CN108160103A - The preparation of high dispersive transition metal nanoparticles support type porous zeotile aggregation - Google Patents
The preparation of high dispersive transition metal nanoparticles support type porous zeotile aggregation Download PDFInfo
- Publication number
- CN108160103A CN108160103A CN201711296181.7A CN201711296181A CN108160103A CN 108160103 A CN108160103 A CN 108160103A CN 201711296181 A CN201711296181 A CN 201711296181A CN 108160103 A CN108160103 A CN 108160103A
- Authority
- CN
- China
- Prior art keywords
- transition metal
- aggregation
- molecular sieve
- metal nanoparticles
- high dispersive
- 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.)
- Granted
Links
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 230000002776 aggregation Effects 0.000 title claims abstract description 19
- 238000004220 aggregation Methods 0.000 title claims abstract description 19
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 title claims abstract description 17
- 239000010457 zeolite Substances 0.000 claims abstract description 35
- 229910021536 Zeolite Inorganic materials 0.000 claims abstract description 33
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002808 molecular sieve Substances 0.000 claims abstract description 28
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000463 material Substances 0.000 claims abstract description 25
- -1 transition metal salt Chemical class 0.000 claims abstract description 17
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 12
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
- 239000011148 porous material Substances 0.000 claims abstract description 8
- 150000003624 transition metals Chemical class 0.000 claims abstract description 7
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims abstract description 5
- 238000002425 crystallisation Methods 0.000 claims abstract description 3
- 230000008025 crystallization Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 30
- 239000002184 metal Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 239000002243 precursor Substances 0.000 claims description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229910052748 manganese Inorganic materials 0.000 claims 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 claims description 5
- 229910052802 copper Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 150000003839 salts Chemical class 0.000 claims description 3
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 3
- 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 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- SMZOGRDCAXLAAR-UHFFFAOYSA-N aluminium isopropoxide Chemical group [Al+3].CC(C)[O-].CC(C)[O-].CC(C)[O-] SMZOGRDCAXLAAR-UHFFFAOYSA-N 0.000 claims description 2
- 239000006229 carbon black Substances 0.000 claims description 2
- 239000000411 inducer Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- 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 claims 2
- 229910052708 sodium Inorganic materials 0.000 claims 2
- 239000011734 sodium Substances 0.000 claims 2
- 239000006193 liquid solution Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 11
- 239000013078 crystal Substances 0.000 abstract description 7
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 34
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 15
- 238000000034 method Methods 0.000 description 13
- 239000002082 metal nanoparticle Substances 0.000 description 7
- 239000002105 nanoparticle Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052911 sodium silicate Inorganic materials 0.000 description 5
- 235000013339 cereals Nutrition 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- 229910000329 aluminium sulfate Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 229910052684 Cerium Inorganic materials 0.000 description 2
- 229910003294 NiMo Inorganic materials 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- NBBJYMSMWIIQGU-UHFFFAOYSA-N Propionic aldehyde Chemical compound CCC=O NBBJYMSMWIIQGU-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- MYAQZIAVOLKEGW-UHFFFAOYSA-N DMDBT Natural products S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- ZTQSAGDEMFDKMZ-UHFFFAOYSA-N butyric aldehyde Natural products CCCC=O ZTQSAGDEMFDKMZ-UHFFFAOYSA-N 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 150000002191 fatty alcohols Chemical class 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229960005150 glycerol Drugs 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000007327 hydrogenolysis reaction Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001388 sodium aluminate Inorganic materials 0.000 description 1
- 235000019795 sodium metasilicate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001931 tungsten(III) oxide Inorganic materials 0.000 description 1
- 239000013598 vector Substances 0.000 description 1
- 229910003158 γ-Al2O3 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
- B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
- B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
- B01J29/46—Iron group 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
- B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
- B01J29/72—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing iron group metals, noble metals or copper
- B01J29/76—Iron group metals or copper
- B01J29/7615—Zeolite Beta
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C01B39/365—Type ZSM-8; Type ZSM-11; ZSM 5/11 intermediate
-
- 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
-
- 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
- C01B39/46—Other types characterised by their X-ray diffraction pattern and their defined composition
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Materials Engineering (AREA)
- Geology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Crystallography & Structural Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- Composite Materials (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparations of high dispersive transition metal nanoparticles support type porous zeotile aggregation, its main feature is that inorganic silicon source and transition metal salt mixed liquor are added drop-wise in the solution of inorganic silicon source, basicity is adjusted with KOH or NaOH, stir to obtain transition metal silicon-aluminum sol gel solution, then by adding the crystal seed gel of different crystal structure, crystallization 10 ~ 48 hours at a temperature of 80~200 DEG C, transition metal nanoparticles support type multi-stage pore zeolite molecular sieve aggregation catalysis material of the product obtained for 1.5~2nm particle sizes of high dispersive.The present invention has the synthesis of step control multi-stage pore zeolite molecular sieve material compared with prior art, the duct openness of Effective Regulation porous zeotile, successfully transition metal nanoparticles are modified on the surface of porous zeotile aggregate material, it obtains more active sites and is not easy the zeolite aggregation catalysis material reunited, it prepares simple, it is easy to operate, it is easily isolated, there is certain industrialization promotion to use prospect and significant economic value.
Description
Technical field
The present invention relates to zeolite molecular sieve synthetic technology field, especially a kind of high dispersive transition metal nanoparticles load
The preparation of type porous zeotile aggregation.
Background technology
Nano Transition Metal Catalyst is received significant attention and is studied due to its excellent catalytic performance, becomes modern chemical industry
One of leading type catalyst, and occupy very crucial status in catalyst field, since metal nanoparticle is with very high
Surface can easily reunite so that activity reduces, in order to solve this problem, can the nano particle of high activity is immobilized to carrier
On, the aggregation of nano particle is inhibited to inactivate by the interaction with carrier.
Nano particle load is mainly synthesized by the method impregnated, and one kind is first synthetic vectors, then passes through dipping
Method loads to metal salt on carrier, then by the post processing etc. such as calcining, restore, obtain metal nanoparticle load
On carrier.Such as patent（CN 104874417 A）Disclose the Co based Fischer-Tropsch synthesis catalyst and its system of a kind of composite carrier load
Preparation Method and application, this method are that one or more of soluble salt solutions of Ni, Mn, Zr, La, Ce, Ca and Re are isometric
It is impregnated on complex carrier, is then made through drying, roasting.Patent（CN 101497047 B ）Disclose a kind of X-type molecular sieve
Application of the Ni base catalyst supported in hydrogenolysis of glycyl alcohol, the catalyst using Ni as active component, Ca, Mo, W, Mn, Fe,
One or more of Co, Cu, Sn, Ce are addition metal, are successfully loaded in X types molecular sieve carrier using equi-volume impregnating
Catalyst is made in the active component nickel of 5~15 wt%.Patent（CN 101855013 B）One kind is disclosed for being split in catalysis
Change during reduce content of sulfur in gasoline carbon monoxide-olefin polymeric, the catalyst with rare earth metal, Zn, Mn, Zr, Al, Mg, Ni and
One or more metals in Cu can successfully be supported on Y, USY, REY, REUSY, zeolite beta, ZSM-5 and its mixture composition
Zeolite molecular sieve carrier on.Patent（CN 101591222 B）A kind of method that glucose hydrogenation prepares sorbierite is disclosed,
This method is supported on molecular sieve or Al using Co, Mn, Cu, Cr, Mo, Ca, Zn, Fe or W2O3、SiO2、TiO2, MgO and without fixed
On choosing any one kind of them in shape alumina silicate or several mixtures, Ni-A/X loaded catalysts are made.Patent（CN
103418427 B ）Disclose a kind of NH3Catalyst of selective reduction NOx and preparation method and application, the catalyst use
The oxide CuO or Cu of Ni metal2O, molecular sieve carrier for H beta-molecular sieves either modenite (MOR) type molecular sieve or
The low temperature sulfur resistive method of ZRP molecular sieves or their mixtures is made.Patent（CN100344370 C）Disclose a kind of 3- hydroxyls
Base hydrogenation of propionaldehyde prepares the catalyst of 1,3-PD, and the catalyst is using the mixture of molecular sieve, oxide or the two as load
Body, using Ni, Mo and third metal as the Ni-Mo-X/A supported catalysts of active component, the catalyst is water-soluble for-hydroxy propanal
When liquid Hydrogenation reacts for 1,3-PD, activity, high selectivity, reaction condition is mild, and catalyst stabilization is good.Patent（CN
1274789 C）A kind of hollow scaffold board is disclosed, acidic zeolite is supported on using 0-20 wt% group VIII metals
40-80 wt%；γ-Al2O3:On 0-60 wt%, a kind of catalyst for olefinic naphtha fraction hydrogenating modification is obtained.
Patent（CN 102631934 B）A kind of hydrodesulfurization of porous zeolite load C oMo, NiMo, NiW metal sulfide is disclosed to urge
Agent and preparation method thereof, the metal sulfide desulphurization catalyst prepared using porous zeolite load C oMo, NiMo or NiW, solution
Traditional metal sulfide catalyst of having determined can not achieve the problem of removing 4,6-DM-DBT under mild conditions, pass through this
Invention can prepare the desulphurizing activated novel hydro-desulfurizatiocatalyst catalyst far above traditional catalyst.
In addition, a kind of preparation method of nano particle supported catalyst is first to be respectively synthesized carrier and metal nanoparticle,
Then nano particle is loaded on carrier by infusion process, can be prepared by without post processing.Such as patent（CN 102441421
B）A kind of preparation method containing modified B- β zeolite hydrocracking catalysts is disclosed, this method will modified B- β zeolites and macropore
Amorphous silica-alumina is uniformly mixed, and adds in adhesive or peptizing agent, through being molded, drying, roast obtained catalyst carrier, is then used
Infusion process loads hydrogenation active component, obtains hydrocracking catalyst through dry and roasting, being hydrocracked for this method preparation is urged
Agent is while catalyst activity and intermediate oil selectivity is taken into account, moreover it is possible to produce high-grade low-freezing diesel oil.Above-mentioned infusion process
Metal nanoparticle can be successfully loaded on carrier, but it is cumbersome, in many cases, disperse uneven, metal
Grain diameter is difficult control, and is assembled under pyroreaction.Therefore other methods are also developed, such as patent（CN
106349507 A）A kind of preparation method of modenite-red phosphorus synergistic fire retardant is disclosed, by modenite and a certain amount of 0
.1mol/L NiCl2Solution mixes, and by the method for ion exchange, can obtain loading 3-29 % in duct（Mass ratio）It is red
The modenite of phosphorus-red phosphorus synergistic fire retardant.Patent（CN 1147573 C）A kind of polyfilament yarn of polyamide is disclosed, is used
Base metal is supported on modified Y zeolite catalyst by the method for ion exchange, obtains the high Non-precious Metal Catalysts of dispersion degree
Agent material, the excellent in sour resistance in hydrogenation reaction.But these content of metal are all limited.Patent（CN
104858413 B）A kind of preparation method of silicon dioxide carried noble metal nano particles is disclosed, using reverse micro emulsion method
Metal nanoparticle Cu, Au, Ni, Pt, Pd, Rh, Ir, Ru of 1-20 nm are supported on the silica dioxide granule of 20-200 nm,
The preparation needs to use the expensive reagents such as surfactant, long-chain fatty alcohol and preparation process is cumbersome.Above patent document institute is public
The technology contents opened, it is seen that preparation process is all very cumbersome, and all unknown to the nano-particle distribution of acquired material
Really point out particle size.
In conclusion the transition metal nanoparticles catalyst of the different molecular sieve load of prior art preparation, generally all
Synthesis zeolite is first wanted, is then loaded again, preparation process is cumbersome, is also easy to the metallic reunited, obtained
Grain size is larger and uneven, leverages the activity of transition metal loaded catalyst.
Invention content
The purpose of the present invention is in view of the deficiencies of the prior art and provide a kind of high dispersive transition metal nanoparticles bear
The preparation of load type porous zeotile aggregation, inorganic silicon is added drop-wise to after being mixed using inorganic silicon source with inorganic transition metal salt and water
In the solution of source, with ammonium hydroxide and inorganic base salts（KOH or NaOH）Basicity is adjusted, and adds the crystal seed of different structure, one-step synthesis method
The different types of multi-stage pore zeolite molecular sieve of high dispersive transition metal nanoparticles support type is obtained, it can be by 1~2 nm grain sizes
Transition metal nanoparticles are modified on the surface of porous zeotile aggregate material, and both multi-stage pore zeolite molecular sieve material is carried out
Modification, obtains the material of more active sites, while the duct openness of controllable multi-stage porous, effectively the boiling of step control multi-stage porous
The synthesis of stone molecular screen material so that be distributed on carrier to metal nanoparticle high dispersive, and can stablize, it is not easy to roll into a ball
Poly-, preparation process is simple, easy to operate, and material is easily isolated, and is particularly suitable for mass producing, and there is certain industrialization to push away
Extensively use prospect and significant economic value.
Realizing the specific technical solution of the object of the invention is：A kind of high dispersive transition metal nanoparticles support type multi-stage porous
The preparation of zeolite aggregation, its main feature is that be added drop-wise in silicon source after inorganic transition metal salt and silicon source and water are stirred evenly, and
Basicity adjusting is carried out with KOH or NaOH, is configured to molar ratio as 1SiO2: 0~0.05Al2O3:0.001 ~ 0.3 transition metal salt
Ion: 0.05~0.4OH-: 10~100H2The mixed solution of O is transition metal salt-silicon-aluminum sol gel, then in above-mentioned mixing
Molecular sieve seed is at the uniform velocity added dropwise in solution and obtains precursor solution, by precursor solution at a temperature of 80~200 DEG C crystallization 10 ~
48 hours, the multi-stage pore zeolite molecular sieve aggregation catalysis material of obtained high dispersive transition metal nanoparticles load, described point
Son sieve crystal seed is 0.1 ~ 15% with the weight ratio that transition metal salt-silicon-aluminum sol coagulates；The inorganic transition metal salt for Ni, Co,
The inorganic metal soluble salt of one kind or its two or more mixing in Cu, Zn, Fe, Mn, Cr；Source of aluminium is aluminium isopropoxide, partially
Sodium aluminate, aluminum sulfate or aluminum nitrate；The silicon source is sodium metasilicate, waterglass, Ludox or White Carbon black；The molecular sieve seed is
MFI, MEL, the little particle zeolite stoste of structure, aqueous solution or non-crystallized complete structure inducer；The molecular sieve seed
Granular size be 10 ~ 500 nm.
The present invention has load and the multi-stage porous that a step realizes high dispersive transition metal nanoparticles compared with prior art
The synthesis of molecular sieve of Nano zeolite aggregation can modify the transition metal nanoparticles of 1~2 nm grain sizes in porous zeotile
Multi-stage pore zeolite molecular sieve material was both modified in the surface of aggregate material, obtained the material of more active sites, while can
Regulate and control the duct openness of multi-stage porous, effectively the synthesis of step control multi-stage pore zeolite molecular sieve material so that metal nano
It is distributed on carrier to particle high dispersive, and can stablize, be not easy to reunite, preparation process is simple, easy to operate, and material is easy to point
From, be particularly suitable for mass producing, have certain industrialization promotion use prospect and significant economic value.
Description of the drawings
Fig. 1 is the XRD spectra of 1 products therefrom of embodiment；
Fig. 2 is the TEM spectrograms of 1 products therefrom of embodiment.
Specific embodiment
In order to be better understood from and implement, with reference to embodiment, the invention will be further described.
Embodiment 1
By 0.6 g NiSO4With 2.2 g Al2(SO4)3·18H2O is dissolved in 25 ml pure water, and 28 g are added drop-wise to after stirring clarification
Na2SiO3·9H2In the 20 ml aqueous solutions of O, 2 ml NH are added in3·H2O（A concentration of 1 M）Basicity is adjusted, stirring obtains for 23 minutes
Nickel-silicon Aluminum sol gel solution then by the silicate-1 seed-solutions of 0.7 g (13wt%), is added drop-wise to above-mentioned preparation
Precursor solution is stirred 30 minutes to obtain in nickel-silicon Aluminum sol gel solution, hydro-thermal is brilliant at a temperature of 150 DEG C by precursor solution
Change reaction 20 hours, washed after reaction, dry, obtained product is the Ni-ZSM-5 nano zeolite aggregations of high dispersive
Catalyst material.
Refering to attached drawing 1, the XRD spectra of products therefrom Ni-ZSM-5 samples is consistent with the characteristic peak of standard MFI molecular sieves, table
Bright transiting metal nickel does not enter zeolite molecular sieve skeleton, and obtained material is nickel load type ZSM-5 nano zeolite aggregation materials
Material, and there is no other dephasigns.
Refering to attached drawing 2, show that the Ni nano particles that products therefrom is 1~2 nm have successfully been supported on ZSM-5 nano zeolites
Aggregate surface.
Embodiment 2
By 0.4 g CuCl2·6H2O and 1.1 g Al2(SO4)3·18H2O is dissolved in 25 ml pure water, is added drop-wise to after stirring clarification
28 g Na2SiO3·9H2In the 25ml aqueous solutions of O, 2.2 ml NH are added in3·H2O（A concentration of 1 M）Adjust basicity, stirring 25
Minute obtains copper-silicon-aluminum sol gel solution, then by 0.5 g (13wt%)-zeolite zeolite seed crystal solution, is added drop-wise to
It states and precursor solution is stirred 25 minutes to obtain in the nickel-silicon Aluminum sol gel solution of preparation, by precursor solution in 170 DEG C of temperature
Lower hydrothermal crystallizing reacts 26 hours, and washed after reaction, dry, obtained product is received for the Cu--zeolite of high dispersive
Rice zeolite aggregation catalyst material.
Embodiment 3
By 0.5 g CoCl2 · 6H2O and 0.67 g Al2 (SO4)3·18H2O is dissolved in 25 ml pure water, after stirring clarification
It is added drop-wise to 27 g Na2SiO3·9H2In the 23ml aqueous solutions of O, 2.1 ml NH are added in3·H2O（A concentration of 1 M）Adjust basicity,
Stirring 20 minutes cobalt-silicon-aluminum sol gel solution, then by 0.4 g (13wt%) silicate-2 zeolite seed crystal solution,
It is added drop-wise in cobalt-silicon-aluminum sol gel solution of above-mentioned preparation and stirs 30 minutes to obtain precursor solution, by precursor solution 150
Hydrothermal crystallizing reacts 20 hours at a temperature of DEG C, washed after reaction, dry, and obtained product is the Co-ZSM- of high dispersive
11 nano zeolite aggregation catalyst materials.
Embodiment 4
By 0.2 g NiCl2 · 6H2O and 0.67 g Al2(SO4)3·18H2O is dissolved in 25 ml pure water, after stirring clarification
It is added drop-wise to 25 g Na2SiO3·9H2In the 25ml aqueous solutions of O, 2.5 ml NH are added in3·H2O（A concentration of 1 M）Adjust basicity,
Stirring 20 minutes nickel-silicon Aluminum sol gel solution, then by 0.5 g (13wt%) silicate-2 zeolite seed crystal solution,
It is added drop-wise in the nickel-silicon Aluminum sol gel solution of above-mentioned preparation and stirs 25 minutes to obtain precursor solution, by precursor solution 160
Hydrothermal crystallizing reacts 30 hours at a temperature of DEG C, washed after reaction, dry, and obtained product is the Ni- of high dispersive
ZSM-11 nano zeolite aggregation catalyst materials.
Only the invention will be further described for the above various embodiments, and not to limit patent of the present invention, all is this hair
Bright equivalence enforcement is intended to be limited solely by within the right of patent of the present invention.
Claims (2)
1. a kind of preparation of high dispersive transition metal nanoparticles support type porous zeotile aggregation, it is characterised in that will be inorganic
Transition metal salt is added drop-wise to after being stirred evenly with silicon source and water in silicon source, and carries out basicity adjusting with KOH or NaOH, is configured to rub
You are than being 1SiO2: 0~0.05Al2O3:0.001 ~ 0.3 transition metal salt ion: 0.05~0.4OH-: 10~100H2The mixing of O
Solution is transition metal salt-silicon-aluminum sol gel, and molecular sieve seed is at the uniform velocity then added dropwise in above-mentioned mixed solution and obtains forerunner
Liquid solution, by precursor solution at a temperature of 80~200 DEG C crystallization 10 ~ 48 hours, high dispersive transition metal nanoparticles are made
The multi-stage pore zeolite molecular sieve aggregation catalysis material of load, the molecular sieve seed are coagulated with transition metal salt-silicon-aluminum sol
Weight ratio is 0.1 ~ 15%；The inorganic transition metal salt is one kind in Ni, Co, Cu, Zn, Fe, Mn, Cr or its is two or more
The inorganic metal soluble salt of mixing；Source of aluminium is aluminium isopropoxide, sodium metaaluminate, aluminum sulfate or aluminum nitrate；The silicon source is silicon
Sour sodium, waterglass, Ludox or White Carbon black；The molecular sieve seed is MFI, MEL, the little particle zeolite stoste of structure, water
Solution or non-crystallized complete structure inducer.
2. the preparation of high dispersive transition metal nanoparticles support type porous zeotile aggregation according to claim 1,
The granular size for being characterized in that the molecular sieve seed is 10 ~ 500 nm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711296181.7A CN108160103B (en) | 2017-12-08 | 2017-12-08 | Preparation of high-dispersion transition metal nanoparticle supported hierarchical pore zeolite aggregate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711296181.7A CN108160103B (en) | 2017-12-08 | 2017-12-08 | Preparation of high-dispersion transition metal nanoparticle supported hierarchical pore zeolite aggregate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108160103A true CN108160103A (en) | 2018-06-15 |
| CN108160103B CN108160103B (en) | 2020-10-16 |
Family
ID=62525572
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711296181.7A Expired - Fee Related CN108160103B (en) | 2017-12-08 | 2017-12-08 | Preparation of high-dispersion transition metal nanoparticle supported hierarchical pore zeolite aggregate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108160103B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109607563A (en) * | 2018-12-25 | 2019-04-12 | 大连理工大学 | Zinc modification multi-stage porous ZSM-5 nano zeolite and preparation method thereof |
| CN111001360A (en) * | 2019-12-25 | 2020-04-14 | 淄博诺奥化工股份有限公司 | Green method for preparing alkane alcohols by liquid phase hydrogenation |
| CN111804328A (en) * | 2019-04-10 | 2020-10-23 | 中国石油大学(华东) | Preparation method of catalyst for catalyzing thickened oil viscosity reduction |
| CN112156807A (en) * | 2020-10-19 | 2021-01-01 | 西安工程大学 | Preparation method of hierarchical pore Zr- (H) ZSM-11 molecular sieve |
| CN114225940A (en) * | 2021-12-27 | 2022-03-25 | 中国科学院兰州化学物理研究所 | Heterogeneous catalyst for hydrogenation of styrene thermoplastic elastomer |
| CN115970750A (en) * | 2022-11-30 | 2023-04-18 | 嘉庚创新实验室 | Zeolite molecular sieve based catalyst and preparation method thereof, and method for preparing bio-based diesel oil by grease one-step hydroisomerization |
| CN116139915A (en) * | 2021-11-23 | 2023-05-23 | 中国石油天然气股份有限公司 | Catalyst for converting methane and propane into aromatic hydrocarbon and preparation method thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0615182A (en) * | 1992-07-01 | 1994-01-25 | Mazda Motor Corp | Catalyst for purification of exhaust gas |
| CN103495342A (en) * | 2013-09-25 | 2014-01-08 | 北京钟华鼎盛节能技术有限公司 | Method for separating MEOH-DMC (methanol-dimethyl carbonate) through vapor permeation |
| CN103599811A (en) * | 2013-12-04 | 2014-02-26 | 天津工业大学 | Preparation method of nano Fe-MCM-41 molecular sieve catalyst |
| CN103204516B (en) * | 2013-04-09 | 2015-03-04 | 华东师范大学 | Preparation method of FER (Ferritin) zeolite molecular sieve with high silica-alumina ratio |
| CN106830001A (en) * | 2017-03-14 | 2017-06-13 | 中国矿业大学 | A kind of synthetic method of the molecular sieves of c axial directions Zn ZSM 5 with meso-hole structure |
-
2017
- 2017-12-08 CN CN201711296181.7A patent/CN108160103B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0615182A (en) * | 1992-07-01 | 1994-01-25 | Mazda Motor Corp | Catalyst for purification of exhaust gas |
| CN103204516B (en) * | 2013-04-09 | 2015-03-04 | 华东师范大学 | Preparation method of FER (Ferritin) zeolite molecular sieve with high silica-alumina ratio |
| CN103495342A (en) * | 2013-09-25 | 2014-01-08 | 北京钟华鼎盛节能技术有限公司 | Method for separating MEOH-DMC (methanol-dimethyl carbonate) through vapor permeation |
| CN103599811A (en) * | 2013-12-04 | 2014-02-26 | 天津工业大学 | Preparation method of nano Fe-MCM-41 molecular sieve catalyst |
| CN106830001A (en) * | 2017-03-14 | 2017-06-13 | 中国矿业大学 | A kind of synthetic method of the molecular sieves of c axial directions Zn ZSM 5 with meso-hole structure |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109607563A (en) * | 2018-12-25 | 2019-04-12 | 大连理工大学 | Zinc modification multi-stage porous ZSM-5 nano zeolite and preparation method thereof |
| CN109607563B (en) * | 2018-12-25 | 2022-06-17 | 大连理工大学 | Zinc modified hierarchical pore ZSM-5 nano zeolite and preparation method thereof |
| CN111804328A (en) * | 2019-04-10 | 2020-10-23 | 中国石油大学(华东) | Preparation method of catalyst for catalyzing thickened oil viscosity reduction |
| CN111804328B (en) * | 2019-04-10 | 2023-06-06 | 中国石油大学(华东) | Preparation method of catalyst for catalyzing viscosity reduction of thickened oil |
| CN111001360A (en) * | 2019-12-25 | 2020-04-14 | 淄博诺奥化工股份有限公司 | Green method for preparing alkane alcohols by liquid phase hydrogenation |
| CN111001360B (en) * | 2019-12-25 | 2021-11-12 | 淄博诺奥化工有限公司 | Green method for preparing alkane alcohols by liquid phase hydrogenation |
| CN112156807A (en) * | 2020-10-19 | 2021-01-01 | 西安工程大学 | Preparation method of hierarchical pore Zr- (H) ZSM-11 molecular sieve |
| CN116139915A (en) * | 2021-11-23 | 2023-05-23 | 中国石油天然气股份有限公司 | Catalyst for converting methane and propane into aromatic hydrocarbon and preparation method thereof |
| CN116139915B (en) * | 2021-11-23 | 2024-05-14 | 中国石油天然气股份有限公司 | Catalyst for converting methane and propane into aromatic hydrocarbon and preparation method thereof |
| CN114225940A (en) * | 2021-12-27 | 2022-03-25 | 中国科学院兰州化学物理研究所 | Heterogeneous catalyst for hydrogenation of styrene thermoplastic elastomer |
| CN115970750A (en) * | 2022-11-30 | 2023-04-18 | 嘉庚创新实验室 | Zeolite molecular sieve based catalyst and preparation method thereof, and method for preparing bio-based diesel oil by grease one-step hydroisomerization |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108160103B (en) | 2020-10-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108160103A (en) | The preparation of high dispersive transition metal nanoparticles support type porous zeotile aggregation | |
| CN109731608B (en) | Bifunctional catalyst of sodium-free silicon-aluminum molecular sieve for packaging metal nanoparticles and preparation method thereof | |
| CN109772443A (en) | A kind of molecular sieve carried high dispersive Pt catalyst of ZSM-12 and preparation method thereof | |
| EP0622118B1 (en) | Catalyst composition | |
| CN104646050B (en) | Hydrogenation catalyst, preparation and application thereof | |
| CN112028086B (en) | Nano Cu-SSZ-13 molecular sieve and one-step synthesis method and application thereof | |
| WO2004043590A1 (en) | Method for preparing a highly homogeneous amorphous silica-alumina composition | |
| KR20120004935A (en) | A hydrocracking catalyst, process for preparing the same and use thereof | |
| CN108855197B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN105413742B (en) | The application of synthesis and its light paraffins isomerization of zeolite cladding noble metal | |
| CN109745977A (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| JP3341011B2 (en) | Catalyst support and hydrogenation catalyst | |
| CN102451764A (en) | Method for preparing zirconia-alumina composite oxide carrier | |
| CN110407223A (en) | SSZ-13 molecular sieve and preparation, SCR catalyst and preparation | |
| CN102049279B (en) | Hydrocracking catalyst containing small grain Y-type molecular sieve dispersing material | |
| CN101618334B (en) | In situ type molecular sieve hydrogenation cracking catalyst and method for preparing same | |
| CN104549427B (en) | A kind of high-quality industrial chemicals hydrocracking catalyst and preparation method thereof | |
| CN116528978A (en) | Silica-alumina composition comprising 1-30 wt% crystalline basic ammonium aluminum carbonate and process for preparing the same | |
| CN109382131B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN109794299A (en) | Hydrogenation catalyst, preparation method thereof and distillate oil hydrofining method | |
| JP2000288398A (en) | Catalytic composition for upgrading quality of hydrocarbons having boiling point range of naphtha | |
| CN107344105B (en) | Hydrocracking catalyst and preparation method thereof | |
| RU2607905C1 (en) | Catalyst for hydrocracking hydrocarbon material | |
| CN109382134B (en) | The method of propane dehydrogenation catalyst and preparation method thereof and preparing propylene by dehydrogenating propane | |
| CN102049277B (en) | Hydrocracking catalyst for producing naphtha and raw material for preparing ethylene |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20201016 |