CN104903234B - 小晶体镁碱沸石及其制备方法 - Google Patents
小晶体镁碱沸石及其制备方法 Download PDFInfo
- Publication number
- CN104903234B CN104903234B CN201380065429.2A CN201380065429A CN104903234B CN 104903234 B CN104903234 B CN 104903234B CN 201380065429 A CN201380065429 A CN 201380065429A CN 104903234 B CN104903234 B CN 104903234B
- Authority
- CN
- China
- Prior art keywords
- ferrierite
- crystalline
- microporous body
- crystalline microporous
- osda
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910001657 ferrierite group Inorganic materials 0.000 title claims abstract description 91
- 239000013078 crystal Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 81
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 33
- 239000000203 mixture Substances 0.000 claims abstract description 29
- 239000011148 porous material Substances 0.000 claims abstract description 9
- 229910052783 alkali metal Inorganic materials 0.000 claims abstract description 3
- 150000001340 alkali metals Chemical class 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 21
- 239000003795 chemical substances by application Substances 0.000 claims description 17
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 claims description 15
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical compound [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical class NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 10
- 239000002184 metal Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000004215 Carbon black (E152) Substances 0.000 claims description 8
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 8
- 229930195733 hydrocarbon Natural products 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 8
- 150000003235 pyrrolidines Chemical class 0.000 claims description 8
- 238000003421 catalytic decomposition reaction Methods 0.000 claims description 6
- 229910052802 copper Inorganic materials 0.000 claims description 6
- 150000004678 hydrides Chemical class 0.000 claims description 6
- 229910052742 iron Inorganic materials 0.000 claims description 6
- 239000001272 nitrous oxide Substances 0.000 claims description 6
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- 229910052723 transition metal Inorganic materials 0.000 claims description 6
- 150000003624 transition metals Chemical class 0.000 claims description 6
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 5
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 4
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 4
- 239000005700 Putrescine Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 150000003053 piperidines Chemical class 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052702 rhenium Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- AVFZOVWCLRSYKC-UHFFFAOYSA-N 1-methylpyrrolidine Chemical class CN1CCCC1 AVFZOVWCLRSYKC-UHFFFAOYSA-N 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229910044991 metal oxide Inorganic materials 0.000 claims 3
- 150000004706 metal oxides Chemical class 0.000 claims 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 239000010457 zeolite Substances 0.000 abstract description 30
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 abstract description 27
- 229910021536 Zeolite Inorganic materials 0.000 abstract description 26
- 238000001179 sorption measurement Methods 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 4
- 238000005259 measurement Methods 0.000 abstract 1
- 238000000634 powder X-ray diffraction Methods 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 31
- 239000000243 solution Substances 0.000 description 28
- 230000000052 comparative effect Effects 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 16
- 230000015572 biosynthetic process Effects 0.000 description 16
- 239000003513 alkali Substances 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- 229910001868 water Inorganic materials 0.000 description 14
- 229910052905 tridymite Inorganic materials 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 229910052681 coesite Inorganic materials 0.000 description 12
- 229910052906 cristobalite Inorganic materials 0.000 description 12
- 229910052682 stishovite Inorganic materials 0.000 description 12
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 11
- 239000013256 coordination polymer Substances 0.000 description 11
- 239000011777 magnesium Substances 0.000 description 11
- 229910052749 magnesium Inorganic materials 0.000 description 11
- 235000011121 sodium hydroxide Nutrition 0.000 description 11
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 10
- 229910052593 corundum Inorganic materials 0.000 description 10
- 238000010586 diagram Methods 0.000 description 10
- 229910001388 sodium aluminate Inorganic materials 0.000 description 10
- 229910001845 yogo sapphire Inorganic materials 0.000 description 10
- KKCBUQHMOMHUOY-UHFFFAOYSA-N Na2O Inorganic materials [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 8
- 238000002425 crystallisation Methods 0.000 description 7
- XFNJVJPLKCPIBV-UHFFFAOYSA-P trimethylenediaminium Chemical compound [NH3+]CCC[NH3+] XFNJVJPLKCPIBV-UHFFFAOYSA-P 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 6
- 241000408939 Atalopedes campestris Species 0.000 description 6
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 238000007605 air drying Methods 0.000 description 5
- 238000001354 calcination Methods 0.000 description 5
- 238000001878 scanning electron micrograph Methods 0.000 description 5
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Chemical compound [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- 150000001768 cations Chemical class 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Substances [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- RWRDLPDLKQPQOW-UHFFFAOYSA-N Pyrrolidine Chemical compound C1CCNC1 RWRDLPDLKQPQOW-UHFFFAOYSA-N 0.000 description 3
- 229910021529 ammonia Inorganic materials 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 3
- -1 nitrogenous organic compound Chemical class 0.000 description 3
- 239000004575 stone Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000001788 irregular Effects 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 150000003839 salts Chemical group 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 241000276425 Xiphophorus maculatus Species 0.000 description 1
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical compound [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 description 1
- 239000012874 anionic emulsifier Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000009415 formwork Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000012875 nonionic emulsifier Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- ZTRPYTHOEREHEN-UHFFFAOYSA-N piperazine pyridine Chemical compound N1CCNCC1.N1=CC=CC=C1.N1=CC=CC=C1 ZTRPYTHOEREHEN-UHFFFAOYSA-N 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 229910052649 zeolite group Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
-
- 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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
- B01J29/68—Iron group metals or copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/56—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- 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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
-
- 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
- B01J29/65—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively
- B01J29/66—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38, as exemplified by patent documents US4046859, US4016245 and US4046859, respectively containing iron group metals, noble metals or copper
- B01J29/67—Noble metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- C01B39/04—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 using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
-
- 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
- C01B39/44—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
-
- 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
- C01B39/44—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38
- C01B39/445—Ferrierite type, e.g. types ZSM-21, ZSM-35 or ZSM-38 using at least one organic template directing agent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1021—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1023—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1025—Rhodium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/10—Noble metals or compounds thereof
- B01D2255/102—Platinum group metals
- B01D2255/1026—Ruthenium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20738—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20753—Nickel
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/20—Metals or compounds thereof
- B01D2255/207—Transition metals
- B01D2255/20761—Copper
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/50—Zeolites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
- B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
-
- 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
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Combustion & Propulsion (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Toxicology (AREA)
- Mechanical Engineering (AREA)
- General Engineering & Computer Science (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
公开了一种从凝胶制备的高度结晶、小晶体、镁碱沸石沸石,该凝胶含有氧化硅、氧化铝、碱金属的源以及两种模板剂的组合。所得材料包括具有约为或小于200nm的颗粒尺寸的镁碱沸石晶体。可以通过使用凝胶的特定组成获得所需晶体尺寸。使用X射线粉末衍射和扫描电镜测定材料的纯度和晶体尺寸。该材料具有优异的表面积和由氮吸附测定的微孔体积。
Description
本申请要求2012年11月8日提交的美国临时申请No.:61/724136的国内优先权的权益,在此通过引用以其全文并入本文。
技术领域
公开了制备具有小晶体尺寸例如200纳米以下的镁碱沸石沸石的方法。还公开了具有通过所公开的方法制备的具有镁碱沸石(“FER”)框架类型的结晶微孔材料,以及由所公开的方法制备的催化剂。
背景技术
文献中描述了很多镁碱沸石合成的情形。已经从没有有机结构导向剂(“OSDA”)或模板的凝胶合成镁碱沸石,如美国专利号3933974;3966883;4088739和4650654中所示。通常,在没有OSDA时的镁碱沸石合成不提供晶体的尺寸和形态的良好控制。
也将各种OSDA,特别是含氮的有机化合物,用于高纯镁碱沸石的合成。一些实施例包括美国专利号4000248;4016245;4251499;4377502;和4795623。有机模板的使用允许减少结晶温度和时间,如所美国专利号4000248所述。美国专利号5491273描述了使用吡咯烷作为结构导向剂合成约0.5微米或更大的镁碱沸石晶体。
美国专利号6136289描述了从含有硼酸的不含有机的凝胶合成镁碱沸石。形成了0.5微米尺寸和更大的镁碱沸石晶体。
Pinar等人(Collection of Czechoslovak Chemical Communications,vol.72(2007)pp.666-78)显示出四甲铵(“TMA”)阳离子对于镁碱沸石从凝胶结晶的强烈影响,所述凝胶包含1-苄基-1-吡咯烷阳离子作为主要OSDA。获得了平均尺寸约10微米的镁碱沸石晶体。然而,石英存在于合成的镁碱沸石样品中。
Roman-Leshkov等人(Journal of Physical Chemistry C,vol.115(2011)pp.1096-102)记载了从具有不同环尺寸的环胺和TMA的混合物合成镁碱沸石。形成具有超过1微米尺寸的薄板状晶体。
Nishiyama等人(Microporous Materials,vol.12(1997)pp.293-303)显示出在多孔氧化铝载体的空隙中形成了平均直径为30nm的镁碱沸石针状晶体。他们工作的重要方面是,晶体生长和尺寸在物理方面受到载体的孔尺寸而不是在合成过程中的结晶条件或反应凝胶组成的限制。这进一步得到如下事实的支持:在多孔氧化铝载体的外表面上形成的镁碱沸石晶体具有微米级别的尺寸。
Khomaine等人(Journal of Colloid and Interface Science,vol.236(2001)pp.208-13)显示出通过使用不同数量的非离子表面活性剂以及吡咯烷模板,可以将镁碱沸石晶体的尺寸控制在1和3微米之间的范围内。
Chauhan等人(Indian Journal of Chemical Technology,vol.18(2011)pp.335-42)研究了几种阳离子,阴离子和非离子乳化剂对于镁碱沸石结晶的影响。
鉴于所述内容,存在生产高度结晶、小晶体镁碱沸石沸石的方法的需要。已经发现,包括氧化硅和氧化铝的源与水和碱(alkali)的源的混合物,以及两种有机结构导向剂的组合的合成工艺,解决了上述的需要。
发明概述
公开了约为或小于200纳米的单个晶体尺寸的镁碱沸石(“FER”)沸石。在一个实施方案中,通过制备氧化硅和氧化铝的源与水和碱的源的混合物,以及两种有机结构导向剂(“OSDA”)的组合合成了镁碱沸石沸石。例如,公开了一种使用第一OSDA例如包含氢氧化物或盐形式的四甲铵(“TMA”)阳离子和第二OSDA的方法,所述第二OSDA是能促进镁碱沸石结晶的有机化合物,如吡咯烷、1,3-二氨基丙烷、哌啶、吡啶、1-甲基吡咯烷、乙二胺、或1,4-二氨基丁烷。
公开了一种制备结晶微孔材料的方法,该材料具有镁碱沸石(FER)框架类型,大于约10的摩尔硅铝比(“SAR”,molar silica to alumina ratio),和200纳米以下的平均晶体尺寸。在一个实施方案中,该方法包括:
形成合成混合物,该合成混合物包括氧化硅源、氧化铝源、碱金属源,和有机结构导向剂,所述有机结构导向剂包括:第一有机结构导向剂(OSDA-1)和第二有机结构导向剂(OSDA-2),所述第二有机结构导向剂(OSDA-2)促进镁碱沸石结构形成,其中OSDA-1与OSDA-2的摩尔比范围为约0.2到约1.0;和
加热该合成混合物到100-250℃,优选120-200℃的温度,持续足以结晶该材料的一段时间。
在一个实施方案中,将所得的凝胶加热直到获得结晶产物。凝胶组分之间的不同比例,以及不同结晶条件导致不同晶体的形成,各有特定的尺寸、形态和晶体尺寸分布。
还公开了包含结晶微孔材料的催化剂,该结晶微孔材料具有FER框架类型,大于10的摩尔硅铝比(SAR),和约200纳米以下的平均晶体尺寸,其中催化剂对于选自烃转化、氮氧化物的选择性催化还原和氧化亚氮的催化分解中的至少一个过程是催化活性的。
在一个实施方案中,文中所述的催化剂进一步包含至少一种用于烃转换的氢化功能金属,例如选自Pt、Pd、Rh、Ru、Ni、Re或其混合物的至少一种氢化功能金属。
文中所述催化剂还可包含至少一种过渡金属,例如铜或铁,用于氮氧化物的选择性催化还原和/或氧化亚氮的催化分解。
除了上面讨论的主题,本公开还包括许多其他的示例性特征,例如以下所解释那些。要明白,上面的描述和下面的描述都仅是示例性的。
附图简要说明
并入了附图,且其构成本说明书的一部分。
图1是实施例1中描述的镁碱沸石材料的XRD图案。
图2是实施例1中描述的镁碱沸石材料的SEM。
图3是实施例2中描述的镁碱沸石材料的XRD图案。
图4是实施例2中描述的镁碱沸石材料的SEM。
图5是实施例3中描述的镁碱沸石材料的XRD图案。
图6是实施例3中描述的镁碱沸石材料的SEM。
图7是实施例4中描述的镁碱沸石材料的XRD图案。
图8是实施例4中描述的镁碱沸石材料的SEM。
图9是对比例5中描述的镁碱沸石材料的XRD图案。
图10是对比例5中描述的镁碱沸石材料的SEM。
图11是对比例6中描述的镁碱沸石材料的XRD图案。
图12是对比例6中描述的镁碱沸石材料的SEM。
图13是对比例7中描述的镁碱沸石材料的XRD图案。
图14是对比例7中描述的镁碱沸石材料的SEM。
图15是对比例8中描述的镁碱沸石材料的XRD图案。
图16是对比例8中描述的镁碱沸石材料的SEM。
图17是对比例9中描述的镁碱沸石材料的XRD图案。
图18是对比例9中描述的镁碱沸石材料的SEM。
图19是对比例10中描述的镁碱沸石材料的XRD。
图20是对比例10中描述的镁碱沸石材料的SEM。
图21是对比例11中描述的镁碱沸石材料的XRD图案。
图22是对比例11中描述的镁碱沸石材料的SEM。
本发明的详细描述
定义
在本公开中使用的以下术语或短语中具有如下列出的含义:
“由国际沸石协会的结构委员会定义”,旨在意指包括在但不限于Baerlocher等人的“Atlas of Zeolite Framework Types”第六次修订版中(Elsevier 2007)描述的结构的那些结构,在此通过引用以其全文并入本文。
“具有FER框架类型”旨在意指由国际沸石协会的结构委员会定义的属于镁碱沸石家族的沸石矿物。
“用于烃转换的氢化功能金属”旨在意指可催化在烃转换过程中的氢化反应的金属。
“选择性催化还原”或“SCR”是指在氧存在下NOx的还原(通常用氨,产生氨的化合物例如尿素、或烃)以形成氮和H2O。催化该还原以优先促进在氨被氧氧化过程中NOx的还原,因此是“选择性催化还原”。
文中使用的短语“选自”或“选自于”意指单个组分或两个(或更多)组分的组合的选择。例如,“过渡金属可以选自铜和铁”意味着金属可包含铜、或铁,或者铜和铁的组合。
根据本公开制备小晶体镁碱沸石在很大程度上但不完全依赖于前体凝胶的组成。在一个实施方案中,两种有机结构导向剂或模板的存在是用于控制镁碱沸石晶体尺寸的重要条件。氧化硅源的实施例包括但不限于硅酸钠、胶态氧化硅和沉淀氧化硅。氧化铝源的实施例包括但不限于铝异丙醇盐、铝酸钠、以及氧化铝和氢氧化钠的组合。以氢氧化物或盐,例如氯化物、溴化物或碘化物形式使用四甲铵(“TMA”)阳离子。
在一个实施方案中,第二模板可以是吡咯烷、1,3-二氨基丙烷,哌啶,吡啶,1-甲基吡咯烷、乙二胺、1,4-二氨基丁烷或任何促进镁碱沸石沸石结晶的有机结构导向剂(“OSDA”)。任选向混合物添加镁碱沸石籽晶从而进一步协助结晶的速度。
在一个实施方案中,将氧化硅和氧化铝、水、氢氧化钠、模板和任选籽晶的源组合在一起,并充分混合所得的凝胶。
将凝胶的整体组成描述为:
(10-60)SiO2:Al2O3:(0.5-5.6)Na2O:(0.5-25)TMA:(1-25)SDA:(80-1000)H2O
其中TMA表示四甲铵,且SDA表示第二模板分子,例如吡咯烷、1,3-二氨基丙烷、哌啶、吡啶、1-甲基吡咯烷、乙二胺、1,4-二氨基丁烷或任何适于镁碱沸石沸石合成的OSDA。
镁碱沸石晶体的形态可取决于两种模板之间的比例而改变。TMA和第二模板之间的摩尔比的范围可以为约0.20到约1,例如约0.25到约0.80,或甚至约0.30到约0.70。第二模板相对于氧化硅的摩尔比可以选自合理广泛的范围,如从约0.02到约0.80,或甚至从约0.10到约0.40。氢氧化物(“OH”)与SiO2的比例也是控制晶体的尺寸和形状的重要因素。在一个实施方案中,OH与SiO2的比例范围可以为约0.15到约0.30。较低的OH/SiO2比例可导致不希望的晶粒尺寸,而较高的比例可导致杂质例如ZSM-5、石英、或鳞石英的形成。
可以通过使用氢氧化钠或其与氢氧化四甲铵的组合来控制OH/SiO2的比例。当仅氢氧化钠用于控制OH/SiO2比例时,Na2O/SiO2比例通常为约0.05到约0.14,例如约0.07到约0.13。如果将氢氧化钠和氢氧化四甲铵结合使用,这个比例可以稍微降低。
在100到250℃,优选120到200℃的温度下,在自发条件下加热凝胶。通常,在48小时加热内,镁碱沸石相结晶。
可以向凝胶添加镁碱沸石籽晶以减少结晶时间。在一个实施方案中,镁碱沸石沸石,例如CP 914 C(Zeolyst International)可用于引晶。
在一个实施方案中,所得的镁碱沸石产物是纯镁碱沸石,且不包含任何其他沸石或凝结的氧化硅杂质。镁碱沸石具有至少约350m2/g,或者至少约380m2/g的表面面积。镁碱沸石晶体具有不规则的形状。沿着所有晶体维度的平均晶体尺寸约为或小于200nm,如由扫描电子显微镜(“SEM”)所测定的。
所得的镁碱沸石可以转换为NH4-形式,H形式,或载有浸渍或离子交换的金属,用于烃的催化转化、氮氧化物的选择性催化还原或氧化亚氮的催化分解。
在一个实施方案中,镁碱沸石可在废气的SCR方法中用作本发明的催化剂,例如通过使气体混合物接触文中所述的镁碱沸石组合物。
进一步通过下面的非限制性实施例说明本发明的实施方案,其旨在仅为发明的示例。
实施例
实施例1
该实施例说明了根据本发明的一个实施方案的小晶体镁碱沸石的合成。凝胶的摩尔组成如下:
23.4SiO2:1.0Al2O3:2.71Na2O:1.8TMA:3.51,3-DAP:304H2O
将485克的水与28.9克的氢氧化钠(50%w/w)溶液、74.1克的铝酸钠溶液(23.5重量%Al2O3,19.6重量%Na2O)组合以形成水溶液。将65.6克的四甲基氯化铵溶液(50%w/w,Sachem)和44.8克的1,3-二氨基丙烷(“1,3-DAP”)(Sigma Aldrich)混合入水溶液。最后,添加600克的硅溶胶(40重量%SiO2,Nyacol)和2.7克的CP 914 C籽晶(ZeolystInternational),和搅拌所得的凝胶直到它变为均匀。
在180℃加热该凝胶36小时。过滤所得的结晶产物,用去离子水洗涤和在105℃在空气中干燥。将所得的沸石粉末在550℃下煅烧6小时以从孔隙去除有机分子。煅烧的样品具有395m2/g的表面积和0.14cc/g的微孔体积,如由氮吸附所测定的。发现样品为纯相镁碱沸石。样品的X射线衍射图案如图1所示。样品的晶体尺寸为约100纳米以下,如图4的SEM图像所示。
实施例2
该实施例描述了从具有低于实施例1的H2O/SiO2比例的凝胶合成小晶体镁碱沸石材料。该凝胶的摩尔组成如下:
23SiO2:1.0Al2O3:2.07Na2O:0.96TMA:2.881,3-DAP:230H2O
将320克的水与12.0克的氢氧化钠(50%w/w)水溶液、94.5克的铝酸钠溶液(23.5重量%Al2O3,19.6重量%Na2O)组合以形成水溶液。将41.9克的四甲基氯化铵溶液(50%w/w,Sachem)和42.9克的1,3-二氨基丙烷(“1,3-DAP”)(Sigma Aldrich)混合入水溶液。最后,添加700克的硅溶胶(39.4重量%SiO2,Nyacol)和3.1克的CP 914 C籽晶(ZeolystInternational),和搅拌所得的凝胶直到它变为均匀。
在180℃加热该凝胶36小时。过滤所得的结晶产物,用去离子水洗涤和在105℃在空气中干燥。将所得的沸石粉末在550℃下煅烧6小时以从孔隙去除有机分子。煅烧的样品具有406m2/g的表面积和0.14cc/g的微孔体积,如由氮吸附所测定的。发现样品为纯相镁碱沸石。样品的X射线衍射图案如图3所示。样品的晶体尺寸约为或小于100纳米,如图2的SEM图像所示。
实施例3
该实施例描述了具有高于实施例1的SAR的小晶体镁碱沸石材料的合成。该凝胶的摩尔组成如下:
35SiO2:1.0Al2O3:3.50Na2O:1.75TMA:5.251,3-DAP:350H2O
将391克的水与42.3克的氢氧化钠(50%w/w溶液)、64.3克的铝酸钠溶液(23.5重量%Al2O3,19.6重量%Na2O)组合以形成水溶液。将58.3克的四甲基氯化铵溶液(50%w/w,Sachem)和59.8克的1,3-二氨基丙烷(“1,3-DAP”)(SigmaAldrich)混合入水溶液。最后,添加800克的硅溶胶(40重量%SiO2,Nyacol 1440)和3.4克的CP 914C籽晶(ZeolystInternational),和搅拌所得的凝胶直到它变为均匀。
在160℃加热该凝胶48小时。过滤所得的结晶产物,用去离子水洗涤和在105℃在空气中干燥。将所得的沸石粉末在550℃下煅烧6小时以从孔隙去除有机分子。煅烧的样品具有382m2/g的表面积和0.14cc/g的微孔体积,如由氮吸附所测定的。发现样品为纯相镁碱沸石。样品的X射线衍射图案如图5所示。样品的晶体尺寸约为或小于100纳米,如图6的SEM图像所示。
实施例4
该实施例描述了具有高于实施例1的SAR和不同于实施例1的氧化硅源的小晶体镁碱沸石材料的合成。该凝胶的摩尔组成如下:
35SiO2:1.0Al2O3:3.50Na2O:1.75TMA:5.251,3-DAP:350H2O
将724克的水与45.3克的氢氧化钠(50%w/w溶液)、56.7克的铝酸钠溶液(23.5重量%Al2O3,19.6重量%Na2O)组合以形成水溶液。将50.6克的四甲基氯化铵溶液(50%w/w,Sachem)和51.9克的1,3-二氨基丙烷(1,3-DAP)(SigmaAldrich)混合入水溶液。最后,添加300克的沉淀氧化硅(HiSil 233,PPG Industries)和3.0克的CP 914C籽晶(ZeolystInternational),和搅拌所得的凝胶直到它变为均匀。
在160℃加热该凝胶48小时。过滤所得的结晶产物,用去离子水洗涤和在105℃在空气中干燥。将所得的沸石粉末在550℃下煅烧6小时以从孔隙去除有机分子。煅烧的样品具有405m2/g的表面积和0.14cc/g的微孔体积,如由氮吸附所测定的。发现样品为纯相镁碱沸石。样品的X射线衍射图案如图7所示。样品的晶体尺寸约为或小于100纳米,如图8的SEM图像所示。
对比例5
该实施例描述了在不存在四甲铵阳离子时镁碱沸石沸石合成的对比方法。该凝胶的摩尔组成如下:
23.4SiO2:1.0Al2O3:1.65Na2O:2.341,3-DAP:304H2O
将535克的水与74.1克的铝酸钠溶液(23.5重量%Al2O3,19.6重量%Na2O)和29.9克的1,3-二氨基丙烷组合在一起以形成水溶液。最后,添加600克的硅溶胶(40重量%SiO2,Nyacol)和2.7克的CP 914C籽晶(Zeolyst International),和搅拌所得的凝胶直到它变为均匀。在180℃加热该凝胶36小时。发现样品为纯相镁碱沸石。样品的X射线衍射图案如图9所示。形成了具有约300nm到约1000nm的颗粒尺寸的板状镁碱沸石晶体,如图10的SEM图像所示。
对比例6
该实施例描述了对比的镁碱沸石沸石的合成。该凝胶的摩尔组成如下:
23.4SiO2:1.0Al2O3:1.65Na2O:1.8TMA:3.51,3-DAP:304H2O
将503克的水与74.1克的铝酸钠溶液(23.5重量%Al2O3,19.6重量%Na2O)组合以形成水溶液。将65.6克的四甲基氯化铵溶液(50%w/w,Sachem)和44.8克的1,3-二氨基丙烷(“1,3-DAP”)(Sigma Aldrich)混合入水溶液。最后,添加600克的硅溶胶(40重量%SiO2,Nyacol)和2.7克的CP 914C籽晶(Zeolyst International),和搅拌所得的凝胶直到它变为均匀。
在180℃加热该凝胶36小时。过滤所得的结晶产物,用去离子水洗涤和在105℃在空气中干燥。将所得的沸石粉末在550℃下煅烧6小时以从孔隙去除有机分子。煅烧的样品具有392m2/g的表面积和0.14cc/g的微孔体积,如由氮吸附所测定的。发现样品为纯相镁碱沸石。样品的X射线衍射图案如图11所示。样品的晶体尺寸约为300纳米至约1000纳米,如图12的SEM图像所示。
对比例7
该实施例描述了镁碱沸石沸石合成的对比方法。该凝胶的摩尔组成如下:
25SiO2:1.0Al2O3:3.35Na2O:3.75吡咯烷:325H2O
将544克的水与69.4克的铝酸钠溶液(23.5重量%Al2O3,19.6重量%Na2O)和42.6克的吡咯烷组合在一起。最后,添加600克的硅溶胶(40重量%SiO2,Nyacol)和2.6克的CP914C籽晶(Zeolyst International),和搅拌所得的凝胶直到它变为均匀。在170℃加热该凝胶36小时。发现样品为纯相镁碱沸石。样品的X射线衍射图案如图13所示。形成了颗粒尺寸约为300纳米至约1500纳米的镁碱沸石晶体,如图14的SEM图像所示。
对比例8
该实施例描述了在不存在四甲铵阳离子时且具有高于实施例5的Na2O/SiO2比例的镁碱沸石沸石的合成。该凝胶的摩尔组成如下:
23.4SiO2:1.0Al2O3:2.71Na2O:3.511,3-二氨基丙烷:304H2O
将604克的水与33.7克氢氧化钠(50%w/w溶液)、86.4克铝酸钠溶液(23.5重量%Al2O3,19.6重量%Na2O)组合以形成水溶液。将52.3克1,3-二氨基丙烷(“1,3-DAP”)(SigmaAldrich)混入水溶液。最后,添加700克的硅溶胶(40重量%SiO2,Nyacol)和3.0克的CP 914C籽晶(Zeolyst International),和搅拌所得的凝胶直到它变为均匀。在180℃加热该凝胶36小时。发现所得样品为纯相镁碱沸石。样品的X射线衍射图案如图15所示。形成了具有尺寸为约300nm到约500nm的板状晶体的镁碱沸石,如图16的SEM图像所示。
对比例9
该实施例说明了从具有类似于用于小晶体镁碱沸石合成的组成的凝胶合成镁碱沸石材料,当在无搅拌使凝胶结晶时:
23SiO2:1.0Al2O3:2.1Na2O:0.97TMA:2.891,3-DAP:230H2O
将342克的水与13.6克的氢氧化钠(50%w/w溶液)、87.9克的铝酸钠溶液(23.5重量%Al2O3,19.6重量%Na2O)组合以形成水溶液。将42.9克的四甲基氯化铵溶液(50%w/w,Sachem)和43.6克的1,3-二氨基丙烷(“1,3-DAP”)(Sigma Aldrich)混合入水溶液。最后,添加700克的硅溶胶(40重量%SiO2,Nyacol)和3.1克的CP 914C籽晶(ZeolystInternational),和搅拌所得的凝胶直到它变为均匀。
在180℃加热该凝胶36小时。在加热过程中以150rpm用锚叶搅拌该凝胶。然后,以结晶模式进行结晶。过滤所得的结晶产物,用去离子水洗涤和在105℃在空气中干燥。将所得的沸石粉末在550℃下煅烧6小时以从孔隙去除有机分子。发现样品为纯相镁碱沸石。样品的X射线衍射图案如图17所示。样品具有约1微米至约2微米的晶体尺寸,如图18的SEM图像所示。
对比例10
该实施例描述了CP 914C商业小晶体沸石,它是纯相镁碱沸石(ZeolystInternational)。样品的X衍射图案如图19所示。该样品由具有约200纳米到约300纳米颗粒尺寸的不规则形状的晶体组成,如图20的SEM图像所示。
对比例11
该实施例描述了CP 914商业小晶体沸石,它是纯相镁碱沸石(ZeolystInternational)。样品的X衍射图案如图21所示。该样品由具有约0.5微米到约2微米颗粒尺寸的板状晶体组成,如图22的SEM图像所示。
用于说明书和权利要求中的所有表示成分,反应条件等的量的数字可以理解为在所有情形中均受术语“约”的限定,除非另有说明。因此,在以下说明书和所附权利要求中的数值参数是近似值,其取决于通过本发明试图获取的所需性质而可能改变,除非另有说明。
考虑到文中公开的说明书和发明实践,本发明的其他实施方案对于本领域技术人员是清楚的。说明书和实施例旨在仅视为示例性的,本发明的真正范围由以下权利要求指出。
Claims (18)
1.结晶微孔材料,该材料具有镁碱沸石(FER)框架类型,大于10的第一种四价金属氧化物与第二种四价或三价金属氧化物的摩尔比,和200纳米以下的平均晶体尺寸,
其中所述结晶微孔材料的表面积为300m2/g至450m2/g,且所述结晶微孔材料的微孔体积为0.10cc/g至0.20cc/g。
2.权利要求1的结晶微孔材料,其中所述材料在所有晶体维度具有200纳米以下的晶体尺寸。
3.权利要求1的结晶微孔材料,其中所述第一种四价金属氧化物包括氧化硅,所述第二种四价金属氧化物包括氧化铝,且其中所述摩尔硅铝比(SAR)为10至60。
4.权利要求1的结晶微孔材料,其中所述材料在所有晶体维度具有100纳米以下的平均晶体尺寸。
5.权利要求1的结晶微孔材料,还包含至少一种氢化功能金属。
6.权利要求5的结晶微孔材料,其中所述至少一种氢化功能金属选自Pt、Pd、Rh、Ru、Ni、Re和其混合物。
7.权利要求1的结晶微孔材料,还包含至少一种过渡金属,用于氮氧化物的选择性催化还原和/或氧化亚氮的催化分解。
8.权利要求7的结晶微孔材料,其中所述至少一种过渡金属选自Cu和Fe。
9.一种制备结晶微孔材料的方法,该材料具有镁碱沸石(FER)框架类型,大于10的摩尔硅铝比(SAR),和200纳米以下的平均晶体尺寸,所述方法包括:
形成合成混合物,该合成混合物由氧化硅源、氧化铝源、碱金属源,和有机结构导向剂组成,所述有机结构导向剂包括:
-第一有机结构导向剂(OSDA-1),和
-第二有机结构导向剂(OSDA-2),其促进镁碱沸石结构形成,其中OSDA-1与OSDA-2的摩尔比为0.2到1.0;和
加热该合成混合物到120-200℃的温度,持续足以结晶该材料的一段时间,以形成300m2/g至450m2/g的表面积和0.10cc/g至0.20cc/g的微孔体积的结晶微孔材料。
10.权利要求9的方法,其中所述OSDA-1包含四甲铵阳离子。
11.权利要求9的方法,其中所述OSDA-2选自吡咯烷、乙二胺、1,3-二氨基丙烷、1-甲基吡咯烷、哌啶、吡啶、和1,4-二氨基丁烷。
12.权利要求9的方法,其中所述有机结构导向剂包含四甲铵阳离子和1,3-二氨基丙烷。
13.权利要求9的方法,其中所述有机结构导向剂包含四甲铵阳离子和吡咯烷。
14.包含结晶微孔材料的催化剂,该结晶微孔材料具有镁碱沸石(FER)框架类型,大于10的摩尔硅铝比(SAR),300m2/g至450m2/g的表面积,0.10cc/g至0.20cc/g的微孔体积,和在所有维度200纳米以下的平均晶体尺寸,其中所述催化剂对于选自烃转化、氮氧化物的选择性催化还原和氧化亚氮的催化分解中的至少一个过程是催化活性的。
15.权利要求14的催化剂,还包含用于烃转化的至少一种氢化功能金属。
16.权利要求15的催化剂,其中所述至少一种氢化功能金属选自Pt、Pd、Rh、Ru、Ni、Re和其混合物。
17.权利要求14的催化剂,还包含至少一种过渡金属用于氮氧化物的选择性催化还原和/或氧化亚氮的催化分解。
18.权利要求17的催化剂,其中所述至少一种过渡金属选自Cu和Fe。
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US201261724136P | 2012-11-08 | 2012-11-08 | |
US61/724,136 | 2012-11-08 | ||
PCT/US2013/068438 WO2014074492A1 (en) | 2012-11-08 | 2013-11-05 | Small crystal ferrierite and method of making the same |
Publications (2)
Publication Number | Publication Date |
---|---|
CN104903234A CN104903234A (zh) | 2015-09-09 |
CN104903234B true CN104903234B (zh) | 2019-01-22 |
Family
ID=49585651
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201380065429.2A Active CN104903234B (zh) | 2012-11-08 | 2013-11-05 | 小晶体镁碱沸石及其制备方法 |
Country Status (11)
Country | Link |
---|---|
US (1) | US9827560B2 (zh) |
EP (1) | EP2917151B1 (zh) |
JP (1) | JP6382828B2 (zh) |
KR (1) | KR102233921B1 (zh) |
CN (1) | CN104903234B (zh) |
BR (1) | BR112015009957B1 (zh) |
IN (1) | IN2015DN03946A (zh) |
MY (1) | MY194296A (zh) |
RU (1) | RU2640072C9 (zh) |
WO (1) | WO2014074492A1 (zh) |
ZA (1) | ZA201503159B (zh) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106809850A (zh) * | 2015-11-30 | 2017-06-09 | 中国科学院大连化学物理研究所 | 一种小晶粒fer分子筛的合成方法 |
CZ307536B6 (cs) * | 2017-11-02 | 2018-11-14 | Unipetrol výzkumně vzdělávací centrum, a.s. | Způsob výroby zeolitu ferrierit |
CN108816275B (zh) * | 2018-04-19 | 2021-02-05 | 南京红太阳生物化学有限责任公司 | 一种用于合成气制吡啶碱的催化剂及制备方法和应用 |
CN108946764B (zh) * | 2018-07-25 | 2022-04-08 | 中国石油大学(北京) | 多级孔纳米镁碱沸石聚集物及其制备方法 |
CN108793189A (zh) * | 2018-07-25 | 2018-11-13 | 中国石油大学(北京) | 分层纳米薄片镁碱沸石分子筛及其制备方法和用途 |
EP3830031A1 (en) | 2018-07-27 | 2021-06-09 | Basf Se | Process for preparing a zeolitic material having a framework type fer |
CN113697825B (zh) * | 2020-05-20 | 2023-04-25 | 中国石油天然气股份有限公司 | 镁碱沸石及其制备方法和应用 |
CN113979444B (zh) * | 2020-07-27 | 2023-11-24 | 中国石油化工股份有限公司 | 一种具有fer结构的分子筛的制备方法和fer结构的分子筛 |
WO2022099016A1 (en) | 2020-11-05 | 2022-05-12 | Lyondell Chemical Technology, L.P. | Olefin isomerization with small crystallite zeolite catalyst |
EP4240711A1 (en) | 2020-11-05 | 2023-09-13 | Lyondell Chemical Technology, L.P. | Method of improving olefin isomerization |
US11180376B1 (en) | 2021-03-19 | 2021-11-23 | Chevron U.S.A. Inc. | Synthesis of zeolites having the ferrierite structure |
CN113769705B (zh) * | 2021-08-19 | 2024-07-19 | 复榆(张家港)新材料科技有限公司 | 一种无粘结剂亚中孔高硅fer沸石吸附剂及其制备方法 |
Family Cites Families (21)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4016245A (en) | 1973-09-04 | 1977-04-05 | Mobil Oil Corporation | Crystalline zeolite and method of preparing same |
GB1436524A (en) | 1974-03-18 | 1976-05-19 | British Petroleum Co | Synthesis of zeolites |
US3966883A (en) | 1974-10-16 | 1976-06-29 | W. R. Grace & Co. | Synthetic ferrierite synthesis |
US3933974A (en) | 1975-02-18 | 1976-01-20 | Shell Oil Company | Process for the preparation of ferrierite |
US3992466A (en) * | 1975-08-13 | 1976-11-16 | Mobil Oil Corporation | Hydrocarbon conversion |
NL7812162A (nl) | 1978-12-14 | 1980-06-17 | Shell Int Research | Werkwijze voor de bereiding van ferrieriet. |
US4377502A (en) | 1979-12-26 | 1983-03-22 | Standard Oil Company (Indiana) | Synthesis of crystalline aluminosilicate molecular sieves |
US4650654A (en) | 1982-09-20 | 1987-03-17 | Toyo Soda Manufacturing Co., Ltd. | Process for preparation of ferrierite type zeolites |
US4795623A (en) | 1986-08-05 | 1989-01-03 | Shell Oil Company | Time effective method for preparing ferrierite |
JPH07106300B2 (ja) | 1989-12-08 | 1995-11-15 | 財団法人産業創造研究所 | 燃焼排ガス中の窒素酸化物除去法 |
US5491273A (en) * | 1994-11-17 | 1996-02-13 | Mobil Oil Corporation | Catalytic conversion of methanol to linear olefins |
IN192774B (zh) * | 1995-06-07 | 2004-05-15 | Sheel Oil Company | |
CN1250454C (zh) * | 1995-06-07 | 2006-04-12 | 壳牌石油公司 | 制备镁碱沸石的方法 |
FR2766810B1 (fr) | 1997-07-31 | 1999-10-22 | Total Raffinage Distribution | Procede de preparation d'une zeolithe de type ferrierite et son utilisation comme catalyseur d'isomerisation d'une olefine lineaire en isoolefine |
ATE356102T1 (de) * | 2001-07-02 | 2007-03-15 | Exxonmobil Chem Patents Inc | Inhibierung der katalysatorverkokung bei der herstellung eines olefins |
US6709644B2 (en) * | 2001-08-30 | 2004-03-23 | Chevron U.S.A. Inc. | Small crystallite zeolite CHA |
ITMI20012707A1 (it) * | 2001-12-20 | 2003-06-20 | Enichem Spa | Processo per l'alchilazione di composti aromatici |
US6867341B1 (en) * | 2002-09-17 | 2005-03-15 | Uop Llc | Catalytic naphtha cracking catalyst and process |
CA2602506C (en) * | 2005-03-24 | 2014-01-14 | W.R. Grace & Co. -Conn. | Method for controlling nox emissions in the fccu |
ES2304308B1 (es) * | 2007-03-23 | 2009-08-07 | Consejo Superior Investg.Cientificas | Procedimiento de preparacion de un aluminosilicato con estructura tipo ferrierita a partir de geles que contienen tetrametilamonio y bencil-metilpirrolidinio,y sus aplicaciones. |
FR2920757B1 (fr) * | 2007-09-07 | 2009-11-13 | Inst Francais Du Petrole | Materiau cristallise comprenant du silicium a porosite hierarchisee et organisee |
-
2013
- 2013-11-05 JP JP2015541847A patent/JP6382828B2/ja active Active
- 2013-11-05 IN IN3946DEN2015 patent/IN2015DN03946A/en unknown
- 2013-11-05 RU RU2015121786A patent/RU2640072C9/ru not_active IP Right Cessation
- 2013-11-05 WO PCT/US2013/068438 patent/WO2014074492A1/en active Application Filing
- 2013-11-05 BR BR112015009957-2A patent/BR112015009957B1/pt active IP Right Grant
- 2013-11-05 KR KR1020157014607A patent/KR102233921B1/ko active IP Right Grant
- 2013-11-05 US US14/072,202 patent/US9827560B2/en active Active
- 2013-11-05 MY MYPI2015701455A patent/MY194296A/en unknown
- 2013-11-05 EP EP13792197.9A patent/EP2917151B1/en active Active
- 2013-11-05 CN CN201380065429.2A patent/CN104903234B/zh active Active
-
2015
- 2015-05-06 ZA ZA2015/03159A patent/ZA201503159B/en unknown
Also Published As
Publication number | Publication date |
---|---|
US20140128248A1 (en) | 2014-05-08 |
RU2015121786A (ru) | 2016-12-27 |
RU2640072C9 (ru) | 2018-05-30 |
BR112015009957A2 (pt) | 2017-07-11 |
CN104903234A (zh) | 2015-09-09 |
KR20150082443A (ko) | 2015-07-15 |
US9827560B2 (en) | 2017-11-28 |
MY194296A (en) | 2022-11-27 |
JP2015533776A (ja) | 2015-11-26 |
BR112015009957A8 (pt) | 2019-09-17 |
EP2917151B1 (en) | 2023-07-19 |
EP2917151A1 (en) | 2015-09-16 |
ZA201503159B (en) | 2022-11-30 |
BR112015009957B1 (pt) | 2022-03-15 |
IN2015DN03946A (zh) | 2015-10-02 |
JP6382828B2 (ja) | 2018-08-29 |
WO2014074492A1 (en) | 2014-05-15 |
RU2640072C2 (ru) | 2017-12-26 |
KR102233921B1 (ko) | 2021-03-29 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN104903234B (zh) | 小晶体镁碱沸石及其制备方法 | |
JP4919948B2 (ja) | ヘテロ構造非zsm−48シーディングによるzsm−48結晶の合成 | |
WO2015005369A1 (ja) | リンを含有するaei型ゼオライト及びその製造方法 | |
JP2008519748A (ja) | ジエチレントリアミンを使用したベータゼオライトの合成方法 | |
KR20110042740A (ko) | 나노 크기의 결정성 zsm-5 핵을 사용한 zsm-5의 제조 방법 | |
CN108622914A (zh) | 在模板1,6-双(甲基哌啶鎓)己烷二氢氧化物的存在下合成izm-2沸石的方法 | |
JP2010527902A (ja) | Eu−1ゼオライトの新規な調製方法 | |
JP2016166124A (ja) | チタンを含有するaei型ゼオライト及びその製造方法 | |
CN107285330A (zh) | 一种nu-88分子筛的制备方法 | |
WO2019117183A1 (ja) | β型ゼオライト及びその製造方法 | |
CN112551543B (zh) | 在氢氧化物和溴化物形式的含氮有机结构化剂的混合物存在下制备izm-2沸石的方法 | |
CN101514008B (zh) | 丝光沸石/y沸石共生分子筛及其合成方法 | |
CN109694086A (zh) | 纳米zsm-5沸石分子筛聚集体的制备方法 | |
KR100925851B1 (ko) | 높은 실리카/알루미늄 비를 갖는 제올라이트의 제조방법 | |
CN101514011B (zh) | 丝光沸石/β沸石/MCM-22三相共生分子筛及其合成方法 | |
JP2012240867A (ja) | ゼオライトの製造方法 | |
WO2020227886A1 (zh) | 一种快速制备高结晶度的ecr-1分子筛的方法 | |
WO2020227888A1 (zh) | 一种zsm-57分子筛及其制备方法 | |
EP3385226B1 (en) | Beta zeolite and method for producing same | |
CN107519938B (zh) | Y/CeO2/SBA-15/ASA/MOF复合材料及其制备方法 | |
JP5483814B2 (ja) | コロイド状フォージャサイト型ゼオライトおよびその合成方法 | |
CN107519925B (zh) | Y/Sm2O3/SBA-3/ASA复合材料及其制备方法 | |
CN107519922B (zh) | Y/Gd2O3/ZSM-23/ZSM-5/ASA复合材料及其制备方法 | |
JP2020500827A (ja) | 加速したアルミノシリケートゼオライトの結晶化 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
C10 | Entry into substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
TR01 | Transfer of patent right |
Effective date of registration: 20220321 Address after: Pennsylvania, America Patentee after: Ekovist Catalyst Technology Co.,Ltd. Address before: Pennsylvania USA Patentee before: PQ Corp. |
|
TR01 | Transfer of patent right |