JP3794070B2 - Catalyst for ethylene oxide production - Google Patents
Catalyst for ethylene oxide production Download PDFInfo
- Publication number
- JP3794070B2 JP3794070B2 JP24606296A JP24606296A JP3794070B2 JP 3794070 B2 JP3794070 B2 JP 3794070B2 JP 24606296 A JP24606296 A JP 24606296A JP 24606296 A JP24606296 A JP 24606296A JP 3794070 B2 JP3794070 B2 JP 3794070B2
- Authority
- JP
- Japan
- Prior art keywords
- compound
- cesium
- lithium
- catalyst
- silver
- 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 - Lifetime
Links
- 239000003054 catalyst Substances 0.000 title claims description 75
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 title claims description 15
- 238000004519 manufacturing process Methods 0.000 title claims description 6
- 229910052792 caesium Inorganic materials 0.000 claims description 60
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 39
- -1 cesium compound Chemical class 0.000 claims description 38
- 229910052709 silver Inorganic materials 0.000 claims description 36
- 239000004332 silver Substances 0.000 claims description 35
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 25
- 229910052744 lithium Inorganic materials 0.000 claims description 25
- 150000002642 lithium compounds Chemical class 0.000 claims description 21
- 229940100890 silver compound Drugs 0.000 claims description 15
- 150000003379 silver compounds Chemical class 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 12
- 238000005470 impregnation Methods 0.000 claims description 12
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 11
- 239000005977 Ethylene Substances 0.000 claims description 11
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 8
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 7
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical group [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 5
- 229910001882 dioxygen Inorganic materials 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 230000003197 catalytic effect Effects 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- HQRPHMAXFVUBJX-UHFFFAOYSA-M lithium;hydrogen carbonate Chemical compound [Li+].OC([O-])=O HQRPHMAXFVUBJX-UHFFFAOYSA-M 0.000 claims description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910003002 lithium salt Inorganic materials 0.000 claims description 2
- 159000000002 lithium salts Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 description 26
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 25
- 238000000034 method Methods 0.000 description 21
- 239000000243 solution Substances 0.000 description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 description 8
- 239000007864 aqueous solution Substances 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229910052783 alkali metal Inorganic materials 0.000 description 6
- 150000001340 alkali metals Chemical class 0.000 description 6
- NLSCHDZTHVNDCP-UHFFFAOYSA-N caesium nitrate Chemical compound [Cs+].[O-][N+]([O-])=O NLSCHDZTHVNDCP-UHFFFAOYSA-N 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- XNGYKPINNDWGGF-UHFFFAOYSA-L silver oxalate Chemical compound [Ag+].[Ag+].[O-]C(=O)C([O-])=O XNGYKPINNDWGGF-UHFFFAOYSA-L 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 229910052701 rubidium Inorganic materials 0.000 description 4
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 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
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 150000001412 amines Chemical class 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000011261 inert gas Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000000704 physical effect Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 229910052702 rhenium Inorganic materials 0.000 description 3
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-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
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 description 2
- AIYUHDOJVYHVIT-UHFFFAOYSA-M caesium chloride Chemical compound [Cl-].[Cs+] AIYUHDOJVYHVIT-UHFFFAOYSA-M 0.000 description 2
- 150000007942 carboxylates Chemical class 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 150000003378 silver Chemical class 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
- 238000005507 spraying Methods 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000012808 vapor phase Substances 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
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 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
- 229910052684 Cerium Inorganic materials 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- 229910013553 LiNO Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical group [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- MOCSSSMOHPPNTG-UHFFFAOYSA-N [Sc].[Y] Chemical compound [Sc].[Y] MOCSSSMOHPPNTG-UHFFFAOYSA-N 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 150000001342 alkaline earth metals Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000002528 anti-freeze Effects 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical group [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- ZUDYPQRUOYEARG-UHFFFAOYSA-L barium(2+);dihydroxide;octahydrate Chemical compound O.O.O.O.O.O.O.O.[OH-].[OH-].[Ba+2] ZUDYPQRUOYEARG-UHFFFAOYSA-L 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 229910052795 boron group element 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
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 description 1
- 229910000024 caesium carbonate Inorganic materials 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910052800 carbon group element Inorganic materials 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- YNQRWVCLAIUHHI-UHFFFAOYSA-L dilithium;oxalate Chemical compound [Li+].[Li+].[O-]C(=O)C([O-])=O YNQRWVCLAIUHHI-UHFFFAOYSA-L 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- IRXRGVFLQOSHOH-UHFFFAOYSA-L dipotassium;oxalate Chemical compound [K+].[K+].[O-]C(=O)C([O-])=O IRXRGVFLQOSHOH-UHFFFAOYSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 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
- 229910001849 group 12 element Inorganic materials 0.000 description 1
- 229910021480 group 4 element Inorganic materials 0.000 description 1
- 229910021478 group 5 element Inorganic materials 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical class 0.000 description 1
- 150000002483 hydrogen compounds Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical compound [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 description 1
- 239000000395 magnesium oxide Substances 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
- 238000002156 mixing Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-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
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052696 pnictogen Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- GGHDAUPFEBTORZ-UHFFFAOYSA-N propane-1,1-diamine Chemical compound CCC(N)N GGHDAUPFEBTORZ-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000012495 reaction gas Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 239000011819 refractory material Substances 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon 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
- 229910001923 silver oxide Inorganic materials 0.000 description 1
- 230000003381 solubilizing effect Effects 0.000 description 1
- 238000003756 stirring Methods 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
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 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
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 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
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Description
【０００１】
【発明の属する技術分野】
本発明は、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ための改良された銀触媒及びその製造方法に関する。
エチレンオキシドは活性水素化合物に付加重合させて非イオン系界面活性剤の製造に向けられるほか、水を付加させてエチレングリコールとなし、ポリエステルやポリウレタン系高分子の原料、エンジン用不凍液などに使用される。
【０００２】
【従来の技術】
エチレンを分子状酸素により気相接触酸化して工業的にエチレンオキシドを製造する際に使用される触媒は銀触媒である。エチレンオキシドを効率よく生産するために、この銀触媒の改良の要請が強く、より高選択性、長寿命の触媒の出現が望まれている。このため、従来から種々の方法が提案されているが、主活性成分である銀と反応促進剤であるアルカリ金属等との組合せ、その配合比の最適化、これらを担持する担体の改良等がその主なものである。
【０００３】
例えば、特開昭４９−３０２８６号公報には、多孔性の担体に特定量のカリウム、ルビジウム及び／又はセシウムを銀と同時に堆積せしめた触媒により高い選択性が得られると述べられている。特開昭５３−１１９１号公報には、銀及び特定量のナトリウム、カリウム、ルビジウム又はセシウムを含有する触媒により活性及び選択性が改良されると述べられている。また、特公昭６０−１０５４号公報においてナトリウム、カリウム、ルビジウム、及びセシウムの２種以上のアルカリ金属の組合わせによる効果が述べられている。
【０００４】
更に、反応促進剤であるアルカリ金属のうちで、セシウムとリチウムの併用も知られており、特公昭６２−３５８１３号公報や特開昭５５−１２７１４４号公報などに、セシウム成分とリチウム成分を銀と同時に含浸させてなる触媒が示されている。また、特開平４−３１７７４１号公報には、特定物性の多孔性担体にアルカリ金属類を含浸させる場合は、銀と同時含浸する方法か、特にセシウム成分については担体に銀を担持させ後に含浸させる方法が触媒性能を向上させる方法として好ましいと述べられている。
【０００５】
【発明が解決しようとする課題】
以上のように、エチレンオキシド製造用触媒については、反応促進剤がアルカリ金属である場合に限ってもいろいろな提案がなされているが、未だ十分に満足すべきレベルに達しているとは言えず、触媒性能改善のための努力が、継続して行われている状況にある。
本発明の目的は、従来の触媒に比較してより高い選択率と優れた活性を合わせ持ち、且つ長寿命のエチレンオキシド製造用触媒を提供することにある。
【０００６】
【課題を解決するための手段】
本発明者等は、上記課題を解決するために鋭意研究を行った結果、リチウムとセシウムによる前処理を施した多孔性担体に銀とセシウムを担持した触媒を用いることによりエチレンオキシドについて高い選択率が得られることを見出し、本発明を完成した。即ち、本発明は、多孔性担体にリチウム化合物とセシウム化合物を含有する溶液を含浸後、加熱処理し、次いで、銀化合物及びセシウム化合物を含浸させ加熱処理してなることを特徴とするエチレンを酸化してエチレンオキシドを製造するための触媒に存する。
【０００７】
【発明の実施の形態】
以下、本発明の触媒について詳細に説明する。
（多孔性担体）
本発明の触媒は多孔性担体に触媒主成分として銀を担持させた触媒である。多孔性担体としては、アルミナ、炭化珪素、チタニア、ジルコニア、マグネシア等の多孔性耐火物が挙げられるが、主成分がα−アルミナであるものが特に好適である。また、多孔性担体には通常１０％程度を上限としてシリカ成分を含有させたものであってもよい。
【０００８】
本発明においては多孔性担体の諸物性がその触媒活性に大きな影響を与える場合がある。多孔性担体の表面積は、通常０．１〜１０ｍ2/ｇ、好ましくは０．６〜５ｍ2/ｇ、更に好ましくは０．８〜２ｍ2/ｇであるものが望ましい。また、かかる表面積を保持して触媒成分の含浸操作を容易にするという点で、担体の吸水率が好ましくは２０〜５０％、更に好ましくは２５〜４５％であるものが望ましい。
【０００９】
（触媒組成）
本発明の触媒は、全触媒重量に対して、銀を、好ましくは５〜３０重量％、更に好ましくは８〜２０重量％含有する。
また、本発明の触媒は、銀以外にリチウムとセシウムを必須成分とする。かかる成分の触媒中での含有量は、全触媒重量に対して、好ましくは、リチウムが１００〜２０００ｐｐｍ及びセシウム２５０〜２０００ｐｐｍであり、更に好ましくは、リチウムが２００〜１０００ｐｐｍ及びセシウム３００〜１６００ｐｐｍである。かかる範囲以外では公知の銀触媒以上の充分な触媒としての効果が得られにくい。また、セシウムとリチウムの含有割合としては、その重量比（Ｌｉ／Ｃｓ）が、好ましくは０．０５〜８、更に好ましくは０．１〜４である。
【００１０】
更に、本発明の触媒は、リチウムとセシウム以外のアルカリ金属成分の含有を排除するものではなく、本発明の触媒の特徴を損なわない範囲において、ナトリウム、カリウム、ルビジウム、セシウム等を金属原子として通常１０〜１００００ｐｐｍ程度含有していてもよい。
【００１１】
また、本発明の触媒の特徴を損なわない範囲において、助触媒成分として作用しうるその他成分も通常１０〜１００００ｐｐｍ程度含有させてもよく、ベリリウム、カルシウム、ストロンチウム、バリウム、マグネシウム等のアルカリ土類金属、銅、金等の１１族金属、亜鉛、カドミウム、水銀等の１２族元素、ホウ素、ガリウム、インジウム、タリウム等の１３族元素、ゲルマニウム、スズ、鉛等の１４族元素、リン、砒素、アンチモン、ビスマス等の１５族元素、チタン、ジルコニウム、ハフニウム等の４族元素、珪素、バナジウム、ニオブ、タンタル等の５族元素、クロム、モリブデン、タングステン等の６族金属、レニウム等の７族金属、スカンジウムイットリウム、サマリウム、セリウム、ランタン、ネオジウム、プラセオジウム、ユーロピウム等の希土類金属などが例示される。以上の任意成分は、後述の触媒調製における前処理工程及び本処理工程のいずれにおいて担体に担持させてもよいが、好ましくは、本処理工程で銀成分と同時含浸する方法が採用される。
【００１２】
（触媒の調製、前処理工程）
本発明の触媒は、多孔性担体にリチウム化合物とセシウム化合物を含有する溶液で前処理し、次いで、銀化合物及びセシウム化合物を含有する溶液を含浸させ、加熱処理して調製されるものであるが、以下、初めの多孔性担体にリチウム化合物を含有する溶液で前処理する工程を「前処理工程」、また、前処理後の銀化合物及びセシウム化合物を含浸させ、加熱処理する工程を「本処理工程」と、各々定義することで説明する。
【００１３】
本発明の前処理とは、多孔性担体にリチウム及びセシウムを沈着させる処理であり、多孔性担体にリチウム化合物とセシウム化合物を含有する溶液を含浸させ、これを乾燥処理することをいう。含浸させる方法としては、リチウム化合物とセシウム化合物を含有する溶液中に多孔性担体を浸漬する方法または多孔性担体にリチウム化合物とセシウム化合物の含有溶液を噴霧する方法が挙げられる。なお、該処理は、リチウム化合物とセシウム化合物の両方を含有する溶液で行ってもよいし、リチウム化合物含有溶液での処理とセシウム化合物含有溶液の処理を別々に行ってもよい。乾燥処理としては、含浸処理後、多孔性担体と余剰のリチウム化合物とセシウム化合物の含有溶液を分離後、減圧乾燥、あるいは加熱処理による乾燥等が挙げられる。該加熱処理としては、好ましくは１００〜３００℃、更に好ましくは１３０〜２００℃での空気、窒素等の不活性ガス、過熱水蒸気を利用する方法が好ましい。特に好ましいのは過熱水蒸気を利用する方法である。
【００１４】
本発明の前処理工程で使用されるリチウム化合物は特に制限はないが、本処理工程で、一旦担体に担持させたリチウム成分の再溶出の起こりにくいという観点から、水への溶解度が比較的低いものが望ましく、炭酸リチウム、重炭酸リチウムあるいは、シュウ酸リチウム、酢酸リチウム等のカルボン酸のリチウム塩が好ましく、炭酸リチウム又は重炭酸リチウムが特に好ましい。また、溶媒としては、使用するリチウム化合物に対して、不活性で、溶解性が高ければ、特に限定なく使用でき、低沸点の有機溶媒、水等が挙げられる。
【００１５】
また、本発明で使用されるセシウム化合物の種類は特に限定はなく、セシウムの硝酸塩、水酸化物、ハロゲン化物、炭酸塩、重炭酸塩、カルボン酸塩等が例示される。なお、この場合に使用するリチウム化合物と同一のアニオン塩を使用することが取り扱い上、好ましく、例えば、炭酸塩、重炭酸塩、カルボン酸塩等が好ましい。
【００１６】
この場合、担体に含浸させる全セシウム量の好ましくは５〜９５％、更に好ましくは１０〜８０％を、リチウム化合物と同時に前処理工程で含浸加熱処理を行い、担体にリチウムとともにセシウムも沈着担持させる。従って、この前処理工程で担体に担持されるセシウムの含有量は、好ましくは５０〜１８００ｐｐｍ、更に好ましくは７５〜１３７５ｐｐｍである。なお、前処理工程でのセシウムの担持量が多すぎると、後述する本処理工程でのセシウム担持量を少なくすることになり、選択性が低下するので、あまり好ましくない。本発明の方法を採用することで、本処理工程のみで全セシウムを含浸させる方法と比較して、より高い選択性を有する触媒を得ることができる。
【００１７】
（触媒の調製、本処理工程）
本処理工程は、前記の前処理工程でリチウムとセシウムを担持させた多孔性担体に、銀化合物及びセシウム化合物を含有する溶液を含浸させ加熱処理させる工程である。
【００１８】
本処理工程で、銀を担体に沈着担持させるために有利に使用される銀化合物としては、例えばアミン化合物と溶媒中で可溶な錯体を形成し、そして５００℃以下、好ましくは３００℃以下、より好ましくは２６０℃以下の温度で分解して銀を析出するものがある。その例としては、酸化銀、硝酸銀、炭酸銀、あるいは、酢酸銀、シュウ酸銀などの各種カルボン酸銀を挙げることができるが、シュウ酸銀が特に好ましい。錯体形成剤としてのアミン化合物は、上記銀化合物を溶媒中で可溶化し得るものが用いられる。かかるアミン化合物としては、例えばピリジン、アセトニトリル、アンモニア、１〜６個の炭素を有するアミン類などが挙げられる。中でもアンモニア、ピリジン、ブチルアミンなどのモノアミン、エタノールアミンなどのアルカノールアミン、エチレンジアミン、１，３−プロパンジアミンの如きポリアミンが好ましい。特にエチレンジアミン及び／又は１，３−プロパンジアミンの使用、特にその混合使用が最適である。
【００１９】
銀化合物の含浸方法としては、銀化合物をアミン化合物との水溶液の形として用いることが最も現実的であるが、アルコールなどを加えた水溶液としても用い得る。最終的には触媒成分として５〜３０重量％の銀が担持されるように含浸液中の銀濃度は決定される。また、含浸の後、要すれば減圧、加熱、スプレー吹き付けなどを併せて行うこともできる。アミンは銀化合物を錯化するに必要な量（通常アミノ基２個が銀１原子に対応する）で加えられる。この場合アミン化合物は、上記必要量より５〜３０％過剰に加えるのが、反応性の面から好ましい。
【００２０】
本処理工程で使用されるセシウム化合物は、前記の前処理工程の説明で掲げたものを使用すればよい。セシウム化合物は銀化合物水溶液中に溶解し、銀と同時に担体上に担持すればよい。この本処理工程で担体に担持されるセシウムの含有量は好ましくは２００〜２０００ｐｐｍ、更に好ましくは２２５〜１５２５ｐｐｍである。本処理工程でのセシウムの担持量が少なければ、選択性が低下し、逆に多すぎる（即ち全セシウム量が多くなる）と活性、選択性が低下する。
なお、本発明ではリチウム化合物を前処理工程で含浸させることを特徴の一つとしているが、本処理工程でリチウム化合物の一部を含浸させることを排除するものではない。
【００２１】
含浸後の加熱処理は、銀が担体上に析出するのに必要な温度と時間を測定して実施する。担体上に銀ができるだけ均一に、微細な粒子で存在するように析出する条件を選ぶことが最も好ましい。一般的に加熱処理は、高温、長時間となるほど、析出した銀粒子の凝集を促進するので好ましくない。好ましい加熱処理は、１３０℃〜３００℃で、加熱した空気（又は窒素などの不活性ガス）又は、過熱水蒸気を使用して、５分から３０分の短時間行われる。好ましい上記熱処理は、触媒調製工程の時間短縮という観点からも望ましく、他に過熱水蒸気を使用すると、担体上の銀の分布が均一になり触媒性能も向上するので特に好ましい。
【００２２】
（反応方法）
本発明の触媒を用いてエチレンをエチレンオキシドに転換する反応は、慣用操作で実施できる。反応圧力は通常０．１〜３．６ＭＰａ（０〜３５ｋｇ／ｃｍ2 Ｇ）であり、反応温度は通常１８０〜３５０℃、好ましくは２００〜３００℃である。反応原料ガスの組成は、一般に、エチレンが１〜４０容量％、分子状酸素が１〜２０容量％の混合ガスが用いられ、また、一般に希釈剤、例えばメタンや窒素等の不活性ガスを一定割合、例えば１〜７０容量％で存在させることができる。分子状酸素含有ガスとしては、通常、空気あるいは工業用酸素が用いられる。更に、反応改変剤として、例えばハロゲン化炭化水素を０．１〜５０ｐｐｍ程度、反応原料ガスに加えることにより触媒中のホットスポットの形成を防止でき、且つ触媒の性能、殊に触媒選択性を大幅に改善させることができる。
【００２３】
【実施例】
以下に実施例を挙げて本発明を具体的に説明するが、本発明はこれらの実施例により限定されるものではない。なお、実施例等に用いた担体の物性を以下の表−１に示す。
【００２４】
【表１】
実施例１
（１）担体の前処理
α−アルミナ担体Ａ（表面積１．０４ｍ2/ｇ、吸水率３２．３％、平均細孔径１．４μｍ、シリカ３％、８φ×３φ×８ｍｍのリング状）５０ｇを炭酸リチウム（Ｌｉ2ＣＯ3)０．９４ｇと炭酸セシウム（Ｃｓ2ＣＯ3)０．０８７ｇが溶解した水溶液１００ｍｌに浸漬させ、余分な液を切り、次いで、これを１５０℃の過熱水蒸気にて１５分間、２ｍ／秒の流速で加熱し、リチウムとセシウム成分を含浸させた担体を調製した。
【００２６】
（２）シュウ酸銀の調製
硝酸銀（ＡｇＮＯ3 ）２２８ｇとシュウ酸カリウム（Ｋ2Ｃ2Ｏ4・Ｈ2Ｏ）１３５ｇを各々１リットルの水に溶解した後、水溶液中で６０℃に加温しながら徐々に混合し、シュウ酸銀の白色沈殿を得た。濾過後、蒸留水により沈殿を洗浄した。
【００２７】
（３）銀アミン錯体溶液の調製
（２）で得たシュウ酸銀（ＡｇＣ2Ｏ4、含水率１９．４７％）の一部（１２．３ｇ）を、エチレンジアミン３．４２ｇ、プロパンジアミン０．９４ｇ、及び水４．５４ｇよりなるアミン混合水溶液に徐々に添加して溶解させ、銀アミン錯体溶液を調製した。この銀アミン錯体溶液に、攪拌しながら塩化セシウム（ＣｓＣｌ）１．１４重量％と硝酸セシウム（ＣｓＮＯ3)１．９８重量％を含有する混合水溶液１ｍｌを添加した。該混合液に、更に、水酸化バリウム八水和物（Ｂａ（ＯＨ）2 ・８Ｈ2Ｏ）の０．６６重量％水溶液１ｍｌを添加した。
【００２８】
（４）銀触媒の調製
（１）で調製したリチウムとセシウムが含浸されたα−アルミナ担体５０ｇを、（３）で得たセシウム及びバリウムを含有するこの銀アミン錯体溶液に、エバポレーター中で減圧下、４０℃の加温中で含浸した。この含浸担体を２００℃の過熱水蒸気にて１５分間、２ｍ／秒の流速で加熱し、触媒を得た。該触媒における銀（Ａｇ）、セシウム（Ｃｓ）、リチウム（Ｌｉ）及びバリウム（Ｂａ）の担持率は１２％、５９５ｐｐｍ、５００ｐｐｍ、５０ｐｐｍであった。
【００２９】
（５）エチレンの酸化反応
上記方法で調製した触媒を、６〜１０メッシュに砕き、その３ｍｌを内径７．５ｍｍのＳＵＳ製反応管に充填し、反応ガス（エチレン３０％、酸素８．５％、塩化ビニル１．５ｐｐｍ、二酸化炭素６．０％、残り窒素）を、ＧＨＳＶ４３００ｈｒ-1、圧力０．８ＭＰａ（７ｋｇ／ｃｍ2Ｇ）で流し、反応を行った。反応を開始して１週間経過後の、酸素転化率が４０％になるときの反応温度Ｔ40（℃）と酸素転化率が４０％となるときのエチレン基準の酸化エチレンの選択率Ｓ40（％）を表−２に示す。
【００３０】
実施例２
リチウムの担持量が３００ｐｐｍとなるように前処理工程での炭酸リチウムの含浸量を変更した以外は実施例１と同様の方法で触媒を調製し反応を行った。反応結果を表−２に示す。
【００３１】
実施例３
リチウムの担持量が７００ｐｐｍとなるように前処理工程での炭酸リチウムの含浸量を変更した以外は実施例１と同様の方法で触媒を調製し反応を行った。反応結果を表−２に示す。
【００３２】
実施例４、５
前処理工程と本処理工程で担持させるセシウムの量を表−２に示すように変更した以外は実施例１と同様の方法で触媒を調製し反応を行った。反応結果を表−２に示す。
【００３３】
比較例１、２
担体にリチウムを担持せず、かつ、前処理工程ではセシウムを担持させず、本処理工程で担持させるセシウムの量を表−２に示すように変更した以外は実施例１と同様の方法で触媒を調製し反応を行った。反応結果を表−２に示す。
【００３４】
比較例３
前処理工程と本処理工程で担持させるセシウムの量を表−２に示すように変更した以外は比較例１と同様の方法で触媒を調製し反応を行った。反応結果を表−２に示す。
【００３５】
比較例４
リチウムの担持量が５００ｐｐｍとなるように本処理工程で硝酸リチウムを含浸させた以外は比較例１と同様の方法で触媒を調製し反応を行った。反応結果を表−２に示す。なお、硝酸リチウムの代わりに炭酸リチウムの使用を試みたが、銀アミン錯体溶液中への炭酸リチウムの溶解度が低く、リチウムを５００ｐｐｍ相当担持させることができなかった。
【００３６】
比較例５
リチウム原子の担持量が５００ｐｐｍとなるように本処理工程で硝酸リチウムを含浸させた以外は比較例３と同様の方法で触媒を調製し反応を行った。反応結果を表−２に示す。
【００３７】
【表２】
実施例６〜１６
担体の種類、セシウムの担持段階と担持量を表−３に示すように変更した以外は実施例１と同様の方法で触媒を調製し反応を行った。反応結果を表−３に示す。
【００３９】
【表３】
実施例１７
セシウムの担持段階と担持量を表−４に示すように変更し、かつ、銀アミン錯体溶液中に、更に過レニウム酸アンモニウムを添加した以外は実施例１と同様の方法で触媒を調製し反応を行った。該触媒における銀（Ａｇ）、セシウム（Ｃｓ）、リチウム（Ｌｉ）及びレニウム（Ｒｅ）の担持率は１２％、８７０ｐｐｍ、５００ｐｐｍ、３７０ｐｐｍであった．反応結果を表−４に示す。
本実施例の触媒ではレニウム成分添加の影響で反応温度がＴ40が高くなっているが、選択率（Ｓ40）の顕著な向上が認められる。
【００４１】
実施例１８
担体Ａの代わりに担体Ｉを用い、本処理工程で用いる銀アミン錯体溶液中に、所定量の硝酸セシウム（ＣｓＮＯ3)、タングステン酸リチウム（Ｌｉ2ＷＯ4)及び硝酸リチウム（ＬｉＮＯ3）を添加した以外は、実施例１と同様の方法で調製し、反応を行った。Ａｇ、Ｃｓ、Ｗ及びＬｉの担持率は、２０％、９３７ｐｐｍ、４６８ｐｐｍ、６６７ｐｐｍであった。反応結果を表−４に示す。
【００４２】
【表４】
【発明の効果】
本発明の触媒を用いることにより、従来の触媒と比較して温和な条件下で高い選択率でエチレンオキシドを製造することができる。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an improved silver catalyst for producing ethylene oxide by vapor phase catalytic oxidation of ethylene with molecular oxygen and a method for producing the same.
Ethylene oxide is added to active hydrogen compounds for production of nonionic surfactants, and water is added to form ethylene glycol, which is used for polyester and polyurethane polymer raw materials, engine antifreeze, etc. .
[0002]
[Prior art]
A catalyst used when industrially producing ethylene oxide by vapor-phase catalytic oxidation of ethylene with molecular oxygen is a silver catalyst. In order to efficiently produce ethylene oxide, there is a strong demand for improvement of this silver catalyst, and the appearance of a catalyst with higher selectivity and longer life is desired. For this reason, various methods have been proposed in the past, but the combination of silver as the main active ingredient and alkali metal as the reaction accelerator, optimization of the blending ratio, improvement of the carrier supporting these, etc. The main thing.
[0003]
For example, JP-A-49-30286 states that high selectivity can be obtained by a catalyst in which a specific amount of potassium, rubidium and / or cesium is deposited simultaneously with silver on a porous carrier. Japanese Patent Application Laid-Open No. 53-1191 states that the activity and selectivity are improved by a catalyst containing silver and a specific amount of sodium, potassium, rubidium or cesium. Japanese Patent Publication No. 60-1054 describes the effect of a combination of two or more alkali metals such as sodium, potassium, rubidium, and cesium.
[0004]
Further, among the alkali metals that are reaction accelerators, the combined use of cesium and lithium is also known. Japanese Patent Publication No. 62-35813 and Japanese Patent Application Laid-Open No. 55-127144 disclose a cesium component and a lithium component as silver. A catalyst impregnated at the same time is shown. JP-A-4-317741 discloses a method of impregnating a porous carrier having specific physical properties with an alkali metal, or a method of impregnating with a silver at the same time. It is stated that the method is preferable as a method for improving the catalyst performance.
[0005]
[Problems to be solved by the invention]
As described above, for ethylene oxide production catalysts, various proposals have been made even when the reaction accelerator is an alkali metal, but it has not yet reached a sufficiently satisfactory level. Efforts to improve catalyst performance are ongoing.
An object of the present invention is to provide a catalyst for producing ethylene oxide, which has a higher selectivity and superior activity than conventional catalysts, and has a long life.
[0006]
[Means for Solving the Problems]
As a result of diligent research to solve the above problems, the present inventors have achieved a high selectivity for ethylene oxide by using a catalyst in which silver and cesium are supported on a porous carrier that has been pretreated with lithium and cesium. As a result, the present invention was completed. That is, the present invention relates to an oxidation of ethylene characterized in that a porous carrier is impregnated with a solution containing a lithium compound and a cesium compound and then heat-treated, and then impregnated with a silver compound and a cesium compound and heat-treated. Thus, it exists in a catalyst for producing ethylene oxide.
[0007]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the catalyst of the present invention will be described in detail.
(Porous carrier)
The catalyst of the present invention is a catalyst in which silver is supported as a catalyst main component on a porous carrier. Examples of the porous carrier include porous refractories such as alumina, silicon carbide, titania, zirconia, and magnesia, and those having a main component of α-alumina are particularly suitable. In addition, the porous carrier may contain a silica component with an upper limit of usually about 10%.
[0008]
In the present invention, various physical properties of the porous carrier may greatly affect the catalytic activity. The surface area of the porous carrier is usually 0.1 to 10 m 2 / g, preferably 0.6 to 5 m 2 / g, more preferably 0.8 to 2 m 2 / g. Further, in view of facilitating the impregnation operation of the catalyst component while maintaining the surface area, the carrier preferably has a water absorption rate of 20 to 50%, more preferably 25 to 45%.
[0009]
(Catalyst composition)
The catalyst of the present invention preferably contains 5 to 30% by weight, more preferably 8 to 20% by weight of silver based on the total catalyst weight.
The catalyst of the present invention contains lithium and cesium as essential components in addition to silver. The content of such components in the catalyst is preferably 100 to 2000 ppm of lithium and 250 to 2000 ppm of cesium, more preferably 200 to 1000 ppm of lithium and 300 to 1600 ppm of cesium, based on the total catalyst weight. . Outside this range, it is difficult to obtain an effect as a sufficient catalyst more than a known silver catalyst. Moreover, as a content rate of a cesium and lithium, the weight ratio (Li / Cs) becomes like this. Preferably it is 0.05-8, More preferably, it is 0.1-4.
[0010]
Furthermore, the catalyst of the present invention does not exclude the inclusion of alkali metal components other than lithium and cesium, and sodium, potassium, rubidium, cesium and the like are usually used as metal atoms within a range that does not impair the characteristics of the catalyst of the present invention. You may contain about 10-10000 ppm.
[0011]
In addition, other components that can act as a promoter component may be contained in an amount of about 10 to 10,000 ppm as long as the characteristics of the catalyst of the present invention are not impaired. Alkaline earth metals such as beryllium, calcium, strontium, barium, and magnesium Group 11 metals such as copper and gold, Group 12 elements such as zinc, cadmium and mercury, Group 13 elements such as boron, gallium, indium and thallium, Group 14 elements such as germanium, tin and lead, Phosphorus, Arsenic and Antimony Group 15 elements such as bismuth, Group 4 elements such as titanium, zirconium and hafnium, Group 5 elements such as silicon, vanadium, niobium and tantalum, Group 6 metals such as chromium, molybdenum and tungsten, Group 7 metals such as rhenium, Scandium yttrium, samarium, cerium, lanthanum, neodymium, praseodymium Rare earth metal europium, and the like. The above optional components may be supported on the support in any of the pretreatment step and the main treatment step described later, but a method of simultaneous impregnation with the silver component in the main treatment step is preferably employed.
[0012]
(Catalyst preparation, pretreatment process)
The catalyst of the present invention is prepared by pretreating a porous carrier with a solution containing a lithium compound and a cesium compound, then impregnating a solution containing a silver compound and a cesium compound, and heat-treating. Hereinafter, the first step of pretreatment with a solution containing a lithium compound in a porous carrier is referred to as “pretreatment step”, and the step of impregnating the pretreated silver compound and cesium compound and then heat treatment is referred to as “main treatment. “Process” will be described by defining each.
[0013]
The pretreatment of the present invention is a treatment of depositing lithium and cesium on a porous carrier, and impregnating a porous carrier with a solution containing a lithium compound and a cesium compound, and drying this. Examples of the impregnation method include a method of immersing a porous carrier in a solution containing a lithium compound and a cesium compound, or a method of spraying a solution containing a lithium compound and a cesium compound on the porous carrier. In addition, this process may be performed with the solution containing both a lithium compound and a cesium compound, and the process with a lithium compound containing solution and the process of a cesium compound containing solution may be performed separately. Examples of the drying treatment include, after the impregnation treatment, separation of the porous carrier, the excess lithium compound, and the cesium compound-containing solution, followed by drying under reduced pressure or heat treatment. The heat treatment is preferably a method using air, an inert gas such as nitrogen, or superheated steam at 100 to 300 ° C, more preferably 130 to 200 ° C. Particularly preferred is a method using superheated steam.
[0014]
The lithium compound used in the pretreatment step of the present invention is not particularly limited, but the solubility in water is relatively low from the viewpoint that re-elution of the lithium component once supported on the carrier hardly occurs in this treatment step. A lithium salt of carboxylic acid such as lithium carbonate, lithium bicarbonate or lithium oxalate or lithium acetate is preferable, and lithium carbonate or lithium bicarbonate is particularly preferable. Moreover, as a solvent, if it is inactive with respect to the lithium compound to be used and its solubility is high, it can be used without particular limitation, and examples thereof include a low-boiling organic solvent and water.
[0015]
Moreover, the kind of cesium compound used by this invention does not have limitation in particular, A cesium nitrate, a hydroxide, a halide, carbonate, bicarbonate, carboxylate etc. are illustrated. In addition, it is preferable on handling that the same anion salt as the lithium compound used in this case is used, for example, carbonate, bicarbonate, carboxylate, etc. are preferable.
[0016]
In this case, preferably 5 to 95%, more preferably 10 to 80% of the total amount of cesium to be impregnated on the carrier is impregnated and heated in the pretreatment step simultaneously with the lithium compound, and cesium is deposited and supported on the carrier together with lithium. . Therefore, the content of cesium supported on the carrier in this pretreatment step is preferably 50 to 1800 ppm, more preferably 75 to 1375 ppm. If the amount of cesium supported in the pretreatment step is too large, the amount of cesium supported in the main treatment step, which will be described later, is decreased, and the selectivity is lowered, which is not preferable. By adopting the method of the present invention, a catalyst having higher selectivity can be obtained as compared with the method of impregnating all cesium only by this treatment step.
[0017]
(Catalyst preparation, main treatment step)
This treatment step is a step of impregnating a porous carrier carrying lithium and cesium in the pretreatment step with a solution containing a silver compound and a cesium compound and heat-treating it.
[0018]
In the present treatment step, as a silver compound that is advantageously used for depositing and supporting silver on a carrier, for example, a complex soluble in an amine compound and a solvent is formed, and 500 ° C. or lower, preferably 300 ° C. or lower, More preferably, there is one that decomposes at a temperature of 260 ° C. or lower to precipitate silver. Examples thereof include silver carboxylate such as silver oxide, silver nitrate, silver carbonate, or silver acetate and silver oxalate. Silver oxalate is particularly preferable. As the amine compound as the complex forming agent, those capable of solubilizing the silver compound in a solvent are used. Examples of such amine compounds include pyridine, acetonitrile, ammonia, and amines having 1 to 6 carbons. Of these, monoamines such as ammonia, pyridine and butylamine, alkanolamines such as ethanolamine, and polyamines such as ethylenediamine and 1,3-propanediamine are preferred. In particular, the use of ethylenediamine and / or 1,3-propanediamine, especially the mixed use thereof, is optimal.
[0019]
As the impregnation method of the silver compound, it is most realistic to use the silver compound in the form of an aqueous solution with an amine compound, but it can also be used as an aqueous solution to which alcohol or the like is added. Finally, the silver concentration in the impregnating solution is determined so that 5 to 30% by weight of silver is supported as a catalyst component. Further, after impregnation, if necessary, decompression, heating, spraying, etc. can be performed together. The amine is added in the amount necessary to complex the silver compound (usually two amino groups correspond to one silver atom). In this case, the amine compound is preferably added in an amount of 5 to 30% in excess of the above required amount from the viewpoint of reactivity.
[0020]
As the cesium compound used in the present treatment step, those listed in the description of the pretreatment step may be used. The cesium compound may be dissolved in the aqueous silver compound solution and supported on the carrier simultaneously with the silver. The content of cesium supported on the carrier in this treatment step is preferably 200 to 2000 ppm, more preferably 225 to 1525 ppm. If the amount of cesium supported in this treatment step is small, the selectivity is lowered. Conversely, if the amount is too large (that is, the total amount of cesium is increased), the activity and selectivity are lowered.
In the present invention, one of the characteristics is that the lithium compound is impregnated in the pretreatment step. However, impregnation of a part of the lithium compound in the treatment step is not excluded.
[0021]
The heat treatment after impregnation is carried out by measuring the temperature and time required for silver to deposit on the support. Most preferably, conditions are selected so that silver is present on the support as uniformly as possible and in fine particles. In general, the heat treatment is not preferable as the temperature and the time are increased, since the aggregation of the precipitated silver particles is promoted. Preferable heat treatment is performed at 130 ° C. to 300 ° C. for a short time of 5 to 30 minutes using heated air (or an inert gas such as nitrogen) or superheated steam. The preferable heat treatment is also desirable from the viewpoint of shortening the time of the catalyst preparation step, and the use of superheated steam is particularly preferable because the distribution of silver on the support becomes uniform and the catalyst performance is improved.
[0022]
(Reaction method)
The reaction for converting ethylene to ethylene oxide using the catalyst of the present invention can be carried out by a conventional operation. The reaction pressure is usually 0.1 to 3.6 MPa (0 to 35 kg / cm 2 G), and the reaction temperature is usually 180 to 350 ° C., preferably 200 to 300 ° C. 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. In general, a diluent, for example, an inert gas such as methane or nitrogen is constant. It can be present in proportions, for example 1 to 70% by volume. As the molecular oxygen-containing gas, air or industrial oxygen is usually used. Furthermore, as a reaction modifier, for example, by adding about 0.1 to 50 ppm of halogenated hydrocarbon to the reaction raw material gas, the formation of hot spots in the catalyst can be prevented, and the performance of the catalyst, especially the catalyst selectivity is greatly increased. Can be improved.
[0023]
【Example】
EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples. In addition, the physical property of the support | carrier used for the Example etc. is shown in the following Table-1.
[0024]
[Table 1]
Example 1
(1) Pretreatment of carrier α-alumina carrier A (surface area 1.04 m 2 / g, water absorption 32.3%, average pore diameter 1.4 μm, silica 3%, 8φ × 3φ × 8 mm ring shape) 50 g It is immersed in 100 ml of an aqueous solution in which 0.94 g of lithium carbonate (Li 2 CO 3 ) and 0.087 g of cesium carbonate (Cs 2 CO 3 ) are dissolved, and the excess liquid is drained. Heating was performed for 2 minutes at a flow rate of 2 m / sec to prepare a carrier impregnated with lithium and cesium components.
[0026]
(2) Preparation of silver oxalate 228 g of silver nitrate (AgNO 3 ) and 135 g of potassium oxalate (K 2 C 2 O 4 .H 2 O) were each dissolved in 1 liter of water and heated to 60 ° C. in an aqueous solution. The mixture was gradually mixed to obtain a white precipitate of silver oxalate. After filtration, the precipitate was washed with distilled water.
[0027]
(3) Preparation of silver amine complex solution A part (12.3 g) of silver oxalate (AgC 2 O 4 , water content 19.47%) obtained in (2) was added to ethylenediamine 3.42 g and propanediamine 0. A silver amine complex solution was prepared by gradually adding and dissolving it in an amine mixed aqueous solution consisting of 94 g and 4.54 g of water. To this silver amine complex solution, 1 ml of a mixed aqueous solution containing 1.14% by weight of cesium chloride (CsCl) and 1.98% by weight of cesium nitrate (CsNO 3 ) was added with stirring. Further, 1 ml of a 0.66% by weight aqueous solution of barium hydroxide octahydrate (Ba (OH) 2 .8H 2 O) was added to the mixture.
[0028]
(4) Preparation of silver catalyst 50 g of the α-alumina carrier impregnated with lithium and cesium prepared in (1) was reduced in the evaporator to this silver amine complex solution containing cesium and barium obtained in (3). The impregnation was carried out under heating at 40 ° C. The impregnated support was heated with superheated steam at 200 ° C. for 15 minutes at a flow rate of 2 m / second to obtain a catalyst. The supported rates of silver (Ag), cesium (Cs), lithium (Li) and barium (Ba) in the catalyst were 12%, 595 ppm, 500 ppm and 50 ppm.
[0029]
(5) Oxidation reaction of ethylene The catalyst prepared by the above method is crushed into 6 to 10 mesh, 3 ml of the catalyst is filled in a SUS reaction tube having an inner diameter of 7.5 mm, and reaction gas (ethylene 30%, oxygen 8.5%). , 1.5 ppm of vinyl chloride, 6.0% carbon dioxide, remaining nitrogen) was allowed to flow at GHSV 4300 hr −1 , pressure 0.8 MPa (7 kg / cm 2 G). One week after the start of the reaction, the reaction temperature T 40 (° C.) when the oxygen conversion rate becomes 40% and the ethylene-based ethylene oxide selectivity S 40 (when the oxygen conversion rate becomes 40%) %) Is shown in Table-2.
[0030]
Example 2
A catalyst was prepared and reacted in the same manner as in Example 1 except that the amount of impregnation of lithium carbonate in the pretreatment step was changed so that the amount of lithium supported was 300 ppm. The reaction results are shown in Table-2.
[0031]
Example 3
A catalyst was prepared and reacted in the same manner as in Example 1 except that the amount of impregnation of lithium carbonate in the pretreatment step was changed so that the amount of lithium supported was 700 ppm. The reaction results are shown in Table-2.
[0032]
Examples 4 and 5
A catalyst was prepared and reacted in the same manner as in Example 1 except that the amount of cesium supported in the pretreatment step and the main treatment step was changed as shown in Table-2. The reaction results are shown in Table-2.
[0033]
Comparative Examples 1 and 2
A catalyst was prepared in the same manner as in Example 1 except that lithium was not supported on the carrier, cesium was not supported in the pretreatment step, and the amount of cesium supported in this treatment step was changed as shown in Table 2. Was prepared and reacted. The reaction results are shown in Table-2.
[0034]
Comparative Example 3
A catalyst was prepared and reacted in the same manner as in Comparative Example 1 except that the amount of cesium supported in the pretreatment step and the main treatment step was changed as shown in Table-2. The reaction results are shown in Table-2.
[0035]
Comparative Example 4
A catalyst was prepared and reacted in the same manner as in Comparative Example 1 except that lithium nitrate was impregnated in this treatment step so that the supported amount of lithium was 500 ppm. The reaction results are shown in Table-2. Although use of lithium carbonate instead of lithium nitrate was attempted, the solubility of lithium carbonate in the silver amine complex solution was low, and lithium could not be supported in an amount equivalent to 500 ppm.
[0036]
Comparative Example 5
A catalyst was prepared and reacted in the same manner as in Comparative Example 3 except that lithium nitrate was impregnated in this treatment step so that the supported amount of lithium atoms was 500 ppm. The reaction results are shown in Table-2.
[0037]
[Table 2]
Examples 6-16
A catalyst was prepared and reacted in the same manner as in Example 1 except that the type of support, the stage of supporting cesium and the amount supported were changed as shown in Table 3. The reaction results are shown in Table-3.
[0039]
[Table 3]
Example 17
The catalyst was prepared and reacted in the same manner as in Example 1 except that the cesium loading stage and loading were changed as shown in Table 4 and that ammonium perrhenate was further added to the silver amine complex solution. Went. The supported rates of silver (Ag), cesium (Cs), lithium (Li) and rhenium (Re) in the catalyst were 12%, 870 ppm, 500 ppm and 370 ppm. The reaction results are shown in Table-4.
In the catalyst of this example, the reaction temperature T 40 is high due to the effect of the rhenium component addition, but a remarkable improvement in the selectivity (S 40 ) is observed.
[0041]
Example 18
A carrier I is used instead of the carrier A, and predetermined amounts of cesium nitrate (CsNO 3 ), lithium tungstate (Li 2 WO 4 ) and lithium nitrate (LiNO 3 ) are added to the silver amine complex solution used in this treatment step. Except that, it was prepared and reacted in the same manner as in Example 1. The loadings of Ag, Cs, W and Li were 20%, 937 ppm, 468 ppm and 667 ppm. The reaction results are shown in Table-4.
[0042]
[Table 4]
【The invention's effect】
By using the catalyst of the present invention, ethylene oxide can be produced with high selectivity under mild conditions as compared with conventional catalysts.
Claims (14)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24606296A JP3794070B2 (en) | 1995-09-25 | 1996-09-18 | Catalyst for ethylene oxide production |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24605595 | 1995-09-25 | ||
| JP7-246055 | 1995-09-25 | ||
| JP24606296A JP3794070B2 (en) | 1995-09-25 | 1996-09-18 | Catalyst for ethylene oxide production |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2005225345A Division JP4206404B2 (en) | 1995-09-25 | 2005-08-03 | Catalyst for ethylene oxide production |
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| Publication Number | Publication Date |
|---|---|
| JPH09150058A JPH09150058A (en) | 1997-06-10 |
| JP3794070B2 true JP3794070B2 (en) | 2006-07-05 |
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| JP24606296A Expired - Lifetime JP3794070B2 (en) | 1995-09-25 | 1996-09-18 | Catalyst for ethylene oxide production |
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| JP4206404B2 (en) * | 1995-09-25 | 2009-01-14 | 三菱化学株式会社 | Catalyst for ethylene oxide production |
| JP4210255B2 (en) * | 1997-12-25 | 2009-01-14 | 株式会社日本触媒 | Silver catalyst for producing ethylene oxide and method for producing ethylene oxide |
| JP3767251B2 (en) * | 1999-06-24 | 2006-04-19 | 三菱化学株式会社 | Catalyst for producing ethylene oxide and method for producing ethylene oxide |
| JP3767279B2 (en) * | 1999-10-05 | 2006-04-19 | 三菱化学株式会社 | Catalyst for producing ethylene oxide and method for producing ethylene oxide |
| JP3789261B2 (en) * | 1999-10-05 | 2006-06-21 | 三菱化学株式会社 | Catalyst for producing ethylene oxide and method for producing ethylene oxide |
| CN102000571A (en) | 2006-04-10 | 2011-04-06 | 三菱化学株式会社 | Catalyst for manufacturing ethylene oxide and its manufacturing method and manufacturing method for ethylene oxide |
| US9090577B2 (en) | 2009-03-31 | 2015-07-28 | Nippon Shokubai Co., Ltd. | Catalyst for producing ethylene oxide and method for producing ethylene oxide |
| JP5570277B2 (en) * | 2010-03-31 | 2014-08-13 | 株式会社日本触媒 | Catalyst for producing ethylene oxide and method for producing ethylene oxide |
| JP5797143B2 (en) * | 2012-03-26 | 2015-10-21 | 株式会社日本触媒 | A catalyst for producing ethylene oxide and a method for producing ethylene oxide using the same. |
| WO2018128639A1 (en) * | 2017-01-05 | 2018-07-12 | Scientific Design Company, Inc. | Carrier, catalyst, methods for producing them and method for producing ethylene oxide |
-
1996
- 1996-09-18 JP JP24606296A patent/JP3794070B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPH09150058A (en) | 1997-06-10 |
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