JP4630537B2 - 結晶アルミノシリケートに基づく触媒の使用方法 - Google Patents
結晶アルミノシリケートに基づく触媒の使用方法 Download PDFInfo
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- JP4630537B2 JP4630537B2 JP2003402282A JP2003402282A JP4630537B2 JP 4630537 B2 JP4630537 B2 JP 4630537B2 JP 2003402282 A JP2003402282 A JP 2003402282A JP 2003402282 A JP2003402282 A JP 2003402282A JP 4630537 B2 JP4630537 B2 JP 4630537B2
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- catalyst
- catalyst according
- aluminum oxide
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- aluminum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 102
- 229910000323 aluminium silicate Inorganic materials 0.000 title claims abstract description 39
- 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 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 27
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000011230 binding agent Substances 0.000 claims abstract description 24
- 239000003513 alkali Substances 0.000 claims abstract description 20
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 17
- WMWXXXSCZVGQAR-UHFFFAOYSA-N dialuminum;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3] WMWXXXSCZVGQAR-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000002253 acid Substances 0.000 claims abstract description 13
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 13
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 9
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 claims abstract description 5
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract 2
- 229910052753 mercury Inorganic materials 0.000 claims abstract 2
- 238000002459 porosimetry Methods 0.000 claims abstract 2
- 239000013078 crystal Substances 0.000 claims description 68
- 238000000034 method Methods 0.000 claims description 44
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 238000001354 calcination Methods 0.000 claims description 19
- 239000002245 particle Substances 0.000 claims description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 11
- 229910052710 silicon Inorganic materials 0.000 claims description 11
- 239000010703 silicon Substances 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 150000001336 alkenes Chemical class 0.000 claims description 10
- 230000004927 fusion Effects 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 8
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 150000002500 ions Chemical class 0.000 claims description 6
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 6
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 6
- 239000012736 aqueous medium Substances 0.000 claims description 5
- 239000012431 aqueous reaction media Substances 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical group [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- 150000001412 amines Chemical class 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
- 239000012452 mother liquor Substances 0.000 claims description 3
- 150000002894 organic compounds Chemical class 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims description 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 abstract 1
- 239000010457 zeolite Substances 0.000 description 22
- 229910021536 Zeolite Inorganic materials 0.000 description 18
- 239000000047 product Substances 0.000 description 14
- 239000000243 solution Substances 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 229910004298 SiO 2 Inorganic materials 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 229930195733 hydrocarbon Natural products 0.000 description 6
- 150000002430 hydrocarbons Chemical class 0.000 description 6
- 238000005342 ion exchange Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 6
- -1 tetrapropylammonium compound Chemical class 0.000 description 6
- 239000012065 filter cake Substances 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 150000007524 organic acids Chemical class 0.000 description 3
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 3
- 235000012239 silicon dioxide Nutrition 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
- 150000004645 aluminates Chemical class 0.000 description 2
- 239000000908 ammonium hydroxide Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000002283 diesel fuel Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 150000007522 mineralic acids Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 125000003158 alcohol group Chemical group 0.000 description 1
- 150000007824 aliphatic compounds Chemical class 0.000 description 1
- 229910052910 alkali metal silicate Inorganic materials 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 239000007900 aqueous suspension Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000012013 faujasite Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000010414 supernatant solution Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/617—500-1000 m2/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/635—0.5-1.0 ml/g
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/651—50-500 nm
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/66—Pore distribution
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/70—Catalysts, in general, characterised by their form or physical properties characterised by their crystalline properties, e.g. semi-crystalline
- B01J35/77—Compounds characterised by their crystallite size
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
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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
- C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
- C10G3/42—Catalytic treatment
- C10G3/44—Catalytic treatment characterised by the catalyst used
- C10G3/48—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support
- C10G3/49—Catalytic treatment characterised by the catalyst used further characterised by the catalyst support containing crystalline aluminosilicates, e.g. molecular sieves
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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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/20—C2-C4 olefins
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Crystallography & Structural Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
Description
(a)珪素源とアルミニウム源とアルカリ源とテンプレートとを含有する水性反応成分にて高められた温度および場合により高められた圧力で、それ自体公知のようにアルカリ性アルミノシリケートゲルを得ると共に結晶アルミノシリケートまで変換させるが、得られた一次結晶が少なくとも0.01μmかつ0.1μm未満、好ましくは0.01〜0.06μm、特に0.015〜0.05μmの平均直径を有する際に反応を中断させ;
(b)一次結晶を予備凝集体として水性反応媒体から分離し、乾燥させ、更に中間焼成にかけ;
(c)工程(b)の生成物をプロトン含有または加熱に際しプロトンを放出する物質により水性媒体にてアルカリイオンの交換にかけ、分離し、乾燥させ、更に改めて中間焼成を行い、次いで約5〜500μmの凝集体フラクションを分離し;
(d)工程(c)の凝集体フラクションを微細な酸化アルミニウム水和物と混合し;
(e)工程(d)の生成物を融合焼成(Abschlusscalcinierung)にかける。
工程(a)にて先ず最初に珪素源(たとえばコロイド質珪酸もしくはアルカリシリケート)とアルカリ−およびアルミニウム−源(アルカリアルミナート、特にアルミン酸ナトリウム)とテンプレートとを含有する水性反応成分を作成する。
99%≦90μm
95%≦45μm
55%≦25μm
約0.3μmの一次結晶の平均直径を有する欧州特許第0369364号明細書の例1による触媒を作成した(Si/Al比105)。そこに示された方法、並びに生成物の物理的および化学的性質を関連して本明細書に開示する。
ドイツ国特許出願公開第2405909号明細書の例4による触媒を作成したが、ここでは硝酸ニッケルでの処理、すなわちNi交換を全く行わなかった。ドイツ国特許出願公開第2405909号明細書にて例4に示された生成物の作成方法、並びにその物理的および化学的性質を関連して本明細書に開示する。
比較例1に記載したように触媒を作成したが、ここでは一次結晶の平均粒子直径が0.03μmになった直後に変換を中断させた。更に、焼成およびイオン交換を比較例1に従って行った。
実施例1に記載されたように触媒を作成したが、ここではSiO2とNaAlO2との比をこれら化合物の一様な全モル濃度にて触媒のSi/Al比が31となるよう変化させた。平均一次結晶直径が0.03μmになった直後に反応混合物の変換を中断させた。
この使用例は、CMO−法(メタノールからオレフィンへの変換)の触媒データにより等温固定床反応器にて本発明による触媒の利点を示す。
Claims (27)
- メタノールからオレフィンへの変換のためのペンタシル型の結晶アルミノシリケートに基づく触媒の使用方法において、該触媒は、少なくとも0.01μmかつ0.1μm未満の平均直径を有する一次結晶で構築されて少なくとも20%まで5〜500μmの凝集体に合体され、一次結晶もしくは凝集体は微細な酸化アルミニウムにより互いに結合され、そのBET表面積は300〜600m2/gであると共にその気孔容積(水銀気孔測定法により測定)は0.3〜0.8cm3/gであり、H型で存在すると共に、微細な酸化アルミニウム−結合剤の量はアルミノシリケートおよび結合剤の合計重量に対し10〜40重量%であり、反応成分における微細な酸化アルミニウム−結合剤は解凝しうる酸化アルミニウム水和物として存在し、アルミニウム源およびアルカリ源としてはアルミン酸ナトリウムが使用され、さらに結晶アルミノシリケートの一次合成は酸添加なしに行われることを特徴とする触媒の使用方法。
- 前記触媒は、50〜250のSi/Al原子比を有することを特徴とする請求項1に記載の触媒の使用方法。
- 前記触媒は、75〜120のSi/Al原子比を有することを特徴とする請求項1または2に記載の触媒の使用方法。
- 一次結晶の平均直径が0.01〜0.06μmの範囲にあることを特徴とする請求項1〜3のいずれか一項に記載の触媒の使用方法。
- 一次結晶の平均直径が0.015〜0.05μmの範囲にあることを特徴とする請求項1〜4のいずれか一項に記載の触媒の使用方法。
- 融合焼成を500〜850℃の温度にて1〜12時間にわたり行われることを特徴とする請求項1〜5のいずれか一項に記載の触媒の使用方法。
- 融合焼成を680〜800℃の温度にて1〜4時間にわたり行われることを特徴とする請求項1〜6のいずれか一項に記載の触媒の使用方法。
- 酸化アルミニウム水和物の解凝のため酸濃度が0.15〜2.5モルH+/モルAl2O3に調整されることを特徴とする請求項1〜7のいずれか一項に記載の触媒の使用方法。
- 酸化アルミニウム水和物の解凝のため酸濃度が0.20〜1.5モルH+/モルAl2O3に調整されることを特徴とする請求項1〜8のいずれか一項に記載の触媒の使用方法。
- 気孔の少なくとも60%が14〜80nmの直径を有することを特徴とする請求項1〜9のいずれか一項に記載の触媒の使用方法。
- 解凝しうる酸化アルミニウム水和物の粒子の少なくとも95%(平均直径に基づく)が≦55μmであることを特徴とする請求項1〜10のいずれか一項に記載の触媒の使用方法。
- 微細な酸化アルミニウム−結合剤がアルミニウムトリアルキルもしくはアルミニウムアルコラートの加水分解により得られることを特徴とする請求項1〜11のいずれか一項に記載の触媒の使用方法。
- 前記触媒は、以下の方法:すなわち
(a)珪素源とアルミニウム源とアルカリ源とテンプレートとを含有する水性反応成分にて高められた温度でアルカリ性アルミノシリケートゲルを得ると共に、結晶アルミノシリケートまで変換させ、得られた一次結晶が少なくとも0.01μmかつ0.1μm未満の平均直径を有する際に反応を中断させ;
(b)一次結晶を予備凝集体として水性反応媒体から分離し、乾燥させ、更に中間焼成にかけ;
(c)工程(b)の生成物をプロトン含有または加熱に際しプロトンを産出する物質により水性媒体にてアルカリイオンの交換にかけ、分離し、乾燥させ、更に改めて中間焼成を行い、次いで5〜500μmの凝集体フラクションを分離し;
(d)工程(c)の凝集体フラクションを微細な酸化アルミニウム水和物と混合し;
(e)工程(d)の生成物を融合焼成にかける
ことにより得られることを特徴とする請求項1〜12のいずれか一項に記載の触媒の使用方法。 - 前記アルカリ性アルミノシリケートゲルは高められた圧力で得られることを特徴とする請求項13に記載の触媒の使用方法。
- 工程(a)における反応は、得られた一次結晶が0.015〜0.05μmの平均直径を有する際に反応を中断させることを特徴とする請求項13または14に記載の触媒の使用方法。
- 事前合成の母液からのアルミノシリケートゲルを得るため珪素源とアルカリ源とアルミニウム源とテンプレートと水とが使用されると共に、アルミノシリケートゲルの合成につき事前合成の母液の珪素源とアルカリ源とアルミニウム源とテンプレートと水をそれぞれ追加することにより補充されることを特徴とする請求項1〜15のいずれか一項に記載の触媒の使用方法。
- テンプレートがテトラプロピルアンモニウム水酸化物(TPAOH)もしくはテトラプロピルアンモニウム臭化物(TPABr)であることを特徴とする請求項1〜16のいずれか一項に記載の触媒の使用方法。
- テンプレートがアンモニアもしくは有機アミンと、アルコールの群から選択される有機化合物との混合物であることを特徴とする請求項1〜17のいずれか一項に記載の触媒の使用方法。
- アルコールはブタノールであることを特徴とする請求項18に記載の触媒の使用方法。
- 工程(a)の水性反応成分が10〜13のpH値を有すると共に、アルミノシリケート一次結晶の形成が90〜190℃にて撹拌下に行われることを特徴とする請求項1〜19のいずれか一項に記載の触媒の使用方法。
- 攪拌速度が最高900rpmであることを特徴とする請求項1〜20のいずれか一項に記載の触媒の使用方法。
- 工程(b)における一次結晶が凝集剤の添加下で水性反応媒体から分離されることを特徴とする請求項1〜21のいずれか一項に記載の触媒の使用方法。
- 工程(b)における中間焼成が雰囲気下に200〜350℃、次いで酸化性雰囲気下に500〜600℃にて行われて、まだ存在するテンプレートの残量を分離することを特徴とする請求項1〜22のいずれか一項に記載の触媒の使用方法。
- 工程(b)における中間焼成の温度が不活性雰囲気下に350℃であることを特徴とする請求項23に記載の触媒の使用方法。
- 工程(c)における中間焼成が400〜800℃にて5〜20時間にわたり行われることを特徴とする請求項1〜24のいずれか一項に記載の触媒の使用方法。
- 工程(c)における中間焼成の温度が540℃であることを特徴とする請求項25に記載の触媒の使用方法。
- メタノールからオレフィンへの変換は、メタノールからプロピレン(MTP)変換方法であることを特徴とする請求項1〜26のいずれか一項に記載の触媒の使用方法。
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US7253331B2 (en) * | 2004-05-12 | 2007-08-07 | Exxonmobil Chemical Patents Inc. | Molecular sieve catalyst composition, its making and use in conversion processes |
DE102005052016B4 (de) * | 2005-10-31 | 2009-05-20 | Süd-Chemie AG | Verfahren zur Herstellung poröser Formkörper und Formkörper erhältlich durch das Verfahren |
DE102006037314A1 (de) * | 2006-08-08 | 2008-02-14 | Süd-Chemie AG | Verwendung eines Katalysators auf Basis von Zeolithen bei der Umsetzung von Oxygenaten zu niederen Olefinen sowie Verfahren hierzu |
DE102007059129A1 (de) * | 2007-12-07 | 2009-06-10 | Süd-Chemie AG | Katalysator mit erhöhter Olefinselektivität zur Umsetzung von Oxygenaten zu Olefinen |
EP2446964A4 (en) | 2009-06-22 | 2015-04-29 | Jgc Corp | CATALYST FOR THE PRODUCTION OF LOWER OLEFINS AND PROCESS FOR PRODUCING LOWER OLEFINS USING SAID CATALYST |
DE102009053922A1 (de) | 2009-11-19 | 2011-05-26 | Lurgi Gmbh | Kugelförmiger, zeolithischer Katalysator zur Umsetzung von Methanol zu Olefinen |
DE102010005704A1 (de) | 2010-01-26 | 2011-07-28 | Süd-Chemie AG, 80333 | Verbesserter Katalysator auf Zeolithbasis zur Herstellung von Olefinen und zur Oligomerisierung von Olefinen |
DE102010026880A1 (de) * | 2010-07-12 | 2012-01-12 | Süd-Chemie AG | Verfahren zur Herstellung von Katalysatoren auf Zeolithbasis zur Umsetzung von Oxygenaten zu niederen Olefinen |
DE102010052258A1 (de) | 2010-11-23 | 2012-05-24 | Süd-Chemie AG | Verfahren zur Herstellung geträgerter ZSM-5-Zeolithe |
DE102011013909A1 (de) | 2011-03-15 | 2012-09-20 | Süd-Chemie AG | Verfahren zur Herstellung eines Katalysators auf Zeolithbasis zur Umwandlung von Methanol in Olefine |
DE102011013911A1 (de) | 2011-03-15 | 2012-09-20 | Süd-Chemie AG | Verbessertes Verfahren zur Herstellung eines Katalysators auf Zeolithbasis zur Umwandlung von Methanol in Olefine |
HUE066140T2 (hu) | 2012-11-13 | 2024-07-28 | Basf Se | Eljárás oxigenátok olefinekké történõ átalakítására |
US9598326B2 (en) | 2012-11-13 | 2017-03-21 | Basf Se | Process for the conversion of oxygenates to olefins |
RU2635567C1 (ru) | 2013-12-20 | 2017-11-14 | Клариант Продукте (Дойчланд) Гмбх | Фосфорсодержащий катализатор для превращения оксигенатов в олефины |
FR3116447B1 (fr) | 2020-11-23 | 2022-11-18 | Ifp Energies Now | Procede de preparation d’un catalyseur a base de zeolithe de code structural mfi presentant une densite et une tenue mecanique ameliorees |
KR102609812B1 (ko) | 2021-10-08 | 2023-12-05 | 주식회사 케이엘티 | 윤활유 주입기 |
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