WO2016017794A1 - 複合体触媒、複合体触媒の製造方法、低級オレフィンの製造方法および複合体触媒の再生方法 - Google Patents
複合体触媒、複合体触媒の製造方法、低級オレフィンの製造方法および複合体触媒の再生方法 Download PDFInfo
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- WO2016017794A1 WO2016017794A1 PCT/JP2015/071761 JP2015071761W WO2016017794A1 WO 2016017794 A1 WO2016017794 A1 WO 2016017794A1 JP 2015071761 W JP2015071761 W JP 2015071761W WO 2016017794 A1 WO2016017794 A1 WO 2016017794A1
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- Prior art keywords
- composite catalyst
- zeolite
- catalyst
- iron
- producing
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 282
- 239000002131 composite material Substances 0.000 title claims abstract description 190
- 150000001336 alkenes Chemical class 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 83
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 68
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 9
- 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 248
- 239000010457 zeolite Substances 0.000 claims abstract description 228
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 227
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 220
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 179
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 106
- 229910052742 iron Inorganic materials 0.000 claims abstract description 42
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 41
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 37
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 37
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 36
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 27
- 229910000323 aluminium silicate Inorganic materials 0.000 claims abstract description 22
- 238000006243 chemical reaction Methods 0.000 claims description 126
- 239000000203 mixture Substances 0.000 claims description 56
- 239000002994 raw material Substances 0.000 claims description 54
- 239000002253 acid Substances 0.000 claims description 35
- 229910052799 carbon Inorganic materials 0.000 claims description 34
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
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- 238000005342 ion exchange Methods 0.000 claims description 24
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 17
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 14
- 229910052782 aluminium Inorganic materials 0.000 claims description 12
- 229920002472 Starch Polymers 0.000 claims description 10
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- 239000008107 starch Substances 0.000 claims description 10
- 238000002485 combustion reaction Methods 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000011261 inert gas Substances 0.000 claims description 4
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- 239000007858 starting material Substances 0.000 abstract 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 69
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- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 25
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- 238000011156 evaluation Methods 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 22
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 18
- 239000000243 solution Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 18
- 239000000571 coke Substances 0.000 description 15
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- 239000000047 product Substances 0.000 description 11
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 10
- 239000005977 Ethylene Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 10
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 230000035484 reaction time Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 8
- 239000007788 liquid Substances 0.000 description 8
- 239000001301 oxygen Substances 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 8
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- 208000012839 conversion disease Diseases 0.000 description 7
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- 150000001335 aliphatic alkanes Chemical class 0.000 description 6
- -1 ammonium ions Chemical class 0.000 description 6
- 230000008859 change Effects 0.000 description 6
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- 238000001035 drying Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- CHPZKNULDCNCBW-UHFFFAOYSA-N gallium nitrate Chemical compound [Ga+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CHPZKNULDCNCBW-UHFFFAOYSA-N 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 125000004432 carbon atom Chemical group C* 0.000 description 5
- 239000008119 colloidal silica Substances 0.000 description 5
- 238000010304 firing Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 5
- 239000008213 purified water Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 238000006356 dehydrogenation reaction Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 238000007493 shaping process Methods 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000011973 solid acid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000003085 diluting agent Substances 0.000 description 3
- 229940044658 gallium nitrate Drugs 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 239000012071 phase Substances 0.000 description 3
- 230000001737 promoting effect Effects 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 229910001195 gallium oxide Inorganic materials 0.000 description 2
- 239000011491 glass wool Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000000017 hydrogel Substances 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 229910002016 Aerosil® 200 Inorganic materials 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 239000007848 Bronsted acid Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000011362 coarse particle Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910021485 fumed silica Inorganic materials 0.000 description 1
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 1
- 229910000154 gallium phosphate Inorganic materials 0.000 description 1
- 229910000373 gallium sulfate Inorganic materials 0.000 description 1
- UPWPDUACHOATKO-UHFFFAOYSA-K gallium trichloride Chemical compound Cl[Ga](Cl)Cl UPWPDUACHOATKO-UHFFFAOYSA-K 0.000 description 1
- SRVXDMYFQIODQI-UHFFFAOYSA-K gallium(iii) bromide Chemical compound Br[Ga](Br)Br SRVXDMYFQIODQI-UHFFFAOYSA-K 0.000 description 1
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 description 1
- LWFNJDOYCSNXDO-UHFFFAOYSA-K gallium;phosphate Chemical compound [Ga+3].[O-]P([O-])([O-])=O LWFNJDOYCSNXDO-UHFFFAOYSA-K 0.000 description 1
- SBDRYJMIQMDXRH-UHFFFAOYSA-N gallium;sulfuric acid Chemical compound [Ga].OS(O)(=O)=O SBDRYJMIQMDXRH-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000000415 inactivating effect Effects 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- 229910000398 iron phosphate Inorganic materials 0.000 description 1
- 229910000358 iron sulfate Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000011017 operating method Methods 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 238000010979 pH adjustment Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000007363 ring formation reaction Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 238000004876 x-ray fluorescence Methods 0.000 description 1
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- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
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- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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- B01J38/12—Treating with free oxygen-containing gas
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
- C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
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- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
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- B01J2229/10—After treatment, characterised by the effect to be obtained
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- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
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- B01J2229/30—After treatment, characterised by the means used
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- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2521/00—Catalysts comprising the elements, oxides or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium or hafnium
- C07C2521/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- C07C2521/08—Silica
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C07C2529/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11 containing iron group metals, noble metals or copper
- C07C2529/46—Iron group metals or copper
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
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- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
- C07C2529/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65 containing iron group metals, noble metals or copper
- C07C2529/76—Iron group metals or copper
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Definitions
- the present invention relates to a composite catalyst for producing a lower olefin used when producing a lower olefin from a hydrocarbon raw material, a method for producing the composite catalyst, a method for producing a lower olefin using the composite catalyst, and the lower olefin.
- the present invention relates to a method for regenerating a composite catalyst.
- a lower olefin can be stably and continuously produced over a long period of time by using a fixedly arranged zeolite catalyst, and further life extension of the zeolite catalyst is required.
- the zeolite catalyst has an acid point as a solid acid, and at this acid point, a hydrocarbon molecule as a raw material is decomposed and dehydrogenated to produce a lower olefin. If the catalyst stays at the acid point without leaving, the reaction further proceeds by catalytic action, and aromatic hydrocarbons are produced by cyclization and dehydrogenation reactions. Coke is generated from this aromatic hydrocarbon, and the catalytic ability of the zeolite catalyst is reduced as described above.
- the present invention has been made in view of the above circumstances, and in the production of a lower olefin using a zeolite catalyst, a composite catalyst capable of further extending the life of the catalyst, a method for producing the composite catalyst, It is an object of the present invention to provide a method for producing a lower olefin using a composite catalyst and a method for regenerating a composite catalyst in the method for producing a lower olefin.
- the composite catalyst of the present invention is a composite catalyst for producing a lower olefin from a hydrocarbon raw material, It is characterized in that it contains gallium and iron or zeolite, which is a crystalline aluminosilicate having a skeleton structure having 8 to 12 member rings, and silicon dioxide.
- a composite catalyst composed of zeolite or silicon dioxide which is a crystalline aluminosilicate containing iron or iron and gallium and silicon dioxide as a binder (binder) having catalytic action
- Combining can reduce the production of coke by suppressing the production of aromatic hydrocarbons while suppressing the decrease in the production of ethylene and propylene, and further extend the life of the composite catalyst.
- aluminum oxide (alumina powder) is used as a binder, it has been found that the use of silicon dioxide (silica) as a binder clearly extends the catalyst life. That is, it has been found that the catalyst life is extended by mixing silicon dioxide with the above-mentioned zeolite.
- the zeolite is A crystalline aluminosilicate containing iron and gallium
- the acid density as a composition ratio of the number of moles of silicon to the sum of the number of moles of iron, gallium and aluminum is 75.0 to 200.0, and the number of moles of gallium relative to the sum of the number of moles of iron, gallium and aluminum
- the composition ratio of the number of moles of iron with respect to the sum of the number of moles of iron, gallium and aluminum is preferably 0.2 to 0.6.
- the amount of propylene produced can be increased with respect to ethylene by setting the acid density, the molar composition ratio of iron (Fe), and the molar composition ratio of gallium (Ga) within the above ranges.
- the production of aromatic hydrocarbons can be further suppressed in the presence of silicon dioxide as a binder.
- iron has a function of suppressing the acid strength at the acid sites of zeolite
- gallium has a function of promoting the dehydrogenation reaction of alkane.
- the zeolite is a crystalline aluminosilicate containing iron
- the acid density as a composition ratio of the number of moles of silicon to the sum of the number of moles of iron and aluminum is 75.0 to 200.0, and the composition ratio of the number of moles of iron to the sum of the number of moles of iron and aluminum is 0. It is preferably 4 to 0.7.
- the amount of propylene produced can be increased with respect to ethylene, and the binder.
- silicon dioxide it is possible to further enhance the effect of suppressing the generation of aromatic hydrocarbons.
- the silicon dioxide concentration is preferably 5 to 50 wt%, and more preferably 5 to 40 wt%.
- a method for producing the composite catalyst of the present invention comprising: It includes a hydrothermal synthesis process, a molding process, and an ion exchange process.
- the zeolite component in the composite catalyst of the present invention which is a crystalline aluminosilicate containing iron and gallium, is synthesized.
- a composite catalyst having a predetermined shape is manufactured by adding silicon dioxide as a binder to the zeolite synthesized in the hydrothermal synthesis step and kneading, molding, drying, firing and the like.
- silicon dioxide as a binder used at this time.
- the zeolite is made to exhibit properties as a solid acid.
- the order of steps in the production of the composite catalyst can be performed, for example, after the ion exchange step, the molding step, but in the order of the hydrothermal synthesis step, the molding step, and the ion exchange step. Is preferred. Workability is improved when the ion exchange step is performed on the composite catalyst formed into a predetermined shape, rather than the ion exchange step on the powdery zeolite obtained in the hydrothermal synthesis step. Moreover, after shaping
- an alkaline aqueous solution containing starch as a molding aid when molding a mixture of zeolite and silicon dioxide in the molding step.
- a method for producing a lower olefin which comprises producing a lower olefin from a hydrocarbon raw material using the composite catalyst having the above-described structure according to the present invention
- the composite catalyst is supplied as a gas containing the hydrocarbon raw material in an amount of 15 wt% or more, more preferably 50 wt% or more, and the reaction for generating the lower olefin from the hydrocarbon raw material is performed in a temperature range of 530 ° C. to 650 ° C. More preferably, the process proceeds in a temperature range of 550 ° C. to 640 ° C.
- the reaction temperature is lower than that of the steam cracking method, the energy efficiency is excellent, and the cost can be reduced.
- the generation of aromatic hydrocarbons can be suppressed and the life of the composite catalyst can be extended.
- the reaction can be carried out while adjusting the temperature in the temperature range of 530 ° C to 650 ° C.
- the composite catalyst for a long period of time, but a gradual decrease in the amount of lower olefin produced due to deterioration of the catalyst with time. Therefore, for example, by gradually increasing the reaction temperature over time, the production amount of lower olefin can be stabilized over a long period of time, and the replacement time and regeneration time of the composite catalyst can be postponed. Is possible.
- the present invention also relates to a method for producing a lower olefin, which comprises producing a lower olefin from a hydrocarbon raw material using the composite catalyst having the above-described configuration, Supplying the composite catalyst as a gas containing the hydrocarbon raw material at 15 wt% or more, more preferably 50 wt% or more, and the contact time of the hydrocarbon raw material with the composite catalyst is 0.08 to 1.0 h; More preferably, it is 0.08 to 0.4 h.
- the contact time between the composite catalyst and the hydrocarbon raw material is 0.08 to 1.0 h, and more preferably 0.08 to 0.4 h.
- lower olefins can be produced, and the production amount of aromatic hydrocarbons can be suppressed to extend the life of the composite catalyst. That is, when the contact time is shortened, the production amount of the lower olefin is reduced, but the production amount of the aromatic hydrocarbon is also lowered, the life of the composite catalyst is increased, and when the contact time is lengthened, the production amount of the lower olefin is increased. Although it increases, the amount of aromatic hydrocarbons generated increases, and the life of the composite catalyst is shortened. Therefore, it is preferable to set the contact time in consideration of the production amount of the lower olefin and the life of the composite catalyst.
- the composite catalyst can be used for a long period of time, but a gradual decrease in the amount of lower olefin produced due to deterioration of the catalyst with time. Therefore, for example, by gradually increasing the contact time between the raw material and the composite catalyst with the passage of time, the production amount of the lower olefin can be stabilized over a long period of time, and the replacement time of the composite catalyst, It becomes possible to postpone the reproduction time.
- a method for regenerating a composite catalyst, wherein deposited carbon is removed by combustion from the composite catalyst used in the method for producing an olefin having the above constitution according to the present invention The composite catalyst is supplied with air diluted with an inert gas, and the deposited carbon is burned and removed in a temperature range of 450 ° C. to 600 ° C., more preferably in a temperature range of 500 ° C. to 550 ° C. To do.
- the temperature at which the deposited carbon is burned and removed is lower than or equal to the reaction temperature at the time of the production of the lower olefin. Regeneration is possible without the need for improvement or enhancement of heating equipment and without increasing equipment costs.
- the catalyst life can be extended by suppressing the deterioration of the catalyst.
- FIG. 3 is a diagram for explaining a performance comparison of each composite catalyst of Example 1, Example 2, and Comparative Example 1. It is a figure for demonstrating the composition from which content of silicon dioxide of each composite catalyst of Example 1, Example 3, and Example 4 differs.
- FIG. 4 is a diagram for explaining a performance comparison of each composite catalyst of Example 1, Example 3, and Example 4.
- 6 is a graph showing the change over time in the yield of lower olefins in reaction tests using the composite catalysts of Example 1, Example 4, and Comparative Example 1. Contact times in Example 4, Example 5, Example 6 and Comparative Example 3 as reaction tests using the same composite catalyst as in Example 4 and different contact times between the raw material and the composite catalyst.
- FIG. 10 is a graph showing the results of a long-term reaction test as Example 9. 6 is a graph showing the results of a regeneration test of a composite catalyst as Example 10.
- Embodiments of the present invention will be described below.
- a composite catalyst for efficiently producing a lower olefin such as propylene over a long period of time a method for producing the composite catalyst, and a method for producing a lower olefin using the composite catalyst And the regeneration method of this composite catalyst in manufacture of a lower olefin is demonstrated.
- the composite catalyst of the present embodiment includes a zeolite that is a crystalline aluminosilicate containing gallium and iron or iron and having a skeleton structure having 8 to 12 member rings, and silicon dioxide that functions as a binder for molding. And a complex containing
- the zeolite which is a crystalline aluminosilicate has a skeleton structure having 8 to 12 member rings.
- the framework structure of zeolite is made into a database by the International Zeolite Society, and a structure code consisting of three uppercase letters is given. This structure code specifies only the geometric structure of the skeleton.
- the structure code of the 8-membered skeleton structure includes LTA
- the structure code of the 10-membered skeleton structure includes FER, MWW, MFI, etc.
- the structure code of the 12-membered ring skeleton structure includes , MOR, LTL, FAU, BEA etc.
- MOR, LTL, FAU, BEA etc.
- the pore diameter of zeolite is affected by the number of member rings in the skeleton structure, and the diameter of the pores is defined to some extent by the number of member rings being 8 to 12.
- the pore diameter is about 0.2 to 1.0 nm, and in the case of zeolite having a typical skeleton structure having 8 to 12 member rings, the pore diameter is about 0.40 nm to 0.75 nm.
- the pore size of the zeolite is suitably used when, for example, C4 to C8 lower olefin is used as the hydrocarbon raw material and propylene (ethylene) is produced by utilizing the catalytic function of the zeolite.
- the thickness is preferably about 0.40 nm to 0.75 nm, but is not limited to this range.
- the number of member rings in the framework structure of the zeolite is preferably 8 to 12 as described above, and more preferably 10 to 12.
- ZSM-5 Zeolite Socony Mobile-5
- MFI type zeolite or beta type zeolite can be suitably used as the zeolite having 8 to 12 member rings as described above.
- MFI type zeolite can be preferably used.
- crystalline aluminosilicate containing iron (Fe) element and gallium (Ga) element or iron element is used as zeolite.
- Fe has a function of suppressing the acid strength at the acid sites of zeolite.
- Ga has a function of promoting alkane dehydrogenation.
- the zeolite catalyst of the present embodiment is a composite catalyst obtained by molding and firing with a binder (binder) added, and silicon dioxide is used as the binder.
- the molar composition ratio of iron element is 0.4. Is preferably 0.7, and more preferably 0.4 to 0.6.
- the acid density (ratio of silicon element (Si) / (iron element + aluminum element) element) is 75.0. Is preferably 200.0, more preferably 80.0-200.0.
- the element ratio is a composition ratio based on the number of moles of each element described above.
- the molar composition ratio of iron element is 0.2 to It is preferably 0.6, and more preferably 0.3 to 0.5.
- the elemental molar composition ratio of gallium element is 0.1 to It is preferably 0.4, and more preferably 0.2 to 0.4.
- the acid density (ratio of silicon element / (iron element + gallium element + aluminum element) element) is preferably 75.0 to 200.0, Further, it is more preferably 80.0 to 200.0.
- the acid strength can be adjusted from the content of the iron element and the acid density.
- gallium element By adding gallium element, the promoting action of dehydrogenation of alkane can be improved.
- the alkane is divided and a carbon double bond is generated by the decarbonization reaction, resulting in a lower olefin.
- the composition ratio of the number of moles of iron element, the composition ratio of the number of moles of gallium element, and the acid density within the above ranges, the yield of propylene can be further improved, and aromatic carbon that causes coke formation Generation can be further suppressed.
- the content of silicon dioxide (silica) as a binder in the composite catalyst is preferably 5 to 50 wt% (wt%), more preferably 5 to 40 wt%. .
- silicon dioxide as a binder has a stronger action to coat and inactivate acid sites on the outer surface of zeolite than aluminum oxide (alumina) as a binder.
- Such an action mechanism is a zeolite having a distinct catalytic action for the reaction of producing a lower olefin from an alkane, for example, a crystal having a skeleton structure containing gallium and iron or iron and having 8 to 12 member rings. It effectively acts on zeolite that functions as a catalyst for producing a lower olefin from a hydrocarbon raw material as well as a functional aluminosilicate.
- Zeolite as such a solid acid catalyst is roughly classified as follows: 1. Hydrothermal synthesis process 2. molding step; Manufactured through three ion exchange steps.
- Hydrothermal synthesis method is a general term for the synthesis of substances carried out in the presence of high-temperature and high-pressure water. Many zeolites as crystalline aluminosilicates are used in this hydrothermal synthesis method. Are synthesized. Raw materials used in the synthesis include silica sources (sodium silicate, colloidal silica, fumed silica, etc.), alumina sources (aluminum hydroxide, sodium aluminate, etc.), structure directing agents (amines, etc.), mineralizers ( Alkali metal hydroxides) and water are common.
- silica sources sodium silicate, colloidal silica, fumed silica, etc.
- alumina sources aluminum hydroxide, sodium aluminate, etc.
- structure directing agents amines, etc.
- mineralizers Alkali metal hydroxides
- an iron source for example, iron nitrate, iron oxide, iron sulfate, iron phosphate, iron chloride, iron bromide, metallic iron (iron powder), organic acid iron, etc.
- a gallium source for example, gallium nitrate, gallium oxide, gallium sulfate, gallium phosphate, gallium chloride, gallium bromide, gallium hydroxide.
- a mother liquor gel A composed of colloidal silica having a particle size of 8 to 11 nm as fine silica as a silicon source and sodium hydroxide (NaOH) for pH adjustment, and an aluminum source.
- a mother liquor gel B containing tetrapropylammonium (TPrABr) is prepared.
- the mother liquor gel A and the mother liquor gel B are stirred and mixed (for example, 15 minutes). Thereby, a highly reactive amorphous hydrogel is prepared.
- the mixed and stirred mother liquor gel is aged (eg, overnight at 60 ° C.).
- stirring is performed at 120 ° C. to 150 ° C. and at a rotational speed of 150 rpm to 300 rpm (for example, hydrothermal synthesis is performed under self-pressure in an autoclave). That is, crystallization is performed under high temperature and high pressure. However, the reaction temperature is relatively low, and the generation of coarse particles is suppressed by nucleating at a low temperature.
- the stirring speed is relatively high and the amount of nuclei generated is increased.
- stirring is performed for 24 hours to obtain crystals.
- the obtained crystal is washed with water, and dehydration is performed by centrifugation. Thereafter, the crystal is dried, for example, at 120 ° C. for 3 hours and fired at 550 ° C. for 3 hours to remove TPrABr.
- gallium is not included, no gallium source is added to the mother liquor gel B.
- zeolite when used industrially as a catalyst, it is often used after being molded into a cylindrical shape from the viewpoint of improving mechanical properties and reducing pressure loss.
- This process mainly includes steps such as kneading, molding, drying, and firing of zeolite synthesized as described above and silicon dioxide as a binder (binder).
- steps such as kneading, molding, drying, and firing of zeolite synthesized as described above and silicon dioxide as a binder (binder).
- zeolite synthesized as described above silicon dioxide as a binder (binder).
- binder binder
- silica powder and starch as a molding aid are mixed with powdered zeolite obtained through the hydrothermal synthesis process (or ion exchange process) described above, and an aqueous sodium hydroxide solution (alkaline aqueous solution) is added. Knead to obtain a blocky mixture.
- the molding aid is not limited to starch.
- water when water is added, the viscosity increases.
- the zeolite powder and the silica powder are kneaded with water, the mixture is agglomerated.
- PVA polyvinyl pyrrolidone
- PVA polyvinyl pyrrolidone
- This mixture is processed into a cylindrical shape by, for example, extrusion molding and dried at 120 ° C. for about 3 hours.
- the composite catalyst of the present embodiment can be obtained through calcination at 550 ° C. for 3 hours under air flow.
- molding process may be performed after an ion exchange process or an ion exchange process may be performed after a shaping
- the zeolite obtained by the hydrothermal synthesis method contains a sodium cation (Na + ) in order to maintain the balance of electric charges, but this is replaced with protons (H + ) by ion exchange.
- a method may be adopted in which ion exchange is performed with ammonium ions (NH 4 + ) using an NH 4 NO 3 solution, followed by drying and baking to remove ammonia to convert it into protons (H + ).
- ion exchange with ammonium nitrate aqueous solution under boiling reflux and subsequent washing with water are repeated four times, followed by drying at 120 ° C. for 3 hours and firing at 550 ° C. for 3 hours under air flow, to form a proton-type composite
- a body catalyst can be obtained.
- the zeolite catalyst formed after the forming step is easier to handle than the powdery crystalline aluminosilicate in the hydrothermal synthesis step, and the workability of the ion exchange step can be improved.
- a reactor without diluting a raw material gas such as light naphtha with an inert gas such as nitrogen or a diluent such as water vapor is used.
- the hydrocarbon raw material is reacted with the composite catalyst.
- the raw material gas may contain a diluent.
- the gas supplied to the composite catalyst preferably contains 15 wt% or more of a hydrocarbon material such as light naphtha, and more preferably 50 wt%. % Is more preferable.
- a method is used in which the composite catalyst described above is arranged as a fixed bed in the reactor, and the raw material gas supplied into the reactor is passed while contacting the composite catalyst. At this time, the reaction is allowed to proceed in a moderate temperature range of 530 ° C. to 650 ° C., more preferably 550 ° C. to 640 ° C. to produce ethylene and propylene.
- the lower olefin hydrocarbon raw material is, for example, a low-boiling hydrocarbon raw material such as light naphtha, and naphtha (full-range naphtha) is a boiling point among products obtained by distilling and separating crude oil using an atmospheric distillation apparatus.
- the range is about 30-200 ° C.
- these naphtha those having a boiling range of about 30-100 ° C. are called light (light) naphtha, and those having a boiling range of about 100-200 ° C. are called heavy (heavy) naphtha.
- Light naphtha corresponds to a fraction mainly composed of pentane having 5 carbon atoms and hexane having 6 carbon atoms.
- the low boiling point hydrocarbon raw material is basically light naphtha, but may contain, for example, heavy naphtha or full range naphtha. Further, the low boiling point hydrocarbon raw material may be other than naphtha.
- natural gas other than petroleum or other hydrocarbon raw material having a fraction corresponding to light naphtha can be used. Further, by-products and the like when various products are produced from petroleum and natural gas can be used as the hydrocarbon raw material, and basically a hydrocarbon having a low boiling point can be used as the raw material.
- the lower olefin includes, for example, ethylene, propylene, butene, or an olefin having a higher carbon number (for example, 5 to 8 carbon atoms) as the olefin having a lower carbon number.
- the lower olefin includes at least ethylene having 2 carbon atoms and propylene having 3 carbon atoms.
- the contact time as the reciprocal of LHSV (Liquid Hourly Space Velocity) of the raw material hydrocarbon in the composite catalyst of the present embodiment is 0.08 to 1.0 h. It is preferable to set it to 0.08 to 0.4 h.
- LHSV is preferably 1.0 to 12.5 h ⁇ 1 , more preferably 2.5 to 12.5 h ⁇ 1 .
- LHSV is the speed at which the raw material hydrocarbon is supplied as a liquid to the composite catalyst
- the contact time is the time for the raw material hydrocarbon to pass through the composite catalyst as a liquid (composite catalyst).
- the raw material When the raw material is supplied to the reactor, the raw material is gasified from the liquid as described above, but here, the space velocity of the raw material as the liquid before gasification supplied to the reaction vessel is used) .
- the space velocity (GHSV) of source gas (gas) may be used as the space velocity, or the space velocity (WHSV) of weight (weight) may be used.
- the life of the composite catalyst is prolonged because the amount of aromatic hydrocarbons produced is small compared to the conventional case, thereby reducing the amount of precipitated carbon.
- the yield of lower olefins is It will gradually decrease with time. Therefore, by lowering the yield of lower olefins by increasing the reaction temperature or increasing the contact time (decreasing LHSV (space velocity)) corresponding to the passage of time, The olefin yield can be stabilized over a long period of time.
- the production amount of aromatic hydrocarbons may increase due to an increase in reaction temperature or a decrease in space velocity, but the production amount of aromatic hydrocarbons also decreases with time, and the reaction temperature
- the increase in aromatic hydrocarbons and the decrease in space velocity do not significantly change the decreasing tendency of the amount of aromatic hydrocarbons produced over time, and the possibility of increasing aromatic hydrocarbons is low.
- the increase in reaction temperature with time and the reduction in space velocity of the raw material may be performed independently or in combination with the increase in reaction temperature and the reduction in space velocity. May be. Further, in the case where the reaction temperature rise and the space velocity deceleration are combined, the reaction temperature increase and the space velocity deceleration may be performed at the same time, or may be performed at different times.
- the space velocity may be initially reduced, and the reaction temperature may be increased in the latter phase, or vice versa.
- the reaction temperature may be increased and the space velocity may be reduced alternately, for example, if the reaction temperature is increased three times, the space velocity is decreased once, and the reaction temperature is increased at different frequencies.
- the space velocity may be reduced.
- the present embodiment for example, it is possible to extend the catalyst life by at least 3 to 5 times or more as compared with the case where alumina is used as a binder, and further, as described above, the reaction temperature and the space velocity. By adjusting (contact time), it is possible to extend the catalyst life by 10 times or more.
- the yield of the lower olefin is reduced to a set value, it is necessary to replace the composite catalyst.
- the deterioration of the composite catalyst is mainly due to the generation of coke, it is possible to regenerate the composite catalyst by burning and removing the coke which is carbon.
- coke which is precipitated carbon can be burned and removed as carbon dioxide by supplying air diluted with nitrogen as an inert gas.
- the temperature of the coke burn when it comes into contact with oxygen.
- the temperature of the reaction vessel is preferably 450 ° C. to 600 ° C., and more preferably 500 ° C. to 550 ° C. It is more preferable.
- This temperature range overlaps with the above-mentioned reaction temperature range, but is slightly lower than the reaction temperature range, and even if heat is generated by combustion, the air is diluted with nitrogen as described above to suppress combustion. By doing so, the temperature range is at a level that does not cause a problem in the reaction vessel or the composite catalyst. Since the deterioration of the composite catalyst is mainly due to the precipitation of carbon, it is possible to regenerate the composite catalyst to a state close to the initial state before use by burning and removing the carbon.
- the binder used for forming the powdery zeolite is made of silica, so that the coke is obtained. Generation can be suppressed. Therefore, in the production of lower olefins using the composite catalyst, it is efficient in a moderate temperature range of about 530 to 650 ° C. (low temperature range in the production of lower olefins) and continuously for a long period of 1000 hours or more. Thus, it is possible to produce lower olefins.
- the method for regenerating a composite catalyst of the present embodiment it is possible to regenerate the composite catalyst that has been used for a long period of time as described above, and to use the composite catalyst for a longer period of time. .
- Colloidal silica 58.9 g (SiO 2 30.6 wt%, Na 2 O 0.4 wt%, H 2 O 69.0 wt%)
- a solution of 1.69 g sodium hydroxide was prepared as solution A, aluminum sulfate / n hydrate 0
- a solution consisting of .19 g, 0.11 g of gallium nitrate ⁇ n hydrate, 0.24 g of iron nitrate ⁇ 9 hydrate, 3.10 g of tetrapropylammonium bromide and 187.8 g of purified water was designated as solution B.
- Liquid A and liquid B were gradually mixed while stirring at room temperature, and then vigorously stirred for 15 minutes in a mixer.
- the mixed solution was kept at 60 ° C. and allowed to stand overnight, and then hydrothermal synthesis reaction was performed in an autoclave under self-pressure at 150 ° C. for 72 hours at 300 rpm. After cooling, it was thoroughly washed with purified water. Thereafter, the FeGaAl-MFI zeolite was synthesized by drying at 120 ° C. for 3 hours and firing in an air stream at 550 ° C. for 3 hours. The elemental molar composition ratio of this zeolite was determined by X-ray fluorescence measurement.
- the composite was subjected to ion exchange with a 2.2 mol / L aqueous ammonium nitrate solution under boiling reflux and subsequent water washing four times (one ion exchange was performed for 2 hours, and each time a new 2.2 mol / L was added). It was replaced with an aqueous ammonium nitrate solution), dried at 120 ° C. for 3 hours, and calcined at 550 ° C. for 3 hours under air flow to obtain a proton-type FeGaAl-MFI zeolite / silica composite catalyst.
- the cylindrical FeGaAl-MFI zeolite / silica composite prepared according to the above procedure was sized so as to be within the range of 1.0 to 2.0 mm, and used as a catalyst sample for performance evaluation. .
- the catalytic cracking reaction of n-hexane was conducted in a fixed bed flow type reactor.
- the reaction conditions were a reaction temperature of 565 ° C., a total pressure of 0.1 MPa, n-hexane LHSV (Liquid Hourly Space Velocity) of 4.5 h ⁇ 1 (n-hexane supply flow rate: 9.0 mL / h), and n-hexane.
- the catalytic cracking reaction was carried out for about 340 hours. About 30 hours after the start of the reaction, gas phase and liquid phase products were collected and subjected to gas chromatography analysis, and the raw material conversion (wt%) and the yield of lower olefins (ethylene, propylene) and aromatic hydrocarbons were collected. The rate (wt%) was determined and used as an index of catalyst performance at the initial stage of the reaction.
- FIG. 2 shows a summary of the catalyst performance of this sample
- FIG. 5 shows changes over time in the catalyst performance.
- FeAl-MFI zeolite was synthesized.
- a method for preparing a FeAl-MFI zeolite / silica composite catalyst (Zeolite / SiO 2 mixing ratio 75 wt% / 25 wt%) will be described.
- a powdered Na-type FeAl-MFI zeolite, silica powder, and starch synthesized according to the above procedure it was shaped and ion-exchanged by the same method as in Example 1 to obtain a cylindrical proton-type FeAl-MFI zeolite. / Silica composite catalyst.
- Na-type FeGaAl-MFI zeolite was synthesized.
- the elemental molar composition ratio of this zeolite was determined by X-ray fluorescence measurement.
- Si / (Fe + Ga + Al) 121.3
- Fe / (Fe + Ga + Al) 0.4
- Ga / (Fe + Ga + Al) 0.3
- Al / (Fe + Ga + Al) It was determined to be 0.3 (see FIG. 1).
- FIG. 2 shows a summary of the catalyst performance of this sample
- FIG. 5 shows changes over time in the catalyst performance.
- the initial propylene yield showed a high value of about 18 wt%, but as can be seen from the change over time in FIG. A decrease in yield was observed from the beginning, and a clear decrease in catalyst performance was confirmed after 100 hours.
- silica as the binder and molding and compounding at substantially the same mixing ratio as the sample of Comparative Example 1 (Example 1)
- the initial propylene yield is slightly low, but the aromatic yield is kept low. As a result, a long catalyst life of 340 hours or more was achieved (see FIG. 5).
- Na-type FeGaAl-MFI zeolite was synthesized.
- the elemental molar composition ratio of this zeolite was determined by X-ray fluorescence measurement.
- Si / (Fe + Ga + Al) 121.3
- Fe / (Fe + Ga + Al) 0.4
- Ga / (Fe + Ga + Al) 0.3
- Al / (Fe + Ga + Al) It was determined to be 0.3 (see FIG. 3).
- the cylindrical FeGaAl-MFI zeolite / silica composite prepared according to the above procedure was sized so as to be within the range of 1.0 to 2.0 mm, and used as a catalyst sample for performance evaluation. .
- the catalytic cracking reaction of n-hexane was conducted in a fixed bed flow type reactor.
- the reaction conditions were as follows: n-hexane with a reaction temperature of 565 ° C., a total pressure of 0.1 MPa, and a WHSV (Weight Hourly Space Velocity) of n-hexane of 6.0 h ⁇ 1 (n-hexane supply flow rate of 5.9 g / h).
- the catalytic cracking reaction was carried out for about 360 hours. About 30 hours after the start of the reaction, gas phase and liquid phase products were collected and subjected to gas chromatography analysis, and the raw material conversion (wt%) and the yield of lower olefins (ethylene, propylene) and aromatic hydrocarbons were collected. The rate (wt%) was determined and used as an index of catalyst performance at the initial stage of the reaction.
- Na-type FeGaAl-MFI zeolite was synthesized.
- the elemental molar composition ratio of this zeolite was determined by X-ray fluorescence measurement.
- Si / (Fe + Ga + Al) 121.3
- Fe / (Fe + Ga + Al) 0.4
- Ga / (Fe + Ga + Al) 0.3
- Al / (Fe + Ga + Al) It was determined to be 0.3 (see FIG. 3).
- FIG. 4 shows a summary of the catalyst performance of this sample
- FIG. 5 shows changes over time in the catalyst performance.
- FIG. 4 summarizes the performance of FeGaAl-MFI / SiO 2 composite catalysts having different mixed compositions.
- Three types of samples with different zeolite contents (68 wt%, 74 wt%, 90 wt%) were prepared and the initial performance was examined. As the zeolite content increased, the reaction conversion rate, lower olefin yield, aroma Family yield increased. Moreover, the aromatic yield was suppressed to a low value of 5.0 wt% or less regardless of which sample was used, and as a result, a long catalyst life of 340 hours or more was realized.
- Na-type FeGaAl-MFI zeolite was synthesized.
- the elemental molar composition ratio of this zeolite was determined by X-ray fluorescence measurement.
- Si / (Fe + Ga + Al) 121.3
- Fe / (Fe + Ga + Al) 0.4
- Ga / (Fe + Ga + Al) 0.3
- Al / (Fe + Ga + Al) It was calculated to be 0.3.
- a method for preparing an FeGaAl-MFI zeolite / silica composite catalyst (Zeolite / SiO 2 mixing ratio 90 wt% / 10 wt%) will be described.
- a cylindrical proton-type FeGaAl-MFI zeolite / silica composite catalyst was prepared in the same manner as in Example 4.
- Na-type FeGaAl-MFI zeolite was synthesized.
- the elemental molar composition ratio of this zeolite was determined by X-ray fluorescence measurement.
- Si / (Fe + Ga + Al) 121.3
- Fe / (Fe + Ga + Al) 0.4
- Ga / (Fe + Ga + Al) 0.3
- Al / (Fe + Ga + Al) It was calculated to be 0.3.
- a method for preparing an FeGaAl-MFI zeolite / silica composite catalyst (Zeolite / SiO 2 mixing ratio 90 wt% / 10 wt%) will be described.
- a cylindrical proton-type FeGaAl-MFI zeolite / silica composite catalyst was prepared in the same manner as in Example 4.
- Na-type FeGaAl-MFI zeolite was synthesized.
- the elemental molar composition ratio of this zeolite was determined by X-ray fluorescence measurement.
- Si / (Fe + Ga + Al) 121.3
- Fe / (Fe + Ga + Al) 0.4
- Ga / (Fe + Ga + Al) 0.3
- Al / (Fe + Ga + Al) It was calculated to be 0.3.
- a method for preparing an FeGaAl-MFI zeolite / silica composite catalyst (Zeolite / SiO 2 mixing ratio 90 wt% / 10 wt%) will be described.
- a cylindrical proton-type FeGaAl-MFI zeolite / silica composite catalyst was prepared in the same manner as in Example 4.
- FIG. 6 summarizes the effect of LHSV (contact time) on the initial performance of the FeGaAl-MFI / SiO 2 composite catalyst.
- LHSV contact time
- the composite catalyst using the silica binder gives a high propylene yield exceeding 15 wt% in a wide LHSV (contact time) region.
- the contact time with n-hexane is shown as the reciprocal of LHSV, and 0.23 (Example) as the reciprocal of LHSV4.5, 6.0, 7.0, 15.0h ⁇ 1. 4), 017 (Example 5), 0.14 (Example 6), and 0.07 (Comparative Example 2).
- Na-type FeGaAl-MFI zeolite was synthesized.
- the elemental molar composition ratio of this zeolite was determined by X-ray fluorescence measurement.
- Si / (Fe + Ga + Al) 121.3
- Fe / (Fe + Ga + Al) 0.4
- Ga / (Fe + Ga + Al) 0.3
- Al / (Fe + Ga + Al) It was calculated to be 0.3.
- a method for preparing an FeGaAl-MFI zeolite / silica composite catalyst (Zeolite / SiO 2 mixing ratio 90 wt% / 10 wt%) will be described.
- a cylindrical proton-type FeGaAl-MFI zeolite / silica composite catalyst was prepared in the same manner as in Example 4.
- Na-type FeGaAl-MFI zeolite was synthesized.
- the elemental molar composition ratio of this zeolite was determined by X-ray fluorescence measurement.
- Si / (Fe + Ga + Al) 121.3
- Fe / (Fe + Ga + Al) 0.4
- Ga / (Fe + Ga + Al) 0.3
- Al / (Fe + Ga + Al) It was calculated to be 0.3.
- a method for preparing an FeGaAl-MFI zeolite / silica composite catalyst (Zeolite / SiO 2 mixing ratio 90 wt% / 10 wt%) will be described.
- a cylindrical proton-type FeGaAl-MFI zeolite / silica composite catalyst was prepared in the same manner as in Example 4.
- FIG. 7 summarizes the influence of the reaction temperature on the initial performance of the FeGaAl-MFI / SiO 2 composite catalyst.
- the reaction conversion rate, the lower olefin yield and the aromatic yield were improved.
- the ethylene yield was 13.3 wt%.
- a lower olefin yield as high as 20.5 wt% was achieved.
- the aromatic yield is also 6.5 wt% at 635 ° C., and the value (7.3 wt%, see FIG. 2) in the reaction test at 565 ° C. using the composite catalyst with alumina binder (Comparative Example 1). ). Therefore, it was confirmed that the composite catalyst using the silica binder gives a high lower olefin yield while suppressing aromatic generation even when subjected to catalytic cracking at a high reaction temperature exceeding 600 ° C.
- Na-type FeGaAl-MFI zeolite was synthesized.
- the elemental molar composition ratio of this zeolite was determined by X-ray fluorescence measurement.
- Si / (Fe + Ga + Al) 121.3
- Fe / (Fe + Ga + Al) 0.4
- Ga / (Fe + Ga + Al) 0.3
- Al / (Fe + Ga + Al) It was calculated to be 0.3.
- a method for preparing an FeGaAl-MFI zeolite / silica composite catalyst (Zeolite / SiO 2 mixing ratio 90 wt% / 10 wt%) will be described.
- a cylindrical proton-type FeGaAl-MFI zeolite / silica composite catalyst was prepared in the same manner as in Example 4.
- a catalyst sample for performance evaluation was prepared by adjusting the cylindrical FeGaAl-MFI zeolite / silica composite to 1.0 to 2.0 mm prepared according to the above procedure.
- the same reaction test apparatus as in Examples 1 to 8 was used, the catalyst filling amount was set to 2.0 mL, and the total pressure was set to 0.1 MPa (the catalyst filling method was the same as in Examples 1 to 8).
- the n-hexane catalytic cracking reaction was carried out for about 1,000 hours under the operating conditions.
- Step 1 (from the start of the reaction to about 200 hours): The reaction temperature was 565 ° C., and the LHSV of n-hexane was 7.0 h ⁇ 1 .
- Step 2 (about 200 hours to about 380 hours after the start of the reaction): The reaction temperature was kept at 565 ° C., and the contact time with n-hexane was extended by setting the LHSV of n-hexane to 6.0 h ⁇ 1 .
- Step 3 (about 380 hours to about 540 hours after the start of the reaction): The reaction temperature was kept at 565 ° C., and the contact time with n-hexane was extended by setting the LHSV of n-hexane to 5.0 h ⁇ 1 .
- Step 4 (about 540 hours to about 620 hours after the start of the reaction):
- the reaction temperature was kept at 565 ° C., and the contact time with n-hexane was extended by setting the LHSV of n-hexane to 4.5 h ⁇ 1 .
- Step 5 (about 620 hours to about 740 hours after the start of the reaction): The reaction temperature was raised to 570 ° C., and the LHSV of n-hexane was maintained at 4.5 h ⁇ 1 .
- Step 6 (about 740 hours to about 835 hours after the start of the reaction): The reaction temperature was raised to 580 ° C., and the LHSV of n-hexane was maintained at 4.5 h ⁇ 1 .
- Step 7 (about 835 hours to about 920 hours after the start of the reaction): The reaction temperature was raised to 585 ° C., and the LHSV of n-hexane was maintained at 4.5 h ⁇ 1 .
- Step 8 (about 920 hours to about 1,000 hours after the start of the reaction): The reaction temperature was raised to 595 ° C., and the LHSV of n-hexane was maintained at 4.5 h ⁇ 1 .
- solution B A solution consisting of 0.76 g, gallium nitrate n-hydrate 0.44 g, iron nitrate nonahydrate 0.98 g, tetrapropylammonium bromide 4.65 g, and purified water 187.2 g was used as solution B.
- a catalyst regeneration test method for an FeGaAl-MFI zeolite / silica composite catalyst (Zeolite / SiO 2 mixing ratio 65 wt% / 35 wt%) will be described.
- the reaction test was conducted in the same manner as in Example 1 except that the reaction was carried out 2, 20, 28, 32, and 44 hours after the start of the reaction. Further, when about 45 hours had elapsed after the start of the reaction, the reaction test was temporarily stopped, and a catalyst regeneration process (combustion removal process for carbon deposited on the catalyst) was performed under the following operating conditions.
- Step 1 The supply of n-hexane raw material to the reactor was stopped, and the mixture was naturally cooled to room temperature under a nitrogen flow.
- Step 2 While supplying air diluted with nitrogen (oxygen concentration 0.5 vol%) at a flow rate of about 67 NL / h, the temperature of the catalyst layer was gradually raised to about 100 ° C. and then held for 1 hour.
- Step 3 While supplying air diluted with nitrogen (oxygen concentration 0.5 vol%) at a flow rate of about 67 NL / h, the temperature of the catalyst layer was gradually raised to about 350 ° C. and then held for 1 hour.
- Step 4 The temperature of the catalyst layer was gradually raised to about 450 ° C.
- Step 5 While supplying air diluted with nitrogen (oxygen concentration: 1.0 vol%) at a flow rate of about 67 NL / h, the catalyst layer temperature was gradually raised to about 500 ° C., and then maintained for 18 hours.
- Step 6 While supplying air diluted with nitrogen (oxygen concentration 2.0 vol%) at a flow rate of about 67 NL / h, the catalyst layer temperature was maintained at about 500 ° C. for 1 hour.
- Step 7 While supplying air diluted with nitrogen (oxygen concentration 2.0 vol%) at a flow rate of about 67 NL / h, the temperature of the catalyst layer was gradually raised to about 535 ° C. and held for 2 hours.
- Step 8 After switching the flowing gas to pure nitrogen, the heating of the catalyst layer was stopped and naturally cooled to room temperature.
- FIG. 10 shows the change with time in the catalyst performance (conversion rate of n-hexane).
- the regeneration of the catalyst was examined.
Abstract
Description
例えば、鉄または鉄およびガリウムを含むMFI型構造を有する結晶性アルミノシリケートをライトナフサ等の低沸点炭化水素原料から低級オレフィンを生成する際の触媒として利用することが提案されている(例えば、特許文献1~3参照)。
これら特許文献1~3に記載されたゼオライト触媒によれば、比較的低い反応温度で、エチレンに対してプロピレンの生成量を多くすることが可能となるとともに、触媒寿命の延長が可能になる。
ガリウムおよび鉄または鉄を含むとともに員環数が8~12の骨格構造を有する結晶性アルミノシリケートであるゼオライトと、二酸化珪素とを含むことを特徴とする。
なお、特許文献1~3では、酸化アルミニウム(アルミナ粉末)を結合剤として用いているが、結合剤として二酸化珪素(シリカ)を用いることにより、明らかに触媒寿命が延びることを見出した。すなわち、二酸化珪素を上述のゼオライトに混在させることにより触媒寿命を延ばすことを見出した。これは、ゼオライトの外表面に存在する酸点の少なくとも一部に共存する二酸化珪素が影響し、例えば、酸点の酸強度の低下により、ゼオライトの外表面で低級オレフィンから芳香族炭化水素が生成するのを抑制し、コークの生成を阻害していると思われる。これにより、十分に効率的に長期に渡って低級オレフィンの製造を行うことが可能であり、固定床方式での炭化水素原料から低級オレフィンの製造が実現可能となる。
鉄およびガリウムを含む結晶性アルミノシリケートであり、
かつ、鉄、ガリウムおよびアルミニウムのモル数の和に対する珪素のモル数の組成比としての酸密度が75.0~200.0であり、鉄、ガリウムおよびアルミニウムのモル数の和に対するガリウムのモル数の組成比が0.1~0.4であり、鉄、ガリウムおよびアルミニウムのモル数の和に対する鉄のモル数の組成比が0.2~0.6であることが好ましい。
鉄およびアルミニウムのモル数の和に対する珪素のモル数の組成比としての酸密度が75.0~200.0であり、鉄およびアルミニウムのモル数の和に対する鉄のモル数の組成比が0.4~0.7であることが好ましい。
水熱合成工程、成形化工程、イオン交換工程を含むことを特徴とする。
前記複合体触媒に、前記炭化水素原料を15wt%以上、さらに好ましくは、50wt%以上含む気体として供給し、前記炭化水素原料から前記低級オレフィンを生成する反応を530℃~650℃の温度領域で、さらに好ましくは550℃~640℃の温度領域で進行させることを特徴とする。
前記複合体触媒に、前記炭化水素原料を15wt%以上、さらに好ましくは、50wt%以上含む気体として供給し、前記炭化水素原料の前記複合体触媒との接触時間が0.08~1.0h、さらに好ましくは、0.08~0.4hであることが好ましい。
前記複合体触媒に不活性ガスで希釈された空気を供給し、450℃~600℃の温度領域で、さらに好ましくは、500℃~550℃の温度領域で析出炭素を燃焼除去することを特徴とする。
この実施の形態においては、プロピレン等の低級オレフィンを長期に渡って効率的に製造するための複合体触媒と、この複合体触媒の製造方法と、この複合体触媒を用いた低級オレフィンの製造方法と、低級オレフィンの製造におけるこの複合体触媒の再生方法を説明する。
「水熱合成法」とは、高温高圧の水の存在下にて行われる物質の合成法の総称であり、結晶性アルミノシリケ-トとしての多くのゼオライトはこの水熱合成法にて合成される。合成する際に使用する原料としては、シリカ源(珪酸ナトリウム、コロイダルシリカ、ヒュ-ムドシリカなど)、アルミナ源(水酸化アルミニウム、アルミン酸ナトリウムなど)、構造規定剤(アミン等)、鉱化剤(アルカリ金属の水酸化物など)、水などが一般的である。
一般的にゼオライトを触媒として工業的に使用する場合、機械的性質の向上や圧力損失の低減といった観点から、円筒状などに成形加工して使用されることが多い。本工程は、主として上述のように合成されたゼオライトと、結合剤(バインダー)である二酸化珪素との混練、成形化、乾燥、焼成などのステップを含む。なお、成形化においては、例えば、押し出し成形法などが用いられる。
この混合物を例えば押出成形により円筒状に加工し、120℃で3時間程度乾燥する。次に、空気流通下において、550℃での3時間の焼成を経て、本実施の形態の複合体触媒を得ることができる。
なお、イオン交換工程後に成形化工程を行っても、成形化工程後にイオン交換工程を行ってもよいが、成形化工程後にイオン交換工程を行うことが好ましい。
ゼオライトを触媒として利用する化学反応の多くは、固体酸としての性質を利用したものであり、この酸としての性質はゼオライトに酸性のOH基(ブレンステッド酸点)を導入することで発現する。
(実施例1)
まず、実施例1のGa、Alを含有するNa型のMFIゼオライト(FeGaAl-MFIゼオライト(Si/(Fe+Ga+Al)=121.3))の合成方法を説明する。
コロイダルシリカ58.9g(SiO2 30.6wt%、Na2O 0.4wt%、H2O 69.0wt%)水酸化ナトリウム1.69gからなる溶液をA液、硫酸アルミニウム・n水和物0.19g、硝酸ガリウム・n水和物0.11g、硝酸鉄・9水和物0.24g、臭化テトラプロピルアンモニウム3.10g、精製水187.8gからなる溶液をB液とした。A液とB液を室温で撹拌しながら徐々に混合した後、さらにミキサー中で15分間激しく撹拌した。
上記の手順に沿って合成した粉末状のNa型FeGaAl-MFIゼオライト、バインダーとしてのシリカ粉末(エボニックデグサGmbH(有限会社)、製品名:アエロジル200)、成形助剤としてのでんぷんを所定量混合した後、水酸化ナトリウム水溶液(NaOH濃度4.5wt%)を適量加えながら混練し、塊状のゼオライト/シリカ混合物を得た。その後、押し出し成形器にて円筒状(1.0mmφ)に加工し、120℃での3時間乾燥、空気流通下における550℃での3時間焼成を経て、FeGaAl-MFIゼオライト/シリカ複合体を得た。
上記の手順に沿って調製した円筒状のFeGaAl-MFIゼオライト/シリカ複合体を、長さが1.0~2.0mmの範囲内に収まるように整粒し、性能評価用の触媒試料とした。反応試験はn-ヘキサンの接触分解反応を固定床流通式反応装置にて行った。触媒2.0mL(充填重量としては1.32gとなる。)を内径12.6mmのステンレス反応管(SUS316製)に触媒層の層高が約20mmとなるように充填し、触媒層の前後にガラスウールを、さらにその前後にアルミナビーズを充填した。
次に、実施例2のFeAl-MFIゼオライト(Si/(Fe+Al)=120.3)の合成方法を説明する。
コロイダルシリカ58.9g(SiO2 30.6wt%、Na2O 0.4wt%、H2O 69.0wt%)、水酸化ナトリウム1.69gからなる溶液をA液、硫酸アルミニウム・n水和物 0.29g、硝酸鉄・9水和物0.24g、臭化テトラプロピルアンモニウム3.10g、精製水187.8gからなる溶液をB液とした以外は実施例1と同様にして、Na型のFeAl-MFIゼオライトを合成した。このゼオライトの元素モル組成比は蛍光X線測定により、Si/(Fe+Al)=120.3、Fe/(Fe+Al)=0.5、Al/(Fe+Al)=0.5と求められた(図1参照)。
上記の手順に沿って合成した粉末状のNa型FeAl-MFIゼオライト、シリカ粉末、でんぷんを用いて、実施例1と同様の方法によって成形化・イオン交換し、円筒状のプロトン型FeAl-MFIゼオライト/シリカ複合体触媒とした。この複合体触媒の重量組成は蛍光X線測定により、ゼオライト/シリカ=75wt%/25wt%となった(図1参照)。
上記の手順に沿って調製した、円筒状のFeAl-MFIゼオライト/シリカ複合体を1.0~2.0mmに整粒したものを性能評価用の触媒試料とし、反応時間を約330時間とした以外は実施例1と同様の方法で性能評価試験を実施した。また、LECO-Carbon分析法により、反応試験後の触媒上への炭素析出量を測定した。本試料の触媒性能のまとめを図2に示す。
次に、比較例1のFeGaAl-MFIゼオライト(Si/(Fe+Ga+Al)=121.3)の合成方法を説明する。
実施例1と同様にして、Na型のFeGaAl-MFIゼオライトを合成した。このゼオライトの元素モル組成比は蛍光X線測定により、Si/(Fe+Ga+Al)=121.3、Fe/(Fe+Ga+Al)=0.4、Ga/(Fe+Ga+Al)=0.3、Al/(Fe+Ga+Al)=0.3と求められた(図1参照)。
上記の手順に沿って合成した、粉末状のNa型FeGaAl-MFIゼオライトとアルミナ粉末(日揮触媒化成(株)、カタロイドAP-1、Al2O3含有率71.7wt%)に精製水を適量加えながら混練し、塊状のゼオライト/アルミナ混合物を得た。その後、押し出し成形器にて円筒状(1.0mmφ)に加工し、120℃での3時間乾燥、空気流通下における550℃での3時間焼成を経て、FeGaAl-MFIゼオライト/アルミナ複合体を得た。この複合体に、沸騰還流下での2.2mol/L硝酸アンモニウム水溶液によるイオン交換とそれに続く水洗浄を4回施した後(1回当りのイオン交換は2時間とし、毎回新しい2.2mol/L硝酸アンモニウム水溶液と入れ替えた)、120℃での3時間乾燥、空気流通下における550℃での3時間焼成を経て、プロトン型のFeGaAl-MFIゼオライト/アルミナ複合体触媒とした。この複合体触媒の重量組成は蛍光X線測定により、ゼオライト/アルミナ=77wt%/23wt%となった(図1参照)。
上記の手順に沿って調製した、円筒状のFeGaAl-MFIゼオライト/アルミナ複合体を1.0~2.0mmに整粒したものを性能評価用の触媒試料とし、n-ヘキサンのLHSVを5.0h-1(n-ヘキサンの供給流量10.0mL/h)、反応時間を約100時間とした以外は実施例1と同様の方法で反応試験を実施した。また、LECO-Carbon分析法により、反応試験後の触媒上への炭素析出量を測定した。本試料の触媒性能のまとめを図2に、触媒性能の経時変化を図5にそれぞれ示す。
次に、実施例3のFeGaAl-MFIゼオライト(Si/(Fe+Ga+Al)=121.3)の合成方法について説明する。
実施例1と同様にして、Na型のFeGaAl-MFIゼオライトを合成した。このゼオライトの元素モル組成比は蛍光X線測定により、Si/(Fe+Ga+Al)=121.3、Fe/(Fe+Ga+Al)=0.4、Ga/(Fe+Ga+Al)=0.3、Al/(Fe+Ga+Al)=0.3と求められた(図3参照)。
上記の手順に沿って合成した粉末状のNa型FeGaAl-MFIゼオライト、シリカ粉末、でんぷんを用いて、実施例1と同様の方法によって成形化・イオン交換し、混合比を変えた円筒状のプロトン型FeGaAl-MFIゼオライト/シリカ複合体触媒を調製した。この複合体触媒の重量組成は蛍光X線測定により、ゼオライト/シリカ=68wt%/32wt%となった(図3参照)。
上記の手順に沿って調製した円筒状のFeGaAl-MFIゼオライト/シリカ複合体を、長さが1.0~2.0mmの範囲内に収まるように整粒し、性能評価用の触媒試料とした。反応試験はn-ヘキサンの接触分解反応を固定床流通式反応装置にて行った。触媒1.44g(ゼオライト含有量0.98g:充填容積としては2.0mLとなる)を内径12.6mmのステンレス反応管(SUS316製)に充填し、触媒層の前後にガラスウールを、さらにその前後にアルミナビーズを充填した。
次に、実施例4のFeGaAl-MFIゼオライト(Si/(Fe+Ga+Al)=121.3)の合成方法を説明する。
実施例1と同様にして、Na型のFeGaAl-MFIゼオライトを合成した。このゼオライトの元素モル組成比は蛍光X線測定により、Si/(Fe+Ga+Al)=121.3、Fe/(Fe+Ga+Al)=0.4、Ga/(Fe+Ga+Al)=0.3、Al/(Fe+Ga+Al)=0.3と求められた(図3参照)。
上記の手順に沿って合成した粉末状のNa型FeGaAl-MFIゼオライト、シリカ粉末、でんぷんを用いて、実施例1と同様の方法によって成形化・イオン交換し、混合比を変えた円筒状のプロトン型FeGaAl-MFIゼオライト/シリカ複合体触媒を調製した。この複合体触媒の重量組成は蛍光X線測定により、ゼオライト/シリカ=90wt%/10wt%となった(図3参照)。
上記の手順に沿って調製した、円筒状のFeGaAl-MFIゼオライト/シリカ複合体を1.0~2.0mmに整粒したものを性能評価用の触媒試料とし、触媒充填量を1.09g(ゼオライト含有量0.98g:充填容積としては2.0mLとなる)、反応時間を約480時間とした以外は実施例3と同様の方法で反応試験を実施した。また、LECO-Carbon分析法により、反応試験後の触媒上への炭素析出量を測定した。
図4は混合組成が異なるFeGaAl-MFI/SiO2複合体触媒の性能についてまとめたものである。ゼオライトの含有率が異なる試料を3種類調製(68wt%,74wt%,90wt%)し、初期性能について検討したところ、ゼオライトの含有率が高くなるにしたがい、反応転化率、低級オレフィン収率、芳香族収率は増加した。また、どの試料を用いても芳香族収率は5.0wt%以下の低い値に抑えられ、結果として340時間以上の長い触媒寿命を実現した。とりわけ、高いゼオライト含有率(90wt%)を有する試料(実施例4)においても、初期芳香族収率は4.6wt%と低く抑えられ、480時間以上の極めて長い触媒寿命が達成された(図5参照)。
従って、シリカバインダーによる複合体触媒は、幅広いシリカ混合率(10~30wt%程度)で高いプロピレン収率と長い触媒寿命を同時に与えることが確認された。
次に、実施例5のFeGaAl-MFIゼオライト(Si/(Fe+Ga+Al)=121.3)の合成方法を説明する。
実施例1と同様にして、Na型のFeGaAl-MFIゼオライトを合成した。このゼオライトの元素モル組成比は蛍光X線測定により、Si/(Fe+Ga+Al)=121.3、Fe/(Fe+Ga+Al)=0.4、Ga/(Fe+Ga+Al)=0.3、Al/(Fe+Ga+Al)=0.3と求められた。
実施例4と同様にして、円筒状のプロトン型FeGaAl-MFIゼオライト/シリカ複合体触媒を調製した。この複合体触媒の重量組成は蛍光X線測定により、ゼオライト/シリカ=90wt%/10wt%となった(図6参照)。
上記の手順に沿って調製した、円筒状のFeGaAl-MFIゼオライト/シリカ複合体を1.0~2.0mmに整粒したものを性能評価用の触媒試料とし、n-ヘキサンのLHSVを6.0h-1(n-ヘキサンの供給流量12.0mL/h)、反応時間を約30時間(サンプリングは反応を開始してから5、24、30時間後に実施した)とした以外は実施例4と同様の方法で反応試験を実施した。本試料の初期触媒性能を図6に示す。
次に、実施例6のFeGaAl-MFIゼオライト(Si/(Fe+Ga+Al)=121.3)の合成方法を説明する。
実施例1と同様にして、Na型のFeGaAl-MFIゼオライトを合成した。このゼオライトの元素モル組成比は蛍光X線測定により、Si/(Fe+Ga+Al)=121.3、Fe/(Fe+Ga+Al)=0.4、Ga/(Fe+Ga+Al)=0.3、Al/(Fe+Ga+Al)=0.3と求められた。
実施例4と同様にして、円筒状のプロトン型FeGaAl-MFIゼオライト/シリカ複合体触媒を調製した。この複合体触媒の重量組成は蛍光X線測定により、ゼオライト/シリカ=90wt%/10wt%となった(図6参照)。
上記の手順に沿って調製した、円筒状のFeGaAl-MFIゼオライト/シリカ複合体を1.0~2.0mmに整粒したものを性能評価用の触媒試料とし、n-ヘキサンのLHSVを7.0h-1(n-ヘキサンの供給流量14.0mL/h)、反応時間を約30時間(サンプリングは反応を開始してから5、24、30時間後に実施した)とした以外は実施例4と同様の方法で反応試験を実施した。本試料の初期触媒性能を図6に示す。
次に、比較例2のFeGaAl-MFIゼオライト(Si/(Fe+Ga+Al)=121.3)の合成方法を説明する。
実施例1と同様にして、Na型のFeGaAl-MFIゼオライトを合成した。このゼオライトの元素モル組成比は蛍光X線測定により、Si/(Fe+Ga+Al)=121.3、Fe/(Fe+Ga+Al)=0.4、Ga/(Fe+Ga+Al)=0.3、Al/(Fe+Ga+Al)=0.3と求められた。
実施例4と同様にして、円筒状のプロトン型FeGaAl-MFIゼオライト/シリカ複合体触媒を調製した。この複合体触媒の重量組成は蛍光X線測定により、ゼオライト/シリカ=90wt%/10wt%となった(図6参照)。
上記の手順に沿って調製した、円筒状のFeGaAl-MFIゼオライト/シリカ複合体を1.0~2.0mmに整粒したものを性能評価用の触媒試料とし、n-ヘキサンのLHSVを15.0h-1(n-ヘキサンの供給流量30.0mL/h)、反応時間を約30時間(サンプリングは反応を開始してから5、24、30時間後に実施した)とした以外は実施例4と同様の方法で反応試験を実施した。本試料の初期触媒性能を図6に示す。
次に、実施例7のFeGaAl-MFIゼオライト(Si/(Fe+Ga+Al)=121.3)の合成方法を説明する。
実施例1と同様にして、Na型のFeGaAl-MFIゼオライトを合成した。このゼオライトの元素モル組成比は蛍光X線測定により、Si/(Fe+Ga+Al)=121.3、Fe/(Fe+Ga+Al)=0.4、Ga/(Fe+Ga+Al)=0.3、Al/(Fe+Ga+Al)=0.3と求められた。
実施例4と同様にして、円筒状のプロトン型FeGaAl-MFIゼオライト/シリカ複合体触媒を調製した。この複合体触媒の重量組成は蛍光X線測定により、ゼオライト/シリカ=90wt%/10wt%となった(図7参照)。
上記の手順に沿って調製した、円筒状のFeGaAl-MFIゼオライト/シリカ複合体を1.0~2.0mmに整粒したものを性能評価用の触媒試料とし、反応温度を585℃、反応時間を約15時間(サンプリングは反応を開始してから5、15時間後に実施した)とした以外は実施例5と同様の方法で反応試験を実施した。本試料の初期触媒性能を図7に示す。
次に、実施例8のFeGaAl-MFIゼオライト(Si/(Fe+Ga+Al)=121.3)の合成方法を説明する。
実施例1と同様にして、Na型のFeGaAl-MFIゼオライトを合成した。このゼオライトの元素モル組成比は蛍光X線測定により、Si/(Fe+Ga+Al)=121.3、Fe/(Fe+Ga+Al)=0.4、Ga/(Fe+Ga+Al)=0.3、Al/(Fe+Ga+Al)=0.3と求められた。
実施例4と同様にして、円筒状のプロトン型FeGaAl-MFIゼオライト/シリカ複合体触媒を調製した。この複合体触媒の重量組成は蛍光X線測定により、ゼオライト/シリカ=90wt%/10wt%となった(図7参照)。
上記の手順に沿って調製した、円筒状のFeGaAl-MFIゼオライト/シリカ複合体を1.0~2.0mmに整粒したものを性能評価用の触媒試料とし、反応温度を635℃、反応時間を約15時間(サンプリングは反応を開始してから5、15時間後に実施した)とした以外は実施例5と同様の方法で反応試験を実施した。本試料の初期触媒性能を図7に示す。
次に、実施例9のFeGaAl-MFIゼオライト(Si/(Fe+Ga+Al)=121.3)の合成方法を説明する。
実施例1と同様にして、Na型のFeGaAl-MFIゼオライトを合成した。このゼオライトの元素モル組成比は蛍光X線測定により、Si/(Fe+Ga+Al)=121.3、Fe/(Fe+Ga+Al)=0.4、Ga/(Fe+Ga+Al)=0.3、Al/(Fe+Ga+Al)=0.3と求められた。
実施例4と同様にして、円筒状のプロトン型FeGaAl-MFIゼオライト/シリカ複合体触媒を調製した。この複合体触媒の重量組成は蛍光X線測定により、ゼオライト/シリカ=90wt%/10wt%となった。
上記の手順に沿って調製した、円筒状のFeGaAl-MFIゼオライト/シリカ複合体を1.0~2.0mmに整粒したものを性能評価用の触媒試料とした。実施例1~8と同一の反応試験装置を使用し、触媒充填量を2.0mL、全圧を0.1MPaとした上で(触媒の充填方法も実施例1~8と同様)、下記の操作条件にて約1,000時間のn-ヘキサン接触分解反応を実施した。
Step2(反応開始後約200時間~約380時間):反応温度565℃のままとし、n-ヘキサンのLHSVを6.0h-1としてn-ヘキサンとの接触時間を延ばした。
Step3(反応開始後約380時間~約540時間):反応温度565℃のままとし、n-ヘキサンのLHSVを5.0h-1としてn-ヘキサンとの接触時間を延ばした。
Step4(反応開始後約540時間~約620時間):反応温度565℃のままとし、n-ヘキサンのLHSVを4.5h-1としてn-ヘキサンとの接触時間を延ばした。
Step6(反応開始後約740時間~約835時間):反応温度580℃に上げ、n-ヘキサンのLHSVを4.5h-1に保持した。
Step7(反応開始後約835時間~約920時間):反応温度585℃に上げ、n-ヘキサンのLHSVを4.5h-1に保持した。
Step8(反応開始後約920時間~約1,000時間):反応温度595℃に上げ、n-ヘキサンのLHSVを4.5h-1に保持した。
次に、実施例10のFeGaAl-MFIゼオライト(Si/(Fe+Ga+Al)=31.3)の合成方法を説明する。
コロイダルシリカ58.9g (SiO2 30.6wt%、Na2O 0.4wt%、H2O 69.0wt%)、水酸化ナトリウム2.25gからなる溶液をA液、硫酸アルミニウム・n水和物0.76g、硝酸ガリウム・n水和物0.44g、硝酸鉄・9水和物0.98g、臭化テトラプロピルアンモニウム4.65g、精製水187.2gからなる溶液をB液とした以外は実施例1と同様にして、Na型のFeGaAl-MFIゼオライトを合成した。このゼオライトの元素モル組成比は蛍光X線測定により、Si/(Fe+Ga+Al)=31.3、Fe/(Fe+Ga+Al)=0.4、Ga/(Fe+Ga+Al)=0.3、Al/(Fe+Ga+Al)=0.3と求められた。
上記の手順に沿って合成した粉末状のNa型FeGaAl-MFIゼオライト、シリカ粉末、でんぷんを用いて、実施例3と同様の方法によって成形化・イオン交換し、円筒状のプロトン型FeGaAl-MFIゼオライト/シリカ複合体触媒を調製した。この複合体触媒の重量組成は蛍光X線測定により、ゼオライト/シリカ=65wt%/35wt%となった。
上記の手順に沿って調製した、円筒状のFeGaAl-MFIゼオライト/シリカ複合体を1.0~2.0mmに整粒したものを性能評価用の触媒試料とし、反応時間を約45時間(サンプリングは反応を開始してから2、20、28、32、44時間後に実施した)とした以外は実施例1と同様の方法で反応試験を実施した。また、反応開始後約45時間が経過した時点で一旦反応試験を停止し、下記の操作条件にて触媒の再生処理(触媒上へ析出したカーボンの燃焼除去処理)を実施した。
Step2:窒素で希釈された空気(酸素濃度0.5vol%)を約67NL/hの流量で供給しながら、触媒層温度を徐々に約100℃まで昇温させた後、1時間保持した。
Step3:窒素で希釈された空気(酸素濃度0.5vol%)を約67NL/hの流量で供給しながら、触媒層温度を徐々に約350℃まで昇温させた後、1時間保持した。
Step4:窒素で希釈された空気(酸素濃度0.5vol%)を約67NL/hの流量で供給しながら、触媒層温度を徐々に約450℃まで昇温させた後、2時間保持した。
Step5:窒素で希釈された空気(酸素濃度1.0vol%)を約67NL/hの流量で供給しながら、触媒層温度を徐々に約500℃まで昇温させた後、18時間保持した。
Step6:窒素で希釈された空気(酸素濃度2.0vol%)を約67NL/hの流量で供給しながら、触媒層温度を約500℃で1時間保持した。
Step7:窒素で希釈された空気(酸素濃度2.0vol%)を約67NL/hの流量で供給しながら、触媒層温度を徐々に約535℃まで昇温させた後、2時間保持した。
Step8:流通ガスを純窒素に切替えた後、触媒層の加熱を停止して常温まで自然冷却した。
Claims (9)
- 炭化水素原料から低級オレフィンを製造するための複合体触媒であって、
ガリウムおよび鉄または鉄を含むとともに員環数が8~12の骨格構造を有する結晶性アルミノシリケートであるゼオライトと、二酸化珪素とを含むことを特徴とする複合体触媒。 - 前記ゼオライトは、
鉄およびガリウムを含む結晶性アルミノシリケートであり、
かつ、鉄、ガリウムおよびアルミニウムのモル数の和に対する珪素のモル数の組成比としての酸密度が75.0~200.0であり、鉄、ガリウムおよびアルミニウムのモル数の和に対するガリウムのモル数の組成比が0.1~0.4であり、鉄、ガリウムおよびアルミニウムのモル数の和に対する鉄のモル数の組成比が0.2~0.6であることを特徴とする請求項1に記載の複合体触媒。 - 前記ゼオライトは、鉄を含む結晶性アルミノシリケートであり、
鉄およびアルミニウムのモル数の和に対する珪素のモル数の組成比としての酸密度が75.0~200.0であり、鉄およびアルミニウムのモル数の和に対する鉄のモル数の組成比が0.4~0.7であることを特徴とする請求項1に記載の複合体触媒。 - 前記二酸化珪素の含有濃度が、5~50wt%であることを特徴とする請求項1~請求項3のいずれか1項に記載の複合体触媒。
- 請求項1から請求項4のいずれか1項に記載の複合体触媒の製造方法であって、
水熱合成工程,成形化工程,イオン交換工程を含むことを特徴とする複合体触媒の製造方法。 - 前記成形化工程で、ゼオライトと二酸化珪素の混合物を成形する際に、でんぷんを含むアルカリ性水溶液を用いることを特徴とする請求項5に記載の複合体触媒の製造方法。
- 請求項1から請求項4のいずれか1項に記載の複合体触媒を用いて炭化水素原料から低級オレフィンを製造する低級オレフィンの製造方法であって、
前記複合体触媒に、前記炭化水素原料を15wt%以上含む気体として供給し、前記炭化水素原料から前記低級オレフィンを生成する反応を530℃~650℃の温度領域で進行させることを特徴とする低級オレフィンの製造方法。 - 請求項1から請求項4のいずれか1項に記載の複合体触媒を用いて炭化水素原料から低級オレフィンを製造する低級オレフィンの製造方法であって、
前記複合体触媒に、前記炭化水素原料を15wt%以上含む気体として供給し、前記炭化水素原料の前記複合体触媒との接触時間が0.08~1.0hであることを特徴とする低級オレフィンの製造方法。 - 請求項7または請求項8に記載のオレフィンの製造方法で用いられた複合体触媒から析出炭素を燃焼除去する複合体触媒の再生方法であって、
前記複合体触媒に不活性ガスで希釈された空気を供給し、かつ、450℃~600℃の温度領域で、析出炭素を燃焼除去することを特徴とする複合体触媒の再生方法。
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WO2022186010A1 (ja) * | 2021-03-04 | 2022-09-09 | 千代田化工建設株式会社 | 複合体触媒、複合体触媒の製造方法および低級オレフィンの製造方法 |
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