CN110961090A - Titanium-silicon composite oxide, preparation method and application thereof - Google Patents

Titanium-silicon composite oxide, preparation method and application thereof Download PDF

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CN110961090A
CN110961090A CN201811135672.8A CN201811135672A CN110961090A CN 110961090 A CN110961090 A CN 110961090A CN 201811135672 A CN201811135672 A CN 201811135672A CN 110961090 A CN110961090 A CN 110961090A
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titanium
composite oxide
silicon composite
silicon
product
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CN110961090B (en
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彭欣欣
林民
夏长久
张进
史延强
朱斌
罗一斌
舒兴田
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
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    • 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
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    • 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
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    • 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
    • B01J35/638—Pore volume more than 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
    • 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
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    • B01J35/69—Pore distribution bimodal
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    • 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
    • C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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    • 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
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    • 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
    • C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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    • 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
    • C07D303/38—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals
    • C07D303/40—Compounds containing oxirane rings with hydrocarbon radicals, substituted by carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals by ester radicals
    • C07D303/42—Acyclic compounds having a chain of seven or more carbon atoms, e.g. epoxidised fats
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    • Y02P20/00—Technologies relating to chemical industry
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Abstract

The invention discloses a titanium-silicon composite oxide which is characterized in that the titanium-silicon composite oxide is an amorphous structure, is formed by aggregating nano particles, has mesopores in the range of 16-50nm, and has the ratio of the volume of the mesopores to the total pore volume of not less than 80 percent and the volume of the mesopores of not less than 0.5cm3(ii) in terms of/g. The material has the advantages of high reaction efficiency and low cost in the olefin epoxidation reaction by taking organic peroxide as oxidationGood catalytic performance.

Description

Titanium-silicon composite oxide, preparation method and application thereof
Technical Field
The invention relates to a titanium-silicon composite oxide material containing silicon and titanium elements, a preparation method and application thereof in catalytic oxidation reaction, in particular to olefin epoxidation reaction, and relates to the field of preparation of inorganic catalytic materials and catalytic oxidation reaction.
Background
Epoxy compounds are important organic chemicals, and due to the fact that active cyclic ether bonds are arranged in molecules, the epoxy compounds are easily attacked by nucleophilic reagents such as water, alcohol, amine and halogen ions to generate ring opening reaction under acidic and alkaline conditions, and then polyhydric alcohol, alcohol ether, alcohol amine, halogenated alcohol, long-chain alcohol and the like are generated.
The earliest production of epoxy compounds by a chlorohydrin method, and as early as 1925, united states carbide company established an industrial device for producing ethylene oxide by the chlorohydrin method. Then, some companies have developed industrial production methods for producing propylene oxide, epichlorohydrin, and the like by a chlorohydrin method. However, the chlorohydrin process has serious environmental problems, and the production of the chlorohydrin process cannot meet the increasing environmental protection requirements of people. Thus, for the production of ethylene oxide, silver-catalyzed air/oxygen oxidation processes have long been developed, which are cleaner than the chlorohydrin process, but suffer from the side reaction of direct oxidation of ethylene to carbon dioxide, and have lower raw material utilization. Moreover, the method cannot be extended to the production of other epoxy compounds such as propylene oxide, epichlorohydrin and the like for a long time. The chlorohydrin process is still used as one of the main production processes for producing epoxy compounds such as propylene oxide and epichlorohydrin.
In order to solve the environmental problems of the chlorohydrin process, the co-oxidation process and the HPPO process have been successively developed for the production of propylene oxide. The HPPO method uses a titanium silicalite molecular sieve to catalyze propylene to react with hydrogen peroxide to generate propylene oxide, and simultaneously the hydrogen peroxide is converted into water. The reaction atom has high economy, the reaction process is green and efficient, but the preparation of the high-performance titanium-silicon molecular sieve is difficult, so the application of the titanium-silicon molecular sieve is limited. The co-oxidation process was first disclosed and successfully developed by ARCO, using isobutane as the oxygen carrier, generating tert-butyl hydroperoxide by air oxidation, and then reacting with propylene to generate propylene oxide and tert-butanol under the action of a catalyst. The method does not produce a large amount of waste water and waste residue, and is obviously improved in the aspect of environmental protection compared with a chlorohydrin method. Depending on the carrier used, isobutane co-oxidation, ethylbenzene co-oxidation, cumene co-oxidation, and the like can be classified.
The catalyst for the co-oxidation process can be divided into molybdenum-containing catalyst and titanium-containing catalyst, wherein the molybdenum-containing catalyst is mainly a homogeneous catalyst, and the titanium-containing catalyst is mainly a heterogeneous catalyst. Homogeneous catalysts, due to their well-known recovery difficulties, make the process more complicated for industrial applications. Therefore, in recent years, titanium-containing heterogeneous catalysts have been used and studied relatively more. For example, the Shell company uses silica supported on titanium as the epoxidation catalyst, while the Sumitomo company uses titanium silica as the epoxidation catalyst.
The titanium-containing catalyst has good catalytic activity when being used as an olefin epoxidation catalyst.
CN106334583A discloses a method for preparing titanium-containing catalyst supported on silica carrier by using organosilane reagent, the prepared catalyst can catalyze olefin and organic peroxide to convert efficiently, but the prepared catalyst precursor needs low-temperature plasma treatment and decomposition, and the preparation process is complex.
CN103212437A discloses a method for preparing a titanium-based catalyst from an alkaline solution of hexadecyl trimethyl ammonium bromide, tetrabutyl titanate and tetraethyl silicate, and then treating the titanium-based catalyst with a toluene solution of trichlorosilane to obtain a molecular sieve catalyst. The method can be used only after silanization treatment, the preparation process is complex, and the silanization treatment cost is high.
CN104437450A discloses a titanium-containing silicon dioxide crystal catalyst, which contains titanium and silicon elements, wherein part of the silicon elements are also connected with C1-12 alkyl, alkenyl and aryl, the preparation method of the catalyst needs to use a silanization reagent for coupling, and the problems of complex preparation process and higher silanization treatment cost exist.
CN103357432A discloses a preparation method of a mesoporous nano titanium silicalite TS-1, the method needs to use a micropore template and a mesoporous template, the aperture of the obtained molecular sieve is less than 6nm, certain application limitation is realized, and the cost of the template is higher.
Therefore, the titanium-containing catalyst for preparing the epoxy compound by oxidizing the olefin by using the organic peroxide as the oxidant in the prior art has the problems of complex preparation process, higher cost, smaller pore channel size and the like.
Disclosure of Invention
The inventor finds that compared with a crystalline titanium-silicon catalyst, a bulk amorphous structure is more beneficial to forming a titanium-silicon composite oxide which is rich in mesopores and adjustable in pore size, and has better catalytic performance in an olefin epoxidation reaction in which organic peroxide is used as oxidation. Based on this, the present invention was made.
The invention aims to provide a titanium-silicon composite oxide material with rich mesopores.
The second purpose of the invention is to provide a preparation method of the titanium-silicon composite oxide material with rich mesopores.
The invention also aims to provide the application of the titanium-silicon composite oxide material in catalytic oxidation reaction, in particular to the application in catalyzing olefin epoxidation reaction by using organic peroxide as an oxidant.
In order to achieve one of the above objects, the present invention provides a titanium silicon composite material, wherein the titanium silicon composite oxide is an amorphous structure, is formed by aggregating nanoparticles, has mesopores in a range of 16 to 50nm, and has a ratio of a mesopore volume to a total pore volume of not less than 80%, and a mesopore volume of not less than 0.5cm3/g。
In order to achieve the second object, the present invention provides a method for preparing a titanium-silicon composite oxide material, comprising the steps of:
(1) mixing optional silicon source, titanium source, alkali source and water, and treating at 5-90 ℃ for 0.5-24h to obtain a mixture with a molar composition of SiO2, TiO2, alkali source and water of 1: (0.001-0.2): (0.05-0.2): (10-100) the first product;
(2) according to TiO2 halogen ions (according to X)-X is halogen) in a molar ratio of 1: (0.5-3) adding a halogen ion compound to obtain a second product;
(3) treating the second product at the temperature of 100-150 ℃ for 1-72h to obtain gel;
(4) recovering the solid product to obtain the titanium-silicon composite oxide.
In order to achieve the third purpose, the invention provides the application of the titanium-silicon composite oxide material in catalytic oxidation reaction; preferably, the present invention provides the use of the titanium silicon composite described above in a process for the epoxidation of an olefin, which process comprises: in the epoxidation of olefin, the olefin is contacted with an organic peroxide in the presence of a catalyst, wherein the catalyst comprises the titanium-silicon composite oxide material
Compared with the prior art, the titanium-silicon composite oxide material has nano-scale particles and rich mesopores; the preparation method is simple, does not use expensive raw materials and has lower cost. Compared with a crystalline titanium-silicon catalyst, the titanium-silicon composite oxide material disclosed by the invention has the advantages that the bulk amorphous structure is more favorable for forming the titanium-silicon composite oxide which is rich in mesopores and adjustable in pore size, and the titanium-silicon composite oxide material has better catalytic performance in an olefin epoxidation reaction taking organic peroxide as oxidation.
Drawings
FIG. 1 is an XRD spectrum of a titanium silicon composite oxide prepared in example 1;
FIG. 2 is a pore distribution diagram of the titanium silicon composite oxide prepared in example 1;
FIG. 3 is a UV-Vis spectrum of the titanium silicon composite oxide prepared in example 1;
fig. 4 is an SEM image of the titanium silicon composite oxide prepared in example 1.
Detailed Description
The invention provides a titanium-silicon composite material which is characterized in that the titanium-silicon composite oxide is in an amorphous structure, is formed by aggregating nano particles, has mesopores in the range of 16-50nm, and has the ratio of the volume of the mesopores to the total pore volume of not less than 80 percent and the volume of the mesopores of not less than 0.5cm3/g。
The amorphous structure of the titanium-silicon composite material is obtained by means of XRD or electron diffraction analysis, and the measurement by XRD is preferred.
The titanium-silicon composite material contains silicon element, titanium element and oxygen element, wherein the silicon element, the titanium element and the oxygen element account for more than 95 percent of the weight of the titanium-silicon composite oxide under the anhydrous drying condition. Titanium is the main catalytic active center of the titanium-silicon composite oxide, and the mass percentage of the titanium element calculated by titanium dioxide is not less than 0.1%, preferably not less than 1%, not less than 2%, not less than 4%, preferably not more than 15%.
The titanium-silicon composite material is formed by aggregating nano particles, wherein the particle size of the nano particles is larger than 5nm, preferably larger than 8nm, and not larger than 40nm, preferably not larger than 30nm, and more preferably not larger than 20 nm.
The specific surface area of the titanium-silicon composite oxide is 200-550m2Per g, preferably 240-400m2Per g, more preferably 260-330m2(ii) in terms of/g. The volume of the mesoporous is more than or equal to 0.5cm3In g, preferably ≥ 0.8cm3G, more preferably 1.0cm or more3G, most preferably 1.1cm or more3/g。
The titanium-silicon composite material has 16-50nm mesopores, further 24-48nm mesopores and further 30-42nm mesopores, the titanium-silicon composite oxide has a very small amount of microporous structures and is mainly mesoporous, and the ratio of the mesopore volume (2-50nm measured by a BET method) to the total pore volume is more than or equal to 80%, preferably more than or equal to 90%, more preferably more than or equal to 93% and most preferably more than or equal to 95%.
The titanium-silicon composite oxide has L acidity, and in pyridine-infrared characterization, the titanium-silicon composite oxide is 1450 +/-5 cm-1Has a first absorption peak at 1612 +/-5 cm-1Has a second absorption peak, and the ratio of the intensity of the first absorption peak to the intensity of the second absorption peak is at least 1.5 and at most 6, preferably 2 to 5, more preferably 2.5 to 4.
The titanium-silicon composite material has wide strong absorption within the range of 200-250nm and weak absorption above 300nm by the characterization of UV-Vis. The strong absorption at 200-250nm indicates that the titanium is mainly present in the four-coordinate state (high catalytic activity), while the weak absorption above 300nm indicates that the anatase titanium species (low catalytic activity) is low in content.
In order to obtain the titanium-silicon composite oxide catalytic material with the characteristics of the invention, the invention also provides a preparation method, which is characterized by comprising the following steps:
(1) mixing optional silicon source, titanium source, alkali source and water, and treating at 5-90 deg.C for 0.5-24 hr to obtain SiO2:TiO2The alkali source comprises 1: (0.001-0.2): (0.05-0.2): (10-100) the first product;
(2) according to TiO aspect2Halogen ion (according to X)-X is halogen) in a molar ratio of 1: (0.5-3) adding a halogen ion compound to obtain a second product;
(3) treating the second product at the temperature of 100-150 ℃ for 1-72h to obtain gel;
(4) recovering the solid product to obtain the titanium-silicon composite oxide;
the silicon source in step (1) has no special requirement, and silicon content of more than 80%, 90%, 95% and 99% calculated by dry silicon dioxide of the silicon source can be used as the silicon source, preferably the silicon source is at least one of tetraalkoxysilicon, white carbon black, silica gel and silica sol, more preferably contains tetraalkoxysilicon, and most preferably contains at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.
There is no particular requirement for a titanium source, and a common titanium source known to those skilled in the art can be used as the titanium source of the present invention, and preferably, the titanium source is at least one selected from the group consisting of titanium tetraalkoxide, titanium tetrachloride, titanium trichloride, titanium sulfate, and titanium nitrate, more preferably, at least one selected from the group consisting of titanium tetraalkoxide, titanium tetrachloride, and most preferably, tetraethyl titanate, tetrapropyl titanate, and tetrabutyl titanate.
The alkali is not particularly required, preferably, the alkali source is at least one selected from the group consisting of aliphatic amines, aliphatic alcohol amines, quaternary ammonium bases and inorganic alkali compounds, the aliphatic amines and the aliphatic alcohol amines are preferably at least one having less than 10 carbon atoms, the inorganic alkali is preferably at least one selected from the group consisting of hydroxide compounds of main group I and/or main group II and ammonia water, more preferably at least one selected from the group consisting of aliphatic amines of C1-C5, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, sodium hydroxide and ammonia water, and most preferably, the alkali is tetraethylammonium hydroxide. .
The water is not particularly limited and may be deionized water, distilled water, redistilled water, industrial water, domestic water, and the water may have a conductivity of at most 3000 microsiemens/cm, at most 1000 microsiemens/cm, at most 500 microsiemens/cm, at most 100 microsiemens/cm, at most 10 microsiemens/cm, or at most 5 microsiemens/cm.
The raw material feeding sequence, the mixing mode, the mixing atmosphere and the mixing equipment in the step (1) have no special requirements, and from the viewpoint of simple and convenient operation, the raw materials can be mixed in a reaction kettle according to the feeding proportion and treated under the normal pressure in the air atmosphere. The treatment is preferably carried out at 20-60 ℃ for 4-18h, more preferably at 30-50 ℃ for 6-12 h. The composition of the first product after the treatment in the step (1) is preferably SiO2: TiO2: alkali source: water: 1: (0.01-0.17): (0.07-0.17): (25-90), more preferably SiO2: TiO2: alkali source: water ═ 1: (0.03-0.14): (0.09-0.15): (35-80), SiO2: TiO2: alkali source: water 1: (0.05-0.12): (0.10-0.14): (45-70), most preferred are SiO2: TiO2: alkali source: water ═ 1: (0.07-0.10): (0.12-0.13): (50-65).
The halogen ion compound in the step (2) is a salt containing halogen ions, preferably, a salt containing a group I element, an ammonium salt and a quaternary ammonium salt, more preferably at least one of a sodium salt, a potassium salt, an ammonium salt and a quaternary ammonium salt, and most preferably, the salt is at least one of a sodium salt and a quaternary ammonium salt; the halogenIons include fluorine, chlorine, bromine and iodine, and preferably, the halogen ions are chloride ions; more preferably, the halogen ion compound is at least one selected from the group consisting of sodium chloride, tetramethylammonium chloride, tetraethylammonium chloride, and cetyltrimethylammonium chloride, and most preferably tetraethylammonium chloride. The halogen ions are preferably added in an amount of TiO2 halogen ions (in terms of X)-X is halogen) in a molar ratio of 1: (0.8-2.5), more preferably 1: (1.2-2.2), and more preferably 1: (1.5-2.0), most preferably 1: (1.7-1.9).
According to the preparation method, the product after the treatment in the steps (1) and (2) is still liquid, and the product after the treatment in the step (3) is gelatinous solid; the treatment conditions in the step (3) are preferably treatment at 110-140 ℃ for 12-48h, more preferably treatment at 120-135 ℃ for 18-36h, and further preferably treatment at 125-130 ℃ for 24-30 h.
And (4) the step of recovering the solid product comprises the step of carrying out first drying and first roasting on the gel product obtained in the step (3). The first drying is preferably carried out at 60 to 130 ℃, more preferably 80 to 110 ℃, more preferably 90 to 100 ℃, for a treatment time of preferably 1 to 24 hours, preferably 6 to 18 hours, more preferably 8 to 12 hours, in air or inert gas, and may be carried out in a suitable drying oven or by spray drying. The first calcination is to treat the product at a temperature above 350 ℃, and the calcination of the invention generally comprises treating at a temperature of 400-700 ℃, preferably 450-600 ℃, under a suitable atmosphere (such as air, lean air, oxygen, nitrogen) for 1-10h, preferably 3-8h, more preferably 4-6 h.
And the step of recovering the solid product further comprises the steps of treating the product after the first roasting under a liquid phase condition, at least partially separating the solid product, and performing second drying and second roasting to obtain the titanium-silicon composite oxide material.
The liquid phase condition is ammonium salt-containing solution with the concentration of 0.1-5mol/L, preferably 0.5-3mol/L, more preferably 1-2mol/L, the ammonium salt is ammonium chloride, ammonium nitrate and ammonium carbonate, preferably ammonium nitrate, the pH value of the solution is 1-5, preferably 2-3, the pH value of the solution is measured by a pH meter, and the weight ratio of the first roasted product to the ammonium salt-containing solution is 1: (10-50), preferably 1: (20-40), more preferably 1: (25-30) the treatment temperature is 40-90 ℃, preferably 60-85 ℃, more preferably 70-80 ℃, and the treatment time is 1-18h, preferably 3-14h, more preferably 5-10h, most preferably 6-8 h.
The method for separating the solid product can be centrifugation, filtration, nanofiltration, membrane separation and the like, and the method has no special requirements.
The second drying is preferably carried out at 60 to 130 ℃, more preferably 80 to 110 ℃, more preferably 90 to 100 ℃, for a treatment time of preferably 1 to 24 hours, preferably 6 to 18 hours, more preferably 8 to 12 hours, in air or inert gas, either in a suitable drying oven or by spray drying. The second calcination is to treat the product at a temperature above 350 ℃, and the calcination of the invention generally comprises treating at a temperature of 400-700 ℃, preferably 450-600 ℃, under a suitable atmosphere (such as air, lean air, oxygen, nitrogen) for 1-10h, preferably 3-8h, more preferably 4-6 h.
The invention also provides application of the titanium-silicon composite oxide in catalytic oxidation reaction. Further, the invention provides an application of the titanium-silicon composite oxide in catalytic oxidation reaction, which is a method for olefin epoxidation, and the method comprises the following steps: the catalyst is a titanium-silicon composite oxide catalyst of the invention or a titanium-silicon composite oxide catalyst obtained by any one of the preparation methods of the invention.
In the catalytic oxidation reaction provided by the invention, the titanium-silicon composite oxide can be used in the form of raw powder, can also be used after being molded, and can be mixed with other oxidation catalysts for use; the titanium-silicon composite oxide can be used in various reactors such as a kettle reactor, a slurry bed reactor, a fixed bed reactor, a fluidized bed reactor, a moving bed reactor, a micro-channel reactor and the like; the reaction raw materials and the catalyst can be fed at one time, intermittently or continuously, and the invention is not limited.
Alternatively, the olefin epoxidation reaction is carried out in a tank reactor or a slurry bed reactor. The conditions for the epoxidation of the olefin are preferably: the weight ratio of the olefin to the catalyst is 1: (0.001-3), preferably 1: (0.01-1), more preferably, 1: (0.03-0.5) further preferably 1: (0.05-0.2); the molar ratio of the olefin to the organic peroxide is 1: (0.1-10), preferably 1: (0.5-6), more preferably 1: (0.8-3), most preferably 1: (1-2); the reaction temperature is 20-200 ℃, preferably 80-150 ℃, more preferably 100-130 ℃; the absolute pressure of the reaction is 0.1 to 10MPa, preferably 0.5 to 5MPa, more preferably 1 to 3 MPa; the reaction time is 0.5 to 12 hours, preferably 1 to 8 hours, more preferably 2 to 5 hours.
Alternatively, the olefin epoxidation reaction is carried out in a fixed bed reactor. The molar ratio of the olefin to the organic peroxide is 1: (0.1-10), preferably 1: (0.5-6), more preferably 1: (0.8-3), most preferably 1: (1-2); the weight hourly space velocity with organic peroxidation is 0.01-20h-1, preferably 0.5-14h-1, preferably 0.8-8h-1, more preferably 1-5 h-1; the reaction temperature is 20-200 ℃, preferably 80-150 ℃, more preferably 100-130 ℃; the absolute pressure of the reaction is from 0.1 to 10MPa, preferably from 0.5 to 5MPa, more preferably from 1 to 3 MPa.
In the olefin epoxidation reaction of the present invention, the olefin may be at least one selected from a substituted or unsubstituted monoolefin having C2-C30 and a substituted or unsubstituted multiolefin having C2-C30, and in the substituted monoolefin and the substituted multiolefin, the substituent may be at least one selected from an alkyl group, a phenyl group, an ether group, a carbonyl group, a halogen group, a carboxyl group, a hydroxyl group, a nitro group and an ester group. The olefin may be at least one selected from the group consisting of C2-C30 substituted or unsubstituted monoolefin and C2-C30 substituted or unsubstituted polyene, and in the substituted monoolefin and substituted polyene, the substituent may be at least one selected from the group consisting of an alkyl group, a phenyl group, an ether group, a carbonyl group, a halogen group, a carboxyl group, a hydroxyl group, a nitro group and an ester group. Preferably, the olefin is selected from the group consisting of ethylene, propylene, 1-butene, isobutylene, n-pentene, isopentene, cyclopentene, n-hexene, cyclohexene, 1-heptene, 1-octene, cyclooctene, decene, dodecene, tetradecene, hexadecene, octadecene, eicosene, docosene, tetracosene, triacontene, 3-nitrostyrene, vinyl methyl ether, vinyl isobutyl ether, vinyl ethyl ether, dodecyl vinyl ether, octadecyl vinyl ether, cyclohexyl vinyl ether, chloropropene, bromopropylene, allyl alcohol, acrylic acid, 3-phenylacrylic acid, 4-allylanisole, allyl methyl ether, 2- (chloromethyl) methyl acrylate, methacrylic acid, 4-phenyl-3-butenoic acid, methyl acrylate, methyl methacrylate, and mixtures thereof, At least one of ethyl methacrylate, 4-hydroxycinnamic acid, trans-2-dodecenoic acid, cis-4-hydroxy-6-dodecenoic acid lactone, methyl 2-nonenoic acid, oleic acid, methyl oleate, octadeca-9, 12, 15-trienoic acid, 5,8,11, 14-eicosatetraenoic acid, docosahexenyl-13-enoic acid, and Z-13-docosenoic acid methyl ester.
In the olefin epoxidation reaction of the present invention, the peroxide is an organic peroxide, and preferably at least one of t-butyl hydroperoxide, cyclohexyl hydroperoxide, ethyl phenyl hydroperoxide, isopropyl hydroperoxide, cumene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, t-butyl peroxypivalate, t-amyl hydroperoxide, and di-t-butyl peroxide.
It will be understood by those skilled in the art that the separation of the product from the catalyst can be achieved in various ways, for example, when the original powdery titanium silicalite molecular sieve is used as the catalyst, the separation of the product and the recovery and reuse of the catalyst can be achieved by settling, filtering, centrifuging, evaporating, membrane separation, or the like, or the catalyst can be molded and then loaded into a fixed bed reactor, and the catalyst is recovered after the reaction is finished, and various methods for separating and recovering the catalyst are often referred to in the prior art and will not be described herein again.
The present invention is further illustrated by the following examples, which are not intended to limit the scope of the invention.
In each of the following examples and comparative examples, the material structure was determined by XRD analysis; the chemical composition was determined by XRF analysis; the pore volume and pore distribution were determined according to the method described in RIPP 151-90 in "analytical methods for petrochemical industry" compiled by Yangchi et al (published by scientific Press in 1990, 9 months, first edition); the appearance analysis adopts an SEM method to observe the particle size and appearance; the acid analysis is carried out by adopting a pyridine infrared spectrum method; the state of the titanium species was analyzed by UV-Vis spectroscopy
The raw materials used are analytically pure reagents, unless otherwise specified.
The reaction product is analyzed by gas chromatography, and the analysis result is quantified by an external standard method. Wherein, the chromatographic analysis conditions are as follows: agilent-6890 type chromatograph, HP-5 capillary chromatographic column, sample amount of 0.5 μ L, and sample inlet temperature of 280 deg.C. The column temperature was maintained at 100 ℃ for 2min, then ramped up to 250 ℃ at a rate of 15 ℃/min and maintained for 10 min. FID detector, detector temperature 300 ℃.
In each of the examples and comparative examples:
olefin conversion (%) - (% of olefin conversion) (moles of olefin in feed-moles of olefin in product)/moles of olefin in feed × 100%
Conversion ratio (%) of organic peroxide (number of moles of organic peroxide in raw material-number of moles of organic peroxide in product)/number of moles of organic peroxide in raw material X100%
Epoxidation product selectivity (%). The moles of epoxidation product produced in the product/(moles of olefin in the feed-moles of olefin in the product). times.100%
Example 1
(1) Mixing ethyl orthosilicate, tetrabutyl titanate, tetraethylammonium hydroxide and water, and treating at 30 ℃ for 12 hours to obtain a mixture with a molar composition of SiO2, TiO2, tetraethylammonium hydroxide and water of 1: 0.1: 0.12: 60;
(2) according to the molar ratio of TiO2 to chloride ion of 1: 1.8 adding tetraethyl ammonium chloride to obtain a second product;
(3) treating the second product at 130 ℃ for 24h to obtain gel;
(4) and (3) drying the gel obtained in the step (3) at 100 ℃ for 10h, roasting at 550 ℃ for 4h, recovering a first roasted product, treating at 80 ℃ for 8h according to the weight ratio of the first roasted product to ammonium nitrate solution with the pH of 2.2 and the concentration of 1.5mol/L, drying at 90 ℃ for 8h, and roasting at 500 ℃ for 6h to obtain a titanium-silicon composite oxide sample with the number of A1.
And performing physicochemical characterization on A1.
Fig. 1 shows XRD analysis results, indicating that a1 is an amorphous structure.
FIG. 2 shows the result of pore distribution, and it can be seen that A1 has a distribution of mesopores in the range of 16-50 nm.
FIG. 3 is a UV-Vis spectrum for characterizing the titanium species state, which shows that the absorption is broad in the range of 200-250nm and weak above 300 nm.
Fig. 4 is an SEM, and it can be seen that a1 is formed by aggregation of a plurality of nanoparticles, and the average size of the individual nanoparticles is measured to be about 9 nm.
Other results such as titanium, silicon, oxygen element content, specific surface area, mesoporous volume, titanium dioxide content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L-acid and the like are shown in Table 1.
Example 2
(1) Mixing ethyl orthosilicate, tetrabutyl titanate, tetraethylammonium hydroxide and water, and treating for 6 hours at 50 ℃ to obtain a mixture with a molar composition of SiO2, TiO2, tetraethylammonium hydroxide and water of 1: 0.07: 0.13: 50;
(2) according to the molar ratio of TiO2 to chloride ion of 1: 1.7 adding tetraethyl ammonium chloride to obtain a second product;
(3) treating the second product at 125 ℃ for 30h to obtain gel;
(4) drying the gel obtained in the step (3) at 90 ℃ for 12h, roasting at 550 ℃ for 6h, recovering the first roasted product, treating at 70 ℃ for 6h according to the weight ratio of the first roasted product to ammonium nitrate solution with pH of 3.0 and concentration of 1.0mol/L of 1:30, drying at 100 ℃ for 12h, and roasting at 600 ℃ for 4h to obtain the titanium-silicon composite oxide with the number of A2
A2 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, titanium, silicon, oxygen content, specific surface area, mesoporous volume, titanium dioxide content, particle size, mesoporous range, mesoporous to total pore ratio, and first peak of L acid (1450 + -5 cm)-1) Second peak (1612. + -. 5 cm)-1) Other results such as ratios are shown in Table 1.
Example 3
(1) Mixing ethyl orthosilicate, tetrabutyl titanate, tetraethylammonium hydroxide and water, and treating for 6 hours at 50 ℃ to obtain a mixture with a molar composition of SiO2, TiO2, tetraethylammonium hydroxide and water of 1: 0.05: 0.1: 45;
(2) according to the molar ratio of TiO2 to chloride ion of 1: 1.5 adding tetraethyl ammonium chloride to obtain a second product;
(3) treating the second product at 135 deg.C for 18h to obtain gel;
(4) firstly drying the gel obtained in the step (3) at 110 ℃ for 10h, firstly roasting at 600 ℃ for 5h, recovering a first roasted product, then treating at 75 ℃ for 7h according to the weight ratio of the first roasted product to an ammonium nitrate solution with the pH of 2.0 and the concentration of 2.0mol/L, and secondly drying the recovered product at 95 ℃ for 10h, and secondly roasting at 450 ℃ for 4h to obtain a titanium-silicon composite oxide with the number of A3;
a3 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, and other results of Ti, Si, O element content, specific surface area, mesoporous volume, titania content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L acid, etc. are shown in Table 1.
Example 4
(1) Mixing ethyl orthosilicate, tetrabutyl titanate, tetraethylammonium hydroxide and water, and treating at 35 ℃ for 10 hours to obtain a mixture with a molar composition of SiO2, TiO2, tetraethylammonium hydroxide and water of 1: 0.12: 0.14: 70;
(2) according to the molar ratio of TiO2 to chloride ion of 1:2 adding tetraethyl ammonium chloride to obtain a second product;
(3) treating the second product at 120 ℃ for 36h to obtain gel;
(4) drying the gel obtained in the step (3) at 90 ℃ for 8h, roasting at 450 ℃ for 4h, recovering a first roasted product, treating at 80 ℃ for 6h according to the weight ratio of the first roasted product to an ammonium nitrate solution with the pH of 2.6 and the concentration of 2.0mol/L, drying at 90 ℃ for 12h, and roasting at 550 ℃ for 5h to obtain a titanium-silicon composite oxide, wherein the number is A4;
a4 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, and other results of Ti, Si, O element content, specific surface area, mesoporous volume, titania content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L acid, etc. are shown in Table 1.
Example 5
(1) Mixing propyl orthosilicate, tetraethyl titanate, tetramethylammonium hydroxide and water, and treating at 20 ℃ for 18 hours to obtain a mixture with a molar composition of SiO2, TiO2, tetramethylammonium hydroxide and water of 1: 0.035: 0.09: 35;
(2) according to the molar ratio of TiO2 to chloride ion of 1: 1.2 adding tetramethylammonium chloride to obtain a second product;
(3) treating the second product at 110 ℃ for 48h to obtain gel;
(4) firstly drying the gel obtained in the step (3) at 110 ℃ for 6h, firstly roasting the gel at 400 ℃ for 8h, recovering a first roasted product, then treating the gel at 85 ℃ for 9h according to the weight ratio of the first roasted product to an ammonium chloride solution with the pH of 1.3 and the concentration of 0.5mol/L, and secondly drying the recovered product at 110 ℃ for 18h, and secondly roasting the gel at 700 ℃ for 3h to obtain a titanium-silicon composite oxide with the number of A5;
a5 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, and other results of Ti, Si, O element content, specific surface area, mesoporous volume, titania content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L acid, etc. are shown in Table 1.
Example 6
(1) Mixing n-butyl silicate, tetrapropyl titanate, hexadecyl trimethyl ammonium hydroxide and water, and treating for 4 hours at the temperature of 60 ℃ to obtain a mixture with a molar composition of SiO2, TiO2, hexadecyl trimethyl ammonium hydroxide and water of 1: 0.13: 0.15: 80;
(2) according to the molar ratio of TiO2 to chloride ion of 1: 2.2 adding hexadecyl trimethyl ammonium chloride to obtain a second product;
(3) treating the second product at 140 ℃ for 12h to obtain gel;
(4) firstly drying the gel obtained in the step (3) at 110 ℃ for 6h, firstly roasting the gel at 600 ℃ for 3h, recovering a first roasted product, then treating the gel at 90 ℃ for 4h according to the weight ratio of the first roasted product to an ammonium chloride solution with the pH of 4.5 and the concentration of 3.0mol/L of 1:40, and secondly drying the recovered product at 100 ℃ for 6h, and secondly roasting the recovered product at 550 ℃ for 3h to obtain a titanium-silicon composite oxide with the number of A6;
a6 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, and other results of Ti, Si, O element content, specific surface area, mesoporous volume, titania content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L acid, etc. are shown in Table 1.
Example 7
(1) Mixing tetrabutyl orthosilicate, tetrapropyl titanate, tetramethylammonium hydroxide and water, and treating for 18 hours at 25 ℃ to obtain a mixture with a molar composition of SiO2, TiO2, tetramethylammonium hydroxide and water of 1: 0.02: 0.08: 25;
(2) according to the molar ratio of TiO2 to chloride ion of 1: 0.8 adding tetramethylammonium chloride to obtain a second product;
(3) treating the second product at 110 ℃ for 12h to obtain gel;
(4) firstly drying the gel obtained in the step (3) at 80 ℃ for 18h, firstly roasting at 550 ℃ for 8h, recovering a first roasted product, then treating at 90 ℃ for 12h according to the weight ratio of the first roasted product to an ammonium chloride solution with the pH of 5.0 and the concentration of 0.8mol/L, and secondly drying the recovered product at 80 ℃ for 12h, and secondly roasting at 600 ℃ for 6h to obtain a titanium-silicon composite oxide with the number of A7;
a7 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, and other results of Ti, Si, O element content, specific surface area, mesoporous volume, titania content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L acid, etc. are shown in Table 1.
Example 8
(1) Mixing n-butyl silicate, tetrapropyl titanate, sodium hydroxide and water, and treating at 70 ℃ for 24 hours to obtain a mixture with a molar composition of SiO2, TiO2, sodium hydroxide and water of 1: 0.2: 0.2: 100;
(2) according to the molar ratio of TiO2 to chloride ion of 1: 0.5 adding sodium chloride to obtain a second product;
(3) treating the second product at 100 ℃ for 72h to obtain gel;
(4) firstly drying the gel obtained in the step (3) at 120 ℃ for 24h, firstly roasting at 500 ℃ for 10h, recovering a first roasted product, then treating at 90 ℃ for 18h according to the weight ratio of the first roasted product to an ammonium chloride solution with the pH of 1.1 and the concentration of 5.0mol/L, and secondly drying the recovered product at 130 ℃ for 24h, and secondly roasting at 600 ℃ for 10h to obtain a titanium-silicon composite oxide with the number of A8;
a8 has the characteristics of FIG. 1, FIG. 2, FIG. 3 and FIG. 4, and other results of Ti, Si, O element content, specific surface area, mesoporous volume, titania content, particle size, mesoporous range, mesoporous to total pore ratio, first peak to second peak ratio of L acid, etc. are shown in Table 1.
Comparative example 1
(1) Mixing ethyl orthosilicate, tetrabutyl titanate, tetrapropylammonium hydroxide and water, and treating for 12 hours at the temperature of 30 ℃ to obtain a mixture with a molar composition of SiO2, TiO2, tetrapropylammonium hydroxide, water, 1: 0.07: 0.13: 50;
(2) treating the product obtained in the step (1) at 170 ℃ for 72 h;
(3) filtering and washing the product obtained in the step (2), drying a filter cake at 90 ℃ for 12h, and roasting at 550 ℃ for 6h to obtain a titanium-silicon molecular sieve with the number of D1;
physicochemical characterization of D1 revealed that the structure was MFI type, and other results, such as contents of titanium, silicon and oxygen elements, specific surface area, mesoporous volume, titanium dioxide content, particle size, mesoporous range, mesoporous to total pore ratio, and ratio of first peak to second peak of L acid, are shown in Table 1.
Comparative example 2
(1) Mixing ethyl orthosilicate, tetrabutyl titanate, tetrapropylammonium hydroxide and water, and treating for 12 hours at the temperature of 30 ℃ to obtain a mixture with a molar composition of SiO2, TiO2, tetrapropylammonium hydroxide, water, 1: 0.07: 0.13: 50;
(2) treating the product obtained in the step (1) at 90 ℃ for 12 h;
(3) mixing the product obtained in the step (2) (calculated as SiO 2) with a silanization reagent according to the molar ratio of 1: 0.1 adding N-phenyl-3-aminopropyl trimethoxy silanization reagent and processing for 48h at 170 ℃;
(4) filtering and washing the product obtained in the step (3), drying a filter cake at 90 ℃ for 12h, and roasting at 550 ℃ for 6h to obtain a silylation reagent expanded titanium silicalite molecular sieve with the number of D2;
physicochemical characterization of D2 revealed that the structure was MFI type, and other results, such as contents of titanium, silicon and oxygen elements, specific surface area, mesoporous volume, titanium dioxide content, particle size, mesoporous range, mesoporous to total pore ratio, and ratio of first peak to second peak of L acid, are shown in Table 1.
TABLE 1
Figure BDA0001814597210000171
The titanium-silicon composite oxide provided by the invention has an amorphous structure, is formed by aggregating nano particles, and contains silicon element, titanium element and oxygen element, wherein the silicon element, the titanium element and the oxygen element account for more than 98% of the weight of the titanium-silicon composite oxide under the condition of anhydrous drying, and the specific surface area of the titanium-silicon composite oxide is 200-550 m-2Per g, the mesoporous volume is more than or equal to 0.5cm3The/g, the mesoporous is rich,
example 9
A reaction kettle is used as a reactor, the titanium-silicon composite oxide A1 in example 1 is used as a catalyst, tert-butyl hydroperoxide is used as an oxidant, oleic acid and the catalyst are put into the reaction kettle according to the weight ratio of 1:0.05, and the oleic acid and the tert-butyl hydroperoxide are put into the reaction kettle according to the mol ratio of 1:1 and react for 2 hours at the temperature of 120 ℃ and under the normal pressure, and the reaction results are shown in Table 2.
Example 10
In contrast to example 9, propylene was used as a raw material, the reaction pressure was 5MPa, and the reaction results are shown in Table 2.
Example 11
In contrast to example 9, chloropropene was used as the starting material, the reaction pressure was 1MPa, and the reaction results are shown in Table 2.
Example 12
In contrast to example 9, 1-butene was used as a starting material, the reaction pressure was 3MPa, and the reaction results are shown in Table 2.
Example 13
In contrast to example 9, 1-hexene was used as the starting material, the reaction pressure was 1MPa, and the reaction results are shown in Table 2.
Example 14
The reaction results are shown in Table 2, using the titanium-silicon composite oxide A2 of example 2 as a catalyst, in contrast to example 9.
Example 15
In contrast to example 14, styrene was used as a raw material, cumene hydroperoxide was used as an oxidizing agent, and the reaction pressure was 2MPa, and the reaction results are shown in Table 2.
Example 16
In contrast to example 14, the reaction results are shown in Table 2, using methyl oleate as the starting material and cumene hydroperoxide as the oxidizing agent.
Example 17
The reaction results are shown in Table 2, using the titanium-silicon composite oxide A3 of example 3 as a catalyst, in contrast to example 9.
Example 18
The reaction results are shown in Table 2, using the titanium-silicon composite oxide A4 of example 4 as a catalyst, in contrast to example 9.
Example 19
The reaction results are shown in Table 2, using the titanium-silicon composite oxide A5 of example 5 as a catalyst, in contrast to example 9.
Example 20
The reaction results are shown in Table 2, using the titanium-silicon composite oxide A6 of example 6 as a catalyst, in contrast to example 9.
Example 21
The reaction results are shown in Table 2, using the titanium-silicon composite oxide A7 of example 7 as a catalyst, in contrast to example 9.
Example 22
The reaction results are shown in Table 2, using the titanium-silicon composite oxide A8 of example 8 as a catalyst, in contrast to example 9.
Example 23
A fixed bed is used as a reactor, the titanium-silicon composite oxide A1 in example 1 is used as a catalyst, the catalyst is tabletted, crushed and selected to be 30-80 meshes of particles to be filled into a reaction tube, tert-butyl hydroperoxide is used as an oxidant, oleic acid and tert-butyl hydroperoxide are fed according to the molar ratio of 1:1, the weight hourly space velocity of the tert-butyl hydroperoxide is 1h < -1 >, the reaction is carried out at 120 ℃ and under normal pressure, and the reaction results are shown in Table 2.
Comparative example 3
In contrast to example 9, the titanium silicalite molecular sieve sample D1 of comparative example 1 was used as a catalyst, and the reaction results are shown in Table 2.
Comparative example 4
In contrast to example 9, the titanium silicalite molecular sieve sample D2 of comparative example 2 was used as a catalyst, and the reaction results are shown in Table 2.
TABLE 2
Numbering Catalyst sample Olefin conversion/%) Organic peroxide conversion/%) β -halohydrin selectivity/%)
Example 9 A1 100 100 99.9
Example 10 A1 100 100 99.9
Example 11 A1 100 100 99.9
Example 12 A1 100 100 99.9
Example 13 A1 100 100 99.9
Example 14 A2 100 100 99.9
Example 15 A2 100 100 99.9
Example 16 A2 100 100 99.9
Example 17 A3 100 100 99.9
Example 18 A4 100 100 99.9
Example 19 A5 99 99 99.9
Example 20 A6 99 99 99.9
Example 21 A7 98 98 99.9
Example 22 A8 96 96 99.9
Example 23 A1 100 100 99.9
Comparative example 3 D1 21 21 98.1
Comparative example 4 D2 64 65 99.2
As can be seen from the results of examples 9 to 23 and comparative examples 3 to 4, the titanium-silicon composite oxide of the present invention has excellent catalytic performance in the epoxidation reaction of an olefin using an organic peroxide as an oxidant.
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 the various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present invention, as long as the combination does not depart from the spirit of the present disclosure.

Claims (19)

1. A titanium-silicon composite oxide is characterized in that the titanium-silicon composite oxide is an amorphous structure,is formed by aggregating nano particles, has mesopores with the range of 16-50nm, the ratio of the volume of the mesopores to the total pore volume is more than or equal to 80 percent, and the volume of the mesopores is more than or equal to 0.5cm3/g。
2. The titanium silicon composite oxide according to claim 1, wherein said amorphous structure is analyzed by XRD.
3. The titanium-silicon composite oxide according to claim 1, wherein the silicon-titanium composite oxide contains silicon, titanium and oxygen, the silicon, titanium and oxygen account for 95% or more of the weight of the titanium-silicon composite oxide under anhydrous drying, and the titanium accounts for not less than 0.1% by mass of the titanium dioxide.
4. The titanium silicon composite oxide according to claim 1, said nanoparticles having a particle size of not more than 40nm, preferably not more than 30nm, more preferably not more than 20nm, said nanoparticles having a particle size of more than 5nm, preferably more than 8 nm.
5. The titanium-silicon composite oxide according to claim 1, which has a specific surface area of 200-550m2The ratio of the mesoporous volume to the total pore volume is preferably equal to or greater than 90%, more preferably equal to or greater than 93%, most preferably equal to or greater than 95%.
6. The titanium silicon composite oxide according to any one of claims 1 to 5, wherein said titanium silicon composite oxide has L acidity, and said titanium silicon composite oxide is 1450 ± 5cm in pyridine-infrared characterization-1Has a first absorption peak at 1612 +/-5 cm-1The titanium-silicon composite oxide has a second absorption peak, the intensity ratio of the first absorption peak to the second absorption peak is at least 1.5 and at most 6, the titanium-silicon composite oxide has wide strong absorption within the range of 200-250nm and weak absorption above 300nm by the characterization of UV-Vis.
7. The preparation method of the titanium-silicon composite oxide is characterized by comprising the following steps:
(1) will be provided withOptionally mixing silicon source, titanium source, alkali source and water, and treating at 5-90 deg.C for 0.5-24 hr to obtain SiO2:TiO2The alkali source comprises 1: (0.001-0.2): (0.05-0.2): (10-100) the first product;
(2) according to TiO aspect2Halogen ion molar ratio is 1: (0.5-3) adding a halogen ion compound to obtain a second product;
(3) treating the second product at the temperature of 100-150 ℃ for 1-72h to obtain gel;
(4) recovering the solid product to obtain the titanium-silicon composite oxide; the titanium-silicon composite oxide is an amorphous structure, is formed by aggregating nano particles, contains silicon element, titanium element and oxygen element, accounts for more than 95% of the weight of the titanium-silicon composite oxide under the anhydrous drying condition, has mesopores in the range of 16-50nm, the ratio of the volume of the mesopores to the total pore volume is more than or equal to 80%, and the volume of the mesopores is more than or equal to 0.5cm3/g。
8. The method according to claim 7, wherein the silicon source is preferably silicon tetraalkoxide, more preferably at least one of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, butyl orthosilicate.
9. The method according to claim 7, wherein the titanium source is preferably a titanium tetraalkoxide, more preferably at least one of tetraethyl titanate, tetrapropyl titanate, tetrabutyl titanate.
10. The method according to claim 7, wherein the alkali source is at least one selected from the group consisting of aliphatic amines, aliphatic alcohol amines, quaternary ammonium bases, inorganic alkali compounds, preferably at least one of aliphatic amines and aliphatic alcohol amines having less than 10 carbon atoms, preferably at least one of hydroxide compounds of main group I and/or II, and ammonia water, more preferably at least one of aliphatic amines of C1-C5, tetramethylammonium hydroxide, tetraethylammonium hydroxide, hexadecyltrimethylammonium hydroxide, sodium hydroxide, and ammonia water, and most preferably tetraethylammonium hydroxide.
11. The method according to claim 7, wherein the halide ion compound is a halide ion-containing salt, preferably comprising at least one of a group I element salt, an ammonium salt, a quaternary ammonium salt, more preferably a sodium salt, a potassium salt, an ammonium salt, a quaternary ammonium salt, most preferably a quaternary ammonium salt; the halogen ions comprise fluorine, chlorine, bromine and iodine, and chlorine is preferred.
12. The method according to any one of claims 7 to 11, wherein the step of recovering the solid product comprises subjecting the gel obtained in step (3) to a first drying and a first calcination.
13. The method as claimed in any one of claims 7 to 12, wherein the step of recovering the solid product further comprises subjecting the first calcined titanium silicon composite oxide to a liquid phase treatment, at least partially separating the solid product, and subjecting the solid product to a second drying and a second calcination to obtain the titanium silicon composite oxide.
14. The method according to claim 13, wherein the liquid phase condition is an ammonium salt-containing solution with a concentration of 0.1-5mol/L, the ammonium salt is ammonium chloride, ammonium nitrate or ammonium carbonate, the pH of the solution is 1-5, and the weight ratio of the gel to the ammonium salt-containing solution is 1: (10-50), the treatment temperature is 40-90 ℃, and the treatment time is 1-18 h.
15. A titanium silicon composite oxide produced by the method of any one of claims 7 to 14.
16. Use of a titanium silicon composite oxide in a catalytic oxidation reaction, preferably a process for the epoxidation of an olefin, which process comprises: a process for the epoxidation of an olefin by contacting the olefin with an organic peroxide in the presence of a catalyst, wherein the catalyst comprises a titanium silicon composite oxide as claimed in any one of claims 1 to 6 and 15.
17. The process of claim 16, wherein the olefin epoxidation conditions are: the molar ratio of the olefin to the organic peroxide is 1: (0.1-10), the reaction temperature is 20-200 ℃, and the absolute pressure of the reaction is 0.1-10 Mpa.
18. The method of claim 16, wherein the olefin is at least one selected from the group consisting of C2-C30 substituted or unsubstituted mono-olefins and C2-C30 substituted or unsubstituted polyenes, and wherein the substituent is at least one selected from the group consisting of alkyl groups, phenyl groups, ether groups, carbonyl groups, halogens, carboxyl groups, hydroxyl groups, nitro groups, and ester groups.
19. The method according to claim 16, wherein the organic peroxide is at least one selected from the group consisting of t-butyl hydroperoxide, cyclohexyl hydroperoxide, ethyl phenyl hydroperoxide, isopropyl hydroperoxide, cumene hydroperoxide, benzoic acid peroxide, methyl ethyl ketone peroxide, t-butyl peroxypivalate, t-amyl hydroperoxide, and di-t-butyl peroxide.
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114669286A (en) * 2022-03-29 2022-06-28 中国科学院过程工程研究所 Platinum-based catalyst for CO oxidation and preparation method and application thereof
CN115368097A (en) * 2022-08-22 2022-11-22 湖北大学 High-capacity carbon fixation material and preparation method thereof
CN115724808A (en) * 2021-08-30 2023-03-03 中国石油化工股份有限公司 Olefin epoxidation method
WO2023210199A1 (en) * 2022-04-25 2023-11-02 住友化学株式会社 Method for producing titanium-containing silicon oxide, method for producing epoxide, and titanium-containing silicon oxide

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1048660A1 (en) * 1999-04-28 2000-11-02 Agency of Industrial Science and Technology Manufacturing method of epoxides
CN1287878A (en) * 2000-08-24 2001-03-21 中国科学院上海硅酸盐研究所 Process for preparing mesopore titania photocatalyst
CN1394676A (en) * 2002-06-18 2003-02-05 山西大学 Preparation method of high specific area and high dispersity silicone-titanium compound oxide
CN106345489A (en) * 2016-07-29 2017-01-25 南京工程学院 Sandwich-structured nanometer catalytic material and preparation method thereof
CN107930610A (en) * 2017-11-29 2018-04-20 万华化学集团股份有限公司 A kind of preparation method of olefin epoxidation catalysts and the catalyst thus prepared
US20180147560A1 (en) * 2016-11-28 2018-05-31 Oriental Union Chemical Corp. Method for fabricating a titanium-containing silicon oxide material with high thermal stability and applications of the same

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1048660A1 (en) * 1999-04-28 2000-11-02 Agency of Industrial Science and Technology Manufacturing method of epoxides
CN1287878A (en) * 2000-08-24 2001-03-21 中国科学院上海硅酸盐研究所 Process for preparing mesopore titania photocatalyst
CN1394676A (en) * 2002-06-18 2003-02-05 山西大学 Preparation method of high specific area and high dispersity silicone-titanium compound oxide
CN106345489A (en) * 2016-07-29 2017-01-25 南京工程学院 Sandwich-structured nanometer catalytic material and preparation method thereof
US20180147560A1 (en) * 2016-11-28 2018-05-31 Oriental Union Chemical Corp. Method for fabricating a titanium-containing silicon oxide material with high thermal stability and applications of the same
CN107930610A (en) * 2017-11-29 2018-04-20 万华化学集团股份有限公司 A kind of preparation method of olefin epoxidation catalysts and the catalyst thus prepared

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115724808A (en) * 2021-08-30 2023-03-03 中国石油化工股份有限公司 Olefin epoxidation method
CN115724808B (en) * 2021-08-30 2024-05-17 中国石油化工股份有限公司 Olefin epoxidation method
CN114669286A (en) * 2022-03-29 2022-06-28 中国科学院过程工程研究所 Platinum-based catalyst for CO oxidation and preparation method and application thereof
WO2023210199A1 (en) * 2022-04-25 2023-11-02 住友化学株式会社 Method for producing titanium-containing silicon oxide, method for producing epoxide, and titanium-containing silicon oxide
CN115368097A (en) * 2022-08-22 2022-11-22 湖北大学 High-capacity carbon fixation material and preparation method thereof

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