CN101360562B - Catalyst for ethylene oxide production, method for producing the same, and method for producing ethylene oxide - Google Patents
Catalyst for ethylene oxide production, method for producing the same, and method for producing ethylene oxide Download PDFInfo
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- CN101360562B CN101360562B CN2007800017373A CN200780001737A CN101360562B CN 101360562 B CN101360562 B CN 101360562B CN 2007800017373 A CN2007800017373 A CN 2007800017373A CN 200780001737 A CN200780001737 A CN 200780001737A CN 101360562 B CN101360562 B CN 101360562B
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- 239000003054 catalyst Substances 0.000 title claims abstract description 186
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 32
- 239000011734 sodium Substances 0.000 claims abstract description 61
- 229910052702 rhenium Inorganic materials 0.000 claims abstract description 54
- 229910052792 caesium Inorganic materials 0.000 claims abstract description 51
- 229910052709 silver Inorganic materials 0.000 claims abstract description 37
- 239000004332 silver Substances 0.000 claims abstract description 36
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 23
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000005977 Ethylene Substances 0.000 claims abstract description 22
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 20
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 20
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims abstract description 18
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 15
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 15
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 15
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 15
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 15
- 229910052708 sodium Inorganic materials 0.000 claims abstract description 13
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 12
- 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 claims abstract description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000010703 silicon Substances 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 25
- 229910052744 lithium Inorganic materials 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 238000011068 loading method Methods 0.000 claims description 10
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical group [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 5
- 238000002203 pretreatment Methods 0.000 claims 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 5
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 22
- 239000002253 acid Substances 0.000 description 15
- -1 silver amine Chemical class 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 230000000694 effects Effects 0.000 description 12
- 239000000203 mixture Substances 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000005470 impregnation Methods 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 150000001875 compounds Chemical class 0.000 description 6
- 230000006866 deterioration Effects 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 5
- 229910000024 caesium carbonate Inorganic materials 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 description 5
- 229910052808 lithium carbonate Inorganic materials 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 239000002994 raw material Substances 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000011819 refractory material Substances 0.000 description 4
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 description 4
- 239000011230 binding agent Substances 0.000 description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000003426 co-catalyst Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- JCYPECIVGRXBMO-UHFFFAOYSA-N 4-(dimethylamino)azobenzene Chemical compound C1=CC(N(C)C)=CC=C1N=NC1=CC=CC=C1 JCYPECIVGRXBMO-UHFFFAOYSA-N 0.000 description 2
- ZPLCXHWYPWVJDL-UHFFFAOYSA-N 4-[(4-hydroxyphenyl)methyl]-1,3-oxazolidin-2-one Chemical compound C1=CC(O)=CC=C1CC1NC(=O)OC1 ZPLCXHWYPWVJDL-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 2
- 229910013553 LiNO Inorganic materials 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 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
- 239000003513 alkali Substances 0.000 description 2
- 150000001339 alkali metal compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 229910001882 dioxygen Inorganic materials 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- CEQFOVLGLXCDCX-WUKNDPDISA-N methyl red Chemical compound C1=CC(N(C)C)=CC=C1\N=N\C1=CC=CC=C1C(O)=O CEQFOVLGLXCDCX-WUKNDPDISA-N 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 229910001961 silver nitrate Inorganic materials 0.000 description 2
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Chemical compound [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 238000004448 titration Methods 0.000 description 2
- ZXSQEZNORDWBGZ-UHFFFAOYSA-N 1,3-dihydropyrrolo[2,3-b]pyridin-2-one Chemical compound C1=CN=C2NC(=O)CC2=C1 ZXSQEZNORDWBGZ-UHFFFAOYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 102100028168 BET1 homolog Human genes 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 241001330002 Bambuseae Species 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 1
- 101000697381 Homo sapiens BET1 homolog Proteins 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- QCPTVXCMROGZOL-UHFFFAOYSA-L dipotassium;oxalate;hydrate Chemical compound O.[K+].[K+].[O-]C(=O)C([O-])=O QCPTVXCMROGZOL-UHFFFAOYSA-L 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- IBIKHMZPHNKTHM-RDTXWAMCSA-N merck compound 25 Chemical compound C1C[C@@H](C(O)=O)[C@H](O)CN1C(C1=C(F)C=CC=C11)=NN1C(=O)C1=C(Cl)C=CC=C1C1CC1 IBIKHMZPHNKTHM-RDTXWAMCSA-N 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N nitrate group Chemical group [N+](=O)([O-])[O-] NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 150000003891 oxalate salts Chemical class 0.000 description 1
- 239000006187 pill Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000012495 reaction gas 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
- 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
- 229910001958 silver carbonate Inorganic materials 0.000 description 1
- LKZMBDSASOBTPN-UHFFFAOYSA-L silver carbonate Substances [Ag].[O-]C([O-])=O LKZMBDSASOBTPN-UHFFFAOYSA-L 0.000 description 1
- 229940100890 silver compound Drugs 0.000 description 1
- 150000003379 silver compounds Chemical class 0.000 description 1
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- HRLYFPKUYKFYJE-UHFFFAOYSA-N tetraoxorhenate(2-) Chemical compound [O-][Re]([O-])(=O)=O HRLYFPKUYKFYJE-UHFFFAOYSA-N 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
-
- 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
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- Catalysts (AREA)
- Epoxy Compounds (AREA)
Abstract
Disclosed is a catalyst for ethylene oxide production which is used for producing ethylene oxide from ethylene. This catalyst is composed of at least silver (Ag), caesium (Cs), rhenium (Re) and a carrier, and improved especially in selectivity. Specifically disclosed is a catalyst for ethylene oxide production, which is used for producing ethylene oxide from ethylene and composed of at least silver (Ag), caesium (Cs), rhenium (Re) and a carrier. If necessary, an alkali metal is loaded onto the carrier as a pretreatment, and then Ag, Cs and Re are loaded onto the carrier, thereby obtaining the catalyst. The carrier has a specific surface area of 0.6-3.0 m2/g, and a weight ratio between the silicon (Si) content and the sodium (Na) content in terms of SiO2/Na2O of 2-50. The Re content (based on the carrier) is 170-600 ppm per 1 m2/g of the specific surface area of the carrier, and the molar ratio Cs/Re is 0.3-19.
Description
Technical Field
The present invention relates to a catalyst for ethylene oxide production, a method for producing the same, and a method for producing ethylene oxide.
Background
The main component of the catalyst for manufacturing ethylene oxide from ethylene is silver (Ag), which is supported on a carrier. In order to improve the catalytic performance, an element such as an alkali metal or rhenium (Re) is industrially added to Ag as a main component of the catalyst as a co-catalyst (patent document 1).
As for the effect of the alkali metal, the following effects are reported: the effect of acid ionization constants present on the support, neutralizing the support, or the effect of catalytic action of Ag adjusted by the presence on the Ag surface; however, the details are not clear. On the other hand, the site of Re in the catalyst and the mechanism of action as a co-catalyst are not clear, but Re must coexist with an alkali metal to function as a co-catalyst (patent document 2).
The carrier is generally produced by sintering a mixture of a raw material powder, a binder and a pore former. The carrier thus produced usually contains impurities such as silicon (Si) and sodium (Na) as impurities, wherein the Si content is SiO2Calculated as 0.1 to several tens wt%, and Na content is Na2The O value is 0.01 to several wt%.
It has been reported that: the amounts of Si and Na in the carrier have a great influence on the performance of a catalyst composed of Ag, an alkali metal and the carrier but not containing Re (patent documents 3 and 4). Therefore, it is necessary to control the amounts of Si and Na in the α -alumina raw material powder, the binder, and the pore former to adjust the amounts of Si and Na in the carrier. Further, with respect to Re-containing catalysts, catalysts in which the Ag content is limited to 20 wt% or more have been reported (patent documents 5 and 6).
Patent document 1: japanese unexamined patent publication No. 9-150058
Patent document 2: japanese patent laid-open publication No. 63-126552
Patent document 3: japanese patent laid-open publication No. 63-116743
Patent document 4: japanese unexamined patent publication Hei 1-123629
Patent document 5: japanese unexamined patent publication Hei 3-207447
Patent document 6: WO2005-097318 publication
Disclosure of Invention
Problems to be solved by the invention
The present inventors have conducted intensive studies with a view to providing an improved catalyst for ethylene oxide production comprising at least Ag, Cs, Re and a carrier, or comprising at least Ag, Li, Cs, Re and a carrier, and as a result, have arrived at the following findings.
(1) Conventionally, when a catalyst is composed of a large surface area support, Ag, Cs, and Re, the nature of Re as a promoter is generally not affected by the Si and Na components in the support. However, if the ratio of the Si component to the Na component in the support is limited to a certain range, it is unexpectedly possible to enhance the co-catalysis of Re, resulting in a catalyst with significantly improved selectivity.
(2) By using a support with a large specific surface area and increasing the Li content in the catalyst, a catalyst maintaining a high selectivity and having a significantly improved catalyst life is surprisingly obtained.
Means for solving the problems
The present invention has been completed based on the above recognition and includes a group of related inventions, and the gist of each invention is as follows.
The invention of claim 1 is based on the above knowledge (1), and the gist thereof is: a catalyst for ethylene oxide production, which is used for producing ethylene oxide from ethylene, comprising at least silver (Ag), cesium (Cs), rhenium (Re) and a carrier; wherein, as the carrier, an alkali metal is carried on the carrier as a pretreatment, and then Ag, Cs and Re are carried on the carrier to obtain the catalyst, and the carrier used is one having a specific surface area of 0.6 to 3.0m2In terms of the weight ratio of the contents of Si and Na in terms of SiO2/Na2A carrier having an O equivalent of 2 to 50, per 1m of the carrier2The specific surface area per gram, the Re content (based on the carrier) is 170 to 600ppm, and the Cs/Re molar ratio is 0.3 to 19.
The 2 nd invention is based on the above knowledge (1) and as a result of further intensive studies, and has the gist that: a catalyst for ethylene oxide production for producing ethylene oxide from ethylene, comprising at least silver (Ag), cesium (Cs), rhenium (Re) and a carrier; wherein, as the carrier, an alkali metal is carried on the carrier as a pretreatment, and then Ag, Cs and Re are carried on the carrier to obtain the catalyst, and the carrier used is one having a specific surface area of 0.6 to 3.0m2(ii) a vector having an acid ionization constant of pKa5.0 or less per 1m of the vector2The specific surface area per gram, the Re content (based on the carrier) is 170 to 600ppm, and the Cs/Re molar ratio is 0.3 to 19.
Other key points of the invention are as follows: a method for producing a catalyst according to claim 1, wherein the catalyst comprises at least silver (Ag), cesium (Cs), rhenium (Re) and a carrier, wherein the supporting operation of Ag is performed 2 or more times, and at least a part of the amount of Cs and Re contained in the catalyst is supported at the last supporting operation of Ag.
Other key points of the invention are as follows: a method for producing a catalyst according to claim 2, wherein the catalyst comprises at least silver (Ag), cesium (Cs), rhenium (Re), and a carrier, wherein the supporting operation of Ag is performed 2 or more times, and at least a part of Cs and Re contained in the catalyst is supported at the time of the final supporting operation of Ag.
Other key points of the invention are as follows: a process for producing ethylene oxide, wherein ethylene is oxidized in the presence of the catalyst of claim 1.
Other key points of the invention are as follows: a process for producing ethylene oxide, wherein ethylene is oxidized in the presence of the catalyst of claim 2.
The invention of claim 3 is based on the above knowledge (2), and is characterized in that: a catalyst for ethylene oxide production, which is used for producing ethylene oxide from ethylene, and which comprises at least silver (Ag), lithium (Li), cesium (Cs), rhenium (Re), and a carrier; wherein the carrier has a specific surface area of 0.6-3.0 m2The carrier has a Li content of 400 to 1000ppm per g of carrier weight.
Other key points of the invention are as follows: a method for producing a catalyst according to claim 3, wherein the catalyst comprises at least silver (Ag), lithium (Li), cesium (Cs), rhenium (Re) and a carrier, wherein the supporting operation of Ag is performed 2 or more times, and at least a part of the amount of Cs and Re contained in the catalyst is supported at the last supporting operation of Ag.
Other key points of the invention are as follows: a process for producing ethylene oxide, wherein ethylene is oxidized in the presence of the catalyst of claim 3.
That is, the present invention provides the following technical means.
1. A catalyst for ethylene oxide production, which is used for producing ethylene oxide from ethylene, comprising at least silver (Ag), cesium (Cs), rhenium (Re) and a carrier; wherein,
if necessary, the catalyst is obtained by loading an alkali metal on a carrier as a pretreatment and then loading Ag, Cs and Re on the carrier,
the carrier has a specific surface area of 0.6-3.0 m2Per g, and the weight ratio of the contents of silicon (Si) and sodium (Na) is SiO2/Na2A carrier having an O equivalent of 6 to 27,
per 1m of the support2The specific surface area per gram is 170 to 600ppm of Re, the content is based on the carrier, the molar ratio of Cs/Re is 2.2 to 4.5, and Cs in the molar ratio of Cs/Re refers to the content of Cs supported on the catalyst in post-treatment, namely treatment for supporting Ag, Cs and Re.
2. The catalyst according to 1, wherein the carrier comprises α -alumina as a main component.
3. The catalyst according to 1, wherein the Si content in the carrier is SiO2The equivalent is 0.5 to 7.0 wt%.
4. The catalyst according to 2, wherein the Si content in the carrier is SiO2The equivalent is 0.5 to 7.0 wt%.
5. The catalyst according to 1, wherein the Na content in the carrier is Na2The O equivalent is 0.05 to 0.50 wt%.
6. The catalyst according to 2, wherein the Na content in the carrier is Na2The O equivalent is 0.05 to 0.50 wt%.
7. The catalyst according to 3, wherein Na is contained in the carrier as Na2The O equivalent is 0.05 to 0.50 wt%.
8. The catalyst according to 4, wherein the Na content in the carrier is Na2The O equivalent is 0.05 to 0.50 wt%.
9. The catalyst according to any one of 1 to 8, wherein the alkali metal used for the pretreatment of the carrier is lithium, and the Li content in the pretreated carrier is 100 to 1000 ppm.
10. The catalyst according to any one of 1 to 8, wherein the alkali metal used for the pretreatment of the carrier is cesium (Cs), and the Cs content in the carrier after the pretreatment is 100 to 1000 ppm.
11. The catalyst according to the above 9, wherein the alkali metal used for the pretreatment of the carrier further comprises cesium (Cs), and the Cs content in the pretreated carrier is 100 to 1000 ppm.
12. The catalyst according to any one of the above 1 to 8, wherein the silver content is 5 to 40% by weight based on the total weight of the catalyst.
13. The catalyst of 9, wherein the silver content is 5 to 40 wt% based on the total weight of the catalyst.
14. The catalyst of 10, wherein the silver content is 5 to 40 wt% based on the total weight of the catalyst.
15. The catalyst of 11, wherein the silver content is 5 to 40 wt% based on the total weight of the catalyst.
16. A method for producing a catalyst according to any one of 1 to 15, which comprises at least silver (Ag), cesium (Cs), rhenium (Re) and a carrier, wherein the supporting operation of Ag is performed 2 or more times, and at least a part of the amount of Cs and Re contained in the catalyst is supported at the last supporting operation of Ag.
17. A process for producing ethylene oxide, wherein ethylene is oxidized in the presence of the catalyst according to any one of the above 1 to 15.
Effects of the invention
According to the invention 1 and the invention 2, there is provided a catalyst for ethylene oxide production, which comprises at least Ag, Cs, Re and a carrier and is particularly improved in selectivity. Further, according to the invention of claim 3, there is provided a catalyst for ethylene oxide production comprising at least Ag, Li, Cs, Re and a carrier, in particular, having an improved catalyst life.
Detailed Description
The present invention will be described in detail below.
< catalyst of the invention 1 >
The catalyst for ethylene oxide production according to claim 1 preferably contains at least Ag, Cs, Re and a carrier, and preferably Li.
Examples of the carrier include porous refractory materials such as alumina, silicon carbide, titania, zirconia, and magnesia, and particularly, a material whose main component is α -alumina is suitable. These porous refractories are produced by sintering a mixture of a raw material powder, a binder, and a pore former, and contain Si components and Na components as impurities. Si content in SiO2The equivalent is usually 0.5 to 7.0 wt%, preferably 1.8 to 7.0 wt%; na content is as Na2The amount of O is usually 0.05 to 0.50 wt%, preferably 0.16 to 0.45 wt%. The content ranges of the Si component and the Na component are values determined from the viewpoint of improving the catalyst selectivity.
In the invention 1, the carrier having a large surface area and a specific surface area of 0.6 to 3.0m is used, wherein the ratio of the Si component to the Na component is in a predetermined range2The weight ratio of the contents of Si and Na in terms of SiO2/Na2The carrier has an O conversion value of 2-50. When a support satisfying such conditions is used, the co-catalysis of Re can be enhanced, resulting in a catalyst with significantly improved selectivity.
Particularly, from the viewpoint of maintaining the catalyst life such as catalyst selectivity, the specific surface area of the carrier is preferably 0.8 to 2.0m2A more preferable range is 1.2 to 1.6 m/g2(ii)/g; particularly, the weight ratio of the contents of Si and Na (SiO) from the viewpoint of improving the selectivity of the catalyst2/Na2O equivalent) is preferably 6 to 27. Also, the specific surface area is a value measured by the b.e.t. method.
With respect to the porous refractory material for catalyst support, particularly α -alumina, various grades of products having different specific surface areas and impurity contents have been commercialized. Therefore, in the invention 1, a product satisfying the above properties can be selected from commercially available porous refractory materials and used as a support. Further, the contents of the Si component and the Na component in the carrier can be adjusted by washing the carrier with an acid aqueous solution of an appropriate concentration.
The silver content is usually 5 to 40% by weight based on the total weight of the catalyst, and preferably 15 to 30% by weight from the viewpoint of the effect of improving the catalyst life. As in the case of the conventional known catalyst, the Cs content is usually 10 to 10000ppm, preferably 50 to 5000ppm, based on the total weight of the catalyst.
The Cs content depends on the Re content described later, and it is necessary that the Cs/Re molar ratio is in the range of 0.3 to 19. The Cs/Re molar ratio is preferably 1.7-4.5, and more preferably 2.2-4.5. When the Cs/Re molar ratio is less than 0.3 or more than 19, the effect of improving the selectivity of the catalyst is insufficient.
Further, the Re content depends on the specific surface area of the carrier used, per 1m of the carrier2The specific surface area (specific surface area of the carrier before being embedded in the catalyst) of/g, and the Re content is 170 to 600ppm, preferably 200 to 500ppm, and more preferably 250 to 450 ppm. Re content less than 170 ppm/(m)2/g) or more than 600 ppm/(m)2In the case of/g), the effect of improving the selectivity of the catalyst is insufficient.
In the invention 1, the support may be pretreated by supporting an alkali metal thereon as required. Such pretreatment of the support is recommended from the viewpoint of further improving the catalyst performance. Here, the pretreatment refers to a treatment for supporting an alkali metal before supporting a silver compound. As the alkali metal used in the pretreatment, Li and/or Cs are generally used, and Li and Cs are preferably used. Further, the Cs in the above "Cs/Re molar ratio" means the content of Cs supported on the catalyst in the post-treatment (treatment of supporting Ag, Re and Cs). Cs supported on the catalyst in the post-treatment is considered to be present on the surface of Ag together with Re.
The amount of Li and Cs is usually 100 to 1000ppm based on the Li or Cs content in the carrier after the previous treatment. The Li content is preferably 400 to 1000ppm, more preferably 550 to 1000ppm, and particularly preferably 585 to 1000 ppm. The Cs content is preferably 100 to 500 ppm. When the Li and Cs contents in the carrier are less than 100ppm, the effect of improving the catalyst life is insufficient; when it exceeds 1000ppm, the effect cannot be further improved and hence it is not economical. Further, Cs used herein is directly supported on a carrier, and is different from Cs in the above-mentioned post-treatment in this point. Since Cs in the post-treatment is believed to adhere to Ag together with Re, as described earlier.
In the catalyst for ethylene oxide production according to claim 1, the Li/Re molar ratio is usually 6 to 63, preferably 25 to 63, more preferably 35 to 63, and particularly preferably 37 to 63, from the viewpoint of the effect of improving the catalyst life; the weight ratio of Li to Ag is usually 0.0007 to 0.0073, preferably 0.0029 to 0.0073, more preferably 0.0040 to 0.0073, and particularly preferably 0.0043 to 0.0073.
The loading of the alkali metals (Li and Cs) in the pretreatment can be carried out by a conventionally known method using a water-soluble alkali metal compound. Examples of the alkali metal compound include nitrates, hydroxides, halides, carbonates, bicarbonates, oxalates, and carboxylates, with carbonates being particularly preferred. They may be used in the form of aqueous solutions of appropriate concentrations depending on the content.
In the above-mentioned post-treatment, it is convenient to use a catalyst-containing immersion liquid prepared as follows: a water-soluble Re compound and a water-soluble Cs compound are dissolved in a silver amine complex solution, and a water-soluble Li compound is redissolved as necessary.
Examples of the Ag compound used in the silver-amine complex solution include silver oxide, silver nitrate, silver carbonate, silver acetate, silver oxalate, and the like; examples of the amine include monoamines such as ammonia, pyridine, and butylamine; alcohol amines such as ethanolamine; polyamines such as ethylenediamine and 1, 3-propylenediamine. Examples of the water-soluble Re compound include rhenium halide, rhenium hydrohalide, rhenate, perrhenate, and the like. The water-soluble Cs compound may be the same as that used in the pretreatment, but is preferably a nitrate or hydroxide. The concentration of each component in the catalyst-containing immersion liquid can be determined appropriately according to the content of each component.
The impregnation method in the pretreatment step may be a method of immersing the carrier in a solution or a method of spraying a solution onto the carrier. Examples of the drying treatment include the following methods: after the impregnation treatment, the support is separated from the residual solution, and then dried under reduced pressure or dried by a heating treatment. Examples of the heat treatment include a method using an inert gas such as air or nitrogen, or superheated steam. The heating temperature is usually 100 to 300 ℃, preferably 130 to 270 ℃.
The impregnation method in the post-treatment step may be the same as described above. The heat treatment after the impregnation is carried out by measuring the temperature and time necessary for the deposition of Ag on the carrier. The conditions are preferably selected such that the silver is present on the support in the form of as homogeneous and fine particles as possible. The heating treatment may be performed using heated air (or an inert gas such as nitrogen) or superheated steam. The heating temperature is usually 130-300 deg.C, and the heating time is usually 5-30 minutes.
The catalyst with high Ag loading rate, such as a catalyst with Ag loading rate of 15-30 wt% (based on the catalyst), can be easily obtained by the catalyst manufacturing method of the invention, which is the following method: the supporting operation of Ag was carried out 2 times or more, and at least a part of the amount of Cs and Re contained in the catalyst was supported at the last supporting operation of Ag. From the viewpoint of catalytic performance, it is preferable that Cs and Re are supported in an amount of more than half of the amount at the time of the final supporting operation of Ag. The amount of Cs and Re loaded at the last loading operation of Ag is more preferably 3/4 or more, preferably the total amount of Cs and Re. The same applies to components other than Cs and Re. According to the method for producing a catalyst of the present invention, when Cs, Re, or the like is supported together with Ag at the time of the last supporting operation of Ag, and a method of supporting Cs, Re, or the like after the last supporting operation of Ag is adopted, independently of the operation, the performance of the catalyst is lowered.
The process for producing ethylene oxide using the catalyst for producing ethylene oxide of the invention 1 can be carried out under known conditions. The reaction pressure is usually 0 to 3.5 MPaG; the reaction temperature is usually 180 to 350 ℃, preferably 200 to 300 ℃. The composition of the reaction raw material gas is generally a mixed gas of 1 to 40% by volume of ethylene and 1 to 20% by volume of molecular oxygen, and a diluent such as methane or nitrogen may be present in a predetermined ratio (for example, 1 to 70% by volume). As the molecular oxygen-containing gas, air or industrial oxygen is generally used. In addition, the halogenated hydrocarbon is added to the reaction raw material gas as a reaction regulator, for example, in an amount of about 0.1 to 50ppm, so that the formation of hot spots in the catalyst can be prevented and the performance, particularly the selectivity, of the catalyst can be greatly improved.
< catalyst of the invention 2 >
The catalyst for ethylene oxide production of the invention of claim 2, for producing ethylene oxide from ethylene, comprising at least silver (Ag), cesium (Cs), rhenium (Re) and a carrier; wherein, as the carrier, an alkali metal is carried on the carrier as a pretreatment, and then Ag, Cs and Re are carried on the carrier to obtain the catalyst, and the carrier used is one having a specific surface area of 0.6 to 3.0m2(ii) a vector having an acid ionization constant of pKa5.0 or less per 1m of the vector2The specific surface area per gram, the Re content (based on the carrier) is 170 to 600ppm, and the Cs/Re molar ratio is 0.3 to 19. That is, the 2 nd invention defines the acid ionization constant instead of SiO made for the carrier in the 1 st invention2/Na2The O ratio is defined, and in this point, it is different from that of the invention 1. And, with the definition of SiO2/Na2The co-catalysis of Re can be similarly improved by the above-mentioned limitation of the acid ionization constant, similarly to the case of the O ratio.
Suitable acid ionization constants as defined in invention 2 are: having a pKa5.0 or less intensity and having a color reaction with methyl red as an indicator. When the intensity of the acid dissociation constant is not more than pKa3.2, the selectivity of the catalyst is not affected if the amount is such that a weak color reaction is caused, but the selectivity of the catalyst is lowered if the amount is increased to such an extent that a strong color reaction is caused, which is not preferable. An acid ionization constant of pKa3.2 or less means that the color reaction with methyl yellow as an indicator is exhibited. Further, the alkali ionization constant of pKa7.3 or more is not preferable, which means that a color reaction can be exhibited by bromothymol blue.
The acidity or alkalinity of the surface of the carrier can be easily judged by a color reaction based on an indicator method (26 days 4 and 26 years 4 of Showa 41, book of Industrial book company, 161 pages of acid-base catalyst, commonly known under "Tian Johao san and bamboo, 1 day 5 and 61 years 1 of Showa 61, journal society of lecture, catalyst handbook of catalyst lecture and other papers, 170 pages of Showa 59, 25 days 6 and 25 months 6 of Showa 59, pill good company, 3 rd edition of chemical toilet base, II-342 pages of Japan).
Further, the value of the acid ionization constant can be found by the following method: the sample developed with the indicator is titrated with a base such as n-butylamine. In general, it is entirely feasible to determine the end point of the indicator color reaction and the base titration reaction by visual inspection.
< catalyst of the invention 3 >
The catalyst for ethylene oxide production of the invention 3 comprises at least silver (Ag), lithium (Li), cesium (Cs), rhenium (Re) and a carrier. In this regard, it is the same as the catalyst of the preferred embodiment of the invention 1.
In the invention 3, the specific surface area is 0.6 to 3.0m2Per g of carrier. The vector used in the invention 1 is the same as that used in this connection. The ratio of Si component to Na component (SiO) in the carrier defined in invention 12/Na2O) is a preferred condition, not a necessary condition. Other conditions for the carrier are the same as in the invention 1.
In the invention 3, the Li content of the catalyst is 400 to 1000ppm based on the weight of the carrier. The Li content is a value described as a preferable range in the invention 1. The contents of Cs and Re and the Cs/Re molar ratio defined in invention 1 are preferable conditions, not essential conditions. Other conditions for the catalyst components are the same as in the invention 1. The method for producing and using the catalyst of the invention 3 is also the same as the method of the invention 1.
Examples
The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples as long as the gist thereof is not deviated. The methods for measuring physical properties used in the following examples are as follows. Further, the symbol "a" in "example" and "comparative example" indicates that these examples are related to the aforementioned invention 1; and the symbol "B" indicates that it is related to the aforementioned 3 rd invention.
(1) Specific surface area:
the method is adopted for determination. The nitrogen adsorption was carried out at 77K, and the specific surface area was calculated by the BET1 point method.
(2) Si and Na content in the carrier:
the sample was pulverized, then press-molded, and measured by fluorescent X-ray analysis.
(3) CS, Re and Li contents in the pretreated support and catalyst:
the above components were extracted with nitric acid, and Cs and Li were measured by an atomic absorption method and Re was measured by an ICP emission method.
(4) Ag content in catalyst:
extracting Ag by nitric acid, and measuring by a potential difference titration method.
(5) Acid and alkalinity of the carrier:
the acid and alkali values of the carrier were measured as follows. That is, the carrier was dried at 120 ℃ for 3 hours, cooled, and then added to dry toluene. To this was added a few drops of an indicator (0.001 wt%) dissolved in toluene, shaken well, and then allowed to stand. Then, for each indicator, it was examined whether there was a color reaction.
Example 1A:
(1) and (3) measuring the acid and the alkalinity of the carrier:
for alpha-alumina carrier (surface area 1.0 m)2Water absorption 35.7 wt.% SiO23.0 wt.% Na20.35% by weight of O and SiO2/Na2O weight ratio of 9 and a ring shape of 8 mm. phi. times.8 mm) was measured.
The color reaction of red did not appear when methyl yellow having a pKa of 3.2 or less was used, and the color reaction of red appeared when methyl red having a pKa of 5.0 or less was used. Further, a blue color development reaction did not occur with bromothymol blue having a pKa of 7.3 or more. As is clear from the above, the carrier has an acid ionization constant of 3.2 < pKa.ltoreq.5.0 and does not have a base ionization constant of pKa.gtoreq.7.3.
(2) Pretreatment of the carrier:
100g of the above-mentioned alpha-alumina carrier was impregnated with a solution of 0.156g of cesium carbonate (Cs)2CO3) And 1.69g lithium carbonate (Li)2CO3) To 200mL of the aqueous solution of (1), the residual liquid was removed, and then it was heated in superheated steam at 150 ℃ for 15 minutes at a flow rate of 2 m/sec, thereby preparing a carrier impregnated with Li and Cs components. The Li content in the carrier was 500ppm, and the Cs content was 230 ppm. The physical properties of the carriers used are shown in table 1.
(3) Preparation of silver amine complex solution:
322g of silver nitrate (AgNO)3) Dissolved in 1.4L of water, 192g of potassium oxalate monohydrate (K)2C2O4·H2O) was dissolved in 1.6L of water, they were heated to 60 ℃ in a hot water bath and slowly mixed during this time to give a white precipitatePrecipitating silver oxalate (Ag)2C2O4). The precipitate was recovered by filtration and washed with distilled water to give hydrous silver oxalate (water content 23.3 wt%). 375g of the thus obtained aqueous silver oxalate was slowly added to and dissolved in a solution composed of 103g of ethylenediamine, 28.1g of 1, 3-propanediamine, and 133g of water to prepare a silver amine complex solution.
(4) Preparation of Ag catalyst:
to 12.7g of the silver amine complex solution obtained above, 0.6mL of cesium nitrate (CsNO) was added3) 5.54 wt% aqueous solution, 0.6mL ammonium perrhenate (NH)4ReO4) An aqueous solution having a concentration of 3.05% by weight and 2.1mL of water were used to obtain an impregnation solution. The impregnation solution thus obtained was heated to 40 ℃ under reduced pressure in a rotary evaporator, and was impregnated with 30g of an α -alumina carrier impregnated with Li and Cs. The impregnated carrier was then heated in superheated steam at 200 ℃ for 15 minutes at a flow rate of 2 m/sec to obtain a catalyst. The contents of Ag, Cs, Re and Li in the catalyst (based on the carrier) were 13.6 wt% (12.0 wt% based on the catalyst), 980ppm, 420ppm and 500ppm, respectively.
(5) Oxidation of ethylene
Pulverizing the Ag catalyst prepared above to 6-10 mesh, filling 3mL of the Ag catalyst into SUS reaction tube with inner diameter of 7.5mm, and culturing at GHSV of 4300 hr-1The reaction was carried out under the pressure of 0.7MPaG by using a reaction gas (ethylene 30%, oxygen 8.5%, vinyl chloride 1.5ppm, carbon dioxide 6.0%, and nitrogen as the remainder). The reaction temperature was adjusted so that the ethylene oxide yield per catalyst volume per unit time (STY) was 0.25 kg-EO/h.L-cat. The selectivity to ethylene oxide increased and then decreased with increasing evaluation time. The catalyst composition and catalytic performance are shown in tables 3 and 4. Furthermore, the selectivity to ethylene oxide is expressed on an ethylene basis. In addition, Cs of "Cs/Re" in tables 3 and 4 represents the Cs content supported by the catalyst in the post-treatment. Further, "rate of deterioration" of catalyst performance means with respect to accumulationThe selectivity of Ethylene Oxide (EO)1000kg-EO/L-cat decreases, in units of "%/EO 1000".
Examples 2A to 12A and comparative examples 1A to 11A
Pretreatment was carried out as in example 1A, except that: carriers having physical properties shown in tables 1 and 2 were used, and the amounts of lithium carbonate and cesium carbonate were changed so that the contents of Li and Cs at the time of pretreatment were as shown in tables 3 and 4. Then, a "silver amine complex solution" having the same composition as in example 1A was prepared, but in the "preparation of Ag catalyst" of example 1A, the concentrations of cesium nitrate and ammonium perrhenate were changed to prepare catalysts having Cs and Re contents as shown in tables 3 and 4. The Ag content of each catalyst (based on the support) was 13.6 wt%. Then, ethylene oxidation reaction was carried out in the same manner as in example 1A using various catalysts. Table 3 and table 4 show the catalyst composition and catalyst performance.
As can be seen from tables 1 to 4 above:
(1) among catalysts comprising Ag, Cs, Re and a carrier, the highest selectivity was 84.7 to 86.5% in examples 1A to 12A satisfying the following conditions, which isWherein the conditions are: SiO of the support used2/Na2An O weight ratio of 2 to 50 (or an acid ionization constant of pKa5.0 or less); for every 1m2A specific surface area per gram of the carrier, wherein the content of Re (based on the carrier) is 170 to 600 ppm; the Cs/Re molar ratio is 0.3-19.
(2) In particular SiO in the support used2/Na2The highest selectivity was 85.7 to 86.5% in examples 1A to 8A in which the O weight ratio was 6 to 27 and the Cs/Re molar ratio was 2.2 to 4.5, and it was found that the above range is more preferable.
(3) SiO of the support, as compared with the cases of examples 1A to 12A2/Na2In comparative examples 1A to 3A in which the O weight ratio was out of the range of 2 to 50, the highest selectivity was as low as 80.8 to 83.4%, and it was found that: for increasing the selectivity of the catalyst, SiO of the support2/Na2The O weight ratio must be within the above range. Furthermore, SiO of the carrier2/Na2When the O weight ratio is in the range of 2 to 50 or not, the difference in selectivity is 3.1% as compared with the maximum value, which is very large.
(4) Compared with the cases of examples 1A to 12A, per 1m2Comparative example 4A, in which the Re content per g of the specific surface area of the carrier (based on the carrier) was not in the range of 170 to 600ppm, exhibited a low maximum selectivity of 81.9%. Thus, it can be seen that: in order to improve the selectivity of the catalyst, the Re content must be within the above range.
(5) Comparative examples 5A to 11A show that: SiO of the support for catalysts without Re2/Na2The O weight ratio has substantially no effect on the selectivity of the catalyst. I.e. SiO in the carrier2/Na2The weight ratio of O is in the range of 2 to 50 (i.e. SiO)2/Na2O weight ratio of 11), the results of optimizing the Cs content in comparative examples 5A and 6A were: the highest selectivity was 81.9%. In contrast, SiO in the carrier2/Na2In comparative examples 7A and 8A in which the O weight ratio was 0.6, the results of optimizing the Cs content were: the maximum selectivity is 80.8%, while the SiO in the support2/Na2The results of optimizing the Cs content in comparative examples 9A to 11A having an O weight ratio of 68 are: the highest selectivity is 81.6 percent; SiO of the support2/Na2The selectivity of the catalyst with the O weight ratio out of the range of 2-50 is 80.8-81.6%. I.e. SiO of the carrier2/Na2When the O weight ratio is in the range of 2 to 50 or not, the difference in selectivity is 0.3% as compared with the maximum value, and this value is very small and is only 1/10 containing Re catalyst, and it is found that this is not effective basically.
Example 1B:
(1) pretreatment of the support
The procedure was carried out analogously to example 1A, with the exception that: the surface area was 1.4m2/g, the water absorption was 41.6 wt%, and SiO content was used22.8 wt.% Na20.25% by weight of O and SiO2/Na2A cyclic α -alumina carrier having an O weight ratio of 11 and a shape of 8mm Φ × 8mm was prepared, and the amounts of lithium carbonate and cesium carbonate were changed so that the contents of Li and Cs at the time of pretreatment were as shown in table 6, thereby preparing a carrier impregnated with the Li and Cs components. The Li content in the carrier was 600ppm, and the Cs content was 340 ppm. The physical properties of the carriers used are shown in Table 5.
(2) Preparation of silver amine complex solution:
a silver amine complex solution was prepared in the same operation as in example 1A.
(3) Preparation of Ag catalyst:
a catalyst was obtained in the same manner as in example 1A. The contents of Ag, Cs, Re and Li in the catalyst (based on the carrier) were 13.6 wt% (12.0 wt% in terms of the catalyst), 1090ppm, 420ppm and 600ppm, respectively.
(4) Oxidation reaction of ethylene:
the reaction was carried out in the same manner as in example 1A. Table 6 shows the catalyst composition and catalyst performance. The meanings of the terms in table 6 are the same as in tables 3 and 4.
Examples 2B to 6B and comparative examples 1B to 8B:
first, a carrier having a Li/Cs content as shown in table 6 was obtained as in example 1B, except that: in the "pretreatment of support" of example 1B, a support having the characteristics shown in table 5 was used, and the amounts of lithium carbonate and cesium carbonate were changed so that the contents of Li and Cs at the time of pretreatment were as shown in table 6. Then, a "silver amine complex solution" having the same composition as in example 1B was prepared, but in the "preparation of Ag catalyst" step described in example 1B, the concentrations of cesium nitrate and ammonium perrhenate were changed to prepare catalysts having Cs and Re contents as shown in table 6. At this time, for the case where Li is further supported in the post-treatment, in the "preparation of Ag catalyst" step, a certain amount of lithium nitrate (LiNO) is added3). The Ag content of each catalyst (based on the support) was 13.6 wt%. Then, ethylene oxidation was carried out in the same manner as in example 1B using various catalysts. The catalyst composition and catalyst performance are shown in table 6.
Example 7B:
first, a carrier having a Li/Cs content as shown in table 6 was obtained as in example 1B, except that: an α -alumina carrier having the characteristics shown in table 5 (water absorption rate 34.6 wt%) was used in the "pretreatment of carrier" of example 1B, and the amounts of lithium carbonate and cesium carbonate were changed so that the contents of Li and Cs at the time of pretreatment were as shown in table 6. Then, a "silver amine complex solution" having the same composition as in example 1B was prepared, and the Ag supporting operation was performed 2 times as follows.
(1 st Ag Loading operation)
To 12.7g of the silver amine complex solution obtained above, 1.3mL of water was added to obtain an impregnated solution. The impregnation solution thus obtained was heated to 40 ℃ under reduced pressure in a rotary evaporator, and was impregnated with 30g of an α -alumina carrier impregnated with Li and Cs. The impregnated carrier was then heated in superheated steam at 200 ℃ for 15 minutes at a flow rate of 2 m/sec.
(2 nd Ag Loading operation)
To 12.7g of the silver amine complex solution obtained above, 0.5mL of cesium nitrate (CsNO) was added3) 9.97 wt% aqueous solution, 0.5mL ammonium perrhenate (NH)4ReO4) 5.75% by weight aqueous solution, 0.2mL of lithium nitrate (LiNO)3) An aqueous solution having a concentration of 10.1% by weight and 0.2mL of water were added to obtain an impregnation solution. The impregnation solution thus obtained was heated to 40 ℃ under reduced pressure in a rotary evaporator, and impregnated into the above-mentioned carrier having completed the 1 st Ag supporting operation. The impregnated carrier was then heated in superheated steam at 200 ℃ for 15 minutes at a flow rate of 2 m/sec to obtain a catalyst. The contents of Ag, Cs, Re and Li in the catalyst (based on the carrier) were 26.2 wt% (20.8 wt% in terms of the catalyst), 1500ppm, 530ppm and 660ppm, respectively. The ethylene oxidation reaction was carried out in the same manner as in example 1B using this catalyst. The catalyst composition and catalyst performance are shown in table 6.
[ Table 5]
As can be seen from tables 5 and 6 above:
(1) in the carriers containing Ag, Li, Cs and Re, the highest selectivity is 85.3-86.2% and the deterioration rate is 4.8-24.0 in the examples 1B-6B in which the total Li content (based on the carrier) is in the range of 400-1000 ppm. In contrast, in comparative examples 1B and 2B in which the Li content is not in the above range, the highest selectivity was 83.4 to 84.0%, the degradation rate was 33.0 to 80.0, the selectivity was decreased by 2.1%, and the degradation rate was 6.9 times. That is, from this, it is known that: limiting the Li content to the above range can stabilize the catalyst life.
(2) Particularly, in examples 1B to 4B in which the total Li content (based on the carrier) is 550 to 1000ppm, the highest selectivity is 85.3 to 86.2% and the deterioration rate is 4.8 to 9.1. In contrast, in comparative examples 5B and 6B in which the Li content is not in the above range, the highest selectivity was 85.5 to 86.1%, the deterioration rate was 11.0 to 24.0, and the deterioration rate was 2.3 times. That is, from this, it is known that: limiting the Li content to the above range can stabilize the catalyst life.
(3) In examples 1B to 5B and comparative examples 3B to 6B, or example 6B and comparative examples 7B and 8B, as shown in table 5, the carriers used in the catalysts were the same, and the total Li content was in the range of 400 to 1000ppm, which was different in whether Re was contained or not. The selectivity of the former was 85.3 to 86.2% and 81.3 to 81.7%, respectively, and the selectivity of the latter was 86.1% and 81.6%, respectively, indicating that the Re-containing catalyst had high selectivity. That is, from this, it is known that: when the specific surface area is 0.6-3.0 m2When the amount of Re is 400 to 1000ppm based on the total weight of the catalyst per g of the carrier, the addition of Re is effective for improving the selectivity of the catalyst.
(4) In example 7B in which the Ag supporting operation was performed 2 times to increase the Ag supporting rate, the catalyst deterioration rate was 2.5, and the catalyst life was significantly improved.
Claims (17)
1. A catalyst for ethylene oxide production, which is used for producing ethylene oxide from ethylene, comprising at least silver (Ag), cesium (Cs), rhenium (Re) and a carrier; wherein,
if necessary, the catalyst is obtained by loading an alkali metal on a carrier as a pretreatment and then loading Ag, Cs and Re on the carrier,
the carrier has a specific surface area of 0.6-3.0 m2Per g, and the weight ratio of the contents of silicon (Si) and sodium (Na) is SiO2/Na2Carrier with O equivalent value of 6-27，
Per 1m of the support2The specific surface area per gram is 170 to 600ppm of Re, the content is based on the carrier, the molar ratio of Cs/Re is 2.2 to 4.5, and Cs in the molar ratio of Cs/Re refers to the content of Cs supported on the catalyst in post-treatment, namely treatment for supporting Ag, Cs and Re.
2. The catalyst of claim 1 wherein the support has a major component of alpha-alumina.
3. The catalyst of claim 1, wherein the Si content in the support is SiO2The equivalent is 0.5 to 7.0 wt%.
4. The catalyst of claim 2, wherein the Si content in the support is SiO2The equivalent is 0.5 to 7.0 wt%.
5. The catalyst of claim 1, wherein the Na content in the carrier is Na2The O equivalent is 0.05 to 0.50 wt%.
6. The catalyst of claim 2, wherein the Na content in the support is Na2The O equivalent is 0.05 to 0.50 wt%.
7. The catalyst of claim 3, wherein the Na content in the carrier is Na2The O equivalent is 0.05 to 0.50 wt%.
8. The catalyst of claim 4, wherein the Na content in the carrier is Na2The O equivalent is 0.05 to 0.50 wt%.
9. The catalyst according to any one of claims 1 to 8, wherein the alkali metal used for pretreatment of the carrier is lithium, and the Li content in the pretreated carrier is 100 to 1000 ppm.
10. The catalyst according to any one of claims 1 to 8, wherein the alkali metal used for the pretreatment of the support is cesium (Cs), and the Cs content in the support after the pretreatment is 100 to 1000 ppm.
11. The catalyst of claim 9, wherein the alkali metal used for pre-treatment of the support further comprises cesium (Cs), and the Cs content in the pre-treated support is 100 to 1000 ppm.
12. A catalyst as claimed in any one of claims 1 to 8 wherein the silver is present in an amount of from 5 to 40% by weight based on the total weight of the catalyst.
13. The catalyst of claim 9 wherein the silver is present in an amount of 5 to 40 weight percent based on the total weight of the catalyst.
14. The catalyst of claim 10 wherein the silver is present in an amount of 5 to 40 weight percent based on the total weight of the catalyst.
15. The catalyst of claim 11 wherein the silver is present in an amount of 5 to 40 weight percent based on the total weight of the catalyst.
16. A method for producing a catalyst according to any one of claims 1 to 15, comprising at least silver (Ag), cesium (Cs), rhenium (Re) and a carrier, wherein the supporting operation of Ag is performed 2 times or more, and at least a part of Cs and Re contained in the catalyst is supported at the time of the final supporting operation of Ag.
17. A process for producing ethylene oxide, wherein ethylene is oxidized in the presence of the catalyst according to any one of claims 1 to 15.
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| JP107330/2006 | 2006-04-10 | ||
| JP2006107330 | 2006-04-10 | ||
| JP2006107329 | 2006-04-10 | ||
| JP107329/2006 | 2006-04-10 | ||
| PCT/JP2007/000352 WO2007116585A1 (en) | 2006-04-10 | 2007-03-30 | Catalyst for ethylene oxide production, method for producing the same, and method for producing ethylene oxide |
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| CN2010105270742A Division CN102000571A (en) | 2006-04-10 | 2007-03-30 | Catalyst for manufacturing ethylene oxide and its manufacturing method and manufacturing method for ethylene oxide |
| CN2010105270738A Division CN102029154A (en) | 2006-04-10 | 2007-03-30 | Catalyst for ethylene oxide production, method for producing the same, and method for producing ethylene oxide |
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| JP5570500B2 (en) * | 2009-03-31 | 2014-08-13 | 株式会社日本触媒 | Catalyst for producing ethylene oxide and method for producing ethylene oxide |
| US11400437B2 (en) * | 2016-08-08 | 2022-08-02 | Basf Se | Catalyst for the oxidation of ethylene to ethylene oxide |
| TWI808125B (en) * | 2018-02-07 | 2023-07-11 | 德商巴斯夫歐洲公司 | Catalyst effective in the oxidative conversion of ethylene to ethylene oxide |
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| CN1060839A (en) * | 1989-10-18 | 1992-05-06 | 联合碳化化学品及塑料有限公司 | The alkylene oxide catalyst that contains high silver content |
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| JP2011212681A (en) | 2011-10-27 |
| CN101360562A (en) | 2009-02-04 |
| JP5644705B2 (en) | 2014-12-24 |
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