JP5972694B2 - Fe(II)置換MEL型ゼオライト、それを含むガス吸着剤及びその製造方法、並びに一酸化窒素及びハイドロカーボンの除去方法 - Google Patents
Fe(II)置換MEL型ゼオライト、それを含むガス吸着剤及びその製造方法、並びに一酸化窒素及びハイドロカーボンの除去方法 Download PDFInfo
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- JP5972694B2 JP5972694B2 JP2012159149A JP2012159149A JP5972694B2 JP 5972694 B2 JP5972694 B2 JP 5972694B2 JP 2012159149 A JP2012159149 A JP 2012159149A JP 2012159149 A JP2012159149 A JP 2012159149A JP 5972694 B2 JP5972694 B2 JP 5972694B2
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- zeolite
- type zeolite
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- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 title claims description 172
- 239000010457 zeolite Substances 0.000 title claims description 171
- 229910021536 Zeolite Inorganic materials 0.000 title claims description 170
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 title claims description 81
- 229930195733 hydrocarbon Natural products 0.000 title claims description 33
- 150000002430 hydrocarbons Chemical class 0.000 title claims description 33
- 238000000034 method Methods 0.000 title claims description 26
- 239000004215 Carbon black (E152) Substances 0.000 title claims description 24
- 238000004519 manufacturing process Methods 0.000 title claims description 22
- 239000003463 adsorbent Substances 0.000 title claims description 12
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 136
- 239000007789 gas Substances 0.000 claims description 76
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 42
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 33
- 238000003756 stirring Methods 0.000 claims description 25
- 150000002500 ions Chemical class 0.000 claims description 20
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 11
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 10
- 238000001179 sorption measurement Methods 0.000 claims description 9
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 5
- 235000010323 ascorbic acid Nutrition 0.000 claims description 5
- 239000011668 ascorbic acid Substances 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 42
- 238000006467 substitution reaction Methods 0.000 description 26
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 24
- 239000013078 crystal Substances 0.000 description 22
- 238000010438 heat treatment Methods 0.000 description 17
- 239000000377 silicon dioxide Substances 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 238000005342 ion exchange Methods 0.000 description 12
- -1 iron ions Chemical class 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- 230000032683 aging Effects 0.000 description 9
- 230000000704 physical effect Effects 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- 238000005259 measurement Methods 0.000 description 8
- 239000012535 impurity Substances 0.000 description 7
- 239000011541 reaction mixture Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 6
- 238000001165 gas chromatography-thermal conductivity detection Methods 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 239000003513 alkali Substances 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 5
- 229910001388 sodium aluminate Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical group [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 4
- 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 4
- 239000012298 atmosphere Substances 0.000 description 4
- 239000012159 carrier gas Substances 0.000 description 4
- 150000001768 cations Chemical group 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 4
- 229910052680 mordenite Inorganic materials 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052708 sodium Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000009616 inductively coupled plasma Methods 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 3
- 239000012299 nitrogen atmosphere Substances 0.000 description 3
- 229910001415 sodium ion Inorganic materials 0.000 description 3
- FYGHSUNMUKGBRK-UHFFFAOYSA-N 1,2,3-trimethylbenzene Chemical compound CC1=CC=CC(C)=C1C FYGHSUNMUKGBRK-UHFFFAOYSA-N 0.000 description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 239000004115 Sodium Silicate Substances 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 150000002506 iron compounds Chemical class 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 2
- 229910052911 sodium silicate Inorganic materials 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- IRUDSQHLKGNCGF-UHFFFAOYSA-N 2-methylhex-1-ene Chemical compound CCCCC(C)=C IRUDSQHLKGNCGF-UHFFFAOYSA-N 0.000 description 1
- JMMZCWZIJXAGKW-UHFFFAOYSA-N 2-methylpent-2-ene Chemical compound CCC=C(C)C JMMZCWZIJXAGKW-UHFFFAOYSA-N 0.000 description 1
- 238000004400 29Si cross polarisation magic angle spinning Methods 0.000 description 1
- 229910017090 AlO 2 Inorganic materials 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 1
- 239000012494 Quartz wool Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 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 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001273 butane Substances 0.000 description 1
- 239000008119 colloidal silica Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000002431 foraging effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000010534 mechanism of action Effects 0.000 description 1
- 239000012452 mother liquor Substances 0.000 description 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- YWAKXRMUMFPDSH-UHFFFAOYSA-N pentene Chemical compound CCCC=C YWAKXRMUMFPDSH-UHFFFAOYSA-N 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
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- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
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- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/72—Organic compounds not provided for in groups B01D53/48 - B01D53/70, e.g. hydrocarbons
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- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
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- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
- C01B39/065—Galloaluminosilicates; Group IVB- metalloaluminosilicates; Ferroaluminosilicates
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
- C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
- C01B39/36—Pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
- C01B39/38—Type ZSM-5
- C01B39/40—Type ZSM-5 using at least one organic template directing agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
- B01D2253/1085—Zeolites characterized by a silicon-aluminium ratio
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/112—Metals or metal compounds not provided for in B01D2253/104 or B01D2253/106
- B01D2253/1122—Metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/306—Surface area, e.g. BET-specific surface
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/30—Physical properties of adsorbents
- B01D2253/302—Dimensions
- B01D2253/311—Porosity, e.g. pore volume
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/20—Carbon monoxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
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- B01D2257/404—Nitrogen oxides other than dinitrogen oxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/702—Hydrocarbons
Description
(a)
SiO2/Al2O3=40〜200、特に44〜200
Na2O/SiO2=0.24〜0.4、特に0.25〜0.35
H2O/SiO2=10〜50、特に15〜25
(b)
SiO2/Al2O3=10〜40、特に12〜40
Na2O/SiO2=0.05〜0.25、特に0.1〜0.25
H2O/SiO2=5〜50、特に10〜25
粉末X線回折装置:マック サイエンス社製、粉末X線回折装置 MO3XHF22、Cukα線使用、電圧40kV、電流30mA、スキャンステップ0.02°、スキャン速度2°/min
SiO2/Al2O3比:MEL型ゼオライトを、フッ化水素(HF)を用いて溶解させ、溶解液を、ICPを用いて分析しAlを定量した。またMEL型ゼオライトを、水酸化カリウム(KOH)を用いて溶解させ、溶解液を、ICPを用いて分析しSiを定量した。定量したSi及びAlの量に基づきSiO2/Al2O3比を算出した。
BET表面積、ミクロ孔比表面積及びミクロ孔容積測定装置:(株)カンタクローム インスツルメンツ社製 AUTOSORB−1
(1)置換前MEL型ゼオライトの製造
SiO2/Al2O3比が19.0であるFe(II)置換MEL型ゼオライトを製造した例である。純水12.88gに、アルミン酸ナトリウム0.113gと、36%水酸化ナトリウム2.582gを溶解して水溶液を得た。微粉状シリカ(Cab−O−Sil、M−5)2.427gと、0.243gの種結晶とを混合したものを、前記の水溶液に少しずつ添加して攪拌混合し、ゲルを得た。種結晶は以下の方法で製造した。このゲルは、SiO2/Al2O3比が100、Na2O/SiO2比が0.300、H2O/SiO2比が20であり、これのみからゼオライトを合成すると、モルデナイト(MOR)が生成する組成のものであった。ゲルと種結晶の混合物を60ccのステンレス製密閉容器に入れて、熟成及び攪拌することなしに140℃で15時間、自生圧力下で静置加熱した。密閉容器を冷却後、生成物を濾過、温水洗浄して白色粉末を得た。この生成物は不純物を含まないMEL型ゼオライトであった。このようにして得られた置換前MEL型ゼオライトの物性値を表1に示す。
テトラエチルアンモニウムヒドロキシドを有機SDAとして用い、アルミン酸ナトリウムをアルミナ源、微粉状シリカ(Cab−O−Sil、M−5)をシリカ源とする従来公知の方法により撹拌加熱を行ってMEL型ゼオライトを得た。撹拌加熱の条件は180℃、96時間である。MEL型ゼオライトのSiO2/Al2O3比は34.0であった。これを電気炉中で空気を流通しながら550℃で10時間焼成して、有機物を含まない結晶を製造した。X線回折の結果から、この結晶はMEL型ゼオライトであることが確認された。このMEL型ゼオライトは、SDAを含まないものであった。このMEL型ゼオライトを種結晶として用いた。
ポリプロピレン容器に60mlの蒸留水、置換前MEL型ゼオライト1g及び加える鉄化合物の2倍のモル数のアスコルビン酸を加えた後、Fe(II)SO4・7H2Oを、置換前MEL型ゼオライトに対して10質量%加え、窒素雰囲気下、室温で1日撹拌した。その後、沈殿物を吸引濾過し、蒸留水で洗浄後、乾燥させFe2+を0.041mmol/g担持したFe(II)置換MEL型ゼオライトを得た。Fe2+の担持量は、上述した方法で求めた。得られたFe(II)置換MEL型ゼオライトについてXRD測定を行ったところ、ピーク位置及びピーク強度が置換前MEL型ゼオライトとほぼ変わらないことが観察され、イオン交換後もMEL型ゼオライトの構造を維持していることが確認された。
Fe(II)置換MEL型ゼオライト20mgを電子天秤で正確に秤量した後、希釈剤としてシリコンカーバイトを180mg用いて、両者を均等になるように混合した。混合物を、内径6mmの石英ガラス管に詰めた。混合中の吸着水をマントルヒーターで加温して除去した後、室温まで冷却した。次に、石英ガラス管内に2分おきに1030ppmの一酸化窒素ガスを、室温で、5cm3パルスした。吸着されずに石英ガラス管から出てきた一酸化窒素ガスの量を、熱伝導度型ガスクロマトグラフ(GC−TCD、島津製作所製、GC−8A)のピーク面積及び化学発光式NO分析装置(NOx analyzer、柳本製作所製、ECL−77A)で検出される値から算出した。熱伝導度型ガスクロマトグラフ(GC−TCD)の測定条件は、以下に示すとおりである。そして、算出した値を、一酸化窒素ガスの供給量から差し引くことで、単位質量あたりのFe(II)置換MEL型ゼオライトに吸着した一酸化窒素ガスの量を求めた。その結果を以下の表1に示す。
・キャリアガス:Heガス
・キャリアガス流量:30cm3・min-1
・検出部温度:100℃
・検出部電流:80mA
内燃機関から排出される排気ガスに含まれるハイドロカーボンの典型であるトルエンを吸着の対象ガスとして用いた。Fe(II)置換MEL型ゼオライト20mgを内径4mmの石英管に入れ、石英ウールとガラスビーズとの間に保持した。移動相としてヘリウムを用い、試料を390℃で約1時間活性化させた。カラムを50℃に冷却した後、トルエンを飽和状態になるまで注入した。吸着されずに石英ガラス管から出てきたトルエンガスの量を、熱伝導度型ガスクロマトグラフ(GC−TCD、島津製作所製、GC−8A)のピーク面積で検出される値から算出した。熱伝導度型ガスクロマトグラフ(GC−TCD)の測定条件は、以下に示すとおりである。そして、算出した値を、トルエンガスの供給量から差し引くことで、単位質量あたりのFe(II)置換MEL型ゼオライトに吸着したトルエンガスの量を求めた。その結果を以下の表1に示す。
・キャリアガス:Heガス
・キャリアガス流量:30cm3・min-1
・検出部温度:150℃
・検出部電流:50mA
Fe(II)SO4・7H2Oを、置換前MEL型ゼオライトに対して20質量%(実施例2)及び40質量%(実施例3)加える以外は実施例1と同様にしてFe(II)置換MEL型ゼオライトを得た。Fe2+の担持量は表1に示すとおりとなった。得られたFe(II)置換MEL型ゼオライトについて実施例1と同様の評価を行った。その結果を表1に示す。
(1)置換前MEL型ゼオライトの製造
SiO2/Al2O3比が15.4であるFe(II)置換MEL型ゼオライトを製造した例である。実施例1において、ゲルの組成として、SiO2/Al2O3比が30、Na2O/SiO2比が1.93、H2O/SiO2比が20のものを用いた。また、種結晶としてSiO2/Al2O3比が66.0であるMEL型ゼオライトを用いた。この種結晶は、実施例1と同様に、テトラエチルアンモニウムヒドロキシドを有機SDAとして用いて製造されたものである。これ以外は実施例1と同様にして白色粉末を得た。この生成物についてXRD測定を行ったところ、この生成物はSDA等の不純物を含まないMEL型ゼオライトであることが確認された。このようにして得られた置換前MEL型ゼオライトの物性値を表1に示す。
ポリプロピレン容器に60mlの蒸留水、置換前MEL型ゼオライト1g及び加える鉄化合物の2倍のモル数のアスコルビン酸を加えた後、Fe(II)SO4・7H2Oを、置換前MEL型ゼオライトに対して10質量%加え、窒素雰囲気下、室温で1日撹拌した。その後、沈殿物を吸引濾過し、蒸留水で洗浄後、乾燥させFe2+を0.029mmol/g担持したFe(II)置換MEL型ゼオライトを得た。得られたFe(II)置換MEL型ゼオライト及び置換前MEL型ゼオライトについてXRD測定を行ったところ、ピーク位置及びピーク強度がほぼ変わらないことが観察され、イオン交換後もMEL型ゼオライトの構造を維持していることが確認された。得られたFe(II)置換MEL型ゼオライトについて実施例1と同様の評価を行った。その結果を表1に示す。
Fe(II)SO4・7H2Oを、置換前MEL型ゼオライトに対して20質量%(実施例5)及び40質量%(実施例6)加える以外は実施例4と同様にしてFe(II)置換MEL型ゼオライトを得た。Fe2+の担持量は表1に示すとおりとなった。得られたFe(II)置換MEL型ゼオライトについて実施例1と同様の評価を行った。その結果を表1に示す。
Claims (11)
- SiO2/Al2O3比が10以上30以下であり、Fe(II)イオンによってイオン交換されたFe(II)置換MEL型ゼオライト。
- Fe(II)の担持量が、Fe(II)置換MEL型ゼオライトに対して0.001〜0.4mmol/gである請求項1に記載のFe(II)置換MEL型ゼオライト。
- Fe(II)イオンによってイオン交換される前のMEL型ゼオライトとして、SiO2/Al2O3比が10以上30以下であるものを用いた請求項1又は2に記載のFe(II)置換MEL型ゼオライト。
- BET比表面積が200〜550m2/gであり、ミクロ孔比表面積が180〜450m2/gであり、かつミクロ孔容積が0.10〜0.20cm3/gである請求項1ないし3のいずれか一項に記載のFe(II)置換MEL型ゼオライト。
- 請求項1ないし4のいずれか一項に記載のFe(II)置換MEL型ゼオライトを含むガス吸着剤。
- 一酸化窒素の吸着に用いられる請求項5に記載のガス吸着剤。
- ハイドロカーボンの吸着に用いられる請求項5に記載のガス吸着剤。
- SiO2/Al2O3比が10以上30以下であるMEL型ゼオライトを、二価の鉄の水溶性化合物水溶液中に分散し、混合撹拌することで、該MEL型ゼオライトにFe(II)イオンを担持させる工程を有する、Fe(II)置換MEL型ゼオライトの製造方法。
- 前記混合撹拌に際し、前記水溶液に、前記二価の鉄のモル数の0.1〜3倍のアスコルビン酸を添加する請求項8に記載の製造方法。
- SiO2/Al2O3比が10以上30以下であり、Fe(II)イオンによってイオン交換されたFe(II)置換MEL型ゼオライトを一酸化窒素又は一酸化窒素を含むガスと接触させて、一酸化窒素を該Fe(II)置換MEL型ゼオライトに吸着させる一酸化窒素の除去方法。
- SiO2/Al2O3比が10以上30以下であり、Fe(II)イオンによってイオン交換されたFe(II)置換MEL型ゼオライトをハイドロカーボン又はハイドロカーボンを含むガスと接触させて、ハイドロカーボンを該Fe(II)置換MEL型ゼオライトに吸着させるハイドロカーボンの除去方法。
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US14/414,500 US9409785B2 (en) | 2012-07-18 | 2013-07-16 | Fe(II)-substituted MEL-type zeolite, production method therefor and gas adsorbent including same, and nitric oxide and hydrocarbon removal method |
EP13820072.0A EP2876085B1 (en) | 2012-07-18 | 2013-07-16 | Fe(II)-SUBSTITUTED MEL-TYPE ZEOLITE, PRODUCTION METHOD THEREFOR AND GAS ADSORBENT INCLUDING SAME, AND NITRIC OXIDE AND HYDROCARBON REMOVAL METHOD |
CN201380036741.9A CN104507863B (zh) | 2012-07-18 | 2013-07-16 | Fe(II)置换MEL型沸石的制造方法 |
KR1020157000812A KR102074755B1 (ko) | 2012-07-18 | 2013-07-16 | Fe(II) 치환 MEL형 제올라이트, 그를 포함하는 가스 흡착제 및 그의 제조 방법, 및 일산화질소 및 히드로카본의 제거 방법 |
PCT/JP2013/069250 WO2014013968A1 (ja) | 2012-07-18 | 2013-07-16 | Fe(II)置換MEL型ゼオライト、それを含むガス吸着剤及びその製造方法、並びに一酸化窒素及びハイドロカーボンの除去方法 |
BR112015000915A BR112015000915A2 (pt) | 2012-07-18 | 2013-07-16 | zeólita do tipo mel substituída com fe(ii), método de produção para a mesma e adsorvente de gás incluindo a mesma, e método de remoção de óxido nítrico e de hidrocarbonetos |
CN201810470599.3A CN108640127B (zh) | 2012-07-18 | 2013-07-16 | Fe(II)置换MEL型沸石及包含其的气体吸附剂 |
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CN101711991B (zh) * | 2009-10-15 | 2012-07-18 | 清华大学 | 一种Fe分子筛复合催化剂及其制备方法 |
FR2959749B1 (fr) * | 2010-05-06 | 2012-06-01 | Inst Francais Du Petrole | Procede flexible de transformation de l'ethanol en distillats moyens. |
JP5351216B2 (ja) * | 2010-07-01 | 2013-11-27 | 日本化学工業株式会社 | ゼオライトの製造方法 |
US8518242B2 (en) * | 2011-05-26 | 2013-08-27 | Uop Llc | Fibrous substrate-based hydroprocessing catalysts and associated methods |
CN103008002B (zh) * | 2012-12-11 | 2015-02-18 | 清华大学 | Fe和Cu复合分子筛催化剂的制备方法及应用 |
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CN104507863B (zh) | 2018-11-02 |
US20150166356A1 (en) | 2015-06-18 |
EP2876085A1 (en) | 2015-05-27 |
US9409785B2 (en) | 2016-08-09 |
JP2014019602A (ja) | 2014-02-03 |
KR102074755B1 (ko) | 2020-02-10 |
EP2876085B1 (en) | 2020-04-29 |
EP2876085A4 (en) | 2015-08-05 |
KR20150036054A (ko) | 2015-04-07 |
CN108640127B (zh) | 2022-06-07 |
WO2014013968A1 (ja) | 2014-01-23 |
CN108640127A (zh) | 2018-10-12 |
BR112015000915A2 (pt) | 2017-06-27 |
CN104507863A (zh) | 2015-04-08 |
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