JP3233652B2 - Silver catalyst for ethylene oxide production - Google Patents
Silver catalyst for ethylene oxide productionInfo
- Publication number
- JP3233652B2 JP3233652B2 JP11582491A JP11582491A JP3233652B2 JP 3233652 B2 JP3233652 B2 JP 3233652B2 JP 11582491 A JP11582491 A JP 11582491A JP 11582491 A JP11582491 A JP 11582491A JP 3233652 B2 JP3233652 B2 JP 3233652B2
- Authority
- JP
- Japan
- Prior art keywords
- carrier
- silver
- cesium
- catalyst
- alumina
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 239000003054 catalyst Substances 0.000 title claims description 139
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims description 120
- 229910052709 silver Inorganic materials 0.000 title claims description 120
- 239000004332 silver Substances 0.000 title claims description 120
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims description 33
- 238000004519 manufacturing process Methods 0.000 title description 13
- 229910052792 caesium Inorganic materials 0.000 claims description 83
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 73
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 65
- 239000000243 solution Substances 0.000 claims description 64
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 47
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 claims description 44
- FLJPGEWQYJVDPF-UHFFFAOYSA-L caesium sulfate Chemical compound [Cs+].[Cs+].[O-]S([O-])(=O)=O FLJPGEWQYJVDPF-UHFFFAOYSA-L 0.000 claims description 43
- 239000011148 porous material Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 28
- 238000005470 impregnation Methods 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 19
- 239000001301 oxygen Substances 0.000 claims description 19
- 229910052760 oxygen Inorganic materials 0.000 claims description 19
- 239000011261 inert gas Substances 0.000 claims description 18
- 229940100890 silver compound Drugs 0.000 claims description 15
- 150000003379 silver compounds Chemical class 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 239000008119 colloidal silica Substances 0.000 claims description 10
- 239000002245 particle Substances 0.000 claims description 10
- 229910001111 Fine metal Inorganic materials 0.000 claims description 7
- 230000003213 activating effect Effects 0.000 claims 1
- 229910052783 alkali metal Inorganic materials 0.000 description 27
- 150000001340 alkali metals Chemical class 0.000 description 25
- 238000000034 method Methods 0.000 description 25
- 230000000694 effects Effects 0.000 description 18
- -1 alkali metal salt Chemical class 0.000 description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 14
- 239000005977 Ethylene Substances 0.000 description 14
- 239000011734 sodium Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical class 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 9
- 230000000052 comparative effect Effects 0.000 description 9
- 229910052708 sodium Inorganic materials 0.000 description 9
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical class [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 8
- 229910052700 potassium Chemical class 0.000 description 8
- 239000011591 potassium Chemical class 0.000 description 8
- 229910052701 rubidium Inorganic materials 0.000 description 7
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 5
- 230000004913 activation Effects 0.000 description 5
- 150000001412 amines Chemical class 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910001882 dioxygen Inorganic materials 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 5
- 150000007524 organic acids Chemical class 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000011068 loading method Methods 0.000 description 4
- 229910052751 metal Chemical class 0.000 description 4
- 239000002184 metal Chemical class 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 150000001342 alkaline earth metals Chemical class 0.000 description 3
- 125000002947 alkylene group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000001569 carbon dioxide Substances 0.000 description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 150000003839 salts Chemical class 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
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-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
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
- 229910052731 fluorine Inorganic materials 0.000 description 2
- 150000004820 halides Chemical class 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000011163 secondary particle Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 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
- LAXBNTIAOJWAOP-UHFFFAOYSA-N 2-chlorobiphenyl Chemical compound ClC1=CC=CC=C1C1=CC=CC=C1 LAXBNTIAOJWAOP-UHFFFAOYSA-N 0.000 description 1
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-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
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 125000000129 anionic group Chemical group 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
- 239000011230 binding agent Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 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
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 229910052754 neon Inorganic materials 0.000 description 1
- GKAOGPIIYCISHV-UHFFFAOYSA-N neon atom Chemical compound [Ne] GKAOGPIIYCISHV-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000002683 reaction inhibitor Substances 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
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 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 1
- 239000002904 solvent 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
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 150000003606 tin compounds Chemical class 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 239000012808 vapor phase Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
Description
【０００１】[0001]
【産業上の利用分野】本発明はエチレンを分子状酸素に
より接触気相酸化してエチレンオキシドを製造するに際
して使用される銀触媒に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a silver catalyst used for producing ethylene oxide by catalytically oxidizing ethylene with molecular oxygen.
【０００２】[0002]
【従来の技術】工業的にエチレンを分子状酸素により接
触気相酸化してエチレンオキシドを製造するに際し使用
される触媒には、その性能として高選択性、高活性、お
よび触媒寿命の耐久性が要求される。2. Description of the Related Art Catalysts used for industrially producing ethylene oxide by catalytic vapor-phase oxidation of ethylene with molecular oxygen are required to have high selectivity, high activity and durability of catalyst life. Is done.
【０００３】これらの要求に対し、その性能を改善する
目的で触媒調製上今日迄種々検討がなされており担体の
種類、銀触媒に添加する促進剤の種類、銀化合物等の改
良に多くの努力が払われてきた。促進剤に関する報告は
多数提案されている。たとえば、米国特許第２１２５３
３３号明細書には、ナトリウムまたはカリウムおよびそ
の金属塩を含有するアルカリ金属塩はエチレンオキシド
製造用銀触媒の添加剤として使用されることが記載され
ている。To meet these demands, various studies have been made to date on the preparation of catalysts for the purpose of improving their performance. Many efforts have been made to improve the type of carrier, the type of promoter added to the silver catalyst, the silver compound and the like. Has been paid. Many reports on accelerators have been proposed. For example, US Pat.
No. 33 describes that an alkali metal salt containing sodium or potassium and a metal salt thereof is used as an additive of a silver catalyst for producing ethylene oxide.
【０００４】米国特許第２２３８４７４号明細書には、
水酸化ナトリウムはエチレンオキシド製造用銀触媒の活
性度を向上させるが、水酸化カリウムは触媒作用に悪影
響を及ぼすことが記載されている。[0004] US Patent No. 2,238,474 discloses that
Although sodium hydroxide improves the activity of the silver catalyst for producing ethylene oxide, it is described that potassium hydroxide adversely affects the catalytic action.
【０００５】米国特許第２７６５２８３号明細書には、
担体に銀を担持する前に触媒担体に塩化ナトウムのごと
き無機塩素化物を１〜２０００ｐｐｍ重量添加すること
により触媒が改善される旨が記載されている。[0005] US Pat. No. 2,765,283 describes:
It is described that the catalyst is improved by adding 1 to 2000 ppm by weight of an inorganic chlorinated compound such as sodium chloride to the catalyst support before loading silver on the support.
【０００６】米国特許第２７９９６８７号明細書には、
２０〜１６０００ｐｐｍ重量の塩化ナトリウム、塩化カ
リウムのごときハロゲン化物は抑制剤として作用し、触
媒の活性低下を起すことが記載されている。US Pat. No. 2,799,687 describes:
It is described that halides such as sodium chloride and potassium chloride having a weight of 20 to 16000 ppm act as an inhibitor and cause a decrease in the activity of the catalyst.
【０００７】特公昭４６−３２２４２号明細書には、銀
触媒の特性が促進剤の添加によって向上されることは公
知である。促進剤としては、アルカリおよびアルカリ土
類金属の酸化物が特に有効である。促進剤は、完成した
触媒中、担体の重量を基準にして０．０３ないし０．５
重量％で一般に十分であることを開示している。また銀
触媒の製造方法として、促進剤は、銀含有溶液による含
浸と、その後につづく乾燥の後で添加することもできる
が、担体をアルカリおよびアルカリ土類金属の化合物の
水溶液で含浸させそのあとで酸素または空気のごとき酸
素含有ガス中３５０〜６５０℃乾燥後、銀含有溶液によ
る含浸と、その後につづく乾燥によりエチレンオキシド
製造用銀触媒が得られることを開示している。[0007] It is known from JP-B-46-32242 that the properties of silver catalysts are improved by the addition of promoters. Oxides of alkali and alkaline earth metals are particularly effective as accelerators. The promoter is present in the finished catalyst in an amount of from 0.03 to 0.5, based on the weight of the support.
It discloses that weight percent is generally sufficient. As a method for producing a silver catalyst, the promoter can be added after impregnation with a silver-containing solution and subsequent drying.However, the carrier is impregnated with an aqueous solution of a compound of an alkali and an alkaline earth metal, followed by impregnation. Discloses that after drying in an oxygen-containing gas such as oxygen or air at 350 to 650 ° C., impregnation with a silver-containing solution and subsequent drying yield a silver catalyst for ethylene oxide production.
【０００８】特開昭４９−３０２８６号明細書には、最
終触媒１Ｋｇあたり０．０００３ないし０．００３０グ
ラム当量のカリウム、ルビジウムおよび／またはセシウ
ムが担体上に銀と同時に堆積した銀触媒が使用できる。
触媒の表面上に存在するアルカリ金属の量は臨界的であ
る。０．０００３ないし０．００３０グラム当量の範囲
外では改良をもたらさないように見える。またアルカリ
金属の量は触媒の表面に存在する量でありそして故意
に、銀の添加と同時に触媒に添加されたものであると開
示している。JP-A-49-30286 can use a silver catalyst in which 0.0003 to 0.0030 gram equivalent of potassium, rubidium and / or cesium is deposited on a carrier simultaneously with silver on 1 kg of the final catalyst. .
The amount of alkali metal present on the surface of the catalyst is critical. Outside the 0.0003 to 0.0030 gram equivalent range, no improvement appears to result. It also discloses that the amount of alkali metal is the amount present on the surface of the catalyst and is intentionally added to the catalyst simultaneously with the addition of silver.
【０００９】特開昭５０−７４５８９号明細書には、担
体をアルカリ金属化合物の溶液で含浸処理し、少なくと
も一部乾燥し、銀含有溶液による含浸と、その後につづ
く乾燥によりエチレンオキシド製造用銀触媒が得られる
ことを開示している。JP-A-50-74589 discloses a silver catalyst for ethylene oxide production by impregnating a carrier with a solution of an alkali metal compound, drying at least partially, impregnating with a silver-containing solution, and subsequently drying. Is obtained.
【００１０】特開昭５０−１６０１８９号明細書には、
銀と一緒にアルカリ金属を沈着せしめ、カリウム、ルビ
ジウムおよび／またはセシウムが全体の触媒１Ｋｇにつ
き０．００００４〜０．００８グラム当量重量の範囲で
ある銀触媒が使用できる。またアルカリ金属の量は触媒
の表面に存在する量でありそして故意に、銀の添加と同
時に触媒に計画的に加えられる分量であると開示してい
る。[0010] JP-A-50-160189 discloses that
Alkali metals can be deposited with silver, and silver catalysts can be used in which potassium, rubidium and / or cesium range from 0.00004 to 0.008 gram equivalent weight per kg of total catalyst. It also discloses that the amount of alkali metal is the amount present on the surface of the catalyst and is intentionally the amount that is intentionally added to the catalyst at the same time as the silver is added.
【００１１】特開昭５２−１１７２９３号明細書には、
銀を含む銀触媒を１５０〜９００℃で安定化処理をし、
安定化された触媒上にカリウム、ルビジウムまたはセシ
ウムのイオンを０．００００４〜０．００８グラム当量
重量沈着させた銀触媒が使用できると開示している。[0011] JP-A-52-117293 discloses that
Stabilize the silver catalyst containing silver at 150 to 900 ° C,
It discloses that a silver catalyst having 0.00004 to 0.008 gram equivalent weight of potassium, rubidium or cesium ions deposited on the stabilized catalyst can be used.
【００１２】特開昭５０−９０５９１号明細書には、担
体中に不純物またはセメントとして存在するよりも過剰
量であって促進作用を有する量の銅、金、亜鉛、カドミ
ウム、水銀、ニオブウム、タンタル、モリリブデン、タ
ングステン、バナジウム、または好ましくはクロム、カ
ルシウム、マグネシウム、ストロンチウムおよび／また
はさらに好ましくはバリウム、ならびに好ましくはさら
に、アルカリ金属を含有するアルキレンオキシド製造用
触媒を開示している。Japanese Patent Application Laid-Open No. 50-90591 discloses copper, gold, zinc, cadmium, mercury, niobium, and tantalum in an excess amount which has an accelerating effect in excess of those present as impurities or cement in a carrier. , Molybdenum, tungsten, vanadium, or preferably a catalyst for the production of alkylene oxides containing chromium, calcium, magnesium, strontium and / or more preferably barium, and more preferably also an alkali metal.
【００１３】特開昭５２−１５１６９０号明細書には、
比表面積０．０５〜１０ｍ2 ／ｇを有する多孔質の耐熱
性担体に担持された銀を含有しさらに担体中の不純物も
しくは結合剤としての存在量以外に、促進量のナトリウ
ムとカリウム、ルビジウムおよびセシウムより成る群か
ら選ばれた少なくとも１種の促進量の他のアルカリ金属
とを含有するアルキレンオキシド製造用触媒を開示して
いる。JP-A-52-151690 discloses that
It contains silver supported on a porous refractory carrier having a specific surface area of 0.05 to 10 m 2 / g and further contains, in addition to the amount of impurities or binders in the carrier, promoting amounts of sodium and potassium, rubidium and A catalyst for the production of alkylene oxides containing at least one promoting amount of another alkali metal selected from the group consisting of cesium is disclosed.
【００１４】特開昭５４−７９１９３号明細書には、担
体上に先ず銀および場合によりナトリウムまたはリチウ
ムを該当する塩の形で施し、常法により加熱し、そして
後続の処理においてカリウム、ルビジウムおよびセシウ
ムのアルカリ金属の塩をアミンおよび／またはアンモニ
アと共に施すことによりアルキレンオキシド製造用触媒
が得られることを開示している。JP-A-54-79193 discloses that silver and optionally sodium or lithium are first applied to the support in the form of the corresponding salts, heated in a conventional manner, and then subjected to potassium, rubidium and It is disclosed that a catalyst for producing an alkylene oxide can be obtained by applying an alkali metal salt of cesium together with an amine and / or ammonia.
【００１５】特開昭５５−１２９１５０号明細書には、
担体に分解可能な銀化合物または錯体の溶液を１１０℃
以下含浸し、８５〜２００℃で銀化合物が分解して担体
に銀を担体に沈着させるのに十分な時間保つ、引続いて
残留溶液を溶媒例えばエタノールで銀含有担体から洗浄
除去する。洗浄銀含有触媒を１００℃以下で乾燥し、乾
燥銀触媒にアルカリ金属を含浸することによって担持し
てなる銀触媒を開示している。JP-A-55-129150 discloses that
A solution of a silver compound or a complex decomposable into a carrier at 110 ° C.
The impregnation is then carried out and kept at 85-200 ° C. for a time sufficient for the silver compound to decompose and deposit the silver on the carrier, followed by washing off the residual solution from the silver-containing carrier with a solvent such as ethanol. It discloses a silver catalyst obtained by drying a washed silver-containing catalyst at a temperature of 100 ° C. or lower and impregnating the dried silver catalyst with an alkali metal.
【００１６】特開昭５５−１４５６７７号明細書には、
酸化反応触媒としてアルミナ、シリカおよびチタニアの
合計含有量が９９重量％以上であり、周期率表のＶa 、
ＶＩa 、ＶＩＩa 、ＶＩＩＩ、Ｉb およびＩＩb の各族
の金属の含有量が金属酸化物合計量として０．１重量％
未満であり、かつｐＫa が＋４．８のメチルレッドによ
り酸性いろを呈しない非酸性担体に銀および必要に応じ
てさらにアルカリ金属成分又はアルカリ土類金属成分を
担持してなる銀触媒を開示している。Japanese Patent Application Laid-Open No. 55-145677 discloses that
The total content of alumina, silica and titania as an oxidation reaction catalyst is 99% by weight or more, and Va,
The content of the metal of each group of VIa, VIIa, VIII, Ib and IIb is 0.1% by weight as the total amount of metal oxides.
A silver catalyst comprising a non-acidic carrier having a pKa of less than +4.8 and having a pKa of +4.8 and not exhibiting an acidic color, and further supporting silver and, if necessary, an alkali metal component or an alkaline earth metal component. I have.
【００１７】特開昭５６−１０５７５０号明細書には、
ナトリウム成分が０．０７重量％以下、比表面積が１〜
５ｍ2 ／ｇのα―アルミナ主成分担体を、完成触媒に対
し５〜２５重量％担持率となる如き分解性銀溶液に、完
成触媒１キログラムあたり０．００１〜０．０５グラム
当量のアルカリ金属とホウ素の錯合物、アルカリ金属と
モリブデンの錯合物および／またはアルカリ金属とタン
グステンの錯合物含む含浸液で含浸処理をおこない、加
熱し、還元または熱分解して製造されたエチレンオキシ
ド製造用銀触媒を開示している。JP-A-56-105750 describes that
The sodium component is 0.07% by weight or less, and the specific surface area is 1 to
5 m 2 / g of α-alumina main component carrier was added to a decomposable silver solution having a loading of 5 to 25% by weight based on the finished catalyst, and 0.001 to 0.05 gram equivalent of alkali metal per 1 kg of the finished catalyst. For the production of ethylene oxide produced by impregnating with an impregnating solution containing a complex of iron and boron, a complex of alkali metal and molybdenum and / or a complex of alkali metal and tungsten, and heating, reducing or pyrolyzing A silver catalyst is disclosed.
【００１８】特開昭５７−１０７２４０号明細書には、
銀と触媒１キログラムあたり０．００１〜０．０５グラ
ム当量のアルカリ金属および／またはタリウムとを担体
上に担持した後、最終的に、含有酸素濃度が３容量％以
下の不活性ガス中で５００〜９５０℃の範囲で高温加熱
処理したエチレンオキシド製造用銀触媒の製造方法を開
示している。JP-A-57-107240 discloses that
After loading silver and 0.001 to 0.05 gram equivalent of alkali metal and / or thallium per kilogram of catalyst on a carrier, finally, 500 mg of inert metal having an oxygen concentration of 3% by volume or less is contained in an inert gas. A method for producing a silver catalyst for producing ethylene oxide which has been heat-treated at a high temperature in the range of ９950 ° C. is disclosed.
【００１９】特開昭５７−１０７２４１号明細書には銀
の他にカチオン成分としてナトリウム（Ｎａ）およびア
ニオン成分として塩素（Ｃｌ）を少なくとも含有し、か
つＣＩ／Ｎａの原子比が１未満となるよう割合で加えら
れているエチレンオキシド製造用銀触媒を開示してい
る。JP-A-57-107241 discloses that, in addition to silver, sodium (Na) is contained as a cation component and chlorine (Cl) is contained as an anion component, and the atomic ratio of CI / Na is less than 1. Disclosed are silver catalysts for the production of ethylene oxide which are added in proportions.
【００２０】特開昭５７−１４０６５４号明細書には銀
の他にカチオン成分としてナトリウムおよびセシウム
を、アニオン成分として塩素を少なくとも含有するエチ
レンオキシド製造用銀触媒を開示している。JP-A-57-140654 discloses a silver catalyst for producing ethylene oxide which contains sodium and cesium as cationic components and at least chlorine as anionic components in addition to silver.
【００２１】特開昭５７−１７１４３５号明細書には、
ナトリウム成分が０．０７重量％以下、比表面積が０．
５〜５ｍ2 ／ｇのα―アルミナ担体に完成触媒に対し５
〜２５重量％担持された金属銀粒子と、担体中の存在量
以外に完成触媒１キログラムあたり０．００１〜０．０
５グラム当量を担持されたアルカリ金属またはアルカリ
金属の化合物の少なくとも１種とを含有するエチレンオ
キシド製造用銀触媒を開示している。JP-A-57-171435 discloses that
The sodium component is 0.07% by weight or less, and the specific surface area is 0.1%.
5 to 5 m 2 / g of α-alumina support
-25% by weight of the supported metallic silver particles and 0.001 to 0.0
Disclosed is a silver catalyst for the production of ethylene oxide containing 5 gram equivalents of a supported alkali metal or at least one alkali metal compound.
【００２２】特開昭５９−１５６４３６号明細書には、
銀を３〜１５重量％、カチオンとしてセシウムを原子比
Ｃｓ／Ａｇが０．０１／１００〜０．４／１００になる
ように、またアニオンとしてフッ素を原子比Ｆ／Ｃｓが
５／１００〜１０になるように含有し、セシウム及び／
又はフッ素の少なくとも一部は銀と同時に担体に担持さ
れたものであるか、又は銀の担持に先立つて担体に担持
された触媒を開示している。JP-A-59-156436 describes:
Silver is used in an amount of 3 to 15% by weight, cation is cesium in an atomic ratio Cs / Ag of 0.01 / 100 to 0.4 / 100, and fluorine is an anion in an atomic ratio F / Cs of 5/100 to 10/100. Containing cesium and / or
Alternatively, a catalyst is disclosed in which at least a part of fluorine is supported on a carrier at the same time as silver, or a catalyst is supported on a carrier prior to supporting silver.
【００２３】特開昭５９−１９６７４３号明細書には、
銀を３〜１５重量％含有し、カチオンとしてセシウム及
びアニオンとして塩素を含有し、セシウム及塩素の少な
くとも一部を銀と同時に担体に担持させるか、又は銀担
持以前にあらかじめ担体に担持された触媒を開示してい
る。JP-A-59-196743 describes:
A catalyst containing 3 to 15% by weight of silver, containing cesium as a cation and chlorine as an anion, and supporting at least a part of cesium and chlorine on a carrier simultaneously with silver, or a catalyst previously supported on a carrier before carrying silver. Is disclosed.
【００２４】特開昭６２−４４４３号明細書には、アル
ミニウム化合物をスズ化合物と混合して得られた混合物
を焼成した担体に、銀とアルカリ金属を担持した触媒を
開示している。JP-A-62-2443 discloses a catalyst in which silver and an alkali metal are supported on a carrier obtained by calcining a mixture obtained by mixing an aluminum compound with a tin compound.
【００２５】特開昭６２−４４４４号明細書には、アル
ミニウム化合物を元素周期表第１Ａ族の金属の塩と混合
して得られた混合物を焼成した担体に、銀とアルカリ金
属を担持した触媒を開示している。JP-A-62-4444 discloses a catalyst in which silver and an alkali metal are supported on a carrier obtained by calcining a mixture obtained by mixing an aluminum compound with a salt of a metal of Group 1A of the periodic table. Is disclosed.
【００２６】特開昭６２−４４４５号明細書には、アル
ミニウム化合物を塩素化合物と混合して得られた混合物
を焼成した担体に、銀とアルカリ金属を担持した触媒を
開示している。Japanese Patent Application Laid-Open No. 62-4445 discloses a catalyst in which silver and an alkali metal are supported on a carrier obtained by calcining a mixture obtained by mixing an aluminum compound with a chlorine compound.
【００２７】特開昭６３−１１６７４３号明細書には、
触媒成分として銀の他にカチオン成分として少くともナ
トリウム、カリウム、ルビジウム及び／又はセシウムを
含み、かつ担体が主としてα―アルミナよりなりその表
面積が０．６〜２ｍ2 ／ｇ、吸水率が２０〜５０％、シ
リカ含量０．５〜１２重量％、かつ表面積当りのシリカ
含量（重量％／ｍ2 ／ｇ）が０．５〜１２，好ましくは
１〜８であって、ナトリウム含量が０．０８〜２重量％
であるエチレンオキシド製造用銀触媒を開示している。JP-A-63-116743 describes:
It contains at least sodium, potassium, rubidium and / or cesium as a cation component in addition to silver as a catalyst component, and mainly comprises α-alumina, has a surface area of 0.6 to 2 m 2 / g, and has a water absorption of 20 to 50%, a silica content of 0.5 to 12% by weight, a silica content per surface area (% by weight / m 2 / g) of 0.5 to 12, preferably 1 to 8, and a sodium content of 0.08 ~ 2% by weight
And a silver catalyst for producing ethylene oxide.
【００２８】特開平２−１９４８３９号明細書には、α
―アルミナ担体にコロイド状シリカを含有する水溶液を
含浸し、ついで加熱乾燥し、さらに焼成して得られた担
体の外表面上および担体の気孔の表面上が非晶質シリカ
で被覆されたα―アルミナ担体に完成触媒当り５〜２５
重量％の金属銀微粒子および完成触媒１キログラム当り
０．００１〜０．０５グラム当量重量のセシウムを担持
せしめた後、賦活化処理して、銀とセシウムとを多孔性
無機質耐火性担体に析出した後、含有酸素濃度が３容量
％以下の不活性ガス中で４００〜９５０℃の範囲で高温
加熱処理して得られるエチレンオキシド製造用銀触媒触
媒を開示している。In the specification of Japanese Patent Application Laid-Open No. 2-194839, α
-An alumina carrier is impregnated with an aqueous solution containing colloidal silica, then heated and dried, and further calcined.The outer surface of the carrier and the surface of pores of the carrier are coated with amorphous silica. 5-25 per finished catalyst on alumina carrier
% Of metallic silver fine particles and 0.001 to 0.05 gram equivalent weight of cesium per kilogram of the finished catalyst, and then activated to deposit silver and cesium on the porous inorganic refractory carrier. A silver catalyst catalyst for producing ethylene oxide, which is obtained by subsequently performing high-temperature heat treatment at 400 to 950 ° C. in an inert gas having an oxygen concentration of 3% by volume or less is disclosed.
【００２９】以上の特許公報明細書で開示されたエチレ
ンオキシド製造用銀触媒触媒の多くは担体を限定し、促
進剤としてアルカリ金属担持量を限定し、アルカリ金属
以外の促進剤の担持量を限定し、銀とアルカリ金属また
は銀とアルカリ金属およびアルカリ金属以外の促進剤を
担体に担持する方法を限定して触媒性能を向上させてい
るものである。Most of the silver catalysts for ethylene oxide production disclosed in the above-mentioned patent publications have a limited carrier, a limited amount of an alkali metal as a promoter, and a limited amount of a promoter other than an alkali metal. The catalyst performance is improved by limiting the method of loading a carrier with silver and an alkali metal or an accelerator other than silver and an alkali metal or an alkali metal.
【００３０】[0030]
【発明が解決しようとする課題】エチレンオキシド製造
用銀触媒の調製方法についてまだ不明な点も多く改良す
べき問題が数多く存在する。たとえば特開昭４９−３０
２８６号明細書に開示されている最終触媒１Ｋｇあたり
０．０００３ないし０．００３０グラム当量のカリウ
ム、ルビジウムおよび／またはセシウムが担体上に銀と
同時に堆積した銀触媒は反応の初期のエチレンのエチレ
ンオキシドへの選択率の向上は大きいが選択率の低下が
早期に起きるため触媒の寿命に問題がある。There are still many unclear points about the method for preparing a silver catalyst for producing ethylene oxide, and there are many problems to be improved. For example, JP-A-49-30
The silver catalyst disclosed in US Pat. No. 286, in which 0.0003 to 0.0030 gram equivalents of potassium, rubidium and / or cesium per kg of the final catalyst are deposited simultaneously with silver on the support, converts the ethylene into ethylene oxide at the beginning of the reaction. The selectivity of the catalyst is greatly improved, but the selectivity is reduced at an early stage.
【００３１】一方、特開昭５７−１０７２４０号明細書
に開示されている銀と触媒１キログラムあたり０．００
１〜０．０５グラム当量のアルカリ金属および／または
タリウムとを担体上に担持した後、最終的に、含有酸素
濃度が３容量％以下の不活性ガス中で５００〜９５０℃
の範囲で高温加熱処理したエチレンオキシド製造用銀触
媒は、反応の初期のエチレンのエチレンオキシドへの選
択率の向上および触媒の寿命が改善されている。On the other hand, silver disclosed in JP-A-57-107240 and 0.00 per kilogram of catalyst are disclosed.
After supporting 1 to 0.05 gram equivalent of alkali metal and / or thallium on the carrier, finally, the carrier is placed in an inert gas having an oxygen concentration of 3% by volume or less at 500 to 950 ° C.
The silver catalyst for producing ethylene oxide heat-treated at a high temperature in the range described above has improved selectivity of ethylene to ethylene oxide in the initial stage of the reaction and improved catalyst life.
【００３２】現在までに銀触媒に添加する促進剤に関す
る特許が数多く出されているが、その多くは限定された
範囲内のアルカリ金属およびアルカリ金属以外の促進剤
を銀触媒に添加することにより触媒性能を向上させてい
るものである。さらにはアルカリ金属および促進剤を銀
触媒に添加する順序を変えて銀触媒を調製し触媒性能を
向上させているものである。しかしながらこれらの特許
公報明細書で開示されたエチレンオキシド製造用銀触媒
はエチレンのエチレンオキシドへの選択率の向上および
その後の触媒寿命の点で改良の課題がある。To date, a number of patents have been issued relating to promoters to be added to silver catalysts, and most of them have been obtained by adding promoters other than alkali metals and non-alkali metals within a limited range to silver catalysts. The performance is improved. Further, the order of adding the alkali metal and the promoter to the silver catalyst is changed to prepare a silver catalyst to improve the catalytic performance. However, the silver catalysts for producing ethylene oxide disclosed in these patent publications have a problem of improvement in selectivity of ethylene to ethylene oxide and subsequent catalyst life.
【００３３】したがって、本発明の目的は特定の担体の
選択、担体に担持するセシウム化合物の選択、担体にセ
シウム化合物を担持する方法の選択、セシウムの担持し
た担体に添加する銀化合物およびセシウム化合物の選
択、セシウムの担持した担体に銀触媒およびセシウムを
担持する方法の選択、以上の組み合せの最適化を図るこ
とにより高選択性、高活性および触媒寿命の耐久性の各
性能を合せもった新規なエチレンオキシド製造用銀触媒
を提供することにある。Accordingly, an object of the present invention is to select a specific carrier, a cesium compound to be supported on a carrier, a method of supporting a cesium compound on a carrier, and a method of selecting a silver compound and a cesium compound to be added to a cesium-supported carrier. Selection, selection of the method of supporting the silver catalyst and cesium on the cesium-supported carrier, and optimization of the above combination provide a new selectivity that combines high selectivity, high activity, and durability of catalyst life. An object of the present invention is to provide a silver catalyst for producing ethylene oxide.
【００３４】本発明の他の目的は、α―アルミナ担体の
外表面上および担体の気孔の表面上が非晶質シリカで被
覆された担体を使用し、担体にセシウム化合物を担持す
る方法の選択、セシウムの担持した担体に添加する銀化
合物およびセシウム化合物の選択、セシウムの担持した
担体に銀触媒およびセシウムを担持する方法の選択、以
上の組み合せの最適化を図ることにより触媒性能を向上
した新規なエチレンオキシド製造用銀触媒を提供するこ
とにある。Another object of the present invention is to use a carrier coated with amorphous silica on the outer surface of an α-alumina carrier and on the surface of pores of the carrier, and to select a method for supporting a cesium compound on the carrier. , The selection of a silver compound and a cesium compound to be added to a cesium-supported carrier, the selection of a method of supporting a cesium-supported silver catalyst and a cesium on a cesium-supported carrier, and optimization of the above combination to improve the catalyst performance. To provide a silver catalyst for producing ethylene oxide.
【００３５】本発明者等はエチレンオキシド製造用銀触
媒に用いる好適な担体を構成する成分および担体の比表
面積に関する研究を行なった結果、従来当分野の工業的
規模で用いられている銀触媒に使用される担体の中で担
体の外表面上および担体の気孔の表面上が非晶質シリカ
の層で被覆されたα―アルミナ担体を用い、硝酸セシウ
ム溶液で含浸処理を行ない、ついで乾燥し、さらに４０
０〜１２００℃の範囲で高温加熱処理した後、担体に銀
化合物溶液および硫酸セシウム溶液で含浸処理を行な
い、ついで乾燥、賦活化処理して、銀とセシウムとを担
体に析出担持した銀触媒は、これまでになく、高選択性
でしかも高活性を長期に渡って維持できる触媒が得られ
ることを見出して本発明を完成した。The present inventors have conducted studies on the components constituting the carrier suitable for use in the silver catalyst for producing ethylene oxide and the specific surface area of the carrier. As a result, the inventors have found that the silver catalyst used for the silver catalyst conventionally used on an industrial scale in this field is used. Using an α-alumina carrier in which the outer surface of the carrier and the surface of the pores of the carrier are coated with a layer of amorphous silica, the carrier is impregnated with a cesium nitrate solution, then dried, and further dried. 40
After heat treatment at a high temperature in the range of 0 to 1200 ° C., the carrier is impregnated with a silver compound solution and a cesium sulfate solution, then dried and activated to deposit silver and cesium on the carrier. As a result, the present inventors have found that a catalyst which has high selectivity and can maintain high activity for a long period of time can be obtained, and completed the present invention.
【００３６】[0036]
【課題を解決するための手段】本発明はα―アルミナ担
体にコロイド状シリカを含有する水溶液を含浸し、つい
で加熱乾燥し、さらに焼成して得られた担体の外表面上
および担体の気孔の表面上が非晶質シリカの層で被覆さ
れたα―アルミナ担体に、セシウムが担体１キログラム
当り０．０００１〜０．０４５グラム当量重量の濃度に
なるように、硝酸セシウム溶液で含浸処理を行ない、つ
いで乾燥し、含有酸素濃度が３容量％以下の不活性ガス
中で４００〜１２００℃の範囲で高温加熱処理した後、
担体に完成触媒当り５〜２５重量％の金属銀微粒子およ
びセシウムが完成触媒１キログラム当り０．００１〜
０．０５グラム当量重量の濃度になるように、銀化合物
溶液および硫酸セシウム溶液で含浸処理を行ない、つい
で乾燥、賦活化処理して、銀とセシウムとを担体に析出
担持したことを特徴とするエチレンオキシド製造用銀触
媒に関するものである。According to the present invention, an α-alumina carrier is impregnated with an aqueous solution containing colloidal silica, then heated and dried, and then calcined. An α-alumina carrier whose surface is coated with a layer of amorphous silica is impregnated with a cesium nitrate solution so that cesium has a concentration of 0.0001 to 0.045 gram equivalent weight per kilogram of carrier. Then, after drying and heating at a high temperature of 400 to 1200 ° C. in an inert gas having an oxygen content of 3% by volume or less,
The carrier contains 5 to 25% by weight of fine metal silver and cesium per finished catalyst in an amount of 0.001 to 1 kg per finished catalyst.
Impregnated with a silver compound solution and a cesium sulfate solution so as to have a concentration of 0.05 gram equivalent weight, then dried and activated to deposit silver and cesium on the carrier. The present invention relates to a silver catalyst for producing ethylene oxide.
【００３７】[0037]
【作用】エチレンオキシド製造用銀触媒に用いる好適な
担体に関する研究によれば、比表面積が０．１〜５ｍ2
／ｇ、見掛気孔率４５〜７０％よりなる担体の外表面上
および担体の気孔の表面上が非晶質シリカの層で被覆さ
れたα―アルミナ担体を用いた場合、触媒にしたときの
選択率の低さのゆえに当該分野の工業的規模において一
般的に用いられることのなかった比較的高比表面績の担
体をも有効に使用でき、これと特にセシウムが担体１キ
ログラム当り０．０００１〜０．０４５グラム当量重量
の濃度になるように、硝酸セシウム溶液で含浸処理を行
ない、ついで乾燥し、含有酸素濃度が３容量％以下の不
活性ガス中で４００〜１２００℃の範囲で高温加熱処理
した後、担体に完成触媒当り５〜２５重量％の金属銀微
粒子およびセシウムが完成触媒１キログラム当り０．０
０１〜０．０５グラム当量重量の濃度になるように、銀
化合物溶液および硫酸セシウム溶液で含浸処理を行な
い、ついで乾燥、賦活化処理して、銀とセシウムとを担
体に析出担持して得られた触媒はこれまでになく高活、
高選択性、耐久性の触媒が得られることを見い出したも
のである。According to a study on a suitable carrier used for a silver catalyst for producing ethylene oxide, the specific surface area is 0.1 to 5 m 2.
/ G, an α-alumina carrier coated with a layer of amorphous silica on the outer surface of the carrier having an apparent porosity of 45 to 70% and on the surface of the pores of the carrier when the catalyst is used. Due to the low selectivity, carriers having a relatively high specific surface, which have not been commonly used on an industrial scale in the field, can also be used effectively, and in particular cesium can be used in an amount of 0.0001 kg / kg of carrier. Impregnation with a cesium nitrate solution to a concentration of ０．０0.045 gram equivalent weight, followed by drying and heating at a high temperature in the range of 400 to 1200 ° C. in an inert gas having an oxygen concentration of 3% by volume or less. After the treatment, the carrier contains 5 to 25% by weight of fine metal silver particles and cesium per 0.0 kg of the finished catalyst per kilogram of the finished catalyst.
An impregnation treatment with a silver compound solution and a cesium sulfate solution is performed so as to have a concentration of 01 to 0.05 gram equivalent weight, followed by drying and activation treatment to deposit and carry silver and cesium on a carrier. Catalyst is more active than ever,
It has been found that a highly selective and durable catalyst can be obtained.
【００３８】エチレンを分子状酸素により接触気相酸化
してエチレンオキシドを製造する際に用いられる触媒は
銀触媒であり、そのほとんどが担体を使用した担持触媒
であることは言うまでもないことである。また、用いら
れる担体が多孔性粒状耐火物であることも周知である。The catalyst used in producing ethylene oxide by subjecting ethylene to catalytic gas phase oxidation with molecular oxygen is a silver catalyst. It goes without saying that most of the catalyst is a supported catalyst using a carrier. It is also well known that the carrier used is a porous granular refractory.
【００３９】しかしながら、単に多孔性粒状耐火物担体
と言っても千差万別で担体の比表面積、細孔分布、細孔
容積、粒径、形状等の物理的性質及び担体を構成する材
質、例えばα―アルミナ、シリカ、シリコンカ―バイ
ド、ジルコニア、粘土等のもつ化学的性質等、これらの
物理的および化学的性質が触媒の性能に及ぼす影響は大
きい。However, the porous granular refractory carrier is simply different in physical properties such as specific surface area, pore distribution, pore volume, particle size, shape, etc. of the carrier and the material constituting the carrier. These physical and chemical properties, such as the chemical properties of α-alumina, silica, silicon carbide, zirconia, clay and the like, have a great effect on the performance of the catalyst.
【００４０】したがつてどのような性質の担体を選ぶか
は、当業者にとって大きな問題である。担体の物性の中
でも比表面積は細孔径にも関係し、触媒性能に与える影
響は大きく大いに留意しなければならない。即ち、活
性、耐久性の面から考えると触媒比表面積は大きい方が
良く、その為には担体比表面は大きい方が望ましいが担
体比表面積を大きくする為には担体材料のアルミナ粒子
は小さいものを選ぶ必要がある。そのことは必然的に小
さな細孔径の形成を意味する。このことはガスの拡散滞
留、反応熱の除去という点から考えると不利になる。ま
た担体表面の露出面積が増大することからも不利であ
る。これ等のことはいずれも選択率の低下につながる。
このような事実から、必ずしも比表面積は大きい方が良
いとばかりは言えず自ずと制限が出てくる。これ迄の工
業的規模に採用されている大部分の担体の比表面積は１
ｍ2 ／ｇ以下であり、さらには０．５ｍ2 ／ｇ以下であ
る。例外的には１ｍ2 ／ｇ以上の担体を使った例もある
が、低表面積のものより選択率は低い。Thus, the nature of the carrier to be selected is a major problem for those skilled in the art. Among the physical properties of the support, the specific surface area is also related to the pore diameter, and the effect on the catalyst performance has to be paid great attention. In other words, from the viewpoint of activity and durability, the larger the specific surface area of the catalyst is, the better the specific surface area of the carrier is. For this purpose, the larger the specific surface area of the carrier is, the larger the specific surface area of the carrier is. You need to choose That necessarily implies the formation of small pore sizes. This is disadvantageous in terms of gas diffusion retention and removal of reaction heat. It is also disadvantageous because the exposed area of the carrier surface increases. All of these lead to a decrease in selectivity.
From such a fact, it is not always possible to say that a larger specific surface area is better, and there is naturally a limitation. The specific surface area of most of the carriers used up to now on an industrial scale is 1
m 2 / g or less, and further 0.5 m 2 / g or less. Exceptionally, there is a case where a carrier of 1 m 2 / g or more is used, but the selectivity is lower than that of a carrier having a low surface area.
【００４１】本発明者等は、これ等の欠点を無くすべく
検討した結果、これまでの０．５ｍ2 ／ｇ以下の比表面
積のものだけでなく０．５ｍ2 ／ｇ以上の大きな比表面
積の担体を用いても選択率の低下を招くことなく、さら
に向上させかつ高活性、耐久性を維持、促進させる方法
を発見した。それは簡単にはα―アルミナ担体にコロイ
ド状シリカを含有する水溶液を含浸し、ついで加熱乾燥
し、さらに焼成して得られた担体の外表面上および担体
の気孔の表面上が非晶質シリカの層で被覆されたα―ア
ルミナ担体に、セシウムが担体１キログラム当り０．０
００１〜０．０４５グラム当量重量の濃度になるよう
に、硝酸セシウム溶液で含浸処理を行ない、ついで乾燥
し、含有酸素濃度が３容量％以下の不活性ガス中で４０
０〜１２００℃の範囲で高温加熱処理した後、担体に完
成触媒当り５〜２５重量％の金属銀微粒子およびセシウ
ムが完成触媒１キログラム当り０．００１〜０．０５グ
ラム当量重量の濃度になるように、銀化合物溶液および
硫酸セシウム溶液で含浸処理を行ない、ついで乾燥、賦
活化処理して、銀とセシウムとを担体に析出担持したこ
とにより達成される。このことは、特に０．７５ｍ2 ／
ｇ以上の高比表面積担体に有効で、また増量されたセシ
ウム化合物添加触媒に有効である。このような物性面か
らの不利益が担体の化学的性質特に担体の外表面上およ
び担体の気孔の表面上が非晶質シリカの層で被覆された
α―アルミナ担体を、硝酸セシウム溶液で含浸処理を行
ない、４００〜１２００℃の範囲で高温加熱処理した
後、銀化合物溶液および硫酸セシウム溶液で含浸処理を
行ない、銀とセシウムとを担体に析出担持したことによ
って改善されることは驚くべきことである。The present inventors have studied to eliminate these drawbacks, and as a result, they have found that not only those having a specific surface area of 0.5 m 2 / g or less but also those having a large specific surface area of 0.5 m 2 / g or more. The present inventors have found a method of further improving the activity and maintaining and promoting high activity and durability without lowering the selectivity even when a carrier is used. Briefly, an α-alumina carrier is impregnated with an aqueous solution containing colloidal silica, then heated and dried, and then calcined.The outer surface of the carrier obtained and the surface of the pores of the carrier are made of amorphous silica. Cesium was added to the α-alumina carrier coated with
Impregnation with a cesium nitrate solution is performed to a concentration of 001 to 0.045 gram equivalent weight, followed by drying and 40% in an inert gas having an oxygen concentration of 3% by volume or less.
After high-temperature heat treatment in the range of 0 to 1200 ° C., the carrier is provided with a concentration of 5 to 25% by weight of fine metal silver and cesium per finished catalyst in a concentration of 0.001 to 0.05 gram equivalent weight per kilogram of the finished catalyst. Then, a silver compound solution and a cesium sulfate solution are used for impregnation, followed by drying and activation to deposit silver and cesium on a carrier. This is especially true for 0.75 m 2 /
It is effective for a carrier having a high specific surface area of at least g and a catalyst for adding an increased amount of a cesium compound. Such disadvantages in terms of physical properties are due to the fact that the chemistry of the carrier, particularly the outer surface of the carrier and the surface of the pores of the carrier, are covered with an amorphous silica layer by impregnating the α-alumina carrier with a cesium nitrate solution. It is surprising that the improvement is achieved by performing the treatment, performing high-temperature heat treatment in the range of 400 to 1200 ° C., performing impregnation with a silver compound solution and a cesium sulfate solution, and depositing and supporting silver and cesium on the carrier. It is.
【００４２】本発明によれば担体の外表面上および担体
の気孔の表面上は触媒性能に微妙に影響し、特に従来当
分野で通常使われている比表面積０．５ｍ2 ／ｇ以下の
担体ではその悪い影響は、比表面積が小さくなる程小さ
いが、０．５ｍ2 ／ｇ以上になるとだんだん大きくなり
０．７５ｍ2 ／ｇ以上になるとその影響は顕著になる。
ところがこれまで選択率が低くなるゆえに使われなかっ
た比表面積０．７５ｍ2 ／ｇ以上の担体、すなわち比表
面積が０．７５〜５ｍ2 ／ｇ、見掛気孔率４５〜７０
％、５０〜１００μのアルミナ２次粒子を使用したα―
アルミナ担体が本発明においては使用可能になるばかり
でなく、さらには活性、選択性において優位にさえなる
ことか見い出された。そのことは後述の実施例でも解る
様に、同じ０．８９ｍ2 ／ｇぐらいの比表面積の担体で
も担体の外表面上および担体の気孔の表面上が非晶質シ
リカの層で被覆されたα―アルミナ担体に、セシウムが
担体１キログラム当り０．０００１〜０．０４５グラム
当量重量の濃度になるように、硝酸セシウム溶液で含浸
処理を行ない、ついで乾燥し、含有酸素濃度が３容量％
以下の不活性ガス中で４００〜１２００℃の範囲で高温
加熱処理した担体では他の物性が多少関係あるにして
も、この担体にさらに銀化合物溶液および硫酸セシウム
溶液で含浸処理を行ない、銀とセシウムを添加した触媒
にしたときの触媒の寿命に性能の差が出ることは驚くべ
きことである。このことがどういう作用によるか、我々
には正確には分らない。ただ担体の外表面上および担体
の気孔の表面上に一定の範囲で非晶質シリカの層が存在
することが良いということ、また非晶質シリカの層で被
覆されたα―アルミナ担体に、硝酸セシウム溶液で含浸
処理を行ない、ついで乾燥し、含有酸素濃度が３容量％
以下の不活性ガス中で４００〜１２００℃の範囲で高温
加熱処理した後、担体に完成触媒当り５〜２５重量％の
金属銀微粒子およびセシウムが完成触媒１キログラム当
り０．００１〜０．０５グラム当量重量の濃度になるよ
うに、銀化合物溶液および硫酸セシウム溶液で含浸処理
を行ない、ついで乾燥、賦活化処理して、銀とセシウム
とを担体に析出担持したことにより、従来の触媒に比較
し、選択率の向上があることが触媒性能に関係してい
る。According to the present invention, the catalytic performance is slightly affected on the outer surface of the support and on the surface of the pores of the support, and particularly, the support having a specific surface area of 0.5 m 2 / g or less conventionally used in the art. However, the adverse effect is smaller as the specific surface area is smaller, but is gradually increased when the specific surface area is 0.5 m 2 / g or more, and becomes remarkable when the specific surface area is 0.75 m 2 / g or more.
However, a carrier having a specific surface area of 0.75 m 2 / g or more, which has not been used because of low selectivity, ie, a specific surface area of 0.75 to 5 m 2 / g and an apparent porosity of 45 to 70, has been used.
%, Using an alumina secondary particle of 50 to 100 μ
It has been found that alumina supports are not only usable in the present invention, but are even superior in activity and selectivity. As will be understood from the examples described later, even with the same specific surface area of about 0.89 m 2 / g, α is such that the outer surface of the support and the surface of the pores of the support are coated with a layer of amorphous silica. -Impregnating the alumina carrier with a cesium nitrate solution so that cesium has a concentration of 0.0001 to 0.045 gram equivalent weight per kilogram of the carrier, and then dried, and the oxygen content is 3% by volume.
In the following inert gas, the carrier heat-treated at a high temperature in the range of 400 to 1200 ° C. is impregnated with a silver compound solution and a cesium sulfate solution. It is surprising that there is a difference in the performance of the catalyst when cesium is added to the catalyst. We do not know exactly what effect this is. However, it is good that the amorphous silica layer is present in a certain range on the outer surface of the carrier and on the surface of the pores of the carrier.Also, in the α-alumina carrier coated with the amorphous silica layer, Impregnation treatment with cesium nitrate solution, then drying, containing oxygen concentration of 3% by volume
After high-temperature heat treatment in the range of 400 to 1200 ° C. in the following inert gas, 5 to 25% by weight of fine metal silver and cesium per kilogram of the finished catalyst are added to the carrier in an amount of 0.001 to 0.05 grams per kilogram of the finished catalyst. Impregnation was performed with a silver compound solution and a cesium sulfate solution so as to obtain a concentration of equivalent weight, followed by drying and activation treatment to deposit and carry silver and cesium on a carrier. The improvement in selectivity is related to the catalyst performance.
【００４３】本発明のα―アルミナ担体にコロイド状シ
リカを含有する水溶液を含浸し、ついで加熱乾燥し、さ
らに焼成して得られた担体の外表面上および担体の気孔
の表面上が非晶質シリカの層で被覆されたα―アルミナ
担体に、セシウムが担体１キログラム当り０．０００１
〜０．０４５グラム当量重量の濃度になるように、硝酸
セシウム溶液で含浸処理する際の好適な添加量の範囲
は、セシウムが担体１キログラム当り０．０００１〜
０．０４５グラム当量重量、好ましくは０．０００１〜
０．０２５グラム当量重量であり、特に好ましくは０．
００１グラム当量重量を越えかつ０．０２５グラム当量
重量以下である。The α-alumina carrier of the present invention is impregnated with an aqueous solution containing colloidal silica, then dried by heating, and then calcined. The outer surface of the carrier and the surface of the pores of the carrier are amorphous. On an α-alumina support coated with a layer of silica, cesium was added at 0.0001 / kg of support.
The preferred range of the amount of the cesium nitrate solution to be impregnated with the cesium nitrate solution is 0.0001 to 0.045 gram equivalent weight per kilogram of the carrier.
0.045 gram equivalent weight, preferably 0.0001 to
0.025 gram equivalent weight, particularly preferably 0.1 g.
Not less than 001 gram equivalent weight and not more than 0.025 gram equivalent weight.
【００４４】また、本発明のα―アルミナ担体にコロイ
ド状シリカを含有する水溶液を含浸し、ついで加熱乾燥
し、さらに焼成して得られた担体の外表面上および担体
の気孔の表面上が非晶質シリカの層で被覆されたα―ア
ルミナ担体に、セシウムが担体１キログラム当り０．０
００１〜０．０４５グラム当量重量の濃度になるよう
に、硝酸セシウム溶液で含浸処理を行ない、ついで乾燥
し、含有酸素濃度が３容量％以下の不活性ガス中で４０
０〜１２００℃の範囲で高温加熱処理した後、担体に完
成触媒当り５〜２５重量％の金属銀微粒子およびセシウ
ムが完成触媒１キログラム当り０．００１〜０．０５グ
ラム当量重量のセシウムを担持せしめる際の好適な硫酸
セシウムの添加量の範囲は、セシウムが完成触媒１キロ
グラム当り０．００１〜０．０５グラム当量重量、好ま
しくは０．００１〜０．０３グラム当量重量であり、特
に好ましくは０．００６グラム当量重量を越えかつ０．
０３グラム当量重量以下である。Further, the α-alumina carrier of the present invention is impregnated with an aqueous solution containing colloidal silica, then dried by heating, and then calcined. Cesium was added to the α-alumina carrier coated with a layer of
Impregnation with a cesium nitrate solution is performed to a concentration of 001 to 0.045 gram equivalent weight, followed by drying and 40% in an inert gas having an oxygen concentration of 3% by volume or less.
After high-temperature heat treatment in the range of 0 to 1200 ° C., 5 to 25% by weight of fine metal silver particles and cesium on the carrier are loaded with 0.001 to 0.05 gram equivalent weight of cesium per kilogram of the finished catalyst on the carrier. The preferred range of the amount of cesium sulfate added is 0.001 to 0.05 gram equivalent weight of cesium per kilogram of the finished catalyst, preferably 0.001 to 0.03 gram equivalent weight, particularly preferably 0 to 0.03 gram equivalent weight. Over 0.006 gram equivalent weight and 0.
Not more than 03 gram equivalent weight.
【００４５】本発明のα−アルミナ担体の比表面積とし
ては、比表面積が０．１〜５ｍ2 ／ｇの範囲、好ましく
は０．３〜３ｍ2 ／ｇ、さらに好ましくは０．７５〜２
ｍ2／ｇのものが有効である。５ｍ2 ／ｇを越えるもの
は実質的に良いものは得られてないので実際的でない。[0045] As the specific surface area of α- alumina carrier of the present invention, ranges specific surface area of 0.1 to 5 m 2 / g, preferably 0.3~3m 2 / g, more preferably 0.75 to 2
Those with m 2 / g are effective. Those exceeding 5 m 2 / g are not practical because substantially no good ones have been obtained.
【００４６】本明細書における比表面積はＢｒｕｎａｕ
ｅｒ−Ｅｍｍｅｔｔ−Ｔｅｌｌｅｒ（以下、ＢＥＴとい
う）法により測定される値である。The specific surface area in this specification is Brunau
This is a value measured by the er-Emmett-Teller (hereinafter, referred to as BET) method.
【００４７】さらにまたα−アルミナの担体成分は当分
野で慣用の担体に含まれる程度の成分および量が好まし
い。Further, the component and amount of the carrier component of α-alumina are preferably such that they are contained in a carrier commonly used in the art.
【００４８】本発明のα−アルミナ担体の見かけの気孔
率は４５〜７０％、特に５０〜６０％が好ましい。The apparent porosity of the α-alumina carrier of the present invention is preferably 45 to 70%, particularly preferably 50 to 60%.
【００４９】本発明のα−アルミナ担体の比気孔容積は
０．１〜０．８ｃｃ／ｇ、特に０．２〜０．５ｃｃ／ｇ
が好ましい。The α-alumina carrier of the present invention has a specific pore volume of 0.1 to 0.8 cc / g, particularly 0.2 to 0.5 cc / g.
Is preferred.
【００５０】本発明のα−アルミナ担体は粒径３〜２０
ｍｍのα−アルミナ主成分、好ましくは９０重量％以上
がα−アルミナ成分であり、１〜１００μのアルミナ２
次粒子であるα―アルミナ担体が使用できる。なお、本
発明で使用される担体は球、ペレット、リング等の粒状
の耐火性担体であり、その平均相当直径は３〜２０ｍ
ｍ、特に担体を構成する成分、担体の比表面積は触媒性
能に大きく関係し、触媒製造時、銀とセシウムおよび／
またはセシウム化合物の担持工程において均一なる担持
の容易な担体の形状を選ぶことが選択性に優れた触媒を
得ることになる。またα―アルミナ担体としては、例え
ば好ましくはＢＥＴ比表面積０．７５〜２ｍ2 ／ｇ、見
掛気孔率５０〜６０％、細孔容積０．２〜０．５ｃｃ／
ｇ、粒径３〜２０ｍｍのα−アルミナ主成分、好ましく
は９０重量％以上がα−アルミナ成分であるα−アルミ
ナ担体に、粒径５〜５０ミリミクロンのコロイド状シリ
カを担体含水量分の水に分散した液を含浸し、加熱濃縮
乾燥後、７００〜１５００℃で１〜１０時間焼成し、得
られた担体の外表面上および担体の気孔の表面上が非晶
質シリカの層で被覆されたα―アルミナ担体が好適であ
る。The α-alumina carrier of the present invention has a particle size of 3 to 20.
mm of α-alumina main component, preferably 90% by weight or more is α-alumina component, and 1 to 100 μm of alumina 2
An α-alumina carrier as a secondary particle can be used. The carrier used in the present invention is a granular refractory carrier such as a sphere, a pellet, and a ring, and the average equivalent diameter thereof is 3 to 20 m.
m, especially the components constituting the carrier and the specific surface area of the carrier are greatly related to the catalyst performance.
Alternatively, a catalyst having excellent selectivity can be obtained by selecting a uniform and easily supported carrier shape in the cesium compound supporting step. As the α-alumina carrier, for example, preferably a BET specific surface area of 0.75 to 2 m 2 / g, an apparent porosity of 50 to 60%, and a pore volume of 0.2 to 0.5 cc /
g, an α-alumina main component having a particle size of 3 to 20 mm, preferably 90% by weight or more of an α-alumina component, and colloidal silica having a particle size of 5 to 50 mm are added to the carrier water content. Impregnated with a liquid dispersed in water, heat-concentrated and dried, and calcined at 700 to 1500 ° C. for 1 to 10 hours. The outer surface of the obtained carrier and the surface of pores of the carrier are covered with a layer of amorphous silica. Α-alumina supports are preferred.
【００５１】本発明のα−アルミナ担体はα―アルミナ
担体に対して、担体１グラムあたりＳｉとして３×１０
-4〜２×１０-1ｇ／ｇ担体、特に５×１０-4〜１×１０
-1ｇ／ｇ担体になるように非晶質シリカの層で被覆され
たα―アルミナ担体であることが好適である。The α-alumina carrier of the present invention is 3 × 10
-4 to 2 × 10 -1 g / g carrier, especially 5 × 10 -4 to 1 × 10
It is preferred that the carrier is an α-alumina carrier coated with a layer of amorphous silica to give a carrier of -1 g / g.
【００５２】本発明の担体の外表面上および担体の気孔
の表面上が非晶質シリカの層で被覆されたα―アルミナ
担体に、セシウムが担体１キログラム当り０．０００１
〜０．０４５グラム当量重量の濃度になるようにセシウ
ムを担持する方法は、あらかじめ加熱した、担体の外表
面上および担体の気孔の表面上が非晶質シリカの層で被
覆されたα―アルミナ担体に、セシウムが担体１キログ
ラム当り０．０００１〜０．０４５グラム当量重量の濃
度になるように、硝酸セシウムを水溶液あるいはアルコ
―ル性溶液の形で、好ましくは硝酸セシウム水溶液で含
浸処理を行ない、ついで１００〜３００℃、好ましくは
１２０〜２００℃で加熱濃縮乾燥し、ついで含有酸素濃
度が３容量％以下の不活性ガス中で４００〜１２００
℃、好ましくは５００〜８００℃での範囲で高温加熱処
理して得られる。Cesium was added to the α-alumina carrier coated with an amorphous silica layer on the outer surface of the carrier of the present invention and on the surface of the pores of the carrier in an amount of 0.0001 kg / kg of the carrier.
The method of supporting cesium to a concentration of ０．０0.045 gram equivalent weight is carried out by heating α-alumina coated on the outer surface of the carrier and the surface of pores of the carrier with a layer of amorphous silica. The carrier is impregnated with cesium nitrate in the form of an aqueous solution or an alcoholic solution, preferably with an aqueous solution of cesium nitrate, such that the concentration of cesium is 0.0001 to 0.045 gram equivalent weight per kilogram of carrier. Then, it is heated and concentrated and dried at 100 to 300 ° C., preferably 120 to 200 ° C., and then 400 to 1200 in an inert gas having an oxygen concentration of 3% by volume or less.
C., preferably in the range of 500 to 800.degree.
【００５３】本発明の非晶質シリカの層で被覆されたα
―アルミナ担体に、セシウムを担持する際の高温加熱処
理は含有酸素濃度が３容量％以下の不活性ガス中で４０
０〜１２００℃の高温加熱処理を行なわなければ有効で
ないことも重要である。有効な不活性ガスとしては窒
素、二酸化炭素、ヘリウム、アルゴン、ネオンが挙げら
れ、特に窒素または二酸化炭素が好ましい。Α coated with a layer of amorphous silica according to the invention
-High-temperature heat treatment for supporting cesium on an alumina carrier is carried out in an inert gas containing 3% by volume or less of oxygen.
It is also important that the heat treatment is not effective unless a high-temperature heat treatment at 0 to 1200 ° C. is performed. Effective inert gases include nitrogen, carbon dioxide, helium, argon, neon, with nitrogen or carbon dioxide being particularly preferred.
【００５４】高温加熱処理時間は高温側では少なくとも
５分以上、好ましくは３０分以上である。The high temperature heat treatment time is at least 5 minutes or more, preferably 30 minutes or more on the high temperature side.
【００５５】本発明の担体にセシウムを担持する際に、
担体として担体１グラムあたりＳｉとして３×１０-4〜
２×１０-1ｇ／ｇ担体、特に５×１０-4〜１×１０-1ｇ
／ｇ担体になるように非晶質シリカの層で被覆されたα
―アルミナ担体を使用すること、担体に担持するセシウ
ム化合物として硝酸セシウムを使用すること、含浸処
理、加熱濃縮乾燥し、ついで含有酸素濃度が３容量％以
下の窒素、不活性ガス中で４００〜１２００℃の範囲で
高温加熱処理することのいずれの構成要件を欠いても本
発明の効果を達成することはできない。When supporting cesium on the carrier of the present invention,
3 × 10 -4 as Si per gram of carrier as carrier
2 × 10 -1 g / g carrier, especially 5 × 10 -4 to 1 × 10 -1 g
/ G coated with a layer of amorphous silica to become a carrier
-Using an alumina carrier, using cesium nitrate as a cesium compound supported on the carrier, impregnating, heating and drying, and then containing 400 to 1200 in nitrogen or an inert gas having an oxygen concentration of 3% by volume or less. The effect of the present invention cannot be achieved without any of the constituent requirements of high-temperature heat treatment in the range of ° C.
【００５６】本発明の担体にセシウムを担持する際に使
用する硝酸セシウムは水に溶解させて使用することが好
ましいが、メタノール、エタノール等の低級アルコール
に溶解させて使用することができる。The cesium nitrate used for supporting cesium on the carrier of the present invention is preferably used by dissolving it in water. However, it can be used by dissolving it in a lower alcohol such as methanol or ethanol.
【００５７】本発明の担体の外表面上および担体の気孔
の表面上が非晶質シリカの層で被覆されたα―アルミナ
担体にセシウムを担持した担体に、銀とセシウムとを析
出担持する方法は、本発明の担体の外表面上および担体
の気孔の表面上が非晶質シリカの層で被覆されたα―ア
ルミナ担体にセシウムを担持した担体を使用し、これに
完成触媒当り５〜２５重量％の金属銀微粒子およびセシ
ウムが完成触媒１キログラム当り０．００１〜０．０５
グラム当量重量の濃度になるように、有機酸銀のアミン
錯体等の分解性銀溶液および硫酸セシウム溶液ので含浸
処理を行ない、含浸後１００〜３００℃に加熱し、還
元、あるいは熱分解し、銀とセシウムおよび／またはセ
シウム化合物とを多孔性無機質耐火性担体に担持せしめ
エチレンオキシド製造用銀触媒が得られる。A method of depositing and supporting silver and cesium on a carrier in which cesium is carried on an α-alumina carrier in which the outer surface of the carrier and the surface of pores of the carrier are coated with a layer of amorphous silica according to the present invention. Uses a carrier in which cesium is carried on an α-alumina carrier in which the outer surface of the carrier of the present invention and the surface of the pores of the carrier are coated with a layer of amorphous silica, and the carrier comprises 5 to 25 % By weight of metallic silver fine particles and cesium are contained in an amount of 0.001 to 0.05 per kilogram of the finished catalyst.
Impregnating with a decomposable silver solution such as an amine complex of organic acid silver and a cesium sulfate solution so as to have a concentration of gram equivalent weight, and after impregnation, heating to 100 to 300 ° C. to reduce or thermally decompose, And cesium and / or a cesium compound are supported on a porous inorganic refractory carrier to obtain a silver catalyst for producing ethylene oxide.
【００５８】本発明の担体の外表面上および担体の気孔
の表面上が非晶質シリカの層で被覆されたα―アルミナ
担体にセシウムを担持した担体に、銀とセシウムとを析
出担持するする際に、完成触媒当り５〜２５重量％の金
属銀微粒子およびセシウムが完成触媒１キログラム当り
０．００１〜０．０５グラム当量重量の濃度になるよう
に、有機酸銀のアミン錯体等の分解性銀溶液および硫酸
セシウム溶液で含浸処理を行なうことの構成要件を欠い
ても本発明の効果を達成することはできない。Silver and cesium are deposited and supported on a carrier in which cesium is carried on an α-alumina carrier in which the outer surface of the carrier of the present invention and the surface of pores of the carrier are coated with a layer of amorphous silica. At this time, the decomposability of amine complex of organic acid silver or the like is adjusted so that 5 to 25% by weight of metallic silver fine particles and cesium per finished catalyst are in a concentration of 0.001 to 0.05 gram equivalent weight per kilogram of finished catalyst. The effect of the present invention cannot be achieved even without the constituent elements of performing the impregnation treatment with a silver solution and a cesium sulfate solution.
【００５９】本発明の銀化合物溶液は、分解性銀塩の水
溶液域いは有機溶媒溶液、例えば硝酸銀水溶液、無機酸
銀、有機酸銀のアンモニア錯体、域いは有機酸銀のアミ
ン錯体、乳酸銀水溶液等を前記のごとき担体に含浸する
方法が採用される。The silver compound solution of the present invention may be an aqueous solution of a decomposable silver salt or an organic solvent solution, for example, an aqueous solution of silver nitrate, inorganic acid silver, an ammonia complex of organic acid silver, or an amine complex of organic acid silver or lactic acid. A method of impregnating the carrier with an aqueous silver solution or the like as described above is employed.
【００６０】本発明の銀触媒の銀は触媒に対し５〜２５
重量％好ましくは５〜２０重量％を微粒状に担体内外表
面に析出させることができる。The silver of the silver catalyst of the present invention is 5 to 25 parts by weight of the catalyst.
% By weight, preferably 5 to 20% by weight, can be precipitated in fine particles on the inner and outer surfaces of the carrier.
【００６１】本発明の外表面上および担体の気孔の表面
上が非晶質シリカの層で被覆されたα―アルミナ担体に
セシウムを担持した担体に銀とセシウムとを析出担持す
る際に使用する硫酸セシウムは水に溶解させて使用する
ことが好ましいが、メタノール、エタノール等の低級ア
ルコールに溶解させて使用することができる。硫酸セシ
ウムはセシウムが完成触媒１キログラムあたり０．００
１〜０．０５グラム当量、特に０．００６グラム当量を
越え、かつ、０．０３グラム当量以下の範囲内を銀溶液
に加えて銀と同時に析出させる。The present invention is used for depositing and supporting silver and cesium on a carrier in which cesium is carried on an α-alumina carrier in which the surface of the pores of the carrier and the outer surface of the carrier are coated with an amorphous silica layer. Cesium sulfate is preferably used by dissolving it in water, but can be used by dissolving it in a lower alcohol such as methanol or ethanol. Cesium sulphate contains 0.001 kg of cesium per kilogram of finished catalyst.
A range of 1 to 0.05 gram equivalent, especially more than 0.006 gram equivalent and not more than 0.03 gram equivalent is added to the silver solution to precipitate simultaneously with silver.
【００６２】本発明のα−アルミナ担体を用いた銀触媒
の調製方法としては、たとえばエチレンを分子状酸素に
より気相接触酸化してエチレンオキシドを製造する際に
使用する銀触媒において、α―アルミナ担体にコロイド
状シリカを含有する水溶液を含浸し、ついで加熱乾燥
し、さらに焼成して得られた担体の外表面上および担体
の気孔の表面上が非晶質シリカの層で被覆されたα―ア
ルミナ担体に、セシウムが担体１キログラム当り０．０
００１〜０．０４５グラム当量重量の濃度になるよう
に、硝酸セシウム溶液で含浸処理を行ない、ついで１０
０〜３００℃で加熱乾燥し、含有酸素濃度が３容量％以
下の不活性ガス中で４００〜１２００℃の範囲で高温加
熱処理した後、この担体に完成触媒当り５〜２５重量％
の金属銀微粒子およびセシウムが完成触媒１キログラム
当り０．００１〜０．０５グラム当量重量の濃度になる
ように、有機酸銀のアミン錯体等の分解性銀溶液および
硫酸セシウム溶液で含浸処理を行ない、ついで１００〜
３００℃に加熱し、還元、あるいは熱分解して得られる
エチレンオキシド製造用銀触媒の製造方法等を採用する
ことができる。As a method for preparing a silver catalyst using an α-alumina carrier of the present invention, for example, a silver catalyst used for producing ethylene oxide by subjecting ethylene to gas-phase catalytic oxidation with molecular oxygen may be used. Is impregnated with an aqueous solution containing colloidal silica, then heated and dried, and further calcined.The α-alumina coated on the outer surface of the carrier and on the surface of the pores of the carrier with a layer of amorphous silica. Cesium is added to the carrier in an amount of 0.0
Impregnation with a cesium nitrate solution was carried out to a concentration of 001 to 0.045 gram equivalent weight.
After drying by heating at 0 to 300 ° C. and heat-treating at a high temperature in the range of 400 to 1200 ° C. in an inert gas having an oxygen content of 3% by volume or less, 5 to 25% by weight based on the finished catalyst is added to this carrier.
Is impregnated with a decomposable silver solution such as an amine complex of an organic acid silver and a cesium sulfate solution such that the concentration of the metallic silver fine particles and cesium is 0.001 to 0.05 gram equivalent weight per kilogram of the finished catalyst. Then 100 ~
A method for producing a silver catalyst for producing ethylene oxide, which is obtained by heating to 300 ° C. and reducing or thermally decomposing, may be employed.
【００６３】本発明の銀触媒を使用してエチレンを分子
状酸素により酸化して酸化エチレンを製造する方法にお
いて採用できる反応条件は、これまで当分野で知られて
いる全ての条件が採用できるが、工業的製造規模におけ
る一般的な条件、すなわち原料ガス組成としてエチレン
０．５〜４０容量％、酸素３〜１０容量％、炭酸ガス５
〜３０容量％、残部が窒素、アルゴン、水蒸気等の不活
性ガスおよびメタン、エタン等の低級炭化水素類さらに
また反応抑制剤としての二塩化エチレン、塩化ジフェニ
ル等のハロゲン化物、空間速度１０００〜３００００ｈ
ｒ-1（ＳＴＰ）、圧力２〜４０Ｋｇ／ｃｍ2 Ｇ等が好適
に採用できる。As the reaction conditions that can be employed in the method of producing ethylene oxide by oxidizing ethylene with molecular oxygen using the silver catalyst of the present invention, all the conditions known so far in the art can be employed. General conditions on an industrial production scale, that is, 0.5 to 40% by volume of ethylene, 3 to 10% by volume of oxygen,
To 30% by volume, the balance being inert gases such as nitrogen, argon and water vapor and lower hydrocarbons such as methane and ethane, as well as halides such as ethylene dichloride and diphenyl chloride as reaction inhibitors, space velocities of 1000 to 30000 h
r -1 (STP), a pressure of 2 to 40 Kg / cm 2 G, etc. can be suitably adopted.
【００６４】[0064]
【実施例】以下さらに具体的にするために実施例および
比較例をあげて詳細に説明するが、本発明はその主旨に
反しない限りこれらの実施例に限定されるものではな
い。なお、実施例および比較例に記載する変化率および
選択率は次式により算出されたものである。EXAMPLES Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples, but the present invention is not limited to these examples unless it violates the gist of the present invention. The rate of change and selectivity described in the examples and comparative examples are calculated by the following equations.
【００６５】 変化率（％）＝反応したエチレンのモル数Χ１００／原
料ガス中のエチレンのモル数 選択率（％）＝エチレンオキシドに変化したエチレンの
モル数Χ１００／反応したエチレンのモル数 ［担体Ａの製造方法］ ＢＥＴ比表面積０．８９ｍ2 ／ｇ、見掛気孔率５２．８
％、比気孔容積０．２８ｃｃ／ｇ、Ａｌ2 Ｏ3 （９
８．９重量％）担体（ノートン社製担体ＳＡ−５１０
２）に、粒径２〜５０ミリミクロンのコロイド状シリカ
を担体含水量分の水に分散した液を含浸し、加熱濃縮乾
燥後、１０００℃で４時間焼成し、得られたＢＥＴ比表
面積０．８９ｍｌ／ｇ、見掛気孔率５２．８％、細孔容
積０．２８ｃｃ／ｇ、Ａｌ2 Ｏ3 （９８．９重量％）の
気孔の表面上が非晶質シリカの層で被覆されたα―アル
ミナ担体をα―アルミナ担体Ａとした。Change rate (%) = mol number of reacted ethyleneΧ100 / mol number of ethylene in raw material gas Selectivity (%) = mol number of ethylene converted to ethylene oxideΧ100 / mol number of reacted ethylene [Carrier A Production method] BET specific surface area 0.89 m 2 / g, apparent porosity 52.8
%, Specific pore volume 0.28 cc / g, Al 2 O 3 (9
(8.9% by weight) carrier (Norton carrier SA-510)
2) impregnated with a liquid obtained by dispersing colloidal silica having a particle diameter of 2 to 50 mm in water corresponding to the water content of the carrier, drying by heating and concentration, and calcining at 1000 ° C for 4 hours; .89 ml / g, apparent porosity 52.8%, pore volume 0.28 cc / g, Al 2 O 3 (98.9 wt%) pores coated on the surface with amorphous silica layer The α-alumina carrier was designated as α-alumina carrier A.
【００６６】担体Ａに担持した非晶質シリカ量は以下の
方法による測定によれば、５×１０-3 Ｓｉ ｇ／ｇ担
体であった。The amount of the amorphous silica supported on the carrier A was 5 × 10 −3 Sig / g according to the measurement by the following method.
【００６７】「得られたα―アルミナ担体Ａの担体の外
表面上および担体の気孔の表面上の非晶質シリカの量の
測定方法］１０ｇの担体を８〜１０メッシュにくだき４
６重量％フッ化水素酸水溶液２０ｍｌに１時間浸した
後、濾過を行ない溶液中のＳｉイオンを原子吸光分析器
で測定して求めた。[Method of measuring the amount of amorphous silica on the outer surface of the obtained α-alumina support A and on the surface of pores of the support] 10 g of the support was cut into 8 to 10 mesh.
After immersion in 20 ml of a 6% by weight aqueous solution of hydrofluoric acid for 1 hour, the solution was filtered, and the Si ion in the solution was measured by an atomic absorption analyzer.
【００６８】実施例１ 硝酸セシウム１４．２ｇを水１２００ｍｌに溶解した液
を、予め約１００℃に加熱したα−アルミナ担体Ａの４
０００ｍｌに含浸後、加熱濃縮乾燥し、さらに、空気浴
中１２０℃で３時間加熱した。この担体を外部から不活
性ガスを導入できるステンレス製密閉容器に充填し、窒
素ガスを送り込みながら電気炉中で担体層温度７００℃
で３時間高温加熱処理した。（これをα−アルミナ担体
Ｂとした。） 次いでシュウ酸銀８３０ｇを２００ｍｌ
と泥状にしておき、これにエタノールアミン７００ｍｌ
を加え良く撹拌して溶解した。さらに水１００ｍｌと
９．９ｇの硫酸セシウムを水２００ｍｌに溶解した液を
加えて良く撹拌して、含浸溶液を調整した。Example 1 A solution prepared by dissolving 14.2 g of cesium nitrate in 1200 ml of water was mixed with a solution of α-alumina carrier A, which was previously heated to about 100 ° C.
After impregnation in 000 ml, the solution was heated, concentrated and dried, and further heated in an air bath at 120 ° C. for 3 hours. This carrier is filled in a stainless steel sealed container into which an inert gas can be introduced from the outside, and the carrier layer temperature is 700 ° C. in an electric furnace while feeding nitrogen gas.
For 3 hours. (This was designated as α-alumina carrier B.) Then, 830 g of silver oxalate was added to 200 ml.
And put the ethanolamine in 700ml
Was added and stirred well to dissolve. Further, a solution prepared by dissolving 100 ml of water and 9.9 g of cesium sulfate in 200 ml of water was added and stirred well to prepare an impregnation solution.
【００６９】この含浸溶液を予め１００℃に加熱したα
−アルミナ担体Ｂの４０００ｍｌに含浸し、加熱濃縮乾
燥に続き、空気浴中１２０℃で３時間加熱した後、空気
気流中で４８時間２８０℃で賦活化して完成触媒とし
た。This impregnating solution was previously heated to 100 ° C.
-Impregnated in 4000 ml of alumina carrier B, heated, concentrated and dried, heated in an air bath at 120 ° C for 3 hours, and then activated in an air stream at 280 ° C for 48 hours to obtain a finished catalyst.
【００７０】［α−アルミナ担体Ｂの全セシウムの量の
測定方法］α−アルミナ担体Ｂの約２０ｇを粉末にし、
（２０Ｋｇ／ｃｍ2 で）圧縮してテストシートにした。
セシウム濃度既知の触媒を同様に処理し標準とした。テ
ストシートを、蛍光Ｘ線分光分析装置で標準サンプルの
記録データのより得られた計算グラフを使って評価し
た。その結果０．２６重量％のセシウムが測定された。
この量は１９×１０-3グラム当量／Ｋｇ触媒と計算され
た。[Method of Measuring the Total Cesium Content of α-Alumina Support B] About 20 g of α-alumina support B was powdered,
Compressed (at 20 Kg / cm 2 ) into test sheets.
A catalyst having a known cesium concentration was treated in the same manner as a standard. The test sheet was evaluated with a fluorescent X-ray spectrometer using a calculation graph obtained from the recorded data of the standard sample. As a result, 0.26% by weight of cesium was measured.
This amount was calculated as 19 × 10 −3 gram equivalent / Kg catalyst.
【００７１】［完成触媒の全セシウムの量の測定方法］
サンプルの約２０ｇを粉末にし、（２０Ｋｇ／ｃｍ2
で）圧縮してテストシートにした。セシウム濃度既知の
触媒を同様に処理し標準とした。テストシートを、蛍光
Ｘ線分光分析装置で標準サンプルの記録データのより得
られた計算グラフを使って評価した。その結果０．２６
重量％のセシウムが測定された。[Method of Measuring Total Cesium in Finished Catalyst]
Approximately 20 g of the sample is powdered and (20 kg / cm 2
) And compressed into test sheets. A catalyst having a known cesium concentration was treated in the same manner as a standard. The test sheet was evaluated with a fluorescent X-ray spectrometer using a calculation graph obtained from the recorded data of the standard sample. As a result, 0.26
Weight percent cesium was measured.
【００７２】この量は１９×１０-3グラム当量／Ｋｇ触
媒と計算された。This amount was calculated as 19 × 10 −3 gram equivalent / Kg catalyst.
【００７３】得られた完成触媒を内径２５ｍｍ、管長１
０００ｍｍの外部が加熱型の二重管式ステンレス製反応
器に充填し、その充填層にエチレン２０容量％、酸素７
容量％、炭酸ガス７容量％、残余がメタン、窒素、アル
ゴン、エタンからなり、さらに二塩化エチレン１ｐｐｍ
からなる混合ガスを導入し、反応圧力２５Ｋｇ／ｃｍ2
Ｇ、空間速度５５００Ｈｒ-1、熱媒温度２４０℃まで昇
温し反応を行った。その結果および１年後の結果を表１
に示す。The obtained completed catalyst was used for an inner diameter of 25 mm and a tube length of 1
2,000 mm outside is filled in a heating-type double-tube stainless steel reactor, and the packed bed is filled with 20% by volume of ethylene and 7% of oxygen.
% By volume, 7% by volume of carbon dioxide, the balance consists of methane, nitrogen, argon and ethane, and 1 ppm of ethylene dichloride
And a reaction pressure of 25 kg / cm 2
G, a space velocity of 5500 Hr -1 and a heating medium temperature of 240 ° C. were carried out to carry out a reaction. Table 1 shows the results and one year later.
Shown in
【００７４】実施例２〜３ 実施例１において高温加熱処理を表１に示す条件にした
以外は実施例１と同様な方法で行なった。その１０日後
の結果および１年後の結果を表１に示す。Examples 2-3 The procedure of Example 1 was repeated, except that the high-temperature heat treatment was performed under the conditions shown in Table 1. The results after 10 days and one year are shown in Table 1.
【００７５】実施例４〜５ 実施例１において硝酸セシウムとして表１に示すα−ア
ルミナ担体Ｂの全セシウムの量を用いる以外は実施例１
と同様な方法で行なった。その１０日後の結果および１
年後の結果を表１に示す。Examples 4-5 Example 1 was repeated except that the amount of cesium in α-alumina carrier B shown in Table 1 was used as cesium nitrate in Example 1.
Was performed in the same manner as described above. 10 days later and 1
The results after one year are shown in Table 1.
【００７６】実施例６ 実施例１において硝酸セシウムと硫酸セシウムが表１に
示すα−アルミナ担体Ｂの全セシウムの量および完成触
媒の全セシウムの量を用いる以外は実施例１と同様な方
法で行なった。その１０日後の結果および１年後の結果
を表１に示す。実施例７ 実施例１において硫酸セシウムとして表１に示す完成触
媒の全セシウムの量を用いる以外は実施例１と同様な方
法で行なった。その１０日後の結果および１年後の結果
を表１に示す。Example 6 In Example 1, cesium nitrate and cesium sulfate were prepared in the same manner as in Example 1 except that the total amount of cesium in the α-alumina carrier B and the total amount of cesium in the completed catalyst shown in Table 1 were used. Done. The results after 10 days and one year are shown in Table 1. Example 7 Example 7 was carried out in the same manner as in Example 1 except that the amount of cesium in the finished catalyst shown in Table 1 was used as cesium sulfate. The results after 10 days and one year are shown in Table 1.
【００７７】実施例８〜９ 実施例１において担体表面の非晶質シリカの量を表１に
示す量を用いる以外は実施例１と同様な方法で行なっ
た。その１０日後の結果および１年後の結果を表１に示
す。Examples 8 to 9 The procedure of Example 1 was repeated, except that the amount of amorphous silica on the surface of the carrier was changed as shown in Table 1. The results after 10 days and one year are shown in Table 1.
【００７８】比較例１〜２ 実施例１において高温加熱処理を表１に示す条件にした
以外は実施例１と同様な方法で行なった。その１０日後
の結果を表２に示す。Comparative Examples 1 and 2 The procedure of Example 1 was repeated, except that the high-temperature heat treatment was performed under the conditions shown in Table 1. Table 2 shows the results 10 days later.
【００７９】比較例３ シュウ酸銀８３０ｇを２００ｍｌと泥状にしておき、こ
れにエタノールアミン７００ｍｌを加え良く撹拌して溶
解した。さらに水１００ｍｌと９．９ｇの硫酸セシウム
を水２００ｍｌに溶解した液を加えて良く撹拌して、含
浸溶液を調整した。Comparative Example 3 830 g of silver oxalate was prepared in a slurry state with 200 ml, and 700 ml of ethanolamine was added thereto and dissolved with sufficient stirring. Further, a solution prepared by dissolving 100 ml of water and 9.9 g of cesium sulfate in 200 ml of water was added and stirred well to prepare an impregnation solution.
【００８０】この含浸溶液を予め１００℃に加熱したα
−アルミナ担体Ａの４０００ｍｌに含浸し、加熱濃縮乾
燥に続き、空気浴中１２０℃で３時間加熱した後、空気
気流中で４８時間２８０℃で賦活化して完成触媒とし
た。This impregnating solution was previously heated to 100 ° C.
-Impregnated in 4000 ml of alumina carrier A, heated and concentrated and dried, heated in an air bath at 120 ° C for 3 hours, and activated in an air stream at 280 ° C for 48 hours to obtain a completed catalyst.
【００８１】実施例１と同様な方法で行なった１０日後
の結果および１年後の結果を表２に示す。Table 2 shows the results after 10 days and one year after the same method as in Example 1.
【００８２】比較例４〜５ 実施例１において硝酸セシウムとして表１に示すα−ア
ルミナ担体Ｂの全セシウムの量を用いる以外は実施例１
と同様な方法で行なった。その１０日後の結果および１
年後の結果を表２に示す。Comparative Examples 4 and 5 Example 1 was repeated except that the amount of cesium in the α-alumina carrier B shown in Table 1 was used as cesium nitrate in Example 1.
Was performed in the same manner as described above. 10 days later and 1
The results after a year are shown in Table 2.
【００８３】比較例６ 実施例１において硝酸セシウムと硫酸セシウムが表１に
示すα−アルミナ担体Ｂの全セシウムの量および完成触
媒の全セシウムの量を用いる以外は実施例１と同様な方
法で行なった。その１０日後の結果および１年後の結果
を表２に示す。 比較例７ 実施例１において硫酸セシウムとして表１に示す完成触
媒の全セシウムの量を用いる以外は実施例１と同様な方
法で行なった。その１０日後の結果および１年後の結果
を表２に示す。Comparative Example 6 Cesium nitrate and cesium sulfate were prepared in the same manner as in Example 1 except that the amount of cesium in the α-alumina carrier B and the amount of cesium in the finished catalyst shown in Table 1 were used. Done. Table 2 shows the results 10 days later and 1 year later. Comparative Example 7 The same procedure as in Example 1 was carried out except that the amount of cesium in the finished catalyst shown in Table 1 was used as cesium sulfate in Example 1. Table 2 shows the results 10 days later and 1 year later.
【００８４】比較例８ 実施例１において担体としてノートン社製担体ＳＡ−５
１０２をそのまま用いる以外は実施例１と同様な方法で
行なった。その１０日後の結果を表２に示す。 比較例９ シュウ酸銀８３０ｇを２００ｍｌと泥状にしておき、こ
れにエタノールアミン７００ｍｌを加え良く撹拌して溶
解した。さらに水１００ｍｌと９．９ｇの硫酸セシウム
を水２００ｍｌに溶解した液を加えて良く撹拌して、含
浸溶液を調整した。Comparative Example 8 In Example 1, the carrier SA-5 manufactured by Norton was used as the carrier.
The procedure was performed in the same manner as in Example 1 except that 102 was used as it was. Table 2 shows the results 10 days later. Comparative Example 9 830 g of silver oxalate was prepared in a slurry state with 200 ml, to which 700 ml of ethanolamine was added and dissolved with good stirring. Further, a solution prepared by dissolving 100 ml of water and 9.9 g of cesium sulfate in 200 ml of water was added and stirred well to prepare an impregnation solution.
【００８５】この含浸溶液を予め１００℃に加熱したノ
ートン社製担体ＳＡ−５１０２の４０００ｍｌに含浸
し、加熱濃縮乾燥に続き、空気浴中１２０℃で３時間加
熱した後、空気気流中で４８時間２８０℃で賦活化して
完成触媒とした。The impregnating solution was impregnated into 4000 ml of Norton carrier SA-5102 previously heated to 100 ° C., heated and concentrated, dried, heated in an air bath at 120 ° C. for 3 hours, and then in an air stream for 48 hours. Activation was performed at 280 ° C. to obtain a finished catalyst.
【００８６】実施例１と同様な方法で行なった１０日後
の結果および１年後の結果を表２に示す。Table 2 shows the results after 10 days and one year after the same method as in Example 1.
【００８７】[0087]
【表１】 [Table 1]
【００８８】[0088]
【表２】 [Table 2]
【００８９】[0089]
【発明の効果】本発明はα―アルミナ担体にコロイド状
シリカを含有する水溶液を含浸し、ついで加熱乾燥し、
さらに焼成して得られた担体の外表面上および担体の気
孔の表面上が非晶質シリカの層で被覆されたα―アルミ
ナ担体に、セシウムが担体１キログラム当り０．０００
１〜０．０４５グラム当量重量の濃度になるように、硝
酸セシウム溶液で含浸処理を行ない、ついで乾燥し、含
有酸素濃度が３容量％以下の不活性ガス中で４００〜１
２００℃の範囲で高温加熱処理した後、担体に完成触媒
当り５〜２５重量％の金属銀微粒子およびセシウムが完
成触媒１キログラム当り０．００１〜０．０５グラム当
量重量の濃度になるように、銀化合物溶液および硫酸セ
シウム溶液で含浸処理を行ない、ついで乾燥、賦活化処
理して、銀とセシウムとを担体に析出担持したことによ
り高選択性および高活性を長期間に渡って維持できる効
果をもった新規なエチレンオキシド製造用銀触媒が得ら
れるものである。According to the present invention, an α-alumina carrier is impregnated with an aqueous solution containing colloidal silica, and then dried by heating.
Further, on an α-alumina carrier in which the outer surface of the carrier obtained by calcination and the surface of pores of the carrier were coated with a layer of amorphous silica, cesium was added in an amount of 0.000 kg / kg of carrier.
Impregnation is performed with a cesium nitrate solution to a concentration of 1 to 0.045 gram equivalent weight, then dried, and dried in an inert gas having an oxygen concentration of 3% by volume or less.
After the high-temperature heat treatment in the range of 200 ° C., 5-25% by weight of the fine metal silver particles and cesium on the carrier are brought to a concentration of 0.001 to 0.05 gram equivalent weight per kilogram of the finished catalyst. Impregnation with a silver compound solution and a cesium sulfate solution, followed by drying and activation treatment to deposit and carry silver and cesium on the carrier, thereby achieving the effect of maintaining high selectivity and high activity over a long period of time. Thus, a novel silver catalyst for producing ethylene oxide can be obtained.
───────────────────────────────────────────────────── フロントページの続き (56)参考文献 特開 平２−131140（ＪＰ，Ａ) 特開 平２−119940（ＪＰ，Ａ) 特開 平２−48040（ＪＰ，Ａ) ────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-2-131140 (JP, A) JP-A-2-119940 (JP, A) JP-A-2-48040 (JP, A)
Claims (1)
含有する水溶液を含浸し、ついで加熱乾燥し、さらに焼
成して得られた担体の外表面上および担体の気孔の表面
上が非晶質シリカの層で被覆されたα―アルミナ担体
に、セシウムが担体１キログラム当り０．０００１〜
０．０４５グラム当量重量の濃度になるように、硝酸セ
シウム溶液で含浸処理を行ない、ついで乾燥し、含有酸
素濃度が３容量％以下の不活性ガス中で４００〜１２０
０℃の範囲で高温加熱処理した後、担体に完成触媒当り
５〜２５重量％の金属銀微粒子およびセシウムが完成触
媒１キログラム当り０．００１〜０．０５グラム当量重
量の濃度になるように、銀化合物溶液および硫酸セシウ
ム溶液で含浸処理を行ない、ついで乾燥、賦活化処理し
て、銀とセシウムとを担体に析出担持したことを特徴と
するエチレンオキシド製造用銀触媒。An α-alumina carrier is impregnated with an aqueous solution containing colloidal silica, heated and dried, and then calcined to form amorphous silica on the outer surface of the carrier and on the surface of pores of the carrier. Α-alumina carrier coated with a layer of
Impregnation with a cesium nitrate solution is carried out to a concentration of 0.045 gram equivalent weight, followed by drying and 400-120 in an inert gas having an oxygen concentration of 3% by volume or less.
After the high-temperature heat treatment in the range of 0 ° C., 5-25% by weight of the fine metal silver particles and cesium on the carrier are brought to a concentration of 0.001 to 0.05 gram equivalent weight per kilogram of the finished catalyst. A silver catalyst for producing ethylene oxide, comprising: impregnating with a silver compound solution and a cesium sulfate solution, and then drying and activating to deposit silver and cesium on a carrier.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11582491A JP3233652B2 (en) | 1991-05-21 | 1991-05-21 | Silver catalyst for ethylene oxide production |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP11582491A JP3233652B2 (en) | 1991-05-21 | 1991-05-21 | Silver catalyst for ethylene oxide production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04346835A JPH04346835A (en) | 1992-12-02 |
| JP3233652B2 true JP3233652B2 (en) | 2001-11-26 |
Family
ID=14672021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP11582491A Expired - Fee Related JP3233652B2 (en) | 1991-05-21 | 1991-05-21 | Silver catalyst for ethylene oxide production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP3233652B2 (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4172827B2 (en) † | 1994-12-15 | 2008-10-29 | シエル・インターナシヨネイル・リサーチ・マーチヤツピイ・ベー・ウイ | Method for producing ethylene oxide catalyst |
| AU754631B2 (en) | 1998-11-17 | 2002-11-21 | Nippon Shokubai Co., Ltd. | Carrier for catalyst for use in production of ethylene oxide, catalyst for use in production of ethylene oxide, and method for production of ethylene oxide |
| CA2490892C (en) * | 2002-06-28 | 2012-03-20 | Shell Internationale Research Maatschappij B.V. | A method for the start-up of an epoxidation process, a catalyst and a process for the epoxidation of an olefin |
| US8148555B2 (en) | 2003-06-26 | 2012-04-03 | Shell Oil Company | Method for improving the selectivity of a catalyst and a process for the epoxidation of an olefin |
| JP5313665B2 (en) * | 2006-05-02 | 2013-10-09 | 株式会社日本触媒 | Olefin partial oxidation catalyst, method for producing the same, and method for producing alkylene oxide |
| RU2757051C2 (en) | 2016-12-02 | 2021-10-11 | Шелл Интернэшнл Рисерч Маатсхаппий Б.В. | Methods for processing ethylene epoxidation catalyst and related methods for producing ethylene oxide |
-
1991
- 1991-05-21 JP JP11582491A patent/JP3233652B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH04346835A (en) | 1992-12-02 |
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