CN112742471B - Core-shell structure titanium-silicon material, preparation method thereof and method for producing epoxy compound through oxidation reaction of macromolecular olefin - Google Patents

Core-shell structure titanium-silicon material, preparation method thereof and method for producing epoxy compound through oxidation reaction of macromolecular olefin Download PDF

Info

Publication number
CN112742471B
CN112742471B CN201911063296.0A CN201911063296A CN112742471B CN 112742471 B CN112742471 B CN 112742471B CN 201911063296 A CN201911063296 A CN 201911063296A CN 112742471 B CN112742471 B CN 112742471B
Authority
CN
China
Prior art keywords
titanium
silicon
core
shell structure
ratio
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201911063296.0A
Other languages
Chinese (zh)
Other versions
CN112742471A (en
Inventor
杨永佳
林民
夏长久
朱斌
彭欣欣
刘聿嘉
罗一斌
舒兴田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Original Assignee
Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Sinopec Research Institute of Petroleum Processing, China Petroleum and Chemical Corp filed Critical Sinopec Research Institute of Petroleum Processing
Priority to CN201911063296.0A priority Critical patent/CN112742471B/en
Publication of CN112742471A publication Critical patent/CN112742471A/en
Application granted granted Critical
Publication of CN112742471B publication Critical patent/CN112742471B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/89—Silicates, aluminosilicates or borosilicates of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/617—500-1000 m2/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • 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
    • C01B39/06—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis
    • C01B39/08—Preparation of isomorphous zeolites characterised by measures to replace the aluminium or silicon atoms in the lattice framework by atoms of other elements, i.e. by direct or secondary synthesis the aluminium atoms being wholly replaced
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/02—Synthesis of the oxirane ring
    • C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
    • C07D301/12—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with hydrogen peroxide or inorganic peroxides or peracids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/01—Particle morphology depicted by an image
    • C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2004/00—Particle morphology
    • C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

The invention relates to a core-shell structure titanium-silicon material, a preparation method thereof and a method for producing epoxy compounds by oxidation reaction of macromolecular olefins2With SiO2In a molar ratio of 1: (30-100); the ratio of the surface titanium-silicon ratio of the core-shell structure titanium-silicon material to the bulk titanium-silicon ratio is 2.0-4.4, wherein the titanium-silicon ratio refers to TiO2With SiO2The molar ratio of (A) to (B); the most probable pore diameter of the mesoporous titanium-silicon material with the core-shell structure is 14-34 nm. The shell surface of the core-shell structure titanium silicon material disclosed by the invention is rich and has a proper most probable pore size, and the application of the core-shell structure titanium silicon material in a process for producing an epoxy compound by a macromolecular olefin oxidation reaction is beneficial to improving the conversion rate of raw materials and the selectivity of a target product, and improving the utilization rate of an oxidant in the oxidation reaction.

Description

Core-shell structure titanium-silicon material, preparation method thereof and method for producing epoxy compound through oxidation reaction of macromolecular olefin
Technical Field
The disclosure relates to a core-shell structure titanium-silicon material, a preparation method thereof and a method for producing an epoxy compound through oxidation reaction of macromolecular olefin.
Background
The titanium-silicon molecular sieve is a novel heteroatom molecular sieve developed in the beginning of the eighties of the 20 th century and refers to a class of heteroatom molecular sieves containing framework titanium. The microporous titanium silicalite molecular sieves synthesized at present comprise TS-1 (MFI structure), TS-2(MEL structure), Ti-Beta (BEA structure), Ti-ZSM-12(MTW structure), Ti-MCM-22(MWW structure) and the like, and the mesoporous titanium silicalite molecular sieves comprise Ti-MCM-41, Ti-SBA-15 and the like. The development and application of the titanium-silicon molecular sieve successfully expand the zeolite molecular sieve from the acid catalysis field to the catalytic oxidation field, and have milestone significance. Of these, Enichem, Italy, first published TS-1 in 1983 as the most representative titanium silicalite molecular sieve. TS-1 has MFI topology with a two-dimensional ten-membered ring channel system, which [100 ]]The direction is a straight channel with a pore diameter of 0.51X 0.55nm, [010]The direction is sinusoidal channels with pore diameter of 0.53 x 0.56 nm. Due to the introduction of Ti atoms and the special pore channel structure, TS-1 and H2O2The formed oxidation system has the advantages of mild reaction conditions, green and environment-friendly oxidation process, good selectivity of oxidation products and the like in the oxidation reaction of organic matters. At present, the catalytic oxidation system can be widely applied to reactions such as alkane oxidation, olefin epoxidation, phenol hydroxylation, ketone (aldehyde) ammoximation, oil oxidation desulfurization and the like, wherein industrial application is successively realized in phenol hydroxylation, ketone (cyclohexanone, butanone and acetone) ammoximation and propylene epoxidation.
The US patent 4410501 first discloses a method for synthesizing a titanium silicalite TS-1 by a classical hydrothermal crystallization method. The method is mainly carried out by two steps of glue preparation and crystallization, and comprises the following specific steps: putting silicon source Tetraethoxysilane (TEOS) into nitrogen to protect CO2Slowly adding template tetrapropylammonium hydroxide (TPAOH), slowly dropwise adding titanium source tetraethyl titanate (TEOT), stirring for 1h,preparing a reaction mixture containing silicon, titanium and organic base, heating, removing alcohol, supplementing water, crystallizing for 10 days at 175 ℃ under the stirring of an autogenous pressure kettle, and then separating, washing, drying and roasting to obtain the TS-1 molecular sieve. However, in the process, factors influencing insertion of titanium into the framework are numerous, conditions of hydrolysis, crystallization nucleation and crystal growth are not easy to control, a certain amount of titanium cannot be effectively inserted into the molecular sieve framework and is retained in a pore channel in a non-framework titanium form, the generation of non-framework titanium not only reduces the number of catalytic active centers, but also promotes ineffective decomposition of hydrogen peroxide by non-framework titanium silicon species to cause raw material waste, so that the TS-1 molecular sieve synthesized by the method has the defects of low catalytic activity, poor stability, difficulty in reproduction and the like.
CN1301599A discloses a method for preparing a novel hollow titanium silicalite molecular sieve HTS with a hollow structure and less non-framework titanium, which comprises the steps of uniformly mixing a synthesized TS-1 molecular sieve, an acidic compound and water, reacting for 5 minutes to 6 hours at 5 to 95 ℃ to obtain an acid-treated TS-1 molecular sieve, uniformly mixing the acid-treated TS-1 molecular sieve, an organic base and the water, putting the obtained mixture into a sealed reaction kettle, and reacting for 1 hour to 8 days at the temperature of 120 to 200 ℃ and the autogenous pressure. The molecular sieve has less non-framework titanium and better catalytic oxidation activity and stability.
Disclosure of Invention
The shell surface of the core-shell structure titanium-silicon material provided by the disclosure is rich in titanium and has a proper mesopore and largest-probable-pore diameter, and the conversion rate of raw materials and the selectivity of a target product can be improved when the core-shell structure titanium-silicon material is used in a process for producing an epoxy compound by oxidizing macromolecular olefin.
In order to achieve the above object, the disclosure provides, in a first aspect, a core-shell structure titanium-silicon material, which includes an inner core and an outer shell, where the inner core is an all-silicon molecular sieve having an intra-crystal multi-hollow structure, and the outer shell is a titanium-silicon molecular sieve, and the TiO of the core-shell structure titanium-silicon material is calculated as an oxide and calculated as a molar amount2With SiO2In a molar ratio of 1: (30-100) (ii) a The ratio of the surface titanium-silicon ratio of the core-shell structure titanium-silicon material to the bulk titanium-silicon ratio is 2.0-4.4, wherein the titanium-silicon ratio refers to TiO2With SiO2The molar ratio of (A) to (B); the most probable pore diameter of the mesoporous titanium-silicon material with the core-shell structure is 14-34 nm.
Optionally, the mesoporous and several-pore diameter of the core-shell structure titanium silicon material is 16-32 nm.
Optionally, the titanium silicalite molecular sieve has a BET total specific surface area of 415-2The volume ratio of the mesoporous volume to the total pore volume is 40-70%.
The second aspect of the present disclosure provides a method for preparing a core-shell structure titanium-silicon material, including:
a. mixing a first structure directing agent, a first silicon source and water, and performing first hydrolysis at 40-97 ℃ for 2-50 hours to obtain a first hydrolysis mixture;
b. carrying out first hydrothermal treatment on the first hydrolysis mixture for 1-720 hours at 90-200 ℃ in a pressure-resistant closed container, and collecting a first solid product;
c. mixing the second structure directing agent, a second silicon source, a titanium source and water, and performing second hydrolysis at 35-95 ℃ for 3-60 hours to obtain a second hydrolysis mixture;
d. mixing the first solid product and the second hydrolysis mixture to obtain a mixed material, carrying out second hydrothermal treatment on the mixed material in a pressure-resistant closed container at 90-200 ℃ for 1-170h, and collecting a second solid product;
wherein the first structure directing agent is a double-head organic quaternary ammonium salt compound, or a mixture of the double-head organic quaternary ammonium salt compound and organic amine; the second structure directing agent is a single-head quaternary ammonium base compound or a mixture of the single-head quaternary ammonium base compound and organic amine.
Optionally, in step a, the double-headed organic quaternary ammonium base compound and the double-headed organic quaternary ammonium salt compound have the following structures, respectively:
Figure BDA0002256330580000031
wherein R is1Is C3-C30 chain normal alkyl, R2Is a chain normal alkylene of C1-C10, R3Is C1-C15 chain normal alkyl, R4、R5、R6And R7Each independently being methyl, ethyl or propyl, X is OH-、F-、Cl-Or Br-。
Alternatively, R1Is C9-C23 chain normal alkyl, R2Is a chain normal alkylene of C6-C8, R3Is C1-C7 chain normal alkyl, R4、R5、R6And R7Each independently being methyl or ethyl, X is OH-Or Br-。
Optionally, in step c, the single-headed quaternary ammonium base compound has the formula (R)9)3NOH，R9Is C1-C4 alkyl;
the molecular formula of the single-head quaternary ammonium salt compound is (R)10)3NX，R10Is C1-C4 alkyl, X is F-、Cl-Or Br-。
Optionally, the organic amine is an aliphatic amine compound, an alcohol amine compound, or an aromatic amine compound, or a combination of two or three thereof.
Optionally, the fatty amine compound is ethylamine, n-butylamine, butanediamine, or hexamethylenediamine, or a combination of two or three thereof;
the alcohol amine compound is monoethanolamine, diethanolamine or triethanolamine, or a combination of two or three of the monoethanolamine, diethanolamine and triethanolamine;
the aromatic amine compound is aniline, toluidine or p-phenylenediamine, or a combination of two or three of them.
Optionally, in step a, the molar ratio of the first structure directing agent, the first silicon source and the water is (0.01-1): 1: (50-4000), wherein the first silicon source is SiO2Counting;
preferably, the molar ratio of the amounts of the first structure directing agent, the first silicon source and water is (0.06-0.5): 1: (200-2000).
Optionally, the first silicon source and the second silicon source are each an organic silicone grease, preferably, the first silicon source and the second silicon source are each independently tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate, or dimethoxydiethoxysilane, or a combination of two or three of them;
the titanium source is inorganic titanium salt and/or organic titanate.
Optionally, in step a, the temperature of the first hydrolysis is 65-95 ℃ and the time is 3-35 hours; and/or the like and/or,
in the step b, the temperature of the first hydrothermal treatment is 120-.
Optionally, in step c, the molar ratio of the second structure directing agent, the second silicon source, the titanium source and the water is (1.5-5): (10-100): 1: (400-1000), the second silicon source is SiO2The titanium source is calculated as TiO2And (6) counting.
Optionally, in step c, the temperature of the second hydrolysis is 55-90 ℃ and the time is 5-40 hours.
Optionally, in the step d, the temperature of the second hydrothermal treatment is 110-.
Optionally, TiO in the mixed material2And SiO2In a molar ratio of 1: (10-200), preferably, TiO2And SiO2In a molar ratio of 1: (20-100).
Optionally, step d further comprises: collecting the second solid product, and then drying and roasting; the drying temperature is 100-200 ℃, and the drying time is 1-24 hours; the roasting temperature is 350-650 ℃, and the roasting time is 1-6 hours.
The third aspect of the disclosure provides a core-shell structure titanium-silicon material prepared by the method provided by the second aspect of the disclosure.
The fourth aspect of the present disclosure provides a catalyst containing the core-shell structure titanium-silicon material provided in the first or third aspect of the present disclosure.
In a fifth aspect of the present disclosure, there is provided a process for the oxidation of a macromolecular olefin to produce an epoxide using the catalyst provided in the fourth aspect of the present disclosure.
Optionally, the macromolecular olefin is cyclohexene, cyclooctene, styrene, or limonene.
Through the technical scheme, the titanium-silicon molecular sieve has the advantages that the surface of the shell is rich in titanium, the pore diameter of the mesoporous is suitable at most, the catalytic activity is high, and the titanium-silicon molecular sieve is used in the process of producing the epoxy compound through the oxidation reaction of the macromolecular olefin, so that the conversion rate of raw materials and the selectivity of a target product are improved, and the utilization rate of an oxidant in the oxidation reaction is improved.
Additional features and advantages of the disclosure will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:
FIG. 1 is a TEM electron micrograph of a titanium silicalite molecular sieve prepared in example 1 of the present disclosure;
FIG. 2 is a TEM-EDX electron micrograph of a titanium silicalite molecular sieve prepared in example 1 of the present disclosure;
fig. 3 is a schematic diagram of the mesopore size distribution of the titanium silicalite molecular sieve prepared in example 1 and the titanium silicalite molecular sieve prepared in comparative example 2 according to the present disclosure.
Detailed Description
The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.
The first aspect of the disclosure provides a core-shell structure titanium-silicon material, which includes an inner core and an outer shell, wherein the inner core is an all-silicon molecular sieve with an intra-crystal multi-hollow structure, and the outer shell is a titanium-silicon molecular sieve, and calculated by oxides and calculated by mol, the TiO of the core-shell structure titanium-silicon material2With SiO2In a molar ratio of 1: (30-100); the surface titanium-silicon ratio of the core-shell structure titanium-silicon material is compared with the bulk phase titanium-silicon ratioThe ratio of (A) to (B) is 2.0-4.4, and the ratio of titanium to silicon is TiO2With SiO2The molar ratio of (A) to (B); the most probable pore diameter of the mesoporous titanium-silicon material with the core-shell structure is 14-34 nm.
According to the present disclosure, the molecular sieve is an MFI-type molecular sieve, an MEL-type molecular sieve, or a BEA-type molecular sieve. The shell surface of the core-shell structure titanium-silicon material disclosed by the invention is rich in titanium, has a proper mesopore with the most probable pore diameter, and the utilization rate of the titanium active center is high, so that the conversion rate of raw materials and the selectivity of a target product can be improved when the titanium active center is used in the process for producing an epoxy compound by oxidizing macromolecular olefin, and the utilization rate of an oxidant in an oxidation reaction is improved.
In the present disclosure, the BET nitrogen adsorption and desorption test can be performed according to a conventional method, which is not particularly limited in the present disclosure and is well known to those skilled in the art, for example, using N2Static adsorption and the like. Surface titanium to silicon ratio refers to the atomic layer of TiO not more than 5nm (e.g., 1-5nm) from the surface of the titanium silicalite molecular sieve grains2With SiO2The bulk titanium-silicon ratio of (A) means TiO in the whole molecular sieve crystal grains2With SiO2In a molar ratio of (a). The surface titanium-silicon ratio and the bulk titanium-silicon ratio can be determined by methods conventionally adopted by those skilled in the art, for example, the TiO of the edge and central target point of the titanium-silicon molecular sieve can be determined by a transmission electron microscope-energy dispersive X-ray spectroscopy (TEM-EDX) method2With SiO2Molar ratio, TiO at edge targets2With SiO2TiO with the molar ratio of surface titanium to silicon and a central target point2With SiO2The molar ratio is the bulk phase titanium-silicon ratio. Alternatively, the surface titanium-silicon ratio can be determined by ion-excited etching X-ray photoelectron spectroscopy (XPS), and the bulk titanium-silicon ratio can be determined by chemical analysis or by X-ray fluorescence spectroscopy (XRF).
Preferably, the mesoporous and microporous pore diameter of the titanium silicon material with the core-shell structure is 16-32nm, and more preferably 18-25 nm.
According to the present disclosure, the BET total specific surface area of the titanium silicalite molecular sieve can be 415-2The volume ratio of the mesoporous volume to the total pore volume can be 40-70%. Preferably, the BET total ratio of the titanium silicaliteArea of 450-600m2The volume ratio of the mesoporous volume to the total pore volume is 45-66%. In the present disclosure, the BET total specific surface area and the adsorption amount can be measured according to a conventional method, which is not particularly limited in the present disclosure and is well known to those skilled in the art, for example, using N2Static adsorption and the like. The particle size of the molecular sieve may be measured by conventional methods, such as by a laser particle size analyzer, and the specific test conditions may be those routinely employed by those skilled in the art.
The second aspect of the present disclosure provides a method for preparing a core-shell structure titanium-silicon material, including:
a. mixing a first structure directing agent, a first silicon source and water, and performing first hydrolysis at 40-97 ℃ for 2-50 hours to obtain a first hydrolysis mixture;
b. carrying out first hydrothermal treatment on the first hydrolysis mixture for 1-720 hours at 90-200 ℃ in a pressure-resistant closed container, and collecting a first solid product;
c. mixing the second structure directing agent, a second silicon source, a titanium source and water, and performing second hydrolysis at 35-90 ℃ for 3-60 hours to obtain a second hydrolysis mixture;
d. mixing the first solid product and the second hydrolysis mixture to obtain a mixed material, carrying out second hydrothermal treatment on the mixed material in a pressure-resistant closed container at 90-200 ℃ for 1-170h, and collecting a second solid product;
wherein the first structure directing agent is a double-head organic quaternary ammonium salt compound, or a mixture of the double-head organic quaternary ammonium salt compound and organic amine; the second structure directing agent is a single head quaternary ammonium base compound or a mixture of a single head quaternary ammonium compound and an organic amine.
The surface of the core-shell structure titanium-silicon material prepared by the method disclosed by the invention is rich in titanium and has a proper mesoporous but most probable pore diameter. Specifically, the inner core of the material is an all-silicon molecular sieve with an intragranular multi-hollow structure, so that the diffusion performance of macromolecules can be improved, and the manufacturing cost is reduced; the surface of the shell is rich in titanium, and the titanium active center is positioned on the surface layer, so that the utilization rate of the titanium active center is improved, and the catalytic activity is high. The method can improve the conversion rate of raw materials and the selectivity of target products and improve the utilization rate of an oxidant in the oxidation reaction when being used in the process of producing the epoxy compound by oxidizing macromolecular olefin.
According to the present disclosure, in step a, the double-headed organic quaternary ammonium base compound and the double-headed organic quaternary ammonium salt compound have the following structures, respectively:
Figure BDA0002256330580000081
wherein R is1Is C3-C30 chain normal alkyl, R2Is a chain normal alkylene of C1-C10, R3Is C1-C15 chain normal alkyl, R4、R5、R6And R7Each independently being methyl, ethyl or propyl, X is OH-、F-、Cl-Or Br-。
The double-headed organic quaternary ammonium base compound and the double-headed organic quaternary ammonium salt compound may be denoted as Ci-j-k-l-m-n-oX2Wherein i, j, k, l, m, n and o are sequentially represented by structural formulas
Figure BDA0002256330580000082
R in (1)1、R2、R3、R4、R5、R6And R7X may be OH-、F-、Cl-Or Br-。
Preferably, R1Is C9-C23 chain normal alkyl, R2Is a chain normal alkylene of C6-C8, R3Is C1-C7 chain normal alkyl, R4、R5、R6And R7Each independently being methyl or ethyl, X is OH-Or Br-。
In step c, the single head quaternary ammonium base compound has the formula (R)9)3NOH，R9Is C1-C4 alkyl; the molecular formula of the single-head quaternary ammonium salt compound is (R)10)3NX，R10Is C1-C4 alkyl, X is F-、Cl-Or Br-。
According to the present disclosure, the organic amine may be a fatty amine compound, an alcohol amine compound, or an aromatic amine compound, or a combination of two or three thereof.
According to the present disclosure, the fatty amine compound has the general formula R5(NH2)nWherein R is5Is C1-C4 alkyl or C1-C4 alkylene, and n is 1 or 2. Preferably, the fatty amine compound is ethylamine, n-butylamine, butanediamine or hexamethylenediamine, or may be a combination of two or three thereof.
According to the present disclosure, the alcohol amine compound has the general formula (HOR)6)mNH(3-m)Wherein R is6Is C1-C4 alkyl, and m is 1,2 or 3. Preferably, the alkanolamine compound may be monoethanolamine, diethanolamine or triethanolamine, or may be a combination of two or three thereof;
according to the present disclosure, the aromatic amine compound may be an amine having one aromatic substituent. Preferably, the aromatic amine compound may be aniline, toluidine or p-phenylenediamine, or may be a combination of two or three thereof.
According to the present disclosure, in step a, the molar ratio of the amounts of the first structure directing agent, the first silicon source and water is (0.01-1): 1: (50-4000), wherein the first silicon source is SiO2And (6) counting. Preferably, the molar ratio of the amounts of the first structure directing agent, the first silicon source and water is (0.06-0.5): 1: (200-2000).
The first and second sources of silicon may be those commonly used to synthesize titanium silicalite molecular sieves well known to those skilled in the art in light of the present disclosure. In one embodiment, the first silicon source and the second silicon source may be respectively organic silicone grease, preferably, the first silicon source and the second silicon source may be respectively and independently tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate or dimethoxydiethoxysilane, or may be a combination of two or three of them.
The titanium source may be a conventional choice in the art in light of this disclosure. Preferably, the titanium source may be an inorganic titanium salt and/or an organic titanate. For example, the inorganic titanium salt may be titanium tetrachloride, titanium sulfate or titanium nitrate, and the organic titanate may be ethyl titanate, tetrapropyl titanate or tetrabutyl titanate.
According to the present disclosure, the temperature of the first hydrolysis in step a is preferably 65 to 95 ℃ and the time is preferably 3 to 35 hours. Both the mixing and the first hydrolysis may be carried out under stirring in order to obtain the desired effect. After the first hydrolysis, the alcohol generated by the hydrolysis of the first titanium source and the first silicon source in the reaction system may be removed to obtain a first hydrolysis mixture. The present disclosure is not particularly limited in the manner and conditions for removing the alcohol, and any known suitable manner and conditions may be used, for example, the alcohol may be removed from the reaction system by azeotropic distillation and water lost by azeotropic distillation may be replenished.
According to the present disclosure, in step b, the temperature of the first hydrothermal treatment is preferably 120-. The pressure of the first hydrothermal treatment is not particularly limited, and may be the autogenous pressure of the reaction system.
According to the present disclosure, in step c, the molar ratio of the amounts of the second structure directing agent, the second silicon source, the titanium source and the water may be (1.5-5): (10-100): 1: (400-1000), the second silicon source is SiO2The titanium source is calculated as TiO2And (6) counting.
According to the present disclosure, the temperature of the second hydrolysis in step c is preferably 55-90 ℃ and the time is preferably 5-40 hours. Both mixing and the second hydrolysis may be carried out under stirring in order to obtain the desired effect.
According to the present disclosure, in step d, the temperature of the second hydrothermal treatment is preferably 110-. The pressure of the second hydrothermal treatment is not particularly limited, and may be the autogenous pressure of the reaction system.
In a specific embodiment, step d may further include: collecting the second solid product, and then drying and roasting; the drying temperature can be 100-200 ℃, and the drying time can be 1-24 hours; the temperature for calcination can be 350-650 deg.C, and the time can be 1-6 hours. Preferably, the second solid product may be filtered, washed (optionally) and then dried and calcined. The filtration method is not particularly limited, for example, a suction filtration method can be adopted, and a washing method is not particularly limited, for example, mixed washing or rinsing can be carried out at room temperature to 50 ℃ by using water, and the water amount can be 1-20 times of the mass of the solid product.
According to the disclosure, TiO in the mixture of step d2And SiO2May be 1: (10-200), preferably, TiO2And SiO2In a molar ratio of 1: (20-100).
According to the present disclosure, the temperature rising manner in any of the above steps is not particularly limited, and a temperature rising program manner, such as 0.5-1 ℃/min, may be adopted.
In a third aspect of the disclosure, a core-shell structure titanium-silicon material prepared by the method provided in the second aspect of the disclosure is provided.
The fourth aspect of the present disclosure provides a catalyst containing the core-shell structure titanium-silicon material provided in the first aspect of the present disclosure or the third aspect of the present disclosure.
In a fifth aspect of the present disclosure, there is provided a process for the oxidation of a macromolecular olefin to produce an epoxide using the catalyst provided in the fourth aspect of the present disclosure.
In one embodiment, the macromolecular olefin may be cyclohexene, cyclooctene, styrene or limonene.
The present disclosure is further illustrated by the following examples, but is not to be construed as being limited thereby.
In the examples and comparative examples, the surface titanium-silicon ratio and bulk titanium-silicon ratio of the titanium-silicon molecular sieve were measured by transmission electron microscopy-energy dispersive X-ray spectroscopy (TEM-EDX) (the photographs are shown in fig. 2). Firstly, dispersing a sample by using ethanol, ensuring that crystal grains are not overlapped and loaded on a copper net. The sample amount is reduced as much as possible during dispersion so that the particles are not superposed together, then the appearance of the sample is observed through a Transmission Electron Microscope (TEM), single isolated particles are randomly selected in a field of view and made into a straight line along the diameter direction of the particles, 6 measuring points with the sequence of 1,2, 3, 4, 5 and 6 are uniformly selected from one end to the other end, the energy spectrum analysis microcosmic composition is sequentially carried out, and the SiO is respectively measured2Content and TiO2Content of TiO calculated from the above2With SiO2The molar ratio of (a) to (b). Target TiO of titanium silicalite molecular sieve edge2With SiO2Molar ratio (TiO at 1 st measuring point and 6 th measuring point)2With SiO2Average value of molar ratio) is surface titanium-silicon ratio, and target point TiO of titanium-silicon molecular sieve center2With SiO2Molar ratio (TiO at measurement points 3 and 42With SiO2The average value of the mole ratio) is the bulk titanium-silicon ratio.
The grain size (minor axis direction) of the titanium-silicon molecular sieve is measured by a TEM-EDX method, a TEM electron microscope experiment is carried out on a Tecnai F20G2S-TWIN type transmission electron microscope of FEI company, an energy filtering system GIF2001 of Gatan company is provided, and an X-ray energy spectrometer is provided as an accessory. The electron microscope sample is prepared on a micro-grid with the diameter of 3mm by adopting a suspension dispersion method.
The BET specific surface area, pore volume and adsorption amount were measured by a nitrogen adsorption capacity method according to the BJH calculation method (see petrochemical analysis method (RIPP test method), RIPP151-90, scientific Press, 1990).
The raw materials used in the examples and comparative examples had the following properties:
tetrapropylammonium hydroxide, 20% strength by weight aqueous solution, available from Guangdong chemical plant.
Tetraethyl silicate, analytically pure, chemical reagents of the national pharmaceutical group, ltd.
Ammonia, analytically pure, 25% strength by weight aqueous solution.
Hydrogen peroxide, analytically pure, aqueous solution with concentration of 30 wt%.
The other reagents are not further explained, are all commercial products and are analytically pure.
Example 1
The titanium silicalite molecular sieve, labeled RTTS-1, is prepared as follows:
a. first Structure directing agent A (C)22-6-6-1-1-1-1OH2) Tetraethyl orthosilicate (TEOS), and deionized water, according to the ratio of directing agent a: TEOS: h2O ═ 0.3: 1: weighing raw materials according to the molar ratio of 800, sequentially adding the raw materials into a beaker, and putting the beaker with the heating and stirring functionsThe mixture is uniformly mixed on the magnetic stirrer, stirred for 3 hours at the temperature of 80 ℃, and evaporated water is supplemented at any time to obtain colorless transparent hydrolysate, namely a first hydrolysis mixture.
b. And transferring the first hydrolysis mixture into a stainless steel closed reaction kettle, crystallizing at the constant temperature of 170 ℃ for 15 days, filtering a crystallized product, washing with deionized water for 10 times, wherein the water consumption is 10 times of the weight of the molecular sieve each time, placing a filter cake at 110 ℃ for drying for 24 hours, and then placing at 550 ℃ for roasting for 6 hours to obtain an intermediate all-silicon molecular sieve, which is marked as HS-1.
c. 25 wt% aqueous tetrapropylammonium hydroxide (TPAOH), tetraethyl orthosilicate (TEOS), tetrabutyl titanate (TBOT) and deionized water were mixed according to TPAOH: TEOS: TBOT: h2O ═ 2.8: 15: 1: weighing raw materials according to the molar ratio of 600, sequentially adding the raw materials into a beaker, putting the beaker into a magnetic stirrer with heating and stirring functions, uniformly mixing the raw materials, stirring the mixture for 10 hours at 70 ℃ for second hydrolysis, and supplementing evaporated water at any time to obtain colorless transparent hydrolysate, namely a second hydrolysis mixture.
d. Mixing the intermediate full-silicon molecular sieve HS-1, the second hydrolysis mixture and ammonium chloride to obtain a mixed material, wherein TiO in the mixed material2And SiO2In a molar ratio of 1: 35. and (3) transferring the mixed material into a stainless steel reaction kettle, carrying out second hydrothermal treatment at 170 ℃ for 24 hours, filtering, washing, drying at 120 ℃ for 24 hours, and roasting at 550 ℃ for 6 hours to obtain the titanium silicalite molecular sieve, which is recorded as RTTS-1 and prepared in the embodiment.
Wherein the structural formula of the first structure directing agent A is C22-6-6-1-1-1-1OH2. The first structure directing agent A is prepared by adopting the following method: 1-bromodocosane (7.8g) and N, N, N ', N' -tetramethyl-1, 6-hexanediamine (34.4g) were dissolved in a volume ratio of 1:1 acetonitrile-toluene mixed solution (200 ml); the solution was then heated to 70 ℃ and held for 10 hours for reaction. After the reaction is finished, cooling to room temperature, filtering and separating the product, and washing a filter cake with diethyl ether; the filter cake was taken out and dried in a vacuum oven at 50 ℃. 24.6g of the dried solid and 1-bromohexane (24.6g) were dissolved together in acetonitrile (300 ml); heating and refluxing the acetonitrile solutionThe reaction time is 10 hours; after the reaction is finished, cooling to room temperature, filtering and separating the product, and washing a filter cake with diethyl ether; the filter cake was taken out and dried in a vacuum oven at 50 ℃. Dissolving the dried solid in water to obtain an aqueous solution, and performing ion exchange by using strongly basic anion exchange resin to obtain the compound C22-6-6-1-1-1-1OH2An aqueous solution.
The TEM electron micrograph of the titanium silicalite RTTS-1 is shown in FIG. 1, and the TEM-EDX electron micrograph of the RTTS-1 is shown in FIG. 2. The parameters of the titanium silicalite molecular sieve such as the mesopore diameter, the surface titanium-silicon ratio, the bulk titanium-silicon ratio and the like are shown in Table 5.
Examples 2 to 16
Titanium silicalite molecular sieves, labeled RTTS-2 to RTTS-16, were prepared according to the procedure of example 1 and the raw material ratios and synthesis conditions in tables 1 to 4, respectively. The pore size, surface titanium to silicon ratio, and bulk titanium to silicon ratio are shown in Table 5.
Comparative example 1
This comparative example illustrates the preparation of a conventional TS-1 molecular sieve according to the prior art (Zeolite, 1992, Vol.12, pp. 943 to 950).
41.6g tetraethyl orthosilicate was mixed with 24.4g aqueous tetrapropylammonium hydroxide (25.05 wt%), 95.2g deionized water was added and mixed uniformly; then hydrolyzing for 1.0h at 60 ℃ to obtain a hydrolysis solution of tetraethyl silicate. Under the action of vigorous stirring, a solution consisting of 2.0g of tetrabutyl titanate and 10.0g of isopropanol is slowly dropped into the solution, and the mixture is stirred for 3 hours at 75 ℃ to obtain a clear and transparent colloid. And then the colloid is moved into a stainless steel closed reaction kettle, and is crystallized for 3 days at the constant temperature of 170 ℃, so that a conventional TS-1 molecular sieve sample, which is marked as CTS-1, can be obtained.
Comparative example 2
This comparative example illustrates a method of preparing titanium silicalite molecular sieves according to the prior art treatment with a silylating agent (chem. Commun., 2009,11: 1407-.
Under the condition of stirring, mixing ethyl orthosilicate, tetrapropylammonium hydroxide, tetrabutyl titanate and deionized water to obtain SiO in molar ratio2: structure directing agent: TiO 22：H2O is 1: 0.2: 0.025: 50 of a homogeneous mixture; pre-crystallizing at 90 deg.C for 24 hr, and mixing with SiO2: silylation reagent ═ 1: 0.12, adding N-phenyl-triaminopropyltrimethoxysilane into the titanium silicalite molecular sieve precursor gel obtained by pre-crystallization, uniformly stirring, and transferring the obtained titanium silicalite molecular sieve precursor into a pressure-resistant stainless steel reaction kettle; heating to 170 ℃ under stirring and crystallizing for 8h under autogenous pressure. And after the stainless steel pressure-resistant reaction kettle is cooled to room temperature, recovering the obtained titanium silicalite molecular sieve which is not roasted, drying the titanium silicalite molecular sieve at 110 ℃ for 6 hours, and roasting the titanium silicalite molecular sieve at 550 ℃ for 4 hours to obtain the hierarchical pore titanium silicalite molecular sieve which is prepared by silanization and marked as CTS-2.
Comparative example 3
This comparative example illustrates a process for preparing an all-silicon molecular sieve according to the prior art.
23.1g of tetraethyl silicate was mixed with 22.1g of an aqueous tetrapropyl ammonium hydroxide solution (concentration: 25% by weight), and 7.2g of deionized water was added and mixed uniformly; the mixture was then stirred at 75 ℃ for 6 hours with vigorous stirring to give a clear and transparent colloid. Then the colloid is transferred into a stainless steel closed reaction kettle and crystallized for 3 days at the constant temperature of 170 ℃; the obtained sample is filtered, washed, dried at 110 ℃ and roasted at 550 ℃ to obtain the all-silicon S-1 molecular sieve which is marked as CTS-3.
Comparative example 4
This comparative example illustrates the process for preparing a titanium silicalite molecular sieve according to example 1, except that the all-silica molecular sieve used in step d is the all-silica molecular sieve CTS-3 prepared in comparative example 3, and the resulting multi-stage pore titanium silicalite molecular sieve is designated CTS-4.
TABLE 1
Figure BDA0002256330580000151
TABLE 2
Figure BDA0002256330580000161
TABLE 3
Figure BDA0002256330580000162
Figure BDA0002256330580000171
TABLE 4
Figure BDA0002256330580000172
TABLE 5
Figure BDA0002256330580000173
Figure BDA0002256330580000181
Test example
This test example demonstrates the catalytic effect of the samples CSTS-1 to CSTS-16 obtained in examples 1 to 16 of the present invention and the molecular sieve samples CTS-1 to CTS-4 obtained by the method of comparative example, for the epoxidation reaction of limonene.
The epoxidation reaction of limonene is carried out in a three-mouth bottle reaction device with an automatic temperature control water bath, magnetic stirring and condensation reflux system. And (3) respectively adding the samples obtained in the above embodiments and the molecular sieve samples obtained by the method of the comparative example into a three-neck flask according to 1g of molecular sieve catalyst, 0.1moL of limonene and 0.1moL of hydrogen peroxide in sequence, placing the three-neck flask into a water bath kettle with the preset reaction temperature, reacting at 60 ℃ for 2 hours, and cooling to stop the reaction after the reaction is finished. The product was sampled and the composition of the product was determined on an Agilent 6890N chromatograph using HP-5 capillary column and quantified by the calibrated normalization method, the results of which are shown in Table 6.
The conversion rate of limonene and the selectivity of 1, 2-epoxy product are respectively calculated according to the following formulas:
limonene conversion ═ M [ ("M0－MCN)/M0]×100％
1, 2-epoxide product selectivity ═ MCNOX/(M0－MCN)]×100％
Wherein the mass of the initial limonene is designated M0The mass of unreacted limonene is denoted as MCNThe mass of the 1, 2-epoxy product is designated MCNOX。
TABLE 6
Figure BDA0002256330580000182
Figure BDA0002256330580000191
As can be seen from table 6, the titanium silicalite molecular sieve disclosed by the present disclosure has high catalytic activity, and is beneficial to improving the raw material conversion rate and the target product selectivity when being used in the process of producing an epoxy compound by a macromolecular olefin oxidation reaction.
The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.
It should be noted that, in the foregoing embodiments, various features described in the above embodiments may be combined in any suitable manner, and in order to avoid unnecessary repetition, various combinations that are possible in the present disclosure are not described again.
In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims (24)

1. The core-shell structure titanium-silicon material is characterized by comprising a core and a shell, wherein the core is made of titanium-silicon alloyThe inner core is an all-silicon molecular sieve with an in-crystal multi-hollow structure, the outer shell is a titanium-silicon molecular sieve, and the TiO of the titanium-silicon material with the core-shell structure is calculated by oxides and calculated by mol2With SiO2In a molar ratio of 1: (30-100); the ratio of the surface titanium-silicon ratio of the core-shell structure titanium-silicon material to the bulk titanium-silicon ratio is 2.0-4.4, wherein the titanium-silicon ratio refers to TiO2With SiO2The molar ratio of (A) to (B); the most probable pore diameter of the mesoporous titanium-silicon material with the core-shell structure is 14-34 nm;
wherein the surface titanium silicon ratio refers to TiO of an atomic layer which is not more than 5nm away from the surface of the crystal grain of the titanium silicon molecular sieve2With SiO2In a molar ratio of (a).
2. The core-shell structure titanium-silicon material according to claim 1, wherein the mesoporous and mode-able pore diameter of the core-shell structure titanium-silicon material is 16-32 nm.
3. The core-shell structure titanium-silicon material as claimed in claim 1, wherein the titanium-silicon molecular sieve has a BET total specific surface area of 415-645m2The volume ratio of the mesoporous volume to the total pore volume is 40-70%.
4. The method for preparing the core-shell structure titanium-silicon material of any one of claims 1 to 3, which is characterized by comprising the following steps:
a. mixing a first structure directing agent, a first silicon source and water, and performing first hydrolysis at 40-97 ℃ for 2-50 hours to obtain a first hydrolysis mixture;
b. carrying out first hydrothermal treatment on the first hydrolysis mixture for 1-720 hours at 90-200 ℃ in a pressure-resistant closed container, and collecting a first solid product;
c. mixing the second structure directing agent, a second silicon source, a titanium source and water, and performing second hydrolysis at 35-95 ℃ for 3-60 hours to obtain a second hydrolysis mixture;
d. mixing the first solid product and the second hydrolysis mixture to obtain a mixed material, carrying out second hydrothermal treatment on the mixed material in a pressure-resistant closed container at 90-200 ℃ for 1-170h, and collecting a second solid product;
wherein the first structure directing agent is a double-head organic quaternary ammonium salt compound, or a mixture of the double-head organic quaternary ammonium salt compound and organic amine; the second structure directing agent is a single-head quaternary ammonium base compound or a mixture of the single-head quaternary ammonium base compound and organic amine.
5. The method of claim 4, wherein in step a, the double-headed organic quaternary ammonium base compound and the double-headed organic quaternary ammonium salt compound each have the following structure:
Figure FDA0003404363810000021
wherein R is1Is C3-C30 chain normal alkyl, R2Is a chain normal alkylene of C1-C10, R3Is C1-C15 chain normal alkyl, R4、R5、R6And R7Each independently being methyl, ethyl or propyl, X is OH-、F-、Cl-Or Br-。
6. The method of claim 5, wherein R1Is C9-C23 chain normal alkyl, R2Is a chain normal alkylene of C6-C8, R3Is C1-C7 chain normal alkyl, R4、R5、R6And R7Each independently being methyl or ethyl, X is OH-Or Br-。
7. The method as claimed in claim 4, wherein, in step c, the single-headed quaternary ammonium base compound has the formula (R)9)3NOH，R9Is C1-C4 alkyl;
the molecular formula of the single-head quaternary ammonium salt compound is (R)10)3NX，R10Is C1-C4 alkyl, X is F-、Cl-Or Br-。
8. The method of claim 4, wherein the organic amine is an aliphatic amine compound, an alcohol amine compound, or an aromatic amine compound, or a combination of two or three thereof.
9. The method of claim 8, wherein the fatty amine compound is ethylamine, n-butylamine, butanediamine, or hexanediamine, or a combination of two or three thereof;
the alcohol amine compound is monoethanolamine, diethanolamine or triethanolamine, or a combination of two or three of the monoethanolamine, diethanolamine and triethanolamine;
the aromatic amine compound is aniline, toluidine or p-phenylenediamine, or a combination of two or three of them.
10. The method of claim 4, wherein in step a, the molar ratio of the amounts of the first structure directing agent, the first silicon source and water is (0.01-1): 1: (50-4000), wherein the first silicon source is SiO2And (6) counting.
11. The method of claim 10, wherein the molar ratio of the amounts of the first structure directing agent, the first silicon source, and water is (0.06-0.5): 1: (200-2000).
12. The method of claim 4, wherein the first and second silicon sources are each an organosilicate;
the titanium source is inorganic titanium salt and/or organic titanate.
13. The method of claim 12, wherein the first and second silicon sources are each independently tetramethyl orthosilicate, tetraethyl orthosilicate, tetrapropyl orthosilicate, tetrabutyl orthosilicate, or dimethoxydiethoxysilane, or a combination of two or three thereof.
14. The process of claim 4, wherein in step a, the temperature of the first hydrolysis is 65-95 ℃ for 3-35 hours; and/or the like and/or,
in the step b, the temperature of the first hydrothermal treatment is 120-.
15. The method of claim 4, wherein in step c, the second structure directing agent, the second silicon source, the titanium source and water are used in a molar ratio of (1.5-5): (10-100): 1: (400-1000), the second silicon source is SiO2The titanium source is calculated as TiO2And (6) counting.
16. The process according to claim 4, wherein in step c, the temperature of the second hydrolysis is 55-90 ℃ for 5-40 hours.
17. The method as claimed in claim 4, wherein the temperature of the second hydrothermal treatment in step d is 110-180 ℃ for 5-120 hours.
18. The method of claim 4, wherein the TiO in the mixed material2And SiO2In a molar ratio of 1: (10-200).
19. The method of claim 18, wherein the TiO in the mixed material2And SiO2In a molar ratio of 1: (20-100).
20. The method of claim 4, wherein step d further comprises: collecting the second solid product, and then drying and roasting; the drying temperature is 100-200 ℃, and the drying time is 1-24 hours; the roasting temperature is 350-650 ℃, and the roasting time is 1-6 hours.
21. Core-shell titanium-silicon material prepared by the method of any one of claims 4 to 20.
22. A catalyst comprising the core-shell titanium silicalite material of any one of claims 1 to 3 and 21.
23. A process for the oxidation of a large olefin to produce an epoxy compound, which process uses the catalyst of claim 22.
24. A process according to claim 23, wherein the macromolecular alkene is cyclohexene, cyclooctene, styrene or limonene.
CN201911063296.0A 2019-10-31 2019-10-31 Core-shell structure titanium-silicon material, preparation method thereof and method for producing epoxy compound through oxidation reaction of macromolecular olefin Active CN112742471B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201911063296.0A CN112742471B (en) 2019-10-31 2019-10-31 Core-shell structure titanium-silicon material, preparation method thereof and method for producing epoxy compound through oxidation reaction of macromolecular olefin

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201911063296.0A CN112742471B (en) 2019-10-31 2019-10-31 Core-shell structure titanium-silicon material, preparation method thereof and method for producing epoxy compound through oxidation reaction of macromolecular olefin

Publications (2)

Publication Number Publication Date
CN112742471A CN112742471A (en) 2021-05-04
CN112742471B true CN112742471B (en) 2022-03-11

Family

ID=75645761

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201911063296.0A Active CN112742471B (en) 2019-10-31 2019-10-31 Core-shell structure titanium-silicon material, preparation method thereof and method for producing epoxy compound through oxidation reaction of macromolecular olefin

Country Status (1)

Country Link
CN (1) CN112742471B (en)

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1256122A (en) * 1984-05-02 1989-06-20 Eduard P. Kieffer Process for the preparation of an aromatic hydrocarbon mixture
CN104556087B (en) * 2013-10-29 2017-11-28 中国石油化工股份有限公司 A kind of silica zeolite and its synthetic method
CN104556085B (en) * 2013-10-29 2017-01-04 中国石油化工股份有限公司 A kind of method synthesizing the micro-mesoporous composite material of total silicon
CN104495867B (en) * 2014-11-28 2017-10-20 巨化集团技术中心 The preparation method of big particle diameter HTS
CN107840348A (en) * 2016-09-21 2018-03-27 中国石油化工股份有限公司 The preparation method and mesopore molecular sieve and catalyst of a kind of mesopore molecular sieve
CN107879357B (en) * 2016-09-30 2019-11-15 中国石油化工股份有限公司 The method of a kind of HTS and its synthetic method and application and a kind of oxidation of cyclic ketones
CN107915234B (en) * 2017-11-09 2020-10-16 华东师范大学 Preparation method of hierarchical porous TS-1 nano zeolite aggregate molecular sieve

Also Published As

Publication number Publication date
CN112742471A (en) 2021-05-04

Similar Documents

Publication Publication Date Title
JP4897321B2 (en) Titanium silicalite molecular sieve and method for producing the same
US6710193B2 (en) Process for preparing crystalline microporous and mesoporous metal silicates, products obtainable by said process and their use
CN106032277B (en) Titanium Si-Al molecular sieve and its preparation method and application and a kind of method of cyclic ketones oxidation
CN108726528B (en) Hierarchical pore titanium silicalite molecular sieve, preparation method thereof and olefin epoxidation method
CN106032283B (en) Tin Titanium Sieve Molecular Sieve and its preparation method and application and a kind of method of cyclic ketones oxidation
JP4270901B2 (en) Titanosilicate, method for producing the same, and method for producing an oxidized compound using titanosilicate
WO2008119252A1 (en) A noble metal-containing ti-si material and the preparing method thereof
CN106145149A (en) A kind of method preparing multi-stage porous HTS
CN103896302B (en) A kind of si molecular sieves and preparation method thereof
CN106145151A (en) A kind of multi-stage porous HTS and synthetic method thereof
CN112007690B (en) Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime by macromolecular ketone ammoximation reaction
CN112744836B (en) Titanium-silicon molecular sieve, preparation method thereof and method for producing ketoxime by ammoximation reaction of macromolecular ketone
CN112744837B (en) Titanium-silicon molecular sieve, preparation method thereof and method for producing epoxy compound through oxidation reaction of macromolecular olefin
CN112742470B (en) Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime through macromolecular ketone ammoximation reaction
CN112742471B (en) Core-shell structure titanium-silicon material, preparation method thereof and method for producing epoxy compound through oxidation reaction of macromolecular olefin
CN112744838B (en) Titanium-silicon molecular sieve, preparation method thereof and method for producing ketoxime by macromolecular ketone ammoximation reaction
CN112744825B (en) Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime through macromolecular ketone ammoximation reaction
CN112239212A (en) Silicon molecular sieve with MFI topological structure and preparation method and application thereof
CN112010321B (en) Titanium-silicon molecular sieve, preparation method thereof and method for producing ketoxime by macromolecular ketone ammoximation reaction
CN112742469B (en) Core-shell structure titanium-silicon material, preparation method thereof and method for producing ketoxime through macromolecular ketone ammoximation reaction
CN107879355B (en) Modified with noble metals Titanium Sieve Molecular Sieve and its preparation method and application and a kind of method of alkene direct oxidation
CN111348657B (en) Ultrasonic-assisted titanium silicalite molecular sieve modification method
CN106032279B (en) Si-Al molecular sieve and its preparation method and application and a kind of method of cyclic ketones conversion
CN104557632A (en) Method for preparing dimethyl sulfoxide
JPH10316417A (en) Production of titanium-containing beta-zeolite

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant