WO2010016338A1 - ゼオライト含有触媒及びその製造方法並びにプロピレンの製造方法 - Google Patents
ゼオライト含有触媒及びその製造方法並びにプロピレンの製造方法 Download PDFInfo
- Publication number
- WO2010016338A1 WO2010016338A1 PCT/JP2009/061560 JP2009061560W WO2010016338A1 WO 2010016338 A1 WO2010016338 A1 WO 2010016338A1 JP 2009061560 W JP2009061560 W JP 2009061560W WO 2010016338 A1 WO2010016338 A1 WO 2010016338A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- zeolite
- containing catalyst
- catalyst
- silica
- mass
- Prior art date
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- 239000003054 catalyst Substances 0.000 title claims abstract description 341
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims abstract description 333
- 239000010457 zeolite Substances 0.000 title claims abstract description 333
- 229910021536 Zeolite Inorganic materials 0.000 title claims abstract description 328
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title claims description 33
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title claims description 33
- 238000000034 method Methods 0.000 title description 50
- 230000008569 process Effects 0.000 title description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 222
- 239000002245 particle Substances 0.000 claims abstract description 208
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 80
- 239000011148 porous material Substances 0.000 claims abstract description 40
- 239000002994 raw material Substances 0.000 claims description 79
- 239000008119 colloidal silica Substances 0.000 claims description 55
- 150000001875 compounds Chemical class 0.000 claims description 46
- 239000000843 powder Substances 0.000 claims description 44
- 238000004519 manufacturing process Methods 0.000 claims description 42
- 239000000203 mixture Substances 0.000 claims description 25
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 238000010304 firing Methods 0.000 claims description 20
- 238000001694 spray drying Methods 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 12
- 229930195733 hydrocarbon Natural products 0.000 claims description 11
- 150000002430 hydrocarbons Chemical class 0.000 claims description 11
- 239000004215 Carbon black (E152) Substances 0.000 claims description 9
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 6
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 5
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 5
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005695 Ammonium acetate Substances 0.000 claims description 4
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 4
- 235000019257 ammonium acetate Nutrition 0.000 claims description 4
- 229940043376 ammonium acetate Drugs 0.000 claims description 4
- 239000001099 ammonium carbonate Substances 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 2
- 150000004649 carbonic acid derivatives Chemical class 0.000 claims description 2
- 150000002823 nitrates Chemical class 0.000 claims description 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims description 2
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 76
- 238000005342 ion exchange Methods 0.000 description 66
- 239000002002 slurry Substances 0.000 description 64
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 55
- 229910001868 water Inorganic materials 0.000 description 52
- 239000005977 Ethylene Substances 0.000 description 38
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 37
- 229910004298 SiO 2 Inorganic materials 0.000 description 36
- 238000001354 calcination Methods 0.000 description 36
- 230000000704 physical effect Effects 0.000 description 35
- 238000000635 electron micrograph Methods 0.000 description 34
- 239000011734 sodium Substances 0.000 description 33
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 29
- 230000000052 comparative effect Effects 0.000 description 27
- 229910052708 sodium Inorganic materials 0.000 description 23
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 22
- 239000007789 gas Substances 0.000 description 21
- 239000000243 solution Substances 0.000 description 16
- 239000000126 substance Substances 0.000 description 16
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 15
- 229910017604 nitric acid Inorganic materials 0.000 description 15
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
- 229910052783 alkali metal Inorganic materials 0.000 description 14
- 150000001340 alkali metals Chemical class 0.000 description 14
- 239000007809 chemical reaction catalyst Substances 0.000 description 14
- 235000019353 potassium silicate Nutrition 0.000 description 13
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 12
- 150000001768 cations Chemical class 0.000 description 11
- 238000001035 drying Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 238000009826 distribution Methods 0.000 description 10
- 239000007921 spray Substances 0.000 description 10
- 239000004115 Sodium Silicate Substances 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 238000005259 measurement Methods 0.000 description 9
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- 239000002184 metal Substances 0.000 description 9
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- 239000002253 acid Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
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- 239000007788 liquid Substances 0.000 description 7
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 6
- 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 6
- 239000011230 binding agent Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 230000035484 reaction time Effects 0.000 description 6
- 238000010025 steaming Methods 0.000 description 6
- 239000000571 coke Substances 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 239000011574 phosphorus Substances 0.000 description 5
- 235000010724 Wisteria floribunda Nutrition 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 description 4
- 239000012013 faujasite Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000012495 reaction gas Substances 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 3
- 239000004254 Ammonium phosphate Substances 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 description 3
- 235000019289 ammonium phosphates Nutrition 0.000 description 3
- 150000003863 ammonium salts Chemical class 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 239000000706 filtrate Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
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- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 2
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- UNYSKUBLZGJSLV-UHFFFAOYSA-L calcium;1,3,5,2,4,6$l^{2}-trioxadisilaluminane 2,4-dioxide;dihydroxide;hexahydrate Chemical compound O.O.O.O.O.O.[OH-].[OH-].[Ca+2].O=[Si]1O[Al]O[Si](=O)O1.O=[Si]1O[Al]O[Si](=O)O1 UNYSKUBLZGJSLV-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/08—Silica
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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
-
- 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
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- B01J35/40—
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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
- B01J37/0027—Powdering
- B01J37/0045—Drying a slurry, e.g. spray drying
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
- C07C6/02—Metathesis reactions at an unsaturated carbon-to-carbon bond
- C07C6/04—Metathesis reactions at an unsaturated carbon-to-carbon bond at a carbon-to-carbon double bond
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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
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
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- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
-
- 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
Definitions
- the present invention relates to a zeolite-containing catalyst containing zeolite and silica, a method for producing the same, and a method for producing propylene using the zeolite-containing catalyst.
- the reaction gas is usually supplied from the lower part of the reactor filled with the catalyst, the catalyst particles flow in the reactor by the gas flow, and the reaction is caused by the contact between the catalyst particles and the reaction gas.
- the catalyst used for the fluidized bed reaction has not only chemical performance but also physical characteristics suitable for the fluidized bed reaction such as the shape, size, distribution, fluidity, and strength of the particles. Is required.
- Suitable properties of the catalyst particles that realize a good fluidized state in the fluidized bed reaction process are described, for example, on page 16 of the fluidized bed handbook (edited by Japan Powder Industrial Technology Association, Baifukan, published on March 25, 1999). Has been. According to this document, “It is desirable that the mass transfer between the bubbles and the emulsion phase containing the catalyst is sufficiently fast in order to improve the reaction rate and selectivity. For this purpose, it is desirable that the bubbles are small, the particles are fine and the surface is smooth. It is said that it is preferable that the particles have a light bulk density of 0.6 to 1.0 g ⁇ cm ⁇ 3 and an average diameter of 60 to 80 ⁇ m ”. .
- the catalyst particles wear or crush due to collision or contact between the catalyst particles, between the catalyst particles and the reactor, and between the catalyst particles and the reaction gas, the catalyst particles flow. Deterioration and scattering of crushed particles occur. Therefore, as a property of the fluidized bed reaction catalyst, a mechanical strength sufficient to withstand abrasion and crushing is also required.
- the catalyst used for the fluidized bed reaction has a shape, particle size distribution, etc. excellent in fluidity, and between the catalyst particles, between the catalyst particles and the reactor, and between the catalyst particles and the reaction gas. It is necessary to have mechanical strength (abrasion resistance) that can withstand collision and contact.
- a method in which a catalytically active component such as zeolite is molded together with a carrier component serving as a binder such as alumina, silica and clay so as to have mechanical strength suitable for a fluidized bed reaction, and the molded body is fired.
- a silica sol obtained by adding sulfuric acid and aluminum sulfate to sodium silicate and buffering is prepared, and clay and zeolite are added thereto to prepare a raw material slurry adjusted to a specific pH. Describes a process for producing a hydrocarbon conversion catalyst with high wear resistance by spray drying.
- Patent Document 2 discloses a fluidized bed catalyst having mesoporosity composed of zeolite, gibbsite (aluminum hydroxide), rare earth metal and silica matrix, wherein the silica matrix is a silica sol produced by an ion exchange method, Alternatively, a method for producing a fluid catalytic cracking catalyst, which is prepared from an acidic silica sol containing sodium silicate, sulfuric acid and aluminum sulfate, is disclosed.
- the mechanical strength of the zeolitic catalyst has a correlation with its surface shape, and the zeolitic catalyst having a smoother surface shape tends to have higher mechanical strength. .
- a zeolite-based catalyst having a particle shape closer to a sphere is desirable from the viewpoint of mechanical strength, and a catalyst that does not have sufficient mechanical strength ejects gas or the like contained from a part of the sphere.
- the ratio including the shape of such a shape is high.
- any of the catalysts obtained by the methods described in those documents had remarkable unevenness on the surface and were smooth. It was recognized that the spherical shape has a shape far from that.
- the present invention provides a zeolite-containing catalyst having an excellent shape, fluidity, and mechanical strength as a fluidized bed reaction catalyst, a method for producing the same, and a method for producing propylene using the zeolite-containing catalyst.
- the purpose is to provide.
- a zeolite-containing catalyst which is: [2] The zeolite-containing catalyst according to [1], wherein the zeolite is MFI-type zeolite. [3] The zeolite content is 10 to 90% by mass, the silica content is 10 to 90% by mass, and the total content of the zeolite and the silica is 50% by mass or more.
- any one of [1] to [3], comprising: a step of spray-drying a raw material mixture containing zeolite and colloidal silica to obtain a dry powder; and a step of firing the dry powder.
- [5] The method for producing a zeolite-containing catalyst according to [4], wherein the ratio of the colloidal silica is 50% by mass or more with respect to the total amount of silica contained in the raw material mixture.
- [6] The method for producing a zeolite-containing catalyst according to [4] or [5], wherein the raw material mixture is acidic.
- a method for producing propylene comprising a step of contacting the zeolite-containing catalyst according to any one of [1] to [3] with a hydrocarbon and / or an alcohol in a fluidized bed reactor.
- a zeolite-containing catalyst having an excellent shape, fluidity, and mechanical strength as a fluidized bed reaction catalyst, a method for producing the same, and a method for producing propylene using the zeolite-containing catalyst. it can.
- FIG. 2 is an electron micrograph (magnification 150 times) showing the zeolite-containing catalyst of Example 1.
- FIG. 2 is an electron micrograph (magnification 1500 times) showing a particle cross section of the zeolite-containing catalyst of Example 1.
- FIG. 4 is an electron micrograph (magnification 150 times) showing the zeolite-containing catalyst of Example 2.
- FIG. 4 is an electron micrograph (magnification 1700 times) showing a particle cross section of a zeolite-containing catalyst of Example 2.
- FIG. 4 is an electron micrograph (magnification 150 times) showing the zeolite-containing catalyst of Example 3.
- FIG. 4 is an electron micrograph (magnification: 1600 times) showing a particle cross section of a zeolite-containing catalyst of Example 3.
- FIG. 4 is an electron micrograph (magnification 1700 times) showing the particle surface of the zeolite-containing catalyst of Example 2.
- FIG. It is an electron micrograph (magnification 1600 times) showing the particle surface of the zeolite-containing catalyst of Example 25.
- It is an electron micrograph (magnification 150 times) which shows the zeolite containing catalyst after 1000-hour operation of Example 26.
- 2 is an electron micrograph (magnification 150 times) showing a zeolite-containing catalyst of Comparative Example 1.
- 2 is an electron micrograph (magnification: 1600 times) showing a particle cross section of a zeolite-containing catalyst of Comparative Example 1.
- 4 is an electron micrograph (magnification 150 times) showing a zeolite-containing catalyst of Comparative Example 2.
- 6 is an electron micrograph (magnification 1500 times) showing a particle cross section of a zeolite-containing catalyst of Comparative Example 2.
- 4 is an electron micrograph (magnification 150 times) showing a zeolite-containing catalyst of Comparative Example 3.
- 4 is an electron micrograph (magnification 1500 times) showing a particle cross section of a zeolite-containing catalyst of Comparative Example 3.
- 6 is an electron micrograph (magnification 150 times) showing a zeolite-containing catalyst of Comparative Example 8.
- 6 is an electron micrograph (magnification 1500 times) showing a particle cross section of a zeolite-containing catalyst of Comparative Example 8.
- silica refers to silica contained in a silica raw material used in the production of a zeolite-containing catalyst, and does not mean silica constituting zeolite unless otherwise specified.
- the zeolite-containing catalyst of the present embodiment is a catalyst of particles containing zeolite and silica, has an average particle diameter of 20 to 300 ⁇ m, and the ratio of the pore area in the cross section of the particle is relative to the cross sectional area of the particle. 30% or less.
- zeolite means crystalline porous aluminosilicate or metallosilicate (a part or all of the aluminum atoms constituting the skeleton of crystalline porous aluminosilicate are Ga, Fe, B, Cr, Zeolite substituted with a substitutable element such as Ti), and phosphate-based porous crystals having a structure similar to or similar to them.
- zeolite having a small pore diameter structure having an oxygen 8-membered ring or less
- chabazite is a code according to a code that classifies zeolites determined by the International Zeolite Society. The same applies hereinafter
- Elionite (ERI) A type LHA
- zeolite intermediate pore size (10-membered oxygen ring structures), ferrierite (FER), ZSM-11 ( MEL), ZSM-5 (MFI), include AlPO 4 -11 (AEL).
- zeolites having a large pore size oxygen 12-membered ring structure
- X type FAU
- Y type FAU
- faujasite FAU
- ⁇ type BEA
- mordenite MOR
- ZSM-12 MTW
- ALPO 4 -5 AFI
- UTD-1 DON
- CIT-5 CFI
- VPI-5 VFI
- zeolite having an intermediate pore diameter having an oxygen 10-membered ring is preferable, MFI type zeolite is more preferable, and ZSM-5 is particularly preferable.
- a catalyst containing a zeolite having such an intermediate pore size is subjected to a hydrocarbon conversion reaction carried out in a gas phase such as a catalytic cracking (FCC) reaction, a zeolite having a large pore size is used. Compared with the reaction, there is a tendency that the amount of coke generated with the reaction is small. As a result, pore clogging due to coke hardly occurs and the catalyst life can be extended. Therefore, zeolite having the above intermediate pore diameter is preferred.
- zeolite having an intermediate pore size is preferred because reactive molecules such as hydrocarbons and alcohols can easily enter the pores and can effectively utilize the active sites on the catalyst, compared to zeolite having a small pore size.
- zeolite having a small pore diameter tends to have a higher rate of activity deterioration due to coke generated by the reaction than zeolite having an intermediate pore diameter.
- zeolites having an intermediate pore size zeolites having an MFI type structure (MFI type zeolite; in particular, ZSM-5) have a high heat resistance and a characteristic catalytic activity due to shape selectivity and strong solid acidity. preferable.
- the cation type of zeolite may be H + type, but may be one in which part or all of H + is replaced with a metal cation as required.
- the zeolite-containing catalyst of the present embodiment is used as a fluidized bed reaction catalyst in contact with a hydrocarbon containing ethylene to produce propylene
- the zeolite-containing catalyst is a metal belonging to Group IB of the periodic table. That is, it is preferable to contain at least one metal selected from the group consisting of copper, silver and gold.
- the metal contained in the zeolite-containing catalyst is more preferably copper and / or silver, and particularly preferably silver.
- the “periodic table” refers to CRC Handbook of Chemistry and Physics, 75th edition David R.
- the metal contained in the zeolite-containing catalyst is contained in the zeolite in the catalyst in the state of a corresponding cation, or is supported on the catalyst. It is also preferable to use zeolite modified with a phosphorus compound.
- the phosphorus compound include phosphoric acid, phosphorous acid, hypophosphorous acid, pyrophosphoric acid, polyphosphoric acid, ammonium monohydrogen phosphate, ammonium dihydrogen phosphate, ammonium phosphate, and aluminum phosphate.
- a material obtained by adsorbing or impregnating about 0.1 to 5% by mass of these phosphorus compounds as a phosphorus element with respect to zeolite can be used.
- the zeolite-containing catalyst of the present embodiment has an average particle size in the range of 20 to 300 ⁇ m.
- the average particle diameter is preferably 20 to 200 ⁇ m, more preferably 40 to 100 ⁇ m, still more preferably 40 to 80 ⁇ m, and particularly preferably 40 to 60 ⁇ m.
- the zeolite-containing catalyst of the present embodiment has a particle size distribution such that the particle diameter of 80% or more of the entire particles falls within the particle diameter range of 2 to 0.2 times the average particle diameter. What has is preferable.
- particle diameter and “particle size distribution” mean values measured by a laser diffraction / scattering particle size analyzer.
- the “average particle size” means that the particle size distribution (ratio of particles in a certain particle size interval) of the powdery zeolite-containing catalyst is measured with the above analyzer, and the total volume is 100%. Is the particle diameter at which the accumulation is 50%, that is, the cumulative average diameter (center diameter, median diameter).
- the zeolite-containing catalyst of the present embodiment is preferably spherical from the viewpoint of fluidity and strength.
- the conventional zeolite-containing catalyst may have a shape in which a cavity formed in the vicinity of the center is ruptured, or may have significant irregularities on the particle surface. Many are far from spherical.
- the term “spherical”, which is a term used as the shape of the catalyst in the present specification, is intended to contrast with such a conventional catalyst shape, and therefore does not necessarily need to be a true sphere or a shape close thereto, but a ruptured shape. It does not mean that there is no conspicuous protrusion or dent.
- the shape of the zeolite-containing catalyst is preferably as close to a true sphere as possible.
- the spherical zeolite-containing catalyst flows smoothly in the fluidized bed reactor, and tends to have a high strength, so that it is advantageous in terms of durability.
- the average particle size of the zeolite-containing catalyst is less than 20 ⁇ m, the angle of repose, which is an indicator of the fluidity of the catalyst, tends to increase, and when used as a fluidized bed reaction catalyst, the fluidity of the catalyst tends to deteriorate.
- the average particle diameter exceeds 300 ⁇ m, the mechanical strength of the catalyst tends to decrease, and when used as a fluidized bed reaction catalyst, the central part of the catalyst particles tends not to be used effectively for the reaction.
- the zeolite-containing catalyst of the present embodiment has a structure in which the ratio of the pore area in the cross section of the particle is 30% or less with respect to the cross sectional area of the particle.
- the ratio of the pore area is preferably 20% or less, more preferably 15% or less, and particularly preferably 10% or less.
- the ratio of the pore area in the cross section of the particle here means a value measured as follows. That is, first, the particles of the zeolite-containing catalyst are embedded in a resin, and the cross-section of the catalyst particles is cut out by polishing it. The cross section is observed with an electron microscope equipped with an image analysis device, and the cross sectional area of one particle and the area of the pores in the cross section of the particle are measured with an image analysis device at a magnification of 800 to 2000 times.
- the “cross-sectional area” is a value including the area of the hole portion.
- the area of the enclosed range is the cross-sectional area.
- the actual part is C-shaped, but the area of the entire range surrounded by the straight line connecting the opening and the C-shaped actual part is the cross-sectional area (near the center of the figure).
- the area of the opening that is observed in black is also included in the cross sectional area).
- the area of the hole part in this example is the area of the part surrounded by the straight line connecting the opening part and the inner wall of the C-shaped substance part.
- the ratio of the area of the pores to the cross-sectional area of the particles is calculated.
- the series of operations is performed on 100 particles, and an arithmetic average (arithmetic average) is taken as the ratio of the pore area in the cross section of the particles.
- an arithmetic average is taken as the ratio of the pore area in the cross section of the particles.
- all particles having a diameter within a range of ⁇ 10% of the average particle diameter are selected.
- the ratio of the pore area exceeds 30%, the mechanical strength of the particles tends to be weakened.
- the conventional zeolite-containing catalyst has a shape in which a large cavity or a cavity is ruptured in the vicinity of the center, or a shape having remarkably unevenness on the particle surface.
- the high mechanical strength of the catalyst used in the fluidized bed reaction is extremely important for industrial processes because the catalyst is less pulverized even when used for a long period of time, and a suitable fluidized state can be stably maintained.
- the zeolite-containing catalyst having a high mechanical strength tends to be hard to wear, so the mechanical strength of the catalyst depends on the wear loss of the catalyst.
- the wear loss at a certain time is measured.
- the wear loss is preferably 3% by mass or less, more preferably the wear loss is 2% by mass or less, and particularly preferably the wear loss is 1% by mass or less.
- the zeolite-containing catalyst of the present embodiment preferably has an angle of repose of 25 to 30 °, and more preferably 25 to 28 °. When the angle of repose is 30 ° or less, the fluidity of the catalyst is better. The angle of repose is measured according to the method described in the examples described later.
- the content of (I) zeolite in the form after calcination, is 10 to 90% by mass with respect to the total amount of the zeolite-containing catalyst, and (II) the content of silica
- the ratio is preferably 10 to 90% by mass, and the total content of (III) zeolite and silica is preferably 50% by mass or more. More preferably, the content of (I) zeolite is 20 to 60% by mass, (II) the content of silica is 80 to 40% by mass, and (III) the total content of zeolite and silica is 70%. It is at least mass%.
- the content of (I) zeolite is 30 to 50% by mass
- (II) the content of silica is 70 to 50% by mass
- (III) the total content of zeolite and silica is 90%. It is at least mass%.
- the zeolite-containing catalyst of the present embodiment has a specific average particle diameter and the ratio of the pore area in the cross section of the particle is 30% or less with respect to the cross sectional area of the particle, high fluidity and mechanical strength are obtained. Have Therefore, it is particularly suitable as a catalyst for fluidized bed reaction.
- the method for producing a zeolite-containing catalyst of the present embodiment provides a zeolite-containing catalyst having an average particle diameter of 20 to 300 ⁇ m and a ratio of pore area in the cross section of the particle to 30% or less with respect to the cross sectional area of the particle. In order to obtain such a zeolite-containing catalyst, various conditions may be adjusted as described in detail below.
- the method for producing a zeolite-containing catalyst of the present embodiment preferably comprises (ii) a step of spray-drying a raw material mixture containing zeolite and colloidal silica to obtain a dry powder, and (iii) firing the dry powder. The process of carrying out.
- the method for producing the zeolite-containing catalyst includes (i) a step of preparing the raw material mixture containing zeolite and colloidal silica, and / or a step (iii) after (iv) ) You may have the process of ion-exchange the baked powder obtained by baking.
- Step (i) Preparation of raw material mixture
- Step (i) is preferably a raw material mixture (hereinafter, referred to as “a”) containing zeolite, colloidal silica, and at least one water-soluble compound selected from the group consisting of nitrate, acetate, carbonate, sulfate and chloride. It is also a step of preparing “raw slurry”.
- the SiO 2 / Al 2 O 3 ratio (silica / alumina ratio) of the zeolite is preferably 15 to 1000, more preferably 20 to 300, in terms of molar ratio.
- the zeolite is a metallosilicate
- the number of moles of alumina containing aluminum atoms substituted with substitutable elements such as Ga, Fe, B, Cr, Ti is also the number of moles of alumina present in the metallosilicate.
- the SiO 2 / Al 2 O 3 ratio (silica / alumina ratio) is calculated.
- the raw material zeolite is preferably in a state where the primary particles of the zeolite are dispersed.
- the zeolite has a primary aggregation of about 0.05 to 10 ⁇ m in which primary particles are partially bonded to each other to form secondary aggregation.
- zeolite with secondary agglomeration is formed together with a binder such as silica, the surface of the formed particles tends to be rough, and voids tend to be formed inside the particles, and the mechanical strength tends to be weakened. Therefore, when the zeolite is secondary agglomerated, it is preferable to mechanically pulverize using a jet mill or the like to deagglomerate and use the zeolite.
- a jet mill in which high-pressure air is converted into an ultra-high speed jet and pulverized, rather than a simple ball mill.
- deagglomeration is particularly preferred until the average particle size of the zeolite is in the range of 0.05 to 5 ⁇ m.
- the agglomeration form of zeolite can be observed with an electron microscope. Further, the average particle diameter of zeolite is measured by a laser diffraction / scattering particle size analyzer in the same manner as described above.
- the colloidal silica used as the catalyst raw material is preferably prepared by an ion exchange method.
- water glass sodium silicate
- water glass sodium silicate
- the colloidal silica prepared by the ion exchange method is the main component
- the surface of the catalyst particles becomes smooth.
- “the surface of (particles) is smooth” means that the surface of the particles does not appear uneven when observed with a 150 ⁇ magnification micrograph.
- colloidal silica is the main component, the sodium content in the raw material is small, so that an ion exchange step is not necessarily required, and sodium can be removed by a simple operation.
- a catalyst formed by spray drying has a problem that a large cavity is formed at the center of the catalyst and the catalyst particles become fragile particles.
- this problem has been solved by allowing a predetermined amount of a water-soluble compound described later to coexist in the catalyst raw material.
- the proportion of silica obtained from colloidal silica as a raw material (derived from colloidal silica) relative to the total amount of silica (excluding silica constituting zeolite) contained in the zeolite-containing catalyst is preferably as large as possible.
- the ratio of colloidal silica is preferably 50% by mass or more, more preferably 60% by mass or more, based on the total amount of silica (excluding silica constituting zeolite) contained in the raw material mixture. Still more preferably, it is 70 mass% or more, Most preferably, it is 80 mass% or more, Most preferably, it is 90 mass% or more.
- the ratio of colloidal silica to the total amount of silica contained in the raw material mixture is, for example, when the silica source contained in the raw material mixture is water glass and colloidal silica (silica contained in colloidal silica) / (colloidal). (Silica contained in silica + silica contained in water glass) Means. As the proportion of colloidal silica contained in the raw material mixture is higher, the surface of the resulting catalyst tends to be smoother. In particular, when it is 70% by mass or more, protrusions and depressions are observed on the surface even when observed at 1600 times or more. Fewer particles (40% or less). “Protrusions and depressions” indicate a state in which local irregularities are generated on the surface, and are different from a state in which a linear “crack” is formed on the surface.
- colloidal silica can be used as the colloidal silica prepared by the ion exchange method.
- Colloidal silica stabilized with ammonia or amine is particularly preferred because of its low alkali metal content.
- the content (mass basis) of the alkali metal in the colloidal silica is preferably as small as possible, more preferably 1000 ppm or less as an alkali metal, and still more preferably 250 ppm or less.
- the alkali metal content is preferably 5000 ppm or less based on the total mass of the zeolite-containing catalyst, more preferably in the range of 10 to 3000 ppm, still more preferably in the range of 10 to 1000 ppm, still more preferably in the range of 10 to It is in the range of 300 ppm, particularly preferably in the range of 10 to 100 ppm. If the alkali metal content exceeds 5000 ppm, the catalytic activity tends to decrease, while if it is less than 10 ppm, there is no beneficial effect on the catalytic activity. When a plurality of alkali metals are included, it is preferable that the total content of the alkali metals is within this range.
- the catalyst was dissolved in aqua regia at 210 ° C. using a microwave (Milestone Co., Ltd., model: ETOS PLUS), and a small amount of residual metal was left. Filter the minutes. Thereafter, the amount of alkali metal in the filtrate is measured by an ordinary method using ICP emission spectrometry.
- the content of alkali metal in the zeolite-containing catalyst can be derived from the amount of alkali metal contained in the filtrate.
- the measurement conditions for ICP emission analysis can be set to high frequency power: 1 kW, plasma gas: 13 L / min, sheath gas: 0.15 L / min, nebulizer gas: 0.25 L / min.
- the average particle size of silica contained in the colloidal silica is preferably 3 to 50 nm, more preferably 4 to 25 nm. There exists a tendency for the mechanical strength of a shaping
- the average particle size of silica is measured by a laser dynamic light scattering particle size distribution analyzer.
- At least one water-soluble compound selected from the group consisting of nitrate, acetate, carbonate, sulfate and chloride is added to the raw slurry.
- salt refers to a compound produced by neutralization reaction between an acid and a base, as described on page 1014 of the 1st edition of the Encyclopedia of Chemical Sciences, Volume 39 (Kyoritsu Shuppan Co., Ltd., June 15, 2006). And consisting of an acid negative component and a base positive component.
- the “water-soluble compound” means a compound having a solubility of 1 g or more in 100 g of water at 25 ° C. This water-soluble compound is preferably a compound having a solubility of 10 g or more in 100 g of water at 25 ° C., and examples thereof include ammonium salts, aluminum salts, and sodium salts.
- a more preferable water-soluble compound is an ammonium salt that has high water solubility and can be decomposed and removed from the catalyst in the firing step described below. More specifically, the water-soluble compound is more preferably one or more ammonium salts selected from the group consisting of ammonium nitrate, ammonium acetate, ammonium carbonate, ammonium sulfate and ammonium chloride, and most preferably ammonium nitrate.
- the amount of the water-soluble compound added to the raw material slurry is in the range of 0.01 to 5.0 in terms of mass ratio to the silica contained in the colloidal silica (hereinafter referred to as “water-soluble compound / colloidal silica ratio”).
- the amount of the water-soluble compound added is more preferably in the range of 0.03 to 3.0, still more preferably in the range of 0.05 to 2.0, and particularly preferably in the range of 0.1 to 1.0.
- a range of 0.25 to 0.5 is very preferable.
- the addition amount of the water-soluble compound is less than 0.01 by mass ratio with respect to silica using the colloidal silica as a raw material, the ratio of the pore area of the particle cross section increases, and the mechanical strength of the particles tends to be weakened. .
- the added amount of the water-soluble compound is larger than 5.0 by mass ratio with respect to the silica, the amount of the added water-soluble compound is increased when it is decomposed at the time of the catalyst calcination described later. And the mechanical strength of the particles tends to be weakened.
- the drying property of a droplet falls at the time of the spray drying mentioned later, and there exists a tendency for adhesion of the raw material slurry to the inside of a spray dryer to increase.
- the raw material slurry is preferably acidic.
- the pH of the raw material slurry is preferably 0.01 to 3.0, more preferably 0.1 to 2.0, and particularly preferably 0.5 to 1.5. This is to prevent the colloidal silica from becoming unstable and gelling when the water-soluble compound and the colloidal silica coexist in the raw slurry. Particles with higher mechanical strength can be obtained by preventing gelation of colloidal silica and spray drying while keeping the sol form.
- a) and b) To the slurry obtained by adding zeolite to colloidal silica, an acid such as nitric acid, sulfuric acid, hydrochloric acid, etc. is added to adjust the pH in advance, and then a water-soluble compound is added thereto to add an acidic raw material slurry. How to prepare.
- an acid such as nitric acid, sulfuric acid, hydrochloric acid, etc. is added to adjust the pH in advance, and then a water-soluble compound is added thereto to add an acidic raw material slurry. How to prepare.
- Acids such as nitric acid, sulfuric acid, and hydrochloric acid are added to colloidal silica to adjust pH in advance, then a water-soluble compound is added thereto, and then zeolite is added to prepare an acidic raw material slurry. Method.
- the solid content concentration of the raw material slurry after addition of zeolite, colloidal silica, water-soluble compound, etc. is preferably 5 to 60% by mass, more preferably 15 to 40% by mass.
- water may be appropriately added to the raw slurry.
- the solid content concentration of the raw material slurry is the ratio of the mass of the residue obtained by drying the raw material slurry at 100 ° C. with respect to the total mass of the raw material slurry.
- the temperature at which the raw slurry is prepared is preferably 5 to 95 ° C, more preferably 10 to 70 ° C, and particularly preferably 10 to 40 ° C.
- the stirring power and stirring time at which the raw material components are sufficiently mixed with each other are selected.
- the stirring time is preferably 0.5 to 48 hours, more preferably 1 to 5 hours.
- the raw slurry may contain clay minerals such as kaolin, diatomaceous earth, alumina, titania, zirconia, ceria, etc. for the purpose of adjusting the mechanical strength, bulk density, shape, catalyst performance, etc. of the catalyst particles. These can be added to the raw slurry in the form of powder, solution or sol. Furthermore, a surfactant that adjusts the surface tension of the raw slurry may be added to the raw slurry for the purpose of making the shape of the catalyst particles close to a true sphere.
- clay minerals such as kaolin, diatomaceous earth, alumina, titania, zirconia, ceria, etc.
- Step (ii) is a step of obtaining a dry powder by spray drying the raw slurry obtained in the step (i).
- the spray drying is preferably performed using an industrially used spray dryer (spray dryer).
- the raw material slurry can be sprayed by a rotating disk method, a two-fluid nozzle method, a high-pressure nozzle method, or the like.
- a particularly preferable spraying method is a rotating disk method.
- the spray drying can be performed by spraying the raw slurry together with a fluid such as air heated by steam, an electric heater or the like, or an inert gas such as nitrogen or helium.
- the fluid temperature at the inlet of the spray dryer is preferably 100 to 400 ° C, more preferably 150 to 300 ° C.
- the fluid temperature at the outlet of the spray dryer is preferably 80 to 200 ° C, more preferably 90 to 150 ° C.
- the spray drying conditions such as the number of rotations of the disk in the rotating disk system, the amount of spray gas in the nozzle system, the supply amount of raw material slurry, the supply amount of heated fluid, the ratio of the supply amounts, etc. It can be adjusted as appropriate so that the average particle size of the catalyst particles in the form after firing is less in the range of 20 to 300 ⁇ m.
- Step (iii) is a step of firing the dry powder obtained in the above step (ii) to obtain a fired powder.
- the dried powder can be fired using a muffle furnace, a rotary furnace, a tunnel furnace, a tubular furnace, a fluidized firing furnace, a kiln furnace, or the like.
- An industrially preferred method is a method of firing using a continuous feed rotary kiln furnace.
- the firing temperature is preferably 400 to 1000 ° C., more preferably 500 to 800 ° C., from the viewpoint of improving the strength of the catalyst particles.
- the calcination time is preferably 0.1 to 48 hours, more preferably 0.5 to 24 hours, and further preferably 1 to 10 hours from the viewpoint of the strength of the catalyst particles. Firing of the dry powder is preferably performed in an atmosphere of an inert gas such as air, water vapor, nitrogen, helium, or the like. Moreover, you may carry out under pressure and pressure reduction. The firing may be performed repeatedly and repeatedly.
- an inert gas such as air, water vapor, nitrogen, helium, or the like.
- nitrate, acetate, carbonate, sulfate, and chloride added as raw material components can be removed from the dry powder.
- mechanical strength of the catalyst particles can be dramatically improved by firing the dried powder and sintering the silica.
- the alkali metal component in the calcined powder is removed by bringing the calcined powder obtained in the above step (iii) into contact with a mineral acid and / or (metal) cation-containing aqueous solution, Further, it is an ion exchange process for converting the cation of the zeolite into H + or a desired metal cation.
- the ion exchange method in the ion exchange step may be the same method as the conventional zeolite-containing catalyst.
- (metal) cation such as aqueous solution of mineral acid such as nitric acid, sulfuric acid, hydrochloric acid and / or ammonium nitrate solution at 0.1 to 48 hours at 10 to 95 ° C. for 0.1 to 48 hours.
- the aqueous solution and the fired powder are brought into contact with each other. Thereafter, it is washed with water, dried, and fired again at 500 to 600 ° C. as necessary.
- the method for producing a zeolite-containing catalyst according to the present embodiment preferably includes a step of performing a steaming treatment by bringing the calcined powder or the powder subjected to the ion exchange step into contact with a gas containing steam at 500 to 700 ° C.
- a steaming treatment by bringing the calcined powder or the powder subjected to the ion exchange step into contact with a gas containing steam at 500 to 700 ° C.
- the zeolite-containing catalyst obtained by the steaming treatment the acid property of the zeolite is controlled, and deterioration due to the generation (coking) of the carbonaceous material during the reaction is suppressed.
- the yield of the target substance can be improved.
- the zeolite-containing catalyst according to the present embodiment may be a calcined powder obtained by the calcining step, may be obtained by the ion exchange step, or obtained by the steaming step. It may be a thing.
- spray drying, (iii) calcination step, and (iv) ion exchange step have been described as described above, but when the silica raw material contains water glass, the sodium content of the resulting zeolite-containing catalyst is reduced. From a viewpoint, it is preferable to perform ion exchange before firing the spray-dried powder. When ion exchange is performed after the firing step, sodium contained in the fired body tends to be difficult to remove.
- a fixed bed reaction catalyst is used in a state where an active component such as zeolite is formed into a sphere, granule, columnar shape, ring shape, honeycomb shape or the like of about 1 mm to several mm with a binder such as silica.
- the fixed bed reaction catalyst with high mechanical strength and few alkali contents can be manufactured by changing suitably the manufacturing method of the above-mentioned zeolite containing catalyst.
- High mechanical strength is also important for fixed bed catalysts. That is, when the catalyst is charged into the reactor, or when the catalyst is used for a long-term reaction in the reactor, cracking and powdering due to external stress and thermal history can be suppressed due to the high mechanical strength of the catalyst. .
- the method for producing a zeolite-containing catalyst of the present embodiment it is possible to form strong fluidized bed reaction catalyst particles in which the number of pores inside the particles is extremely small and the packing state of zeolite and silica is uniform and dense.
- the present inventors presume as follows. However, the reason is not limited to this.
- the added water-soluble compound forms a state of being adsorbed on the surface of the colloidal silica silica particles and enters between the particles of the silica particles.
- the silica particles are not closely bonded.
- the vapor inside the particles obtained from the droplets can be quickly moved from between the silica particles to the outside without being confined, and the pressure inside the particles does not increase or negative pressure does not occur.
- a structure in which zeolite and silica are densely and uniformly filled with very few pores on the particle surface and pores inside the particle is formed.
- the method for producing propylene of this embodiment includes a step of bringing the zeolite-containing catalyst into contact with hydrocarbons and / or alcohols in a fluidized bed reactor.
- the hydrocarbon and / or alcohol as the raw material preferably has 2 to 12 carbon atoms.
- the hydrocarbon preferably contains an olefin other than propylene.
- the hydrocarbon and / or alcohol that is a reaction raw material does not necessarily have to be highly pure, and may be of industrial grade.
- the reaction raw material used in the method for producing propylene of the present embodiment preferably contains 20% by mass or more of ethylene, and more preferably contains 25% by mass or more of ethylene. Moreover, it is preferable to supply water to a reactor with the reaction raw material containing ethylene.
- the supply ratio of water is preferably 1 part by mass or more with respect to 100 parts by mass of the ethylene-containing raw material, more preferably 5 to 100 parts by mass, and still more preferably 10 to 80 parts by mass.
- propylene is separated from the reaction product, and at least a part of the remaining low-boiling components including ethylene and / or high-boiling components including butene is supplied to a fluidized bed reactor as a raw material. Supplying and recycling as is an example of a preferable form.
- reaction raw material containing ethylene one obtained by thermal decomposition of ethane, steam cracking, oxidative dehydrogenation reaction, ethanol dehydration reaction, or the like can be used.
- This reaction raw material may contain olefin and paraffin.
- paraffin include methane, ethane, propane, butane, pentane, hexane, heptane, octane, and nonane.
- the olefin include propylene, butene, pentene, hexene, heptene, octene, and nonene.
- ethylene-containing reaction raw materials include cycloparaffins such as cyclopentane, methylcyclopentane, and cyclohexane; cycloolefins such as cyclopentene, methylcyclopentene, and cyclohexene; dienes such as cyclohexadiene, butadiene, pentadiene, and cyclopentadiene. And / or acetylene such as acetylene and methylacetylene.
- cycloparaffins such as cyclopentane, methylcyclopentane, and cyclohexane
- cycloolefins such as cyclopentene, methylcyclopentene, and cyclohexene
- dienes such as cyclohexadiene, butadiene, pentadiene, and cyclopentadiene.
- acetylene such as acetylene and methylacetylene.
- the reaction raw material containing ethylene may further contain oxygen-containing compounds such as t-butyl alcohol, methyl-t-butyl ether, diethyl ether, methyl ethyl ether, dimethyl ether, ethanol, and methanol.
- oxygen-containing compounds such as t-butyl alcohol, methyl-t-butyl ether, diethyl ether, methyl ethyl ether, dimethyl ether, ethanol, and methanol.
- the reaction raw material containing ethylene may further contain water, hydrogen, nitrogen, carbon dioxide, and carbon monoxide.
- ethanol biological ethanol obtained from plant resources
- plant resources such as waste wood, thinned wood, rice straw, and agricultural crops.
- the reaction temperature in the fluidized bed reaction is preferably 300 to 650 ° C., more preferably 400 to 600 ° C.
- the reaction pressure is preferably 0.1 to 30 atm, more preferably 0.5 to 10 atm.
- the feed rate of the reaction raw material is preferably 0.1 to 20 hr ⁇ 1 , more preferably 0.5 to 10 hr ⁇ 1 in terms of weight hourly space velocity (WHSV) based on zeolite-containing catalyst.
- WHSV weight hourly space velocity
- the conversion rate of ethylene can be controlled by using the reaction raw material containing ethylene by adjusting the reaction conditions.
- a carbonaceous compound may be generated on the catalyst, and the catalytic activity may be reduced.
- a part of the zeolite-containing catalyst may be continuously or intermittently extracted from the fluidized bed reactor, and the coke adhering to the catalyst may be burned and removed using a gas containing oxygen.
- the zeolite-containing catalyst is regenerated, and the regenerated zeolite-containing catalyst can be returned to the fluidized bed reactor.
- the regeneration of the catalyst is carried out at a temperature of 400 to 700 ° C. in the air containing oxygen or in an oxygen-containing gas atmosphere.
- the zeolite-containing catalyst of the present embodiment has a low porosity, good fluidity, and high mechanical strength (wear resistance).
- the manufacturing method involves spray drying and firing a specific raw material, and is simple.
- the zeolite-containing catalyst of the present embodiment can be used for the production of propylene and is particularly suitable as a fluidized bed reaction catalyst because of its high mechanical strength.
- the measuring method of various physical properties is as follows. (1) Average particle size and particle size distribution of zeolite-containing catalyst Using a laser diffraction / scattering particle size analyzer (trade name “MT3000”, manufactured by Microtrac), according to the attached manual, The average particle diameter (cumulative average diameter) and particle size distribution were measured. (2) Ratio of pore area of zeolite-containing catalyst First, particles after firing of the zeolite-containing catalyst were embedded in a polyester resin. Next, it was polished to cut out the cross section of the catalyst particles.
- the series of operations was performed on 100 catalyst particles, and the arithmetic average (arithmetic average) was taken as the ratio of the pore area in the cross section of the particles.
- the arithmetic average of the major axis (the longest diameter among the diameters passing through the center of gravity) and the minor axis (the shortest diameter among the diameters passing through the center of gravity) was defined as the particle diameter.
- the amounts of Si and Al contained in the solution are measured by an ordinary method using an ICP (inductively coupled plasma) emission spectrometer (trade name “JY138”, manufactured by Rigaku). From the results, SiO 2 / Al 2 O A 3 ratio (molar ratio) was derived. Measurement conditions are set to high frequency power: 1 kW, plasma gas: 13 L / min, sheath gas: 0.15 L / min, nebulizer gas: 0.25 L / min, Si measurement wavelength: 251.60 nm, Al measurement wavelength: 396.152 nm did.
- ICP inductively coupled plasma
- Wear loss (mass%) A / (BC) ⁇ 100
- A represents the mass (g) of the fine powder of the zeolite-containing catalyst recovered 5 to 20 hours after the start of measurement
- C represents the zeolite-containing catalyst recovered 0 to 5 hours after the start of measurement
- B represents the total mass (g) of the zeolite-containing catalyst subjected to the test.
- Na content of zeolite-containing catalyst The content of Na in the zeolite-containing catalyst after calcination and ion exchange was measured as follows. First, a catalyst was dissolved in aqua regia at 210 ° C. using a microwave (Milestone, model: ETO'S PLUS), and a trace amount of residue was filtered. Subsequently, the amount of Na in the filtrate was measured by an ordinary method using ICP emission analysis, and the Na content in the zeolite-containing catalyst was derived from the result. The measurement conditions were set to high frequency power: 1 kW, plasma gas: 13 L / min, sheath gas: 0.15 L / min, nebulizer gas: 0.25 L / min, and Na measurement wavelength: 589.592 nm.
- the SiO 2 / Al 2 O 3 ratio of the zeolite was 280 in molar ratio.
- zeolite was hydrothermally synthesized in the same manner as in Example 2 of JP-B-61-21985 (JP-A-50-5335).
- the obtained zeolite was sufficiently washed with water, dried at 120 ° C., and then calcined in an electric furnace at 550 ° C. for 3 hours in an air atmosphere. Thereafter, in order to convert the cation type of the calcined zeolite into NH 4 + , ion exchange was performed at 25 ° C.
- the MFI type ZSM-5 measured by the above method had a SiO 2 / Al 2 O 3 ratio (molar ratio) of 280, and the structure type was identified by the above method.
- SiO 2 / Al 2 O 3 ratio molar ratio
- the zeolite was prepared in the same manner as in Example 3 of Japanese Examined Patent Publication No. 2-44771 (JP 59-54620 A) except that a wet cake of homogeneous compound D was prepared so that the 3 ratio was 27 in molar ratio. Hydrothermal synthesis was performed. The obtained zeolite was sufficiently washed with water and dried at 120 ° C. Thereafter, in order to convert the cation type of the zeolite to H + , ion exchange was performed at 25 ° C.
- the MFI type ZSM-5 measured by the above method had a SiO 2 / Al 2 O 3 ratio (molar ratio) of 27, and the structure type was identified by the above method. Since this zeolite had aggregated primary particles, it was pulverized using a jet mill (manufactured by Nippon Pneumatic Kogyo Co., Ltd., model: LJ) so that the average particle size was 3 ⁇ m.
- a wet cake of homogeneous compound D was prepared so that the SiO 2 / Al 2 O 3 ratio of zeolite was 42 in molar ratio.
- Zeolite was hydrothermally synthesized in the same manner as in Example 3 of Japanese Patent No. 44771 (JP 59-54620 A). The obtained zeolite was sufficiently washed with water and dried at 120 ° C. Thereafter, in order to convert the cation type of the zeolite to H + , ion exchange was performed at 25 ° C. for 1 hour using a 1 molar aqueous nitric acid solution, further washed with water, and dried at 120 ° C.
- the MFI type ZSM-5 measured by the above method had a SiO 2 / Al 2 O 3 ratio (molar ratio) of 42, and the structure type was identified by the above method.
- the liquid A was adjusted so that the SiO 2 / Al 2 O 3 ratio of the zeolite was 80 in molar ratio.
- solution B made by Fuji Chemical Co., Ltd., trade name “No. 3 sodium silicate”, SiO 2 29.0 mass
- Na 2 O 9.5 mass% the balance being water.
- zeolite was hydrothermally synthesized in the same manner as in Example 2 of JP-B-61-21985 (JP-A-50-5335).
- the obtained zeolite was sufficiently washed with water, dried at 120 ° C., and then calcined in an electric furnace at 550 ° C. for 3 hours in an air atmosphere. Thereafter, in order to convert the cation type of the calcined zeolite into NH 4 + , ion exchange was performed at 25 ° C. for 1 hour using a 1 molar aqueous ammonium chloride solution, followed by washing with water and drying at 120 ° C.
- the MFI type ZSM-5 measured by the above method had a SiO 2 / Al 2 O 3 ratio (molar ratio) of 80, and the structure type was identified by the above method.
- MFI type ZSM-5 used in Example 3 and Comparative Example 3, a trade name “MFI-1000” manufactured by ZEOLYST was used.
- the MFI type ZSM-5 measured by the above method had a SiO 2 / Al 2 O 3 ratio (molar ratio) of 1000, and the structure type was identified by the above method.
- BEA type beta ( ⁇ type zeolite) used in Example 20
- a trade name “BEA-25” manufactured by PQ Co., Ltd. was used.
- the ⁇ -type zeolite measured by the above method had a SiO 2 / Al 2 O 3 ratio (molar ratio) of 25, and the structure type was identified by the above method.
- For identification of the structure type reference was made to the description in US Pat. No. 3,308,069.
- MFI type ZSM-5 used in Example 22 was hydrothermally synthesized according to Example 4 of Japanese Patent No. 3905948.
- the MFI type ZSM-5 measured by the above method had a SiO 2 / Al 2 O 3 ratio (molar ratio) of 39, and its structure type was identified by the above method.
- Example 1 Colloidal silica (manufactured by Nalco, silica average particle size: 5 nm, silica content: 15% by mass, Na content: 185 ppm) is added to 2000 g of nitric acid (manufactured by Wako Pure Chemical, 60% by mass of nitric acid containing reagent, the same shall apply hereinafter) 40 g. The pH was adjusted to 1.1 by addition. Thereafter, 100 g of ammonium nitrate (manufactured by Wako Pure Chemicals, special grade reagent, solubility in water at 0 ° C .: 118 g / 100 g water, the same applies hereinafter) as a water-soluble compound was added thereto.
- nitric acid manufactured by Wako Pure Chemical, 60% by mass of nitric acid containing reagent, the same shall apply hereinafter
- the pH was adjusted to 1.1 by addition.
- 100 g of ammonium nitrate manufactured by Wak
- raw material mixture preparation step 300 g of MFI type ZSM-5 having a molar ratio of SiO 2 / Al 2 O 3 of 280 as zeolite was added thereto to prepare a raw material slurry (raw material mixture preparation step).
- the obtained raw material slurry was stirred at 25 ° C. for 3 hours.
- the raw material slurry was in the form of a sol, and the viscosity was 5 cP (manufactured by Tokyo Keiki Co., Ltd., measured with a B-type viscometer).
- the raw material slurry was spray-dried with a spray dryer to obtain a dry powder (drying step).
- the fluid temperature at the inlet of the spray dryer was set to 220 ° C.
- the fluid temperature at the outlet of the spray dryer was set to 130 ° C.
- the raw slurry was spray-dried by a rotating disk method.
- the obtained dry powder was baked in an air atmosphere at 700 ° C. for 5 hours using an electric furnace (baking step).
- the obtained fired powder was mixed with a 0.1 molar aqueous nitric acid solution to adjust the solid content concentration to 10% by mass, and an ion exchange treatment was performed at 25 ° C. for 1 hour (ion exchange step). Thereafter, the ion exchanger powder that had undergone the ion exchange step was sufficiently washed with water and dried at 120 ° C.
- the Na content in the form after ion exchange (ion exchanger powder) was measured according to the method described above.
- the content of zeolite, the content of silica, and the content of other components were calculated from the charging ratio (the same applies hereinafter).
- the measured values are shown in Table 1.
- the electron micrograph of a catalyst particle is shown in FIG. 1
- the electron micrograph of a catalyst particle cross section is shown in FIG.
- the fired body had a particle size distribution in which 95% of the total particle volume was in the particle size range of 2 to 0.2 times the average particle size.
- Example 2 A zeolite-containing catalyst was prepared in the same manner as in Example 1, except that the zeolite was replaced with MFI type ZSM-5 having a molar ratio of SiO 2 / Al 2 O 3 of 27. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 1. Moreover, the electron micrograph of a catalyst particle is shown in FIG. 3, and the electron micrograph of a catalyst particle cross section is shown in FIG. Moreover, the electron micrograph of the catalyst particle surface is shown in FIG. Thin cracks were observed on the particle surface, but no irregularities were observed.
- Example 3 A zeolite-containing catalyst was prepared in the same manner as in Example 1 except that the zeolite was replaced with MFI type ZSM-5 having a molar ratio of SiO 2 / Al 2 O 3 of 1000. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 1.
- FIG. 5 shows an electron micrograph of the catalyst particles
- FIG. 6 shows an electron micrograph of the catalyst particle cross section.
- Example 4 A zeolite-containing catalyst was prepared in the same manner as in Example 1 except that the zeolite was replaced with MFI type ZSM-5 in which the molar ratio of SiO 2 / Al 2 O 3 was 42. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 1.
- Example 5 A zeolite-containing catalyst was prepared in the same manner as in Example 1, except that the water-soluble compound was replaced with ammonium acetate (manufactured by Wako Pure Chemicals, special grade reagent, solubility in water at 4 ° C .: 148 g / 100 g water). About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 1.
- Example 6 The colloidal silica was replaced with 795 g of colloidal silica (manufactured by Nalco, wide particle distribution type, silica average particle size: 15 nm, silica content: 38 mass%, Na content: 300 ppm), and the water-soluble compound was ammonium sulfate (manufactured by Wako Pure Chemical).
- Zeolite-containing catalyst was prepared in the same manner as in Example 1 except that the solubility in water at 0 ° C. was changed to 71 g / 100 g water. It should be noted that pure water was appropriately added to the raw slurry so that the solid content concentration of the raw slurry immediately before spray drying was 30% by mass. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 1.
- Example 7 The zeolite was replaced with MFI type ZSM-5 having a SiO 2 / Al 2 O 3 ratio of 80 in molar ratio, and the water-soluble compound was ammonium chloride (manufactured by Wako Pure Chemicals, special grade reagent, solubility in water at 0 ° C .: 29 g / 100 g water)
- a zeolite-containing catalyst was prepared in the same manner as in Example 1 except that 72 g was used. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 1.
- Example 8 A zeolite-containing catalyst was prepared in the same manner as in Example 7 except that 60 g of ammonium carbonate (made by Wako Pure Chemicals, special grade reagent, solubility in water at 15 ° C .: 25 g / 100 g water) was used. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 1.
- Example 9 The colloidal silica is replaced with 1800 g of colloidal silica (manufactured by Nalco, silica average particle size: 5 nm, silica content: 15 mass%, Na content: 185 ppm), and the water-soluble compound is aluminum nitrate nonahydrate (Wako Pure Chemical Industries, Ltd.)
- Zeolite-containing catalyst was prepared in the same manner as in Example 1, except that 221 g (manufactured, special grade reagent, solubility in water at 25 ° C .: 77.5 g / 100 g water) was used. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 2.
- Example 10 A zeolite-containing catalyst was prepared in the same manner as in Example 2 except that 106 g of sodium nitrate (manufactured by Wako Pure Chemicals, special grade reagent, solubility in water at 0 ° C .: 73 g / 100 g water) was used. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 2.
- Example 11 In order to reduce the average particle size of the zeolite-containing catalyst, a zeolite-containing catalyst was prepared in the same manner as in Example 2 except that the number of revolutions of the rotating disk at the time of spray drying the raw slurry was increased in the drying step. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 2. The average particle size of the zeolite-containing catalyst was 21 ⁇ m.
- Example 12 In order to increase the average particle size of the zeolite-containing catalyst, a zeolite-containing catalyst was prepared in the same manner as in Example 2, except that the number of revolutions of the rotating disk when the raw material slurry was spray-dried in the drying step was reduced. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 2. The average particle size of the zeolite-containing catalyst was 87 ⁇ m.
- Example 13 In order to increase the average particle diameter of the zeolite-containing catalyst, zeolite was reduced in the same manner as in Example 2 except that the rotational speed of the rotating disk and the supply amount of the raw slurry were reduced in the drying process. A containing catalyst was prepared. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 2. The average particle size of the zeolite-containing catalyst was 293 ⁇ m.
- Example 14 Zeolite-containing catalyst was prepared in the same manner as in Example 1 except that zeolite was replaced with MFI type ZSM-5 having a SiO 2 / Al 2 O 3 ratio of 80 in molar ratio, and the amount of the water-soluble compound was replaced with 10 g of ammonium nitrate.
- zeolite was replaced with MFI type ZSM-5 having a SiO 2 / Al 2 O 3 ratio of 80 in molar ratio, and the amount of the water-soluble compound was replaced with 10 g of ammonium nitrate.
- the measured values are shown in Table 2.
- Example 15 A zeolite-containing catalyst was prepared in the same manner as in Example 14 except that the amount of the water-soluble compound was changed to 30 g of ammonium nitrate. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 2.
- Example 16 A zeolite-containing catalyst was prepared in the same manner as in Example 14 except that the amount of the water-soluble compound was changed to 1440 g of ammonium nitrate. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 2.
- Example 17 The colloidal silica is replaced with 1235 g of colloidal silica (manufactured by Nalco, silica average particle size: 12 nm, silica content: 34 mass%, Na content: 12 ppm), and the amount of water-soluble compound is replaced with 140 g of ammonium nitrate, which is zeolite.
- a zeolite-containing catalyst was prepared in the same manner as in Example 2 except that the amount of MFI type ZSM-5 having a SiO 2 / Al 2 O 3 ratio of 27 in molar ratio was changed to 180 g. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 3.
- Example 18 60 g of nitric acid was added to 3800 g of colloidal silica (manufactured by Nalco, silica average particle size: 5 nm, silica content: 15 mass%, Na content: 185 ppm) to adjust the pH to 1.5. Thereafter, 188 g of ammonium nitrate, which is a water-soluble compound, was added thereto. Next, 30 g of MFI type ZSM-5 having a molar ratio of SiO 2 / Al 2 O 3 of 80 zeolite was added thereto to prepare a raw slurry. A zeolite-containing catalyst was prepared in the same manner as in Example 1 except for this step. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 3.
- Example 19 The colloidal silica was replaced with 1200 g of colloidal silica (manufactured by Nalco, silica average particle size: 5 nm, silica content: 15 mass%, Na content: 185 ppm), the amount of nitric acid added was changed to 24 g, and the amount of water-soluble compound was replaced with 60 g of ammonium nitrate and the zeolite-containing catalyst was prepared in the same manner as in Example 18 except that the amount of MFI type ZSM-5 having a molar ratio of SiO 2 / Al 2 O 3 of 80 was changed to 420 g. Prepared. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 3.
- Example 20 In the step of preparing the raw material mixture, 56 g of nitric acid was added to 2800 g of colloidal silica (manufactured by Nalco, silica average particle size: 5 nm, silica content: 15 mass%, Na content: 185 ppm) to adjust the pH to 0.9. . Thereafter, 140 g of ammonium nitrate as a water-soluble compound was added thereto, and then 180 g of zeolite ⁇ having a molar ratio of SiO 2 / Al 2 O 3 of 25 was added to prepare a raw material slurry. A zeolite-containing catalyst was prepared in the same manner as in Example 1 except for this step. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 3.
- Example 21 MFI in which the SiO 2 / Al 2 O 3 ratio of zeolite is 42 in molar ratio to 2000 g of colloidal silica (manufactured by Nalco, silica average particle size: 5 nm, silica content: 15 mass%, Na content: 185 ppm) 300 g of type ZSM-5 was added, and 40 g of nitric acid was added thereto to adjust the pH to 1.2. Thereafter, 100 g of ammonium nitrate, which is a water-soluble compound, was added thereto to obtain a raw material slurry (preparation step of raw material mixture). Thereafter, a zeolite-containing catalyst was prepared in the same manner as in Example 1. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 3.
- Example 22 According to Example 4 of Japanese Patent No. 3905948, MFI-type ZSM-5 zeolite (SiO 2 / Al 2 O 3 ratio was 39 in molar ratio) was hydrothermally synthesized. This zeolite slurry was washed with water using a rotary filter until the pH reached 9 in the slurry state. Further, ion exchange was performed with a 1 molar aqueous sulfuric acid solution at 25 ° C. for 1 hour, and the mixture was washed with water until the pH reached 4. Thus, a slurry containing 29 mass% H + type MFI type ZSM-5 zeolite was obtained.
- a zeolite-containing catalyst was prepared in the same manner as in Example 1 except that 1034 g of this slurry (containing 300 g of zeolite) was used as a raw material zeolite and ammonium nitrate, which is a water-soluble compound, was replaced with 60 g. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 3.
- Example 23 Colloidal silica (manufactured by Nalco, silica average particle diameter: 5 nm, silica content: 15% by mass, Na content: 185 ppm) was added to 98 g of nitric acid and the pH was adjusted to 0.3. Some ammonium nitrate 75g was added thereto. Next, 300 g of water glass (made by Fuji Chemical Co., Ltd., trade name “Special No. 3 sodium silicate”, SiO 2 25.0 mass%, Na 2 O 9.0 mass%, the balance is water, the same applies hereinafter) 200 g of pure water The aqueous solution diluted with was added thereto.
- silica sol 75% by mass of the silica component was made from colloidal silica, and 25% by mass was made from water glass.
- 300 g of MFI type ZSM-5 having a molar ratio of SiO 2 / Al 2 O 3 of 27 of zeolite was added to prepare a raw slurry.
- the pH of the raw slurry was 1.1.
- This raw slurry was spray dried in the same manner as in Example 1.
- the obtained dry powder was washed with water while stirring with 10 L of pure water at 60 to 85 ° C. for 1 hour. This was repeated twice.
- the solid content concentration was adjusted to 10% by mass with a 1 molar aqueous nitric acid solution, and ion exchange treatment was performed at 60 to 85 ° C.
- Example 24 MFI-type ZSM-5 in which ammonium phosphate was supported on MFI-type ZSM-5 (SiO 2 / Al 2 O 3 ratio was 27 in molar ratio) used in Example 2 was prepared as follows. First, 72.2 g of ammonium phosphate (manufactured by Wako Pure Chemicals, special grade reagent) was dissolved in 1 L of pure water, and 500 g of the zeolite was added to the solution. Water was distilled off from the obtained slurry under reduced pressure at 60 ° C. over about 1 hour by an evaporator, and the remaining solid was recovered, dried, and then fired at 500 ° C. for 1 hour.
- ammonium phosphate manufactured by Wako Pure Chemicals, special grade reagent
- a zeolite-containing catalyst was prepared in the same manner as in Example 2, except that 300 g of MFI-type ZSM-5 carrying the phosphorus component was replaced by 150 g of ammonium nitrate, which is a water-soluble compound. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 3.
- Example 25 160 g of nitric acid was added to 1200 g of colloidal silica (manufactured by Nalco, silica average particle size: 5 nm, silica content: 15 mass%, Na content: 185 ppm), and the pH was adjusted to 0.1. Some 59 g of ammonium nitrate was added. Next, an aqueous solution obtained by diluting 480 g of water glass (manufactured by Fuji Chemical Co., Ltd., trade name “Special No. 3 sodium silicate”) with 400 g of pure water was added thereto. In this silica sol, 60% by mass of the silica component was made from colloidal silica, and 40% by mass was made from water glass.
- Example 26 In the same manner as in Example 2, 500 kg of zeolite-containing catalyst was produced. This catalyst was packed in a transparent vinyl chloride fluidized bed reactor cold model apparatus (inner diameter 60 cm, height 5 m) provided with a cyclone portion. Subsequently, 700 m 3 / hr of air is supplied from the lower part of the apparatus by a blower, and the catalyst is allowed to flow for 1000 hours while flowing the catalyst under the condition of an industrial fluidized bed reaction operating condition level of gas linear velocity of 70 cm / sec (empty standard). Drove.
- the catalyst wear loss after operation for 1000 hours is 0.20% by mass, the average particle size is 58 ⁇ m, and the catalyst is almost free from powdering, cracking and chipping, and is stable under industrial fluidized bed reaction operating conditions. Was able to continue.
- An electron micrograph of the catalyst after 1000 hours of operation is shown in FIG.
- Example 27 The zeolite-containing catalyst obtained in Example 2 was steamed under the conditions of 650 ° C., 24 hours, water vapor partial pressure of 0.8 atm, and nitrogen gas partial pressure of 0.2 atm. 22.9 g of the catalyst was charged into a stainless steel fluidized bed reactor having an inner diameter of 1 inch. Thereafter, 9.9 g / hr of ethylene, 0.7 g / hr of hydrogen, 4.9 g / hr of water, and 5.3 g / hr of nitrogen were passed through the reactor at the flow rates, the reaction temperature was 550 ° C., and the reaction pressure was 0.14 MPa.
- the fluidized bed reaction was carried out for 100 hours under the conditions of WHSV 0.43 hr ⁇ 1 (based on zeolite-containing catalyst). During the reaction, no catalyst pulverization was observed.
- the analysis of the reaction product was performed by gas chromatography (manufactured by Shimadzu Corporation, GC-17A, TCD-FID series connection type) directly connected to the reactor. The transition of the ethylene conversion rate in each reaction time is shown in FIG. The propylene yield at an ethylene conversion rate of 70% was 24.5% by mass.
- Example 28 In order to remove excess phosphorus component from the zeolite-containing catalyst obtained in Example 24, the catalyst was washed with water at 25 ° C. for 1 hour. Steaming treatment was performed on the zeolite-containing catalyst after water washing under the same conditions as in Example 27. A fluidized bed reaction was conducted in the same manner as in Example 27 using 22.9 g of the catalyst. The transition of the ethylene conversion rate in each reaction time is shown in FIG. The propylene yield at an ethylene conversion rate of 70% was 25.5% by mass.
- Example 29 Except for not performing ion exchange, the calcined zeolite-containing catalyst obtained in the same manner as in Example 17 was 560 ° C., 12 hours, 0.8 atm water vapor partial pressure, 0.2 atm nitrogen gas content. Steaming treatment was performed under pressure conditions. A fluidized bed reaction was conducted in the same manner as in Example 27 using 22.9 g of the catalyst. The ethylene conversion rate in each reaction time is shown in FIG. The propylene yield at an ethylene conversion rate of 70% was 23.0% by mass.
- Example 30 The zeolite-containing catalyst obtained in Example 25 was steamed under the same conditions as in Example 27. A fluidized bed reaction was conducted in the same manner as in Example 27 using 22.9 g of the catalyst. The ethylene conversion rate in each reaction time is shown in FIG. The propylene yield at an ethylene conversion rate of 70% was 24.0% by mass.
- Example 31 The zeolite-containing catalyst obtained in Example 17 was steamed under the same conditions as in Example 27. A fluidized bed reaction was conducted in the same manner as in Example 27 using 22.9 g of the catalyst. The ethylene conversion rate in each reaction time is shown in FIG. The propylene yield at an ethylene conversion rate of 70% was 24.2% by mass.
- Example 1 A zeolite-containing catalyst was prepared in the same manner as in Example 1 except that ammonium nitrate was not added to the raw slurry. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 4.
- FIG. 10 shows an electron micrograph of the catalyst particles
- FIG. 11 shows an electron micrograph of the catalyst particle cross section.
- Example 2 A zeolite-containing catalyst was prepared in the same manner as in Example 2 except that ammonium nitrate was not added to the raw slurry. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 4. Moreover, the electron micrograph of a catalyst particle is shown in FIG. 12, and the electron micrograph of a catalyst particle cross section is shown in FIG.
- Example 3 A zeolite-containing catalyst was prepared in the same manner as in Example 3 except that ammonium nitrate was not added to the raw slurry. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 4. Moreover, the electron micrograph of a catalyst particle is shown in FIG. 14, and the electron micrograph of a catalyst particle cross section is shown in FIG.
- Example 4 A zeolite-containing catalyst was prepared in the same manner as in Example 1 except that the amount of ammonium nitrate added in the raw material slurry preparation step was changed to 1.5 g. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 4.
- Example 5 A zeolite-containing catalyst was prepared in the same manner as in Example 1, except that the amount of ammonium nitrate added in the raw slurry preparation process was changed to 1800 g. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 4.
- a zeolite-containing catalyst was prepared in the same manner as in Example 2 except that the number of revolutions of the rotating disk at the time of spray drying the raw slurry was increased in the drying step.
- the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 4.
- the average particle size of the zeolite-containing catalyst was 12 ⁇ m.
- Example 7 In order to increase the average particle diameter of the zeolite-containing catalyst, zeolite was reduced in the same manner as in Example 2 except that the rotational speed of the rotating disk and the supply amount of the raw slurry were reduced in the drying process. A containing catalyst was prepared. About the zeolite containing catalyst obtained in this way, the said various physical property in the form after the calcination and ion exchange was measured. The measured values are shown in Table 4. The average particle size of the zeolite-containing catalyst was 386 ⁇ m.
- a catalyst was prepared according to Example 1 of JP-A-10-146529. First, an ultrastable type Y zeolite (manufactured by Tosoh Corporation) in the amount described in Example 1, gibbsite (aluminum hydroxide, Alcoa) having a particle size of 1 to 2 ⁇ m, Georgia kaolin, and LUDOX silica sol (manufactured by DuPont). , HS-40, SiO 2 content: 40 mass%) and pure water mixture slurry was prepared.
- gibbsite aluminum hydroxide, Alcoa
- LUDOX silica sol manufactured by DuPont
- Example 1 An aqueous solution of sulfuric acid (manufactured by Wako Pure Chemicals, special grade reagent) and aluminum sulfate 15 hydrate (manufactured by Wako Pure Chemicals, special grade reagent, the same shall apply hereinafter) in the amount described in Example 1 was prepared.
- sodium silicate in the amount described in Example 1 separately prepared manufactured (manufactured by PQ Corp, “N” brand, SiO 2 content: 28.8% by mass, Na 2 O content: 8.9% by mass)
- Aqueous solution was added.
- an aqueous solution of aluminum sulfate 15 hydrate in the amount described in Example 1 was added thereto.
- Example 9 In order to compare with the reaction performance of the zeolite-containing catalyst obtained in Example 17 (Example 31), the active ingredient zeolite was SiO 2 / Al 2 O 3 used in Example 17 at a molar ratio of 27.
- a zeolite-containing catalyst was prepared in the same manner as in Comparative Example 8 except that the MFI type ZSM-5 was changed.
- the zeolite-containing catalyst thus obtained was steamed in the same manner as in Example 27.
- a fluidized bed reaction was conducted in the same manner as in Example 27 using 22.9 g of the catalyst. The transition of the ethylene conversion rate in each reaction time is shown in FIG. For reference, a part of the dry powder was collected and the sodium content before ion exchange was measured and found to be 5.36% by mass.
- the zeolite-containing catalyst of the present invention has a dense structure with a small pore area in the particle cross section and excellent mechanical strength. It was.
- the particle shape was spherical with a smooth surface, and the angle of repose, which is an index of fluidity measured by the above method, was in the range of 25 to 30 °. This means that it exhibits the best fluidity as described in page 42 of a fluidized bed handbook (edited by Japan Powder Industry Technology Association, Baifukan, published on March 25, 1999). From these facts, the zeolite-containing catalyst of the present invention has an excellent shape, fluidity and strength as a fluidized bed reaction catalyst.
- Example 29 the zeolite-containing catalyst prepared using colloidal silica as in Example 17 showed sufficiently high activity only by calcination without ion exchange because the Na in the catalyst composition was extremely small. This leads to simplification of the catalyst production process and is extremely useful for industrial practical use.
- the zeolite-containing catalysts of Comparative Examples including known ones have a large number of pores inside the particles.
- the repose strength was inferior, and the angle of repose was extremely large as in Comparative Example 6 and the fluidity was poor.
- the zeolite-containing catalyst prepared using a silica sol containing a large amount of water glass has insufficient sodium removal even by ion exchange, and it has been difficult to obtain a highly active catalyst (Comparative Example 9).
- the zeolite-containing catalyst of the present invention has suitable physical properties as a catalyst for a fluidized bed reaction, it is suitable as a catalyst for producing propylene from a hydrocarbon reaction raw material containing ethylene or the like by a fluidized bed reaction. Can be used.
Abstract
Description
一方、本発明者らが特許文献1及び2に記載の触媒調製方法を追試したところ、それらの文献に記載の方法によって得られたいずれの触媒も、表面には顕著な凹凸があり、しかも滑らかな球状とは程遠い形状を有するものであることが認められた。
[1]ゼオライトとシリカとを含有する粒子である触媒であって、20~300μmの平均粒子径を有し、前記粒子の断面における空孔面積の割合が前記粒子の断面積に対して30%以下であるゼオライト含有触媒。
[2]前記ゼオライトがMFI型ゼオライトである、[1]に記載のゼオライト含有触媒。
[3]前記ゼオライトの含有率が10~90質量%であり、前記シリカの含有率が10~90質量%であり、かつ前記ゼオライトと前記シリカとの合計の含有率が50質量%以上である、[1]又は[2]に記載のゼオライト含有触媒。
[4]ゼオライトとコロイダルシリカとを含有する原料混合物を噴霧乾燥して乾燥粉体を得る工程と、前記乾燥粉体を焼成する工程とを有する、[1]~[3]のいずれか1つに記載のゼオライト含有触媒を製造する方法であって、前記原料混合物が、硝酸塩、酢酸塩、炭酸塩、硫酸塩及び塩化物よりなる群から選ばれる少なくとも1種の水溶性化合物を、前記コロイダルシリカに含まれるシリカに対して0.01~5.0の質量比で含有するゼオライト含有触媒の製造方法。
[5]前記原料混合物に含まれるシリカの全量に対して、前記コロイダルシリカの割合が50質量%以上である、[4]に記載のゼオライト含有触媒の製造方法。
[6]前記原料混合物が酸性である、[4]又は[5]に記載のゼオライト含有触媒の製造方法。
[7]前記水溶性化合物が硝酸アンモニウム、酢酸アンモニウム、炭酸アンモニウム、硫酸アンモニウム及び塩化アンモニウムよりなる群から選ばれる少なくとも1種である、[4]~[6]のいずれか1つに記載のゼオライト含有触媒の製造方法。
[8][1]~[3]のいずれか1つに記載のゼオライト含有触媒を流動層反応器内で炭化水素及び/又はアルコールと接触させる工程を含む、プロピレンの製造方法。
なお、本明細書中で「シリカ」とは、ゼオライト含有触媒の製造に用いられるシリカ原料に含まれるシリカを指し、特に断りのある場合を除き、ゼオライトを構成するシリカを意味しない。
本実施形態のゼオライト含有触媒は、ゼオライトとシリカとを含有する粒子の触媒であって、20~300μmの平均粒子径を有し、粒子の断面における空孔面積の割合が粒子の断面積に対して30%以下である。
中間細孔径を有するゼオライトの中でも、MFI型構造を有するゼオライト(MFI型ゼオライト;特にZSM-5)は、耐熱性が高く、形状選択性や強い固体酸性により特徴的な触媒活性を有するため、特に好ましい。
特に、本実施形態のゼオライト含有触媒を、エチレンを含有する炭化水素と接触させてプロピレンを製造する際の流動層反応触媒として用いる場合、そのゼオライト含有触媒は、周期律表第IB族に属する金属、すなわち、銅、銀及び金よりなる群から選ばれる少なくとも1種の金属を含有することが好ましい。ゼオライト含有触媒に含有される金属は、より好ましくは銅及び/又は銀であり、特に好ましくは銀である。なお、本明細書において、「周期律表」とは、CRC Handbook of Chemistry and Physics, 75th edition David R. Lideら著、CRC Press Inc.発行(1994-1995年)、1-15頁に記載の周期律表を示すものとする。
ゼオライト含有触媒に含有される上記金属は、対応する陽イオンの状態で触媒中のゼオライトに含まれるか、又は、触媒に担持される。
また、リン化合物で修飾したゼオライトを用いることも好ましい。リン化合物としては、リン酸、亜リン酸、次亜リン酸、ピロリン酸、ポリリン酸、リン酸一水素アンモニウム、リン酸二水素アンモニウム、リン酸アンモニウム、リン酸アルミニウムが挙げられる。これらのリン化合物をゼオライトに対してリン元素として0.1~5質量%程度、吸着又は含浸して得られるものを用いることができる。
また、流動性の観点から、本実施形態のゼオライト含有触媒は、全体の80%以上の粒子の粒子径が平均粒子径の2倍~0.2倍の粒子径範囲に入るような粒度分布を有するものが好ましい。
すなわち、まず、ゼオライト含有触媒の粒子を樹脂に包埋し、それを研磨することにより触媒粒子の断面を削り出す。その断面を、画像解析装置を付設した電子顕微鏡により観察し、800~2000倍の倍率で、粒子1個の断面積とその粒子の断面における空孔部の面積とを画像解析装置により測定する。ここで、上述の従来例のように空洞を有する触媒の場合、「断面積」は空孔部分の面積を含む値とする。また空洞が破裂したような形状の場合、“破裂”により円周の一部が切れた部分(開口部)の両端を、開口部を塞ぐようにして直線で結び、その直線と粒子の外周によって囲まれた範囲の面積を断面積とする。例えば図11に示す触媒の場合、実体部分はC字型であるが、その開口部分を結ぶ直線とC字型の実体部分とによって囲まれる範囲全体の面積を断面積とする(図の中央付近に黒く観察されている開口部分の面積も断面積に含まれる)。この例における空孔部の面積は、開口部分を結ぶ直線と、C字型の実体部分の内壁とによって囲まれる部分の面積とする。
次いで粒子の断面積に対する空孔部の面積の割合を計算する。そして、その一連の操作を100個の粒子に対して行い、算術平均(相加平均)したものを粒子の断面における空孔面積の割合とする。ただし、粒子の中心付近の断面を測定するために、測定対象の100個の粒子として、いずれもその直径が平均粒子径の±10%の範囲にある粒子を選択する。
この空孔面積の割合が30%を越えると、粒子の機械的強度が弱くなる傾向がある。
(II)シリカの含有率が10質量%未満の場合、上記と同様の理由で、触媒粒子の機械的強度が低下する傾向がある。シリカの含有率が90質量%を越える場合も、上記と同様の理由で、触媒の単位量当たりの活性が低くなり、所望の活性を得るには触媒の必要量が多くなる傾向がある。
(III)ゼオライトとシリカとの合計の含有率が50質量%未満の場合も、上記と同様の理由で所望の活性を得るには触媒の必要量が多くなる傾向があり、また、触媒粒子の機械的強度が低下する傾向がある。
本実施形態のゼオライト含有触媒の製造方法は、20~300μmの平均粒子径を有し、粒子の断面における空孔面積の割合が粒子の断面積に対して30%以下であるゼオライト含有触媒を得る方法であり、そのようなゼオライト含有触媒を得るために、以下に詳述するよう各種の条件を調整すればよい。本実施形態のゼオライト含有触媒の製造方法は、好ましくは、(ii)ゼオライトとコロイダルシリカとを含有する原料混合物を噴霧乾燥して乾燥粉体を得る工程と、(iii)前記乾燥粉体を焼成する工程とを有する。そのゼオライト含有触媒の製造方法は、上記工程(ii)に先だって、(i)ゼオライトとコロイダルシリカとを含有する前記原料混合物を調製する工程、及び/又は、(iii)の工程の後に、(iv)焼成して得られた焼成粉末をイオン交換する工程を有していてもよい。
工程(i)は、好ましくは、ゼオライトと、コロイダルシリカと、硝酸塩、酢酸塩、炭酸塩、硫酸塩及び塩化物よりなる群から選ばれる少なくとも1種の水溶性化合物とを含む原料混合物(以下、「原料スラリー」ともいう。)を調製する工程である。
一般に流動層触媒の製造原料には、水ガラス(ケイ酸ナトリウム)が多く用いられる。しかし、本発明者らが検討したところ、水ガラスをバインダーシリカの主成分として用いた場合、触媒の粒子表面の形状が悪化する傾向があるばかりか、触媒性能の点でも問題があることが判明した。つまり、バインダーシリカの原料にケイ酸ナトリウムを用いると、固体酸触媒にとって触媒毒であるナトリウムが、触媒中に多量に含まれることになる。バインダーに含まれるナトリウムの濃度を低減することは可能ではあるものの、触媒反応に悪影響を与えない低濃度にまで触媒からナトリウムを除去するには、複数回の熱水洗浄、粒子の破壊を防ぐために特別の装置を用いるイオン交換といった、極めて煩雑な操作が必要である。
ゼオライト含有触媒に含まれるシリカ(ゼオライトを構成するシリカを除く。)の全量に対するコロイダルシリカを原料として得られる(コロイダルシリカに由来する)シリカの割合は多い程好ましく、具体的には、好ましくは50質量%以上であり、より好ましくは60質量%以上であり、更に好ましくは70質量%以上であり、なおも更に好ましくは80質量%以上であり、特に好ましくは90質量%以上である。
同様に、原料混合物に含まれるシリカ(ゼオライトを構成するシリカを除く。)の全量に対して、コロイダルシリカの割合は、好ましくは50質量%以上であり、更に好ましくは60質量%以上であり、なおも更に好ましくは70質量%以上であり、特に好ましくは80質量%以上であり、極めて好ましくは90質量%以上である。なお、原料混合物に含まれるシリカの全量に対するコロイダルシリカの割合は、例えば、原料混合物に含まれるシリカ源が水ガラス及びコロイダルシリカである場合、質量基準で
(コロイダルシリカが含有するシリカ)/(コロイダルシリカが含有するシリカ+水ガラスが含有するシリカ)
を意味する。原料混合物に含まれるコロイダルシリカの割合が高いほど、得られる触媒の表面が滑らかになる傾向があり、特に70質量%以上であると、1600倍以上で観察しても、表面に突起や陥没を有する粒子が少ない(40%以下)。なお「突起や陥没」は、表面に局所的な凹凸が生じた状態を示すもので、表面に線状の「ひび」が入った状態とは異なる。
ここでいう「塩」とは、化学大事典1巻縮小版39刷(共立出版株式会社 2006年6月15日)第1014頁に記載のように、酸と塩基との中和反応によって生じる化合物で、酸の陰性成分と塩基の陽性成分とからなるものである。
また、「水溶性化合物」とは、25℃において100gの水に対して1g以上の溶解度を有する化合物であることを意味する。この水溶性化合物は、好ましくは、25℃において100gの水に対して10g以上の溶解度を有する化合物であり、例えば、アンモニウム塩、アルミニウム塩、ナトリウム塩が挙げられる。
a)コロイダルシリカにゼオライトを添加して得られるスラリーに、硝酸、硫酸、塩酸などの酸を添加してpHを予め酸性に調整した後、そこに水溶性化合物を添加して、酸性の原料スラリーを調製する方法。
b)コロイダルシリカに硝酸、硫酸、塩酸などの酸を添加してpHを予め酸性に調整した後、そこに水溶性化合物を添加して、その後にゼオライトを添加して酸性の原料スラリーを調製する方法。
工程(ii)は、上記工程(i)で得られた原料スラリーを噴霧乾燥して、乾燥粉体を得る工程である。噴霧乾燥は工業的に用いられる噴霧乾燥機(スプレードライヤー)を用いて行うことが好ましい方法である。原料スラリーの噴霧方法は、回転円盤方式、二流体ノズル方式又は高圧ノズル方式等により行うことができる。これらの中で特に好ましい噴霧方法は、回転円盤方式である。噴霧乾燥は、スチーム、電気ヒーター等によって加熱された空気、又は窒素、ヘリウム等の不活性ガスなどの流体と共に原料スラリーを噴霧することにより行うことができる。
工程(iii)は、上記工程(ii)で得られた乾燥粉体を焼成して、焼成粉末を得る工程である。乾燥粉体の焼成は、マッフル炉、回転炉、トンネル炉、管状炉、流動焼成炉、キルン炉等を用いて行うことができる。工業的に好ましい方法は、連続供給式ロータリーキルン炉を用いて焼成する方法である。焼成温度は、触媒粒子の強度を向上させる観点から、好ましくは400~1000℃、より好ましくは500~800℃である。焼成時間も、触媒粒子の強度の観点から、好ましくは0.1~48時間、より好ましくは0.5~24時間、更に好ましくは1~10時間である。乾燥粉体の焼成は、空気、水蒸気、あるいは、窒素、ヘリウム等の不活性ガス雰囲気下で行われることが好ましい。また、加圧下、減圧下で行われてもよい。焼成は繰り返し反復して行われてもよい。
工程(iv)は、上記工程(iii)で得られた焼成粉末を、好ましくは鉱酸及び/又は(金属)陽イオン含有水溶液と接触させることにより、焼成粉末中のアルカリ金属成分を除去し、また、ゼオライトのカチオンをH+や所望の金属陽イオンに変換するイオン交換工程である。
イオン交換工程におけるイオン交換方法は、従来のゼオライト含有触媒と同様の方法であってもよい。イオン交換方法として、例えば、10~95℃において、0.1~48時間、0.1~3モル濃度の硝酸、硫酸、塩酸等の鉱酸水溶液及び/又は硝酸アンモニウム水溶液等の(金属)陽イオン含有水溶液と焼成粉末とを接触させる。その後、水洗、乾燥し、必要に応じて再度500~600℃で焼成する。
また、(ii)噴霧乾燥、(iii)焼成工程及び(iv)イオン交換工程を上述のとおり説明したが、シリカ原料が水ガラスを含有する場合、得られるゼオライト含有触媒のナトリウム含有量を低減する観点で、噴霧乾燥粉末を焼成する前に、イオン交換するのが好ましい。焼成工程の後でイオン交換する場合、焼成体に含まれるナトリウムを除去し難くなる傾向にある。
過程1)噴霧した液滴表面から液体が気化することで、液滴の収縮が始まり、液滴表面が主にシリカ粒子同士の結合により固化及び収縮する。
過程2)その後も、液滴内部での液体の気化が続くが、液滴表面の固化により、発生した気体が液滴内部に閉じ込められ、それにより液滴の内部圧が上昇する。その結果、内部から気体が噴出して、液滴から得られる粒子の破壊(割れ、欠け)や粒子表面の開孔、陥没が生じる。
過程3)噴霧乾燥の後、温度が低下した時点で、粒子内部が負圧になることでも粒子の表面が陥没する。このような過程を経て、得られた粒子はその内部に空孔部の多い脆弱な粒子となる。
本実施形態のプロピレンの製造方法は、上記ゼオライト含有触媒を流動層反応器内で炭化水素及び/又はアルコールと接触させる工程を含む。プロピレンを高収率で製造する観点から、原料である炭化水素及び/又はアルコールの炭素数は2~12の範囲にあることが好ましい。同様の観点から、炭化水素がプロピレン以外のオレフィンを含有することが好ましい。
各種物性の測定方法は下記の通りである。
(1)ゼオライト含有触媒の平均粒子径及び粒度分布
レーザー回折・散乱式粒度分析計(Microtrac社製、商品名「MT3000」)を用い、付属のマニュアルに従い、ゼオライト含有触媒の焼成後の形態での平均粒子径(累積平均径)及び粒度分布を測定した。
(2)ゼオライト含有触媒の空孔面積の割合
まず、ゼオライト含有触媒の焼成後の粒子をポリエステル樹脂に包埋した。次いで、それを研磨し触媒粒子の断面を削り出した。次に、画像処理システム(旭化成工業製、高精細画像解析ファイリングシステム、商品名「IP-1000」)を付設した電子顕微鏡(SEM、株式会社日立製作所製、商品名「S-800」)を用いて、削り出した触媒粒子の断面を観察した。この際、触媒の粒子の平均粒子径に対して直径が±10%の範囲にある粒子を選択した。選択した粒子について、800~2000倍の倍率で観察した粒子1個の断面積とその粒子の断面における空孔部の面積とを画像解析装置により測定した。次に、測定した粒子の断面積に対する空孔部の面積の割合を計算した。その一連の操作を100個の触媒の粒子について行い、算術平均(相加平均)したものを粒子の断面における空孔面積の割合とした。
やや楕円の粒子や形が歪な粒子については、その長径(重心を通る径のうち最も長い径)と短径(重心を通る径のうち最も短い径)の算術平均を粒子直径とした。また、破裂したような粒子形状であり、その断面が円周の一部が切れたような形状(C字形状)で観察された粒子については、円周の一部が切れた部分(開口部)の両端を開口部を塞ぐようにして直線で結び、その直線が粒子の外周の一部であると仮定して、粒子断面積と空孔部の面積を求めた。
粉末回折X線装置(Rigaku製、商品名「RINT」)を用いて、ゼオライトのX線回折パターンを測定し、公知のゼオライトの回折パターンを参照することで構造タイプを同定した。測定条件は、Cu陰極、管球電圧:40kV、管球電流:30mA、スキャンスピード:1deg/minに設定した。
(4)ゼオライトのSiO2/Al2O3比(モル比)
ゼオライトを水酸化ナトリウム溶液に完全に溶解した溶解液を準備した。その溶解液中に含まれるSi及びAlの量をICP(誘導結合プラズマ)発光分析装置(Rigaku製、商品名「JY138」)を用いて常法により測定し、その結果からSiO2/Al2O3比(モル比)を導出した。測定条件は、高周波パワー:1kw、プラズマガス:13L/min、シースガス:0.15L/min、ネブライザーガス:0.25L/min、Si測定波長:251.60nm、Al測定波長:396.152nmに設定した。
ゼオライト含有触媒の粒子の機械的強度の指標である摩耗損失を、噴流式流動装置を用いて測定した。噴流式流動装置として、ガス導入口に0.4mm孔三個を有するオリフィスを設置した、内径35mm、長さ700mmの粉体上昇部と、内径110mm、長さ600mmの粉体分離部と、微粉末捕集部とを備えるものを用いた。室温で水分2.5gを含むゼオライト含有触媒52.5gを噴流式流動装置内に投入後、蒸気圧相当量の水分を含む空気を5.8NL/分でガス導入口から流通し、測定開始後0~5時間及び5~20時間に微粉末捕集部に回収されたゼオライト含有触媒の微粉末の質量を測定した。そして、下式に従って、摩耗損失を求めた。
摩耗損失(質量%)=A/(B-C)×100
ここで、上記式中、Aは測定開始後5~20時間に回収されたゼオライト含有触媒の微粉末の質量(g)を示し、Cは測定開始後0~5時間に回収されたゼオライト含有触媒の微粉末の質量(g)を示し、Bは試験に供したゼオライト含有触媒の全質量(g)を示す。
ゼオライト含有触媒の流動性の指標である安息角は、円筒回転法安息角測定器(筒井理化学器械社製)を用いて測定した。500ccのガラス製試料容器(円筒形測定瓶)にゼオライト含有触媒を250cc充填し、それを測定器のローラー部上に円筒形測定瓶の側面とローラーとが接するように、かつ円筒形測定瓶の中心軸が水平になるように置いた。次いで、ローラー部を2.4rpmで回転させて円筒形測定瓶の中心軸を中心に回転させながら、円筒形測定瓶内部の粉体層の表面が水平面となす角度を測定した。
(7)ゼオライト含有触媒のNa含有量
焼成後及びイオン交換後のゼオライト含有触媒中のNaの含有量は、下記のようにして測定した。まず、マイクロウエーブ(マイルストーン社製、型式:ETOS PLUS)を用いて、210℃で王水に触媒を溶解させ、微量の残分をろ過した。次いで、そのろ液中のNa量をICP発光分析法を用いて常法により測定し、その結果からゼオライト含有触媒中のNa含有量を導出した。測定条件は、高周波パワー:1kw、プラズマガス:13L/min、シースガス:0.15L/min、ネブライザーガス:0.25L/min、Na測定波長:589.592nmに設定した。
エチレン転化率、並びに、プロピレン収率は下記式によって導出した。
(a)エチレン転化率=(反応器入口の供給流中のエチレン濃度-反応器出口の供給流中のエチレン濃度)/反応器入口の供給流中のエチレン濃度×100
(b)プロピレン収率=反応により生成したプロピレン質量/反応器に供給したエチレン質量×100
実施例1、5、6、9及び比較例1、4、5に用いたMFI型ZSM-5に関しては、まず、ゼオライトのSiO2/Al2O3比がモル比で280になるように、A液に含まれる硫酸アルミニウム・x水和物(和光純薬製、特級試薬)の量と、B液に含まれる水ガラス(富士化学社製、商品名「3号珪酸ソーダ」、SiO229.0質量%、Na2O9.5質量%、残分は水)の量とを決定した。次いで、その量のA液とB液との混合をホモジナイザーを用いて5000回転/分で30分間行い、更に水熱合成を160℃で3日間(撹拌速度600回転/分)行った。それ以外は、特公昭61-21985号公報(特開昭50-5335号公報)の実施例2と同様にして、ゼオライトを水熱合成した。
得られたゼオライトを十分水洗し、120℃で乾燥した後、電気炉中で空気雰囲気下に550℃で3時間焼成した。その後、焼成したゼオライトのカチオンタイプをNH4 +に変換するために、1モル濃度の塩化アンモニウム水溶液を用いて25℃で1時間イオン交換し、更に水洗し、120℃で乾燥した。
なお、上述の方法により測定した上記MFI型ZSM-5のSiO2/Al2O3比(モル比)は280であり、その構造タイプは上述の方法により同定された。構造タイプの同定に際しては、特公昭46-10064号公報の記載を参照した(以下、特に断りがない限り同様。)。
得られたゼオライトを十分水洗し、120℃で乾燥した。その後、ゼオライトのカチオンタイプをH+に変換するために、1モル濃度の硝酸水溶液を用いて25℃で1時間、イオン交換し、更に水洗し、120℃で乾燥した。
なお、上述の方法により測定した上記MFI型ZSM-5のSiO2/Al2O3比(モル比)は27であり、その構造タイプは上述の方法により同定された。
このゼオライトは1次粒子が凝集していたため、ジェットミル(日本ニューマチック工業社製、型式:LJ)を用いて、平均粒子径が3μmになるよう粉砕処理をした。
得られたゼオライトを十分水洗し、120℃で乾燥した。その後、ゼオライトのカチオンタイプをH+に変換するために、1モル濃度の硝酸水溶液を用いて25℃で1時間、イオン交換し、更に水洗し、120℃で乾燥した。
なお、上述の方法により測定した上記MFI型ZSM-5のSiO2/Al2O3比(モル比)は42であり、その構造タイプは上述の方法により同定された。
得られたゼオライトを十分水洗し、120℃で乾燥した後、電気炉中で空気雰囲気下に550℃で3時間焼成した。その後、焼成したゼオライトのカチオンタイプをNH4+に変換するために、1モル濃度の塩化アンモニウム水溶液を用いて25℃で1時間イオン交換し、更に水洗し、120℃で乾燥した。
なお、上述の方法により測定した上記MFI型ZSM-5のSiO2/Al2O3比(モル比)は80であり、その構造タイプは上述の方法により同定された。
なお、上述の方法により測定した上記MFI型ZSM-5のSiO2/Al2O3比(モル比)は1000であり、その構造タイプは上述の方法により同定された。
なお、上述の方法により測定した上記β型ゼオライトのSiO2/Al2O3比(モル比)は25であり、その構造タイプは上述の方法により同定された。構造タイプの同定に際しては、米国特許第3308069号明細書の記載を参照した。
コロイダルシリカ(Nalco社製、シリカ平均粒子径:5nm、シリカ含有率:15質量%、Na含有量:185ppm)2000gに硝酸(和光純薬製、硝酸60質量%含有試薬、以下同様。)40gを添加しpHを1.1に調整した。その後、水溶性化合物である硝酸アンモニウム(和光純薬製、特級試薬、0℃の水に対する溶解度:118g/100g水、以下同様。)100gをそこに添加した。次いで、そこにゼオライトであるSiO2/Al2O3比がモル比で280のMFI型ZSM-5を300g添加して、原料スラリーを調製した(原料混合物の調製工程)。得られた原料スラリーを25℃で3時間撹拌した。原料スラリーはゾル状を呈しており、粘度は5cP(東京計器製、B型粘度計により測定した。)であった。その原料スラリーを噴霧乾燥機で噴霧乾燥し乾燥粉末を得た(乾燥工程)。噴霧乾燥機入口の流体温度を220℃、噴霧乾燥機出口の流体温度を130℃に設定し、回転円盤方式で原料スラリーの噴霧乾燥を行った。得られた乾燥粉末を電気炉を用いて700℃で5時間、空気雰囲気下で焼成した(焼成工程)。
得られた焼成粉末を、0.1モル濃度の硝酸水溶液と混合し10質量%の固形分濃度に調節し、25℃で1時間のイオン交換処理を行った(イオン交換工程)。その後イオン交換工程を経たイオン交換体粉末を十分に水洗し、120℃で乾燥した。
ゼオライトを、SiO2/Al2O3比がモル比で27であるMFI型ZSM-5に代えた他は実施例1と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表1に示す。また、触媒粒子の電子顕微鏡写真を図3に、触媒粒子断面の電子顕微鏡写真を図4に示す。また、触媒粒子表面の電子顕微鏡写真を図7に示す。粒子表面には、薄いひびが観察されるが、凹凸は有していなかった。
ゼオライトを、SiO2/Al2O3比がモル比で1000であるMFI型ZSM-5に代えた他は実施例1と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表1に示す。触媒粒子の電子顕微鏡写真を図5に、触媒粒子断面の電子顕微鏡写真を図6に示す。
ゼオライトを、SiO2/Al2O3比がモル比で42であるMFI型ZSM-5に代えた他は実施例1と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後およびイオン交換後の形態における上記各種物性を測定した。その測定値を表1に示す。
水溶性化合物を酢酸アンモニウム(和光純薬製、特級試薬、4℃の水に対する溶解度:148g/100g水)に代えた他は実施例1と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表1に示す。
コロイダルシルカをコロイダルシリカ(Nalco社製、広範囲粒子分布タイプ、シリカ平均粒子径:15nm、シリカ含有率:38質量%、Na含有量:300ppm)795gに代え、水溶性化合物を硫酸アンモニウム(和光純薬製、特級試薬、0℃の水に対する溶解度:71g/100g水)に代えた他は実施例1と同様にして、ゼオライト含有触媒を調製した。なお、噴霧乾燥する直前の原料スラリーの固形分濃度を30質量%とするように、原料スラリーに適宜純水を加えた。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表1に示す。
ゼオライトを、SiO2/Al2O3比がモル比で80であるMFI型ZSM-5に代え、水溶性化合物を塩化アンモニウム(和光純薬製、特級試薬、0℃の水に対する溶解度:29g/100g水)72gに代えた他は実施例1と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表1に示す。
水溶性化合物を炭酸アンモニウム(和光純薬製、特級試薬、15℃の水に対する溶解度:25g/100g水)60gに代えた他は実施例7と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表1に示す。
コロイダルシリカをコロイダルシリカ(Nalco社製、シリカ平均粒子径:5nm、シリカ含有率:15質量%、Na含有量:185ppm)1800gに代え、水溶性化合物を硝酸アルミニウム・9水和物(和光純薬製、特級試薬、25℃の水に対する溶解度:77.5g/100g水)221gに代えた他は実施例1と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表2に示す。
水溶性化合物を硝酸ナトリウム(和光純薬製、特級試薬、0℃の水に対する溶解度:73g/100g水)106gに代えた他は実施例2と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表2に示す。
ゼオライト含有触媒の平均粒子径を小さくするために、乾燥工程において原料スラリーを噴霧乾燥する際の回転円盤の回転数を増加させた他は実施例2と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表2に示す。ゼオライト含有触媒の平均粒子径は21μmであった。
ゼオライト含有触媒の平均粒子径を大きくするために、乾燥工程において原料スラリーを噴霧乾燥する際の回転円盤の回転数を減少させた他は実施例2と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表2に示す。ゼオライト含有触媒の平均粒子径は87μmであった。
ゼオライト含有触媒の平均粒子径を大きくするために、乾燥工程において原料スラリーを噴霧乾燥する際の回転円盤の回転数及び原料スラリーの供給量を減少させた他は実施例2と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表2に示す。ゼオライト含有触媒の平均粒子径は293μmであった。
ゼオライトを、SiO2/Al2O3比がモル比で80であるMFI型ZSM-5に代え、水溶性化合物の量を硝酸アンモニウム10gに代えた他は実施例1と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表2に示す。
水溶性化合物の量を硝酸アンモニウム30gに代えた他は実施例14と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表2に示す。
水溶性化合物の量を硝酸アンモニウム1440gに代えた他は実施例14と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表2に示す。
コロイダルシリカを、コロイダルシリカ(Nalco社製、シリカ平均粒子径:12nm、シリカ含有率:34質量%、Na含有量:12ppm)1235gに代え、水溶性化合物の量を硝酸アンモニウム140gに代え、ゼオライトであるSiO2/Al2O3比がモル比で27のMFI型ZSM-5の量を180gに代えた他は実施例2と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表3に示す。
コロイダルシリカ(Nalco社製、シリカ平均粒子径:5nm、シリカ含有率:15質量%、Na含有量:185ppm)3800gに硝酸60gを添加しpHを1.5に調整した。その後、水溶性化合物である硝酸アンモニウム188gをそこに添加した。次いで、そこにゼオライトであるSiO2/Al2O3比がモル比で80のMFI型ZSM-5を30g添加して、原料スラリーを調製した。この工程の他は実施例1と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表3に示す。
コロイダルシリカを、コロイダルシリカ(Nalco社製、シリカ平均粒子径:5nm、シリカ含有率:15質量%、Na含有量:185ppm)1200gに代え、硝酸の添加量を24gに代え、水溶性化合物の量を硝酸アンモニウム60gに代え、ゼオライトであるSiO2/Al2O3比がモル比で80のMFI型ZSM-5の量を420gに代えた他は、実施例18と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表3に示す。
原料混合物の調製工程において、コロイダルシリカ(Nalco社製、シリカ平均粒子径:5nm、シリカ含有率:15質量%、Na含有量:185ppm)2800gに硝酸56gを添加しpHを0.9に調整した。その後、水溶性化合物としての硝酸アンモニウム140gをそこに添加し、次いで、ゼオライトであるSiO2/Al2O3比がモル比で25のβ型ゼオライトを180g添加して原料スラリーを調製した。この工程の他は実施例1と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表3に示す。
コロイダルシリカ(Nalco社製、シリカ平均粒子径:5nm、シリカ含有率:15質量%、Na含有量:185ppm)2000gに、ゼオライトであるSiO2/Al2O3比がモル比で42であるMFI型ZSM-5を300g添加し、そこに硝酸40gを添加しpHを1.2に調整した。その後、水溶性化合物である硝酸アンモニウム100gをそこに添加して、原料スラリーを得た(原料混合物の調製工程)。これ以降は実施例1と同様にしてゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表3に示す。
特許第3905948号の実施例4に従ってMFI型ZSM-5ゼオライト(SiO2/Al2O3比がモル比で39)を水熱合成した。このゼオライトスラリーをロータリーフィルターを用いてスラリー状態のままpHが9になるまで水洗した。更に、1モル濃度の硫酸水溶液により25℃で1時間イオン交換し、pHが4になるまで水洗し、29質量%H+タイプMFI型ZSM-5ゼオライト含有スラリーを得た。このスラリー1034g(ゼオライトとして300g含有する。)を原料のゼオライトとして用い、水溶性化合物である硝酸アンモニウムを60gに代えた他は、実施例1と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表3に示す。
コロイダルシリカ(Nalco社製、シリカ平均粒子径:5nm、シリカ含有率:15質量%、Na含有量:185ppm)1500gに硝酸98gを添加し、pHを0.3に調整した後、水溶性化合物である硝酸アンモニウム75gをそこに添加した。次いで、水ガラス(富士化学社製、商品名「特3号珪酸ソーダ」、SiO225.0質量%、Na2O9.0質量%、残分は水。以下同様。)300gを純水200gで希釈した水溶液をそこに添加した。なお、このシリカゾルは、シリカ成分の75質量%がコロイダルシリカを原料とし、25質量%が水ガラスを原料とするものであった。ここにゼオライトであるSiO2/Al2O3比がモル比で27のMFI型ZSM-5を300g添加して、原料スラリーを調製した。原料スラリーのpHは1.1であった。
この原料スラリーを実施例1と同様にして噴霧乾燥した。得られた乾燥粉末を60~85℃、1時間、10Lの純水で攪拌しながら水洗した。これを2回繰り返した。次に1モル濃度の硝酸水溶液で固形分濃度10質量%に調節し、60~85℃で1時間イオン交換処理を行った。これを2回繰り返した。その後十分に水洗し、120℃で乾燥した。
得られた乾燥粉末を電気炉を用いて700℃で1時間、空気雰囲気下で焼成した。
こうして得られたゼオライト含有触媒について、そのイオン交換後焼成した形態における上記各種物性を測定した。その測定値を表3に示す。
なお、参考のために、乾燥粉末の一部を採取し、イオン交換前のナトリウム含有量を測定したところ、3.27質量%であった。
実施例2で用いたMFI型ZSM-5(SiO2/Al2O3比がモル比で27)にリン酸アンモニウムを担持させたMFI型ZSM-5を次のように調製した。まず、リン酸アンモニウム72.2g(和光純薬製、特級試薬)を純水1Lに溶解し、上記ゼオライト500gをその溶液に添加した。得られたスラリーからエバポレーターによって減圧下に60℃で約1時間かけて水分を留去させ、残った固形分を回収し、乾燥後、500℃で1時間焼成した。ゼオライトを、このリン成分を担持させたMFI型ZSM-5 300gに代え、水溶性化合物である硝酸アンモニウムを150gに代えた他は、実施例2と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表3に示す。
コロイダルシリカ(Nalco社製、シリカ平均粒子径:5nm、シリカ含有率:15質量%、Na含有量:185ppm)1200gに硝酸160gを添加し、pHを0.1に調整した後、水溶性化合物である硝酸アンモニウム59gを添加した。次いで、水ガラス(富士化学社製、商品名「特3号珪酸ソーダ」)480gを純水400gで希釈した水溶液をそこに添加した。なお、このシリカゾルは、シリカ成分の60質量%がコロイダルシリカを原料とし、40質量%が水ガラスを原料とするものであった。ここにゼオライトであるSiO2/Al2O3比がモル比で27のMFI型ZSM-5を300g添加して、原料スラリーを調製した。原料スラリーのpHは0.5であった。
この原料スラリーについて、噴霧乾燥以降、実施例23と同様にして、ゼオライト含有触媒を得た。
こうして得られたゼオライト含有触媒について、そのイオン交換後焼成した形態における上記各種物性を測定した。その測定値を表3に示す。
なお、参考のために、乾燥粉末の一部を採取し、イオン交換前のナトリウム含有量を測定したところ、5.11質量%であった。
また、触媒粒子表面の電子顕微鏡写真を図8に示す。
実施例2と同様にしてゼオライト含有触媒を500kg製造した。この触媒を、サイクロン部を付設した透明塩化ビニール製流動層反応器コールドモデル装置(内径60cm、高さ5m)に充填した。次いで、ブロワーにより装置下部から空気700m3/hrを供給し、工業的な流動層反応操作条件レベルであるガス線速70cm/sec(空塔基準)の条件で触媒を流動させながら、1000時間連続運転を行った。1000時間運転後の触媒の摩耗損失は0.20質量%、平均粒子径は58μmであり、触媒の粉化、割れ、欠けはほとんど認められず、工業的な流動層反応操作条件で安定な運転が継続できた。1000時間運転後の触媒の電子顕微鏡写真を図9に示す。
[実施例27]
実施例2で得られたゼオライト含有触媒に対して、650℃、24時間、0.8気圧の水蒸気分圧、0.2気圧の窒素ガス分圧の条件でスチーミング処理を施した。その触媒22.9gを内径1インチのステンレス製流動層反応器に充填した。その後、エチレン9.9g/hr、水素0.7g/hr、水4.9g/hr、窒素5.3g/hrを、その流量で反応器に流通させ、反応温度550℃、反応圧力0.14MPa、WHSV0.43hr-1(ゼオライト含有触媒基準)の条件で100時間流動層反応を行った。反応中、触媒の粉化は全く認められなかった。反応生成物の分析は反応器と直結したガスクロマトグラフィー(島津製作所製、GC-17A、TCD-FID直列連結型)で行った。各反応時間におけるエチレン転化率の推移を図18に示す。エチレン転化率70%におけるプロピレン収率は24.5質量%であった。
実施例24で得られたゼオライト含有触媒から余剰のリン成分を除くために、その触媒を25℃で1時間水洗した。水洗後のゼオライト含有触媒に対して、実施例27と同じ条件でスチーミング処理を施した。その触媒22.9gを用いて実施例27と同様に流動層反応を行った。各反応時間におけるエチレン転化率の推移を図18に示す。エチレン転化率70%におけるプロピレン収率は25.5質量%であった。
イオン交換を行わない他は実施例17と同様にして得られた焼成後のゼオライト含有触媒に対して、560℃、12時間、0.8気圧の水蒸気分圧、0.2気圧の窒素ガス分圧の条件でスチーミング処理を施した。その触媒22.9gを用いて実施例27と同様に流動層反応を行った。各反応時間におけるエチレン転化率を図18に示す。エチレン転化率70%におけるプロピレン収率は23.0質量%であった。
実施例25で得られたゼオライト含有触媒に対して、実施例27と同じ条件でスチーミング処理を施した。その触媒22.9gを用いて実施例27と同様に流動層反応を行った。各反応時間におけるエチレン転化率を図18に示す。エチレン転化率70%におけるプロピレン収率は24.0質量%であった。
実施例17で得られたゼオライト含有触媒に対して、実施例27と同じ条件でスチーミングした。その触媒22.9gを用いて実施例27と同様に流動層反応を行った。各反応時間におけるエチレン転化率を図19に示す。エチレン転化率70%におけるプロピレン収率は24.2質量%であった。
原料スラリーに硝酸アンモニウムを添加しなかった他は実施例1と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表4に示す。また、触媒粒子の電子顕微鏡写真を図10に、触媒粒子断面の電子顕微鏡写真を図11に示す。
原料スラリーに硝酸アンモニウムを添加しなかった他は実施例2と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表4に示す。また、触媒粒子の電子顕微鏡写真を図12に、触媒粒子断面の電子顕微鏡写真を図13に示す。
原料スラリーに硝酸アンモニウムを添加しなかった他は実施例3と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表4に示す。また、触媒粒子の電子顕微鏡写真を図14に、触媒粒子断面の電子顕微鏡写真を図15に示す。
原料スラリーの調製工程における硝酸アンモニウムの添加量を1.5gに変更した他は実施例1と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表4に示す。
原料スラリーの調製工程における硝酸アンモニウムの添加量を1800gに変更した他は実施例1と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表4に示す。
ゼオライト含有触媒の平均粒子径を小さくするために、乾燥工程において原料スラリーを噴霧乾燥する際の回転円盤の回転数を増加させた他は実施例2と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表4に示す。ゼオライト含有触媒の平均粒子径は12μmであった。
ゼオライト含有触媒の平均粒子径を大きくするために、乾燥工程において原料スラリーを噴霧乾燥する際の回転円盤の回転数及び原料スラリーの供給量を減少させた他は実施例2と同様にして、ゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒について、その焼成後及びイオン交換後の形態における上記各種物性を測定した。その測定値を表4に示す。ゼオライト含有触媒の平均粒子径は386μmであった。
特開平10-146529号公報の実施例1に従い触媒調製を行った。初めに、その実施例1に記載の量の超安定型Yゼオライト(東ソー社製)と、粒子径1~2μmのギブサイト(水酸化アルミニウム、Alcoa)と、ジョージアカオリンと、LUDOXシリカゾル(DuPont社製、HS-40、SiO2含有率:40質量%)と、純水との混合物スラリーを調合した。次に、その実施例1に記載の量の硫酸(和光純薬製、特級試薬)と硫酸アルミニウム・15水和物(和光純薬製、特級試薬、以下同じ。)との水溶液を調合した。これに、別に調合した、その実施例1に記載の量のケイ酸ナトリウム(PQCorp製、「N」brand、SiO2含有率:28.8質量%、Na2O含有率:8.9質量%)水溶液を添加した。更に、その実施例1に記載の量の硫酸アルミニウム・15水和物の水溶液をそこに添加した。最後に、初めに調合した混合物スラリーをそこに添加して原料スラリーを得た。
この原料スラリーを噴霧乾燥し、得られた乾燥粉末を85℃で熱水洗浄し、85℃の12質量%硫酸アンモニウム水溶液でイオン交換処理し、更に水洗し、最後に550℃で2時間焼成した。
こうして得られた触媒について、上記各種物性を測定した。その測定値を表4に示す。また、触媒粒子の電子顕微鏡写真を図16に、触媒粒子断面の電子顕微鏡写真を図17に示す。
なお、参考のために、乾燥粉末の一部を採取し、イオン交換前のナトリウム含有量を測定したところ、5.36質量%であった。
実施例17で得られたゼオライト含有触媒の反応性能(実施例31)と比較するために、活性成分であるゼオライトを、実施例17で用いたSiO2/Al2O3比がモル比で27のMFI型ZSM-5に変更した他は、比較例8と同様にしてゼオライト含有触媒を調製した。
こうして得られたゼオライト含有触媒に対して、実施例27と同様にスチーミング処理を施した。その触媒22.9gを用いて実施例27と同様に流動層反応を行った。各反応時間におけるエチレン転化率の推移を図19に示す。
なお、参考のために、乾燥粉末の一部を採取し、イオン交換前のナトリウム含有量を測定したところ、5.36質量%であった。
特に、リン修飾したゼオライトを含有する触媒を用いた場合(実施例28)には、H+型ゼオライトを含有する触媒(実施例27)と比較して、同一のスチーミング処理を施しても高活性を示し、かつ、コーキングによる経時的な劣化も抑制された。
また、実施例17のようなコロイダルシリカを用いて調製したゼオライト含有触媒は、触媒組成物中のNaが極めて少ないため、イオン交換をしなくても、焼成するだけで十分に高活性を示した(実施例29)。これは触媒製造工程の簡略化に繋がり、工業実用上極めて有益である。
また、水ガラスを多く含むシリカゾルを用いて調製したゼオライト含有触媒は、イオン交換によってもナトリウムの除去が不十分であり、高活性な触媒を得ることが困難であった(比較例9)。
Claims (8)
- ゼオライトとシリカとを含有する粒子である触媒であって、
20~300μmの平均粒子径を有し、前記粒子の断面における空孔面積の割合が前記粒子の断面積に対して30%以下であるゼオライト含有触媒。 - 前記ゼオライトがMFI型ゼオライトである、請求項1に記載のゼオライト含有触媒。
- 前記ゼオライトの含有率が10~90質量%であり、前記シリカの含有率が10~90質量%であり、かつ前記ゼオライトと前記シリカとの合計の含有率が50質量%以上である、請求項1又は2に記載のゼオライト含有触媒。
- ゼオライトとコロイダルシリカとを含有する原料混合物を噴霧乾燥して乾燥粉体を得る工程と、前記乾燥粉体を焼成する工程とを有する、請求項1~3のいずれか一項に記載のゼオライト含有触媒を製造する方法であって、
前記原料混合物が、硝酸塩、酢酸塩、炭酸塩、硫酸塩及び塩化物よりなる群から選ばれる少なくとも1種の水溶性化合物を、前記コロイダルシリカに含まれるシリカに対して0.01~5.0の質量比で含有するゼオライト含有触媒の製造方法。 - 前記原料混合物に含まれるシリカの全量に対して、前記コロイダルシリカの割合が50質量%以上である、請求項4に記載のゼオライト含有触媒の製造方法。
- 前記原料混合物が酸性である、請求項4又は5に記載のゼオライト含有触媒の製造方法。
- 前記水溶性化合物が硝酸アンモニウム、酢酸アンモニウム、炭酸アンモニウム、硫酸アンモニウム及び塩化アンモニウムよりなる群から選ばれる少なくとも1種である、請求項4~6のいずれか1項に記載のゼオライト含有触媒の製造方法。
- 請求項1~3のいずれか1項に記載のゼオライト含有触媒を流動層反応器内で炭化水素及び/又はアルコールと接触させる工程を含む、プロピレンの製造方法。
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Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3308069A (en) | 1964-05-01 | 1967-03-07 | Mobil Oil Corp | Catalytic composition of a crystalline zeolite |
JPS505335A (ja) | 1973-02-09 | 1975-01-21 | ||
JPS5140390A (ja) | 1974-08-02 | 1976-04-05 | Grace W R & Co | |
JPS5954620A (ja) | 1982-09-20 | 1984-03-29 | Toyo Soda Mfg Co Ltd | ゼオライトを製造する方法 |
JPS6121985A (ja) | 1984-07-10 | 1986-01-30 | 工業技術院長 | シリコン窒化物系セラミツク融着性合金 |
JPH0244771A (ja) | 1988-06-24 | 1990-02-14 | Thomson Csf | 垂直タイプ・ブルーミング防止システム装備のccdフレーム転送感光マトリックスとその作製方法 |
JPH06170233A (ja) * | 1992-12-03 | 1994-06-21 | Catalysts & Chem Ind Co Ltd | 炭化水素流動接触分解用触媒組成物 |
JPH10146529A (ja) | 1996-10-15 | 1998-06-02 | Exxon Res & Eng Co | ギブサイトおよび希土類酸化物を配合したメソ細孔性流動接触分解触媒 |
JP3905948B2 (ja) | 1996-04-18 | 2007-04-18 | 山陽石油化学株式会社 | 高シリカゼオライト系触媒 |
JP2007530266A (ja) * | 2004-03-31 | 2007-11-01 | 中国石油化工股▲分▼有限公司 | ゼオライト含有炭化水素変換触媒、その製造方法、および該触媒で炭化水素油を変換する方法 |
JP2008512236A (ja) * | 2004-09-10 | 2008-04-24 | エスケー ホルディングス カンパニー リミテッド | 軽質オレフィン製造用固体酸触媒及びこれを用いた方法 |
JP2008202806A (ja) | 2007-02-16 | 2008-09-04 | Sharp Corp | 冷蔵庫 |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS4610064Y1 (ja) | 1965-10-16 | 1971-04-08 | ||
US4207208A (en) * | 1978-12-18 | 1980-06-10 | Mobil Oil Corporation | Method for regeneration and activity improvement of syngas conversion catalyst |
US5194412A (en) | 1991-01-22 | 1993-03-16 | W. R. Grace & Co.-Conn. | Catalytic compositions |
AU652222B2 (en) | 1991-03-12 | 1994-08-18 | Mobil Oil Corporation | Preparation of cracking catalysts, and cracking process using them |
US5110776A (en) | 1991-03-12 | 1992-05-05 | Mobil Oil Corp. | Cracking catalysts containing phosphate treated zeolites, and method of preparing the same |
US5689027A (en) * | 1994-11-18 | 1997-11-18 | Mobil Oil Corporation | Selective ethylbenzene conversion |
TW200918486A (en) * | 2007-09-18 | 2009-05-01 | Asahi Kasei Chemicals Corp | Process for production of propylene |
-
2009
- 2009-06-25 EP EP09804825.9A patent/EP2311561B1/en active Active
- 2009-06-25 CN CN2009801205383A patent/CN102046288B/zh active Active
- 2009-06-25 WO PCT/JP2009/061560 patent/WO2010016338A1/ja active Application Filing
- 2009-06-25 JP JP2010523803A patent/JP5562240B2/ja active Active
- 2009-06-25 US US12/995,803 patent/US8993469B2/en active Active
- 2009-06-25 KR KR1020107027299A patent/KR101271945B1/ko active IP Right Grant
- 2009-06-25 MY MYPI20105763 patent/MY153049A/en unknown
- 2009-07-20 TW TW098124466A patent/TWI406709B/zh active
-
2015
- 2015-02-20 US US14/628,179 patent/US9643167B2/en active Active
Patent Citations (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3308069A (en) | 1964-05-01 | 1967-03-07 | Mobil Oil Corp | Catalytic composition of a crystalline zeolite |
JPS505335A (ja) | 1973-02-09 | 1975-01-21 | ||
JPS5140390A (ja) | 1974-08-02 | 1976-04-05 | Grace W R & Co | |
JPS5954620A (ja) | 1982-09-20 | 1984-03-29 | Toyo Soda Mfg Co Ltd | ゼオライトを製造する方法 |
JPS6121985A (ja) | 1984-07-10 | 1986-01-30 | 工業技術院長 | シリコン窒化物系セラミツク融着性合金 |
JPH0244771A (ja) | 1988-06-24 | 1990-02-14 | Thomson Csf | 垂直タイプ・ブルーミング防止システム装備のccdフレーム転送感光マトリックスとその作製方法 |
JPH06170233A (ja) * | 1992-12-03 | 1994-06-21 | Catalysts & Chem Ind Co Ltd | 炭化水素流動接触分解用触媒組成物 |
JP3905948B2 (ja) | 1996-04-18 | 2007-04-18 | 山陽石油化学株式会社 | 高シリカゼオライト系触媒 |
JPH10146529A (ja) | 1996-10-15 | 1998-06-02 | Exxon Res & Eng Co | ギブサイトおよび希土類酸化物を配合したメソ細孔性流動接触分解触媒 |
JP2007530266A (ja) * | 2004-03-31 | 2007-11-01 | 中国石油化工股▲分▼有限公司 | ゼオライト含有炭化水素変換触媒、その製造方法、および該触媒で炭化水素油を変換する方法 |
JP2008512236A (ja) * | 2004-09-10 | 2008-04-24 | エスケー ホルディングス カンパニー リミテッド | 軽質オレフィン製造用固体酸触媒及びこれを用いた方法 |
JP2008202806A (ja) | 2007-02-16 | 2008-09-04 | Sharp Corp | 冷蔵庫 |
Non-Patent Citations (5)
Title |
---|
"CRC Handbook of Chemistry and Physics", 1994, CRC PRESS INC, article "Periodic Table", pages: 15 |
"Fluidized Bed Handbook", 25 March 1999, BAIFUKAN, pages: 16 |
"Fluidized Bed Handbook", 25 March 1999, BAIFUKAN, pages: 42 |
"Miniature Version of Comprehensive Dictionary of Chemistry", 15 June 2006, KYORITSU SHUPPAN CO., LTD., pages: 1014 |
See also references of EP2311561A4 |
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JP2012091997A (ja) * | 2010-09-28 | 2012-05-17 | Jgc Catalysts & Chemicals Ltd | 結晶性シリカアルミノフォスフェートおよびその合成方法 |
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JP2015187064A (ja) * | 2014-03-13 | 2015-10-29 | 三菱化学株式会社 | ゼオライト成形体 |
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TW201008646A (en) | 2010-03-01 |
CN102046288A (zh) | 2011-05-04 |
US20110092757A1 (en) | 2011-04-21 |
CN102046288B (zh) | 2013-06-19 |
EP2311561A1 (en) | 2011-04-20 |
JPWO2010016338A1 (ja) | 2012-01-19 |
US9643167B2 (en) | 2017-05-09 |
EP2311561A4 (en) | 2012-04-11 |
MY153049A (en) | 2014-12-31 |
JP5562240B2 (ja) | 2014-07-30 |
KR20110007616A (ko) | 2011-01-24 |
EP2311561B1 (en) | 2019-12-25 |
KR101271945B1 (ko) | 2013-06-07 |
US20150165425A1 (en) | 2015-06-18 |
US8993469B2 (en) | 2015-03-31 |
TWI406709B (zh) | 2013-09-01 |
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