore diameters are determined by Hg porosimetry (DIN 66133).
- bimodal pore distribution with peak maxima in the range from 0.1 to 10 ⁇ and 15 to 100 ⁇ means that one of the two peak maxima in the range of 0.1 to 10 ⁇ and the other peak maximum in the range of 15 to 100 ⁇ .
- the present invention also describes a process as described above for preparing a catalyst and a catalyst preparable by this process, wherein the support has a bimodal pore distribution, preferably a bimodal pore distribution at least containing pores having a pore diameter in the range of 0.1 to 15 ⁇ and pores with a pore diameter in the range of 15 to 100 ⁇ , determined by Hg porosimetry.
- the present invention also relates to a catalyst as described above and a carrier as described above, wherein the carrier has a bimodal pore distribution, preferably a bimodal pore distribution, at least containing pores having a pore diameter in the range of 0.1 to 10 ⁇ and pores with a pore diameter in the range of 15 to 100 ⁇ , determined by Hg porosimetry (DIN 66133).
- the carrier has a bimodal pore distribution, preferably a bimodal pore distribution, at least containing pores having a pore diameter in the range of 0.1 to 10 ⁇ and pores with a pore diameter in the range of 15 to 100 ⁇ , determined by Hg porosimetry (DIN 66133).
- the carrier is used as a shaped body, for example as a strand, hollow strand, star strand, sphere, ring or hollow ring.
- the carrier is preferably a shaped body with the geometry of a hollow body.
- cylinders with the following geometries (outer diameter x length x inner diameter, in each case in mm): 5x5x2, 6x6x3, 7x7x3, 8x8x3, 8x8.5x3, 8x8.5x3.5, 8.5x8x3.5, 8.5x8x3, 9x9x3, 9.5x9x3, 9.5x9x3.5.
- Each length specification includes tolerances in the range of ⁇ 0.5 mm.
- the catalyst is used in the form of a catalyst split, which is obtained from one or more of said moldings.
- the water absorption of the carriers is, for example, in the range from 0.35 ml / g to 0.65 ml / g, preferably in the range from 0.42 ml / g to 0.52 ml / g, determined by a vacuum cold water absorption.
- the catalyst according to the invention contains silver as the active metal.
- the catalyst may contain silver in an amount of, for example, 5 to 35 wt .-%, in particular from 10 to 30 wt .-%, preferably in an amount of 10 to 25 wt .-%, based on the total weight of the catalyst and calculated as an element.
- the present invention also describes a process as described above and a catalyst preparable by the process, and a catalyst as described above, comprising silver in an amount of 5 to 35 wt .-%, based on the total weight of the catalyst.
- the catalyst furthermore comprises at least one promoter, for example six, five, four, three or two promoters or a promoter.
- promoter is understood as meaning a constituent of the catalyst which, compared with a catalyst which does not contain the constituent, results in an improvement in one or more catalytic properties, eg. B. selectivity, activity, conversion and / or yield or space, time yield is achieved.
- Preferred compounds which are chemically stable under the reaction conditions and do not catalyze undesirable reactions.
- the at least one promoter is selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, manganese, rhenium, cadmium, tungsten, molybdenum, chromium, sulfur and mixtures of two or more of that.
- the catalyst contains at least one promoter selected from the group consisting of rhenium, cesium, lithium, tungsten, chromium, manganese, sulfur and mixtures of two or more thereof.
- the catalyst particularly preferably contains at least rhenium as promoter and at least one further promoter selected from the group consisting of cesium, lithium, tungsten, chromium, manganese, sulfur and mixtures of two or more thereof. Accordingly, the present invention also describes a process as described above and a catalyst preparable by the process, and a catalyst as described above, comprising at least rhenium as a promoter, preferably comprising silver in an amount of 5 to 35 wt .-%, based on the total weight of the catalyst, and at least rhenium as a promoter.
- the catalyst when the catalyst contains rhenium as described above, it preferably contains rhenium in an amount of 50 to 600 ppm, more preferably in an amount of 100 to 450 ppm, still more preferably in an amount of 150 to 400 ppm by total weight of the catalyst and calculated as element.
- the catalyst additionally comprises at least one further promoter selected from the group consisting of lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, manganese, rhenium, cadmium, tungsten, chromium, Molybdenum, sulfur and mixtures of two or more thereof.
- the catalyst additionally comprises at least one promoter selected from the group consisting of cesium, lithium, tungsten, chromium, manganese, sulfur and mixtures of two or more thereof and mixtures of two or more thereof.
- the catalyst additionally contains at least cesium, lithium, tungsten, and sulfur, in particular the catalyst contains rhenium and additionally cesium, lithium, tungsten and sulfur, as promoters.
- the catalyst contains at least one further promoter, it preferably contains a total amount of these promoters in an amount of 10 to 2000 ppm, preferably in an amount of 10 to 1500 ppm, more preferably in an amount of 50 to 1300 ppm and more preferably each in an amount of 80 to 1300 ppm, based on the total weight of the catalyst and calculated as the sum of the elements.
- the catalyst contains tungsten, it preferably contains it in an amount of 10 to 500 ppm, preferably in an amount of 50 to 300 ppm.
- the catalyst contains, for example, cesium, it preferably contains this in an amount of from 20 to 850 ppm, in particular in an amount of from 100 to 600 ppm, based on the total weight of the catalyst and calculated as an element.
- the catalyst when it contains lithium, it preferably contains it in an amount of 10 to 450 ppm, more preferably in an amount of 50 to 300 ppm, based on the total weight of the catalyst and calculated as an element.
- the catalyst when it contains sulfur, it preferably contains it in an amount of 5 to 300 ppm, more preferably in an amount of 5 to 150 ppm, based on the total weight of the catalyst and calculated as an element.
- the catalyst contains rhenium in an amount of 150 to 450 ppm, tungsten in an amount of 50 to 300 ppm, cesium in an amount of 100 to 600 ppm, lithium in an amount of 50 to 300 ppm and sulfur in one Amount of 5 to 150 ppm.
- silver it may be applied to the support by any of the prior art impregnation and deposition processes for preparing silver catalysts for the production of ethylene oxide, which processes may comprise one or more impregnation and calcination steps.
- the production processes for silver catalysts as described in DE-A 2300512, DE-A 2521906, EP-A 0 014 457, EP-A 0 085 237, EP-A 0 0384 312, DE-A 2454972, DE-A 3321895, EP-A 0 229 465, DE-A 3150205, EP-A 0 172 565 and EP-A 0 357 293 are disclosed.
- the catalyst contains at least one promoter in addition to silver, it is preferred to apply at least one mixture comprising silver or at least one promoter, for example by impregnation or spraying or mixing processes, to the support.
- the order of application of the at least one promoter and silver is generally arbitrary, i. Embodiments are contemplated in which silver and the at least one promoter are applied simultaneously to the support. Also included are embodiments in which silver and the at least one promoter are applied to the support in various steps, the order of the steps being generally arbitrary. Furthermore, embodiments are encompassed in which a part of the at least one promoter, which is applied to the carrier only after application of the silver, and the remaining part is applied simultaneously with silver. Preferably, silver and the at least one promoter are applied simultaneously to the support.
- the silver is preferably applied to the support according to the invention in the form of a silver compound, which may be a salt or a silver complex.
- the silver compound is preferably dissolved, in particular dissolved in water.
- the silver compound such as silver (I) oxide or silver (I) oxalate may further suitably contain a complexing agent such as ethanolamine, EDTA, 1, 3 or 1, 2-propanediamine, ethylenediamine and or alkali metal oxalate can be added, which can act simultaneously as a reducing agent.
- a complexing agent such as ethanolamine, EDTA, 1, 3 or 1, 2-propanediamine, ethylenediamine and or alkali metal oxalate can be added, which can act simultaneously as a reducing agent.
- silver is applied in the form of a silver amine compound, more preferably in the form of a silver ethylenediamine compound.
- the present invention also relates to a process as described above, wherein in step (ii) a mixture comprising silver as a silver amine compound, preferably as SilberethylendiaminENS, is applied to the carrier described above.
- a mixture comprising silver as a silver amine compound, preferably as SilberethylendiaminENS, is applied to the carrier described above.
- the present invention likewise relates to a catalyst which can be prepared by this process.
- At least one post-treatment step for example a drying step, e.g. connect one, two or more drying steps.
- the drying is usually carried out at temperatures in the range of 10 to 200 ° C.
- the post-treatment step is a vacuum treatment.
- the carrier is evacuated after application.
- the evacuation is carried out at a pressure in the range of at most 500 mbar, more preferably at a pressure of at most 250 mbar and more preferably at a pressure of 30 mbar, and preferably at a temperature in the range of 2 ° C to 50 ° C, more preferably at a temperature in the range of 5 ° C to 30 ° C, and more preferably at room temperature.
- the vacuum treatment is carried out, for example, for a time of at least 1 min, preferably of at least 5 min, more preferably for a time in the range of 5 min to 120 min, in particular in the range of 10 min to 45 min, particularly preferably in the range of 10 min up to 20 min.
- a time of at least 1 min preferably of at least 5 min, more preferably for a time in the range of 5 min to 120 min, in particular in the range of 10 min to 45 min, particularly preferably in the range of 10 min up to 20 min.
- the present invention also describes a process for preparing a catalyst as described above, and the catalyst obtainable by this process, additionally comprising a step (iii)
- the calcination is carried out at temperatures, for example, in a range of 150 to 750 ° C, generally in the range of 200 to 500 ° C, preferably in the range of 220 to 500 ° C and more preferably in the range of 250 to 350 ° C, wherein the Calcination duration is generally at least 5 minutes or more, for example in the range of 5 minutes to 24 hours or in the range of 10 minutes to 12 hours. More preferably, the calcination time is in the range of 5 minutes to 3 hours.
- the calcination can be carried out at a constant temperature, further embodiments are included, in which the temperature is changed continuously or discontinuously during the Calcini mecanicsdauer.
- the calcination may be carried out under any suitable gas atmosphere, with air, nitrogen and / or lean air being preferred. Furthermore, the calcination is preferably carried out in a muffle furnace, in a rotary kiln, carried out in a convection oven and / or a belt calciner.
- this at least one promoter is preferably applied to the carrier in the form of compounds, for example in the form of complexes or in the form of salts, for example in the form of halides, for example in the form of compounds of fluorides, bromides or chlorides, or in the form of carboxylates, nitrates, sulfates or sulfides, phosphates, cyanides, hydroxides, carbonates or as salts of heteropolyacids, in the form of salts, for example in the form of salts of the heteropolyacids of rhenium and / or tungsten.
- halides for example in the form of compounds of fluorides, bromides or chlorides, or in the form of carboxylates, nitrates, sulfates or sulfides, phosphates, cyanides, hydroxides, carbonates or as salts of heteropolyacids, in the form of salts, for example in the form of salts of the heteropol
- the catalyst contains, for example, rhenium
- this is preferably applied as a compound, for example as halide, oxyhalide, oxide or as acid.
- rhenium can be used, for example, as rhenate or perrhenate in the production process according to the invention.
- rhenium is used as a promoter, it is preferably used as a compound selected from the group consisting of ammonium perrhenate, rhenium (III) chloride, rhenium (V) chloride, rhenium (V) fluoride, rhenium (VI) oxide and Rhenium (VII) oxide used.
- rhenium as ammonium perrhenate to the carrier.
- the tungsten is preferably applied to the support as a tungsten compound.
- any suitable tungsten compound is usable.
- tungsten is applied in the form of tungstate or tungstic acid.
- the lithium is preferably applied to the carrier as a lithium compound.
- any suitable lithium compound is usable.
- lithium is applied in the form of lithium nitrate.
- the cesium is preferably applied to the support as a cesium compound.
- any suitable cesium compound is usable.
- cesium is applied in the form of cesium hydroxide.
- the sulfur is preferably applied to the support as a sulfur compound.
- any suitable sulfur compound is usable.
- sulfur is applied in the form of ammonium sulfate.
- the at least one promoter, more preferably the at least one promoter compound is preferably dissolved in a suitable solution, preferably in water, before application.
- the support is then preferably impregnated with the resulting solution comprising one or more of the promoters. If more promoters are added, they can be applied to the support either together or separately in a single impregnation step or in several impregnation steps.
- the solution comprising one or more of the promoters it may be prepared in any suitable manner.
- the promoters can each be separately dissolved in each case in a solution and the resulting solutions, each containing a promoter, are then used for impregnation. It is also possible that two or more of the promoters are dissolved together in a solution, and the resulting solution is then used for impregnation. In addition, it is possible that the resulting solutions containing at least one promoter are combined prior to impregnation and the resulting solution containing all promoters, is applied to the support.
- At least cesium, tungsten, lithium, sulfur and rhenium are used as promoters
- at least one solution containing cesium and tungsten, another solution containing lithium and sulfur, and another solution containing rhenium prepared.
- the solutions are either applied to the support in separate impregnation steps, or combined to form a solution before application and only then used for impregnation.
- the solutions are applied together, more preferably together with the mixture containing silver as a silver amine compound, preferably as SilberethylendiaminENS, applied to the support.
- the application can in principle be carried out by any suitable method, for example by soaking the carrier.
- the application is carried out by vacuum impregnation at room temperature.
- the support is preferably first at a pressure in the range of at most 500 mbar, more preferably at a pressure of at most 250 mbar and more preferably at a pressure of 30 mbar, and preferably at a temperature in the range of 2 ° C to 50 ° C, more preferably at a temperature in the range of 5 ° C to 30 ° C, and most preferably treated at room temperature.
- the vacuum treatment is carried out, for example, for a time of at least 1 min, preferably of at least 5 min, more preferably for a time in the range of 5 min to 120 min, in particular in the range of 10 min to 45 min, particularly preferably in the range of 15 min up to 30 min.
- the at least one solution for example the mixture containing silver, or at least one solution is contained.
- at least one promoter preferably the mixture containing silver and the at least one promoter, applied to the carrier.
- the solution is dropped or sprayed on, preferably sprayed on.
- the application is preferably carried out by means of a nozzle.
- the support is preferably further evacuated.
- the evacuation is carried out at a pressure in the range of at most 500 mbar, more preferably at a pressure of at most 250 mbar and more preferably at a pressure of 30 mbar, and preferably at a temperature in the range of 2 ° C to 50 ° C, more preferably at a temperature in the range of 5 ° C to 30 ° C, and more preferably at room temperature.
- the vacuum treatment is carried out, for example, for a time of at least 1 min, preferably of at least 5 min, more preferably for a time in the range of 5 min to 120 min, in particular in the range of 10 min to 45 min, particularly preferably in the range of 10 min up to 20 min.
- step (iii) As regards the time of application of the promoter, this can be carried out following the calcining described in step (iii) above. Alternatively, it is possible to apply the at least one promoter together with the silver compound on the support.
- embodiments are encompassed in which the at least one promoter, that is to say, for example, five different promoters, four different promoters, three different promoters, two different promoters or a promoter, are applied to the support and the support treated in this way is subsequently as above is calcined to obtain a catalyst according to the invention.
- the present invention also describes a process for preparing a catalyst, and the catalyst obtainable by this process, comprising the steps of (i) providing a support having a BET constant C in the range from 0 to 800, determined in accordance with DIN ISO 9277, (ii) applying silver and at least one promoter on the support by applying a solution containing silver and the at least one promoter, and (iii) calcining the optionally dried support according to (ii).
- the promoters are preferably applied together with silver in step (ii).
- the catalysts of the invention or the catalysts obtainable by a process according to the invention are particularly suitable as catalysts for the production of ethylene oxide from ethylene, comprising an oxidation of ethylene. High selectivities and good activities are achieved.
- the present invention therefore also relates in a further aspect to a process for the production of ethylene oxide from ethylene comprising an oxidation of ethylene in the presence of a catalyst for the production of ethylene oxide comprising silver supported on a support, the support having a BET constant C in the range of 0 to 800, determined according to DIN ISO 9277, or in the presence of a catalyst obtainable by a process for the preparation of a catalyst for the production of ethylene oxide as described above.
- the present invention therefore also relates to the process for the production of ethylene oxide from ethylene, comprising an oxidation of ethylene as described above, wherein the catalyst additionally contains rhenium.
- the present invention also relates to the use of a catalyst for the production of ethylene oxide, at least comprising silver, supported on a support, wherein the support has a BET constant C in the range of 0 to 800, determined according to DIN ISO 9277.
- the epoxidation can take place according to all methods known to the person skilled in the art.
- Any of the reactors which can be used in the ethylene oxide preparation processes of the prior art can be used here, for example externally cooled tube bundle reactors (compare Ullmann's Encyclopedia of Industrial Chemistry, 5th edition, Vol. A-10, pages 1 17-135, 123-125 , VCH-Verlagsgesellschaft, Weinheim 1987,) or reactors with loose catalyst bed and cooling tubes, for example, the reactors described in DE-A 3414717, EP 0082609 and EP-A 0339748.
- the epoxidation takes place in at least one tubular reactor, preferably in a tube bundle reactor.
- the catalyst according to the invention can be used either alone or in admixture with other catalysts in a combined or structured catalyst bed.
- inert gases such as nitrogen or gases behaving inertly under the reaction conditions such as water vapor, methane and optionally reaction moderators, for example halides, hydrocarbons such as ethyl chloride, vinyl chloride or 1, 2-dichloroethane can be admixed with the reaction gas containing ethylene and molecular oxygen.
- reaction moderators for example halides, hydrocarbons such as ethyl chloride, vinyl chloride or 1, 2-dichloroethane
- the oxygen content of the reaction gas is in a range in which no explosive gas mixtures are present.
- a suitable composition of the reaction gas for the production of ethylene oxide may, for.
- the oxygen content of the reaction gas is expediently in a range of at most 10 vol .-%, preferably of at most 9 vol .-%, more preferably of at most 8 vol .-%, and most preferably of at most 7 vol .-%, based on the total volume of the reaction gas.
- the reaction gas contains a chlorine-containing reaction moderator such as ethyl chloride, vinyl chloride or dichloroethane in an amount of 0 to 15 ppm, preferably in an amount of 0, 1 to 8 ppm.
- the remainder of the reaction gas usually consists of hydrocarbons, such as methane, or of inert gases such as nitrogen.
- other substances such as water vapor, carbon dioxide or noble gases may be contained in the reaction gas.
- the components of the reaction mixture described above may optionally each have small amounts of impurities.
- ethylene may be used at any purity level suitable for the gas phase oxidation of the present invention. Suitable levels of purity include, but are not limited to, polymer grade ethylene, which typically has a purity of at least 99%, and chemical grade ethylene which has low purity, typically less than 95%.
- the impurities typically consist mainly of ethane, propane and / or propene.
- the epoxidation is usually carried out at elevated temperature.
- Preferred are temperatures in the range of 150 to 350 ° C, more preferably in the range of 180 to 300 ° C, more preferably in the range of 190 to 280 ° C, and particularly preferably in the range of 200 to 280 ° C.
- the present invention also relates to a process as described above, wherein the oxidation takes place at a temperature in the range of 180 to 300 ° C, preferably in the range of 200 to 280 ° C.
- the invention likewise relates to the catalyst which can be prepared by this process.
- the oxidation is carried out at a pressure in the range of 5 bar to 25 bar, preferably at a pressure in the range of 10 bar to 20 bar and in particular in the range of 14 bar to 20 bar.
- the present invention also relates to a process as described above, wherein the oxidation takes place at a pressure in the range of 14 bar to 20 bar.
- the invention likewise relates to the catalyst which can be prepared by this process.
- the oxidation is carried out in a continuous process.
- a GHSV gas hourly space velocity
- the size / average area of the reactor the shape and size of the catalyst, which are preferably in the range of 800 to 10,000 / h, preferably in the range of 2,000 to 6,000 / h, more preferably in the range of 2,500 to 5,000 / h, the data relating to the volume of the catalyst.
- the production of ethylene oxide from ethylene and oxygen can be carried out in a cyclic process.
- the reaction mixture is circulated through the reactor, where after each pass the newly formed ethylene oxide and the by-products formed in the reaction are removed from the product gas stream, which is fed back into the reactor after addition of the required amounts of ethylene, oxygen and Mattersmoderatoren becomes.
- the separation of the ethylene oxide from the product gas stream and its work-up can be carried out according to the customary processes of the prior art (compare Ullmann's Encyclopedia of Industrial Chemistry, 5th Edition, Vol. A-10, pages 1 17-135, 123-125 VCH Verlagsgesellschaft, Weinheim 1987).
- the present invention accordingly also relates to the use of a catalyst for the production of ethylene oxide, at least comprising silver, applied to a support, wherein the support has a BET constant C in the range of 0 to 800, determined according to DIN ISO 9277, or as described above, the use of a catalyst obtainable by a process for producing a catalyst for the production of ethylene oxide as described above, as a catalyst for the production of ethylene oxide.
- Catalysts were prepared starting from 5 different carriers, the carriers differing in their C values, determined in accordance with DIN ISO 9277:
- composition of the carrier is shown in Table 1.
- deionized water demineralized water
- deionized water demineralized water
- the solution was heated to 40.degree. 402.62 g of potassium hydroxide solution (47.8%) were mixed with 1.2 L of deionized water.
- 216.31 g of oxalic acid were added and completely dissolved and the solution was heated to 40 ° C.
- the resulting solution was allowed to stir for 1 h at 40 ° C.
- the precipitated silver oxalate was filtered off and washed the filter cake obtained with 1 L portions of water (about 10 L) until it was potassium or nitrate-free (determined by conductivity measurement of the washing solution, potassium or nitrate-free in the present case means a conductivity ⁇ 40 ⁇ 5 / ⁇ " ⁇ )
- the water was removed as completely as possible from the filter cake and the residual moisture of the filter cake was determined to give 620 g of silver oxalate with a water content of 20.80%.
- the resulting solution received 29.14% by weight of silver, calculated as element, and had a density of 1.532 g / mL.
- the solution obtained according to procedure 1.2 was dropped onto the support within 15 minutes, and then the impregnated support was allowed to rotate for a further 15 minutes in vacuo. Thereafter, the support was left for 1 h at room temperature and atmospheric pressure in the apparatus and mixed gently every 15 min.
- the impregnated support was treated for 12 minutes at 283 ° C. under 8.3 m 3 of air per hour in a circulating air oven (HORO, type 129 ALV-SP, make no .: 53270).
- the resulting catalyst rings were coarsely crushed in a porcelain dish with the mortar. Subsequently, the comminuted material was brought to the desired particle size fraction (500-900 ⁇ m) by means of a screening machine, round sieve and balls. Very hard rings were completely crushed with the mortar and then sieved.
- the epoxidation was carried out in a test reactor consisting of a vertical stainless steel reaction tube having an inner diameter of 6 mm and a length of 2200 mm.
- the jacketed reaction tube was heated with hot oil of temperature T flowing through the jacket. With a very good approximation, the temperature of the oil corresponds to the temperature in the reaction tube and thus the reaction temperature.
- the catalyst was used in the form of catalyst split.
- the reaction tube was from bottom to top at a height of 212 mm with inert Steatite balls (1, 0-1, 6 mm), above at a height of 1 100 mm with 38.2 g of catalyst chippings, particle size 0.5-0.9 mm, and above at a height of 707 mm with inert steatite balls (1 , 0 - 1, 6 mm) filled.
- the inlet gas entered the reactor from above and at the bottom, after passing through the catalyst bed again.
- the input gas consisted of 35 vol.% Ethylene, 7 vol.% Oxygen, 1 vol.% C0 2 (EC (ethylene chloride) moderation). At the beginning, 2.5 ppm EC was used for start-up. Depending on the catalyst and performance, the EC concentration was increased every 24 h to a maximum of 4 ppm. The remainder of the input gas was methane.
- the experiments were carried out at a pressure of 15 bar and a gas load (GHSV) of 4750 / h and a space-time yield of 250 kg EO / (m 3 (Kat) xh).
- GHSV gas load
- the reaction temperature was controlled according to the specified ethylene oxide exhaust gas concentration of 2.7%.
- ethylene oxide exhaust gas concentration 2.7%.
- 2.2 and 4.0 ppm of ethylene chloride were added as a moderator to the input gas.
- the gas leaving the reactor was analyzed by online MS.
- the selectivity was determined from the analysis results.
- the catalysts marked with * are comparative examples.
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Abstract
La présente invention concerne un catalyseur pour la production d'oxyde d'éthylène, comprenant au moins de l'argent déposé sur un support, lequel support présente une constante C mesurée selon la méthode BET située entre 0 et 800, selon DIN ISO 9277.
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
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EP12771758.5A EP2696973A4 (fr) | 2011-04-14 | 2012-04-13 | Catalyseur pour la production d'oxyde d'éthylène |
JP2014504442A JP2014514960A (ja) | 2011-04-14 | 2012-04-13 | エチレンオキシド製造用触媒 |
CN201280028677.5A CN103608105A (zh) | 2011-04-14 | 2012-04-13 | 用于制备氧化乙烯的催化剂 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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EP11162382 | 2011-04-14 | ||
EP11162382.3 | 2011-04-14 |
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WO2012140617A1 true WO2012140617A1 (fr) | 2012-10-18 |
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Application Number | Title | Priority Date | Filing Date |
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PCT/IB2012/051837 WO2012140617A1 (fr) | 2011-04-14 | 2012-04-13 | Catalyseur pour la production d'oxyde d'éthylène |
Country Status (4)
Country | Link |
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EP (1) | EP2696973A4 (fr) |
JP (1) | JP2014514960A (fr) |
CN (1) | CN103608105A (fr) |
WO (1) | WO2012140617A1 (fr) |
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US11926019B2 (en) | 2019-12-27 | 2024-03-12 | Saint-Gobain Ceramics & Plastics, Inc. | Abrasive articles and methods of forming same |
US11959009B2 (en) | 2016-05-10 | 2024-04-16 | Saint-Gobain Ceramics & Plastics, Inc. | Abrasive particles and methods of forming same |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US11400437B2 (en) * | 2016-08-08 | 2022-08-02 | Basf Se | Catalyst for the oxidation of ethylene to ethylene oxide |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080081920A1 (en) * | 2006-09-29 | 2008-04-03 | Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg | Catalyst with bimodal pore size distribution and the use thereof |
US20080091038A1 (en) * | 2006-09-29 | 2008-04-17 | Nippon Shokubai Co., Ltd. | Catalyst for production of ethylene oxide and method for production of ethylene oxide |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5100859A (en) * | 1991-01-22 | 1992-03-31 | Norton Company | Catalyst carrier |
US6193412B1 (en) * | 1999-02-26 | 2001-02-27 | General Electric Company | Method for measurement of the surface polarity of inorganic material |
TW201109083A (en) * | 2005-06-07 | 2011-03-16 | Saint Gobain Ceramics & Plastics Inc | A process for preparing a catalyst carrier |
US7932408B2 (en) * | 2006-09-29 | 2011-04-26 | Scientific Design Company, Inc. | Catalyst with bimodal pore size distribution and the use thereof |
-
2012
- 2012-04-13 EP EP12771758.5A patent/EP2696973A4/fr not_active Withdrawn
- 2012-04-13 WO PCT/IB2012/051837 patent/WO2012140617A1/fr active Application Filing
- 2012-04-13 JP JP2014504442A patent/JP2014514960A/ja active Pending
- 2012-04-13 CN CN201280028677.5A patent/CN103608105A/zh active Pending
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US20080081920A1 (en) * | 2006-09-29 | 2008-04-03 | Sd Lizenzverwertungsgesellschaft Mbh & Co. Kg | Catalyst with bimodal pore size distribution and the use thereof |
US20080091038A1 (en) * | 2006-09-29 | 2008-04-17 | Nippon Shokubai Co., Ltd. | Catalyst for production of ethylene oxide and method for production of ethylene oxide |
Non-Patent Citations (1)
Title |
---|
See also references of EP2696973A4 * |
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US11859120B2 (en) | 2012-01-10 | 2024-01-02 | Saint-Gobain Ceramics & Plastics, Inc. | Abrasive particles having an elongated body comprising a twist along an axis of the body |
US11649388B2 (en) | 2012-01-10 | 2023-05-16 | Saint-Gobain Cermaics & Plastics, Inc. | Abrasive particles having complex shapes and methods of forming same |
US9108188B2 (en) | 2012-03-07 | 2015-08-18 | Chevoron Phillip Chemical Company, LP | Selective hydrogenation catalyst and methods of making and using same |
US9144787B2 (en) | 2012-03-07 | 2015-09-29 | Chevron Phillips Chemical Company Lp | Selective hydrogenation catalyst and methods of making and using same |
US9636659B2 (en) | 2012-03-07 | 2017-05-02 | Chevron Phillips Chemical Company Lp | Selective hydrogenation catalyst and methods of making and using same |
US11590632B2 (en) | 2013-03-29 | 2023-02-28 | Saint-Gobain Abrasives, Inc. | Abrasive particles having particular shapes and methods of forming such particles |
WO2015034521A1 (fr) * | 2013-09-06 | 2015-03-12 | Chevron Phillips Chemical Company Lp | Catalyseur sélectif d'hydrogénation contenant un support bimodal et ses méthodes de fabrication et d'utilisation |
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US11643582B2 (en) | 2015-03-31 | 2023-05-09 | Saint-Gobain Abrasives, Inc. | Fixed abrasive articles and methods of forming same |
US11472989B2 (en) | 2015-03-31 | 2022-10-18 | Saint-Gobain Abrasives, Inc. | Fixed abrasive articles and methods of forming same |
US11879087B2 (en) | 2015-06-11 | 2024-01-23 | Saint-Gobain Ceramics & Plastics, Inc. | Abrasive article including shaped abrasive particles |
US11718774B2 (en) | 2016-05-10 | 2023-08-08 | Saint-Gobain Ceramics & Plastics, Inc. | Abrasive particles and methods of forming same |
US11959009B2 (en) | 2016-05-10 | 2024-04-16 | Saint-Gobain Ceramics & Plastics, Inc. | Abrasive particles and methods of forming same |
US11230653B2 (en) | 2016-09-29 | 2022-01-25 | Saint-Gobain Abrasives, Inc. | Fixed abrasive articles and methods of forming same |
US11427740B2 (en) | 2017-01-31 | 2022-08-30 | Saint-Gobain Ceramics & Plastics, Inc. | Method of making shaped abrasive particles and articles comprising forming a flange from overfilling |
US11549040B2 (en) | 2017-01-31 | 2023-01-10 | Saint-Gobain Ceramics & Plastics, Inc. | Abrasive article including shaped abrasive particles having a tooth portion on a surface |
US11932802B2 (en) | 2017-01-31 | 2024-03-19 | Saint-Gobain Ceramics & Plastics, Inc. | Abrasive article including shaped abrasive particles comprising a particular toothed body |
US11926019B2 (en) | 2019-12-27 | 2024-03-12 | Saint-Gobain Ceramics & Plastics, Inc. | Abrasive articles and methods of forming same |
Also Published As
Publication number | Publication date |
---|---|
CN103608105A (zh) | 2014-02-26 |
EP2696973A1 (fr) | 2014-02-19 |
EP2696973A4 (fr) | 2014-12-10 |
JP2014514960A (ja) | 2014-06-26 |
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