Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • 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
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/04—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof using at least one organic template directing agent, e.g. an ionic quaternary ammonium compound or an aminated compound
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
  • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
  • C01B39/46—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
• • 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
  • C07C2/64—Addition to a carbon atom of a six-membered aromatic ring
  • C07C2/66—Catalytic processes

Definitions

• the present invention relates to a silicone porous zeolite, a method for its synthesis, and uses thereof. Background technique
• Porous inorganic oxide materials are widely used as catalysts and catalyst carriers. Porous inorganic oxide materials have a relatively high specific surface area and a clear pore structure and are therefore good catalytic materials or catalyst supports. Porous inorganic oxide materials include amorphous porous oxide materials, crystalline molecular sieves, and modified layered materials.
• the basic skeleton structure of the crystalline porous zeolite is based on the rigid three-dimensional ⁇ 4 (Si0 4 ,
• the T0 4 is a tetrahedral shared oxygen atom.
• the charge of some tetrahedrons constituting the skeleton, such as ⁇ 10 4 is balanced by the presence of surface cations such as Na+, H+.
• surface cations such as Na+, H+.
• This allows the properties of the zeolite to be altered by cation exchange.
• Synthetic crystalline porous zeolites are often synthesized hydrothermally and often employ specific templating or structure directing agents to synthesize specific zeolites. These templating or structure directing agents are often nitrogen-containing organic compounds. Many zeolites and their combinations have been disclosed in the literature. Into the method.
• One object of the present invention is to provide a novel silicone porous zeolite having a skeleton structure containing a silicon atom having at least one organic group selected from the group consisting of an alkyl group, an alkenyl group and a phenyl group.
• Another object of the present invention is to provide a process for synthesizing the novel organoporous porous zeolite.
• Yet another object of the invention is to provide the use of the silicone porous zeolite.
• Figure 1 is an XRD pattern of the zeolite obtained in Example 1. Detailed description of a preferred embodiment
• the solid Si 29 NMR spectrum of the zeolite contained at least one Si 29 nuclear magnetic resonance peak between -80 and +50 ppm.
• the X-ray diffraction pattern of the zeolite has a corresponding value of 12.4 ⁇ 0.2, 11.0 ⁇ 0.3, Diffraction peaks of d-spacing of 9.3 ⁇ 0.3, 6.8 ⁇ 0.2, 6.1 ⁇ 0.2, 5 ⁇ 5 ⁇ 0.2, 4.4 ⁇ 0.2, 4.0 ⁇ 0.2 and 3.4 ⁇ 0.1 angstroms.
• silicone porous zeolite refers to a zeolite having a silicon atom having at least one organic substituent in the zeolite structure after synthesis, the organic substituent being selected, in particular, from an alkyl group or an alkenyl group. And at least one of phenyl groups.
• n 10 to 250, m is 0.01 to 0.8, and x is 0.01 to 1. According to a more preferred embodiment, n is 10 to 150, m is 0.02 - 0.5, and X is 0.02 - 0.5 ⁇ .
• the R group is at least one selected from the group consisting of an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, and a phenyl group. According to a more preferred embodiment, the R group is at least one selected from the group consisting of methyl, ethyl, vinyl and phenyl.
• the silicone porous zeolite of the present invention is named SHY-4.
• the present invention provides a method for synthesizing a silicone porous zeolite of the present invention, comprising:
• step b) recovering the crystalline product obtained in the step b), washing with water, and drying to obtain a porous silica zeolite.
• a source of SiO 2 generally used for zeolite synthesis can be used as the inorganic silicon source in the process of the present invention.
• the inorganic silicon source which can be used in the method of the present invention is preferably at least one selected from the group consisting of silica sol, solid silica, silica gel, silicate, diatomaceous earth and water glass.
• the silicone source useful in the process of the invention may be at least one selected from the group consisting of halosilanes, silazanes, or alkoxysilanes.
• halosilanes include, but are not limited to, trimethylchlorosilane, diyldichlorosilane, triethylchlorosilane, diethyldichlorosilane, dimethylchlorobromosilane, dimethylethylchlorosilane, Dimethyl butyl chlorosilane, dimethyl phenyl chlorosilane pit, dimethyl isopropyl chlorosilane, dimethyl tert-butyl chlorosilane, dimethyl octadecyl chlorosilane, methyl phenyl ethylene Chlorosilane, vinyltrichlorosilane, divinyldichlorosilane and diphenyldichlorosilane.
• Examples of preferred silazanes include, but are not limited to, hexamethyldisilazane, heptadecyldisilazane, tetramethyldisilazane, divinyltetramethyldisilazane, and diphenyl 4 Methyl disilazane.
• Examples of preferred alkoxysilanes include, but are not limited to, trimethylethoxysilane, dimethyldiethoxysilane, trimethylmethoxysilane, dimethyldimethoxysilane, phenyl trimethyl Oxysilane and diphenyldiethoxysilane.
• Aluminum sources commonly used in zeolite synthesis can be used in the process of the invention.
• the aluminum source which can be used in the process of the present invention is preferably at least one selected from the group consisting of sodium aluminate, sodium metaaluminate, aluminum sulfate, aluminum nitrate, aluminum chloride, aluminum hydroxide, aluminum oxide, kaolin and montmorillonite.
• the base which can be used in the process of the present invention is an inorganic base, preferably at least one selected from the group consisting of lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide and barium hydroxide.
• the organic amine templating agent is preferably selected from the group consisting of ethylenediamine, hexamethylenediamine, cyclohexylamine, hexamethyleneimine, heptamethyleneimine, pyridine, hexahydropyridine, butylamine, hexylamine, octylamine, quinine At least one of an amine, dodecylamine, hexadecylamine, and octadecylamine.
• the crystallization reaction temperature is in the range of 100 to 180 ° C
• the crystallization reaction time is in the range of 2 to 60 hours.
• the reaction mixture is aged at 10 to 80 ° C for 2 to 100 hours prior to crystallization.
• the present invention provides the use of the organoporous porous zeolite as a component of a catalyst for the conversion of an adsorbent or an organic compound.
• the silicone porous zeolite of the present invention can be used as an adsorbent, for example, for separating at least one component from a mixture of a plurality of components in a gas phase or a liquid phase. Therefore, according to one embodiment, the present invention provides a separation process comprising contacting a gaseous and/or liquid mixture with a silicone porous zeolite of the present invention to allow said silicone porous zeolite to selectively adsorb said mixture At least one component, thereby partially or substantially completely separating the at least one component from the mixture.
• the organosilicon porous zeolite of the present invention can be used in a sub-organic compound conversion process.
• a catalyst comprising the organoporous silica of the present invention can be used for liquid phase alkylation of benzene with propylene to produce cumene.
• the present invention provides a process for the preparation of cumene comprising liquid phase alkylation of benzene with propylene in the presence of a catalyst comprising a silicone porous zeolite of the present invention.
• the inventors have synthesized a porous zeolite having a specific pore structure and a skeleton containing silicone by controlling the relative content of each component in the reaction mixture and controlling the crystallization process, and achieved good technical results. detailed description
• SiO 2 /Al 2 O 3 40, NaOH/ Si0 2 - 0.025,
• Trimethylchlorosilane / Si0 2 0.05
• reaction mixture was stirred and hooked, it was placed in a stainless steel reaction vessel at 135 with stirring. C was crystallized for 50 hours. The reaction mixture is then drained and filtered, and the filter cake is washed with water and dried to give product. This product had a Si 2 2 /Al 2 0 3 molar ratio of 42.1.
• reaction mixture was stirred and hooked, it was placed in a stainless steel reaction vessel and crystallized at 150 ° C for 55 hours with stirring. The reaction mixture is then drained and filtered, and the filter cake is washed with water and then dried to give the product.
• This product had a SiO 2 /Al 2 0 3 molar ratio of 28.6.
• Example 3 3 ⁇ 0 g of alumina and 16.0 g of sodium hydroxide were added to 450 g of water, and the mixture was stirred to dissolve the solid. Then, 34.7 g of hexamethyleneimine, 60 g of solid silica and 5.9 g of dimethyldiethoxysilane were successively added to the mixture under stirring, so that the reactants had the following molar ratios:
• reaction mixture was stirred well, it was placed in a stainless steel reaction vessel and crystallized at 145 ° C for 70 hours with stirring. The reaction mixture is then drained and filtered, and the filter cake is washed with water and then dried to give the product.
• This product had a 0 2 / 1 2 0 3 molar ratio of 30.1.
• reaction mixture was stirred and hooked, it was placed in a stainless steel reaction vessel and crystallized at 145 ° C for 38 hours with stirring.
• the reaction mixture is then drained and filtered, and the filter cake is washed with water and then dried to give the product.
• This product had a SiO 2 /Al 2 0 3 molar ratio of 17.5.
• reaction mixture was stirred and hooked, it was placed in a stainless steel reaction vessel and crystallized at 135 ° C for 35 hours with stirring.
• the reaction mixture is then drained and filtered, and the filter cake is washed with water and then dried to give the product.
• This product had a SiO 2 /Al 2 0 3 molar ratio of 68.5.
• reaction mixture was stirred and hooked, it was placed in a stainless steel reaction vessel and crystallized at 135 ° C for 35 hours with stirring.
• the reaction mixture is then drained and filtered, and the filter cake is washed with water and then dried to give the product.
• This product had a SiO 2 /Al 2 0 3 molar ratio of 105.3.
• Phenyltrimethoxysilane/Si0 2 0.1
• reaction mixture was stirred and hooked, it was placed in a stainless steel reaction vessel and crystallized at 135 ° C for 35 hours with stirring.
• the reaction mixture is then drained and filtered, and the filter cake is washed with water and then dried to give the product.
• This product had a Si0 2 /Al 2 0 3 molar ratio of 142.0.
• reaction mixture was stirred and hooked, it was placed in a stainless steel reaction vessel and crystallized at 135 ° C for 38 hours with stirring.
• the reaction mixture is then drained and filtered, and the filter cake is washed with water and then dried to give the product.
• This product had a SiO 2 /Al 2 0 3 molar ratio of 68.0.
• Example 1 50 g of the powder product synthesized in [Example 1] was exchanged 4 times with 150 ml of a 1 M aqueous solution of ammonium nitrate, filtered, and dried. Thereafter, the dried solid was thoroughly mixed with 20 g of alumina, and 120 g of 5% by weight of nitric acid was added. The obtained mixture was kneaded and extruded into a strip of ⁇ 1.6 2 2 m, and then baked at 120 ° C and calcined at 520 ° C for 6 hours to prepare a desired catalyst.

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)
• Inorganic Chemistry (AREA)
• Materials Engineering (AREA)
• Engineering & Computer Science (AREA)
• Crystallography & Structural Chemistry (AREA)
• Analytical Chemistry (AREA)
• Silicates, Zeolites, And Molecular Sieves (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)
• Catalysts (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)

Priority Applications (3)

Applications Claiming Priority (2)

Publications (1)

Family

ID=39081921

Family Applications (1)

Country Status (6)

Cited By (1)

Families Citing this family (15)

Citations (14)

Family Cites Families (1)

• 2006
  • 2006-08-11 CN CNB2006100299803A patent/CN100554156C/zh active Active
• 2007
  • 2007-07-17 WO PCT/CN2007/002177 patent/WO2008019570A1/zh not_active Ceased
  • 2007-07-17 KR KR1020097004695A patent/KR101381769B1/ko active Active
  • 2007-07-17 US US12/377,159 patent/US8030508B2/en active Active
  • 2007-07-17 EP EP07764077.9A patent/EP2053021B1/en active Active
  • 2007-07-25 TW TW096127093A patent/TW200904530A/zh unknown

Patent Citations (14)

Non-Patent Citations (3)

Also Published As

Similar Documents

Legal Events