JP4778093B2 - アルミナ担体及びそれを含むオレフィンのエポキシ化用触媒の製法並びにオレフィンのエポキシ化方法 - Google Patents
アルミナ担体及びそれを含むオレフィンのエポキシ化用触媒の製法並びにオレフィンのエポキシ化方法 Download PDFInfo
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- JP4778093B2 JP4778093B2 JP2010025642A JP2010025642A JP4778093B2 JP 4778093 B2 JP4778093 B2 JP 4778093B2 JP 2010025642 A JP2010025642 A JP 2010025642A JP 2010025642 A JP2010025642 A JP 2010025642A JP 4778093 B2 JP4778093 B2 JP 4778093B2
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- Prior art keywords
- catalyst
- support
- alumina
- silver
- olefin
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- 239000003054 catalyst Substances 0.000 title claims description 239
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims description 61
- 238000000034 method Methods 0.000 title claims description 53
- 230000008569 process Effects 0.000 title claims description 32
- 150000001336 alkenes Chemical class 0.000 title claims description 28
- 238000006735 epoxidation reaction Methods 0.000 title claims description 22
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims description 15
- GFQYVLUOOAAOGM-UHFFFAOYSA-N zirconium(iv) silicate Chemical compound [Zr+4].[O-][Si]([O-])([O-])[O-] GFQYVLUOOAAOGM-UHFFFAOYSA-N 0.000 claims description 82
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 66
- 229910052709 silver Inorganic materials 0.000 claims description 64
- 239000004332 silver Substances 0.000 claims description 64
- -1 fluoride anions Chemical class 0.000 claims description 45
- 238000004519 manufacturing process Methods 0.000 claims description 38
- 238000005470 impregnation Methods 0.000 claims description 36
- 229910052760 oxygen Inorganic materials 0.000 claims description 22
- 239000001301 oxygen Substances 0.000 claims description 22
- 239000005977 Ethylene Substances 0.000 claims description 17
- 229910052702 rhenium Inorganic materials 0.000 claims description 15
- 238000000151 deposition Methods 0.000 claims description 14
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims description 14
- 229910052783 alkali metal Inorganic materials 0.000 claims description 13
- 150000001340 alkali metals Chemical class 0.000 claims description 13
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 12
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 9
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 description 57
- 229910052845 zircon Inorganic materials 0.000 description 48
- 239000000203 mixture Substances 0.000 description 38
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 37
- 239000000243 solution Substances 0.000 description 30
- 230000000694 effects Effects 0.000 description 28
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 27
- 229910052726 zirconium Inorganic materials 0.000 description 27
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 24
- 239000007787 solid Substances 0.000 description 24
- 230000000052 comparative effect Effects 0.000 description 21
- 125000002947 alkylene group Chemical group 0.000 description 16
- 239000002994 raw material Substances 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 150000003839 salts Chemical class 0.000 description 15
- 150000001450 anions Chemical class 0.000 description 14
- 150000001768 cations Chemical class 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 12
- 239000002184 metal Substances 0.000 description 12
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 11
- 229910052792 caesium Inorganic materials 0.000 description 11
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 10
- 150000001342 alkaline earth metals Chemical class 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 10
- 238000002156 mixing Methods 0.000 description 10
- 239000011148 porous material Substances 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 8
- 230000002708 enhancing effect Effects 0.000 description 8
- 239000007789 gas Substances 0.000 description 8
- 229910052748 manganese Inorganic materials 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 7
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 7
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 7
- 229910052791 calcium Inorganic materials 0.000 description 7
- 239000011575 calcium Substances 0.000 description 7
- 230000008021 deposition Effects 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 125000002091 cationic group Chemical group 0.000 description 6
- 239000003426 co-catalyst Substances 0.000 description 6
- 239000003623 enhancer Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 6
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 230000032683 aging Effects 0.000 description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 5
- 229940043430 calcium compound Drugs 0.000 description 5
- 150000001674 calcium compounds Chemical class 0.000 description 5
- 230000009849 deactivation Effects 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 239000004615 ingredient Substances 0.000 description 5
- 150000002739 metals Chemical class 0.000 description 5
- 239000002243 precursor Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000012808 vapor phase Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 4
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 4
- 125000000129 anionic group Chemical group 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 239000003607 modifier Substances 0.000 description 4
- 229910052750 molybdenum Inorganic materials 0.000 description 4
- 239000011733 molybdenum Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 229940100890 silver compound Drugs 0.000 description 4
- 150000003379 silver compounds Chemical class 0.000 description 4
- 229910001923 silver oxide Inorganic materials 0.000 description 4
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 125000004429 atom Chemical group 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- HRYZWHHZPQKTII-UHFFFAOYSA-N chloroethane Chemical compound CCCl HRYZWHHZPQKTII-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 229960003750 ethyl chloride Drugs 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002924 oxiranes Chemical class 0.000 description 3
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 229910052701 rubidium Inorganic materials 0.000 description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 3
- 229910052710 silicon Inorganic materials 0.000 description 3
- 239000010703 silicon Substances 0.000 description 3
- 239000000377 silicon dioxide Substances 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 229910001928 zirconium oxide Inorganic materials 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-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
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000002860 competitive effect Effects 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000008139 complexing agent Substances 0.000 description 2
- 230000001186 cumulative effect Effects 0.000 description 2
- KYQODXQIAJFKPH-UHFFFAOYSA-N diazanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [NH4+].[NH4+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O KYQODXQIAJFKPH-UHFFFAOYSA-N 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 229910001679 gibbsite Inorganic materials 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000003112 inhibitor Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- YISKQXFNIWWETM-UHFFFAOYSA-N magnesium;dinitrate;hydrate Chemical compound O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YISKQXFNIWWETM-UHFFFAOYSA-N 0.000 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 description 2
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 2
- 150000002823 nitrates Chemical class 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 229940116315 oxalic acid Drugs 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 150000003281 rhenium Chemical class 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 2
- 239000011949 solid catalyst Substances 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- LSGOVYNHVSXFFJ-UHFFFAOYSA-N vanadate(3-) Chemical compound [O-][V]([O-])([O-])=O LSGOVYNHVSXFFJ-UHFFFAOYSA-N 0.000 description 2
- 150000003755 zirconium compounds Chemical class 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 1
- OAVRWNUUOUXDFH-UHFFFAOYSA-H 2-hydroxypropane-1,2,3-tricarboxylate;manganese(2+) Chemical compound [Mn+2].[Mn+2].[Mn+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O OAVRWNUUOUXDFH-UHFFFAOYSA-H 0.000 description 1
- MGWGWNFMUOTEHG-UHFFFAOYSA-N 4-(3,5-dimethylphenyl)-1,3-thiazol-2-amine Chemical compound CC1=CC(C)=CC(C=2N=C(N)SC=2)=C1 MGWGWNFMUOTEHG-UHFFFAOYSA-N 0.000 description 1
- QSHYGLAZPRJAEZ-UHFFFAOYSA-N 4-(chloromethyl)-2-(2-methylphenyl)-1,3-thiazole Chemical compound CC1=CC=CC=C1C1=NC(CCl)=CS1 QSHYGLAZPRJAEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002706 AlOOH Inorganic materials 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- AXVCDCGTJGNMKM-UHFFFAOYSA-L C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Ag+2] Chemical compound C(C=1C(C(=O)[O-])=CC=CC1)(=O)[O-].[Ag+2] AXVCDCGTJGNMKM-UHFFFAOYSA-L 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229920000388 Polyphosphate Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910006501 ZrSiO Inorganic materials 0.000 description 1
- VDRXMXHYWDRPDY-UHFFFAOYSA-M [Mn+].S(=O)(=O)([O-])[O-].[NH4+] Chemical compound [Mn+].S(=O)(=O)([O-])[O-].[NH4+] VDRXMXHYWDRPDY-UHFFFAOYSA-M 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 150000001339 alkali metal compounds Chemical class 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 150000001447 alkali salts Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000002238 attenuated effect Effects 0.000 description 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-M bromate Inorganic materials [O-]Br(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-M 0.000 description 1
- SXDBWCPKPHAZSM-UHFFFAOYSA-N bromic acid Chemical compound OBr(=O)=O SXDBWCPKPHAZSM-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- HUCVOHYBFXVBRW-UHFFFAOYSA-M caesium hydroxide Inorganic materials [OH-].[Cs+] HUCVOHYBFXVBRW-UHFFFAOYSA-M 0.000 description 1
- KOPBYBDAPCDYFK-UHFFFAOYSA-N caesium oxide Chemical compound [O-2].[Cs+].[Cs+] KOPBYBDAPCDYFK-UHFFFAOYSA-N 0.000 description 1
- 229910001942 caesium oxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 150000005829 chemical entities Chemical class 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- 229940116316 dihydrate oxalic acid Drugs 0.000 description 1
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 235000013312 flour Nutrition 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000010574 gas phase reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000001866 hydroxypropyl methyl cellulose Substances 0.000 description 1
- UFVKGYZPFZQRLF-UHFFFAOYSA-N hydroxypropyl methyl cellulose Chemical compound OC1C(O)C(OC)OC(CO)C1OC1C(O)C(O)C(OC2C(C(O)C(OC3C(C(O)C(O)C(CO)O3)O)C(CO)O2)O)C(CO)O1 UFVKGYZPFZQRLF-UHFFFAOYSA-N 0.000 description 1
- 235000010979 hydroxypropyl methyl cellulose Nutrition 0.000 description 1
- 229920003088 hydroxypropyl methyl cellulose Polymers 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 150000002484 inorganic compounds Chemical class 0.000 description 1
- 150000008040 ionic compounds Chemical class 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- LBSANEJBGMCTBH-UHFFFAOYSA-N manganate Chemical compound [O-][Mn]([O-])(=O)=O LBSANEJBGMCTBH-UHFFFAOYSA-N 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- 239000011564 manganese citrate Substances 0.000 description 1
- 235000014872 manganese citrate Nutrition 0.000 description 1
- 229940097206 manganese citrate Drugs 0.000 description 1
- OKVGBKABWITJQA-UHFFFAOYSA-L manganese dithionate Chemical compound [Mn+2].[O-]S(=O)(=O)S([O-])(=O)=O OKVGBKABWITJQA-UHFFFAOYSA-L 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- RGVLTEMOWXGQOS-UHFFFAOYSA-L manganese(2+);oxalate Chemical compound [Mn+2].[O-]C(=O)C([O-])=O RGVLTEMOWXGQOS-UHFFFAOYSA-L 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- ALTWGIIQPLQAAM-UHFFFAOYSA-N metavanadate Chemical class [O-][V](=O)=O ALTWGIIQPLQAAM-UHFFFAOYSA-N 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
- 150000002826 nitrites Chemical class 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- LYGJENNIWJXYER-UHFFFAOYSA-N nitromethane Chemical compound C[N+]([O-])=O LYGJENNIWJXYER-UHFFFAOYSA-N 0.000 description 1
- 239000001272 nitrous oxide Substances 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- QCTNFXZBLBPELV-UHFFFAOYSA-N oxirane;silver Chemical compound [Ag].C1CO1 QCTNFXZBLBPELV-UHFFFAOYSA-N 0.000 description 1
- DYIZHKNUQPHNJY-UHFFFAOYSA-N oxorhenium Chemical class [Re]=O DYIZHKNUQPHNJY-UHFFFAOYSA-N 0.000 description 1
- OTCVAHKKMMUFAY-UHFFFAOYSA-N oxosilver Chemical class [Ag]=O OTCVAHKKMMUFAY-UHFFFAOYSA-N 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 230000036961 partial effect Effects 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 239000001205 polyphosphate Substances 0.000 description 1
- 235000011176 polyphosphates Nutrition 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 150000003282 rhenium compounds Chemical class 0.000 description 1
- 229910003449 rhenium oxide Inorganic materials 0.000 description 1
- 238000013341 scale-up 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
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- CQLFBEKRDQMJLZ-UHFFFAOYSA-M silver acetate Chemical compound [Ag+].CC([O-])=O CQLFBEKRDQMJLZ-UHFFFAOYSA-M 0.000 description 1
- 229940071536 silver acetate Drugs 0.000 description 1
- 229940071575 silver citrate Drugs 0.000 description 1
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 1
- LMEWRZSPCQHBOB-UHFFFAOYSA-M silver;2-hydroxypropanoate Chemical compound [Ag+].CC(O)C([O-])=O LMEWRZSPCQHBOB-UHFFFAOYSA-M 0.000 description 1
- JKOCEVIXVMBKJA-UHFFFAOYSA-M silver;butanoate Chemical compound [Ag+].CCCC([O-])=O JKOCEVIXVMBKJA-UHFFFAOYSA-M 0.000 description 1
- CYLMOXYXYHNGHZ-UHFFFAOYSA-M silver;propanoate Chemical compound [Ag+].CCC([O-])=O CYLMOXYXYHNGHZ-UHFFFAOYSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- QUTYHQJYVDNJJA-UHFFFAOYSA-K trisilver;2-hydroxypropane-1,2,3-tricarboxylate Chemical compound [Ag+].[Ag+].[Ag+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QUTYHQJYVDNJJA-UHFFFAOYSA-K 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- 150000003658 tungsten compounds Chemical class 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
- 238000004876 x-ray fluorescence Methods 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
-
- 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
- B01J23/66—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
- 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
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/683—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten
- B01J23/686—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum or tungsten with 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
- 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
- B01J23/66—Silver or gold
- B01J23/68—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/688—Silver or gold with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with manganese, technetium or rhenium
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J35/61—Surface area
- B01J35/612—Surface area less than 10 m2/g
-
- 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
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- 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
- B01J35/64—Pore diameter
- B01J35/657—Pore diameter larger than 1000 nm
-
- 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
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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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
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Epoxy Compounds (AREA)
- Catalysts (AREA)
Description
1000℃及び1400℃の間の温度でアルミナを焼成してα−アルミナを含む担体を形成し、そして
次に、担体上に銀を含む触媒種を付着させることを含んでなるオレフィンのエポキシ化触媒の製造方法又はアルミナ中にケイ酸ジルコニウムを含浸させ、
1000℃及び1400℃の間の温度でアルミナを焼成してα−アルミナを含み、かつ層板又は小板の形態を有する粒子を有する担体を形成し、そして
次に、担体上に銀を含む触媒種を付着させることを含んでなるオレフィンのエポキシ化触媒の製造方法である。
によって特徴付けられる。最も好ましくは、アルキレンオキサイドはエチレンオキサイドである。このアルキレンオキサイドは、対応するアルケン、即ちR1HC=CHR2から製造される。下記の検討は、簡潔性及び例示のために、エチレンオキサイド及びエチレンの項目で、そしてこれらを参照して示す。しかしながら、本発明の範囲は、一般的に、適当なアルケンのエポキシ化のための触媒として適用可能である。
ガス再循環付き標準逆混合オートクレーブを、触媒試験のために使用する。使用するプロセス条件に依存して、気相供給濃度に於いて幾つかの変化が存在する。二つのケース、即ち、分子状酸素を供給するために空気が使用される商業的空気タイプエチレンエポキシドプロセスで使用される典型的な条件をシミュレートする空気プロセス条件及び酸素源として純粋な酸素が添加される商業的酸素タイプエチレンエポキシドプロセスに於ける典型的な条件をシミュレートする酸素プロセス条件が示される。それぞれの場合は異なった効率をもたらすが、酸素供給物としての空気では、より低い量の酸素及びエチレンが使用され、これは、酸素源として純粋な酸素が使用されるときのものよりも約2〜5%低い点であるエチレンエポキシドへの効率をもたらすことは、実際的に全ての場合について通例である。Chemical Engineering Progress、第70巻、第5号、第78〜84頁、1974年に於けるJ.M.Bertyによる報文、標題「蒸気相触媒研究用の反応器(Reactor for Vapor Phase-Catalytic Studies)」の図2に記載されている公知の逆混合、底部攪拌「マグネドライブ(Magnedrive)」オートクレーブを、反応器の一つとして使用する。入口条件は以下の通りである。
以下の例の担体を下記方法で製造した。ケイ酸ジルコニウム(使用する場合)を、他の固体原材料と共に添加して、乾燥混合物を得た。ジルコンを使用した全ての場合に、これは、約130ミクロンの半数粒子サイズを有する粉末形で導入した。次いで、液体及び追加の乾燥原材料(任意)を添加した。このような添加剤の量は、出発乾燥混合物の重量%として表す。また、水を、押出可能な混合物を得るために十分な量で添加した。このような量は、多数の要因、例えば環境湿度、原材料の水和レベル等に依存する。以下の説明に於いて他の方法で指摘しない限り、この混合物を、軸に沿った1個の開口を有する円筒として又は多分割円筒として押出した。乾燥した後、押出された素地を、α−アルミナへの押出物の完全な転換を確実にするように選択された条件下で、α−アルミナにまで焼成した。1000℃〜1400℃の焼成温度及び45分間〜5時間の焼成時間を使用した。焼成した素地の外側直径寸法は0.31〜0.35インチ(0.7874〜0.889cm)であり、円筒長さは0.29〜0.34インチ(0.7366〜0.8636cm)でありそして多分割円筒の壁厚さは0.075インチ(0.1905cm)以下であった。変性担体及び比較担体に於ける物理的特性及びジルコンの近似重量%を、表IIに示す。下記の記載中の全ての%は、重量%である。
担体に、典型的には、30重量%の酸化銀、18重量%のシュウ酸、17重量%のエチレンジアミン、6重量%のモノエタノールアミン及び27重量%の蒸留水を含有する第一含浸銀溶液を真空含浸させた。第一含浸溶液は、典型的には、(1)1.14部のエチレンジアミン(高純度グレート)を1.75部の蒸留水と混合する工程、(2)1.16部のシュウ酸二水和物(試薬グレート)を、このエチレンジアミン水溶液に、溶液の温度が40℃を超えないようにして、ゆっくり添加する工程、(3)1.98部の酸化銀をゆっくり添加する工程及び(4)0.40部のモノエタノールアミン(Fe及びClは含まず)を添加する工程によって製造した。
触媒1及び比較触媒2
それぞれの触媒80cm3(61.4g)を、オートクレーブ反応器に装入し、そして空気プロセス条件−I(表I)下で試験した。出口エチレンオキサイドを、それが1.4モル%まで増加した6日まで、1.2モル%に設定した。表IVは、2重量%のジルコンを含有する触媒(触媒1)の性能を、ジルコンを含有しない触媒(比較触媒2)の性能と比較する。ジルコンを含有する触媒は、より高い初期効率及びより低い初期温度(より高い活性)を有する。
触媒3及び比較触媒4
それぞれの触媒の等重量(63.5g)を、オートクレーブ反応器に装入し、そして表Iに記載した空気プロセス条件−I下で試験した。出口エチレンオキサイドを1.4モル%に設定し、そして温度及び効率を、触媒が老化するまでモニターした。表Vは、触媒立方フート当たり製造されたEOのポンドの関数として、この2種の触媒の性能を比較する。初期効率は、比較触媒よりも低いが、時間の経過と共に、ジルコン含有触媒は、効率及び温度に於いて、より遅い速度で老化する。
触媒5及び比較触媒6
それぞれの触媒の等重量(63.5g)を、オートクレーブ内で、酸素プロセス条件−I(表I)下で試験した。出口エチレンオキサイド濃度を1.0モル%に設定した。触媒5は、ジルコンを含有しない比較触媒6に比較して、より高い効率及びより低い温度を有する。
触媒7、触媒8及び比較触媒9
それぞれの触媒の等重量(63.5g)を、オートクレーブ内で、酸素プロセス条件−I(表I)下で試験した。出口エチレンオキサイド濃度を1.2モル%に設定した。約0.3%のジルコンを含有する触媒8は、最高の効率並びに最低の効率老化及び温度老化を有する。約3%のジルコンを含有する触媒7は、添加したジルコンを含有しない比較触媒9よりも、一層活性で、効率的である。
触媒10及び比較触媒11
それぞれの触媒の等重量(63.5g)を、オートクレーブ内で、酸素プロセス条件−I下で試験した。出口エチレンオキサイド濃度を1.0モル%に設定した。触媒10は、ジルコンを含有しない比較触媒11よりも一層安定な温度を示す。
触媒12及び比較触媒13
それぞれの触媒の等重量(63.5g)を、オートクレーブ内で、酸素プロセス条件−I下で試験した。出口エチレンオキサイド濃度を1.0モル%に設定した。ジルコン有りで製造した触媒12は、最初は効率が低く、活性が低いが、ジルコン無しで製造した比較触媒13よりも著しく低い温度老化を示す。
触媒14及び比較触媒15
それぞれの触媒の30cm3(比較触媒14について26.8g及び触媒15について26.1g)を、オートクレーブ反応器に装入し、そして酸素プロセス条件−II(表1)下で試験した。220℃と255℃との間の温度での初期運転の後、条件を21.3SCFH(0.603149標準m3/hr)の全流量のために調節し、そして温度を、1.2モル%の出口エチレンオキサイドを維持するように制御した。ジルコンを含有する触媒14の初期効率は、比較触媒15のものよりも高く、そして効率低下速度は減少する。
態様1.耐火性固体状担体に含浸された銀及び少なくとも1種の効率増強性助触媒を含んでなり、前記担体がジルコニウム成分を含有していない類似触媒に比較したときに、触媒活性、効率及び安定性の少なくとも一つを増強するのに十分な量のジルコニウム成分を含有し、前記ジルコニウム成分が実質的にケイ酸ジルコニウムとして担体中に存在するアルケンの蒸気相エポキシ化によるアルキレンオキサイド製造用触媒。
態様2.アルキレンオキサイドがエチレンオキサイドである態様1に記載の触媒。
態様3.アルキレンオキサイドがプロピレンオキサイドである態様1に記載の触媒。
態様4.含浸された銀が触媒の約2〜60重量%の量で存在する態様1に記載の触媒。
態様5.含浸された銀が触媒の約5〜50重量%の量で存在する態様4に記載の触媒。
態様6.含浸された銀が触媒の約10〜40重量%の量で存在する態様5に記載の触媒。
態様7.効率増強性助触媒の少なくとも1種が、少なくとも1種の、アルカリ金属、アルカリ土類金属及び/又は原子番号が5〜83で周期表の第3b族〜第7b族及び第3a族〜第7a族から選択された、酸素以外の元素のオキシアニオンを含む態様1に記載の触媒。
態様8.効率増強性助触媒の少なくとも1種がレドックス半反応対の一員である態様1に記載の触媒。
態様9.効率増強性助触媒の少なくとも1種がレニウム成分である態様7に記載の触媒。
態様10.ジルコニウム成分を除いた前記耐火性固体状担体が少なくとも95重量%のα−アルミナである態様1に記載の触媒。
態様11.ジルコニウム成分を除いた前記耐火性固体状担体が約2000ppmwよりも少ないカルシウムを含む態様10に記載の触媒。
態様12.ジルコニウム成分を除いた前記耐火性固体状担体が約350ppmwよりも少ないカルシウムを含む態様11に記載の触媒。
態様13.ジルコニウム成分及びカルシウム化合物を除いた前記耐火性固体状担体が、約500ppmwよりも少ない、アルカリ土類金属酸化物として測定されたアルカリ土類金属を含む態様10に記載の触媒。
態様14.ジルコニウム成分を除いた前記耐火性固体状担体が少なくとも99重量%のα−アルミナである態様1に記載の触媒。
態様15.ジルコニウム成分を除いた前記耐火性固体状担体が約2000ppmwよりも少ないカルシウムを含む態様14に記載の触媒。
態様16.ジルコニウム成分を除いた前記耐火性固体状担体が約350ppmwよりも少ないカルシウムを含む態様15に記載の触媒。
態様17.ジルコニウム成分及びカルシウム化合物を除いた前記耐火性固体状担体が約500ppmwよりも少ない、アルカリ土類金属酸化物として測定されたアルカリ土類金属を含む態様14に記載の触媒。
態様18.前記耐火性固体状担体がα−アルミナのインターロッキング小板を含む形態を有する態様14に記載の触媒。
態様19.前記耐火性固体状担体が、少なくとも約0.4m 2 /gの表面積、少なくとも約0.5cc/gの細孔体積及び約1〜25ミクロンの半数細孔直径を有する態様1に記載の触媒。
態様20.前記ジルコニウム成分が、担体の全重量基準で、約0.01〜10.0重量%のケイ酸ジルコニウムを含む態様1に記載の触媒。
態様21.前記ジルコニウム成分が、担体の全重量基準で、約0.1〜5.0重量%のケイ酸ジルコニウムを含む態様20に記載の触媒。
態様22.前記ジルコニウム成分が、担体の全重量基準で、約0.3〜3.0重量%のケイ酸ジルコニウムを含む態様21に記載の触媒。
態様23.アルケンの蒸気相エポキシ化によるアルキレンオキサイドの製造のための、態様1〜22の何れか1項に記載の触媒の使用。
態様24.前記アルキレンオキサイドがエチレンオキサイドである態様23に記載の使用。
Claims (11)
- フッ化物アニオン及びケイ酸ジルコニウムを含浸させたアルミナ担体。
- 層板又は小板の形態を有する粒子及びそれに含浸されたケイ酸ジルコニウムを含むアルミナ担体。
- 担体上に付着された銀を更に含む請求項1又は2に記載の担体。
- アルミナ中にフッ化物アニオン及びケイ酸ジルコニウムを含浸させ、
1000℃及び1400℃の間の温度でアルミナを焼成してα−アルミナを含む担体を形成し、そして
次に、担体上に銀を含む触媒種を付着させることを含んでなるオレフィンのエポキシ化触媒の製造方法。 - アルミナ中にケイ酸ジルコニウムを含浸させ、
1000℃及び1400℃の間の温度でアルミナを焼成してα−アルミナを含み、かつ層板又は小板の形態を有する粒子を有する担体を形成し、そして
次に、担体上に銀を含む触媒種を付着させることを含んでなるオレフィンのエポキシ化触媒の製造方法。 - レニウム及び硝酸塩−又は亜硝酸塩−形成性化合物の1種又はそれ以上を担体上に付着させることを更に含む請求項4又は5に記載の製法。
- 担体上にアルカリ金属助触媒を付着させることを更に含む請求項4又は5に記載の製法。
- 担体上に硫黄のオキシアニオンを助触媒として付着させることを更に含む請求項4又は5に記載の方法。
- オレフィン及び酸素を含む供給物流を、請求項4又は5に記載の方法で得られた触媒と接触させることを含んでなるオレフィンのエポキシ化方法。
- オレフィン及び酸素を含む供給物流を、請求項6に記載の方法で得られた触媒と接触させることを含んでなるオレフィンのエポキシ化方法。
- オレフィンがエチレンを含む請求項10に記載の方法。
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CA2541992C (en) | 2013-07-09 |
JP2007508143A (ja) | 2007-04-05 |
EP1675678B1 (en) | 2011-09-28 |
WO2005039757A1 (en) | 2005-05-06 |
US20070111886A1 (en) | 2007-05-17 |
TWI433720B (zh) | 2014-04-11 |
TW201039915A (en) | 2010-11-16 |
TWI365766B (en) | 2012-06-11 |
CA2541992A1 (en) | 2005-05-06 |
EP2277622A1 (en) | 2011-01-26 |
AR046294A1 (es) | 2005-11-30 |
JP4824569B2 (ja) | 2011-11-30 |
EP1675678A1 (en) | 2006-07-05 |
US20090291847A1 (en) | 2009-11-26 |
CN101757914A (zh) | 2010-06-30 |
RU2006116565A (ru) | 2007-11-27 |
EP2277622B1 (en) | 2013-01-09 |
US20100173771A1 (en) | 2010-07-08 |
TW200523022A (en) | 2005-07-16 |
US8513156B2 (en) | 2013-08-20 |
US20090275763A1 (en) | 2009-11-05 |
CN1867400B (zh) | 2010-04-14 |
US20100298128A1 (en) | 2010-11-25 |
ATE526082T1 (de) | 2011-10-15 |
CN1867400A (zh) | 2006-11-22 |
RU2360735C2 (ru) | 2009-07-10 |
JP2010149121A (ja) | 2010-07-08 |
CN101767039A (zh) | 2010-07-07 |
US8765630B2 (en) | 2014-07-01 |
CN101767039B (zh) | 2015-04-01 |
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