WO2017185820A1 - 一种分子筛、其制造方法及其应用 - Google Patents
一种分子筛、其制造方法及其应用 Download PDFInfo
- Publication number
- WO2017185820A1 WO2017185820A1 PCT/CN2017/000327 CN2017000327W WO2017185820A1 WO 2017185820 A1 WO2017185820 A1 WO 2017185820A1 CN 2017000327 W CN2017000327 W CN 2017000327W WO 2017185820 A1 WO2017185820 A1 WO 2017185820A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- oxide
- molecular sieve
- source
- group
- molar ratio
- Prior art date
Links
Images
Classifications
-
- 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
- C01B39/48—Other types characterised by their X-ray diffraction pattern and their defined composition using at least one organic template directing agent
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
- B01J20/08—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04 comprising aluminium oxide or hydroxide; comprising bauxite
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/165—Natural alumino-silicates, e.g. zeolites
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- 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
- B01J29/047—Germanosilicates; Aluminogermanosilicates
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
- C01B37/02—Crystalline silica-polymorphs, e.g. silicalites dealuminated aluminosilicate zeolites
-
- 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
- C01B39/026—After-treatment
-
- 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
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/02—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons
- C07C2/04—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation
- C07C2/06—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition between unsaturated hydrocarbons by oligomerisation of well-defined unsaturated hydrocarbons without ring formation of alkenes, i.e. acyclic hydrocarbons having only one carbon-to-carbon double bond
- C07C2/08—Catalytic processes
- C07C2/12—Catalytic processes with crystalline alumino-silicates or with catalysts comprising molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
- C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
- C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
- C07C4/06—Catalytic processes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
- C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
- C07C5/2206—Catalytic processes not covered by C07C5/23 - C07C5/31
- C07C5/222—Catalytic processes not covered by C07C5/23 - C07C5/31 with crystalline alumino-silicates, e.g. molecular sieves
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
- C10G11/04—Oxides
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
- C10G45/60—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins characterised by the catalyst used
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/60—Compounds characterised by their crystallite size
-
- 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
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/82—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by IR- or Raman-data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/90—Other crystal-structural characteristics not specified above
-
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/40—Particle morphology extending in three dimensions prism-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/54—Particles characterised by their aspect ratio, i.e. the ratio of sizes in the longest to the shortest dimension
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/61—Micrometer sized, i.e. from 1-100 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
- C01P2006/17—Pore diameter distribution
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2529/00—Catalysts comprising molecular sieves
- C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
- C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- C07C2529/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups C07C2529/08 - C07C2529/65
Definitions
- the present invention relates to a molecular sieve, especially an ultra-large pore molecular sieve.
- the invention also relates to a process for the manufacture of the molecular sieves and to their use as adsorbents or catalysts.
- Molecular sieves are widely used, and different uses often impose different requirements on the skeleton pore structure of the molecular sieve.
- Molecular sieves have four types of skeleton pore structure: small pore, medium pore, large pore and super large pore: small pore molecular sieve has to Apertures such as CHA, LEV, SOD, LTA, ERI, KFI; mesoporous molecular sieves have to Apertures such as MFI, MEL, EUO, MWW, TON, MTT, MFS, AEL, AFO, HEU, FER; large pore molecular sieves have Apertures such as FAU, BEA, MOR, LTL, VFI, MAZ; super-large pore molecular sieves have greater The aperture.
- ultra-large pore molecular sieves have broken through the pore limitation of molecular sieves, and have shown many advantages in improving macromolecular reactivity, prolonging molecular sieve life and improving product selectivity, and are expected to be processed in heavy oil. Good application in the production of organic chemical raw materials.
- the inventors have found through hard research on the basis of the prior art that a novel ultra-large pore molecular sieve has been discovered, and a new molecular sieve manufacturing method has also been discovered, thereby satisfying the aforementioned requirements of the prior art. .
- the invention relates to the following aspects:
- the first oxide has a molar ratio of from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5
- the size of the crystal morphology comprises an effective diameter of from 100 nm to 1000 nm, preferably from 300 nm to 700 nm, a height of from 100 nm to 1000 nm, preferably from 150 nm to 700 nm,
- the aspect ratio is from 1/3 to 8, preferably from 1.5 to 5 or from 2 to 5.
- molecular sieve according to any of the preceding claims, wherein the molecular sieve has a total specific surface area of from 400 m 2 /g to 600 m 2 /g, preferably from 450 m 2 /g to 580 m 2 /g, and a pore volume of from 0.3 Ml/g to 0.5 ml/g, preferably from 0.30 ml/g to 0.40 ml/g.
- a method of producing a molecular sieve comprising the steps of contacting a first oxide source, a second oxide source, an optional alkali source, an organic templating agent, and water under crystallization conditions to obtain a molecular sieve, and optionally Ground, the step of calcining the obtained molecular sieve, wherein the organic templating agent comprises a compound represented by the following formula (I),
- the groups R 1 and R 2 are the same or different from each other, each independently selected from a C 3-12 straight or branched alkylene group and a C 3-12 straight or branched oxaalkylene group, preferably each independently Is selected from C 3-12 linear alkylene and C 3-12 linear oxaalkylene , or preferably one of them is selected from C 3-12 straight or branched alkylene and the other is selected from C 3 -12 linear or branched alkylene and C 3-12 linear or branched oxaalkylene, more preferably one selected from C 3-12 linear alkylene and the other selected from C 3-12 a linear alkylene group and a C 3-12 linear oxaalkylene group, particularly preferably one selected from the group consisting of C 3-12 linear alkylene groups and the other selected from C 4-6 linear alkylene groups and C 4 -6 linear oxaalkylene (preferably C 4-6 linear monooxaalkylene, more preferably -(CH 2 ) m
- the first oxide source is at least one selected from the group consisting of a silica source, a ceria source, a tin dioxide source, a titania source, and a zirconia source.
- a silica source or a combination of a silica source and a cerium oxide source the second oxide source being selected from the group consisting of an alumina source, a boron oxide source, an iron oxide source, a gallium oxide source, a rare earth oxide source, At least one of an indium oxide source and a vanadium oxide source, preferably an alumina source.
- the crystallization conditions comprise: crystallization at a crystallization temperature of from 80 ° C to 120 ° C, preferably from 120 ° C to 170 ° C or from 120 ° C to 200 ° C.
- the time is at least 1 day, preferably at least 2 days, preferably from 3 days to 8 days, from 5 days to 8 days or from 4 days to 6 days
- the firing conditions include: the calcination temperature is from 300 ° C to 750 ° C, Preferably, from 400 ° C to 600 ° C, the calcination time is from 1 hour to 10 hours, preferably from 3 hours to 6 hours.
- the first oxide source (in terms of the first oxide) and the second oxide source (in the second oxide The molar ratio of from 5 to ⁇ , preferably from 25 to 95, more preferably from 30 to 70; the molar ratio of water to the first oxide source (in terms of the first oxide) is from 5 To 50, preferably from 5 to 15; the molar ratio of the organic templating agent to the first oxide source (in terms of the first oxide) is from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5; the alkali source (in OH - as) molar ratio of the first oxide source (in the first oxide basis) is from 0 to 1, preferably from 0.04 To 1, from 0.1 to 1, from 0.2 to 1, from 0.3 to 0.7 or from 0.45 to 0.7.
- a molecular sieve characterized by having a (native) sponge structure and having an X-ray diffraction pattern substantially as shown in the following table,
- the sponge structure comprises coarse Holes and/or mesopores, preferably the coarse holes and/or the intermediate holes are open to the end faces and/or sides of the sponge structure.
- the coarse pores have a diameter of from 80 nm to 2 ⁇ m, preferably from 80 nm to 1.5 ⁇ m
- the mesopores have a diameter of from 2 nm to 30 nm, preferably from 2 nm to 4 nm and/or from 7 nm to 15 nm (preferably from 8 nm to 9 nm).
- the mesopores have a total specific surface area of from 50 m 2 /g to 250 m 2 /g, preferably from 100 m 2 /g to 150 m 2 /g, and the pore volume is from 0.05 ml/g to 0.40 ml/g, preferably from 0.15 ml/g to 0.30 ml/g, and the total specific surface area of the coarse pores is from 10 m 2 /g to 100 m 2 /g, preferably from 50 m 2 /g to 100 m 2 /g, the pore volume is from 0.5 ml/g to 3.0 ml/g, preferably from 1.0 ml/g to 2.0 ml/g.
- the sponge structure comprises microvoids, wherein the microvoids have a diameter of from 0.5 nm to less than 2 nm, preferably from 0.5 nm to 0.8 nm and/or from 1.1nm to 1.8nm, total specific surface area of from 100m 2 / g to 300m 2 / g, preferably from 150m 2 / g to 250m 2 / g, a pore volume of from 0.03ml / g to 0.20ml / g, preferably from 0.05 Ml/g to 0.15 ml/g.
- the size of the crystal morphology comprises: an effective diameter of from 100 nm to 5000 nm, preferably from 1000 nm to 3000 nm, a height of from 500 nm to 3000 nm, preferably from 1000 nm to 3000 nm, high
- the diameter ratio is from 1/3 to 5, preferably from 1/3 to 3.
- first oxide ⁇ second oxide or the formula "first oxide ⁇ second oxide ⁇ organic template agent ⁇ water” a chemical composition, wherein a molar ratio of the first oxide to the second oxide is from 30 to 100, preferably from 55 to 100;
- the first oxide is selected from the group consisting of silica, cerium oxide, and dioxide At least one of tin, titanium dioxide and zirconium dioxide, preferably silica or a combination of silica and ceria;
- the second oxide is selected from the group consisting of alumina, boron oxide, iron oxide, gallium oxide, rare earth oxidation At least one of, indium oxide and vanadium oxide, preferably alumina; a molar ratio of water to the first oxide of from 5 to 50, preferably from 5 to 15; the organic templating agent and the first The molar ratio of the oxide is from 0.02 to 0.5, preferably From 0.05 to 0.5, from 0.15
- a method of producing a molecular sieve comprising the steps of contacting a first oxide source, a second oxide source, an optional alkali source, an organic templating agent, and water under crystallization conditions to obtain a molecular sieve, and optionally Ground, the step of calcining the obtained molecular sieve, wherein the organic templating agent comprises a compound represented by the following formula (I),
- the groups R 1 and R 2 are different from each other, one of which is selected from a C 3-12 straight or branched alkylene group, and the other is selected from a C 3-12 straight or branched oxaalkylene group, preferably One selected from C 3-12 linear alkylene groups and the other selected from C 3-12 linear oxaalkylene groups (preferably C 4-6 linear oxaalkylene groups, more preferably C 4-6 linear chains) a monooxaalkylene group, more preferably -(CH 2 ) m -O-(CH 2 ) m -, wherein each value m is the same or different from each other, each independently representing 2 or 3); the plurality of groups R are identical to each other Or different, each independently selected from a C 1-4 straight or branched alkyl group, preferably each independently selected from the group consisting of methyl and ethyl, more preferably all methyl; X is OH.
- the first oxide source is at least one selected from the group consisting of a silica source, a ceria source, a tin dioxide source, a titania source, and a zirconia source.
- a silica source or a combination of a silica source and a cerium oxide source the second oxide source being selected from the group consisting of an alumina source, a boron oxide source, an iron oxide source, a gallium oxide source, a rare earth oxide source, At least one of an indium oxide source and a vanadium oxide source, preferably an alumina source.
- the crystallization conditions comprise: crystallization at a crystallization temperature of from 80 ° C to 120 ° C, preferably from 120 ° C to 170 ° C or from 120 ° C to 200 ° C.
- the time is at least 1 day, preferably at least 2 days, preferably from 3 days to 8 days, from 5 days to 8 days or from 4 days to 6 days
- the firing conditions include: the calcination temperature is from 300 ° C to 750 ° C, Preferably, from 400 ° C to 600 ° C, the calcination time is from 1 hour to 10 hours, preferably from 3 hours to 6 hours.
- the first oxide source (in terms of the first oxide) and the second oxide source (in the second oxide) The molar ratio is from 30 to 100, preferably from 55 to 100; the molar ratio of water to the first oxide source (in terms of the first oxide) is from 5 to 50, preferably from 5 to 15; a molar ratio of the organic templating agent to the first oxide source (in terms of the first oxide) is from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5, or from 0.3 to 0.5.
- the molar ratio of the alkali source (calculated as OH - ) to the first oxide source (in terms of the first oxide) is from 0 to 1, preferably from 0.04 to 1, from 0.1 to 1 From 0.2 to 1, from 0.3 to 0.7 or from 0.45 to 0.7.
- the size of the crystal morphology comprises an effective diameter of from 100 nm to 1000 nm, preferably from 100 nm to 500 nm, a height of from 100 nm to 1000 nm, preferably from 150 nm to 300 nm,
- the aspect ratio is from 0.1 to 0.9, preferably from 0.4 to 0.7.
- molecular sieve according to any of the preceding claims, wherein the molecular sieve has a total specific surface area of from 400 m 2 /g to 600 m 2 /g, preferably from 450 m 2 /g to 580 m 2 /g, and a pore volume of from 0.3 Ml/g to 0.5 ml/g, preferably from 0.30 ml/g to 0.40 ml/g.
- the molecular sieve according to any one of the preceding aspects having the schematic expression represented by the formula "first oxide ⁇ second oxide” or the formula "first oxide ⁇ second oxide ⁇ organic template agent ⁇ water” a chemical composition, wherein a molar ratio of the first oxide to the second oxide is from 40 to 200, preferably from 40 to 150; the first oxide is selected from the group consisting of silica, cerium oxide, and dioxide At least one of tin, titanium dioxide and zirconium dioxide, preferably silica or a combination of silica and ceria, the second oxide being selected from the group consisting of alumina, boron oxide, iron oxide, gallium oxide, rare earth oxidation At least one of, indium oxide and vanadium oxide, preferably alumina; a molar ratio of water to the first oxide of from 5 to 50, preferably from 5 to 15; the organic templating agent and the first The molar ratio of the oxide is from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.
- a method of producing a molecular sieve comprising the steps of contacting a first oxide source, a second oxide source, an optional alkali source, an organic templating agent, and water under crystallization conditions to obtain a molecular sieve, and optionally Ground, the step of calcining the obtained molecular sieve, wherein the organic templating agent comprises a compound represented by the following formula (I),
- the groups R 1 and R 2 are the same or different from each other, each independently selected from a C 3-12 straight or branched alkylene group, preferably each independently selected from a C 3-12 linear alkylene group, particularly preferably One of them is selected from a C 3-12 linear alkylene group and the other is selected from a C 4-6 linear alkylene group;
- the plurality of groups R are the same or different from each other, and are each independently selected from a C 1-4 straight chain or
- the branched alkyl groups are preferably each independently selected from the group consisting of methyl and ethyl, more preferably all methyl;
- X is OH.
- the first oxide source is at least one selected from the group consisting of a silica source, a ceria source, a tin dioxide source, a titania source, and a zirconia source.
- a silica source or a combination of a silica source and a cerium oxide source the second oxide source being selected from the group consisting of an alumina source, a boron oxide source, an iron oxide source, a gallium oxide source, a rare earth oxide source, At least one of an indium oxide source and a vanadium oxide source, preferably an alumina source.
- the crystallization conditions comprise: crystallization at a crystallization temperature of from 80 ° C to 120 ° C, preferably from 120 ° C to 170 ° C or from 120 ° C to 200 ° C.
- the time is at least 1 day, preferably at least 2 days, preferably from 3 days to 8 days, from 5 days to 8 days or from 4 days to 6 days
- the firing conditions include: the calcination temperature is from 300 ° C to 750 ° C, Preferably, from 400 ° C to 600 ° C, the calcination time is from 1 hour to 10 hours, preferably from 3 hours to 6 hours.
- the first oxide source (in terms of the first oxide) and the second oxide source (in the second oxide The molar ratio is from 40 to 200, preferably from 40 to 150; the molar ratio of water to the first oxide source (in terms of the first oxide) is from 5 to 50, preferably from 5 to 15; a molar ratio of the organic templating agent to the first oxide source (in terms of the first oxide) is from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.08 to 0.5, or from 0.3 to 0.5.
- the molar ratio of the alkali source (calculated as OH - ) to the first oxide source (in terms of the first oxide) is from 0 to 1, preferably from 0.04 to 1, from 0.1 to 1 From 0.2 to 1, from 0.3 to 0.7 or from 0.45 to 0.7.
- a method for producing a molecular sieve comprising the steps of contacting a first oxide source, a second oxide source, an optional alkali source, an organic templating agent and water under crystallization conditions to obtain a molecular sieve, and optionally Ground, the step of calcining the obtained molecular sieve, wherein the organic templating agent comprises a compound represented by the following formula (I),
- the groups R 1 and R 2 are the same or different from each other, each independently selected from a C 3-12 straight or branched alkylene group and a C 3-12 straight or branched oxaalkylene group, preferably each independently Is selected from a C 3-12 linear alkylene group and a C 3-12 linear oxaalkylene group, or preferably one of them is selected from a C 3-12 linear or branched alkylene group, and the other is selected from the group consisting of C 3 -12 linear or branched alkylene and C 3-12 linear or branched oxaalkylene, more preferably one selected from C 3-12 linear alkylene and the other selected from C 3-12 a linear alkylene group and a C 3-12 linear oxaalkylene group, particularly preferably one selected from the group consisting of C 3-12 linear alkylene groups and the other selected from C 4-6 linear alkylene groups and C 4 -6 linear oxaalkylene (preferably C 4-6 linear monooxaalkylene
- the groups R 1 and R 2 are the same or different from each other, each independently selected from a C 3-12 straight or branched alkylene group, preferably each independently selected From the C 3-12 linear alkylene group, it is particularly preferred that one of them is selected from a C 3-12 linear alkylene group and the other is selected from a C 4-6 linear alkylene group; the plurality of groups R are the same or different from each other Each is independently selected from C 1-4 straight or branched alkyl groups, preferably each independently selected from the group consisting of methyl and ethyl, more preferably all methyl; X is OH.
- the first source of oxide is selected from at least one of a source of silica, a source of cerium oxide, a source of tin dioxide, a source of titanium dioxide, and a source of zirconia.
- a silica source or a group of silica source and cerium oxide source is selected from at least one of an alumina source, a boron oxide source, an iron oxide source, a gallium oxide source, a rare earth oxide source, an indium oxide source, and a vanadium oxide source, preferably an alumina source.
- the crystallization conditions comprise: crystallization at a crystallization temperature of from 80 ° C to 120 ° C, preferably from 120 ° C to 170 ° C or from 120 ° C to 200 ° C.
- the time is at least 1 day, preferably at least 2 days, preferably from 3 days to 8 days, from 5 days to 8 days or from 4 days to 6 days
- the firing conditions include: the calcination temperature is from 300 ° C to 750 ° C, Preferably, from 400 ° C to 600 ° C, the calcination time is from 1 hour to 10 hours, preferably from 3 hours to 6 hours.
- the molar ratio is from 5 to ⁇ , especially from 5 to less than 40 (such as from 20 to less than 40), from 40 to 200 (such as from 40 to 150), from more than 200 to ⁇ (such as from more than 200 to 700); a molar ratio of water to the first oxide source (in terms of the first oxide) of from 5 to 50, preferably from 5 to 15; the organic templating agent and the first oxide
- the molar ratio of the source (in terms of the first oxide) is from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.08 to 0.5 or from 0.3 to 0.5; the alkali source (in terms of OH - ) and
- the molar ratio of the first oxide source (calculated as the first oxide) is from 0 to 1, preferably from 0.04 to 1, from 0.1 to 1, from 0.2 to 1, from 0.3 to 0.7, or from 0.45 to
- the molar ratio is from 5 to ⁇ , especially from 5 to less than 30 (such as from 10 to less than 30), from 30 to 100 (such as from 55 to 100), from greater than 100 to ⁇ (such as from 200 to ⁇ ) Or from 200 to 700);
- a molar ratio of water to the first oxide source (in terms of the first oxide) is from 5 to 50, preferably from 5 to 15;
- the molar ratio of the first oxide source (calculated as the first oxide) is from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5;
- the molar ratio to the first oxide source (in terms of the first oxide) is from 0 to 1, preferably from 0.04 to 1, from 0.1 to 1, from 0.2 to 1, from 0.3 to 0.7 or from 0.45 to 0.7.
- a molecular sieve characterized by the production method according to any one of the preceding aspects obtain.
- a molecular sieve composition comprising the molecular sieve according to any one of the preceding aspects, or the molecular sieve obtained by the production method according to any one of the preceding aspects, and a binder.
- a process for the conversion of a hydrocarbon comprising the step of subjecting a hydrocarbon to a conversion reaction in the presence of a catalyst, wherein the catalyst comprises or is produced according to any one of the preceding aspects, according to any of the foregoing aspects
- the molecular sieve according to the present invention has an ultra-large pore skeleton pore structure, which can be reflected at least from its higher pore volume data.
- the molecular sieve according to the invention has good heat/water thermal stability and has a larger pore volume.
- the molecular sieve of the present invention is capable of adsorbing more/larger molecules, thereby exhibiting excellent adsorption/catalytic properties.
- the molecular sieve according to the present invention in one embodiment, has a unique X-ray diffraction spectrum (XRD) with a unique Si/Al 2 ratio. This is a molecular sieve that has not been produced in the prior art.
- XRD X-ray diffraction spectrum
- the molecular sieve according to the present invention in one embodiment, has a unique X-ray diffraction pattern (XRD) with a unique native crystal morphology, such as a crystal morphology from a flat prism to a flat cylinder.
- XRD X-ray diffraction pattern
- the molecular sieve according to the present invention in one embodiment, has a unique X-ray diffraction pattern (XRD) with a unique native crystal morphology, such as a crystal morphology with a sponge structure.
- XRD X-ray diffraction pattern
- This is a molecular sieve that has not been produced in the prior art.
- the molecular sieve of the present invention exhibits the characteristics of the microporous material (i.e., the inherent characteristics of the conventional molecular sieve), and also has the characteristics of a mesoporous material and/or a macroporous material, and is capable of adsorbing more/larger. Molecules, thus exhibiting excellent adsorption/catalytic properties.
- the molecular sieve according to the present invention in one embodiment, has a relatively strong acidity, particularly a large number of L acid centers. This is a molecular sieve that has not been produced in the prior art. As a result, the molecular sieve of the present invention has more excellent performance particularly in an acid-catalyzed reaction.
- an organic template having a specific chemical structure is used, thereby exhibiting the characteristics that the process conditions are simple and the molecular sieve of the product is easily synthesized.
- organic templating agents are sometimes referred to in the art as It is a structure directing agent or an organic guiding agent.
- examples of the C 1-4 linear or branched alkyl group include a methyl group, an ethyl group or a propyl group.
- linear or branched oxaalkylene means that the carbon chain structure of a straight or branched alkylene group is one or more (for example 1 to 3, 1 to 2) Or a divalent group obtained by interrupting the hetero group -O-. From the viewpoint of structural stability, it is preferred that when there are a plurality of, the two of the hetero groups are not directly bonded. It is apparent that the term “interruption” means that the hetero group is not at either end of the linear or branched alkylene group or the linear or branched oxaalkylene group.
- a C 4 linear alkylene group (-CH 2 -CH 2 -CH 2 -CH 2 -) can be obtained by interrupting a hetero group -O- to obtain -CH 2 -O-CH 2 -CH 2 -CH 2 - or -CH 2 -CH 2 -O-CH 2 -CH 2 - C 4 straight chain and other oxaalkylene, after being two heteroaryl radicals interrupted with -O- can be obtained -CH 2 -O -CH 2 -O-CH 2 -CH 2 - or -CH 2 -O-CH 2 -CH 2 -O-CH 2 -etc.
- C 4 straight-chain dioxaalkylene by three hetero-groups -O - after the interruption can be obtained -CH 2 -O-CH 2 -O- CH 2 -O-CH 2 - C 4 straight chain and other three oxaalkylene.
- a C 4 branched alkylene group (-CH 2 (CH 3 )-CH 2 -CH 2 -) can be obtained by interrupting a hetero group -O---CH 2 (CH 3 )- O-CH 2 -CH 2 -, -CH 2 (CH 3 )-CH 2 -O-CH 2 - or -CH 2 (-O-CH 3 )-CH 2 -CH 2 -, etc.
- a heteroalkylene group which is interrupted by two hetero groups -O- can be obtained as -CH 2 (CH 3 )-O-CH 2 -O-CH 2 -, -CH 2 (-O-CH 3 )-O- a C 4 -branched dioxaalkylene group such as CH 2 -CH 2 - or -CH 2 (-O-CH 3 )-CH 2 -O-CH 2 - may be interrupted by three hetero groups -O-
- a C 4 branched trioxaalkylene group such as -CH 2 (-O-CH 3 )-O-CH 2 -O-CH 2 - is obtained.
- total specific surface area refers to the total area of a unit mass molecular sieve, including internal surface area and external surface area.
- Non-porous materials have only an external surface area, such as Portland cement, some clay mineral particles, etc.
- porous materials have an external surface area and an internal surface area, such as asbestos fibers, diatomaceous earth, and molecular sieves.
- pore volume also known as pore volume
- micropore volume means the volume of all micropores (that is, pores having a pore diameter of less than 2 nm) per unit mass of molecular sieve.
- w, m, s, vs represent the intensity of the diffraction peak, w is weak, m is medium, s is strong, and vs is very strong, which is known to those skilled in the art.
- w is less than 20; m is 20-40; s is 40-70; The vs is greater than 70.
- a molecular sieve wherein the molecular sieve has the schematic chemical composition represented by the formula "first oxide ⁇ second oxide". It is known that molecular sieves sometimes contain a certain amount of water (especially just after synthesis), but the present invention does not consider it necessary to specify the amount of moisture because the presence or absence of the moisture does not substantially The XRD spectrum of the molecular sieve is affected. In view of this, the schematic chemical composition actually represents the anhydrous chemical composition of the molecular sieve. Moreover, it is apparent that the schematic chemical composition represents the framework chemical composition of the molecular sieve.
- the molecular sieve may, after synthesis, generally further comprise an organic templating agent and water or the like in the composition, such as those filled in its pores. Therefore, the molecular sieve may sometimes have an illustrative chemical composition represented by the formula "first oxide ⁇ second oxide ⁇ organic template agent ⁇ water".
- the molecular sieve having the schematic chemical composition represented by the formula "first oxide ⁇ second oxide ⁇ organic template agent ⁇ water” is calcined to remove any organic templating agent and water present in the pores thereof.
- the molecular sieve having the schematic chemical composition represented by the formula "first oxide ⁇ second oxide” can be obtained.
- the calcination may be carried out in any manner conventionally known in the art, such as a calcination temperature generally from 300 ° C to 750 ° C, preferably from 400 ° C to 600 ° C, and a calcination time of generally from 1 hour to 10 hours, preferably From 3 hours to 6 hours.
- the calcination is generally carried out under an oxygen-containing atmosphere, such as an air or oxygen atmosphere.
- the first oxide is generally a tetravalent oxide, and may be, for example, selected from the group consisting of silica, ceria, tin dioxide, titanium dioxide, and At least one of zirconia is preferably silica (SiO 2 ) or a combination of silica and ceria.
- These first oxides may be used alone or in combination of any ones in any ratio.
- the molar ratio between any two of the first oxides is, for example, from 20:200 to 35:100.
- silica and cerium oxide may be used in combination, and the molar ratio between the silica and the cerium oxide is, for example, from 20:200 to 35:100.
- the second oxide is generally a trivalent oxide, and may be, for example, selected from the group consisting of alumina, boron oxide, iron oxide, gallium oxide, and rare earth oxide. At least one of indium oxide and vanadium oxide is preferably alumina (Al 2 O 3 ). These second oxides may be used alone or in combination of any ones in any ratio. When a plurality of types are used in combination, the molar ratio between any two of the second oxides is, for example, from 30:200 to 60:150.
- organic templating agent for example, any organic templating agent used in the production of the molecular sieve may be mentioned, and in particular, the molecular sieve of the present embodiment may be mentioned.
- the organic templating agent used (see detailed description below). These organic templating agents may be used alone or in combination of any ones in any ratio. Specifically, specific examples of the organic templating agent include compounds represented by the following formula (I).
- the groups R 1 and R 2 are the same or different from each other, each independently selected from C 3-12 straight or branched alkylene and C 3-12 straight chain Or a branched oxaalkylene group, the plurality of groups R being the same or different from each other, each independently selected from a C 1-4 straight or branched alkyl group, and X is OH.
- a molar ratio of the first oxide to the second oxide is generally from 5 to Preferably, it is from 25 to 95, more preferably from 30 to 70.
- the molar ratio is ⁇ , it means that the content of the second oxide or the second oxide in the schematic chemical composition is negligible.
- the inventors of the present invention have found through careful investigation that the prior art has not produced, in particular, the molar ratio (such as the molar ratio of SiO 2 to Al 2 O 3 ) from 25 to 95 (more particularly from 30 to 70).
- the molecular sieve is generally from 5 to Preferably, it is from 25 to 95, more preferably from 30 to 70.
- water and said The molar ratio of the first oxide is generally from 5 to 50, preferably from 5 to 15.
- the molar ratio of the organic templating agent to the first oxide is generally from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5.
- the molecular sieve may sometimes further contain metal cations such as alkali metals and/or alkaline earth metal cations in its composition (generally filled in its pores).
- metal cations such as alkali metals and/or alkaline earth metal cations in its composition (generally filled in its pores).
- the content of the metal cation at this time, for example, the mass ratio of the metal cation to the first oxide is generally from 0 to 0.02, preferably from 0.0002 to 0.006, but is not limited thereto.
- the molecular sieve has an X-ray diffraction pattern substantially as shown in the following table.
- the X-ray diffraction pattern of the molecular sieve it is preferable to further include an X-ray diffraction peak substantially as shown in the following table.
- the X-ray diffraction pattern of the molecular sieve it is preferable to further include an X-ray diffraction peak substantially as shown in the following table.
- the molecular sieve generally has a columnar crystal morphology when viewed using a scanning electron microscope (SEM).
- the crystal morphology refers to the (overall) outer shape exhibited by a single molecular sieve crystal in the observation field of the scanning electron microscope.
- a prismatic shape in particular, a hexagonal prism shape is preferable.
- the prism refers to a convex prism and generally refers to a right prism and a regular polygonal prism (such as a regular hexagonal prism).
- the actual crystal morphology may be compared with the geometric (true) straight prism or (true) regular polygonal prism.
- any greater or lesser deviations do not depart from the scope of the invention.
- the molecular sieve (single crystal) has an effective diameter generally ranging from 100 nm to 1000 nm, preferably from 300 nm to 700 nm, when observed using a scanning electron microscope (SEM).
- the effective diameter means that two points are arbitrarily selected along the contour (edge) of the cross section of the molecular sieve (single crystal), and the linear distance between the two points is measured. The largest straight line distance is taken as the effective diameter.
- the effective diameter generally refers to the linear distance (diagonal distance) between the two vertices furthest from the polygon.
- the effective diameter corresponds substantially to the diameter of the circumcircle of the polygon represented by the contour of the cross section.
- the molecular sieve (single crystal) has a height generally ranging from 100 nm to 1000 nm, preferably from 150 nm to 700 nm, when observed by a scanning electron microscope (SEM).
- the term "height” refers to a linear distance between the centers of the two end faces of the column in a single crystal (columnar crystal) of the molecular sieve.
- the two end faces of the molecular sieve column are substantially parallel to each other, and the linear distance is the vertical distance between the two end faces, but the invention is not limited thereto.
- the molecular sieve (single crystal) has an aspect ratio of generally from 1/3 to 8, preferably from 1.5 to 5 or from 2 to 5 when observed by a scanning electron microscope (SEM).
- the aspect ratio refers to the ratio of the height to the effective diameter.
- the molecular sieve has a total specific surface area of generally from 400 m 2 /g to 600 m 2 /g, preferably from 450 m 2 /g to 580 m 2 /g.
- the total specific surface area is obtained by a liquid nitrogen adsorption method, calculated by a BET model.
- the molecular sieve has a pore volume (micropore volume) of generally from 0.3 ml/g to 0.5 ml/g, preferably from 0.30 ml/g to 0.40 ml/g.
- the molecular sieve of the present invention has a very high micropore volume, which indicates that it belongs to an ultra-large pore molecular sieve.
- the pore volume is a liquid nitrogen adsorption method, which is calculated according to the Horvath-Kawazoe model.
- the molecular sieve can be produced by the following production method.
- the manufacturing method includes a step of contacting a first oxide source, a second oxide source, an optional alkali source, an organic templating agent, and water under crystallization conditions to obtain a molecular sieve (hereinafter referred to as a contacting step) ).
- the contacting step may be carried out in any manner conventionally known in the art, such as exemplifying the first oxide source, the second oxidation A method of mixing a source, the optional alkali source, the organic templating agent, and water, and subjecting the mixture to crystallization under the crystallization conditions.
- the organic template agent comprises at least a compound represented by the following formula (I).
- the compound represented by the formula (I) may be used alone or in combination of plural kinds in any ratio.
- the groups R 1 and R 2 are the same or different from each other, each independently selected from C 3-12 straight or branched alkylene groups and C 3-12 Linear or branched oxaalkylene.
- the groups R 1 and R 2 are identical or different from each other, one of which is selected from a C 3-12 linear or branched alkylene group, The other is selected from a C 3-12 straight or branched alkylene group and a C 3-12 straight or branched oxaalkylene group.
- the groups R 1 and R 2 are identical or different from one another, one of which is selected from the group consisting of C 3-12 linear alkylene groups, the other option From C 4-6 linear alkylene and C 4-6 linear oxaalkylene.
- the groups R 1 and R 2 are identical or different from one another, each independently selected from C 3-12 straight or branched alkylene groups .
- the groups R 1 and R 2 are identical or different from one another, one of which is selected from the group consisting of C 3-12 linear alkylene groups, the other option From C 4-6 linear alkylene.
- the groups R 1 and R 2 are different from each other, one of which is selected from a C 3-12 linear or branched alkylene group, and the other It is selected from a C 3-12 linear or branched oxaalkylene group.
- a C 3-12 linear or branched alkylene group for example, a C 3-12 linear alkylene group can be exemplified, and specific examples thereof include an n-propylene group and an isopropylidene group.
- examples of the C 3-12 linear alkylene group include a C 4-6 linear alkylene group, and particularly, an n-n-n
- a C 3-12 linear or branched oxaalkylene group for example, a C 3-12 linear oxaalkylene group can be mentioned, and specific examples thereof include -(CH 2 2 -O-(CH 2 )-, -(CH 2 ) 2 -O-(CH 2 ) 2 -, -(CH 2 )-O-(CH 2 ) 3 -, -(CH 2 ) 2 -O -(CH 2 ) 3 -, -(CH 2 )-O-propylene-, -(CH 2 )-O-(CH 2 ) 4 -, -(CH 2 )-O-(CH 2 ) 2 - O-(CH 2 )-, -(CH 2 )-O-(CH 2 ) 2 -O-(CH 2 ) 2 -, -(CH 2 )-O-tert-butyl-, -(CH 2 ) 2 -O-(CH 2
- C 3-12 linear oxaalkylene group more specifically, a C 4-6 linear oxaalkylene group is exemplified, and a C 4-6 linear monooxaalkylene group is particularly exemplified.
- an oxygen represented by the formula -(CH 2 ) m -O-(CH 2 ) m - (wherein the respective values m are the same or different from each other, each independently representing 2 or 3, such as 2) may be mentioned.
- the heteroalkylene group is more specifically -(CH 2 ) 2 -O-(CH 2 ) 2 -, -(CH 2 ) 2 -O-(CH 2 ) 3 -, -(CH 2 ) 3 -O -(CH 2 ) 3 - or -(CH 2 ) 2 -O-(CH 2 ) 4 -.
- the plurality of groups R are the same or different from each other, each independently selected from a C 1-4 straight or branched alkyl group, preferably each independently selected from the group consisting of The group and the ethyl group are more preferably a methyl group.
- X is OH
- the molar ratio of the organic templating agent to the first oxide source (in terms of the first oxide) is generally from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5.
- organic templating agent in addition to the compound represented by the formula (I), other materials conventionally used in the art for producing molecular sieves may be further used in combination.
- Organic templating agent in addition to the compound represented by the formula (I), other materials conventionally used in the art for producing molecular sieves may be further used in combination.
- Organic templating agent in addition to the compound represented by the formula (I), other materials conventionally used in the art for producing molecular sieves may be further used in combination.
- Organic templating agent Preferably, in the contacting step, as the organic templating agent, only the compound represented by the formula (I) is used.
- the compound represented by the formula (I) may be used alone or in combination of plural kinds in any ratio.
- the first oxide source is generally a tetravalent oxide source, and for example, may be selected from a silica source, a ceria source, a tin dioxide source, At least one of a source of titania and a source of zirconium dioxide is preferably a source of silica (SiO 2 ) or a combination of a source of silica and a source of cerium oxide.
- These first oxide sources may be used alone or in combination of any ones in any ratio.
- the molar ratio between any two of the first oxide sources is, for example, from 20:200 to 35:100.
- a silica source and a ceria source may be used in combination, and the molar ratio between the silica source and the ceria source is, for example, from 20:200. To 35:100.
- any corresponding oxide source conventionally used for this purpose in the art may be used, including but not limited to the first oxide.
- the first oxide is silica
- examples of the first oxide source include silica sol, crude silica gel, tetraethyl orthosilicate, water glass, white carbon, and silicic acid. Silica gel or potassium silicate.
- examples of the first oxide source include tetraalkoxy cerium, cerium oxide or cerium nitrate.
- examples of the first oxide source include tin chloride, tin sulfate, tin nitrate, and the like.
- examples of the first oxide source include titanium tetraalkoxide, titanium oxide, titanium nitrate, and the like.
- examples of the first oxide source include zirconium sulfate, zirconium chloride, zirconium nitrate, and the like.
- the second oxide source is generally a trivalent oxide source, and may be, for example, selected from the group consisting of an alumina source, a boron oxide source, an iron oxide source, and a gallium oxide source. At least one of a rare earth oxide source, an indium oxide source, and a vanadium oxide source is preferably an alumina (Al 2 O 3 ) source. These second oxide sources may be used alone or in combination of any ones in any ratio. When a plurality of combinations are used, the molar ratio between any two of the second oxide sources is, for example, from 30:200 to 60:150.
- any corresponding oxide source conventionally used for this purpose in the art may be used, including but not limited to the second oxide.
- the second oxide is alumina
- examples of the second oxide source include aluminum chloride, aluminum sulfate, hydrated alumina, sodium metaaluminate, aluminum sol or aluminum hydroxide.
- examples of the second oxide source include boric acid, borate, borax, and boron trioxide.
- the second oxide is iron oxide
- examples of the second oxide source include gallium nitrate, gallium sulfate, gallium oxide, and the like.
- examples of the second oxide source include cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium nitrate, cerium nitrate, cerium nitrate, ammonium cerium sulfate, and the like. .
- examples of the second oxide source include indium chloride, indium nitrate, indium oxide, and the like.
- examples of the second oxide source include vanadium chloride, ammonium metavanadate, sodium vanadate, vanadium dioxide, vanadyl sulfate, and the like. These second oxide sources may be used singly or in combination of a plurality of them in a desired ratio.
- the first oxide source (the count to the first oxide, such as SiO 2) and the second oxide source (in the second The molar ratio of the oxide such as Al 2 O 3 ) is generally from 5 to ⁇ , preferably from 25 to 95, more preferably from 30 to 70.
- the molar ratio is ⁇ , it means that the second oxide source is not used or the second oxide source is not intentionally introduced into the contacting step.
- the molar ratio of water to the first oxide source (in terms of the first oxide) is generally from 5 to 50, preferably from 5 to 15.
- an alkali source may or may not be used.
- the group X contained in the compound represented by the formula (I) can be used to provide the OH - which is required herein.
- the alkali source any alkali source conventionally used for this purpose in the art may be used, including but not limited to inorganic bases which are cations of alkali metals or alkaline earth metals, particularly sodium hydroxide and potassium hydroxide. . These alkali sources may be used alone or in combination of any ones in any ratio.
- a molar ratio of the alkali source (in terms of OH - ) to the first oxide source (in terms of the first oxide) is generally from 0 to 1, preferably from 0.04 to 1, from 0.1 to 1, from 0.2 to 1, from 0.3 to 0.7 or from 0.45 to 0.7.
- the crystallization temperature is generally from 80 ° C to 120 ° C, preferably from 120 ° C to 170 ° C or from 120 ° C to 200 ° C.
- the crystallization time is generally at least 1 day, preferably at least 2 days, preferably from 3 days to 8 days, from 5 Days to 8 days or from 4 days to 6 days.
- the molecular sieve in the method for producing the molecular sieve, after the contacting step is completed, the molecular sieve can be separated as a product from the obtained reaction mixture by any separation method conventionally known.
- the molecular sieve product comprises the molecular sieve of the present invention.
- the separation method for example, a method of filtering, washing, and drying the obtained reaction mixture can be mentioned.
- the filtration, washing and drying may be carried out in any manner conventionally known in the art.
- the filtration for example, the obtained reaction mixture can be simply suction filtered.
- washing for example, washing with deionized water can be mentioned until the pH of the filtrate reaches 7-9, preferably 8-9.
- the drying temperature is, for example, 40 to 250 ° C, preferably 60 to 150 ° C, and the drying time is, for example, 8 to 30 hours, preferably 10 to 20 hours.
- the drying can be carried out under normal pressure or under reduced pressure.
- the method for producing the molecular sieve may further include, as needed, a step of calcining the obtained molecular sieve (hereinafter referred to as a calcination step) to remove the organic template agent and possible moisture, and the like.
- a calcination step a step of calcining the obtained molecular sieve
- the molecular sieves before and after calcination are also collectively referred to as molecular sieves of the invention or molecular sieves according to the invention.
- the calcination in the method of producing a molecular sieve, may be carried out in any manner conventionally known in the art, such as a calcination temperature generally from 300 ° C to 750 ° C, preferably from 400 ° C to 600 ° C. And the calcination time is generally from 1 hour to 10 hours, preferably from 3 hours to 6 hours. In addition, the calcination is generally carried out under an oxygen-containing atmosphere, such as an air or oxygen atmosphere.
- the molecular sieve of the present invention or any molecular sieve produced by the method for producing a molecular sieve according to the present invention are collectively referred to as the molecular sieve of the present invention or according to the present invention
- Molecular sieves can also be ion exchanged by any means conventionally known in the art, such as by ion exchange or solution impregnation (for example, see, for example, U.S. Patents 3,140,249 and 3,140,253, etc.)
- the metal cations (such as Na ions or K ions, depending on their specific manufacturing method) are replaced in whole or in part by other cations.
- Examples of the other cation include hydrogen ions, other alkali metal ions (including K ions, Rb ions, etc.), ammonium ions (including NH 4 ions, quaternary ammonium ions such as tetramethylammonium ions and tetraethylammonium ions). Etc.), alkaline earth metal ions (including Mg ions, Ca ions), Mn ions, Zn ions, Cd ions, noble metal ions (including Pt ions, Pd ions, Rh ions, etc.), Ni ions, Co ions, Ti ions, Sn ions , Fe ions and/or rare earth metal ions, and the like.
- the molecular sieve according to the present invention may be treated by a dilute acid solution or the like as needed to increase the ratio of silicon to aluminum or treated with steam to improve the acid attack resistance of the molecular sieve crystal.
- the molecular sieve according to the invention has good heat/water thermal stability and has a larger pore volume.
- the molecular sieve of the present invention is capable of adsorbing more/larger molecules, thereby exhibiting excellent adsorption/catalytic properties.
- the molecular sieve according to the present invention has a strong acidity, particularly a large number of L acid centers. This is a molecular sieve that has not been produced in the prior art. As a result, the molecular sieve of the present invention has more excellent performance particularly in an acid-catalyzed reaction.
- the molecular sieve according to the present invention may be in any physical form such as a powder, a granule or a molded article (e.g., a strip, a clover, etc.). These physical forms can be obtained in any manner conventionally known in the art, and are not particularly limited.
- a molecular sieve having an X-ray diffraction pattern substantially as shown in the following table.
- the X-ray diffraction pattern of the molecular sieve it is preferable to further include an X-ray diffraction peak substantially as shown in the following table.
- the X-ray diffraction pattern of the molecular sieve it is preferable to further include an X-ray diffraction peak substantially as shown in the following table.
- the molecular sieve (referred to as a single crystal) has a crystal morphology of a sponge structure, particularly a native crystal morphology having a sponge structure, when observed using a scanning electron microscope (SEM).
- the crystal morphology refers to the (overall) outer shape exhibited by a single molecular sieve crystal in the observation field of the scanning electron microscope.
- the term "primary" refers to a structure in which molecular sieves are objectively presented directly after manufacture, and is not a structure in which molecular sieves are artificially processed after being manufactured.
- the inventors of the present invention have found through careful investigation that the prior art has not produced a molecular sieve having both the aforementioned specific X-ray diffraction pattern and the aforementioned specific (native) crystal morphology.
- the sponge structure generally comprises microvoids (skeletal holes). This is an inherent property of molecular sieves as microporous materials.
- the diameter (average diameter) of the microvoids is generally from 0.5 nm to less than 2 nm.
- the microvoids have a diameter of from 0.5 nm to 0.8 nm, or from 1.1 nm to 1.8 nm.
- the diameter of the microvoids exhibits a bimodal distribution, including both diameters from 0.5 nm to 0.8 nm and from 1.1 nm to 1.8 nm.
- the diameter is a DFT density functional theory by liquid nitrogen adsorption method. On the model calculation obtained.
- the molecular sieve of the present invention is considered to belong to an ultra-large pore molecular sieve.
- the total specific surface area of the micropores is generally from 100 m 2 /g to 300 m 2 /g, preferably from 150 m 2 /g to 250 m 2 /g.
- the total specific surface area is obtained by a liquid nitrogen adsorption method as calculated by a BET model.
- the pore volume of the micropores is generally from 0.03 ml/g to 0.20 ml/g, preferably from 0.05 ml/g to 0.15 ml/g.
- the pore volume is obtained by measurement by the Horvath-Kawazoe method.
- the inventors of the present invention believe that the pore volume of the micropores has such a low value because the coarse and/or mesopores as described below occupy Originally belonging to the location of the micro-hole. Therefore, if these coarse and medium holes are replaced with the micro holes, the pore volume of the micro holes may exhibit a very high value.
- the sponge structure may also comprise coarse pores when viewed using a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the sponge structure of the molecular sieve (single crystal) of the present invention the coarse pores and the micropores communicate with each other and intersect each other to form a complicated network pore structure.
- This is a coarse-pored super-large pore molecular sieve which has not been produced by the prior art.
- the molecular sieve of the present invention exhibits the characteristics of the macroporous material while exhibiting the characteristics of the microporous material.
- the sponge structure may also comprise mesopores when viewed using a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the mesopores and micropores communicate with each other and intersect to form a complex network pore structure.
- This is a mesoporous ultra-large pore molecular sieve which has not been produced in the prior art.
- the molecular sieve of the present invention exhibits the characteristics of the mesoporous material while exhibiting the characteristics of the microporous material.
- the sponge structure may also comprise both coarse and medium pores when viewed using a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the molecular sieve of the present invention exhibits the characteristics of the microporous material as well as the characteristics of the macroporous material and the mesoporous material.
- the coarse holes are opened at one end surface or both end faces of the sponge structure (in this case, the coarse holes become full through holes or half through holes).
- the sponge structure can exhibit, for example, a crystal morphology similar to that of honeycomb coal.
- the sponge structure belongs to an open or semi-open pore sponge structure.
- the coarse holes may also open to one or more sides of the sponge structure, causing the sides to assume a hollowed out condition, thereby further increasing the permeability of the sponge structure.
- the intermediate hole when viewed by a scanning electron microscope (SEM), the intermediate hole is opened at one end surface or both end faces of the sponge structure (at this time, the middle hole becomes a full through hole) Or a half through hole).
- the sponge structure can exhibit, for example, a crystal morphology similar to that of honeycomb coal.
- the open cell sponge structure is an open cell or semi-open cell sponge structure.
- the intermediate hole may also open to one or more sides of the sponge structure, causing the side surface to assume a hollow state, thereby further increasing the permeability of the sponge structure.
- the diameter (average diameter) of the coarse holes is generally from 80 nm to 2 ⁇ m, preferably from 80 nm to 1.5 ⁇ m.
- the diameter is obtained by measurement by a mercury intrusion method.
- the total specific surface area of the coarse pores is generally from 10 m 2 /g to 100 m 2 /g, preferably from 50 m 2 /g to 100 m 2 /g.
- the total specific surface area is obtained by measurement by a mercury intrusion method.
- the pore volume of the coarse pores is generally from 0.5 ml/g to 3.0 ml/g, preferably from 1.0 ml/g to 2.0 ml/g.
- the pore volume is obtained by measurement by a mercury intrusion method.
- the diameter (average diameter) of the mesopores is generally from 2 nm to 30 nm.
- the mesopores have a diameter of from 2 nm to 4 nm, or from 7 nm to 15 nm, and the latter more preferably from 8 nm to 9 nm.
- the diameter of the mesopores appears as a bimodal distribution, including both diameters from 2 nm to 4 nm and from 7 nm to 15 nm.
- the diameter is obtained by a liquid nitrogen adsorption method as calculated by a BET model.
- the total specific surface area of the mesopores is generally from 50 m 2 /g to 250 m 2 /g, preferably from 100 m 2 /g to 150 m 2 /g.
- the total specific surface area is obtained by a liquid nitrogen adsorption method as measured by a BET model calculation method.
- the pore volume of the mesopores is generally from 0.05 ml/g to 0.40 ml/g, preferably from 0.15 ml/g to 0.30 ml/g.
- the pore volume is obtained by a liquid nitrogen adsorption method as measured by a BET model calculation method.
- the sponge structure comprises both coarse, medium and micropores as previously described.
- the coarse pores, the medium pores and the micropores communicate with each other and intersect each other to form a complicated network pore structure.
- This is a porous grade ultra-large pore molecular sieve which has not been produced in the prior art.
- the molecular sieve of the present invention exhibits the characteristics of the microporous material, and also has the characteristics of a mesoporous material and/or a macroporous material, capable of adsorbing more/larger molecules, thereby exhibiting excellent adsorption/ Catalytic performance.
- the molecular sieve generally also has a columnar crystal morphology when viewed using a scanning electron microscope (SEM).
- SEM scanning electron microscope
- the columnar shape a prismatic shape, in particular, a hexagonal prism shape is preferable.
- the prism refers to a convex prism and generally refers to a right prism and a regular polygonal prism (such as a regular hexagonal prism). It should be specially pointed out that since the crystals of the molecular sieve may be disturbed by various factors during the growth process, the actual crystal morphology may be compared with the geometric (true) straight prism or (true) regular polygonal prism.
- the molecular sieve (single crystal) has an effective diameter generally ranging from 100 nm to 5000 nm, preferably from 1000 nm to 3000 nm, when observed using a scanning electron microscope (SEM).
- the effective diameter means that two points are arbitrarily selected along the contour (edge) of the cross section of the molecular sieve (single crystal), and the linear distance between the two points is measured. The largest straight line distance is taken as the effective diameter.
- the effective diameter generally refers to the linear distance (diagonal distance) between the two vertices furthest from the polygon.
- the effective diameter corresponds substantially to the diameter of the circumcircle of the polygon represented by the contour of the cross section.
- the molecular sieve may exhibit a hollow column when the diameter of the coarse pore is sufficiently large (eg, as close to the effective diameter of the molecular sieve) Crystal shape.
- the term "hollow column shape” means a cylindrical structure.
- the wall thickness of the cylindrical structure may be, for example, from 50 nm to 400 nm, but the present invention is not limited thereto, and it is not intended to specifically specify the wall thickness.
- the molecular sieve (single crystal) has a height generally ranging from 500 nm to 3000 nm, preferably from 1000 nm to 3000 nm, when observed using a scanning electron microscope (SEM).
- the term "height” refers to a linear distance between the centers of the two end faces of the column in a single crystal (columnar crystal) of the molecular sieve.
- the two end faces of the molecular sieve column are substantially parallel to each other, and the linear distance is the vertical distance between the two end faces, but the invention is not limited thereto.
- the molecular sieve (single crystal) has an aspect ratio of generally from 1/3 to 5, preferably from 1/3 to 3, when observed by a scanning electron microscope (SEM).
- the aspect ratio refers to the ratio of the height to the effective diameter.
- the molecular sieve generally has the schematic chemical composition represented by the formula "first oxide ⁇ second oxide". It is known that molecular sieves sometimes contain a certain amount of water (especially just after synthesis), but the present invention does not consider it necessary to specify the amount of moisture because the presence or absence of the moisture does not substantially The XRD spectrum of the molecular sieve is affected. In view of this, the schematic chemical composition actually represents the anhydrous chemical composition of the molecular sieve. Moreover, it is apparent that the schematic chemical composition represents the framework chemical composition of the molecular sieve.
- the molecular sieve may, in its composition, typically further comprise an organic templating agent and water or the like, such as those filled in its pores, just after synthesis. Therefore, the molecular sieve may sometimes have an illustrative chemical composition represented by the formula "first oxide ⁇ second oxide ⁇ organic template agent ⁇ water".
- the molecular sieve having the schematic chemical composition represented by the formula "first oxide ⁇ second oxide ⁇ organic template agent ⁇ water” is calcined to remove any organic templating agent and water present in the pores thereof.
- the molecular sieve having the schematic chemical composition represented by the formula "first oxide ⁇ second oxide” can be obtained.
- the calcination may be carried out in any manner conventionally known in the art, such as a calcination temperature generally from 300 ° C to 750 ° C, preferably from 400 ° C to 600 ° C, and a calcination time of generally from 1 hour to 10 hours, preferably From 3 hours to 6 hours.
- the said The calcination is generally carried out under an oxygen-containing atmosphere, such as an air or oxygen atmosphere.
- the first oxide is generally a tetravalent oxide, and may be, for example, selected from the group consisting of silica, ceria, tin dioxide, titanium dioxide, and At least one of zirconia is preferably silica (SiO 2 ) or a combination of silica and ceria.
- These first oxides may be used alone or in combination of any ones in any ratio.
- the molar ratio between any two of the first oxides is, for example, from 20:200 to 35:100.
- silica and cerium oxide may be used in combination, and the molar ratio between the silica and the cerium oxide is, for example, from 20:200 to 35:100.
- the second oxide is generally a trivalent oxide, and may be, for example, selected from the group consisting of alumina, boron oxide, iron oxide, gallium oxide, and rare earth oxide. At least one of indium oxide and vanadium oxide is preferably alumina (Al 2 O 3 ). These second oxides may be used alone or in combination of any ones in any ratio. When a plurality of types are used in combination, the molar ratio between any two of the second oxides is, for example, from 30:200 to 60:150.
- organic templating agent for example, any organic templating agent used in the production of the molecular sieve may be mentioned, and in particular, the molecular sieve of the present embodiment may be mentioned.
- the organic templating agent used (see detailed description below). These organic templating agents may be used alone or in combination of any ones in any ratio. Specifically, specific examples of the organic templating agent include compounds represented by the following formula (I).
- the groups R 1 and R 2 are different from each other, one of which is selected from a C 3-12 straight or branched alkylene group and the other is selected from the group consisting of C 3-12 straight A chain or branched oxaalkylene group, the plurality of groups R being the same or different from each other, each independently selected from a C 1-4 straight or branched alkyl group, and X is OH.
- a molar ratio of the first oxide to the second oxide is generally from 30 to 100, preferably from 55 to 100.
- the molar ratio of water to the first oxide is generally from 5 to 50, preferably from 5 to 15.
- the molar ratio of the organic templating agent to the first oxide is generally from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5.
- the molecular sieve may sometimes further contain metal cations such as alkali metals and/or alkaline earth metal cations in its composition (generally filled in its pores).
- metal cations such as alkali metals and/or alkaline earth metal cations in its composition (generally filled in its pores).
- the content of the metal cation at this time, for example, the mass ratio of the metal cation to the first oxide is generally from 0 to 0.02, preferably from 0.0002 to 0.006, but is not limited thereto.
- the molecular sieve can be produced by the following production method.
- the manufacturing method includes a step of contacting a first oxide source, a second oxide source, an optional alkali source, an organic templating agent, and water under crystallization conditions to obtain a molecular sieve (hereinafter referred to as a contacting step) ).
- the contacting step may be carried out in any manner conventionally known in the art, such as exemplifying the first oxide source, the second oxidation A method of mixing a source, the optional alkali source, the organic templating agent, and water, and subjecting the mixture to crystallization under the crystallization conditions.
- the organic template agent comprises at least a compound represented by the following formula (I).
- the compound represented by the formula (I) may be used alone or in combination of plural kinds in any ratio.
- the groups R 1 and R 2 are different from each other, one of which is selected from a C 3-12 straight or branched alkylene group and the other is selected from C 3 - 12 linear or branched oxaalkylene.
- a C 3-12 linear or branched alkylene group for example, a C 3-12 linear alkylene group can be exemplified, and specific examples thereof include an n-propylene group and an isopropylidene group.
- a C 3-12 linear or branched oxaalkylene group for example, a C 3-12 linear oxaalkylene group can be mentioned, and specific examples thereof include -(CH 2 2 -O-(CH 2 )-, -(CH 2 ) 2 -O-(CH 2 ) 2 -, -(CH 2 )-O-(CH 2 ) 3 -, -(CH 2 ) 2 -O -(CH 2 ) 3 -, -(CH 2 )-O-propylene-, -(CH 2 )-O-(CH 2 ) 4 -, -(CH 2 )-O-(CH 2 ) 2 - O-(CH 2 )-, -(CH 2 )-O-(CH 2 ) 2 -O-(CH 2 ) 2 -, -(CH 2 )-O-tert-butyl-, -(CH 2 ) 2 -O-(CH 2
- C 3-12 linear oxaalkylene group more specifically, a C 4-6 linear oxaalkylene group is exemplified, and a C 4-6 linear monooxaalkylene group is particularly exemplified.
- an oxygen represented by the formula -(CH 2 ) m -O-(CH 2 ) m - (wherein the respective values m are the same or different from each other, each independently representing 2 or 3, such as 2) may be mentioned.
- the heteroalkylene group is more specifically -(CH 2 ) 2 -O-(CH 2 ) 2 -, -(CH 2 ) 2 -O-(CH 2 ) 3 -, -(CH 2 ) 3 -O -(CH 2 ) 3 - or -(CH 2 ) 2 -O-(CH 2 ) 4 -.
- the plurality of groups R are the same or different from each other, each independently selected from a C 1-4 straight or branched alkyl group, preferably each independently selected from the group consisting of The group and the ethyl group are more preferably a methyl group.
- X is OH
- the molar ratio of the organic templating agent to the first oxide source (in terms of the first oxide) is generally from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5.
- the present invention in the contacting step, as the organic template agent, in addition to the compound represented by the formula (I), the present invention may be further used in combination Other organic templating agents conventionally used in the manufacture of molecular sieves.
- the organic templating agent in addition to the compound represented by the formula (I), only the compound represented by the formula (I) is used.
- the compound represented by the formula (I) may be used alone or in combination of plural kinds in any ratio.
- the first oxide source is generally a tetravalent oxide source, and for example, may be selected from a silica source, a ceria source, a tin dioxide source, At least one of a source of titania and a source of zirconium dioxide is preferably a source of silica (SiO 2 ) or a combination of a source of silica and a source of cerium oxide.
- These first oxide sources may be used alone or in combination of any ones in any ratio.
- the molar ratio between any two of the first oxide sources is, for example, from 20:200 to 35:100.
- a silica source and a ceria source may be used in combination, and the molar ratio between the silica source and the ceria source is, for example, from 20:200. To 35:100.
- any corresponding oxide source conventionally used for this purpose in the art may be used, including but not limited to the first oxide.
- the first oxide is silica
- examples of the first oxide source include silica sol, crude silica gel, tetraethyl orthosilicate, water glass, white carbon, and silicic acid. Silica gel or potassium silicate.
- examples of the first oxide source include tetraalkoxy cerium, cerium oxide or cerium nitrate.
- examples of the first oxide source include tin chloride, tin sulfate, tin nitrate, and the like.
- examples of the first oxide source include titanium tetraalkoxide, titanium oxide, titanium nitrate, and the like.
- examples of the first oxide source include zirconium sulfate, zirconium chloride, zirconium nitrate, and the like.
- the second oxide source is generally a trivalent oxide source, and may be, for example, selected from the group consisting of an alumina source, a boron oxide source, an iron oxide source, and a gallium oxide source. At least one of a rare earth oxide source, an indium oxide source, and a vanadium oxide source is preferably an alumina (Al 2 O 3 ) source. These second oxide sources may be used singly or in combination of any ones in any ratio. When a plurality of combinations are used, the molar ratio between any two of the second oxide sources is, for example, from 30:200 to 60:150.
- any corresponding oxide source conventionally used for this purpose in the art may be used, including but not limited to the second oxide.
- the second oxide is alumina
- examples of the second oxide source include aluminum chloride, aluminum sulfate, hydrated alumina, sodium metaaluminate, aluminum sol or aluminum hydroxide.
- examples of the second oxide source include boric acid, borate, borax, and boron trioxide.
- examples of the second oxide source include iron nitrate, iron chloride, iron oxide, and the like.
- examples of the second oxide source include gallium nitrate, gallium sulfate, gallium oxide, and the like.
- examples of the second oxide source include cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium nitrate, cerium nitrate, cerium nitrate, cerium nitrate, ammonium cerium sulfate, and the like. .
- examples of the second oxide source include indium chloride, indium nitrate, indium oxide, and the like.
- examples of the second oxide source include vanadium chloride, ammonium metavanadate, sodium vanadate, vanadium dioxide, vanadyl sulfate, and the like. These second oxide sources may be used singly or in combination of a plurality of them in a desired ratio.
- the first oxide source in terms of the first oxide, such as SiO 2
- the second oxide source in the second The molar ratio of the oxide such as Al 2 O 3
- the first oxide source in terms of the first oxide, such as SiO 2
- the second oxide source in the second The molar ratio of the oxide such as Al 2 O 3
- the first oxide source in terms of the first oxide, such as SiO 2
- the second oxide source in the second The molar ratio of the oxide such as Al 2 O 3
- the molar ratio of water to the first oxide source (in terms of the first oxide) is generally from 5 to 50, preferably from 5 to 15.
- an alkali source may or may not be used.
- the group X contained in the compound represented by the formula (I) can be used to provide the OH - which is required herein.
- the alkali source any alkali source conventionally used for this purpose in the art may be used, including but not limited to inorganic bases which are cations of alkali metals or alkaline earth metals, particularly sodium hydroxide and potassium hydroxide. . These alkali sources may be used alone or in combination of any ones in any ratio.
- a molar ratio of the alkali source (in terms of OH - ) to the first oxide source (in terms of the first oxide) is generally from 0 to 1, preferably from 0.04 to 1, from 0.1 to 1, from 0.2 to 1, from 0.3 to 0.7 or from 0.45 to 0.7.
- the crystallization temperature is generally from 80 ° C to 120 ° C, preferably from 120 ° C to 170 ° C or from 120 ° C to 200 ° C.
- the crystallization time is generally at least 1 day, preferably at least 2 days, preferably from 3 days to 8 days, from 5 days to 8 days or From 4 days to 6 days.
- the molecular sieve in the method for producing the molecular sieve, after the contacting step is completed, the molecular sieve can be separated as a product from the obtained reaction mixture by any separation method conventionally known.
- the molecular sieve product comprises the molecular sieve of the present invention.
- the separation method for example, a method of filtering, washing, and drying the obtained reaction mixture can be mentioned.
- the filtration, washing and drying may be carried out in any manner conventionally known in the art.
- the filtration for example, the obtained reaction mixture can be simply suction filtered.
- washing for example, washing with deionized water can be mentioned until the pH of the filtrate reaches 7-9, preferably 8-9.
- the drying temperature is, for example, 40 to 250 ° C, preferably 60 to 150 ° C, and the drying time is, for example, 8 to 30 hours, preferably 10 to 20 hours.
- the drying can be carried out under normal pressure or under reduced pressure.
- the method for producing the molecular sieve may further include, as needed, a step of calcining the obtained molecular sieve (hereinafter referred to as a calcination step) to remove the organic template agent and possible moisture, and the like.
- a calcination step a step of calcining the obtained molecular sieve
- the molecular sieves before and after calcination are also collectively referred to as molecular sieves of the invention or molecular sieves according to the invention.
- the calcination in the method of producing a molecular sieve, may be carried out in any manner conventionally known in the art, such as a calcination temperature generally from 300 ° C to 750 ° C, preferably from 400 ° C to 600 ° C. And the roasting time is generally from 1 hour to 10 hours, preferably from 3 hours to 6 hours. In addition, the calcination is generally carried out under an oxygen-containing atmosphere, such as an air or oxygen atmosphere.
- the molecular sieve of the present invention or any molecular sieve produced by the method for producing a molecular sieve according to the present invention are collectively referred to as the molecular sieve of the present invention or according to the present invention
- Molecular sieves can also be ion exchanged by any means conventionally known in the art, such as by ion exchange or solution impregnation (for example, see, for example, U.S. Patents 3,140,249 and 3,140,253, etc.)
- the metal cations (such as Na ions or K ions, depending on their specific manufacturing method) are replaced in whole or in part by other cations.
- Examples of the other cation include hydrogen ions, other alkali metal ions (including K ions, Rb ions, etc.), ammonium ions (including NH 4 ions, quaternary ammonium ions such as tetramethylammonium ions and tetraethylammonium ions). Etc.), alkaline earth metal ions (including Mg ions, Ca ions), Mn ions, Zn ions, Cd ions, noble metal ions (including Pt ions, Pd ions, Rh ions, etc.), Ni ions, Co ions, Ti ions, Sn ions , Fe ions and/or rare earth metal ions, and the like.
- the molecular sieve according to the present invention may be treated by a dilute acid solution or the like as needed to increase the ratio of silicon to aluminum or treated with steam to improve the acid attack resistance of the molecular sieve crystal.
- the molecular sieve according to the invention has good heat/water thermal stability and has a larger pore volume.
- the molecular sieve of the present invention is capable of adsorbing more/larger molecules, thereby exhibiting excellent adsorption/catalytic properties.
- the molecular sieve according to the present invention has a strong acidity, particularly a large number of L acid centers. This is a molecular sieve that has not been produced in the prior art. As a result, the molecular sieve of the present invention has more excellent performance particularly in an acid-catalyzed reaction.
- the molecular sieve according to the present invention may be in any physical form such as a powder, a granule or a molded article (e.g., a strip, a clover, etc.). These physical forms can be obtained in any manner conventionally known in the art, and are not particularly limited.
- a molecular sieve having an X-ray diffraction pattern substantially as shown in the following table.
- the X-ray diffraction pattern of the molecular sieve it is preferable to further include an X-ray diffraction peak substantially as shown in the following table.
- the X-ray diffraction pattern of the molecular sieve it is preferable to further include an X-ray diffraction peak substantially as shown in the following table.
- the molecular sieve (referred to as a single crystal) has a crystal morphology from a flat prism to a flat cylinder when viewed by a scanning electron microscope (SEM), particularly having a flat prismatic shape.
- SEM scanning electron microscope
- the crystal morphology refers to the (overall) outer shape exhibited by a single molecular sieve crystal in the observation field of the scanning electron microscope.
- the so-called "primary” refers to the appearance of molecular sieves that are objectively presented directly after manufacture. It is not the artificial manipulation of molecular sieves after they are manufactured. And the appearance of the appearance.
- the term "prism” refers to a convex prism and generally refers to a straight prism and a regular polygonal prism (such as a regular hexagonal prism). It should be specially pointed out that since the crystals of the molecular sieve may be disturbed by various factors during the growth process, the actual crystal morphology and geometrical (true) straight prisms, (true) regular polygonal prisms or The cylinder may have a certain degree of deviation, such as a deviation of 30%, 20% or 5%, resulting in obtaining a beveled prism, an irregular polygon (or even a curved polygon) prism or an elliptical cylinder, but the invention is not intended Specifically, the degree of deviation is specified.
- any greater or lesser deviations do not depart from the scope of the invention.
- flat it is meant that the ratio of height to width (or diameter) (such as the aspect ratio as described below) is less than one.
- flat prismatic to flat cylindrical it is meant that the crystal morphology of the molecular sieve may be a flat prismatic shape, a flat cylindrical shape, or any transition from a flat prism shape to a flat cylindrical shape. shape. Specific examples of the transition shape include a shape obtained by rounding one or more edges of the flat prism. It is obvious that by rounding all the edges of the flat prism, it is possible to obtain the flat cylinder.
- the molecular sieve has a columnar crystal morphology when viewed using a scanning electron microscope (SEM).
- a longitudinal section of the column can be obtained when longitudinally sectioning along the centerline of the column.
- the longitudinal section has an end surface contour line on the upper and lower sides (a range surrounded by two broken lines) and a side contour line on the left and right sides (a range enclosed by two broken lines).
- the molecular sieve of the present modified embodiment is unique in that one or both of the two end face contours have a convex shape, that is, a radius of curvature is a positive value.
- the present invention is not intended to limit the specific range of the radius of curvature as long as it is a positive value.
- the molecular sieve of the present modified embodiment generally has an outer shape obtained by rounding or chamfering the edge of one end surface or both end faces of the column.
- This can be understood, for example, by referring to Figures VI-14(a) and VI-14(b).
- the Figures VI-14(a) and VI-II(b) are only for explaining the present invention and are not intended to limit the present invention.
- Fig. VI-14(c) exemplifies a case where the end face contour does not have a convex shape but a flat shape.
- the inventors of the present invention have found through careful investigation that the prior art has not produced a molecular sieve having both the aforementioned specific X-ray diffraction pattern and the aforementioned specific (native) crystal morphology.
- the observation is carried out using a scanning electron microscope (SEM)
- the effective diameter of the molecular sieve (single crystal) is generally from 100 nm to 1000 nm, preferably from 100 nm to 500 nm.
- the effective diameter means that two points are arbitrarily selected along the contour (edge) of the cross section of the molecular sieve (single crystal), and the linear distance between the two points is measured. The largest straight line distance is taken as the effective diameter. If the profile of the cross section of the molecular sieve is presented as a polygon such as a hexagon, the effective diameter generally refers to the linear distance (diagonal distance) between the two vertices furthest from the polygon.
- the effective diameter corresponds substantially to the diameter of the circumcircle of the polygon represented by the contour of the cross section.
- the effective diameter refers to the diameter of the circle.
- the height of the molecular sieve is generally from 100 nm to 1000 nm, preferably from 150 nm to 300 nm, when observed using a scanning electron microscope (SEM).
- the term "height” refers to a linear distance between the centers of the two end faces of the column in a single crystal (columnar crystal) of the molecular sieve.
- the molecular sieve (single crystal) has an aspect ratio of generally from 0.1 to 0.9, preferably from 0.4 to 0.7, when observed by a scanning electron microscope (SEM).
- the aspect ratio refers to the ratio of the height to the effective diameter.
- the prior art has not produced a molecular sieve having both the aforementioned specific X-ray diffraction pattern and the aforementioned specific aspect ratio.
- the crystal morphology of the molecular sieve at this time is similar to an oral tablet.
- the molecular sieve has a total specific surface area of generally from 400 m 2 /g to 600 m 2 /g, preferably from 450 m 2 /g to 580 m 2 /g.
- the total specific surface area is obtained by a liquid nitrogen adsorption method as calculated by a BET model.
- the molecular sieve generally has a pore volume of from 0.3 ml/g to 0.5 ml/g, preferably from 0.30 ml/g to 0.40 ml/g.
- the molecular sieve of the present invention has a very high pore volume, which indicates that it belongs to an ultra-large pore molecular sieve.
- the pore volume is obtained by low temperature nitrogen adsorption and calculated by the BET model.
- the molecular sieve may have the schematic chemical composition represented by the formula "first oxide ⁇ second oxide". It is known that molecular sieves sometimes contain a certain amount of water (especially just after synthesis), but the present invention does not consider it necessary to specify the amount of moisture because the presence or absence of the moisture does not substantially The XRD spectrum of the molecular sieve is affected. In view of this, the schematic chemical composition actually represents the molecule The anhydrous chemical composition of the sieve. Moreover, it is apparent that the schematic chemical composition represents the framework chemical composition of the molecular sieve.
- the molecular sieve may, in its composition, typically further comprise an organic templating agent and water or the like, such as those filled in its pores, just after synthesis. Therefore, the molecular sieve may sometimes have an illustrative chemical composition represented by the formula "first oxide ⁇ second oxide ⁇ organic template agent ⁇ water".
- the molecular sieve having the schematic chemical composition represented by the formula "first oxide ⁇ second oxide ⁇ organic template agent ⁇ water” is calcined to remove any organic templating agent and water present in the pores thereof.
- the molecular sieve having the schematic chemical composition represented by the formula "first oxide ⁇ second oxide” can be obtained.
- the calcination may be carried out in any manner conventionally known in the art, such as a calcination temperature generally from 300 ° C to 750 ° C, preferably from 400 ° C to 600 ° C, and a calcination time of generally from 1 hour to 10 hours, preferably From 3 hours to 6 hours.
- the calcination is generally carried out under an oxygen-containing atmosphere, such as an air or oxygen atmosphere.
- the first oxide is generally a tetravalent oxide, and may be, for example, selected from the group consisting of silica, ceria, tin dioxide, titanium dioxide, and At least one of zirconia is preferably silica (SiO 2 ) or a combination of silica and ceria.
- These first oxides may be used alone or in combination of any ones in any ratio.
- the molar ratio between any two of the first oxides is, for example, from 20:200 to 35:100.
- silica and cerium oxide may be used in combination, and the molar ratio between the silica and the cerium oxide is, for example, from 20:200 to 35:100.
- the second oxide is generally a trivalent oxide, and may be, for example, selected from the group consisting of alumina, boron oxide, iron oxide, gallium oxide, and rare earth oxide. At least one of indium oxide and vanadium oxide is preferably alumina (Al 2 O 3 ). These second oxides may be used alone or in combination of any ones in any ratio. When a plurality of types are used in combination, the molar ratio between any two of the second oxides is, for example, from 30:200 to 60:150.
- organic templating agent for example, any organic templating agent used in the production of the molecular sieve may be mentioned, and in particular, the molecular sieve of the present embodiment may be mentioned.
- the organic templating agent used (see detailed description below). These organic templating agents may be used alone or in any The ratio of the combinations is varied.
- specific examples of the organic templating agent include compounds represented by the following formula (I).
- the groups R 1 and R 2 are the same or different from each other, each independently selected from a C 3-12 straight or branched alkylene group, and the plurality of groups R are each other The same or different, each independently selected from a C 1-4 straight or branched alkyl group, and X is OH.
- a molar ratio of the first oxide to the second oxide is generally from 40 to 200, preferably from 40 to 150.
- the molar ratio of water to the first oxide is generally from 5 to 50, preferably from 5 to 15.
- the molar ratio of the organic templating agent to the first oxide is generally from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5.
- the molecular sieve may sometimes further contain metal cations such as alkali metals and/or alkaline earth metal cations in its composition (generally filled in its pores).
- metal cations such as alkali metals and/or alkaline earth metal cations in its composition (generally filled in its pores).
- the content of the metal cation at this time, for example, the mass ratio of the metal cation to the first oxide is generally from 0 to 0.02, preferably from 0.0002 to 0.006, but is not limited thereto.
- the molecular sieve can be produced by the following production method.
- the manufacturing method includes a step of contacting a first oxide source, a second oxide source, an optional alkali source, an organic templating agent, and water under crystallization conditions to obtain a molecular sieve (hereinafter referred to as a contacting step) ).
- the contacting step may be carried out in any manner conventionally known in the art, such as exemplifying the first oxide source, the second oxidation A method of mixing a source, the optional alkali source, the organic templating agent, and water, and subjecting the mixture to crystallization under the crystallization conditions.
- the organic template agent comprises at least a compound represented by the following formula (I).
- the compound represented by the formula (I) One type may be used alone or in combination in any ratio.
- the groups R 1 and R 2 are the same or different from each other, and are each independently selected from a C 3-12 straight or branched alkylene group.
- the groups R 1 and R 2 are identical or different from one another, one of which is selected from the group consisting of C 3-12 linear alkylene groups, the other option From C 4-6 linear alkylene.
- a C 3-12 linear or branched alkylene group for example, a C 3-12 linear alkylene group can be exemplified, and specific examples thereof include an n-propylene group and an isopropylidene group.
- the C 4-6 linear alkylene group specifically, an n-n-butyl group, a n-n-pentyl group or an n-hexylene group can be mentioned.
- the plurality of groups R are the same or different from each other, each independently selected from a C 1-4 straight or branched alkyl group, preferably each independently selected from the group consisting of The group and the ethyl group are more preferably a methyl group.
- X is OH
- the molar ratio of the organic templating agent to the first oxide source (in terms of the first oxide) is generally from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5.
- organic templating agent in addition to the compound represented by the formula (I), other materials conventionally used in the art for producing molecular sieves may be further used in combination.
- Organic templating agent in addition to the compound represented by the formula (I), other materials conventionally used in the art for producing molecular sieves may be further used in combination.
- Organic templating agent in addition to the compound represented by the formula (I), other materials conventionally used in the art for producing molecular sieves may be further used in combination.
- Organic templating agent Preferably, in the contacting step, as the organic template agent, only the chemical represented by the formula (I) is used. Compound.
- the compound represented by the formula (I) may be used alone or in combination of plural kinds in any ratio.
- the first oxide source is generally a tetravalent oxide source, and for example, may be selected from a silica source, a ceria source, a tin dioxide source, At least one of a source of titania and a source of zirconium dioxide is preferably a source of silica (SiO 2 ) or a combination of a source of silica and a source of cerium oxide.
- These first oxide sources may be used alone or in combination of any ones in any ratio.
- the molar ratio between any two of the first oxide sources is, for example, from 30:200 to 60:150.
- a silica source and a ceria source may be used in combination, and the molar ratio between the silica source and the ceria source is, for example, from 20:200. To 35:100.
- any corresponding oxide source conventionally used for this purpose in the art may be used, including but not limited to the first oxide.
- the first oxide is silica
- examples of the first oxide source include silica sol, crude silica gel, tetraethyl orthosilicate, water glass, white carbon, and silicic acid. Silica gel or potassium silicate.
- examples of the first oxide source include tetraalkoxy cerium, cerium oxide or cerium nitrate.
- examples of the first oxide source include tin chloride, tin sulfate, tin nitrate, and the like.
- examples of the first oxide source include titanium tetraalkoxide, titanium oxide, titanium nitrate, and the like.
- examples of the first oxide source include zirconium chloride, zirconium sulfate, zirconium nitrate, and the like.
- the second oxide source is generally a trivalent oxide source, and may be, for example, selected from the group consisting of an alumina source, a boron oxide source, an iron oxide source, and a gallium oxide source. At least one of a rare earth oxide source, an indium oxide source, and a vanadium oxide source is preferably an alumina (Al 2 O 3 ) source. These second oxide sources may be used alone or in combination of any ones in any ratio. When a plurality of types are used in combination, the molar ratio between any two of the second oxide sources is, for example, from 20:200 to 35:100.
- any corresponding oxide source conventionally used for this purpose in the art may be used, including but not limited to the second oxide.
- the second oxide is alumina
- examples of the second oxide source include aluminum chloride, aluminum sulfate, hydrated alumina, sodium metaaluminate, aluminum sol or aluminum hydroxide.
- examples of the second oxide source include boric acid, borate, borax, and boron trioxide.
- examples of the second oxide source include iron nitrate, iron chloride, iron oxide, and the like.
- examples of the second oxide source include gallium nitrate, gallium sulfate, gallium oxide, and the like.
- examples of the second oxide source include cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium nitrate, cerium nitrate, cerium nitrate, cerium nitrate, ammonium cerium sulfate, and the like. .
- examples of the second oxide source include indium chloride, indium nitrate, indium oxide, and the like.
- examples of the second oxide source include vanadium chloride, ammonium metavanadate, sodium vanadate, vanadium dioxide, vanadyl sulfate, and the like. These second oxide sources may be used singly or in combination of a plurality of them in a desired ratio.
- the first oxide source in terms of the first oxide, such as SiO 2
- the second oxide source in the second The molar ratio of the oxide such as Al 2 O 3
- the first oxide source in terms of the first oxide, such as SiO 2
- the second oxide source in the second The molar ratio of the oxide such as Al 2 O 3
- the first oxide source in terms of the first oxide, such as SiO 2
- the second oxide source in the second The molar ratio of the oxide such as Al 2 O 3
- the molar ratio of water to the first oxide source (in terms of the first oxide) is generally from 5 to 50, preferably from 5 to 15.
- an alkali source may or may not be used.
- the group X contained in the compound represented by the formula (I) can be used to provide the OH - which is required herein.
- the alkali source any alkali source conventionally used for this purpose in the art may be used, including but not limited to inorganic bases which are cations of alkali metals or alkaline earth metals, particularly sodium hydroxide and potassium hydroxide. . These alkali sources may be used alone or in combination of any ones in any ratio.
- a molar ratio of the alkali source (in terms of OH - ) to the first oxide source (in terms of the first oxide) is generally from 0 to 1, preferably from 0.04 to 1, from 0.1 to 1, from 0.2 to 1, from 0.3 to 0.7 or from 0.45 to 0.7.
- the crystallization temperature is generally from 80 ° C to 120 ° C, preferably from 120 ° C to 170 ° C or from 120 ° C to 200 ° C.
- the crystallization time is generally at least 1 day, preferably at least 2 days, preferably from 3 days to 8 days, from 5 days to 8 days or From 4 days to 6 days.
- the molecular sieve in the method for producing the molecular sieve, after the contacting step is completed, the molecular sieve can be separated as a product from the obtained reaction mixture by any separation method conventionally known.
- the molecular sieve product comprises the molecular sieve of the present invention.
- the separation method for example, a method of filtering, washing, and drying the obtained reaction mixture can be mentioned.
- the filtration, washing and drying may be carried out in any manner conventionally known in the art.
- the filtration for example, the obtained reaction mixture can be simply suction filtered.
- washing for example, washing with deionized water can be mentioned until the pH of the filtrate reaches 7-9, preferably 8-9.
- the drying temperature is, for example, 40 to 250 ° C, preferably 60 to 150 ° C, and the drying time is, for example, 8 to 30 hours, preferably 10 to 20 hours.
- the drying can be carried out under normal pressure or under reduced pressure.
- the method for producing the molecular sieve may further include, as needed, a step of calcining the obtained molecular sieve (hereinafter referred to as a calcination step) to remove the organic template agent and possible moisture, and the like.
- a calcination step a step of calcining the obtained molecular sieve
- the molecular sieves before and after calcination are also collectively referred to as molecular sieves of the invention or molecular sieves according to the invention.
- the calcination in the method of producing a molecular sieve, may be carried out in any manner conventionally known in the art, such as a calcination temperature generally from 300 ° C to 750 ° C, preferably from 400 ° C to 600 ° C. And the calcination time is generally from 1 hour to 10 hours, preferably from 3 hours to 6 hours. In addition, the calcination is generally carried out under an oxygen-containing atmosphere, such as an air or oxygen atmosphere.
- the molecular sieve of the present invention or any molecular sieve produced by the method for producing a molecular sieve according to the present invention are collectively referred to as the molecular sieve of the present invention or according to the present invention
- Molecular sieves can also be ion exchanged by any means conventionally known in the art, such as by ion exchange or solution impregnation (for example, see, for example, U.S. Patents 3,140,249 and 3,140,253, etc.)
- the metal cations (such as Na ions or K ions, depending on their specific manufacturing method) are replaced in whole or in part by other cations.
- Examples of the other cation include hydrogen ions, other alkali metal ions (including K ions, Rb ions, etc.), ammonium ions (including NH 4 ions, quaternary ammonium ions such as tetramethylammonium ions and tetraethylammonium ions). Etc.), alkaline earth metal ions (including Mg ions, Ca ions), Mn ions, Zn ions, Cd ions, noble metal ions (including Pt ions, Pd ions, Rh ions, etc.), Ni ions, Co ions, Ti ions, Sn ions , Fe ions and/or rare earth metal ions, and the like.
- the molecular sieve according to the present invention may be treated by a dilute acid solution or the like as needed to increase the ratio of silicon to aluminum or treated with steam to improve the acid attack resistance of the molecular sieve crystal.
- the molecular sieve according to the invention has good heat/water thermal stability and has a larger pore volume.
- the molecular sieve of the present invention is capable of adsorbing more/larger molecules, thereby exhibiting excellent adsorption/catalytic properties.
- the molecular sieve according to the present invention has a strong acidity, particularly L acid (the number of centers is large. This is a molecular sieve which has not been produced in the prior art. As a result, the molecular sieve of the present invention has more in particular in an acid-catalyzed reaction. For excellent performance.
- the molecular sieve according to the present invention may be in any physical form such as a powder, a granule or a molded article (e.g., a strip, a clover, etc.). These physical forms can be obtained in any manner conventionally known in the art, and are not particularly limited.
- a method of making a molecular sieve includes a step of contacting a first oxide source, a second oxide source, an optional alkali source, an organic templating agent, and water under crystallization conditions to obtain a molecular sieve (hereinafter referred to as a contacting step) ).
- the contacting The step can be carried out in any manner conventionally known in the art, such as by mixing the first oxide source, the second oxide source, the optional alkali source, the organic template, and water. And a method of crystallizing the mixture under the crystallization conditions.
- the organic template agent comprises at least a compound represented by the following formula (I).
- the compound represented by the formula (I) may be used alone or in combination of plural kinds in any ratio.
- the groups R 1 and R 2 are the same or different from each other, and are each independently selected from a C 3-12 straight or branched alkylene group.
- the groups R 1 and R 2 are identical or different from one another, one of which is selected from the group consisting of C 3-12 linear alkylene groups, the other option From C 4-6 linear alkylene.
- a C 3-12 linear or branched alkylene group for example, a C 3-12 linear alkylene group can be exemplified, and specific examples thereof include an n-propylene group and an isopropylidene group.
- the C 4-6 linear alkylene group specifically, an n-n-butyl group, a n-n-pentyl group or an n-hexylene group can be mentioned.
- the plurality of groups R are the same or different from each other, each independently selected from a C 1-4 straight or branched alkyl group, preferably each independently selected from the group consisting of The group and the ethyl group are more preferably a methyl group.
- X is OH
- the molar ratio of the organic templating agent to the first oxide source (in terms of the first oxide) is generally from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5.
- organic templating agent in addition to the compound represented by the formula (I), other materials conventionally used in the art for producing molecular sieves may be further used in combination.
- Organic templating agent in addition to the compound represented by the formula (I), other materials conventionally used in the art for producing molecular sieves may be further used in combination.
- Organic templating agent in addition to the compound represented by the formula (I), other materials conventionally used in the art for producing molecular sieves may be further used in combination.
- Organic templating agent Preferably, in the contacting step, as the organic templating agent, only the compound represented by the formula (I) is used.
- the compound represented by the formula (I) may be used alone or in combination of plural kinds in any ratio.
- the first oxide source is generally a tetravalent oxide source, and for example, may be selected from a silica source, a ceria source, a tin dioxide source, At least one of a source of titania and a source of zirconium dioxide is preferably a source of silica (SiO 2 ) or a combination of a source of silica and a source of cerium oxide.
- These first oxide sources may be used alone or in combination of any ones in any ratio.
- the molar ratio between any two of the first oxide sources is, for example, from 20:200 to 35:100.
- a silica source and a ceria source may be used in combination, and the molar ratio between the silica source and the ceria source is, for example, from 20:200. To 35:100.
- any corresponding oxide source conventionally used for this purpose in the art may be used, including but not limited to the first oxide.
- the first oxide is silica
- examples of the first oxide source include silica sol, crude silica gel, tetraethyl orthosilicate, water glass, white carbon, and silicic acid. Silica gel or potassium silicate.
- examples of the first oxide source include tetraalkoxy cerium, cerium oxide or cerium nitrate.
- examples of the first oxide source include tin chloride, tin sulfate, tin nitrate, and the like.
- examples of the first oxide source include titanium tetraalkoxide, titanium oxide, titanium nitrate, and the like.
- examples of the first oxide source include zirconium chloride, zirconium sulfate, zirconium nitrate, and the like.
- the second oxide source is generally a trivalent oxide source, and may be, for example, selected from the group consisting of an alumina source, a boron oxide source, an iron oxide source, and a gallium oxide source. At least one of a rare earth oxide source, an indium oxide source, and a vanadium oxide source is preferably an alumina (Al 2 O 3 ) source. These second oxide sources may be used alone or in combination of any ones in any ratio. When a plurality of combinations are used, the molar ratio between any two of the second oxide sources is, for example, from 30:200 to 60:150.
- any corresponding oxide source conventionally used for this purpose in the art may be used, including but not limited to the second oxide.
- the second oxide is alumina
- examples of the second oxide source include aluminum chloride, aluminum sulfate, hydrated alumina, sodium metaaluminate, aluminum sol or aluminum hydroxide.
- examples of the second oxide source include boric acid, borate, borax, and boron trioxide.
- examples of the second oxide source include iron nitrate, iron chloride, iron oxide, and the like.
- examples of the second oxide source include gallium nitrate, gallium sulfate, gallium oxide, and the like.
- examples of the second oxide source include cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium nitrate, cerium nitrate, cerium nitrate, cerium nitrate, ammonium cerium sulfate, and the like. .
- examples of the second oxide source include indium chloride, indium nitrate, indium oxide, and the like.
- examples of the second oxide source include vanadium chloride, ammonium metavanadate, sodium vanadate, vanadium dioxide, vanadyl sulfate, and the like. These second oxide sources may be used singly or in combination of a plurality of them in a desired ratio.
- the first oxide source in terms of the first oxide, such as SiO 2
- the second oxide source in the second The molar ratio of the oxide, such as Al 2 O 3
- the molar ratio is generally from 5 to ⁇ , especially from 5 to less than 40 (such as from 20 to less than 40), from 40 to 200 (such as from 40 to 150), from More than 200 to ⁇ (such as from more than 200 to 700).
- the molar ratio is ⁇ , it means that the second oxide source is not used or the second oxide source is not intentionally introduced into the contacting step.
- the molar ratio of water to the first oxide source (in terms of the first oxide) is generally from 5 to 50, preferably from 5 to 15.
- an alkali source may or may not be used.
- the group X contained in the compound represented by the formula (I) can be used to provide the OH - which is required herein.
- the alkali source any alkali source conventionally used for this purpose in the art may be used, including but not limited to inorganic bases which are cations of alkali metals or alkaline earth metals, particularly sodium hydroxide and potassium hydroxide. . These alkali sources may be used alone or in combination of any ones in any ratio.
- a molar ratio of the alkali source (in terms of OH - ) to the first oxide source (in terms of the first oxide) is generally from 0 to 1, preferably from 0.04 to 1, from 0.1 to 1, from 0.2 to 1, from 0.3 to 0.7 or from 0.45 to 0.7.
- the crystallization temperature is generally from 80 ° C to 120 ° C, preferably from 120 ° C to 170 ° C or from 120 ° C to 200 ° C.
- the crystallization time is generally at least 1 day, preferably at least 2 days, preferably from 3 days to 8 days, from 5 days to 8 days or From 4 days to 6 days.
- the molecular sieve in the method for producing the molecular sieve, after the contacting step is completed, the molecular sieve can be separated as a product from the obtained reaction mixture by any separation method conventionally known.
- the molecular sieve product comprises the molecular sieve of the present invention.
- the separation method for example, a method of filtering, washing, and drying the obtained reaction mixture can be mentioned.
- the filtration, washing and drying may be carried out in any manner conventionally known in the art.
- the filtration for example, the obtained reaction mixture can be simply suction filtered.
- washing for example, washing with deionized water can be mentioned until the pH of the filtrate reaches 7-9, preferably 8-9.
- the drying temperature is, for example, 40 to 250 ° C, preferably 60 to 150 ° C, and the drying time is, for example, 8 to 30 hours, preferably 10 to 20 hours.
- the drying can be carried out under normal pressure or under reduced pressure.
- the method for producing the molecular sieve may further include, as needed, a step of calcining the obtained molecular sieve (hereinafter referred to as a calcination step) to remove the organic template agent and possible moisture, and the like.
- a calcination step a step of calcining the obtained molecular sieve
- the molecular sieves before and after calcination are collectively referred to as molecular sieves of the invention or molecular sieves according to the invention.
- the calcination in the method of producing a molecular sieve, may be carried out in any manner conventionally known in the art, such as a calcination temperature generally from 300 ° C to 750 ° C, preferably from 400 ° C to 600 ° C. And the calcination time is generally from 1 hour to 10 hours, preferably from 3 hours to 6 hours. In addition, the calcination is generally carried out under an oxygen-containing atmosphere, such as an air or oxygen atmosphere.
- any molecular sieve produced as previously described may, if desired, be ion exchanged by any means conventionally known in the art, such as
- the metal cations such as Na ions or K ions, depending on the specific manufacturing method thereof
- contained in the composition are replaced in whole or in part by ion exchange method or solution impregnation method (for example, see US Pat. No. 3,140,249 and US Pat. No. 3,140,253, etc.).
- ion exchange method for example, see US Pat. No. 3,140,249 and US Pat. No. 3,140,253, etc.
- Examples of the other cation include hydrogen ions, other alkali metal ions (including K ions, Rb ions, etc.), and ammonium ions (including NH4 ions, quaternary ammonium ions such as tetramethylammonium ions and tetraethylammonium ions, etc.). ), alkaline earth metal ions (including Mg ions, Ca ions), Mn ions, Zn ions, Cd ions, noble metal ions (including Pt ions, Pd ions, Rh ions, etc.), Ni ions, Co ions, Ti ions, Sn ions, Fe ions and/or rare earth metal ions, and the like.
- the molecular sieve according to the present invention may be treated by a dilute acid solution or the like as needed to increase the ratio of silicon to aluminum or treated with steam to improve the acid attack resistance of the molecular sieve crystal.
- the molecular sieve according to the present invention generally has an X-ray diffraction pattern substantially as shown in the following table.
- the X-ray diffraction pattern of the molecular sieve it is preferable to further include an X-ray diffraction peak substantially as shown in the following table.
- the X-ray diffraction pattern of the molecular sieve it is preferable to further include an X-ray diffraction peak substantially as shown in the following table.
- the molecular sieve generally has a columnar crystal morphology when viewed using a scanning electron microscope (SEM).
- the crystal morphology refers to the (overall) outer shape exhibited by a single molecular sieve crystal in the observation field of the scanning electron microscope.
- a prismatic shape in particular, a hexagonal prism shape is preferable.
- the prism refers to a convex prism and generally refers to a right prism and a regular polygonal prism (such as a regular hexagonal prism).
- the actual crystal morphology may be compared with the geometric (true) straight prism or (true) regular polygonal prism.
- any greater or lesser deviations do not depart from the scope of the invention.
- the observation is carried out using a scanning electron microscope (SEM)
- the molecular sieve single crystal
- the effective diameter means that two points are arbitrarily selected along the contour (edge) of the cross section of the molecular sieve (single crystal), and the linear distance between the two points is measured. The largest straight line distance is taken as the effective diameter.
- the effective diameter generally refers to the linear distance (diagonal distance) between the two vertices furthest from the polygon.
- the effective diameter corresponds substantially to the diameter of the circumcircle of the polygon represented by the contour of the cross section.
- the molecular sieve (single crystal) has a height generally ranging from 100 nm to 3000 nm when observed by a scanning electron microscope (SEM).
- the term "height” refers to a linear distance between the centers of the two end faces of the column in a single crystal (columnar crystal) of the molecular sieve.
- the two end faces of the molecular sieve column are substantially parallel to each other, and the linear distance is the vertical distance between the two end faces, but the invention is not limited thereto.
- the molecular sieve (single crystal) has an aspect ratio of generally from 0.1 to 8 when observed by a scanning electron microscope (SEM).
- the aspect ratio refers to the ratio of the height to the effective diameter.
- the molecular sieve has a total specific surface area of generally from 400 m 2 /g to 600 m 2 /g, preferably from 450 m 2 /g to 580 m 2 /g.
- the total specific surface area is obtained by a low-temperature nitrogen adsorption, calculated by a BET model.
- the molecular sieve generally has a pore volume of from 0.3 ml/g to 0.5 ml/g, preferably from 0.30 ml/g to 0.40 ml/g.
- the molecular sieve of the present invention has a very high pore volume, which indicates that it belongs to an ultra-large pore molecular sieve.
- the pore volume is obtained by low temperature nitrogen adsorption and calculated by the BET model.
- the molecular sieve according to the invention has good heat/water thermal stability and has a larger pore volume.
- the molecular sieve of the present invention is capable of adsorbing more/larger molecules, thereby exhibiting excellent adsorption/catalytic properties.
- the molecular sieve according to the present invention has a strong acidity, particularly L acid (the number of centers is large. This is a molecular sieve which has not been produced in the prior art. As a result, the molecular sieve of the present invention has more in particular in an acid-catalyzed reaction. For excellent performance.
- the molecular sieve according to the present invention may be presented in any physical form such as a powder, Granular or molded (such as strips, clover, etc.). These physical forms can be obtained in any manner conventionally known in the art, and are not particularly limited.
- a method of making a molecular sieve includes a step of contacting a first oxide source, a second oxide source, an optional alkali source, an organic templating agent, and water under crystallization conditions to obtain a molecular sieve (hereinafter referred to as a contacting step) ).
- the contacting step may be carried out in any manner conventionally known in the art, such as exemplifying the first oxide source, the second oxidation A method of mixing a source, the optional alkali source, the organic templating agent, and water, and subjecting the mixture to crystallization under the crystallization conditions.
- the organic template agent comprises at least a compound represented by the following formula (I).
- the compound represented by the formula (I) may be used alone or in combination of plural kinds in any ratio.
- the groups R1 and R2 are different from each other, one of which is selected from a C 3-12 straight or branched alkylene group and the other is selected from C 3 - 12 linear or branched oxaalkylene.
- a C 3-12 linear or branched alkylene group for example, a C 3-12 linear alkylene group can be exemplified, and specific examples thereof include an n-propylene group and an isopropylidene group.
- a C 3-12 linear or branched oxaalkylene group for example, a C 3-12 linear oxaalkylene group can be mentioned, and specific examples thereof include -(CH 2 2 -O-(CH 2 )-, -(CH 2 ) 2 -O-(CH 2 ) 2 -, -(CH 2 )-O-(CH 2 ) 3 -, -(CH 2 ) 2 -O -(CH 2 ) 3 -, -(CH 2 )-O-propylene-, -(CH 2 )-O-(CH 2 ) 4 -, -(CH 2 )-O-(CH 2 ) 2 - O-(CH 2 )-, -(CH 2 )-O-(CH 2 ) 2 -O-(CH 2 ) 2 -, -(CH 2 )-O-tert-butyl-, -(CH 2 ) 2 -O-(CH 2
- C 3-12 linear oxaalkylene group more specifically, a C 4-6 linear oxaalkylene group is exemplified, and a C 4-6 linear monooxaalkylene group is particularly exemplified.
- an oxygen represented by the formula -(CH 2 ) m -O-(CH 2 ) m - (wherein the respective values m are the same or different from each other, each independently representing 2 or 3, such as 2) may be mentioned.
- the heteroalkylene group is more specifically -(CH 2 ) 2 -O-(CH 2 ) 2 -, -(CH 2 ) 2 -O-(CH 2 ) 3 -, -(CH 2 ) 3 -O -(CH 2 ) 3 - or -(CH 2 ) 2 -O-(CH 2 ) 4 -.
- the plurality of groups R are the same or different from each other, each independently selected from a C 1-4 straight or branched alkyl group, preferably each independently selected from the group consisting of The group and the ethyl group are more preferably a methyl group.
- X is OH
- the molar ratio of the organic templating agent to the first oxide source (in terms of the first oxide) is generally from 0.02 to 0.5, preferably from 0.05 to 0.5, from 0.15 to 0.5 or from 0.3 to 0.5.
- organic templating agent in addition to the compound represented by the formula (I), other materials conventionally used in the art for producing molecular sieves may be further used in combination.
- Organic templating agent in addition to the compound represented by the formula (I), other materials conventionally used in the art for producing molecular sieves may be further used in combination.
- Organic templating agent in addition to the compound represented by the formula (I), other materials conventionally used in the art for producing molecular sieves may be further used in combination.
- Organic templating agent Preferably, in the contacting step, as the organic templating agent, only the compound represented by the formula (I) is used.
- the compound represented by the formula (I) may be used alone or in combination of plural kinds in any ratio.
- the first oxide source is generally a tetravalent oxide source, and for example, may be selected from a silica source, a ceria source, a tin dioxide source, At least one of a source of titania and a source of zirconium dioxide is preferably a source of silica (SiO 2 ) or a combination of a source of silica and a source of cerium oxide.
- These first oxide sources may be used alone or in combination of any ones in any ratio.
- the molar ratio between any two of the first oxide sources is, for example, from 20:200 to 35:100.
- a silica source and a ceria source may be used in combination, and the molar ratio between the silica source and the ceria source is, for example, from 20:200. To 35:100.
- any corresponding oxide source conventionally used for this purpose in the art may be used, including but not limited to the first oxide.
- the first oxide is silica
- examples of the first oxide source include silica sol, crude silica gel, tetraethyl orthosilicate, water glass, white carbon, and silicic acid. Silica gel or potassium silicate.
- examples of the first oxide source include tetraalkoxy cerium, cerium oxide or cerium nitrate.
- examples of the first oxide source include tin chloride, tin sulfate, tin nitrate, and the like.
- examples of the first oxide source include titanium tetraalkoxide, titanium oxide, titanium nitrate, and the like.
- examples of the first oxide source include zirconium chloride, zirconium sulfate, zirconium nitrate, and the like.
- the second oxide source is generally a trivalent oxide source, and may be, for example, selected from the group consisting of an alumina source, a boron oxide source, an iron oxide source, and a gallium oxide source. At least one of a rare earth oxide source, an indium oxide source, and a vanadium oxide source is preferably an alumina (Al 2 O 3 ) source. These second oxide sources may be used alone or in combination of any ones in any ratio. When a plurality of combinations are used, the molar ratio between any two of the second oxide sources is, for example, from 30:200 to 60:150.
- any corresponding oxide source conventionally used for this purpose in the art may be used, including but not limited to the second oxide.
- the second oxide is alumina
- the second oxide source for example examples thereof include aluminum chloride, aluminum sulfate, hydrated alumina, sodium metaaluminate, aluminum sol or aluminum hydroxide.
- examples of the second oxide source include boric acid, borate, borax, and boron trioxide.
- examples of the second oxide source include iron nitrate, iron chloride, iron oxide, and the like.
- examples of the second oxide source include gallium nitrate, gallium sulfate, gallium oxide, and the like.
- examples of the second oxide source include cerium oxide, cerium oxide, cerium oxide, cerium oxide, cerium nitrate, cerium nitrate, cerium nitrate, cerium nitrate, ammonium cerium sulfate, and the like. .
- examples of the second oxide source include indium chloride, indium nitrate, indium oxide, and the like.
- examples of the second oxide source include vanadium chloride, ammonium metavanadate, sodium vanadate, vanadium dioxide, vanadyl sulfate, and the like. These second oxide sources may be used singly or in combination of a plurality of them in a desired ratio.
- the first oxide source in terms of the first oxide, such as SiO 2
- the second oxide source in the second The molar ratio of the oxide, such as Al 2 O 3
- the first oxide source in terms of the first oxide, such as SiO 2
- the second oxide source in the second The molar ratio of the oxide, such as Al 2 O 3
- the molar ratio is ⁇ , it means that the second oxide source is not used or the second oxide source is not intentionally introduced into the contacting step.
- the molar ratio of water to the first oxide source (in terms of the first oxide) is generally from 5 to 50, preferably from 5 to 15.
- an alkali source may or may not be used.
- the group X contained in the compound represented by the formula (I) can be used to provide the OH - which is required herein.
- the alkali source any alkali source conventionally used for this purpose in the art may be used, including but not limited to inorganic bases which are cations of alkali metals or alkaline earth metals, particularly sodium hydroxide and potassium hydroxide. . These alkali sources may be used alone or in combination of any ones in any ratio.
- a molar ratio of the alkali source (in terms of OH - ) to the first oxide source (in terms of the first oxide) is generally from 0 to 1, preferably from 0.04 to 1, from 0.1 to 1, from 0.2 to 1, from 0.3 to 0.7 or from 0.45 to 0.7.
- the crystallization temperature is generally from 80 ° C to 120 ° C, preferably from 120 ° C to 170 ° C or from 120 ° C to 200 ° C.
- the crystallization time is generally at least 1 day, preferably at least 2 days, preferably from 3 days to 8 days, from 5 days to 8 days or From 4 days to 6 days.
- the molecular sieve in the method for producing the molecular sieve, after the contacting step is completed, the molecular sieve can be separated as a product from the obtained reaction mixture by any separation method conventionally known.
- the molecular sieve product comprises the molecular sieve of the present invention.
- the separation method for example, a method of filtering, washing, and drying the obtained reaction mixture can be mentioned.
- the filtration, washing and drying may be carried out in any manner conventionally known in the art.
- the filtration for example, the obtained reaction mixture can be simply suction filtered.
- washing for example, washing with deionized water can be mentioned until the pH of the filtrate reaches 7-9, preferably 8-9.
- the drying temperature is, for example, 40 to 250 ° C, preferably 60 to 150 ° C, and the drying time is, for example, 8 to 30 hours, preferably 10 to 20 hours.
- the drying can be carried out under normal pressure or under reduced pressure.
- the method for producing the molecular sieve may further include, as needed, a step of calcining the obtained molecular sieve (hereinafter referred to as a calcination step) to remove the organic template agent and possible moisture, and the like.
- a calcination step a step of calcining the obtained molecular sieve
- the molecular sieves before and after calcination are collectively referred to as molecular sieves of the invention or molecular sieves according to the invention.
- the calcination in the method of producing a molecular sieve, may be carried out in any manner conventionally known in the art, such as a calcination temperature generally from 300 ° C to 750 ° C, preferably from 400 ° C to 600 ° C. And the calcination time is generally from 1 hour to 10 hours, preferably from 3 hours to 6 hours. In addition, the calcination is generally carried out under an oxygen-containing atmosphere, such as an air or oxygen atmosphere.
- any molecular sieve produced as previously described may, if desired, be ion exchanged by any means conventionally known in the art, such as
- the metal cations such as Na ions or K ions, depending on the specific manufacturing method thereof
- contained in the composition are replaced in whole or in part by ion exchange method or solution impregnation method (for example, see US Pat. No. 3,140,249 and US Pat. No. 3,140,253, etc.).
- ion exchange method for example, see US Pat. No. 3,140,249 and US Pat. No. 3,140,253, etc.
- Examples of the other cation include hydrogen ions, other alkali metal ions (including K ions, Rb ions, etc.), ammonium ions (including NH 4 ions, quaternary ammonium ions such as tetramethylammonium ions and tetraethylammonium ions). Etc.), alkaline earth metal ions (including Mg ions, Ca ions), Mn ions, Zn ions, Cd ions, noble metal ions (including Pt ions, Pd ions, Rh ions, etc.), Ni ions, Co ions, Ti ions, Sn ions , Fe ions and/or rare earth metal ions, and the like.
- the molecular sieve according to the present invention may be treated by a dilute acid solution or the like as needed to increase the ratio of silicon to aluminum or treated with steam to improve the acid attack resistance of the molecular sieve crystal.
- the molecular sieve according to the present invention generally has an X-ray diffraction pattern substantially as shown in the following table.
- the X-ray diffraction pattern of the molecular sieve it is preferable to further include an X-ray diffraction peak substantially as shown in the following table.
- the selection further includes an X-ray diffraction peak substantially as shown in the following table.
- the molecular sieve generally has a columnar crystal morphology when viewed using a scanning electron microscope (SEM).
- the crystal morphology refers to the (overall) outer shape exhibited by a single molecular sieve crystal in the observation field of the scanning electron microscope.
- a prismatic shape in particular, a hexagonal prism shape is preferable.
- the prism refers to a convex prism and generally refers to a right prism and a regular polygonal prism (such as a regular hexagonal prism).
- the actual crystal morphology may be compared with the geometric (true) straight prism or (true) regular polygonal prism.
- any greater or lesser deviations do not depart from the scope of the invention.
- the molecular sieve (single crystal) has an effective diameter generally ranging from 100 nm to 5000 nm when observed using a scanning electron microscope (SEM).
- the effective diameter means that two points are arbitrarily selected along the contour (edge) of the cross section of the molecular sieve (single crystal), and the linear distance between the two points is measured. The largest straight line distance is taken as the effective diameter.
- the effective diameter generally refers to the linear distance (diagonal distance) between the two vertices furthest from the polygon.
- the effective diameter corresponds substantially to the diameter of the circumcircle of the polygon represented by the contour of the cross section.
- the observation is carried out using a scanning electron microscope (SEM)
- SEM scanning electron microscope
- the height of the molecular sieve is generally from 100 nm to 3000 nm.
- the term "height" refers to a linear distance between the centers of the two end faces of the column in a single crystal (columnar crystal) of the molecular sieve.
- the two end faces of the molecular sieve column are substantially parallel to each other, and the linear distance is the vertical distance between the two end faces, but the invention is not limited thereto.
- the molecular sieve (single crystal) has an aspect ratio of generally from 0.1 to 8 when observed by a scanning electron microscope (SEM).
- the aspect ratio refers to the ratio of the height to the effective diameter.
- the molecular sieve has a total specific surface area of generally from 400 m 2 /g to 600 m 2 /g, preferably from 450 m 2 /g to 580 m 2 /g.
- the total specific surface area is obtained by a liquid nitrogen adsorption method as calculated by a BET model.
- the molecular sieve generally has a pore volume of from 0.3 ml/g to 0.5 ml/g, preferably from 0.30 ml/g to 0.40 ml/g.
- the molecular sieve of the present invention has a very high micropore volume, which indicates that it belongs to an ultra-large pore molecular sieve.
- the pore volume is obtained by a liquid nitrogen adsorption method as calculated by a BET model.
- the molecular sieve according to the invention has good heat/water thermal stability and has a larger pore volume.
- the molecular sieve of the present invention is capable of adsorbing more/larger molecules, thereby exhibiting excellent adsorption/catalytic properties.
- the molecular sieve according to the present invention has a strong acidity, particularly a large number of L acid centers. This is a molecular sieve that has not been produced in the prior art. As a result, the molecular sieve of the present invention has more excellent performance particularly in an acid-catalyzed reaction.
- the molecular sieve according to the present invention may be in any physical form such as a powder, a granule or a molded article (e.g., a strip, a clover, etc.). These physical forms can be obtained in any manner conventionally known in the art, and are not particularly limited.
- the molecular sieve according to the present invention can be used in combination with other materials, thereby obtaining a molecular sieve composition.
- other materials for example, an active material and an inactive material can be mentioned.
- the active material include synthetic zeolite and natural zeolite.
- the inactive material (generally referred to as a binder) include clay, clay, silica gel, and alumina. These other materials may be used alone or in combination of any ones in any ratio.
- As the amount of the other materials it can be directly referred to the conventional dosage in the art. There are no special restrictions.
- the molecular sieve or molecular sieve composition according to the invention is particularly suitable for use as an adsorbent, for example for separating at least one component from a mixture of components in a gas phase or a liquid phase.
- the molecular sieve or molecular sieve composition according to the invention is particularly suitable for use as a catalyst in the conversion of hydrocarbons.
- Examples of the conversion reaction of the hydrocarbon include catalytic cracking, hydrocracking, disproportionation, alkylation, oligomerization, and isomerization.
- the molecular sieve or molecular sieve composition according to the invention is particularly suitable for use as a carrier or carrier component of the catalyst, and the active component is supported thereon in any manner conventionally known in the art, such as solution impregnation.
- active components include, but are not limited to, active metal components (including Ni, Co, Mo, W or Cu, etc.), reactive inorganic auxiliaries (such as F, P, etc.) and organic compounds (such as organic acids, organic amines, etc.) .
- active components may be used alone or in combination of any ones in any ratio.
- As the amount of the active component it can be directly referred to the conventional amount in the art, and is not particularly limited.
- the American Microtek Autochem II 2920 temperature programmed desorber was used. Test conditions: Weigh 0.2g of 20-40 mesh molecular sieve into the sample tube, placed in the heating furnace, the carrier gas is He gas (25mL / min), the temperature is raised to 600 ° C at 20 ° C / min, and the surface of the molecular sieve is removed by blowing for 60 minutes. Impurities.
- the temperature was lowered to 100 ° C, the temperature was kept for 10 min, and the mixture was switched to NH 3 -He mixture (10% NH 3 +90% He) for adsorption for 30 min, and then purged with He gas for 90 min until the baseline was stable to desorb the physically adsorbed NH 3 .
- the temperature was increased to 600 ° C at a temperature increase rate of 10 ° C / min for desorption, and maintained for 30 min, and the desorption was completed.
- the TCD detector is used to detect changes in gas composition, and the instrument automatically integrates to obtain an acid amount distribution.
- XRD testing was performed using a Netherland, PANalytical Corporation equipment. Test conditions: Cu target, K ⁇ radiation, Ni filter, tube voltage 40 kV, tube current 40 mA, scanning range 2-50 °.
- TECNAIG 2 F20 200 kV type scanning electron microscope from FEI Corporation of the United States was used.
- Test conditions Using a suspension method, 0.01 g of a molecular sieve sample was placed in a 2 mL glass bottle. Disperse with absolute ethanol, shake evenly, take a drop with a dropper, drop on a 3 mm diameter sample net, dry it, place it in the sampler, and insert it into the electron microscope for observation. The observation may use a magnification of 10,000 times or a magnification of 50,000 times.
- the molecular sieve was observed at a magnification of 50,000 times, and an observation field was randomly selected, and the average value of the sum of the average diameters and the sums of the heights of the total diameters of all the molecular sieve crystals in the observation field was calculated. Repeat this operation a total of 10 times. The average of the sum of the average values of 10 times is taken as the effective diameter and height, respectively.
- BIO-RAD FTS300 type FT-IR spectrometer was used. Test conditions: vacuuming at 350 ° C to 10-3 Pa, wave number range 1300-3900 cm -1 . The sample was tableted and placed in an in-situ bath of an infrared spectrometer to seal. Vacuum was applied to 10 -3 Pa at 350 ° C for 1 h to desorb the gas molecules on the surface of the sample and cool to room temperature.
- Pyridine/2,4,6-trimethylpyridine with a pressure of 2.67 Pa was introduced into the in-situ cell, and after adsorption for 30 min, the temperature was raised to 200 ° C, and vacuum was again applied to 10 -3 Pa for 30 min, and cooled to room temperature.
- the infrared absorption spectrum of the adsorption of pyridine/2,4,6-trimethylpyridine at 200 ° C was recorded by scanning in the range of 1300-3900 cm -1 .
- the sample in the infrared absorption cell was moved to the heat treatment zone, heated to 350 ° C, evacuated to 10 -3 Pa, held for 30 min, cooled to room temperature, and the infrared spectrum of the pyridine adsorption at 350 ° C was recorded.
- the total specific surface area, pore volume and pore diameter of the molecular sieve were measured by the following analytical methods.
- Measurement conditions The sample was placed in a sample processing system, vacuumed to 1.33 ⁇ 10 -2 Pa at 350 ° C, and held for 15 h at room temperature to purify the sample. At the liquid nitrogen temperature of -196 °C, the adsorption amount and desorption amount of nitrogen in the purified sample under different specific pressure P/P0 conditions were measured, and the adsorption-desorption isotherm curve was obtained. Then, the total specific surface area was calculated by the two-parameter BET formula. The adsorption capacity of the specific pressure P/P0 ⁇ 0.98 was taken as the pore volume of the sample, and the pore size distribution was calculated by the BJH model.
- templating agent B Br replaces Br in templating agent A with OH by ion exchange; ion exchange resin is strongly alkaline styrene anion exchange resin, working solution is 15m% aqueous solution of templating agent A, operating temperature is 25 °C, the mass ratio of the working fluid to the ion exchange resin is 1:3; the flow rate is 3 drops / sec; the exchanged solution is dehydrated by a rotary evaporator to obtain the product.
- the compound of the formula (I) wherein n is 4, m is 6, R is a methyl group, and X is OH has a relative molecular weight of 262.2, a purity of 99.21%, and a bromine content of 0.79 m%.
- templating agent D replacing Br in templating agent C with OH by ion exchange; ion exchange resin is strong alkaline styrene anion exchange resin, working solution is 15m% templating solution C aqueous solution, operating temperature is 25 °C, the mass ratio of the working fluid to the ion exchange resin is 1:3; the flow rate is 3 drops/second; the exchanged solution is dehydrated by a rotary evaporator to obtain a product, wherein n is 9, m in the formula (I)
- the compound having a molecular weight of 332.4 and a purity of 99.8% and a bromine content of 0.2 m% is a compound having a methyl group of 6 and an OH group.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 180 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Figure I-1. It is apparent that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 600 nm, a height of 800 nm, and an aspect ratio of 1.33. The molecular sieve had a total specific surface area of 560 m 2 /g and a pore volume of 0.360 ml/g.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 110 ° C for 1 day and then heated to 160 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Figure I-3. It is obvious that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 1800 nm, a height of 2400 nm, and an aspect ratio of 1.33. The molecular sieve had a total specific surface area of 560 m 2 /g and a pore volume of 0.496 ml/g.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 130 ° C for 2 days and then heated to 160 ° C. 4 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Figure I-5. It is apparent that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 700 nm, a height of 950 nm, and an aspect ratio of 1.36. The molecular sieve had a total specific surface area of 558 m 2 /g and a pore volume of 0.443 ml/g.
- the XRD pattern of the product is shown in Figure I-6.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Figure I-7. It is obvious that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 1200 nm, a height of 1400 nm, and a height to diameter ratio of 1.17. The molecular sieve had a total specific surface area of 533 m 2 /g and a pore volume of 0.295 ml/g.
- the XRD pattern of the product is shown in Figure I-8.
- the results of NH3-TPD indicate ( Figures I-12) that the molecular sieves have significant acidity.
- the results of the infrared spectrum showed (Fig. I-13) that the molecular sieve had a low amount of B acid and a high acid acid amount.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed, and the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and reacted at 160 ° C for 6 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- Figure I-1 is a scanning electron micrograph of the molecular sieve produced in Example I-3.
- Figure I-2 is an XRD pattern of the molecular sieve produced in Example I-3.
- Figure I-3 is a scanning electron micrograph of the molecular sieve produced in Example I-4.
- Figure I-4 is an XRD pattern of the molecular sieve produced in Example I-4.
- Figure I-5 is a scanning electron micrograph of the molecular sieve produced in Example I-5.
- Figure I-6 is an XRD pattern of the molecular sieve made in Example I-5.
- Figure I-7 is a scanning electron micrograph of the molecular sieve made in Example I-6.
- Figure I-8 is an XRD pattern of the molecular sieve made in Example I-6.
- Figure I-9 is a scanning electron micrograph of the molecular sieve made in Example I-7.
- Figure I-10 is an isotherm adsorption-desorption curve of the molecular sieve produced in Example I-7.
- Figure I-11 is a graph showing the pore size distribution of the molecular sieves produced in Example I-7.
- Figure I-12 is a NH3-TPD pattern of the molecular sieve made in Example I-6.
- Figure I-13 is an IR plot of the molecular sieve made in Example I-6.
- templating agent B Br replaces Br in templating agent A with OH by ion exchange; ion exchange resin is strongly alkaline styrene anion exchange resin, working solution is 15m% aqueous solution of templating agent A, operating temperature is 25 °C, the mass ratio of working fluid to ion exchange resin is 1:3; the flow rate is 3 drops / sec; the exchanged solution is dehydrated by rotary evaporator to obtain the product, where n is 4, m in formula (I)
- the compound having a methyl group of 6 and R being an OH has a relative molecular weight of 262.2, a purity of 99.21%, and a bromine content of 0.79 m%.
- templating agent D replacing Br in templating agent C with OH by ion exchange; ion exchange resin is strong alkaline styrene anion exchange resin, working solution is 15m% templating solution C aqueous solution, operating temperature is 25 °C, the mass ratio of the working fluid to the ion exchange resin is 1:3; the flow rate is 3 drops/second; the exchanged solution is dehydrated by a rotary evaporator to obtain a product, wherein n is 9, m in the formula (I)
- the compound having a molecular weight of 332.4 and a purity of 99.8% and a bromine content of 0.2 m% is a compound having a methyl group of 6 and an OH group.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Figure II-1. It is apparent that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 650 nm, a height of 600 nm, and a height to diameter ratio of 1. The molecular sieve had a total specific surface area of 553 m 2 /g and a pore volume of 0.295 ml/g.
- the XRD pattern of the product is shown in Figure II-2. The product has a silicon to aluminum ratio of 35.20.
- the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and heated to 150 ° C after 1 day of reaction at 120 ° C. The reaction was 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Figure II-3. It is apparent that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 1200 nm, a height of 1000 nm, and an aspect ratio of 0.833. The molecular sieve had a total specific surface area of 558 m 2 /g and a pore volume of 0.51 ml/g.
- the XRD pattern of the product is shown in Figure II-4. The product has a silicon to aluminum ratio of 36.38.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a speed of 20 rpm at 120 °C. After the reaction for 1 day, the temperature was raised to 150 ° C for 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Figure II-5. It is obvious that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 900 nm, a height of 1000 nm, and an aspect ratio of 1.11. The molecular sieve had a total specific surface area of 543 m 2 /g and a pore volume of 0.304 ml/g.
- the XRD pattern of the product is shown in Figure II-6. The product has a silicon to aluminum ratio of 33.68.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 4 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Figure II-7. It is apparent that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 1200 nm, a height of 1300 nm, and a height to diameter ratio of 1.08. The molecular sieve had a total specific surface area of 534 m 2 /g and a pore volume of 0.304 ml/g.
- the XRD pattern of the product is shown in Figure II-8. The product has a silicon to aluminum ratio of 30.21.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Figure II-9. It is obvious that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 1500 nm, a height of 2000 nm, and an aspect ratio of 1.33. The molecular sieve had a total specific surface area of 560 m 2 /g and a pore volume of 0.342 ml/g.
- the XRD pattern of the product is shown in Figure II-10. The product has a silicon to aluminum ratio of 35.29.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Figure II-11. It is apparent that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 1000 nm, a height of 1400 nm, and a height to diameter ratio of 1.4. The molecular sieve had a total specific surface area of 498 m 2 /g and a pore volume of 0.403 ml/g.
- the XRD pattern of the product is shown in Figure II-12. The product has a silicon to aluminum ratio of 34.20.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Figure II-13. It is obvious that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 800 nm, a height of 900 nm, and an aspect ratio of 1.125. The molecular sieve had a total specific surface area of 564 m 2 /g and a pore volume of 0.350 ml/g.
- the XRD pattern of the product is shown in Figure II-14. The product has a silicon to aluminum ratio of 35.28.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 110 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Figure II-15. It is apparent that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 300 nm, a height of 900 nm, and an aspect ratio of 3.0. The molecular sieve had a total specific surface area of 473 m 2 /g and a pore volume of 0.356 ml/g.
- the XRD pattern of the product is shown in Figure II-16. The product has a silicon to aluminum ratio of 35.38.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- This example is intended to illustrate the thermal stability (XRD) of the molecular sieves produced in Examples II-3 through II-8.
- Figure II-18 shows that the molecular sieves having a silicon to aluminum ratio of 30 and 40 and a sodium to silicon ratio of 0.08 to 0.30 have good thermal stability after calcination at 550 ° C, 650 ° C and 750 ° C.
- This example is intended to illustrate the acidity of the molecular sieves produced in Examples II-6 and II-8.
- Table II-1 shows that molecular sieves with a silica to alumina ratio of 30 and 40 exhibit a higher B/L ratio and are expected to be used in acidic catalytic reactions.
- Figure II-1 is a scanning electron micrograph of the molecular sieve produced in Example II-3.
- Figure II-2 is an XRD pattern of the molecular sieve produced in Example II-3.
- Figure II-3 is a scanning electron micrograph of the molecular sieve produced in Example II-4.
- Figure II-4 is an XRD pattern of the molecular sieve produced in Example II-4.
- Figure II-5 is a scanning electron micrograph of the molecular sieve produced in Example II-5.
- Figure II-6 is an XRD pattern of the molecular sieve produced in Example II-5.
- Figure II-7 is a scanning electron micrograph of the molecular sieve produced in Example II-6.
- Figure II-8 is an XRD pattern of the molecular sieve made in Example II-6.
- Figure II-9 is a scanning electron micrograph of the molecular sieve produced in Example II-7.
- Figure II-10 is an XRD pattern of the molecular sieve made in Example II-7.
- Figure II-11 is a scanning electron micrograph of the molecular sieve made in Example II-8.
- Figure II-12 is an XRD pattern of the molecular sieve made in Example II-8.
- Figure II-13 is a scanning electron micrograph of the molecular sieve made in Example II-9.
- Figure II-14 is an XRD pattern of the molecular sieve made in Example II-9.
- Figure II-15 is a scanning electron micrograph of the molecular sieve produced in Example II-10.
- Figure II-16 is an XRD pattern of the molecular sieve made in Example II-10.
- Figure II-17 is an XRD pattern of the molecular sieve made in Example II-11.
- Figure II-18 is an XRD pattern of the molecular sieves produced in Examples II-3 to II-8 after firing.
- the total specific surface area, pore volume and pore diameter of the molecular sieve were measured by the following analytical methods.
- Measurement conditions The sample was placed in a sample processing system, vacuumed to 1.33 ⁇ 10 -2 Pa at 350 ° C, and held for 15 h at room temperature to purify the sample. At the liquid nitrogen temperature of -196 °C, the adsorption amount and desorption amount of nitrogen in the purified sample under different specific pressure P/P0 conditions were measured, and the adsorption-desorption isotherm curve was obtained. Then, the total specific surface area was calculated by the two-parameter BET formula, and the adsorption capacity of the specific pressure P/P0 ⁇ 0.98 was taken as the pore volume of the sample, and the pore diameter was calculated according to the BJH model.
- templating agent A 15 g (0.094 mol) of bis[2-(N,N-dimethylaminoethyl)]ether was added to a two-necked flask, 100 mL of isopropanol was added, and 9.5 g of 9.5 g was added dropwise with stirring at 25 ° C ( 0.047mol) of 1,3-dibromopropane, after the addition was completed, the temperature was raised to reflux temperature, refluxed for 30 min, the solution changed from colorless to white turbid, and then reacted at reflux temperature for 12 h, cooled to 25 ° C, and added with 50 mL of acetic acid.
- templating agent B Br replaces Br in templating agent A with OH by ion exchange; ion exchange resin is strongly alkaline styrene anion exchange resin, working solution is 15m% aqueous solution of templating agent A, operating temperature is 25 °C, the mass ratio of the working fluid to the ion exchange resin is 1:3; the flow rate is 3 drops/second; the exchanged solution is dehydrated by a rotary evaporator to obtain a product, where n is 1, m in the formula (I) It is a compound in which 2 is a methyl group and X is OH, and the relative molecular weight is 236.2 and the purity is 98.2%. Its bromine content is 0.79 m%.
- templating agent C A compound of the formula (I) wherein n is 6, m is 2, R is a methyl group, and X is Br is produced by the method of the template A in Example III-1, except that 12.78 is used. g (0.047 mol) of 1,8-dibromooctane was substituted for 1,3-dibromopropane.
- the test yielded 17.6 g of product having a melting point of 288.2 ° C, a relative molecular weight of 432.2, a purity of 99.9 m%, a 1H-NMR spectrum chemical shift (300 MHZ, internal standard TMS, solvent CDCl 2 ) ⁇ (ppm): 1.29 (2H) , s), 1.39 (2H, m), 1.43 (2H, s), 2.27 (2H, m), 2.36 (2H, m), 2.55 (2H, m), 3.63 (4H, m).
- templating agent D replacing Br in templating agent C with OH by ion exchange; ion exchange resin is strong alkaline styrene anion exchange resin, working solution is 15m% templating solution C aqueous solution, operating temperature is 25 °C, the mass ratio of the working fluid to the ion exchange resin is 1:3; the flow rate is 3 drops / sec; the exchanged solution is dehydrated by a rotary evaporator to obtain a product, wherein n is 6, m in the formula (I) 2, R is a methyl group, X is OH, a relative molecular weight is 306.2, and a purity is 99.5 m%. Its bromine content is 0.2 m%.
- the mixture was placed in a 45 mL steel autoclave lined with Teflon and sealed, and the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and reacted at 150 ° C for 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Fig. III-3. It is obvious that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 1000 nm, a height of 1200 nm and a height to diameter ratio of 1.2. The molecular sieve had a total specific surface area of 523 m 2 /g and a pore volume of 0.356 ml/g.
- the XRD pattern of this product is shown in Figure III-4.
- Figure III-1 shows the adsorption curve of 2,2-diethylbutane for the product after calcination at 550 °C for 3 h. It can be seen from the curve that the product adsorbs 2,2-diethylbutane. It is -55 mg/g.
- the mixture was placed in a 45 mL steel autoclave lined with Teflon and sealed, and the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and reacted at 150 ° C for 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Fig. III-6. It is obvious that the molecular sieve has a hexagonal columnar crystal morphology, and the effective diameter is 2200 nm, the height is 3000 nm, and the height to diameter ratio is 1.36.
- the molecular sieve had a total specific surface area of 573 m 2 /g and a pore volume of 0.387 ml/g.
- the mixture was placed in a 45 mL steel autoclave lined with Teflon and sealed, and the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and reacted at 150 ° C for 4 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the mixture was placed in a 45 mL steel autoclave lined with Teflon and sealed, and the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and reacted at 150 ° C for 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- Figure III-5 shows the XRD pattern of the product after calcination at 550 °C for 3 h. It can be seen from the figure that the product is 3-propyl-4-butyloctyl.
- the amount of adsorption of the alkane is as high as -102 mg/g.
- the mixture was placed in a 45 mL steel autoclave lined with Teflon and sealed, and the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and reacted at 150 ° C for 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Fig. III-9. It is obvious that the molecular sieve has a hexagonal columnar crystal morphology, and the effective diameter is 1200 nm, the height is 1400 nm, and the height to diameter ratio is 1.17.
- the molecular sieve had a total specific surface area of 538 m 2 /g and a pore volume of 0.408 ml/g.
- the results of NH3-TPD indicate ( Figures III-11) that the molecular sieves are significantly acidic.
- the results of the infrared spectrum showed (Fig. III-12) that the molecular sieve had a low amount of B acid and a high acid acid amount.
- the mixture was placed in a 45 mL steel autoclave lined with Teflon and sealed, and the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and reacted at 150 ° C for 4 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- Figure III-1 is a graph showing the adsorption of 2,2-diethylbutane by the molecular sieve produced in Example III-3 after calcination.
- Figure III-2 is an adsorption curve of the molecular sieve produced in Example III-6 after calcination to 3-propyl-4-butyloctane.
- Figure III-3 is a scanning electron micrograph of the molecular sieve produced in Example III-3.
- Figure III-4 is an XRD pattern of the molecular sieve produced in Example III-3.
- Figure III-5 is an XRD pattern of the molecular sieve produced in Example III-6 after calcination.
- Figure III-6 is a scanning electron micrograph of the molecular sieve produced in Example III-4.
- Figure III-7 is a scanning electron micrograph of the molecular sieve produced in Example III-5.
- Figure III-8 is a scanning electron micrograph of the molecular sieve made in Example III-6.
- Figure III-9 is a scanning electron micrograph of the molecular sieve made in Example III-7.
- Figure III-10 is a scanning electron micrograph of the molecular sieve made in Example III-8.
- Figure III-11 is a NH3-TPD diagram of the molecular sieve made in Example III-7.
- Figure III-12 is an IR plot of the molecular sieve made in Example III-7.
- templating agent A 15 g (0.094 mol) of bis[2-(N,N-dimethylaminoethyl)]ether was added to a two-necked flask, 100 mL of isopropanol was added, and 9.5 g of 9.5 g was added dropwise with stirring at 25 ° C ( 0.047mol) of 1,3-dibromopropane, after the addition was completed, the temperature was raised to reflux temperature, refluxed for 30 min, the solution changed from colorless to white turbid, and then reacted at reflux temperature for 12 h, cooled to 25 ° C, and added with 50 mL of acetic acid.
- templating agent B Br replaces Br in templating agent A with OH by ion exchange; ion exchange resin is strongly alkaline styrene anion exchange resin, working solution is 15m% aqueous solution of templating agent A, operating temperature is 25 °C, the mass ratio of the working fluid to the ion exchange resin is 1:3; the flow rate is 3 drops/second; the exchanged solution is dehydrated by a rotary evaporator to obtain a product, where n is 1, m in the formula (I) It is a compound in which 2 is a methyl group and X is OH, and the relative molecular weight is 236.2 and the purity is 99.21%. Its bromine content is 0.79 m%.
- templating agent C A compound of the formula (I) wherein n is 6, m is 2, R is a methyl group, and X is Br is produced by the method of the templating agent A in Example IV-1, except that 12.78 is used. g (0.047 mol) of 1,8-dibromooctane was substituted for 1,3-dibromopropane.
- the test yielded 17.6 g of a product having a melting point of 288.2 ° C, a relative molecular weight of 432.2, a purity of 99.9%, a 1H-NMR spectrum chemical shift (300 MHZ, internal standard TMS, solvent CDCl 2 ) ⁇ (ppm): 1.29 (2H, s), 1.39 (2H, m), 1.43 (2H, s), 2.27 (2H, m), 2.36 (2H, m), 2.55 (2H, m), 3.63 (4H, m).
- templating agent D replacing Br in templating agent C with OH by ion exchange; ion exchange resin is strong alkaline styrene anion exchange resin, working solution is 15m% templating solution C aqueous solution, operating temperature is 25 °C, the mass ratio of the working fluid to the ion exchange resin is 1:3; the flow rate is 3 drops / sec; the exchanged solution is dehydrated by a rotary evaporator to obtain a product, wherein n is 6, m in the formula (I) 2, R is a methyl group, X is OH, a relative molecular weight is 306.2, and a purity is 99.8%. Its bromine content is 0.2 m%.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 160 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Figure IV-1. It is apparent that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 800 nm, a height of 1000 nm, and an aspect ratio of 1.25. The molecular sieve had a total specific surface area of 564 m 2 /g and a pore volume of 0.394 ml/g.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 110 ° C for 1 day and then heated to 170 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Fig. IV-3. It is apparent that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 800 nm, a height of 1000 nm, and an aspect ratio of 1.25. The molecular sieve had a total specific surface area of 483 m 2 /g and a pore volume of 0.285 ml/g.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 160 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Fig. IV-5. It is obvious that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 700 nm, a height of 900 nm, and an aspect ratio of 1.285. The molecular sieve had a total specific surface area of 464 m 2 /g and a pore volume of 0.384 ml/g.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Fig. IV-7. It is apparent that the molecular sieve has a hexagonal prismatic crystal morphology with an effective diameter of 1000 nm, a height of 1000 nm, and an aspect ratio of 1.0. The molecular sieve had a total specific surface area of 538 m 2 /g and a pore volume of 0.376 ml/g.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm, and reacted at 120 ° C for 2 days and then heated to 150 ° C. 3 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 6 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the results of NH3-TPD indicate (Fig. IV-9) that the molecular sieve has significant acidity.
- the results of the infrared spectrum showed (Fig. IV-10) that the molecular sieve had a low amount of B acid and a high acid acid amount.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 160 ° C. 4 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- Figure IV-1 is a scanning electron micrograph of the molecular sieve produced in Example IV-3.
- Figure IV-2 is an XRD pattern of the molecular sieve produced in Example IV-3.
- Figure IV-3 is a scanning electron micrograph of the molecular sieve produced in Example IV-4.
- Figure IV-4 is an XRD pattern of the molecular sieve produced in Example IV-4.
- Figure IV-5 is a scanning electron micrograph of the molecular sieve produced in Example IV-5.
- Figure IV-6 is an XRD pattern of the molecular sieve produced in Example IV-5.
- Figure IV-7 is a scanning electron micrograph of the molecular sieve produced in Example IV-6.
- Figure IV-8 is an XRD pattern of the molecular sieve made in Example IV-6.
- Figure IV-9 is a NH3-TPD pattern of the molecular sieve made in Example IV-8.
- Figure IV-10 is an IR plot of the molecular sieve made in Example IV-8.
- the total specific surface area, pore volume and pore diameter of the micropores of the molecular sieve were measured by the following analytical methods.
- Measurement conditions The sample was placed in a sample processing system, and vacuum was evacuated to 1.33 ⁇ 10-2 Pa at 300 ° C, and the sample was purged for 8 hours to purify the sample. At the liquid nitrogen temperature of -196 °C, the adsorption amount and desorption amount of nitrogen in the purified sample under different specific pressure P/P0 conditions were measured, and the adsorption-desorption isotherm curve was obtained. Then, the two-parameter Horvath-Kawaioe formula was used to calculate the specific surface area. The adsorption capacity of the specific pressure P/P0 ⁇ 0.983 was taken as the pore volume of the sample, and the pore size was calculated according to the DFT density functional book theoretical model.
- molecular sieves included in the following examples and comparative examples, molecular sieves The total specific surface area, pore volume and pore diameter of the mesopores were measured by the following analytical methods.
- Measurement conditions The sample was placed in a sample processing system, vacuumed to 1.33 ⁇ 10 -2 Pa at 350 ° C, and held for 15 h at room temperature to purify the sample. At the liquid nitrogen temperature of -196 °C, the adsorption amount and desorption amount of nitrogen in the purified sample under different specific pressure P/P0 conditions were measured, and the adsorption-desorption isotherm curve was obtained. Then, the two-parameter BET formula was used to calculate the specific surface area, and the adsorption capacity of the specific pressure P/P0 ⁇ 0.98 was taken as the pore volume of the sample, and the pore diameter was calculated according to the Horvath-Kawaioe model.
- the total specific surface area, pore volume and pore diameter of the coarse pores of the molecular sieve were measured by the following analytical methods.
- Measurement conditions put the appropriate amount of dry sample into the sample tube and put it into the instrument and evacuate it to 50umg for low pressure operation. Weigh the pressure at low pressure, put the sample tube filled with mercury into the high pressure chamber and continue to pressurize it to 60,000 pisa. In the hole. According to the applied pressure P, the corresponding aperture r (nm) can be obtained. The pore volume of the corresponding size can be obtained from the amount of mercury intrusion, and the curve of the pore volume as a function of the pore size can be calculated, thereby obtaining a pore size distribution curve. The length of the hole is calculated from the pore volume and the pore diameter as calculated by the columnar through hole, and the surface area is obtained by the length of the hole and the length of the hole.
- templating agent A 15 g (0.094 mol) of bis[2-(N,N-dimethylaminoethyl)]ether was added to a two-necked flask, 100 mL of isopropanol was added, and 9.5 g of 9.5 g was added dropwise with stirring at 25 ° C ( 0.047mol) of 1,3-dibromopropane, after the addition was completed, the temperature was raised to reflux temperature, refluxed for 30 min, the solution changed from colorless to white turbid, and then reacted at reflux temperature for 12 h, cooled to 25 ° C, and added with 50 mL of acetic acid.
- templating agent B Br replaces Br in templating agent A with OH by ion exchange; ion exchange resin is strongly alkaline styrene anion exchange resin, working solution is 15m% aqueous solution of templating agent A, operating temperature is 25 °C, the mass ratio of working fluid to ion exchange resin is 1:3; the flow rate is 3 drops/sec; the exchanged solution is dehydrated by a rotary evaporator to obtain a product, wherein n is 1 in the formula (I), 2 is R, and X is OH.
- templating agent C A compound of the formula (I) wherein n is 6, m is 2, R is a methyl group, and X is Br is produced by the method of the templating agent A in Example V-1, except that 12.78 is used. g (0.047 mol) of 1,8-dibromooctane was substituted for 1,3-dibromopropane.
- the test yielded 17.6 g of product having a melting point of 288.2 ° C, a relative molecular weight of 432.2, a purity of 99.9 m%, a 1H-NMR spectrum chemical shift (300 MHZ, internal standard TMS, solvent CDCl 2 ) ⁇ (ppm): 1.29 (2H) , s), 1.39 (2H, m), 1.43 (2H, s), 2.27 (2H, m), 2.36 (2H, m), 2.55 (2H, m), 3.63 (4H, m).
- templating agent D replacing Br in templating agent C with OH by ion exchange; ion exchange resin is strong alkaline styrene anion exchange resin, working solution is 15m% templating solution C aqueous solution, operating temperature is 25 °C, the mass ratio of the working fluid to the ion exchange resin is 1:3; the flow rate is 3 drops / sec; the exchanged solution is dehydrated by a rotary evaporator to obtain a product, wherein n is 6, m in the formula (I) 2, R is a methyl group, X is OH, a relative molecular weight is 306.2, and a purity is 99.5 m%. Its bromine content is 0.2 m%.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed, and the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and reacted at 160 ° C for 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Fig. V-3. It is obvious that the molecular sieve has a hexagonal columnar shape and a sponge structure crystal morphology, and has an effective diameter of 2500 nm, a height of 1000 nm, and a height-to-diameter ratio of 0.4.
- the molecular sieve comprises a coarse pore, a medium pore and a microvoid, wherein the coarse pore has a diameter of 150 nm, a total specific surface area of 89 m 2 /g, a pore volume of 1.36 ml/g, and a diameter of the medium pore.
- the total specific surface area is 126 m 2 /g
- the pore volume is 0.29 ml/g
- the micropores have a diameter of 0.5 nm and 1.2 nm, a total specific surface area of 163 m 2 /g, and a pore volume of 0.07 ml/ g.
- Figure V-4 The XRD pattern of this product is shown in Figure V-4.
- Figure V-1 shows the adsorption curve of 2,2-diethylbutane for the product after calcination at 550 °C for 3 h. It can be seen from the curve that the product adsorbs 2,2-diethylbutane. It is -55 mg/g.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed, and the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and reacted at 160 ° C for 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Fig. V-6. It is obvious that the molecular sieve has a hexagonal columnar shape and a sponge structure, and has an effective diameter of 2500 nm, a height of 850 nm, and an aspect ratio of 0.34.
- the molecular sieve comprises a coarse pore, a medium pore and a micropore, wherein the coarse pore has a diameter of 400 nm, a total specific surface area of 65 m 2 /g, a pore volume of 0.387 ml/g, and a diameter of the medium pore.
- the total specific surface area is 116 m 2 /g
- the pore volume is 0.28 ml/g
- the micropores have a diameter of 0.5 nm and 1.2 nm, a total specific surface area of 149 m 2 /g, and a pore volume of 0.107 ml/ g.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed, and the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and reacted at 160 ° C for 4 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Fig. V-7. It is obvious that the molecular sieve has a hexagonal columnar shape and a sponge structure crystal morphology, and the effective diameter is 2200 nm, the height is 3500 nm, and the height to diameter ratio is 1.59.
- the molecular sieve comprises a coarse pore, a medium pore and a micropore, wherein the coarse pore has a diameter of 100 nm, a total specific surface area of 365 m 2 /g, a pore volume of 0.365 ml/g, and a diameter of the medium pore.
- the total specific surface area is 115 m 2 /g
- the pore volume is 0.22 ml/g
- the micropores have a diameter of 4 nm and 1.2 nm, a total specific surface area of 280 m 2 /g, and a pore volume of 0.145 ml/g. .
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed, and the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and reacted at 160 ° C for 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Fig. V-8. It is obvious that the molecular sieve has a hexagonal columnar shape and a sponge structure, and the effective diameter is 1750 nm, the height is 4000 nm, and the height to diameter ratio is 2.29.
- the molecular sieve comprises a coarse pore, a medium pore and a micropore, wherein the coarse pore has a diameter of 200 nm, a total specific surface area of 65 m 2 /g, a pore volume of 0.390 ml/g, and a diameter of the medium pore.
- the total specific surface area is 145 m 2 /g
- the pore volume is 0.16 ml/g
- the micropores have a diameter of 4 nm and 1.2 nm, a total specific surface area of 220 m 2 /g, and a pore volume of 0.130 ml/g.
- Figure V-5 is a graph showing the adsorption of 3-propyl-4-butyloctane to the product after calcination at 550 °C for 3 h. As can be seen from the figure, the product is 3-propyl-4-butyloctyl. The amount of adsorption of the alkane is as high as -102 mg/g.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed, and the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and reacted at 160 ° C for 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Fig. V-9. It is obvious that the molecular sieve has a hexagonal columnar shape and a sponge structure, and the effective diameter is 1200 nm, the height is 1500 nm, and the height to diameter ratio is 1.25.
- the molecular sieve comprises a coarse pore, a medium pore and a microvoid, wherein the coarse pore has a diameter of 200 nm, a total specific surface area of 67 m 2 /g, a pore volume of 0.354 ml/g, and a diameter of the medium pore.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and After sealing, the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and reacted at 160 ° C for 4 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Fig. V-10. It is obvious that the molecular sieve has a hexagonal columnar shape and a sponge structure, and has an effective diameter of 1200 nm, a height of 1700 nm, and an aspect ratio of 1.42.
- the molecular sieve comprises a coarse pore, a medium pore and a microvoid, wherein the coarse pore has a diameter of 1000 nm, a total specific surface area of 26 m 2 /g, a pore volume of 0.253 ml/g, and a diameter of the medium pore.
- the total specific surface area is 142 m 2 /g
- the pore volume is 0.216 ml/g
- the micropores have a diameter of 4 nm and 1.2 nm, a total specific surface area of 194 m 2 /g, and a pore volume of 0.037 ml/g.
- Figure V-1 is a graph showing the adsorption of 2,2-diethylbutane by the molecular sieve produced in Example V-3 after calcination.
- Figure V-2 is the adsorption curve of the molecular sieve produced in Example V-6 after calcination to 3-propyl-4-butyloctane.
- Figure V-3 is a scanning electron micrograph of the molecular sieve produced in Example V-1.
- Figure V-4 is an XRD pattern of the molecular sieve produced in Example V-3.
- Figure V-5 is an XRD pattern of the molecular sieve produced in Example V-6 after calcination.
- Figure V-6 is a scanning electron micrograph of the molecular sieve produced in Example V-4.
- Figure V-7 is a scanning electron micrograph of the molecular sieve produced in Example V-5.
- Figure V-8 is a scanning electron micrograph of the molecular sieve produced in Example V-6.
- Figure V-9 is a scanning electron micrograph of the molecular sieve made in Example V-7.
- Figure V-10 is a scanning electron micrograph of the molecular sieve produced in Example V-8.
- Figure V-11(a) is a schematic view of a sponge structure containing coarse and/or mesopores
- Figure V-11(b) is a scanning electron micrograph of the sponge structure containing coarse and/or mesopores.
- Figure V-12(a) is a schematic view of the molecular sieve having a hollow columnar crystal morphology
- Figure V-12(b) is a scanning electron micrograph of the molecular sieve having a hollow columnar crystal morphology.
- Figure V-13 is a NH3-TPD diagram of the molecular sieve made in Example V-7.
- Figure V-14 is an IR chart of the molecular sieve made in Example V-7.
- the total specific surface area, pore volume and pore diameter of the molecular sieve were measured by the following analytical methods.
- Measurement conditions The sample was placed in a sample processing system, vacuumed to 1.33 ⁇ 10 -2 Pa at 350 ° C, and held for 15 h at room temperature to purify the sample. At the liquid nitrogen temperature of -196 °C, the adsorption amount and desorption amount of nitrogen in the purified sample under different specific pressure P/P0 conditions were measured, and the adsorption-desorption isotherm curve was obtained. Then, the total specific surface area was calculated by the two-parameter BET formula. The adsorption capacity of the specific pressure P/P0 ⁇ 0.98 was taken as the pore volume of the sample, and the pore size distribution was calculated according to the BJH model.
- templating agent B Br replaces Br in templating agent A with OH by ion exchange; ion exchange resin is strongly alkaline styrene anion exchange resin, working solution is 15m% aqueous solution of templating agent A, operating temperature is 25 °C, the mass ratio of working fluid to ion exchange resin is 1:3; the flow rate is 3 drops / sec; the exchanged solution is dehydrated by rotary evaporator to obtain the product, where n is 4, m in formula (I)
- the compound having a methyl group of 6 and R being an OH has a relative molecular weight of 262.2, a purity of 99.21%, and a bromine content of 0.79 m%.
- templating agent D replacing Br in templating agent C with OH by ion exchange; ion exchange resin is strong alkaline styrene anion exchange resin, working solution is 15m% templating solution C aqueous solution, operating temperature is 25 °C, the mass ratio of the working fluid to the ion exchange resin is 1:3; the flow rate is 3 drops/second; the exchanged solution is dehydrated by a rotary evaporator to obtain a product, wherein n is 9, m in the formula (I)
- the compound having a molecular weight of 332.4 and a purity of 99.8% and a bromine content of 0.2 m% is a compound having a methyl group of 6 and an OH group.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the autoclave was placed in a rotating convection oven at a rotational speed of 20 rpm and heated to 150 ° C after 1 day of reaction at 120 ° C. The reaction was 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 4 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 110 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the scanning electron micrograph of the product is shown in Fig. VI-9. It is obvious that the molecular sieve has a flat prismatic or flat cylindrical crystal morphology with an effective diameter of 400 nm, a height of 200 nm and a height to diameter ratio of 0.5.
- the molecular sieve had a total specific surface area of 412 m 2 /g and a pore volume of 0.372 ml/g.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the XRD pattern of this product is shown in Figure VI-12.
- the above mixture was placed in a 45 mL steel autoclave with a Teflon liner and capped and sealed.
- the autoclave was placed in a rotating convection oven at a rotation speed of 20 rpm, and reacted at 120 ° C for 1 day and then heated to 150 ° C. 5 days.
- the autoclave was taken out and rapidly cooled to room temperature, and the mixture was separated on a high-speed centrifuge at 5000 rpm, and the solid was collected, washed thoroughly with deionized water, and dried at 100 ° C for 5 hours to obtain a product.
- the XRD pattern of this product is shown in Figure VI-13.
- Figure VI-1 is a scanning electron micrograph of the molecular sieve produced in Example VI-3.
- Figure VI-2 is an XRD pattern of the molecular sieve produced in Example VI-3.
- Figure VI-3 is a NH3-TPD diagram of the molecular sieve produced in Example VI-3.
- Figure VI-4 is an infrared spectrum of the molecular sieve produced in Example VI-3.
- Figure VI-5 is a scanning electron micrograph of the molecular sieve produced in Example VI-4.
- Figure VI-6 is an XRD pattern of the molecular sieve produced in Example VI-4.
- Figure VI-7 is a scanning electron micrograph of the molecular sieve produced in Example VI-5.
- Figure VI-8 is a scanning electron micrograph of the molecular sieve produced in Example VI-6.
- Figure VI-9 is a scanning electron micrograph of the molecular sieve produced in Example VI-7.
- Figure VI-10 is a scanning electron micrograph of the molecular sieve produced in Example VI-8.
- Figure VI-11 is an XRD pattern of the molecular sieve made in Example VI-9.
- Figure VI-12 is an XRD pattern of the molecular sieve produced in Example VI-10.
- Figure VI-13 is an XRD pattern of the molecular sieve produced in Example VI-11.
- Figure VI-14 (a) is a schematic view showing the end face contour of the molecular sieve of the present invention having a convex shape
- Figure VI-14 (b) is a schematic view showing the end face contour of the molecular sieve of the present invention having another convex shape
- Fig. VI-14(c) is a schematic view showing that the end face contour of the molecular sieve of the present invention does not have a convex shape but a flat shape.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Inorganic Chemistry (AREA)
- Materials Engineering (AREA)
- Crystallography & Structural Chemistry (AREA)
- Analytical Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Catalysts (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
Description
Claims (30)
- 按照权利要求1所述的分子筛,其中所述海绵结构包含粗孔洞和/或中孔洞,优选所述粗孔洞和/或所述中孔洞开口于所述海绵结构的端面和/或侧面。
- 按照权利要求2所述的分子筛,其中所述粗孔洞的直径为从80nm至2μm,优选从80nm至1.5μm,并且所述中孔洞的直径为从2nm至30nm,优选从2nm至4nm和/或从7nm至15nm(优选从8nm至9nm)。
- 按照权利要求2所述的分子筛,其中所述中孔洞的总比表面积为从50m2/g至250m2/g,优选从100m2/g至150m2/g,孔容为从0.05ml/g至0.40ml/g,优选从0.15ml/g至0.30ml/g,并且所述粗孔洞的总比表面积为从10m2/g至100m2/g,优选从50m2/g至100m2/g,孔容为从0.5ml/g至3.0ml/g,优选从1.0ml/g至2.0ml/g。
- 按照权利要求1所述的分子筛,其中所述海绵结构包含微孔洞,其中所述微孔洞的直径为从0.5nm至小于2nm,优选从0.5nm至0.8nm和/或从1.1nm至1.8nm,总比表面积为从100m2/g至300m2/g,优选从150m2/g至250m2/g,孔容为从0.03ml/g至0.20ml/g,优选从0.05ml/g至0.15ml/g。
- 按照权利要求1所述的分子筛,具有柱状(优选棱柱状,更优选六棱柱状)的晶体形貌,优选具有空心柱状的晶体形貌。
- 按照权利要求6所述的分子筛,所述晶体形貌的尺寸包括:有效直径为从100nm至5000nm,优选从1000nm至3000nm,高度为从500nm至3000nm,优选从1000nm至3000nm,高径比为从1/3至5,优选从1/3至3。
- 按照权利要求1所述的分子筛,具有式“第一氧化物·第二氧化物”或式“第一氧化物·第二氧化物·有机模板剂·水”所代表的示意性化学组成,其中所述第一氧化物与所述第二氧化物的摩尔比为从30至100,优选从55至100;所述第一氧化物选自二氧化硅、二氧化锗、二氧化锡、二氧化钛和二氧化锆中的至少一种,优选二氧化硅或者二氧化硅与二氧化锗的组合;所述第二氧化物选自氧化铝、氧化硼、氧化铁、氧化镓、稀土氧化物、氧化铟和氧化钒中的至少一种,优选氧化铝;水与所述第一氧化物的摩尔比为从5至50,优选从5至15;所述有机模板剂与所述第一氧化物的摩尔比为从0.02至0.5,优选从0.05至0.5、从0.15至0.5或者从0.3至0.5。
- 按照权利要求9所述的分子筛,其中所述晶体形貌的尺寸包括:有效直径为从100nm至1000nm,优选从100nm至500nm,高度为从100nm至1000nm,优选从150nm至300nm,高径比为从0.1至0.9,优选从0.4至0.7。
- 按照权利要求9所述的分子筛,其中所述分子筛的总比表面积 为从400m2/g至600m2/g,优选从450m2/g至580m2/g,孔容为从0.3ml/g至0.5ml/g,优选从0.30ml/g至0.40ml/g。
- 按照权利要求9所述的分子筛,具有式“第一氧化物·第二氧化物”或式“第一氧化物·第二氧化物·有机模板剂·水”所代表的示意性化学组成,其中所述第一氧化物与所述第二氧化物的摩尔比为从40至200,优选从40至150;所述第一氧化物选自二氧化硅、二氧化锗、二氧化锡、二氧化钛和二氧化锆中的至少一种,优选二氧化硅或者二氧化硅与二氧化锗的组合,所述第二氧化物选自氧化铝、氧化硼、氧化铁、氧化镓、稀土氧化物、氧化铟和氧化钒中的至少一种,优选氧化铝;水与所述第一氧化物的摩尔比为从5至50,优选从5至15;所述有机模板剂与所述第一氧化物的摩尔比为从0.02至0.5,优选从0.05至0.5、从0.08至0.5或者从0.3至0.5。
- 一种分子筛,其特征在于,具有式“第一氧化物·第二氧化物”或式“第一氧化物·第二氧化物·有机模板剂·水”所代表的示意性化学组成,其中所述第一氧化物与所述第二氧化物的摩尔比为从5至∞,优选从25至95,更优选从30至70;所述第一氧化物选自二氧化硅、二氧化锗、二氧化锡、二氧化钛和二氧化锆中的至少一种,优选二氧化硅或者二氧化硅与二氧化锗的组合,所述第二氧化物选自氧化铝、氧化硼、氧化铁、氧化镓、稀土氧化物、氧化铟和氧化钒中的至少一种,优选氧化铝;水与所述第一氧化物的摩尔比为从5至50,优选从5至15;所述有机模板剂与所述第一氧化物的摩尔比为从0.02至0.5,优选从0.05至0.5、从0.15至0.5或者从0.3至0.5,并且具有基本上如下表所示的X射线衍射图案,
- 按照权利要求13所述的分子筛,具有柱状(优选棱柱状,更优选六棱柱状)的晶体形貌。
- 按照权利要求14所述的分子筛,其中所述晶体形貌的尺寸包括:有效直径为从100nm至1000nm,优选从300nm至700nm,高度为从100nm至1000nm,优选从150nm至700nm,高径比为从1/3至8,优选从1.5至5或者从2至5。
- 按照权利要求13所述的分子筛,其中所述分子筛的总比表面积为从400m2/g至600m2/g,优选从450m2/g至580m2/g,孔容为从0.3ml/g至0.5ml/g,优选从0.30ml/g至0.40ml/g。
- 一种分子筛的制造方法,包括在晶化条件下使第一氧化物源、 第二氧化物源、任选的碱源、有机模板剂和水接触,以获得分子筛的步骤,和任选地,焙烧所述获得的分子筛的步骤,其中所述有机模板剂包含下式(I)所代表的化合物,其中,基团R1和R2彼此相同或不同,各自独立地选自C3-12直链或支链亚烷基和C3-12直链或支链氧杂亚烷基,优选各自独立地选自C3-12直链亚烷基和C3-12直链氧杂亚烷基,或者优选其中一个选自C3-12直链或支链亚烷基,另一个选自C3-12直链或支链亚烷基和C3-12直链或支链氧杂亚烷基,更优选其中一个选自C3-12直链亚烷基,另一个选自C3-12直链亚烷基和C3-12直链氧杂亚烷基,特别优选其中一个选自C3-12直链亚烷基,另一个选自C4-6直链亚烷基和C4-6直链氧杂亚烷基(优选C4-6直链一氧杂亚烷基,更优选-(CH2)m-O-(CH2)m-,其中各数值m彼此相同或不同,各自独立地代表2或3);多个基团R彼此相同或不同,各自独立地选自C1-4直链或支链烷基,优选各自独立地选自甲基和乙基,更优选均为甲基;X为OH。
- 按照权利要求19所述的制造方法,其中基团R1和R2彼此相同或不同,各自独立地选自C3-12直链或支链亚烷基,优选各自独立地选自C3-12直链亚烷基,特别优选其中一个选自C3-12直链亚烷基,另一个选自C4-6直链亚烷基;多个基团R彼此相同或不同,各自独立地选自C1-4直链或支链烷基,优选各自独立地选自甲基和乙基,更优选均为甲基;X为OH。
- 按照权利要求19所述的制造方法,其中基团R1和R2彼此不同,其中一个选自C3-12直链或支链亚烷基,另一个选自C3-12直链或支链氧杂亚烷基,优选其中一个选自C3-12直链亚烷基,另一个选自C3-12直链氧杂亚烷基(优选C4-6直链氧杂亚烷基,更优选C4-6直链一氧杂亚烷基,更优选-(CH2)m-O-(CH2)m-,其中各数值m彼此相同或不同,各自独立地代表2或3);多个基团R彼此相同或不同,各自独立地选自C1-4直链或支链烷基,优选各自独立地选自甲基和乙基,更优选均为甲基;X为OH。
- 按照权利要求19所述的制造方法,其中所述第一氧化物源选自二氧化硅源、二氧化锗源、二氧化锡源、二氧化钛源和二氧化锆源中的至少一种,优选二氧化硅源或者二氧化硅源与二氧化锗源的组合,所述第二氧化物源选自氧化铝源、氧化硼源、氧化铁源、氧化镓源、稀土氧化物源、氧化铟源和氧化钒源中的至少一种,优选氧化铝源。
- 按照权利要求19所述的制造方法,其中所述晶化条件包括:晶化温度为从80℃至120℃,优选从120℃至170℃或者从120℃至200℃,晶化时间为至少1天,优选至少2天,优选从3天至8天、从5天至8天或者从4天至6天,并且所述焙烧条件包括:焙烧温度为从300℃至750℃,优选从400℃至600℃,焙烧时间为从1小时至10小时,优选从3小时至6小时。
- 按照权利要求20所述的制造方法,其中所述第一氧化物源(以所述第一氧化物为计)与所述第二氧化物源(以所述第二氧化物为计)的摩尔比为从5至∞,特别是从5至小于40(比如从20至小于40)、从40至200(比如从40至150)、从大于200至∞(比如从大于200至700);水与所述第一氧化物源(以所述第一氧化物为计)的摩尔比为从5至50,优选从5至15;所述有机模板剂与所述第一氧化物源(以所述第一氧化物为计)的摩尔比为从0.02至0.5,优选从0.05至0.5、从0.08至0.5或者从0.3至0.5;所述碱源(以OH-为计)与所述第一氧化物源(以所述第一氧化物为计)的摩尔比为从0至1,优选从0.04至1、从0.1至1、从0.2至1、从0.3至0.7或者从0.45至0.7。
- 按照权利要求21所述的制造方法,其中所述第一氧化物源(以所述第一氧化物为计)与所述第二氧化物源(以所述第二氧化物为计)的摩尔比为从5至∞,特别是从5至小于30(比如从10至小于30)、从30至100(比如从55至100)、从大于100至∞(比如从200至∞,或者从200至700);水与所述第一氧化物源(以所述第一氧化物为计)的摩尔比为从5至50,优选从5至15;所述有机模板剂与所述第一氧化物源(以所述第一氧化物为计)的摩尔比为从0.02至0.5,优选从0.05至0.5、从0.15至0.5或者从0.3至0.5;所述碱源(以OH-为计)与所述第一氧化物源(以所述第一氧化物为计)的摩尔比为从0至1,优选从0.04至1、从0.1至1、从0.2至1、从0.3至0.7或者从0.45 至0.7。
- 按照权利要求19所述的制造方法,其中所述第一氧化物源(以所述第一氧化物为计)与所述第二氧化物源(以所述第二氧化物为计)的摩尔比为从5至∞,优选从25至95,更优选从30至70;水与所述第一氧化物源(以所述第一氧化物为计)的摩尔比为从5至50,优选从5至15;所述有机模板剂与所述第一氧化物源(以所述第一氧化物为计)的摩尔比为从0.02至0.5,优选从0.05至0.5、从0.15至0.5或者从0.3至0.5;所述碱源(以OH-为计)与所述第一氧化物源(以所述第一氧化物为计)的摩尔比为从0至1,优选从0.04至1、从0.1至1、从0.2至1、从0.3至0.7或者从0.45至0.7。
- 一种分子筛,其特征在于,由按照权利要求19至26任一项所述的制造方法获得。
- 一种分子筛组合物,其特征在于,包含按照权利要求1至18和27任一项所述的分子筛或者按照权利要求19至26任一项所述的制造方法获得的分子筛,以及粘结剂。
- 一种烃的转化方法,其特征在于,包括在催化剂的存在下使烃发生转化反应的步骤,其中所述催化剂包含或制造自按照权利要求1至18和27任一项所述的分子筛、按照权利要求19至26任一项所述的制造方法获得的分子筛、或者权利要求28所述的分子筛组合物。
- 按照权利要求29所述的转化方法,其中所述转化反应选自催化裂化、加氢裂化、歧化、烷基化、低聚和异构化。
Priority Applications (10)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
RU2018141094A RU2732141C2 (ru) | 2016-04-27 | 2017-04-26 | Молекулярное сито, его получение и применение |
US16/095,208 US10737945B2 (en) | 2016-04-27 | 2017-04-26 | Molecular sieve, its preparation and application thereof |
KR1020187033906A KR102359046B1 (ko) | 2016-04-27 | 2017-04-26 | 분자체, 그 제조 방법 및 용도 |
EP17788483.0A EP3450396A4 (en) | 2016-04-27 | 2017-04-26 | MOLECULAR SIEVE, METHOD FOR THE PRODUCTION THEREOF AND APPLICATION THEREOF |
SG11201808701WA SG11201808701WA (en) | 2016-04-27 | 2017-04-26 | Molecular sieve, its preparation and application thereof |
CA3021606A CA3021606C (en) | 2016-04-27 | 2017-04-26 | Molecular sieve, method for manufacture thereof, and application thereof |
JP2018556388A JP7051709B2 (ja) | 2016-04-27 | 2017-04-26 | 分子篩、その製造方法および応用 |
BR112018071728-2A BR112018071728B1 (pt) | 2016-04-27 | 2017-04-26 | Peneira molecular, processo para sua preparação, composição de peneira molecular e processo para a conversão de um hidrocarboneto |
ZA2018/06888A ZA201806888B (en) | 2016-04-27 | 2018-10-16 | Molecular sieve, its preparation and application thereof |
US16/946,927 US11091372B2 (en) | 2016-04-27 | 2020-07-11 | Molecular sieve, its preparation and application thereof |
Applications Claiming Priority (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201610267141.9 | 2016-04-27 | ||
CN201610267141 | 2016-04-27 | ||
CN201610267143 | 2016-04-27 | ||
CN201610267143.8 | 2016-04-27 | ||
CN201611204950 | 2016-12-23 | ||
CN201611204950.1 | 2016-12-23 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US16/095,208 A-371-Of-International US10737945B2 (en) | 2016-04-27 | 2017-04-26 | Molecular sieve, its preparation and application thereof |
US16/946,927 Continuation US11091372B2 (en) | 2016-04-27 | 2020-07-11 | Molecular sieve, its preparation and application thereof |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2017185820A1 true WO2017185820A1 (zh) | 2017-11-02 |
Family
ID=60160676
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/CN2017/000327 WO2017185820A1 (zh) | 2016-04-27 | 2017-04-26 | 一种分子筛、其制造方法及其应用 |
Country Status (12)
Country | Link |
---|---|
US (2) | US10737945B2 (zh) |
EP (1) | EP3450396A4 (zh) |
JP (1) | JP7051709B2 (zh) |
KR (1) | KR102359046B1 (zh) |
CN (1) | CN107311198B (zh) |
BR (1) | BR112018071728B1 (zh) |
CA (1) | CA3021606C (zh) |
RU (1) | RU2732141C2 (zh) |
SG (1) | SG11201808701WA (zh) |
TW (1) | TWI736616B (zh) |
WO (1) | WO2017185820A1 (zh) |
ZA (1) | ZA201806888B (zh) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111346664A (zh) * | 2018-12-24 | 2020-06-30 | 中国石油化工股份有限公司 | 改性钒硅分子筛及其制备方法以及硫醚氧化方法 |
RU2815006C1 (ru) * | 2020-05-11 | 2024-03-11 | Чайна Петролеум Энд Кемикал Корпорейшн | Молекулярное сито scm-33, способ его приготовления и его применение |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN115231583B (zh) * | 2021-04-22 | 2024-01-30 | 中国石油化工股份有限公司 | 一种eri骨架单晶分子筛及其制备方法和应用 |
CN115676848B (zh) * | 2021-07-29 | 2024-06-11 | 中国石油化工股份有限公司 | Zsm-48分子筛及其制备方法 |
CN114212800B (zh) * | 2022-01-13 | 2023-05-30 | 万华化学(宁波)有限公司 | 一种新型高硅y型沸石及其制备方法与应用 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5538711A (en) * | 1995-01-23 | 1996-07-23 | Mobil Oil Corporation | Foam reduction during synthesis of MCM-41 |
CN104370296A (zh) * | 2014-02-13 | 2015-02-25 | 南京大学 | 一种超大孔硅酸盐分子筛nud-1及其制备方法 |
CN105129816A (zh) * | 2015-08-19 | 2015-12-09 | 青岛大学 | 18元环超大孔道亚磷酸铍分子筛及其制备方法 |
CN106542539A (zh) * | 2016-10-25 | 2017-03-29 | 浙江大学 | 以聚季铵盐模板剂合成大孔emm‑23沸石分子筛的方法 |
Family Cites Families (30)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3140249A (en) | 1960-07-12 | 1964-07-07 | Socony Mobil Oil Co Inc | Catalytic cracking of hydrocarbons with a crystalline zeolite catalyst composite |
US3140253A (en) | 1964-05-01 | 1964-07-07 | Socony Mobil Oil Co Inc | Catalytic hydrocarbon conversion with a crystalline zeolite composite catalyst |
US5167942A (en) * | 1990-11-21 | 1992-12-01 | Board Of Regents, The University Of Texas System | Methods for the preparation of molecular sieves, including zeolites, using metal chelate complexes |
US5271922A (en) * | 1992-10-09 | 1993-12-21 | Chevron Research And Technology Company | Process for preparing molecular sieves using a sparteine template |
US5362695A (en) * | 1993-04-13 | 1994-11-08 | Mobil Oil Corp. | Inorganic molecular sieves encapsulating chelates |
US5362697A (en) * | 1993-04-26 | 1994-11-08 | Mobil Oil Corp. | Synthetic layered MCM-56, its synthesis and use |
ZA953674B (en) * | 1994-05-10 | 1996-10-12 | Shell Int Research | Process for preparing a large pore molecular sieve |
US5689024A (en) * | 1994-06-03 | 1997-11-18 | Mobil Oil Corporation | Use of crystalline SUZ-9 |
US5840264A (en) * | 1994-08-22 | 1998-11-24 | Board Of Trustees Operating Michigan State University | Crystalline inorganic oxide compositions prepared by neutral templating route |
DE19524148C1 (de) * | 1995-07-03 | 1996-08-29 | Bosch Gmbh Robert | Schwingungsaufnehmer |
FR2754809B1 (fr) | 1996-10-21 | 2003-04-04 | Inst Francais Du Petrole | Zeolithe im-5, son procede de preparation et ses applications catalytiques |
DE69907849T2 (de) | 1998-11-02 | 2003-12-24 | Institut Francais Du Petrole, Rueil-Malmaison | Verfahren zur Herstellung eines Zeoliths des EUO-Typs mittels zeolithischen Keimen und dessen Verwendung als Isomerisierungskatalysator von Aromaten mit acht Kohlenstoffatomen |
US6800266B2 (en) * | 2000-04-13 | 2004-10-05 | Board Of Trustees Of Michigan State University | Process for the preparation of hybrid mesoporous molecular sieve silicas from amine surfactants |
ES2186488B1 (es) * | 2000-10-11 | 2004-01-16 | Univ Valencia Politecnica | Zeolita itq-17. |
CA2359825C (en) * | 2000-10-26 | 2008-09-23 | Quanjie Liu | A mesoporous aluminum based molecular sieve and a process for the preparation of the same |
JP2002356323A (ja) * | 2001-06-01 | 2002-12-13 | Nagoya Industrial Science Research Inst | 新規な〔Al〕−SSZ−31(ゼオライト)及びその製造方法 |
JP5485505B2 (ja) * | 2001-10-11 | 2014-05-07 | 三菱樹脂株式会社 | ゼオライト、及び該ゼオライトを含む水蒸気吸着材 |
CN100569647C (zh) * | 2007-02-02 | 2009-12-16 | 华东理工大学 | 一种mww分子筛的合成方法 |
KR101147007B1 (ko) * | 2009-02-02 | 2012-05-22 | 한국과학기술원 | 싸이클릭다이암모늄을 이용한 메조기공 및 마크로기공을 추가적으로 포함하는 bea, mtw, mfi 구조의 제올라이트의 제조과정 |
RU2599745C2 (ru) | 2011-08-04 | 2016-10-10 | Эксонмобил Кемикэл Пейтентс Инк. | Молекулярное сито emm-23, его синтез и применение |
EP3016738B1 (en) * | 2013-07-04 | 2019-04-24 | Total Research & Technology Feluy | Catalyst compositions comprising small size molecular sieves crystals deposited on a porous material |
CN104511271B (zh) * | 2013-09-24 | 2017-12-15 | 中国石油化工股份有限公司 | 一种分子筛、其制造方法及其应用 |
US10173903B2 (en) * | 2014-06-16 | 2019-01-08 | University Of Houston System | Zeolite compositions and methods for tailoring zeolite crystal habits with growth modifiers |
WO2015198268A1 (en) | 2014-06-27 | 2015-12-30 | Sabic Global Technologies B.V. | Processes and systems for preparing glycerol tert-butyl ethers from glycerol and isobutylene |
CN105312024B (zh) * | 2014-07-11 | 2019-04-16 | 中国石油化工股份有限公司 | 一种mww结构分子筛及其制备方法 |
CN106608636B (zh) * | 2015-10-27 | 2019-02-01 | 中国石油化工股份有限公司 | 一种euo或nes结构分子筛的制备方法 |
CN106608857B (zh) * | 2015-10-27 | 2018-11-02 | 中国石油化工股份有限公司 | 一种二氮氧杂环烷二溴盐及制备方法与应用 |
US10449528B2 (en) * | 2016-03-04 | 2019-10-22 | Uop Llc | High charge density silicometallophosphate molecular sieves |
CN107285330B (zh) * | 2016-03-30 | 2019-04-16 | 中国石油化工股份有限公司 | 一种nu-88分子筛的制备方法 |
CN107445178B (zh) * | 2016-06-01 | 2019-08-16 | 中国石油化工股份有限公司 | 一种ssz-26分子筛的制备方法 |
-
2017
- 2017-04-26 SG SG11201808701WA patent/SG11201808701WA/en unknown
- 2017-04-26 CN CN201710282848.1A patent/CN107311198B/zh active Active
- 2017-04-26 US US16/095,208 patent/US10737945B2/en active Active
- 2017-04-26 JP JP2018556388A patent/JP7051709B2/ja active Active
- 2017-04-26 BR BR112018071728-2A patent/BR112018071728B1/pt active IP Right Grant
- 2017-04-26 RU RU2018141094A patent/RU2732141C2/ru active
- 2017-04-26 KR KR1020187033906A patent/KR102359046B1/ko active IP Right Grant
- 2017-04-26 WO PCT/CN2017/000327 patent/WO2017185820A1/zh active Application Filing
- 2017-04-26 EP EP17788483.0A patent/EP3450396A4/en active Pending
- 2017-04-26 CA CA3021606A patent/CA3021606C/en active Active
- 2017-04-26 TW TW106114348A patent/TWI736616B/zh active
-
2018
- 2018-10-16 ZA ZA2018/06888A patent/ZA201806888B/en unknown
-
2020
- 2020-07-11 US US16/946,927 patent/US11091372B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5538711A (en) * | 1995-01-23 | 1996-07-23 | Mobil Oil Corporation | Foam reduction during synthesis of MCM-41 |
CN104370296A (zh) * | 2014-02-13 | 2015-02-25 | 南京大学 | 一种超大孔硅酸盐分子筛nud-1及其制备方法 |
CN105129816A (zh) * | 2015-08-19 | 2015-12-09 | 青岛大学 | 18元环超大孔道亚磷酸铍分子筛及其制备方法 |
CN106542539A (zh) * | 2016-10-25 | 2017-03-29 | 浙江大学 | 以聚季铵盐模板剂合成大孔emm‑23沸石分子筛的方法 |
Non-Patent Citations (1)
Title |
---|
See also references of EP3450396A4 * |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111346664A (zh) * | 2018-12-24 | 2020-06-30 | 中国石油化工股份有限公司 | 改性钒硅分子筛及其制备方法以及硫醚氧化方法 |
CN111346664B (zh) * | 2018-12-24 | 2022-11-15 | 中国石油化工股份有限公司 | 改性钒硅分子筛及其制备方法以及硫醚氧化方法 |
RU2815006C1 (ru) * | 2020-05-11 | 2024-03-11 | Чайна Петролеум Энд Кемикал Корпорейшн | Молекулярное сито scm-33, способ его приготовления и его применение |
Also Published As
Publication number | Publication date |
---|---|
CA3021606C (en) | 2024-01-09 |
US11091372B2 (en) | 2021-08-17 |
CN107311198A (zh) | 2017-11-03 |
TW201806866A (zh) | 2018-03-01 |
SG11201808701WA (en) | 2018-11-29 |
BR112018071728B1 (pt) | 2022-09-27 |
EP3450396A4 (en) | 2019-12-04 |
RU2018141094A (ru) | 2020-05-27 |
US10737945B2 (en) | 2020-08-11 |
EP3450396A1 (en) | 2019-03-06 |
JP2019514828A (ja) | 2019-06-06 |
BR112018071728A2 (pt) | 2019-02-19 |
RU2018141094A3 (zh) | 2020-05-27 |
KR20180137004A (ko) | 2018-12-26 |
TWI736616B (zh) | 2021-08-21 |
CA3021606A1 (en) | 2017-11-02 |
US20200339433A1 (en) | 2020-10-29 |
ZA201806888B (en) | 2020-07-29 |
RU2732141C2 (ru) | 2020-09-11 |
JP7051709B2 (ja) | 2022-04-11 |
KR102359046B1 (ko) | 2022-02-04 |
CN107311198B (zh) | 2020-06-16 |
US20190144289A1 (en) | 2019-05-16 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US11091372B2 (en) | Molecular sieve, its preparation and application thereof | |
JP6697481B2 (ja) | 新規cit−13位相の結晶質ゲルマノケイ酸塩物質およびその調製方法 | |
CN108238611B (zh) | 一种分子筛的制造方法及其产品和产品的应用 | |
US6346140B2 (en) | Porous solid for gas adsorption separation and gas adsorption separation process employing it | |
ES2711549T3 (es) | Tamiz molecular SCM-10, procedimiento para producirlo y uso del mismo | |
WO2015043114A1 (zh) | 一种分子筛、其制造方法及其应用 | |
Yuan et al. | Synthesis and application of metal-containing ZSM-5 for the selective catalytic reduction of NOx with NH3 | |
Liang et al. | CHA-type zeolites with high boron content: Synthesis, structure and selective adsorption properties | |
US11065606B2 (en) | Metal-substituted beta zeolite and method for producing same | |
JP2021524431A (ja) | 有機窒素含有構造化剤存在下での高純度afx構造ゼオライトの合成方法 | |
CN106276964B (zh) | 一种晶内含磷的zsm-5分子筛及其制备方法 | |
JPH0859223A (ja) | 微小−中間細孔ゲルおよびその製造方法 | |
CN109384637B (zh) | 苯和乙烯液相烷基化制乙苯的方法 | |
CN111348662B (zh) | 一种超大孔硅酸盐分子筛nud-6及其制备方法 | |
Chen et al. | Direct synthesis of core–shell MFI zeolites with spatially tapered trimodal mesopores via controlled orthogonal self-assembly | |
KR101816097B1 (ko) | 나노 크기를 갖는 제올라이트 입자를 포함하는 경질 올레핀의 올리고머화 반응용 촉매 및 이의 용도 | |
KR102416759B1 (ko) | Cha 제올라이트 제조방법 및 이로부터 제조된 거대입자의 cha 제올라이트 | |
CN111099613B (zh) | 分子筛、其合成方法及其用途 | |
CN107311190B (zh) | 一种分子筛、其制造方法及其应用 | |
CN114477209A (zh) | 一种硅铝分子筛及其制备方法和应用 | |
CN106608643A (zh) | 一种y型分子筛的改性方法 | |
CN111530497A (zh) | 能够提高mta反应稳定性的催化剂及其制备方法和应用方法 | |
KR20220048255A (ko) | 높은 실리카 골격조성을 갖는 kfi형 제올라이트 및 그 제조방법, 이를 이용한 프로필렌의 선택적 분리 방법 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 3021606 Country of ref document: CA |
|
ENP | Entry into the national phase |
Ref document number: 2018556388 Country of ref document: JP Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
REG | Reference to national code |
Ref country code: BR Ref legal event code: B01A Ref document number: 112018071728 Country of ref document: BR |
|
ENP | Entry into the national phase |
Ref document number: 20187033906 Country of ref document: KR Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2017788483 Country of ref document: EP |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 17788483 Country of ref document: EP Kind code of ref document: A1 |
|
ENP | Entry into the national phase |
Ref document number: 2017788483 Country of ref document: EP Effective date: 20181127 |
|
ENP | Entry into the national phase |
Ref document number: 112018071728 Country of ref document: BR Kind code of ref document: A2 Effective date: 20181023 |