JP2009221030A - Silica molded product - Google Patents
Silica molded product Download PDFInfo
- Publication number
- JP2009221030A JP2009221030A JP2008064843A JP2008064843A JP2009221030A JP 2009221030 A JP2009221030 A JP 2009221030A JP 2008064843 A JP2008064843 A JP 2008064843A JP 2008064843 A JP2008064843 A JP 2008064843A JP 2009221030 A JP2009221030 A JP 2009221030A
- Authority
- JP
- Japan
- Prior art keywords
- silica
- zeolite
- molded body
- weight
- silica molded
- 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.)
- Granted
Links
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 484
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 239
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 170
- 239000010457 zeolite Substances 0.000 claims abstract description 167
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 162
- 239000002245 particle Substances 0.000 claims abstract description 87
- 239000000203 mixture Substances 0.000 claims abstract description 56
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 47
- 239000011574 phosphorus Substances 0.000 claims abstract description 47
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 31
- 239000002994 raw material Substances 0.000 claims description 51
- 239000000843 powder Substances 0.000 claims description 35
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 claims description 35
- 239000005977 Ethylene Substances 0.000 claims description 29
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 26
- -1 phosphorus compound Chemical class 0.000 claims description 24
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 21
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 21
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 21
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 20
- 229930195733 hydrocarbon Natural products 0.000 claims description 17
- 150000002430 hydrocarbons Chemical class 0.000 claims description 17
- 239000004215 Carbon black (E152) Substances 0.000 claims description 16
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 15
- 239000011164 primary particle Substances 0.000 claims description 15
- 238000010304 firing Methods 0.000 claims description 10
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 claims description 8
- 238000001694 spray drying Methods 0.000 claims description 8
- 238000012360 testing method Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 239000007809 chemical reaction catalyst Substances 0.000 claims description 5
- 230000037396 body weight Effects 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 44
- 239000003054 catalyst Substances 0.000 abstract description 41
- 229910052751 metal Inorganic materials 0.000 description 22
- 239000002184 metal Substances 0.000 description 20
- 238000005259 measurement Methods 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 229910001868 water Inorganic materials 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 13
- 230000002776 aggregation Effects 0.000 description 13
- 239000002002 slurry Substances 0.000 description 11
- 235000013339 cereals Nutrition 0.000 description 10
- 230000007423 decrease Effects 0.000 description 10
- 239000012798 spherical particle Substances 0.000 description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 8
- 238000004220 aggregation Methods 0.000 description 7
- 238000005342 ion exchange Methods 0.000 description 7
- 238000005054 agglomeration Methods 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 239000012495 reaction gas Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 5
- 150000001768 cations Chemical class 0.000 description 5
- 239000007795 chemical reaction product Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000009835 boiling Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000002808 molecular sieve Substances 0.000 description 4
- 230000000737 periodic effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 229910052710 silicon Inorganic materials 0.000 description 4
- 239000010703 silicon Substances 0.000 description 4
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 3
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 3
- 238000001354 calcination Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 229910017604 nitric acid Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 238000010298 pulverizing process Methods 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 239000002023 wood Substances 0.000 description 3
- JRZJOMJEPLMPRA-UHFFFAOYSA-N 1-nonene Chemical compound CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-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
- 150000001336 alkenes Chemical class 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 2
- 235000012211 aluminium silicate Nutrition 0.000 description 2
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 description 2
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 2
- ZRIUUUJAJJNDSS-UHFFFAOYSA-N ammonium phosphates Chemical compound [NH4+].[NH4+].[NH4+].[O-]P([O-])([O-])=O ZRIUUUJAJJNDSS-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000000571 coke Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- MGNZXYYWBUKAII-UHFFFAOYSA-N cyclohexa-1,3-diene Chemical compound C1CC=CC=C1 MGNZXYYWBUKAII-UHFFFAOYSA-N 0.000 description 2
- HGCIXCUEYOPUTN-UHFFFAOYSA-N cyclohexene Chemical compound C1CCC=CC1 HGCIXCUEYOPUTN-UHFFFAOYSA-N 0.000 description 2
- ZSWFCLXCOIISFI-UHFFFAOYSA-N cyclopentadiene Chemical compound C1C=CC=C1 ZSWFCLXCOIISFI-UHFFFAOYSA-N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 2
- 229910000388 diammonium phosphate Inorganic materials 0.000 description 2
- 235000019838 diammonium phosphate Nutrition 0.000 description 2
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 2
- 239000012530 fluid Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methylcyclopentane Chemical compound CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 2
- ZGEGCLOFRBLKSE-UHFFFAOYSA-N methylene hexane Natural products CCCCCC=C ZGEGCLOFRBLKSE-UHFFFAOYSA-N 0.000 description 2
- 235000019837 monoammonium phosphate Nutrition 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 150000003018 phosphorus compounds Chemical class 0.000 description 2
- 229920000137 polyphosphoric acid Polymers 0.000 description 2
- 229940005657 pyrophosphoric acid Drugs 0.000 description 2
- 230000009257 reactivity Effects 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- PMJHHCWVYXUKFD-SNAWJCMRSA-N (E)-1,3-pentadiene Chemical compound C\C=C\C=C PMJHHCWVYXUKFD-SNAWJCMRSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- ATQUFXWBVZUTKO-UHFFFAOYSA-N 1-methylcyclopentene Chemical compound CC1=CCCC1 ATQUFXWBVZUTKO-UHFFFAOYSA-N 0.000 description 1
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 239000005909 Kieselgur Substances 0.000 description 1
- XOBKSJJDNFUZPF-UHFFFAOYSA-N Methoxyethane Chemical compound CCOC XOBKSJJDNFUZPF-UHFFFAOYSA-N 0.000 description 1
- BZLVMXJERCGZMT-UHFFFAOYSA-N Methyl tert-butyl ether Chemical compound COC(C)(C)C BZLVMXJERCGZMT-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 240000000111 Saccharum officinarum Species 0.000 description 1
- 235000007201 Saccharum officinarum Nutrition 0.000 description 1
- 229910020175 SiOH Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 240000008042 Zea mays Species 0.000 description 1
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 1
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 1
- GHESRRBMLHAELN-UHFFFAOYSA-N acetylene;prop-1-yne Chemical class C#C.CC#C GHESRRBMLHAELN-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- GJYJYFHBOBUTBY-UHFFFAOYSA-N alpha-camphorene Chemical compound CC(C)=CCCC(=C)C1CCC(CCC=C(C)C)=CC1 GJYJYFHBOBUTBY-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 229910001423 beryllium ion Inorganic materials 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 235000005822 corn Nutrition 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 150000001925 cycloalkenes Chemical class 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000000855 fermentation Methods 0.000 description 1
- 230000004151 fermentation Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 238000004817 gas chromatography Methods 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
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 239000002694 phosphate binding agent Substances 0.000 description 1
- 150000003003 phosphines Chemical class 0.000 description 1
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- DLYUQMMRRRQYAE-UHFFFAOYSA-N phosphorus pentoxide Inorganic materials O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 125000005372 silanol group Chemical group 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
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 239000010902 straw Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000004876 x-ray fluorescence 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
Landscapes
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
Description
本発明は、流動層反応の触媒として使用される、ゼオライト、シリカ及びリンを含有するシリカ成形体及びその製造方法に関する。 The present invention relates to a silica molded article containing zeolite, silica and phosphorus, which is used as a catalyst for a fluidized bed reaction, and a production method thereof.
流動層反応においては、通常、触媒を充填した反応器の下部から反応ガスを供給し、そのガス流れによって反応器内で触媒粒子が流動し、触媒粒子と反応ガスとが接触することで反応が進行する。ここで、流動層反応に用いられる触媒としては、化学的な性能のみならず、粒子の形状、大きさ、分布、流動性、強度等の、流動層反応に好適な物理的特性を備えていることが求められる。
流動層反応プロセスにおいて良好な流動状態を実現するには、触媒粒子が好適な性状を有することが必要であり、例えば、流動ハンドブック（日本粉体工業技術教会 培風館１９９９年）ｐ．１６には、「気泡と触媒を含むエマルジョン相との物質移動が十分早いことが反応率・選択率の向上に望ましい。このためには気泡が小さいことが望ましく、粒子が細かく表面が滑らかですべりやすいことがよいとされる。一般に、粒子の嵩密度が０．６〜１．０ｇ・ｍ−３と軽く、平均直径も６０〜８０μｍのものがよいといわれている。」と記載されている。また、触媒の流動に伴い、触媒粒子間、触媒粒子と反応器、触媒粒子と反応ガスとの衝突や接触による触媒粒子の摩耗や破砕が発生すると、触媒粒子の流動性低下や破砕粒子の飛散が発生するため、流動層反応触媒の性状としては、摩耗や破砕に耐えうるのに充分な機械的強度も求められる。
In the fluidized bed reaction, the reaction gas is usually supplied from the lower part of the reactor filled with the catalyst, the catalyst particles flow in the reactor by the gas flow, and the reaction is caused by the contact between the catalyst particles and the reaction gas. proceed. Here, the catalyst used in the fluidized bed reaction has not only chemical performance but also physical properties suitable for the fluidized bed reaction such as the shape, size, distribution, fluidity, and strength of the particles. Is required.
In order to realize a good fluidized state in the fluidized bed reaction process, it is necessary that the catalyst particles have suitable properties. For example, the Fluid Handbook (Japan Powder Industrial Technology Church Baifukan 1999) p. No. 16 states, “It is desirable that the mass transfer between the bubbles and the emulsion phase containing the catalyst is sufficiently fast in order to improve the reaction rate and selectivity. For this purpose, it is desirable that the bubbles are small, and the particles are fine and the surface is smooth. In general, it is said that a particle having a light bulk density of 0.6 to 1.0 g · m −3 and an average diameter of 60 to 80 μm is good. ” . Also, if the catalyst particles wear or crush due to collision or contact between the catalyst particles, between the catalyst particles and the reactor, or between the catalyst particles and the reaction gas as the catalyst flows, the fluidity of the catalyst particles decreases or the particles are scattered. Therefore, the properties of the fluidized bed reaction catalyst are also required to have sufficient mechanical strength to withstand abrasion and crushing.
すなわち、流動層反応に用いる触媒としては、流動性に優れた形状、粒径分布等を有し、かつ、触媒粒子間、触媒粒子と反応器、触媒粒子と反応ガス、との衝突や接触に耐え得る機械的強度（耐摩耗性）を有することが必要である。こうした特性を付与するため、金属、複合酸化物、ゼオライト等の触媒活性成分をアルミナやシリカ等の担体成分やバインダーとともに成形し、その成形体を焼成する方法が知られている。例えば、特許文献１には、ゼオライトとリン酸アルミニウム含有結合剤とマトリックスからなるゼオライト含有触媒が記載されている。また、特許文献２には、リン酸塩含有水溶液で処理した変性ゼオライトとマトリックスからなるゼオライト含有触媒が記載されている。 That is, the catalyst used for the fluidized bed reaction has a shape, particle size distribution, etc. with excellent fluidity, and in the collision and contact between the catalyst particles, the catalyst particles and the reactor, and the catalyst particles and the reaction gas. It is necessary to have mechanical strength (abrasion resistance) that can be withstood. In order to impart such characteristics, a method is known in which a catalytically active component such as a metal, composite oxide or zeolite is molded together with a carrier component such as alumina or silica and a binder, and the molded body is fired. For example, Patent Document 1 describes a zeolite-containing catalyst comprising a zeolite, an aluminum phosphate-containing binder and a matrix. Patent Document 2 describes a zeolite-containing catalyst comprising a modified zeolite treated with a phosphate-containing aqueous solution and a matrix.
しかしながら、特許文献１においては、ゼオライト（ＺＳＭ−５）／シリカスラリーとリン酸アルミニウム結合剤からは耐摩耗性の低い、柔らかい触媒しか得られず、また、特許文献２においては、リン酸塩変性ゼオライトとカオリンクレー、シリカ、アルミナを組み合わせて調製された触媒はいずれも、流動層反応に供するには、耐摩耗性が不充分であるという問題がある。 However, in Patent Document 1, only a soft catalyst with low wear resistance can be obtained from a zeolite (ZSM-5) / silica slurry and an aluminum phosphate binder. Any catalyst prepared by combining zeolite with kaolin clay, silica, and alumina has a problem of insufficient wear resistance for use in a fluidized bed reaction.
上記事情に鑑み、本発明は、流動層反応の触媒として、優れた形状、流動性及び強度を有する、ゼオライト、シリカ及びリンを特定の組成比で含有するシリカ成形体及びその製造方法を提供することを課題とする。 In view of the above circumstances, the present invention provides a silica molded article containing zeolite, silica, and phosphorus in a specific composition ratio having a superior shape, fluidity and strength as a catalyst for a fluidized bed reaction, and a method for producing the same. This is the issue.
本発明者らは上記課題を解決すべく鋭意検討した結果、ゼオライト、シリカ及びリンを含有するシリカ成形体であって、ゼオライト、シリカ及びリンの組成が特定の範囲に設定され、かつ、ゼオライトとして特定の物性を有するものを含むシリカ成形体が、流動層反応用の触媒として、優れた形状、流動性及び強度を有することを見いだし、本発明を完成させた。 As a result of intensive studies to solve the above problems, the inventors of the present invention are silica molded products containing zeolite, silica and phosphorus, wherein the composition of zeolite, silica and phosphorus is set in a specific range, and as zeolite The present invention was completed by finding that a silica molded body containing a material having specific physical properties has an excellent shape, fluidity and strength as a catalyst for a fluidized bed reaction.
即ち、本発明は以下の通りである。
［１］
ゼオライト、シリカ及びリンを含有し、下記式（Ｉ）：
ゼオライト／シリカ／リン＝１／Ａ／Ｂ （Ｉ）
（式中、Ａはゼオライト重量に対するシリカの重量比、Ｂはゼオライトとシリカの合計重量に対するリン元素の重量比を示し、０＜Ａ≦１０、０＜Ｂ≦０．０５である。）
で表される組成を有するシリカ成形体であって、
前記ゼオライトは、ＳｉＯ２／Ａｌ２Ｏ３モル比が１５〜１０００、平均粒子径が０．０５〜１０μｍの非凝集型のゼオライトである、シリカ成形体。
［２］
下記式（ＩＩ）で表される摩耗損失が３重量％以下である、上記［１］記載のシリカ成形体：
摩耗損失（重量％）＝Ｄ／（Ｅ−Ｃ）×１００ （ＩＩ）
（式中、Ｃは０〜５時間に摩耗逃散したシリカ成形体の重量（ｇ）、Ｄは５〜２０時間に摩耗逃散したシリカ成形体の重量（ｇ）、Ｅは試験に供したシリカ成形体の重量（ｇ）を示す。）。
［３］
安息角が２０〜３０°である、上記［１］又は［２］記載のシリカ成形体。
［４］
嵩密度が０．８〜１．２ｇ／ｃｍ３である、上記［１］〜［３］のいずれか記載のシリカ成形体。
［５］
以下の各工程：
（ｉ）ゼオライト、シリカゾル及びリン化合物を混合して、原料混合物を調製する工程、
（ｉｉ）前記原料混合物を噴霧乾燥して乾燥粉体を得る工程、
を含む、シリカ成形体の製造方法であって、
前記ゼオライトは、ＳｉＯ２／Ａｌ２Ｏ３モル比が１５〜１０００、平均粒子径が０．０５〜１０μｍの非凝集型のゼオライトであり、
前記シリカゾルに含まれるシリカ一次粒子の平均粒子径が３〜５０ｎｍである、
シリカ成形体の製造方法。
［６］
（ｉｉｉ）前記乾燥粉体を焼成する工程をさらに含む、上記［５］記載のシリカ成形体の製造方法。
［７］
前記リン化合物が水溶性リン化合物である、上記［５］又は［６］記載のシリカ成形体の製造方法。
［８］
前記水溶性リン化合物がリン酸である、上記［７］記載のシリカ成形体の製造方法。
［９］
上記［１］〜［４］のいずれか記載のシリカ成形体を流動層反応触媒として用いるプロピレンの製造方法であって、
シリカ成形体と、エチレンを含有する炭化水素原料とを接触させる工程を含む、製造方法。
That is, the present invention is as follows.
[1]
Contains zeolite, silica and phosphorus and has the following formula (I):
Zeolite / silica / phosphorous = 1 / A / B (I)
(In the formula, A represents the weight ratio of silica to the weight of zeolite, B represents the weight ratio of phosphorus element to the total weight of zeolite and silica, and 0 <A ≦ 10 and 0 <B ≦ 0.05.)
A silica molded body having a composition represented by:
The zeolite, SiO 2 / Al 2 O 3 molar ratio of 15 to 1000, an average particle size of the non-aggregated form of the zeolite of 0.05 to 10 [mu] m, the silica molded body.
[2]
The silica molded article according to the above [1], wherein the wear loss represented by the following formula (II) is 3% by weight or less:
Wear loss (% by weight) = D / (EC) × 100 (II)
(Wherein, C is the weight (g) of the silica compact that escaped from wear in 0 to 5 hours, D is the weight (g) of the silica compact that escapes from wear in 5 to 20 hours, and E is the silica compact that was subjected to the test. Body weight (g) is shown.)
[3]
The silica molded article according to the above [1] or [2], wherein the repose angle is 20 to 30 °.
[4]
The silica molded body according to any one of the above [1] to [3], which has a bulk density of 0.8 to 1.2 g / cm 3 .
[5]
The following steps:
(I) a step of mixing a zeolite, silica sol and a phosphorus compound to prepare a raw material mixture;
(Ii) a step of spray-drying the raw material mixture to obtain a dry powder;
A method for producing a silica molded body, comprising:
The zeolite is a non-aggregated zeolite having a SiO 2 / Al 2 O 3 molar ratio of 15 to 1000 and an average particle diameter of 0.05 to 10 μm,
The average particle diameter of the silica primary particles contained in the silica sol is 3 to 50 nm.
A method for producing a silica molded body.
[6]
(Iii) The method for producing a silica molded article according to the above [5], further comprising a step of firing the dry powder.
[7]
The method for producing a silica molded body according to the above [5] or [6], wherein the phosphorus compound is a water-soluble phosphorus compound.
[8]
The method for producing a silica molded article according to the above [7], wherein the water-soluble phosphorus compound is phosphoric acid.
[9]
A method for producing propylene using the silica molded body according to any one of the above [1] to [4] as a fluidized bed reaction catalyst,
The manufacturing method including the process which a silica molded object and the hydrocarbon raw material containing ethylene are made to contact.
本発明により、優れた形状、流動性及び強度を有するシリカ成形体を提供することができる。本発明のシリカ成形体は、流動層反応用の触媒としての好適な物性を有しているため、流動層反応によりエチレン含有炭化水素原料からプロピレンを製造する際の触媒として用いることで、プロピレンを高転化率で収率良くかつ安定に製造することができる。 According to the present invention, a silica molded body having excellent shape, fluidity and strength can be provided. Since the silica molded body of the present invention has suitable physical properties as a catalyst for a fluidized bed reaction, propylene can be used by producing propylene from an ethylene-containing hydrocarbon raw material by a fluidized bed reaction. It can be manufactured stably with high conversion and good yield.
以下、本発明を実施するための最良の形態（以下、本実施の形態）について詳細に説明する。なお、本発明は、以下の実施の形態に限定されるものではなく、その要旨の範囲内で種々変形して実施することができる。 Hereinafter, the best mode for carrying out the present invention (hereinafter referred to as the present embodiment) will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary.
なお、本明細書中で「シリカ」とは、シリカ成形体の製造に用いられるシリカゾルに含まれるシリカを指し、特に断りのない場合を除き、ゼオライトを構成するシリカを意味しない。 In the present specification, “silica” refers to silica contained in a silica sol used for the production of a silica molded article, and does not mean silica constituting zeolite unless otherwise specified.
［シリカ成形体］
本実施の形態のシリカ成形体は、ゼオライト、シリカ及びリンを含有し、下記式（Ｉ）：
ゼオライト／シリカ／リン＝１／Ａ／Ｂ （Ｉ）
（式中、Ａはゼオライト重量に対するシリカの重量比、Ｂはゼオライトとシリカの合計重量に対するリン元素の重量比を示し、０＜Ａ≦１０、０＜Ｂ≦０．０５である。）
で表される組成を有するシリカ成形体であって、前記ゼオライトは、ＳｉＯ２／Ａｌ２Ｏ３モル比が１５〜１０００、平均粒子径が０．０５〜１０μｍの非凝集型のゼオライトである。
[Silica molded body]
The silica molded body of the present embodiment contains zeolite, silica and phosphorus, and has the following formula (I):
Zeolite / silica / phosphorous = 1 / A / B (I)
(In the formula, A represents the weight ratio of silica to the weight of zeolite, B represents the weight ratio of phosphorus element to the total weight of zeolite and silica, and 0 <A ≦ 10 and 0 <B ≦ 0.05.)
The zeolite is a non-agglomerated zeolite having a SiO 2 / Al 2 O 3 molar ratio of 15 to 1000 and an average particle diameter of 0.05 to 10 μm.
シリカ成形体の組成を表す上記式（Ｉ）において、ゼオライト重量に対するシリカの重量比を示すＡは、０＜Ａ≦１０であり、好ましくは０．１≦Ａ≦１０、より好ましくは０．５≦Ａ≦５である。Ａが１０を超えるとシリカ成形体の形状が不良となり、流動性が低下する傾向にある。また、シリカ成形体を流動層反応用の触媒として用いる場合、Ａが１０を超えると、充分な量のゼオライトがシリカ成形体中に含まれないため反応性が低下する傾向にある。 In the above formula (I) representing the composition of the silica compact, A indicating the weight ratio of silica to zeolite weight is 0 <A ≦ 10, preferably 0.1 ≦ A ≦ 10, more preferably 0.5. ≦ A ≦ 5. When A exceeds 10, the shape of the silica molded product becomes poor, and the fluidity tends to decrease. Moreover, when using a silica molded body as a catalyst for a fluidized bed reaction, if A exceeds 10, a sufficient amount of zeolite is not contained in the silica molded body, so that the reactivity tends to decrease.
また、ゼオライトとシリカの合計重量に対するリン元素の重量比を示すＢは、０＜Ｂ≦０．０５であり、好ましくは０．００１≦Ｂ≦０．０５、より好ましくは０．００５≦Ｂ≦０．０４である。Ｂが０であると（リン元素が含まれないと）、シリカ成形体の強度が不充分となる傾向にあり、０．０５を超えるとシリカ成形体の形状が不良となり、流動性が低下する傾向にある。 Further, B indicating the weight ratio of phosphorus element to the total weight of zeolite and silica is 0 <B ≦ 0.05, preferably 0.001 ≦ B ≦ 0.05, more preferably 0.005 ≦ B ≦. 0.04. When B is 0 (when no phosphorus element is contained), the strength of the silica molded product tends to be insufficient, and when it exceeds 0.05, the shape of the silica molded product becomes poor and the fluidity is lowered. There is a tendency.
本実施の形態のシリカ成形体に含まれるゼオライトは、ＳｉＯ２／Ａｌ２Ｏ３モル比が１５〜１０００、平均粒子径が０．０５〜１０μｍの非凝集型のゼオライトである。 The zeolite contained in the silica molded body of the present embodiment is a non-agglomerated zeolite having a SiO 2 / Al 2 O 3 molar ratio of 15 to 1000 and an average particle diameter of 0.05 to 10 μm.
通常、ゼオライトは、水熱合成時に微細な一次粒子同士が凝集し、数μｍ〜２０μｍ程度の二次粒子を形成する。非凝集型のゼオライトとは、こうした凝集型のゼオライトに粉砕、衝撃、せん断等の機械的分散処理やアルカリ性溶液による溶解等の化学的処理等を施して凝集を解き、平均粒子径０．０５〜１０μｍの範囲に脱凝集されたゼオライト、又は、平均粒子径０．０５〜１０μｍの範囲で得られたゼオライトのことを言う。 Usually, in zeolite, fine primary particles aggregate during hydrothermal synthesis to form secondary particles of about several μm to 20 μm. The non-agglomerated zeolite is subjected to mechanical dispersion treatment such as pulverization, impact, shear, etc., or chemical treatment such as dissolution with an alkaline solution, etc. to break up the aggregation, and the average particle size is 0.05 to This refers to zeolite deagglomerated in the range of 10 μm or zeolite obtained in the range of an average particle diameter of 0.05 to 10 μm.
本実施の形態において「非凝集型」とは、ゼオライト一次粒子１００個の電子顕微鏡（ＳＥＭ）像のうち、他の一次粒子と部分的に結合しているゼオライト一次粒子の割合が５０％以下であることを意味する。 In the present embodiment, “non-aggregated type” means that the proportion of zeolite primary particles partially bonded to other primary particles in an electron microscope (SEM) image of 100 zeolite primary particles is 50% or less. It means that there is.
シリカ成形体に含まれるゼオライトの平均粒子径は、０．０５〜１０μｍ、好ましくは０．５〜５μｍ、より好ましくは０．５〜４μｍである。ゼオライトの平均粒子径が１０μｍを超えると、シリカ成形体の摩耗損失が大きくなる傾向があり、０．０５μｍ未満であるとゼオライトの結晶性が低下し、流動層反応用の触媒として用いた際の反応性が低下する傾向にある。 The average particle diameter of the zeolite contained in the silica molded body is 0.05 to 10 μm, preferably 0.5 to 5 μm, more preferably 0.5 to 4 μm. If the average particle size of the zeolite exceeds 10 μm, the wear loss of the silica compact tends to increase. If the average particle size is less than 0.05 μm, the crystallinity of the zeolite decreases, and when used as a catalyst for a fluidized bed reaction. The reactivity tends to decrease.
ここで、ゼオライトの平均粒子径は、レーザー式粒度分布測定装置で測定した値を意味する。 Here, the average particle diameter of zeolite means a value measured by a laser particle size distribution measuring apparatus.
また、シリカ成形体に含まれるゼオライトは、ＳｉＯ２／Ａｌ２Ｏ３モル比が好ましくは１５〜１０００であり、より好ましくは２５〜１０００であり、さらに好ましくは２５〜３００である。ＳｉＯ２／Ａｌ２Ｏ３モル比が１５よりも小さいと、シリカ成形体とエチレンを含有する炭化水素原料とを接触させてプロピレンを製造する際に、プロピレンの選択性が低下する傾向にあり、１０００を超えると、ゼオライトの疎水性が高まりシリカゾルとの親和性が低下するため、シリカ成形体の摩耗損失が大きくなる傾向にある。 Further, the zeolite contained in the silica shaped bodies, SiO 2 / Al 2 O 3 molar ratio is preferably from 15 to 1000, more preferably from 25 to 1000, more preferably from 25 to 300. When the SiO 2 / Al 2 O 3 molar ratio is less than 15, when propylene is produced by contacting a silica molded body with a hydrocarbon raw material containing ethylene, the propylene selectivity tends to decrease, If it exceeds 1000, the hydrophobicity of the zeolite increases and the affinity with the silica sol decreases, so the wear loss of the silica molded product tends to increase.
ここで、ゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比は、例えば、ゼオライトをアルカリ水溶液、或いは、フッ酸水溶液に完全に溶解し、得られた溶液をプラズマ発光分光分析法等により分析することにより求めることができる。 Here, the SiO 2 / Al 2 O 3 molar ratio of the zeolite is determined by, for example, completely dissolving the zeolite in an alkaline aqueous solution or a hydrofluoric acid aqueous solution, and analyzing the obtained solution by plasma emission spectroscopy or the like. Can be sought.
ゼオライトの具体例としては、例えば、酸素１０員環を有するゼオライト、酸素１２員環を有するゼオライト、シリコアルミノリン酸塩モレキュラーシーブ等が挙げられる。 Specific examples of the zeolite include zeolite having an oxygen 10-membered ring, zeolite having an oxygen 12-membered ring, and silicoaluminophosphate molecular sieve.
酸素１０員環を有するゼオライトとは、その結晶構造中に酸素１０員環を有するゼオライトであり、ゼオライト細孔径の範囲が、Ａ型ゼオライトに代表される小細孔径ゼオライトの細孔径と、モルデナイトやＸ型やＹ型ゼオライトに代表される大細孔径ゼオライトの細孔径の中間にあるゼオライトを指す。酸素１０員環を有するゼオライトの例としては、ＺＳＭ−５や、ＺＳＭ−５に類似の構造を有する、ＺＳＭ−８、ＺＳＭ−１１、ＺＳＭ−１２、ＺＳＭ−１８、ＺＳＭ−２３、ＺＳＭ−３５、ＺＳＭ−３９等のいわゆるペンタシル型ゼオライトが挙げられる。中でも、耐熱性が高く、形状選択性や強い固体酸性により特徴的な触媒活性を有するＺＳＭ−５が好ましい。 The zeolite having an oxygen 10-membered ring is a zeolite having an oxygen 10-membered ring in its crystal structure, and the range of the zeolite pore diameter is that of a small pore diameter zeolite represented by A-type zeolite, mordenite, This refers to zeolite in the middle of the pore diameter of large pore diameter zeolites typified by X-type and Y-type zeolites. Examples of zeolites having an oxygen 10-membered ring include ZSM-5, ZSM-8, ZSM-11, ZSM-12, ZSM-18, ZSM-23, and ZSM-35 having structures similar to ZSM-5. And so-called pentasil-type zeolites such as ZSM-39. Among them, ZSM-5 having high heat resistance and characteristic catalytic activity due to shape selectivity and strong solid acidity is preferable.
酸素１２員環を有するゼオライトとは、その結晶構造中に酸素１２員環を有するゼオライトであり、その例としては、ベータ、ホージャサイト、モルデナイト、Ｘ型ゼオライト、Ｙ型ゼオライト、Ｌ型ゼオライト、グメリナイト、ＡｌＰＯ４−５、ＡｌＰＯ４−３１などが挙げられ、中でも、適度な酸強度を有するベータが好ましい。 The zeolite having an oxygen 12-membered ring is a zeolite having an oxygen 12-membered ring in its crystal structure. , AlPO4-5, AlPO4-31, and the like. Among them, beta having an appropriate acid strength is preferable.
シリコアルミノリン酸塩モレキュラーシーブとは、アルミノリン酸塩モレキュラーシーブ中のアルミニウム及びリンの一部をシリコンで置き換えたゼオライトである。シルコアルミノリン酸塩モレキュラーシーブの例としては、ＳＡＰＯ−５、ＳＡＰＯ−３４、ＳＡＰＯ−３５等が挙げられる。 The silicoaluminophosphate molecular sieve is a zeolite in which a part of aluminum and phosphorus in the aluminophosphate molecular sieve is replaced with silicon. Examples of the silcoaluminophosphate molecular sieve include SAPO-5, SAPO-34, and SAPO-35.
また、ゼオライトとして、ゼオライト骨格を構成するアルミニウム原子の一部がＧａ、Ｆｅ、Ｂ、Ｃｒ、Ｔi等の元素で置換されたメタロアルミノシリケートや、ゼオライト骨格を構成するアルミニウム原子が全て上記のような元素で置換されたメタロシリケートを用いることもできる。その場合、メタロアルミノシリケート又はメタロシリケート中における上記の元素の含有量をアルミナのモル数に換算した上で、ＳｉＯ２／Ａｌ２Ｏ３（シリカ／アルミナ）モル比を算出する。 Further, as zeolite, metalloaluminosilicate in which a part of aluminum atoms constituting the zeolite skeleton is substituted with elements such as Ga, Fe, B, Cr, Ti, etc., and all aluminum atoms constituting the zeolite skeleton are all as described above. Metallosilicates substituted with elements can also be used. In that case, after converting the content of the above element in the metalloaluminosilicate or metallosilicate to the number of moles of alumina, the SiO 2 / Al 2 O 3 (silica / alumina) molar ratio is calculated.
また、本実施の形態のシリカ成形体は、下記式（ＩＩ）で表される摩耗損失が、好ましくは３重量％以下である。
摩耗損失（重量％）＝Ｄ／（Ｅ−Ｃ）×１００ （ＩＩ）
（式中、Ｃは０〜５時間に摩耗逃散したシリカ成形体の重量（ｇ）、Ｄは５〜２０時間に摩耗逃散したシリカ成形体の重量（ｇ）、Ｅは試験に供したシリカ成形体の重量（ｇ）を示す。）
Further, the silica molded body of the present embodiment preferably has a wear loss represented by the following formula (II) of 3% by weight or less.
Wear loss (% by weight) = D / (EC) × 100 (II)
(Wherein, C is the weight (g) of the silica compact that escaped from wear in 0 to 5 hours, D is the weight (g) of the silica compact that escapes from wear in 5 to 20 hours, and E is the silica compact that was subjected to the test. Body weight (g) is shown.)
シリカ成形体の摩耗損失が３重量％以下であると、摩耗や破損の極めて少ない、機械的強度に優れたシリカ成形体となり、流動層反応用の触媒として好適に用いることができる。シリカ成形体の摩耗損失は、より好ましくは２重量％、さらに好ましくは１重量％以下である。 When the wear loss of the silica molded body is 3% by weight or less, it becomes a silica molded body with very little wear and breakage and excellent mechanical strength, and can be suitably used as a catalyst for fluidized bed reaction. The wear loss of the silica molded body is more preferably 2% by weight, and further preferably 1% by weight or less.
本実施の形態のシリカ成形体は、安息角が、好ましくは２０〜３０°である。安息角が２０°未満であると、流動性が過剰となるため、取り扱い性が悪化する傾向にあり、３０°を超えると、流動性が低下し粒子間のブリッジングが発生し易くなる傾向にある。 The silica molded body of the present embodiment preferably has an angle of repose of 20 to 30 °. If the angle of repose is less than 20 °, the fluidity tends to be excessive, so the handleability tends to deteriorate. If it exceeds 30 °, the fluidity tends to decrease and bridging between particles tends to occur. is there.
嵩密度は、球状粒子の球状度又は流動状態の指標として極めて重要である。本実施の形態のシリカ成形体は、嵩密度が、好ましくは０．８ｇ／ｃｍ３〜１．３ｇ／ｃｍ３、より好ましくは０．８〜１．２ｇ／ｃｍ３、さらに好ましくは０．８〜０．９５ｇ／ｃｍ３である。この範囲の嵩密度を有するシリカ成形体は、流動層反応における触媒として用いた際に、反応ガス線速が向上し、触媒粒子と反応ガスとの物質移動・熱伝達がより良好となる傾向にある。嵩密度が０．８ｇ／ｃｍ３未満の場合、歪な形状の粒子や、割れ、欠け、中空の粒子の割合が多くなる傾向にあり、１．３ｇ／ｃｍ３を超えると、比表面積が低下し触媒としての化学的性能が不充分となる傾向にある。 The bulk density is extremely important as an index of the sphericity or flow state of the spherical particles. The silica molded body of the present embodiment has a bulk density of preferably 0.8 g / cm 3 to 1.3 g / cm 3 , more preferably 0.8 to 1.2 g / cm 3 , and still more preferably 0.8 to 0.8 g / cm 3 . 0.95 g / cm 3 . Silica compacts with a bulk density in this range tend to improve the linear velocity of the reaction gas when used as a catalyst in a fluidized bed reaction, and better mass transfer and heat transfer between the catalyst particles and the reaction gas. is there. When the bulk density is less than 0.8 g / cm 3 , the proportion of distorted particles, cracks, chips, and hollow particles tends to increase, and when it exceeds 1.3 g / cm 3 , the specific surface area decreases. However, the chemical performance as a catalyst tends to be insufficient.
本実施の形態のシリカ成形体には、必要に応じ金属元素を含有させることができる。特に、シリカ成形体を、エチレンを含有する炭化水素原料と接触させてプロピレンを製造する際の流動層反応触媒として用いる場合には、周期律表第ＩＢ族に属する金属、即ち、銅、銀、金よりなる群から選ばれる少なくとも１種の金属を含有することが好ましい。より好ましくは銅、銀であり、さらに好ましくは銀である。なお、本明細書において、「周期律表」とは、ＣＲＣ Ｈａｎｄｂｏｏｋ ｏｆ Ｃｈｅｍｉｓｔｒｙ ａｎｄ Ｐｈｙｓｉｃｓ， ７５ｔｈ ｅｄｉｔｉｏｎ Ｄａｖｉｄ Ｒ． Ｌｉｄｅら著、ＣＲＣ Ｐｒｅｓｓ Ｉｎｃ.発行（１９９４−１９９５年）、１−１５頁に記載の周期律表を示すものとする。 The silica molded body of the present embodiment can contain a metal element as necessary. In particular, when the silica molded body is used as a fluidized bed reaction catalyst in producing propylene by contacting with a hydrocarbon raw material containing ethylene, a metal belonging to Group IB of the periodic table, that is, copper, silver, It is preferable to contain at least one metal selected from the group consisting of gold. More preferred are copper and silver, and further preferred is silver. In the present specification, the "Periodic Table" is, CRC Handbook of Chemistry and Physics, 75 th edition David R. The periodic table described in Lide et al., CRC Press Inc. (1994-1995), pages 1-15 is shown.
シリカ成形体が周期律表第ＩＢ族に属する金属元素よりなる群から選ばれる少なくとも１種の金属元素を含有するとは、成形体中のゼオライトがＩＢ族金属に対応する陽イオンの状態で含むか、又は、成形体に担持されていることを意味する。ゼオライト又はシリカ成形体にＩＢ族金属元素を含有させる方法としては、ＩＢ族金属を含有していないゼオライト又はシリカ成形体を、公知のイオン交換法により処理する方法、例えば、液相イオン交換処理法や含浸担持触媒を高温下で処理することで固相イオン交換処理する方法等が挙げられる。当該イオン交換法によってゼオライト又はシリカ成形体にＩＢ族金属を含有させる場合には、ＩＢ族金属の塩を使用する必要がある。ＩＢ族金属の塩としては、例えば硝酸銀、酢酸銀、硫酸銀、塩化銅、硫酸銅、硝酸銅、塩化金等が挙げられ、好ましくは、硝酸銀、硝酸銅であり、より好ましくは、硝酸銀である。シリカ成形体中のＩＢ族金属の含有量は、好ましくは０.１〜１０重量％であり、より好ましくは０.２〜５重量％である。また、その含有量は公知の方法、例えばＸ線蛍光分析法等により求めることができる。 The fact that the silica compact contains at least one metal element selected from the group consisting of metal elements belonging to Group IB of the Periodic Table means that the zeolite in the compact contains a cation corresponding to the Group IB metal. Or, it means that it is carried on the molded body. As a method of incorporating a group IB metal element into a zeolite or silica molded body, a method of treating a zeolite or silica molded body not containing a group IB metal by a known ion exchange method, for example, a liquid phase ion exchange treatment method And a method of solid-phase ion exchange treatment by treating the impregnated supported catalyst at a high temperature. When a group IB metal is contained in a zeolite or silica molded article by the ion exchange method, it is necessary to use a group IB metal salt. Examples of the group IB metal salt include silver nitrate, silver acetate, silver sulfate, copper chloride, copper sulfate, copper nitrate, and gold chloride. Preferred are silver nitrate and copper nitrate, and more preferred is silver nitrate. . The content of the group IB metal in the silica molded body is preferably 0.1 to 10% by weight, more preferably 0.2 to 5% by weight. The content can be determined by a known method, for example, X-ray fluorescence analysis.
また、シリカ成形体に含まれるゼオライトのイオン交換サイトの少なくとも一部は、ＩＢ族金属カチオン及び/又はプロトンで交換されていることが好ましい。また、ＩＢ族金属カチオン及び/又はプロトンで交換されたサイト以外のイオン交換サイトは、アルカリ金属カチオン、アルカリ土類金属カチオン及びその他の金属カチオンで交換されていてもよいが、この場合、これらの金属カチオンはゼオライト酸点を被毒し、反応活性低下を引き起こすおそれがある。 Moreover, it is preferable that at least a part of the ion exchange site of the zeolite contained in the silica molded body is exchanged with a group IB metal cation and / or proton. In addition, ion exchange sites other than the sites exchanged with group IB metal cations and / or protons may be exchanged with alkali metal cations, alkaline earth metal cations and other metal cations. Metal cations poison the zeolitic acid sites and may cause a reduction in reaction activity.
シリカ成形体の平均粒子径は、流動層反応プロセスを考慮して、好ましくは１０〜２００μｍであり、より好ましくは２０〜１００μｍであり、さらに好ましくは４０〜８０μｍである。ここで、成形体の平均粒子径は、
レーザー回折・散乱式粒度分析計により測定した値を意味する。また、粒子の形状観察は電子顕微鏡（ＳＥＭ）により行うことができる。
In consideration of the fluidized bed reaction process, the average particle size of the silica molded body is preferably 10 to 200 μm, more preferably 20 to 100 μm, and further preferably 40 to 80 μm. Here, the average particle size of the molded body is
It means a value measured by a laser diffraction / scattering particle size analyzer. Moreover, the shape observation of the particles can be performed by an electron microscope (SEM).
［シリカ成形体の製造方法］
本実施の形態のシリカ成形体の製造方法は、以下の各工程：
（ｉ）ゼオライト、シリカゾル及びリン化合物を混合して、原料混合物を調製する工程、
（ｉｉ）前記原料混合物を噴霧乾燥して乾燥粉体を得る工程、
を含む、シリカ成形体の製造方法であって、
前記ゼオライトは、ＳｉＯ２／Ａｌ２Ｏ３モル比が１５〜１０００、平均粒子径が０．０５〜１０μｍの非凝集型のゼオライトであり、前記シリカゾルに含まれるシリカ一次粒子の平均粒子径が３〜５０ｎｍである。
[Method for producing silica molded article]
The method for producing a silica molded body of the present embodiment includes the following steps:
(I) a step of mixing a zeolite, silica sol and a phosphorus compound to prepare a raw material mixture;
(Ii) a step of spray-drying the raw material mixture to obtain a dry powder;
A method for producing a silica molded body, comprising:
The zeolite is a non-aggregated zeolite having a SiO 2 / Al 2 O 3 molar ratio of 15 to 1000 and an average particle size of 0.05 to 10 μm, and the average particle size of silica primary particles contained in the silica sol is 3 ~ 50 nm.
本実施の形態の製造方法においては、原料として平均粒子径が０．０５〜１０μｍの非凝集型のゼオライトと、シリカ一次粒子の平均粒子径が３〜５０ｎｍのシリカゾルを用いることで、機械的強度に特に優れたシリカ成形体を得ることができる。これらの原料の組合せにより、原料混合物中のゼオライトとシリカゾルの接触が良好となり、その結果、ゼオライトとシリカの充填状態が均一かつ密になるものと推定される。従って、シリカ成形体の機械的強度の発現には、原料混合物中のゼオライトとシリカゾルの混合状態が重要であり、ゼオライトが非凝集状態のままで混合されることが特に重要である。 In the manufacturing method of the present embodiment, mechanical strength is obtained by using non-aggregated zeolite having an average particle diameter of 0.05 to 10 μm and silica sol having an average particle diameter of 3 to 50 nm of silica primary particles as raw materials. In particular, it is possible to obtain a particularly excellent silica molded body. It is estimated that the combination of these raw materials improves the contact between the zeolite and the silica sol in the raw material mixture, and as a result, the packing state of the zeolite and silica becomes uniform and dense. Therefore, the mixed state of the zeolite and the silica sol in the raw material mixture is important for the mechanical strength of the silica molded body, and it is particularly important that the zeolite is mixed in a non-agglomerated state.
［工程（ｉ）：原料調製工程］
工程（ｉ）は、ゼオライト、シリカゾル及びリン化合物を混合して、原料混合物（原料混合スラリー）を調製する工程である。
[Step (i): Raw material preparation step]
Step (i) is a step of preparing a raw material mixture (raw material mixture slurry) by mixing zeolite, silica sol and a phosphorus compound.
シリカ成形体の製造に用いるゼオライトは、ＳｉＯ２／Ａｌ２Ｏ３モル比が１５〜１０００、平均粒子径が０．０５〜１０μｍの非凝集型のゼオライトである。具体的には、上記で列挙したゼオライトが挙げられ、中でも、ＺＳＭ−５が好ましい。 The zeolite used for the production of the silica compact is a non-agglomerated zeolite having a SiO 2 / Al 2 O 3 molar ratio of 15 to 1000 and an average particle diameter of 0.05 to 10 μm. Specific examples include zeolites listed above, among which ZSM-5 is preferable.
原料として用いるゼオライトが凝集体を形成している場合には、ジェットミル等を用いて機械的に粉砕して、非凝集型のゼオライトとして用いることができる。粉砕方法は簡便に用いることのできるボールミルよりも、高圧空気や高圧蒸気を超高速ジェット化して粉砕処理を行うジェットミルの方が好ましい。非凝集型のゼオライトの平均粒子径は０．０５〜１０μｍ、より好ましくは０．５〜５μｍ、さらに好ましくは０．５〜４μｍであり、ＳｉＯ２／Ａｌ２Ｏ３モル比は１５〜１０００であり、より好ましくは２５〜１０００であり、さらに好ましくは２５〜３００である。 When the zeolite used as the raw material forms an aggregate, it can be mechanically pulverized using a jet mill or the like and used as a non-aggregated zeolite. The pulverization method is preferably a jet mill that uses high-pressure air or high-pressure steam to form an ultra-high-speed jet for pulverization rather than a ball mill that can be used simply. The average particle size of the non-aggregated zeolite is 0.05 to 10 μm, more preferably 0.5 to 5 μm, still more preferably 0.5 to 4 μm, and the SiO 2 / Al 2 O 3 molar ratio is 15 to 1000. More preferably, it is 25-1000, More preferably, it is 25-300.
ゼオライトは、ゼオライト粉体、水にゼオライトを分散・懸濁させたスラリー、原料として用いるシリカゾルの一部にゼオライトを分散・懸濁させたスラリー、又は、リン酸化合物の水溶液にゼオライトを分散・懸濁させたスラリーとして用いることができ、好ましくはゼオライト粉体、水にゼオライトを分散・懸濁させたスラリー、又は、原料として用いるシリカゾルの一部にゼオライトを分散・懸濁させたスラリーとして用いる。理由は不明であるが、ゼオライトをリン酸化合物の水溶液に分散・懸濁させた場合、リン酸化合物によるゼオライトの凝集が生じ、それを脱凝集させるのは、ボールミルなどの機械的分散処理では不充分なものとなる傾向がある。 Zeolite is a zeolite powder, a slurry in which zeolite is dispersed and suspended in water, a slurry in which zeolite is dispersed or suspended in a part of silica sol used as a raw material, or a zeolite compound dispersed or suspended in an aqueous solution of a phosphoric acid compound. The slurry can be used as a turbid slurry, and is preferably used as a zeolite powder, a slurry in which zeolite is dispersed and suspended in water, or a slurry in which zeolite is dispersed and suspended in a part of silica sol used as a raw material. The reason is unknown, but when the zeolite is dispersed and suspended in an aqueous solution of a phosphoric acid compound, the agglomeration of the zeolite by the phosphoric acid compound occurs, and it is not possible to deagglomerate it by mechanical dispersion treatment such as ball milling. There is a tendency to be sufficient.
シリカ成形体の製造に用いるシリカ原料としては、シリカ一次粒子の平均粒子径が３〜５０ｎｍのシリカゾルを用いる。 As a silica raw material used for the production of a silica molded body, a silica sol having an average particle diameter of silica primary particles of 3 to 50 nm is used.
シリカゾル中のシリカ一次粒子の平均粒子径は、シリカ成形体の耐摩耗性や嵩密度に極めて密接に関連する。平均粒子径が３ｎｍから５０ｎｍの範囲であれば、ゼオライト粒子との接触面積が増大し、ゼオライト粒子とシリカの充填状態がより均一かつ密となるため、シリカ成形体の耐摩耗性が向上し、嵩密度も大きくなる傾向にある。 The average particle size of the silica primary particles in the silica sol is extremely closely related to the wear resistance and bulk density of the silica molded body. If the average particle diameter is in the range of 3 nm to 50 nm, the contact area with the zeolite particles increases, and the packing state of the zeolite particles and silica becomes more uniform and dense, so that the wear resistance of the silica molded body is improved, The bulk density tends to increase.
シリカ一次粒子の平均粒子径は、好ましくは３〜３０ｎｍ、より好ましくは３〜２０ｎｍ、さらに好ましくは３〜１０ｎｍである。特に好ましくは３〜５ｎｍである。 The average particle diameter of the silica primary particles is preferably 3 to 30 nm, more preferably 3 to 20 nm, and still more preferably 3 to 10 nm. Most preferably, it is 3-5 nm.
また、平均粒子径が５０ｎｍ以下の粒子径の異なる数種類のシリカコロイドを混合して、シリカ一次粒子の粒径分布が広いシリカゾルを用いることもできる。 In addition, silica sol having a broad particle size distribution of silica primary particles can be used by mixing several types of silica colloids having an average particle size of 50 nm or less and different particle sizes.
シリカゾルは、アンモニウムイオンやナトリウムイオン等で安定化させたアルカリ性シリカゾル又は酸性のシリカゾル、アミンで安定化させたシリカゾル等を用いることができる。好ましくはアンモニウムイオンで安定化させたシリカゾルである。また、シリカゾルは、アルミノシリケート、アルミナ、チタニア、ジルコニア、カオリン、珪藻土等とともに用いることができ、これらは２種以上を組み合わせて用いてもよい。 As the silica sol, alkaline silica sol or acidic silica sol stabilized with ammonium ion or sodium ion, silica sol stabilized with amine, or the like can be used. A silica sol stabilized with ammonium ions is preferred. Silica sol can be used with aluminosilicate, alumina, titania, zirconia, kaolin, diatomaceous earth, etc., and these may be used in combination of two or more.
シリカ成形体の製造に用いるリン化合物としては、リン酸、亜リン酸、次亜リン酸、ピロリン酸、ポリリン酸、リン酸一水素アンモニウム、リン酸二水素アンモニウム、リン酸三アンモニウム、過リン酸アンモニウム、次亜リン酸アンモニウム、五酸化リン、ホスフィン類等を用いることができる。好ましくは、リン酸、リン酸一水素アンモニウム、リン酸二水素アンモニウム、リン酸三アンモニウム、ピロリン酸、ポリリン酸等の水溶性のリン化合物であり、より好ましくはリン酸である。これらは単独、混合物、又は水溶液等として用いることができる。 Phosphorus compounds used in the production of the silica molded body include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, triammonium phosphate, and superphosphoric acid. Ammonium, ammonium hypophosphite, phosphorus pentoxide, phosphines, and the like can be used. Preferred are water-soluble phosphorus compounds such as phosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, triammonium phosphate, pyrophosphoric acid, polyphosphoric acid, and more preferably phosphoric acid. These can be used alone, as a mixture, or as an aqueous solution.
シリカ成形体の原料混合物を調製する際のゼオライト、シリカゾル、リン化合物の混合順序としては特に制限されない。シリカ原料であるシリカゾルにゼオライトを添加し、その混合物にリン化合物を加えてもよく、シリカゾルにリン化合物を添加し、その混合物にゼオライトを加えてもよい。またゼオライトは、ゼオライト粉体、水にゼオライトを分散・懸濁させたスラリー、又は、シリカゾルの一部にゼオライトを分散・懸濁させたスラリーとして用いることが好ましい。リン化合物はそのまま用いてもよく、あらかじめ水などに分散させて用いてもよい。 The mixing order of zeolite, silica sol, and phosphorus compound when preparing the raw material mixture of the silica molded body is not particularly limited. Zeolite may be added to silica sol, which is a silica raw material, and a phosphorus compound may be added to the mixture, or a phosphorus compound may be added to silica sol and zeolite may be added to the mixture. The zeolite is preferably used as zeolite powder, a slurry in which zeolite is dispersed and suspended in water, or a slurry in which zeolite is dispersed and suspended in a part of silica sol. The phosphorus compound may be used as it is, or may be used after being dispersed in water or the like.
また、原料混合物中には、原料混合物のｐＨを好適に調整するため酸を適宜加えてもよい。この場合、用いることができる酸としては、硫酸、塩酸、硝酸等が挙げられ、好ましくは硝酸である。原料混合物のｐＨは、好ましくは０．５〜１０であり、より好ましくは０．５〜４である。 Moreover, in order to adjust the pH of a raw material mixture suitably, you may add an acid suitably in a raw material mixture. In this case, examples of the acid that can be used include sulfuric acid, hydrochloric acid, and nitric acid, and nitric acid is preferable. The pH of the raw material mixture is preferably 0.5 to 10, more preferably 0.5 to 4.
原料混合物中には、固形分としてゼオライトとシリカが含まれる。原料混合物の固形分重量濃度は、好ましくは５〜７０重量％、より好ましくは１０〜５０重量％である。原料混合物には、固形分重量濃度を調整するために、適宜、水を加えてもよい。 The raw material mixture contains zeolite and silica as solid contents. The solid content weight concentration of the raw material mixture is preferably 5 to 70% by weight, more preferably 10 to 50% by weight. In order to adjust the solid content weight concentration, water may be appropriately added to the raw material mixture.
また、シリカ成形体の形状をより真球状にする目的で、原料混合物の表面張力を調製する界面活性剤を加えてもよい。 Further, a surfactant for adjusting the surface tension of the raw material mixture may be added for the purpose of making the shape of the silica compact more spherical.
原料混合物の攪拌時間としては、好ましくは０．５〜５０時間、より好ましくは１〜５時間である。攪拌時の混合物の温度としては、好ましくは１０〜９０°Ｃ、より好ましくは１５〜７０°Ｃ、さらに好ましくは１５〜４０°Ｃである。必要に応じて加熱することによって、原料混合物の粘度を上げてもよい。 The stirring time of the raw material mixture is preferably 0.5 to 50 hours, more preferably 1 to 5 hours. As temperature of the mixture at the time of stirring, Preferably it is 10-90 degreeC, More preferably, it is 15-70 degreeC, More preferably, it is 15-40 degreeC. You may raise the viscosity of a raw material mixture by heating as needed.
［工程（ｉｉ）：乾燥工程］
工程（ｉｉ）は、上記工程（ｉ）で得られた原料混合物を噴霧乾燥して乾燥粉体を得る工程である。原料混合物は調製後、直ちに噴霧乾燥しても、調製後に長時間の混合撹拌を行って噴霧乾燥してもよい。原料混合物の噴霧は、工業的に通常用いられる回転円盤方式、二流体ノズル方式又は高圧ノズル方式等の方法を採用することができるが、特に、回転円盤方式で行うことが好ましい。乾燥熱源は、スチーム、電気ヒーター等によって加熱された空気を用いることが好ましい。乾燥機入口の温度は、好ましくは１００〜４００°Ｃ、より好ましくは１５０〜３００°Ｃである。乾燥機出口の温度は、好ましくは８０〜１７０°Ｃ、より好ましくは９０°Ｃ〜１５０°Ｃである。
[Step (ii): Drying step]
Step (ii) is a step of obtaining a dry powder by spray drying the raw material mixture obtained in the step (i). The raw material mixture may be spray-dried immediately after preparation, or may be spray-dried by mixing and stirring for a long time after preparation. Spraying of the raw material mixture can employ a method such as a rotating disk method, a two-fluid nozzle method, or a high-pressure nozzle method that is usually used industrially, and is particularly preferably performed by a rotating disk method. The drying heat source is preferably air heated by steam, an electric heater or the like. The temperature at the inlet of the dryer is preferably 100 to 400 ° C, more preferably 150 to 300 ° C. The temperature at the outlet of the dryer is preferably 80 to 170 ° C, more preferably 90 to 150 ° C.
［工程（ｉｉｉ）：焼成工程］
本実施の形態の製造方法においては、より耐摩耗性の高いシリカ成形体を得ることを目的として、必要に応じて、（ｉｉｉ）前記乾燥粉体を焼成する工程をさらに含んでもよい。乾燥粉体の焼成は、マッフル炉、回転炉、トンネル炉、管状炉、流動焼成炉等を用いて行うことができる。焼成温度としては、好ましくは５００〜９００°Ｃ、より好ましくは５５０〜８５０°Ｃ、さらに好ましくは６００〜７００°Ｃである。焼成時間としては、好ましくは０．５〜８時間、より好ましくは１〜５時間である。焼成工程は大気雰囲気下、イナート雰囲気下、又は、真空下等で実施することができる。また、焼成工程は反復して実施してもよい。焼成後、シリカ成形体中の余剰のリン成分は水又は熱水で洗浄することができる。
[Step (iii): Firing step]
The production method of the present embodiment may further include (iii) a step of firing the dry powder as necessary for the purpose of obtaining a silica molded body having higher wear resistance. The dry powder can be fired using a muffle furnace, a rotary furnace, a tunnel furnace, a tubular furnace, a fluidized firing furnace, or the like. As a calcination temperature, Preferably it is 500-900 degreeC, More preferably, it is 550-850 degreeC, More preferably, it is 600-700 degreeC. The firing time is preferably 0.5 to 8 hours, more preferably 1 to 5 hours. The firing step can be performed in an air atmosphere, an inert atmosphere, a vacuum, or the like. Moreover, you may implement a baking process repeatedly. After firing, the excess phosphorus component in the silica molded body can be washed with water or hot water.
また、シリカ成形体にＩＢ族金属等の金属元素を担持させる場合には、予めイオン交換等の公知の方法により所望の金属元素を担持させたゼオライトを用いてもよく、上述の原料混合物に所望の金属元素を溶解又は分散させておいてもよい。また、焼成後に所望の金属元素を含有する水溶液と接触させて担持させることもできる。更には、焼成後にシリカ成形体を硝酸、塩酸のような鉱酸の水溶液と接触させて、ゼオライトをイオン交換してもよい。 In addition, when a metal element such as a group IB metal is supported on a silica molded body, a zeolite in which a desired metal element is supported in advance by a known method such as ion exchange may be used. These metal elements may be dissolved or dispersed. Moreover, it can be made to contact and carry | support with the aqueous solution containing a desired metal element after baking. Further, the zeolite may be ion exchanged by bringing the silica compact into contact with an aqueous solution of a mineral acid such as nitric acid or hydrochloric acid after firing.
スラリーを噴霧乾燥して造粒する場合、以下のメカニズムにより粉体粒子の破壊や粒子表面の開孔、陥没が生じ、形状が不定で脆弱な粒子となることがある。１）液滴から液体蒸発することで、液滴の収縮が始まり、液滴表面が固化・収縮し、２）次に、液滴内部からの液体蒸発による粉体粒子の内部圧が上昇する結果、粉体粒子の破壊（割れ、欠け）や粒子表面の開孔が生じ、３）その後、常温に温度が下がった時点で、粒子内部圧がなくなる、又は、負圧になることで粉体粒子の表面が陥没する。 When the slurry is granulated by spray drying, the following mechanism may cause breakage of the powder particles, opening of the particle surface, and depression, resulting in unstable and fragile particles. 1) As the liquid evaporates from the droplet, the droplet begins to contract, and the surface of the droplet solidifies and contracts. 2) Next, the internal pressure of the powder particles increases due to the liquid evaporation from inside the droplet. , Powder particle breakage (cracking, chipping) and particle surface opening occur 3) After that, when the temperature drops to room temperature, the particle internal pressure disappears or the powder particle becomes negative pressure The surface of the sunken.
これに対し本実施の形態の製造方法の場合、詳細は不明であるが、噴霧乾燥する前の原料混合物において、リン化合物がシリカ粒子に対して何らかの触媒作用を及ぼし、１）シラノール基（ＳｉＯＨ）の脱水縮合によるシリカ粒子同士が架橋し、２）噴霧乾燥時にシリカ層が液滴表層に形成され、３）粉体粒子の内部圧上昇に伴う破壊や開孔、内部圧低下、又は、負圧化による陥没が抑制されることで、平滑な表面を有する球状の粉体粒子が得られると推定される。特に、平均粒子径の比較的小さなシリカゾルを用いることで、シリカゾル粒子間の接触面積が大きく、シリカ粒子同士の架橋構造がより強固になると考えられる。また、耐摩耗性の向上に関しては、シリカ粒子同士の架橋構造に加え、上述したように、ゼオライトとシリカがより均一かつ密に乾燥粉体中で充填されていることにも起因する。また焼成によるシリカゾル粒子同士の焼結促進にもリン化合物が作用し、更なる耐摩耗性の向上に寄与していると推定される。 On the other hand, in the case of the production method of the present embodiment, details are unknown, but in the raw material mixture before spray drying, the phosphorus compound has some catalytic action on the silica particles. 1) Silanol group (SiOH) Silica particles are crosslinked by dehydration condensation of 2), 2) a silica layer is formed on the surface of the droplet during spray drying, and 3) breakage or opening due to an increase in internal pressure of the powder particles, a decrease in internal pressure, or a negative pressure. It is presumed that spherical powder particles having a smooth surface can be obtained by suppressing depression due to crystallization. In particular, it is considered that by using a silica sol having a relatively small average particle diameter, the contact area between the silica sol particles is large, and the crosslinked structure between the silica particles is further strengthened. In addition to the cross-linked structure of silica particles, the improvement in abrasion resistance is caused by the fact that zeolite and silica are more uniformly and densely packed in the dry powder as described above. It is also presumed that the phosphorus compound acts to promote the sintering of the silica sol particles by firing and contributes to further improvement in wear resistance.
［プロピレンの製造方法］
本実施の形態におけるプロピレンの製造方法においては、シリカ成形体を流動層反応触媒として用いて、シリカ成形体とエチレンを含有する炭化水素原料とを接触させる工程を含む。
[Propylene production method]
The method for producing propylene in the present embodiment includes a step of contacting the silica molded body and the hydrocarbon raw material containing ethylene using the silica molded body as a fluidized bed reaction catalyst.
流動層反応は、流動層反応器で実施される。また、エチレンを含有する炭化水素原料は、必ずしも高純度である必要はなく、工業グレードのものを使用することができる。 The fluidized bed reaction is carried out in a fluidized bed reactor. Moreover, the hydrocarbon raw material containing ethylene does not necessarily need to have high purity, and an industrial grade can be used.
エチレンを含有する炭化水素原料は、エチレンを２０重量％以上含有することが好ましく、より好ましくはエチレンを２５重量％以上含有する。エチレンを含有する炭化水素原料と共に、１重量％以上の水を反応器に供給することが好ましい。好ましい水／炭化水素原料の比率は、１重量％以上であり、より好ましくは５〜１００重量％、さらに好ましくは１０〜８０重量％である。反応生成物からプロピレンを分離し、残りのエチレンを含む低沸成分及び／又はブテンを含む高沸成分の少なくとも一部を、流動層反応器にリサイクルすることは好ましい形態の一例である。 The hydrocarbon raw material containing ethylene preferably contains 20% by weight or more of ethylene, and more preferably contains 25% by weight or more of ethylene. It is preferable to supply 1% by weight or more of water to the reactor together with the hydrocarbon raw material containing ethylene. A preferred water / hydrocarbon raw material ratio is 1% by weight or more, more preferably 5 to 100% by weight, and still more preferably 10 to 80% by weight. An example of a preferred embodiment is to separate propylene from the reaction product and recycle at least a portion of the low boiling component containing the remaining ethylene and / or the high boiling component containing butene to the fluidized bed reactor.
エチレンを含有する炭化水素原料は、エタンの熱分解及び／又は酸化的脱水素反応、又は、バイオマスエタノールの脱水反応により得られたものを使用することができる。この原料は、オレフィン類及びパラフィン類を含んでいてもよい。パラフィン類の例としては、メタン、エタン、プロパン、ブタン、ペンタン、ヘキサン、ヘプタン、オクタン、ノナン等を挙げることができる。また、オレフィン類の例としては、プロピレン、ブテン、ペンテン、ヘキセン、ヘプテン、オクテン、ノネン等が挙げられる。上記以外にシクロペンタン、メチルシクロペンタン、シクロヘキサン等のシクロパラフィン、シクロペンテン、メチルシクロペンテン、シクロヘキセン等のシクロオレフィン類、及び／又は、シクロヘキサジエン、ブタジエン、ペンタジエン、シクロペンタジエン等のジエン類やアセチレン、メチルアセチレン等のアセチレン類を含んでいてもよい。さらに、ｔ−ブチルアルコール、メチル−ｔ−ブチルエーテル、ジエチルエーテル、メチルエチルエーテル、ジメチルエーテル、エタノール、メタノール等の含酸素化合物が含まれていてもよい。また、エチレンを含有する炭化水素原料は、水、水素、窒素、二酸化炭素、一酸化炭素等を含んでいてもよい。 As the hydrocarbon raw material containing ethylene, one obtained by thermal decomposition and / or oxidative dehydrogenation of ethane or dehydration of biomass ethanol can be used. This raw material may contain olefins and paraffins. Examples of paraffins include methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane and the like. Examples of olefins include propylene, butene, pentene, hexene, heptene, octene, and nonene. Other than the above, cycloparaffins such as cyclopentane, methylcyclopentane and cyclohexane, cycloolefins such as cyclopentene, methylcyclopentene and cyclohexene, and / or dienes such as cyclohexadiene, butadiene, pentadiene and cyclopentadiene, acetylene and methylacetylene Acetylenes such as these may be contained. Furthermore, oxygen-containing compounds such as t-butyl alcohol, methyl-t-butyl ether, diethyl ether, methyl ethyl ether, dimethyl ether, ethanol, and methanol may be contained. Moreover, the hydrocarbon raw material containing ethylene may contain water, hydrogen, nitrogen, carbon dioxide, carbon monoxide and the like.
エタンを水蒸気の存在下で熱分解する、いわゆるエタンのスチームクラッキング法によって生成する反応生成物には、エチレンの他に未反応エタン及びアセチレン等の炭化水素と水、水素、二酸化炭素、一酸化炭素等が含まれるが、この反応生成物は、そのまま原料として用いることができる。 In addition to ethylene, hydrocarbons such as unreacted ethane and acetylene and water, hydrogen, carbon dioxide, carbon monoxide are included in the reaction products generated by the so-called steam cracking method of ethane, in which ethane is thermally decomposed in the presence of water vapor. The reaction product can be used as a raw material as it is.
バイオマスエタノールは植物資源から得られるエタノールであり、具体的にはサトウキビやトウモロコシ等の発酵により得られるエタノールや廃材、間伐材、稲わら、農作物等の木質資源から得られるエタノール等が挙げられる。 Biomass ethanol is ethanol obtained from plant resources. Specific examples include ethanol obtained by fermentation of sugarcane and corn, and ethanol obtained from wood resources such as waste wood, thinned wood, rice straw, and crops.
反応生成物から蒸留分離等の方法によりプロピレンを分離し、残りのエチレンを含む低沸成分及び／又はブテンを含む高沸成分の少なくとも一部を反応器にリサイクルしてもよい。 Propylene may be separated from the reaction product by a method such as distillation separation, and at least a part of the remaining low boiling component containing ethylene and / or high boiling component containing butene may be recycled to the reactor.
流動層反応においては、エチレンを含有する炭化水素原料の接触転化反応をエチレンの転化率が４５〜８５％、好ましくは５０〜８０％となる範囲で実施する。 In the fluidized bed reaction, the catalytic conversion reaction of the hydrocarbon raw material containing ethylene is carried out in a range where the ethylene conversion is 45 to 85%, preferably 50 to 80%.
流動層反応における反応温度は、好ましくは３００〜６５０°Ｃ、より好ましくは４００〜６００°Ｃの範囲である。反応圧力は、好ましくは０．１〜３０気圧、より好ましくは０．５〜１０気圧の範囲である。 The reaction temperature in the fluidized bed reaction is preferably in the range of 300 to 650 ° C, more preferably 400 to 600 ° C. The reaction pressure is preferably in the range of 0.1 to 30 atmospheres, more preferably 0.5 to 10 atmospheres.
エチレンを含有する炭化水素原料の供給速度は、シリカ成形体中のゼオライト基準の重量時間空間速度（ＷＨＳＶ）で、０．１〜２０ｈｒ−１、より好ましくは０．５〜１０ｈｒ−１である。 The feed rate of the hydrocarbon raw material containing ethylene is 0.1 to 20 hr −1 , more preferably 0.5 to 10 hr −1 in terms of the zeolite-based weight time space velocity (WHSV).
シリカ成形体を触媒として長期間反応に用いると、触媒上に炭素質化合物（コーク）が生成し、触媒活性が低下することがある。その場合、流動層反応器からシリカ成形体触媒の一部を連続的又は断続的に抜出し、酸素を含むガスを用いて付着したコークを燃焼除去させることによってシリカ成形体触媒の再生を行い、再生後のシリカ成形体触媒を反応器に戻すことができる。通常、上記の再生は、空気中又は空気と不活性ガスよりなる混合ガス中、４００〜７００°Ｃの条件で実施する。 When a silica molded body is used as a catalyst for a long-term reaction, a carbonaceous compound (coke) may be formed on the catalyst, and the catalytic activity may be reduced. In that case, a part of the silica compact catalyst is withdrawn from the fluidized bed reactor continuously or intermittently, and the silica compact catalyst is regenerated by burning and removing the coke adhering using a gas containing oxygen. The later silica compact catalyst can be returned to the reactor. Usually, the above regeneration is performed under conditions of 400 to 700 ° C. in air or in a mixed gas composed of air and an inert gas.
以下に実施例を示して、本発明をより詳細に説明するが、本発明は以下に記載の実施例によって制限されるものではない。
［測定方法］
物性の測定方法は以下の通りである。
（１）シリカ成形体の組成
シリカ成形体の組成は、蛍光Ｘ線定量分析を行って算出した。ケイ素、アルミニウム、リンの各元素の固有Ｘ線量から、ケイ素、アルミニウム、リンのモル数を決定し、シリカ成形体の組成を求めた。
ゼオライト重量に対するシリカの重量比を示すＡ
＝（６０ｘ−３０Ｆｙ）／（５１ｙ＋３０Ｆｙ）
ゼオライトとシリカの合計重量に対するリン元素の重量比を示すＢ
＝３１ｚ／（（５１ｙ＋３０Ｆｙ）＋（６０ｘ−３０Ｆｙ））
（式中、ｘはシリカ成形体中のケイ素のモル数、ｙはシリカ成形体中のアルミニウムのモル数、ｚはシリカ成形体中のリンのモル数、ＦはゼオライトのＳｉＯ２／Ａｌ２Ｏ３モル比である）
（２）シリカ成形体の摩耗損失
シリカ成形体の耐摩耗性の指標である摩耗損失は、噴流式流動装置を用いて測定した。噴流式流動装置は、ガス導入口に０．４ｍｍ孔三個を有するオリフィスを設置した内径３５ｍｍ長さ７００ｍｍの粉体上昇部、内径１１０ｍｍ長さ６００ｍｍの粉体分離部、微粉末捕集部とからなる。室温で水分２．５ｇを含むシリカ成形体５２．５ｇを投入後、蒸気圧相当量の水分を含む空気を空塔線速度１０ｃｍ／秒でガス導入口から流し、測定開始後０〜５時間及び５〜２０時間に微粉末捕集部に回収されたシリカ成形体微粉末重量を測定し、下式に従って、摩耗損失を求めた。
摩耗損失（重量％）＝Ｄ／（Ｅ−Ｃ）×１００
（式中、Ｄは測定開始後０〜５時間に摩耗逃散したシリカ成形体重量（ｇ）、Ｅは測定開始後５〜２０時間に摩耗逃散したシリカ成形体重量（ｇ）、Ｃは試験に供したシリカ成形体重量（ｇ）である。）
（３）シリカ成形体の安息角
シリカ成形体の安息角は、ＰＴ−Ｄ型パウダテスタ（ホソカワミクロン株式会社製）を用いて測定した。具体的には、内径５ｍｍのノズルのある漏斗を水平基板から２２５ｍｍの位置に漏斗上部、１３５ｍｍの位置にノズル下部が来るように保持器を用いて設置し、ノズル下部から７５ｍｍの位置に粉体捕集台を置いた。振動を与えないように注意しながら漏斗にシリカ成形体を静かに注ぎ、粉体捕集台上に形成された円錐状の粉体層の斜面が水平面となす角を測定した。同様の実験を３回繰り返し、その測定角の平均値を安息角とした。
（４）シリカ成形体の嵩密度
ＪＩＳ規格Ｚ−２５０４かさ比重測定器（筒井理化学器械株式会社製）を用い、付属のマニュアルに従い、嵩密度を測定した。
（５）シリカ成形体の形状
シリカ成形体の形状は、電子顕微鏡（ＳＥＭ、株式会社日立製作所製Ｓ−８００）で観察した。
（６）ゼオライトの平均粒子径
レーザー回折・散乱式粒度分析計（Ｍｉｃｒｏｔｒａｃ社製ＭＴ３０００）を用い、付属のマニュアルに従い、ゼオライトの平均粒子径を測定した。
（７）ゼオライトの凝集状態
電子顕微鏡（ＳＥＭ、株式会社日立製作所製Ｓ−８００）を用い、得られた視野像からゼオライトの凝集状態を下式により算出し、凝集割合が５０％以下のゼオライトを非凝集ゼオライトとした。
凝集割合＝他の１次粒子と部分的に結合しているゼオライト粒子の個数／任意のゼオライト粒子１００個×１００
（８）エチレン転化率及びプロピレン収率
（ａ）エチレン転化率＝
（反応器入口の供給流中のエチレン濃度−反応器出口の供給流中のエチレン濃度）
／反応器入口の供給流中のエチレン濃度×１００
（ｂ）プロピレン収率＝
反応生成したプロピレン量／反応転化したエチレン量×１００
EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to the examples described below.
[Measuring method]
The measuring method of physical properties is as follows.
(1) Composition of silica molded body The composition of the silica molded body was calculated by fluorescent X-ray quantitative analysis. The number of moles of silicon, aluminum, and phosphorus was determined from the intrinsic X-ray dose of each element of silicon, aluminum, and phosphorus, and the composition of the silica compact was determined.
A showing the weight ratio of silica to zeolite weight
= (60x-30Fy) / (51y + 30Fy)
B showing the weight ratio of phosphorus element to the total weight of zeolite and silica
= 31z / ((51y + 30Fy) + (60x-30Fy))
(Where, x is the number of moles of silicon in the silica compact, y is the number of moles of aluminum in the silica compact, z is the number of moles of phosphorus in the silica compact, and F is the SiO 2 / Al 2 O of the zeolite. 3 molar ratio)
(2) Wear Loss of Silica Molded Body The wear loss, which is an index of the wear resistance of the silica molded body, was measured using a jet flow device. The jet-type flow device has a powder rising part with an inner diameter of 35 mm and a length of 700 mm, an inner diameter of 110 mm and a length of 600 mm, a fine powder collecting part, and an orifice having three 0.4 mm holes at the gas inlet. Consists of. After charging 52.5 g of a silica compact containing 2.5 g of moisture at room temperature, air containing moisture corresponding to the vapor pressure was allowed to flow from the gas inlet at a superficial linear velocity of 10 cm / sec. The weight of the silica compact fine powder collected in the fine powder collecting part for 5 to 20 hours was measured, and the wear loss was determined according to the following formula.
Wear loss (% by weight) = D / (EC) × 100
(Wherein, D is the weight of silica molded body (g) that escapes wear within 0 to 5 hours after the start of measurement, E is the weight of silica molded body that escapes wear within 5 to 20 hours after the start of measurement, and C is the test. (The weight of the silica compact provided (g).)
(3) Repose Angle of Silica Molded Body The angle of repose of the silica molded body was measured using a PT-D type powder tester (manufactured by Hosokawa Micron Corporation). Specifically, a funnel with a nozzle with an inner diameter of 5 mm is installed using a cage so that the upper part of the funnel is located at 225 mm from the horizontal substrate and the lower part of the nozzle is at 135 mm, and powder is placed at a position 75 mm from the lower part of the nozzle. A collection stand was placed. The silica molded body was gently poured into the funnel while being careful not to give vibration, and the angle between the inclined surface of the conical powder layer formed on the powder collecting table and the horizontal plane was measured. The same experiment was repeated three times, and the average value of the measured angles was defined as the angle of repose.
(4) Bulk density of silica molded body A bulk density was measured using a JIS standard Z-2504 bulk specific gravity measuring instrument (manufactured by Tsutsui Chemical Co., Ltd.) according to the attached manual.
(5) Shape of Silica Molded Body The shape of the silica molded body was observed with an electron microscope (SEM, S-800 manufactured by Hitachi, Ltd.).
(6) Zeolite Average Particle Size Using a laser diffraction / scattering particle size analyzer (Microtrac MT3000), the average particle size of zeolite was measured according to the attached manual.
(7) Aggregation state of zeolite Using an electron microscope (SEM, S-800 manufactured by Hitachi, Ltd.), the aggregation state of zeolite is calculated from the obtained field image by the following formula, and a zeolite having an aggregation ratio of 50% or less is obtained. Non-agglomerated zeolite was obtained.
Aggregation ratio = number of zeolite particles partially bonded to other primary particles / 100 arbitrary zeolite particles × 100
(8) Ethylene conversion and propylene yield (a) Ethylene conversion =
(Ethylene concentration in the feed stream at the reactor inlet-ethylene concentration in the feed stream at the reactor outlet)
/ Ethylene concentration in the feed stream at the reactor inlet × 100
(B) Propylene yield =
Amount of propylene produced by reaction / Amount of ethylene converted by reaction × 100
（実施例１）
シリカ一次粒子の平均粒子径が５ｎｍであるアンモニウム安定型シリカゾル３３３３ｇ（シリカ１５重量％）にリン酸７７ｇ、非凝集ゼオライト（ＭＦＩ型ＺＳＭ−５、ＳｉＯ２／Ａｌ２Ｏ３モル比＝２７、平均粒子径２．９μｍ、ゼオライトの凝集割合１０％以下、）５００ｇを添加し、室温大気下で２時間撹拌した。この原料混合物のｐＨは２．３であった。回転円盤式噴霧乾燥機の熱風入口温度が約１８０°Ｃ、熱風出口温度が約１００°Ｃに維持されるように乾燥空気を導入しながら、得られた原料混合物を供給速度１２Ｋｇ／ｈｒ、回転円盤回転数１２０００ｒｐｍで噴霧乾燥した。得られた乾燥粉体を大気下７００°Ｃで２時間マッフル炉にて静置焼成して、ゼオライト／シリカ／リン＝１／Ａ／Ｂ（Ａ＝１、Ｂ＝０．０２４）の組成を有するシリカ成形体を得た。得られたシリカ成形体の摩耗損失、安息角、嵩密度を測定した。測定結果を表１に示す。
また、得られたシリカ成形体を電子顕微鏡（ＳＥＭ）で観察したところ、平滑な表面を有する球状粒子であり、割れや欠けはほとんど見られなかった。粒子のＳＥＭ像を図１に示す。
Example 1
Ammonium stable silica sol 3333 g (silica 15 wt%) having an average particle size of silica primary particles of 5 nm and phosphoric acid 77 g, non-agglomerated zeolite (MFI type ZSM-5, SiO 2 / Al 2 O 3 molar ratio = 27, average 500 g of particles having a particle diameter of 2.9 μm and an agglomeration ratio of zeolite of 10% or less were added, and the mixture was stirred at room temperature for 2 hours. The pH of this raw material mixture was 2.3. The feedstock mixture obtained was rotated at a feed rate of 12 kg / hr while introducing dry air so that the hot air inlet temperature of the rotary disk spray dryer was maintained at about 180 ° C. and the hot air outlet temperature at about 100 ° C. Spray drying was performed at a disc rotation speed of 12000 rpm. The obtained dry powder was baked by standing in a muffle furnace at 700 ° C. for 2 hours in the atmosphere to obtain a composition of zeolite / silica / phosphorus = 1 / A / B (A = 1, B = 0.024). A silica molded body was obtained. Wear loss, angle of repose, and bulk density of the obtained silica compact were measured. The measurement results are shown in Table 1.
Moreover, when the obtained silica molded object was observed with the electron microscope (SEM), it was the spherical particle | grains which have a smooth surface, and the crack and the chip | tip were hardly seen. An SEM image of the particles is shown in FIG.
（実施例２）
実施例１で得られたシリカ成形体の水洗浄を以下にように行った。シリカ成形体の濃度が１０重量％となるように水を加え、得られたシリカ成形体スラリーを室温大気下で１時間撹拌した。シリカ成形体を濾取し、大気下１２０°Ｃで５時間乾燥させ、ゼオライト／シリカ／リン＝Ａ／Ｂ（Ａ＝１、Ｂ＝０．０１９）の組成を有するシリカ成形体を得た。得られたシリカ成形体の摩耗損失、安息角、嵩密度を実施例１と同様に測定した。測定結果を表１に示す。
また、得られたシリカ成形体を電子顕微鏡（ＳＥＭ）で観察したところ、平滑な表面を有する球状粒子であり、割れや欠けはほとんど見られなかった。粒子のＳＥＭ像を図２に示す。
(Example 2)
The silica molded body obtained in Example 1 was washed with water as follows. Water was added so that the concentration of the silica molded body was 10% by weight, and the resulting silica molded body slurry was stirred for 1 hour at room temperature in the atmosphere. The silica molded body was collected by filtration and dried at 120 ° C. for 5 hours in the atmosphere to obtain a silica molded body having a composition of zeolite / silica / phosphorus = A / B (A = 1, B = 0.199). Wear loss, angle of repose, and bulk density of the obtained silica compact were measured in the same manner as in Example 1. The measurement results are shown in Table 1.
Moreover, when the obtained silica molded object was observed with the electron microscope (SEM), it was the spherical particle | grains which have a smooth surface, and the crack and the chip | tip were hardly seen. A SEM image of the particles is shown in FIG.
（実施例３）
シリカゾル３３３３ｇに代えて９９９９ｇ、リン酸７７ｇに代えて２２８ｇを用い、得られた乾燥粉体を大気下、８５０°Ｃで５時間静置焼成したこと以外は実施例１と同様の方法により、ゼオライト／シリカ／リン＝１／Ａ／Ｂ（Ａ＝３、Ｂ＝０．０３６）で示される組成を有するシリカ成形体を得た。得られたシリカ成形体の摩耗損失、安息角、嵩密度を実施例１と同様に測定した。測定結果を表１に示す。
また、得られたシリカ成形体を電子顕微鏡（ＳＥＭ）で観察したところ、平滑な表面を有する球状粒子であり、割れや欠けはほとんど見られなかった。
(Example 3)
Using the same method as in Example 1, except that 9999 g was used instead of 3333 g of silica sol and 228 g was used instead of 77 g of phosphoric acid, and the obtained dry powder was baked by standing at 850 ° C. for 5 hours in the atmosphere. A silica molded body having a composition represented by: / silica / phosphorus = 1 / A / B (A = 3, B = 0.036) was obtained. Wear loss, angle of repose, and bulk density of the obtained silica compact were measured in the same manner as in Example 1. The measurement results are shown in Table 1.
Moreover, when the obtained silica molded object was observed with the electron microscope (SEM), it was the spherical particle | grains which have a smooth surface, and the crack and the chip | tip were hardly seen.
（実施例４）
リン酸７７ｇに代えて３８ｇを用いたこと以外は、実施例１と同様の方法により、ゼオライト／シリカ／リン＝Ａ／Ｂ（Ａ＝１、Ｂ＝０．０１２）で示される組成を有するシリカ成形体を得た。得られたシリカ成形体の摩耗損失、安息角、嵩密度を実施例１と同様に測定した。測定結果を表１に示す。
また、得られたシリカ成形体を電子顕微鏡（ＳＥＭ）で観察したところ、平滑な表面を有する球状粒子であり、割れや欠けはほとんど見られなかった。
Example 4
Silica having a composition represented by zeolite / silica / phosphorus = A / B (A = 1, B = 0.122) in the same manner as in Example 1 except that 38 g was used instead of 77 g of phosphoric acid. A molded body was obtained. Wear loss, angle of repose, and bulk density of the obtained silica compact were measured in the same manner as in Example 1. The measurement results are shown in Table 1.
Moreover, when the obtained silica molded object was observed with the electron microscope (SEM), it was the spherical particle | grains which have a smooth surface, and the crack and the chip | tip were hardly seen.
（実施例５）
実施例１で得られた乾燥粉体を大気下６００°Ｃで５時間静置焼成してシリカ成形体を得た。得られたシリカ成形体の摩耗損失、安息角、嵩密度を実施例１と同様に測定した。測定結果を表１に示す。
また、得られたシリカ成形体を電子顕微鏡（ＳＥＭ）で観察したところ、球状で、平滑な表面を有する球状粒子であり、割れや欠けはほとんど見られなかった。
(Example 5)
The dried powder obtained in Example 1 was baked by standing at 600 ° C. for 5 hours in the air to obtain a silica molded body. Wear loss, angle of repose, and bulk density of the obtained silica compact were measured in the same manner as in Example 1. The measurement results are shown in Table 1.
Moreover, when the obtained silica molded object was observed with the electron microscope (SEM), it was a spherical particle | grain with a spherical and smooth surface, and the crack and the chip | tip were hardly seen.
（実施例６）
実質的にアルミニウムを含まないハイシリカゼオライトである非凝集ゼオライト（ＭＦＩ型ＺＳＭ−５、ＳｉＯ２／Ａｌ２Ｏ３モル比＝１０００、平均粒子径３．７μｍ、ゼオライトの凝集割合４０％以下）５００ｇを用いたこと以外は、実施例１と同様の方法により、ゼオライト／シリカ／リン＝１／Ａ／Ｂ（Ａ＝１、Ｂ＝０．０２４）で示される組成を有するシリカ成形体を得た。得られたシリカ成形体の摩耗損失、安息角、嵩密度を実施例１と同様に測定した。測定結果を表２に示す。
また、得られたシリカ成形体を電子顕微鏡（ＳＥＭ）で観察したところ、平滑な表面を有する球状粒子であり、割れや欠けはほとんど見られなかった。図３にＳＥＭ像を示す。
(Example 6)
Non-aggregated zeolite which is a high silica zeolite substantially free of aluminum (MFI type ZSM-5, SiO 2 / Al 2 O 3 molar ratio = 1000, average particle diameter 3.7 μm, agglomeration ratio of zeolite 40% or less) 500 g Except that was used, a silica molded body having a composition represented by zeolite / silica / phosphorous = 1 / A / B (A = 1, B = 0.024) was obtained in the same manner as in Example 1. . Wear loss, angle of repose, and bulk density of the obtained silica compact were measured in the same manner as in Example 1. The measurement results are shown in Table 2.
Moreover, when the obtained silica molded object was observed with the electron microscope (SEM), it was the spherical particle | grains which have a smooth surface, and the crack and the chip | tip were hardly seen. FIG. 3 shows an SEM image.
（実施例７）
リン酸２６ｇを用いたこと以外は、実施例１と同様の方法により、ゼオライト／シリカ／リン＝１／Ａ／Ｂ（Ａ＝１、Ｂ＝０．００８）で示される組成を有するシリカ成形体を得た。得られたシリカ成形体の摩耗損失、安息角、嵩密度を実施例１と同様に測定した。測定結果を表２に示す。
また、得られたシリカ成形体を電子顕微鏡（ＳＥＭ）で観察したところ、平滑な表面を有する球状粒子であり、割れや欠けはほとんど見られなかった。
(Example 7)
Except that 26 g of phosphoric acid was used, a silica molded article having a composition represented by zeolite / silica / phosphorous = 1 / A / B (A = 1, B = 0.008) in the same manner as in Example 1. Got. Wear loss, angle of repose, and bulk density of the obtained silica compact were measured in the same manner as in Example 1. The measurement results are shown in Table 2.
Moreover, when the obtained silica molded object was observed with the electron microscope (SEM), it was the spherical particle | grains which have a smooth surface, and the crack and the chip | tip were hardly seen.
（実施例８）
非凝集ゼオライト（ＭＦＩ型ＺＳＭ−５、ＳｉＯ２／Ａｌ２Ｏ３モル比＝４２、平均粒子径４．７μｍ、ゼオライトの凝集割合４０％以下）５００ｇ、シリカ一次粒子の平均粒子径が１２ｎｍのアンモニウム安定型シリカゾル１６６７ｇ（シリカ３０重量％）を用い、得られた乾燥粉体を大気下７００°Ｃで５時間静置焼成したこと以外は、実施例１と同様の方法により、ゼオライト／シリカ／リン＝１／Ａ／Ｂ（Ａ＝１、Ｂ＝０．０２４）で示される組成を有するシリカ成形体を得た。得られたシリカ成形体の摩耗損失、安息角、嵩密度を実施例１と同様に測定した。測定結果を表２に示す。
(Example 8)
500 g of non-agglomerated zeolite (MFI type ZSM-5, SiO 2 / Al 2 O 3 molar ratio = 42, average particle diameter 4.7 μm, aggregation ratio of zeolite of 40% or less), ammonium whose average particle diameter of silica primary particles is 12 nm Zeolite / silica / phosphorus was obtained in the same manner as in Example 1 except that 1667 g of stable silica sol (silica 30% by weight) was used and the obtained dry powder was baked by standing at 700 ° C. for 5 hours in the air. = 1 / A / B (A = 1, B = 0.024) A silica molded body having a composition was obtained. Wear loss, angle of repose, and bulk density of the obtained silica compact were measured in the same manner as in Example 1. The measurement results are shown in Table 2.
（実施例９）
シリカ一次粒子の平均粒子径が２０ｎｍであり、粒径分布が１０〜４０ｎｍの広い粒径分布を持つカリウム安定型シリカゾル１６６７ｇ（シリカ３０重量％）を用い、得られた乾燥粉体を大気下７００°Ｃで２時間静置焼成したこと以外は、実施例１と同様の方法により、ゼオライト／シリカ／リン＝１／Ａ／Ｂ（Ａ＝１、Ｂ＝０．０２４）で示される組成を有するシリカ成形体を得た。得られたシリカ成形体の摩耗損失、安息角、嵩密度を実施例２と同様に測定した。測定結果を表１に示す。
Example 9
Using 1667 g of potassium stable silica sol (silica 30% by weight) having a wide particle size distribution with an average particle size of 20 nm and a particle size distribution of 10 to 40 nm, the obtained dry powder is obtained in the atmosphere. Except that it was calcined for 2 hours at ° C, it had the composition represented by zeolite / silica / phosphorus = 1 / A / B (A = 1, B = 0.024) by the same method as in Example 1. A silica molded body was obtained. The wear loss, angle of repose, and bulk density of the obtained silica molded body were measured in the same manner as in Example 2. The measurement results are shown in Table 1.
（実施例１０）
リン酸１６ｇを用い、得られた乾燥粉体を大気下８５０°Ｃで５時間静置焼成したこと以外は、実施例１と同様の方法により、ゼオライト／シリカ／リン＝１／Ａ／Ｂ（Ａ＝１、Ｂ＝０．００５）で示される組成を有するシリカ成形体を得た。得られたシリカ成形体の摩耗損失、安息角、嵩密度を実施例２と同様に測定した。測定結果を表１に示す。
また、得られたシリカ成形体を電子顕微鏡（ＳＥＭ）で観察したところ、平滑な表面を有する球状粒子であり、割れや欠けはほとんど見られなかった。
(Example 10)
Zeolite / silica / phosphorous = 1 / A / B (by the same method as in Example 1 except that 16 g of phosphoric acid was used and the obtained dry powder was baked by standing at 850 ° C. for 5 hours in the atmosphere. A silica molded body having a composition represented by A = 1, B = 0.005) was obtained. The wear loss, angle of repose, and bulk density of the obtained silica molded body were measured in the same manner as in Example 2. The measurement results are shown in Table 1.
Moreover, when the obtained silica molded object was observed with the electron microscope (SEM), it was the spherical particle | grains which have a smooth surface, and the crack and the chip | tip were hardly seen.
（実施例１１）
非凝集ゼオライト（ベータゼオライト、ＳｉＯ２／Ａｌ２Ｏ３モル比＝４０、平均粒子径５μｍ、ゼオライトの凝集割合４０％以下）５００ｇを用い、得られた乾燥粉体を大気下８５０°Ｃで５時間静置焼成したこと以外は、実施例１と同様の方法により、ゼオライト／シリカ／リン＝１／Ａ／Ｂ（Ａ＝１、Ｂ＝０．０２４）で示される組成を有するシリカ成形体を得た。得られたシリカ成形体の摩耗損失、安息角、嵩密度を実施例１と同様に測定した。測定結果を表３に示す。
また、得られたシリカ成形体を電子顕微鏡（ＳＥＭ）で観察したところ、平滑な表面を有する球状粒子であり、割れや欠けはほとんど見られなかった。
(Example 11)
Using 500 g of non-agglomerated zeolite (beta zeolite, SiO 2 / Al 2 O 3 molar ratio = 40, average particle diameter of 5 μm, agglomeration ratio of zeolite of 40% or less), the obtained dry powder was 5 at 850 ° C. in the atmosphere. A silica molded body having a composition represented by zeolite / silica / phosphorus = 1 / A / B (A = 1, B = 0.024) was obtained in the same manner as in Example 1 except that the calcination was carried out for a period of time. Obtained. Wear loss, angle of repose, and bulk density of the obtained silica compact were measured in the same manner as in Example 1. Table 3 shows the measurement results.
Moreover, when the obtained silica molded object was observed with the electron microscope (SEM), it was the spherical particle | grains which have a smooth surface, and the crack and the chip | tip were hardly seen.
（比較例１）
非凝集ゼオライトに代えて平均粒子径１５μｍの凝集したゼオライト（ＭＦＩ型ＺＳＭ−５、ＳｉＯ２／Ａｌ２Ｏ３モル比＝２７、ゼオライトの凝集割合８０％以上）を用い、得られた乾燥粉体を大気下８５０°Ｃで５時間静置焼成したこと以外は、実施例１と同様の方法により、ゼオライト／シリカ／リン＝１／Ａ／Ｂ（Ａ＝１、Ｂ＝０．０２４）で示される組成を有するシリカ成形体を得た。得られたシリカ成形体の安息角、嵩密度を実施例１と同様に測定した。測定結果を表４に示す。
また、開始後５時間の摩耗損失を下記式から求めたところ、３１重量％と大きく、機械的強度に著しく劣ることが明らかになったため、摩耗損失試験は５時間で終了した。
開始後５時間の摩耗損失（重量％）＝Ａ／Ｂ×１００
（式中、Ａは０〜５時間後に摩耗逃散したシリカ成形体の重量（ｇ）、Ｂは試験に供したシリカ成形体の重量（ｇ）である。）
また、得られたシリカ成形体を電子顕微鏡（ＳＥＭ）で観察したところ、凹凸状の表面でかつ開孔部が存在する粒子で、割れ、欠けが観察された。粒子のＳＥＭ像を図４に示す。
(Comparative Example 1)
Dry powder obtained by using agglomerated zeolite (MFI type ZSM-5, SiO 2 / Al 2 O 3 molar ratio = 27, agglomeration ratio of zeolite of 80% or more) instead of non-agglomerated zeolite with an average particle size of 15 μm In the same manner as in Example 1, except that the mixture was calcined at 850 ° C. for 5 hours in the atmosphere, zeolite / silica / phosphorous = 1 / A / B (A = 1, B = 0.024). A silica molded body having the composition described above was obtained. The angle of repose and bulk density of the obtained silica compact were measured in the same manner as in Example 1. Table 4 shows the measurement results.
Further, when the wear loss for 5 hours after the start was determined from the following formula, it was found to be as great as 31% by weight and extremely inferior in mechanical strength, so the wear loss test was completed in 5 hours.
Wear loss (wt%) for 5 hours after start = A / B × 100
(In the formula, A is the weight (g) of the silica molded body that was worn away after 0 to 5 hours, and B was the weight (g) of the silica molded body subjected to the test.)
Moreover, when the obtained silica molded object was observed with the electron microscope (SEM), the crack and the chip | tip were observed by the particle | grains which have an uneven | corrugated surface and an opening part exists. An SEM image of the particles is shown in FIG.
（比較例２）
リン酸７７ｇを含むリン酸水溶液５００ｇに、比較例１で用いたゼオライト５００ｇを添加し、室温大気下で２時間撹拌後、水を蒸発乾固させ、大気下１２０°Ｃで５時間乾燥し、次いで、大気下６００°Ｃで３時間焼成してリン酸含浸ゼオライトを調製した。得られたリン酸含浸ゼオライト５００ｇを、実施例１で用いたシリカゾル３３３３ｇに添加し、実施例１と同様の方法により、ゼオライト／シリカ／リン＝１／Ａ／Ｂ（Ａ＝１、Ｂ＝０．０２４）で示される組成を有するシリカ成形体を得た。得られたシリカ成形体の摩耗損失、安息角、嵩密度を実施例１と同様に測定した。測定結果を表４に示す。
(Comparative Example 2)
To 500 g of an aqueous phosphoric acid solution containing 77 g of phosphoric acid, 500 g of the zeolite used in Comparative Example 1 was added, stirred for 2 hours at room temperature in the atmosphere, water was evaporated to dryness, and dried at 120 ° C. for 5 hours in the atmosphere. Next, phosphoric acid-impregnated zeolite was prepared by calcining at 600 ° C. for 3 hours in the atmosphere. 500 g of the obtained phosphoric acid-impregnated zeolite was added to 3333 g of the silica sol used in Example 1, and zeolite / silica / phosphorous = 1 / A / B (A = 1, B = 0) in the same manner as in Example 1. A silica molded body having a composition represented by .024) was obtained. Wear loss, angle of repose, and bulk density of the obtained silica compact were measured in the same manner as in Example 1. Table 4 shows the measurement results.
（比較例３）
比較例１で用いたゼオライト５００ｇを、直径２ｃｍ及び２．５ｃｍのＳＵＳ−３０４球（合計重量３Ｋｇ）の入った容積２９００ｃｍ３のＳＵＳ−３０４製ボールミルを用いて１２時間処理したこと以外は、比較例１と同様の方法により、ゼオライト／シリカ／リン＝１／Ａ／Ｂ（Ａ＝１、Ｂ＝０．０２４）で示される組成を有するシリカ成形体を得た。なお、ボールミル処理後のゼオライトの凝集割合は７０％以上であった。得られたシリカ成形体の安息角、嵩密度を実施例１と同様に測定した。測定結果を表４に示す。
また、開始後５時間の摩耗損失が３０重量％と大きく、機械的強度に著しく劣ることが明らかになったため、摩耗損失試験は５時間で終了した。
(Comparative Example 3)
Except that 500 g of the zeolite used in Comparative Example 1 was treated for 12 hours using a 2900 cm 3 SUS-304 ball mill containing SUS-304 balls (total weight 3 Kg) having a diameter of 2 cm and 2.5 cm. By the same method as Example 1, a silica molded body having a composition represented by zeolite / silica / phosphorus = 1 / A / B (A = 1, B = 0.024) was obtained. The agglomeration ratio of the zeolite after the ball mill treatment was 70% or more. The angle of repose and bulk density of the obtained silica compact were measured in the same manner as in Example 1. Table 4 shows the measurement results.
In addition, the wear loss test was completed in 5 hours because the wear loss in 5 hours after the start was as large as 30% by weight and the mechanical strength was remarkably inferior.
（比較例４）
平均粒子径４．７μｍのゼオライト（ＳｉＯ２／Ａｌ２Ｏ３モル比４２）に代えて１５μｍの凝集したゼオライト（ＳｉＯ２／Ａｌ２Ｏ３モル比＝２７、ゼオライトの凝集割合８０％以上）を用いたこと以外は、実施例８と同様の方法により、ゼオライト／シリカ＝１／１で示される組成を有するシリカ成形体を得た。得られたシリカ成形体の安息角、嵩密度を実施例１と同様に測定した。測定結果を表４に示す。
また、開始後５時間の摩耗損失が４２重量％と大きく、機械的強度に著しく劣ることが明らかになったため、摩耗損失試験は５時間で終了した。
得られたシリカ成形体を電子顕微鏡（ＳＥＭ）で観察したところ、凹凸状の表面でかつ開孔部が存在する粒子で、割れ、欠けが観察された。粒子のＳＥＭ像を図５に示す。
(Comparative Example 4)
Instead of zeolite having an average particle size of 4.7 μm (SiO 2 / Al 2 O 3 molar ratio 42), 15 μm aggregated zeolite (SiO 2 / Al 2 O 3 molar ratio = 27, zeolite aggregation ratio of 80% or more) A silica molded body having a composition represented by zeolite / silica = 1/1 was obtained in the same manner as in Example 8 except that it was used. The angle of repose and bulk density of the obtained silica compact were measured in the same manner as in Example 1. Table 4 shows the measurement results.
The wear loss test was completed in 5 hours because the wear loss in 5 hours after the start was as large as 42% by weight and the mechanical strength was remarkably inferior.
When the obtained silica molded body was observed with an electron microscope (SEM), cracks and chips were observed in the particles having an uneven surface and having an aperture. An SEM image of the particles is shown in FIG.
［プロピレンの製造］
（実施例１２）
実施例１で得られたシリカ成形体２５ｇ内径１インチのステンレス製流動層反応器に充填し、エチレン９．９ｇ／ｈｒ、水素０．７ｇ／ｈｒ、水４．９ｇ／ｈｒ、窒素５．３ｇ／ｍｉｎの流量で反応器に流通させ、反応温度５５０°Ｃ、反応圧力０．１４ＭＰａの条件で反応を行った。反応生成物の分析は反応器と直結したガスクロマトグラフィー（ＴＣＤ−ＦＩＤ直列連結）で行った。反応開始後、所定時間における反応結果を表５に示す。
[Propylene production]
Example 12
25 g of the silica compact obtained in Example 1 was packed in a stainless steel fluidized bed reactor having an inner diameter of 1 inch, ethylene 9.9 g / hr, hydrogen 0.7 g / hr, water 4.9 g / hr, nitrogen 5.3 g. The reaction was conducted under the conditions of a reaction temperature of 550 ° C. and a reaction pressure of 0.14 MPa. The analysis of the reaction product was performed by gas chromatography (TCD-FID serial connection) directly connected to the reactor. Table 5 shows the reaction results at a predetermined time after the start of the reaction.
表１〜表３の結果から明らかなように、本実施の形態のシリカ成形体（実施例１〜１１）は、ゼオライト／シリカ／リンの組成が特定範囲に設定されており、かつ、特定の物性を有するゼオライトを含有しているため、摩耗損失が３重量％以下であり、耐摩耗性に優れていた。また、安息角、嵩密度に関しても好適な範囲内であり、流動層反応の触媒として、優れた形状、流動性及び強度を有していた。
また、本実施の形態のシリカ成形体を、流動層反応によりエチレン含有炭化水素原料からプロピレンを製造する際の触媒として用いた場合、エチレン転化率、プロピレン収率が共に良好であり、プロピレンを収率良くかつ安定に製造することが可能であった。
これに対して、比較例１〜４のシリカ成形体は、ゼオライトとして、凝集型のゼオライトを使用しているため、摩耗損失が大きく、耐摩耗性に劣るものであった。また、安息角、嵩密度に関しても、流動層反応の触媒として好適な範囲内にはなかった。
As is apparent from the results of Tables 1 to 3, the silica molded bodies of the present embodiment (Examples 1 to 11) have a composition of zeolite / silica / phosphorus set in a specific range, and a specific range. Since the zeolite having physical properties was contained, the wear loss was 3% by weight or less, and the wear resistance was excellent. Further, the angle of repose and the bulk density were also within suitable ranges, and had excellent shape, fluidity and strength as a catalyst for the fluidized bed reaction.
In addition, when the silica molded body of the present embodiment is used as a catalyst for producing propylene from an ethylene-containing hydrocarbon raw material by a fluidized bed reaction, both the ethylene conversion rate and the propylene yield are good, and propylene is collected. It was possible to manufacture efficiently and stably.
On the other hand, since the silica molded bodies of Comparative Examples 1 to 4 use agglomerated zeolite as the zeolite, the wear loss is large and the wear resistance is inferior. Further, the angle of repose and the bulk density were not within the ranges suitable as a catalyst for the fluidized bed reaction.
本発明のシリカ成形体は、流動層反応用の触媒としての好適な物性を有しているため、流動層反応によりエチレン含有炭化水素原料からプロピレンを製造する際の触媒として用いることで、プロピレンを高転化率で収率良くかつ安定に製造することができる。 Since the silica molded body of the present invention has suitable physical properties as a catalyst for a fluidized bed reaction, propylene can be used by producing propylene from an ethylene-containing hydrocarbon raw material by a fluidized bed reaction. It can be manufactured stably with high conversion and good yield.
Claims (9)
ゼオライト／シリカ／リン＝１／Ａ／Ｂ （Ｉ）
（式中、Ａはゼオライト重量に対するシリカの重量比、Ｂはゼオライトとシリカの合計重量に対するリン元素の重量比を示し、０＜Ａ≦１０、０＜Ｂ≦０．０５である。）
で表される組成を有するシリカ成形体であって、
前記ゼオライトは、ＳｉＯ２／Ａｌ２Ｏ３モル比が１５〜１０００、平均粒子径が０．０５〜１０μｍの非凝集型のゼオライトである、シリカ成形体。 Contains zeolite, silica and phosphorus and has the following formula (I):
Zeolite / silica / phosphorous = 1 / A / B (I)
(In the formula, A represents the weight ratio of silica to the weight of zeolite, B represents the weight ratio of phosphorus element to the total weight of zeolite and silica, and 0 <A ≦ 10 and 0 <B ≦ 0.05.)
A silica molded body having a composition represented by:
The zeolite, SiO 2 / Al 2 O 3 molar ratio of 15 to 1000, an average particle size of the non-aggregated form of the zeolite of 0.05 to 10 [mu] m, the silica molded body.
摩耗損失（重量％）＝Ｄ／（Ｅ−Ｃ）×１００ （ＩＩ）
（式中、Ｃは０〜５時間に摩耗逃散したシリカ成形体の重量（ｇ）、Ｄは５〜２０時間に摩耗逃散したシリカ成形体の重量（ｇ）、Ｅは試験に供したシリカ成形体の重量（ｇ）を示す。）。 The silica molded body according to claim 1, wherein the wear loss represented by the following formula (II) is 3 wt% or less:
Wear loss (% by weight) = D / (EC) × 100 (II)
(Wherein, C is the weight (g) of the silica compact that escaped from wear in 0 to 5 hours, D is the weight (g) of the silica compact that escapes from wear in 5 to 20 hours, and E is the silica compact that was subjected to the test. Body weight (g) is shown.)
（ｉ）ゼオライト、シリカゾル及びリン化合物を混合して、原料混合物を調製する工程、
（ｉｉ）前記原料混合物を噴霧乾燥して乾燥粉体を得る工程、
を含む、シリカ成形体の製造方法であって、
前記ゼオライトは、ＳｉＯ２／Ａｌ２Ｏ３モル比が１５〜１０００、平均粒子径が０．０５〜１０μｍの非凝集型のゼオライトであり、
前記シリカゾルに含まれるシリカ一次粒子の平均粒子径が３〜５０ｎｍである、
シリカ成形体の製造方法。 The following steps:
(I) a step of mixing a zeolite, silica sol and a phosphorus compound to prepare a raw material mixture;
(Ii) a step of spray-drying the raw material mixture to obtain a dry powder;
A method for producing a silica molded body, comprising:
The zeolite is a non-aggregated zeolite having a SiO 2 / Al 2 O 3 molar ratio of 15 to 1000 and an average particle diameter of 0.05 to 10 μm,
The average particle diameter of the silica primary particles contained in the silica sol is 3 to 50 nm.
A method for producing a silica molded body.
シリカ成形体と、エチレンを含有する炭化水素原料とを接触させる工程を含む、製造方法。 A method for producing propylene using the silica molded body according to any one of claims 1 to 4 as a fluidized bed reaction catalyst,
The manufacturing method including the process which a silica molded object and the hydrocarbon raw material containing ethylene are made to contact.
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| JP2008064843A JP5355910B2 (en) | 2008-03-13 | 2008-03-13 | Silica molded body |
| TW097129703A TW200918486A (en) | 2007-09-18 | 2008-08-05 | Process for production of propylene |
| US12/678,740 US9192922B2 (en) | 2007-09-18 | 2008-09-09 | Propylene production process |
| EP08831344A EP2189435A4 (en) | 2007-09-18 | 2008-09-09 | Process for production of propylene |
| MYPI2010001092A MY156277A (en) | 2007-09-18 | 2008-09-09 | Propylene production process |
| CN201510363532.6A CN105016955A (en) | 2007-09-18 | 2008-09-09 | Process for production of propylene |
| CN200880101876A CN101772476A (en) | 2007-09-18 | 2008-09-09 | Process for production of propylene |
| KR1020107004175A KR101083844B1 (en) | 2007-09-18 | 2008-09-09 | Process for production of propylene |
| PCT/JP2008/066236 WO2009037992A1 (en) | 2007-09-18 | 2008-09-09 | Process for production of propylene |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| JP2015187064A (en) * | 2014-03-13 | 2015-10-29 | 三菱化学株式会社 | Zeolite molding |
| JP2016175038A (en) * | 2015-03-20 | 2016-10-06 | 三菱化学株式会社 | Zeolite molding |
| KR20190137081A (en) * | 2017-04-06 | 2019-12-10 | 사솔 절머니 게엠베하 | Method of Making Wear Stability Granulated Material |
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| US11680038B2 (en) | 2018-06-28 | 2023-06-20 | Ascend Performance Materials Operations Llc | Processes and systems for using silica particles in fluid bed reactor |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04354541A (en) * | 1991-01-22 | 1992-12-08 | W R Grace & Co | Catalytic composition |
| JPH0853678A (en) * | 1994-07-15 | 1996-02-27 | Shell Internatl Res Maatschappij Bv | Conversion of hydrocarbon feedstock |
| JP2002537976A (en) * | 1999-03-02 | 2002-11-12 | ダブリュー・アール・グレース・アンド・カンパニー−コーン | High zeolite content and attrition resistant catalyst, method for producing the same, and contact process using the same |
| JP2005169215A (en) * | 2003-12-09 | 2005-06-30 | Catalysts & Chem Ind Co Ltd | Method and apparatus for manufacturing catalyst composition for hydrocarbon fluid catalytic cracking |
| JP2005520874A (en) * | 2002-03-15 | 2005-07-14 | アンスティテュ フランセ デュ ペトロール | Process for multistage conversion of feedstock containing olefins having 4, 5 or more carbon atoms for the purpose of propylene production |
| JP2005232121A (en) * | 2004-02-23 | 2005-09-02 | Mitsubishi Chemicals Corp | Method for producing propylene |
| WO2005097950A1 (en) * | 2004-04-02 | 2005-10-20 | W.R. Grace & Co.-Conn. | Catalyst compositions comprising metal phosphate bound zeolite and methods of using same to catalytically crack hydrocarbons |
| JP2006008655A (en) * | 2003-12-12 | 2006-01-12 | Mitsubishi Chemicals Corp | Method for producing propylene |
| JP2006016345A (en) * | 2004-07-02 | 2006-01-19 | Jfe R & D Corp | Method for producing propylene |
| WO2006050487A1 (en) * | 2004-11-05 | 2006-05-11 | W. R. Grace & Co.- Conn. | Catalyst for light olefins and lpg in fluidized catalytic cracking units |
| WO2007114195A1 (en) * | 2006-03-30 | 2007-10-11 | Mitsubishi Chemical Corporation | Method for producing propylene |
| JP2007291076A (en) * | 2006-03-30 | 2007-11-08 | Mitsubishi Chemicals Corp | Method for producing propylene |
-
2008
- 2008-03-13 JP JP2008064843A patent/JP5355910B2/en active Active
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH04354541A (en) * | 1991-01-22 | 1992-12-08 | W R Grace & Co | Catalytic composition |
| JPH0853678A (en) * | 1994-07-15 | 1996-02-27 | Shell Internatl Res Maatschappij Bv | Conversion of hydrocarbon feedstock |
| JP2002537976A (en) * | 1999-03-02 | 2002-11-12 | ダブリュー・アール・グレース・アンド・カンパニー−コーン | High zeolite content and attrition resistant catalyst, method for producing the same, and contact process using the same |
| JP2005520874A (en) * | 2002-03-15 | 2005-07-14 | アンスティテュ フランセ デュ ペトロール | Process for multistage conversion of feedstock containing olefins having 4, 5 or more carbon atoms for the purpose of propylene production |
| JP2005169215A (en) * | 2003-12-09 | 2005-06-30 | Catalysts & Chem Ind Co Ltd | Method and apparatus for manufacturing catalyst composition for hydrocarbon fluid catalytic cracking |
| JP2006008655A (en) * | 2003-12-12 | 2006-01-12 | Mitsubishi Chemicals Corp | Method for producing propylene |
| JP2005232121A (en) * | 2004-02-23 | 2005-09-02 | Mitsubishi Chemicals Corp | Method for producing propylene |
| WO2005097950A1 (en) * | 2004-04-02 | 2005-10-20 | W.R. Grace & Co.-Conn. | Catalyst compositions comprising metal phosphate bound zeolite and methods of using same to catalytically crack hydrocarbons |
| JP2006016345A (en) * | 2004-07-02 | 2006-01-19 | Jfe R & D Corp | Method for producing propylene |
| WO2006050487A1 (en) * | 2004-11-05 | 2006-05-11 | W. R. Grace & Co.- Conn. | Catalyst for light olefins and lpg in fluidized catalytic cracking units |
| WO2007114195A1 (en) * | 2006-03-30 | 2007-10-11 | Mitsubishi Chemical Corporation | Method for producing propylene |
| JP2007291076A (en) * | 2006-03-30 | 2007-11-08 | Mitsubishi Chemicals Corp | Method for producing propylene |
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101665757B1 (en) * | 2010-11-25 | 2016-10-12 | 아사히 가세이 케미칼즈 가부시키가이샤 | Shaped silica body, process for producing same, and method for manufacturing propylene using shaped silica body |
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| WO2012070605A1 (en) * | 2010-11-25 | 2012-05-31 | 旭化成ケミカルズ株式会社 | Shaped silica body, process for producing same, and method for manufacturing propylene using shaped silica body |
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| JP2012166157A (en) * | 2011-02-15 | 2012-09-06 | Asahi Kasei Chemicals Corp | Conductive catalyst for fluidized bed reaction, manufacturing method for the same and method for producing propylene |
| JP2015501209A (en) * | 2011-10-17 | 2015-01-15 | エクソンモービル リサーチ アンド エンジニアリング カンパニーＥｘｘｏｎ Ｒｅｓｅａｒｃｈ Ａｎｄ Ｅｎｇｉｎｅｅｒｉｎｇ Ｃｏｍｐａｎｙ | Method for producing phosphorus-modified zeolite catalyst |
| JP2013209282A (en) * | 2012-02-28 | 2013-10-10 | Tosoh Corp | Mfi type zeolite, catalyst including mfi type zeolite, and method for producing lower olefin using catalyst |
| JP2015187064A (en) * | 2014-03-13 | 2015-10-29 | 三菱化学株式会社 | Zeolite molding |
| JP2016175038A (en) * | 2015-03-20 | 2016-10-06 | 三菱化学株式会社 | Zeolite molding |
| KR20190137081A (en) * | 2017-04-06 | 2019-12-10 | 사솔 절머니 게엠베하 | Method of Making Wear Stability Granulated Material |
| KR102550130B1 (en) | 2017-04-06 | 2023-07-03 | 사솔 절머니 게엠베하 | Manufacturing method of abrasion stable granulated material |
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