CN111905707A - Amorphous mesoporous TiO2-SiO2Catalyst and preparation method thereof - Google Patents
Amorphous mesoporous TiO2-SiO2Catalyst and preparation method thereof Download PDFInfo
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- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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Abstract
The invention discloses amorphous mesoporous TiO2‑SiO2A catalyst and a preparation method thereof. The preparation method comprises the following steps: mixing a silicon source, a titanium source, an alkali source, alcohol and water to prepare a mixed solution; carrying out hydrothermal crystallization on the mixed solution to obtain a crystallization product; roasting the crystallized product to obtain amorphous mesoporous TiO2‑SiO2A catalyst; the silicon source comprises a silicon source A and a silicon source B; the silicon source A is one or a mixture of more of silica sol, silica gel, tetraethyl silicate and tetramethyl silicate; the silicon source B is represented by the general formula (R)1)nSi(OR2)4‑nOne or a mixture of more than one of alkyl siloxane in the general formula1Is C1‑C16Alkyl of R2Is C1‑C4N is more than or equal to 1 and less than or equal to 3. The method has the advantages of simple adopted raw materials, easily controlled conditions and good preparation repeatability(ii) a The amorphous mesoporous TiO prepared by the invention2‑SiO2The catalyst has high selective oxidation activity and stability to DBT and 4,6-DMDBT, and catalytic products and the catalyst are easily separated from an oil phase.
Description
Technical Field
The invention relates to the technical field of catalyst preparation, in particular to amorphous mesoporous TiO2-SiO2A catalyst and a preparation method thereof.
Background
In recent years, the vigorous development of the automobile industry has greatly increased the usage of fossil fuel gasoline, namely, toxic gas SO generated by the combustion of sulfides in gasolinexThe harm to the environment and human health is also increasing. In order to protect the natural environment and promote the sustainable development of human beings, the regulation on the content of sulfide in gasoline is stricter at present, and the problem of reducing the content of sulfur in fuel oil is a problem which is urgently needed to be solved by oil refining enterprises. Currently, the most widely used desulfurization technique for industrial applications is hydrodesulfurization. However, the hydrodesulfurization method has no significant effect on removing sulfides with large steric hindrance, such as thiophene, benzothiophene and derivatives thereof, and the obtained finished gasoline cannot meet the automotive standards. Therefore, in recent years, various novel desulfurization technologies, such as adsorption desulfurization, biological desulfurization, extraction desulfurization, oxidative desulfurization and the like, have emerged to replace hydrodesulfurization or be combined with hydrodesulfurization to make up for the deficiency, and then the finished fuel oil meeting the fuel oil standard is obtained. Oxidative desulfurization is a process that has received much attention because it can remove thiophene sulfides under mild reaction conditions.
The catalyst for oxidation desulfurization mainly comprises polyoxometallate and composite materials thereof, transition metal composite materials and the like. Among them, titanium-containing catalysts are favored by researchers because of their excellent desulfurization performance. Ghahrananezhad et al (environ. Sci. Polluti. Res.,2020,27,4,4104-2-SiO2The catalytic performance of the nano composite material in the oxidation reaction of Dibenzothiophene (DBT) is researched. The results show thatAfter recycling, the DBT removal rate of the catalyst is reduced from the initial 99.4 percent to 98.0 percent. Bazyari et al (appl. Catal B: environ, 2016,180,65-77) prepared TiO using a sol-gel process2-SiO2A nanocomposite which, while catalytically oxidizing a sulfur-containing compound, also adsorbs the oxidation products of the sulfur-containing compound, containing 50% TiO2The removal rate of the catalyst on DBT is more than 99.0 percent, and the removal rate is obviously reduced after the catalyst is recycled for two times. Yan et al (Catal. Sci. Technol.,2013,3,1985-1992) prepared mesoporous phosphotungstic acid-TiO by evaporation-induced self-assembly method2-SiO2A nanocomposite; when TiO is present2/SiO2When the molar ratio is 1:3, the composite material can oxidize 96% of DBT in an ether-benzene system; however, after 3 times of recycling, the DBT removal rate is reduced to 93.5 percent.
Although the catalytic materials have high oxidative desulfurization activity, the indiscriminate stability of the catalytic materials is poor, and the industrial application is limited.
Disclosure of Invention
The invention aims to overcome the technical defects and provides amorphous mesoporous TiO2-SiO2The catalyst and the preparation method thereof solve the problem of TiO in the prior art2-SiO2The catalyst has poor stability after desulfurization.
In order to achieve the above technical objects, the first aspect of the present invention provides an amorphous mesoporous TiO2-SiO2The preparation method of the catalyst comprises the following steps: mixing a silicon source, a titanium source, an alkali source, alcohol and water to prepare a mixed solution; carrying out hydrothermal crystallization on the mixed solution to obtain a crystallization product; roasting the crystallized product to obtain amorphous mesoporous TiO2-SiO2A catalyst; the silicon source is a composite silicon source and comprises a silicon source A and a silicon source B; the silicon source A is one or a mixture of more of silica sol, silica gel, tetraethyl silicate and tetramethyl silicate; the silicon source B is represented by the general formula (R)1)nSi(OR2)4-nOne or a mixture of more than one of alkyl siloxane in the general formula1Is C1-C16Alkyl of R2Is C1-C4N is more than or equal to 1 and less than or equal to 3.
The second aspect of the invention provides amorphous mesoporous TiO2-SiO2Catalyst, the amorphous mesoporous TiO2-SiO2Catalyst the amorphous mesoporous TiO provided by the first aspect of the invention2-SiO2The catalyst is prepared by the preparation method.
Compared with the prior art, the invention has the beneficial effects that:
the method has the advantages of simple adopted raw materials, easily controlled conditions and good preparation repeatability;
the amorphous mesoporous TiO prepared by the invention2-SiO2The catalyst has high selective oxidation activity and stability to DBT and 4,6-DMDBT, and catalytic products and the catalyst are easily separated from an oil phase.
Drawings
FIG. 1 shows an amorphous mesoporous TiO provided by the present invention2-SiO2A process flow diagram of one embodiment of a method of preparing a catalyst;
FIG. 2 shows amorphous mesoporous TiO obtained in example 1 of the present invention2-SiO2An X-ray diffraction pattern of the catalyst;
FIG. 3 shows amorphous mesoporous TiO obtained in example 1 of the present invention2-SiO2(ii) a uv-visible diffuse reflectance spectrum of the catalyst;
FIG. 4 shows amorphous mesoporous TiO obtained in example 1 of the present invention2-SiO2Nitrogen adsorption-desorption isotherms and BJH pore distribution profiles (inset) of the catalysts;
FIG. 5 shows amorphous mesoporous TiO obtained in example 1 of the present invention2-SiO2A scanning electron microscope spectrogram of the catalyst;
FIG. 6 shows amorphous mesoporous TiO obtained in example 1 of the present invention2-SiO2The repeated application times of the catalyst-desulfurization rate curve.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Referring to FIG. 1, FIG. 1 shows an amorphous mesoporous TiO provided by the present invention2-SiO2A process flow diagram of one embodiment of a method of making a catalyst. The first aspect of the invention provides amorphous mesoporous TiO2-SiO2The preparation method of the catalyst comprises the following steps: s1, mixing a silicon source, a titanium source, an alkali source, alcohol and water to prepare a mixed solution; s2, carrying out hydrothermal crystallization on the mixed solution to obtain a crystallized product; s3 roasting the crystallized product to obtain amorphous mesoporous TiO2-SiO2A catalyst. In the method, the silicon source used is a composite silicon source and comprises a silicon source A and a silicon source B. In the invention, the silicon source A is used as a silicon source to form a three-dimensional Si-O-Si framework, and Ti enters the framework to generate a catalytic oxidation active site; the silicon source B is used as a silicon source and a pore-forming agent, the specific surface area and the mesopore volume of the catalyst can be increased by using the silicon source B, macromolecular organic matters can enter a pore channel and react with an active center exposed in the pore channel, and the catalytic oxidation activity and the stability are improved; the silicon source A and the silicon source B have synergistic effect, generate mesopores and better disperse Ti on a three-dimensional Si-O-Si framework formed by the silicon source A and the silicon source B, generate efficient Ti active sites and improve the thermal stability of the material. In the present embodiment, the mole fraction of the silicon source B in the silicon source is 1% to 40%, preferably 7.5% to 20%. In step S1, the silicon source a is one or a mixture of more of silica sol, silica gel, tetraethyl silicate, tetramethyl silicate, and the like; the silicon source B used is of the general formula (R)1)nSi(OR2)4-nOne or a mixture of more than one of alkyl siloxane(s) in the general formula (I), R is1Is C1-C16Alkyl of R2Is C1-C4N is more than or equal to 1 and less than or equal to 3, and specifically comprises the following components: methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilaneOne or a mixture of more of hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, triethylethoxysilane and trimethylethoxysilane; the titanium source used is a water-soluble or water-hydrolysable titanium compound which may be TiCl3、TiCl4One or a mixture of more of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate, tetramethyl titanate and the like; the alkali source is one or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, ammonia water, methylamine, dimethylamine, trimethylamine, ethylamine, n-propylamine, n-butylamine and the like; the alcohol is one or more of methanol, ethanol, n-propanol, isopropanol, n-butanol and 2-butanol. In the step, the prepared mixed solution specifically comprises the following steps: stirring a silicon source, a titanium source, an alkali source, alcohol and water until a uniform mixed solution is obtained.
In the present embodiment, the molar ratio of the silicon source to the titanium source is 1: (0.01 to 0.15), preferably 1: (0.01 to 0.05); the molar ratio of the silicon source to the alkali source is 1: (0.1 to 1.0), preferably 1: (0.2-0.8); the molar ratio of the silicon source to the alcohol is 1: (1.11 to 17.76), preferably 1: (1.11-13.32); the molar ratio of the silicon source to the water is 1: (15-100), preferably 1: (20 to 50). In the invention, the obtained catalyst has lower titanium content, and is more beneficial to improving the thermal stability.
In the step S2, the temperature of the hydrothermal crystallization is 120-200 ℃, and preferably 140-180 ℃; the time for hydrothermal crystallization is 12-72 h, preferably 24-48 h.
In the step S3, the roasting temperature is 500-700 ℃, and the roasting time is 5-12 h. In the step, the crystallized product is washed and dried before roasting.
The second aspect of the invention provides amorphous mesoporous TiO2-SiO2Catalyst, the amorphous mesoporous TiO2-SiO2Catalyst the amorphous mesoporous TiO provided by the first aspect of the invention2-SiO2The catalyst is prepared by the preparation method.
The experimental methods in the following examples and comparative examples are conventional methods unless otherwise specified; the experimental materials used in the following examples and comparative examples were all commercially available unless otherwise specified.
Example 1
5.312g of tetraethyl silicate, 0.929g of n-propyltriethoxysilane, 10.001g of isopropanol, 0.316g of tetra-n-butyl titanate, 5.033g of tetrapropylammonium hydroxide solution (40%) and 13.189g of deionized water are uniformly mixed under vigorous stirring at room temperature for stirring for 2.5 hours to obtain a clear solution; transferring the clear solution into a high-pressure kettle, and crystallizing at 175 ℃ for 48 hours to obtain a crystallized product; washing and drying the crystallized product, and roasting at 550 ℃ for 8h to obtain mesoporous TiO2-SiO2A catalyst. In this embodiment, the molar ratio of the silicon source, the titanium source, the alkali source, the alcohol, and the deionized water is 1: 0.03: 0.33: 5.55: 30, of a nitrogen-containing gas; the mole fraction of the silicon source B in the silicon source is 15%.
For the mesoporous TiO obtained in inventive example 12-SiO2The catalyst is characterized, and the results are shown in FIGS. 2-5. FIG. 2 shows amorphous mesoporous TiO obtained in example 1 of the present invention2-SiO2An X-ray diffraction pattern of the catalyst; FIG. 3 shows amorphous mesoporous TiO obtained in example 1 of the present invention2-SiO2(ii) a uv-visible diffuse reflectance spectrum of the catalyst; FIG. 4 shows amorphous mesoporous TiO obtained in example 1 of the present invention2-SiO2Nitrogen adsorption-desorption isotherms and BJH pore distribution profiles (inset) of the catalysts; FIG. 5 shows amorphous mesoporous TiO obtained in example 1 of the present invention2-SiO2Scanning electron microscopy of the catalyst. As can be seen from FIG. 2, the obtained catalyst has a wider diffraction peak between 15 and 30 degrees, which indicates that the obtained catalyst is an amorphous material; as can be seen from FIG. 3, the samples were measured at 210 to 220nm and 230 to 270nmThe catalyst has stronger absorption bands of four-coordinate Ti and six-coordinate Ti, which are active sites for selective catalytic oxidation reaction, and the obtained catalyst has better catalytic oxidation activity; as can be seen in FIG. 4, the samples exhibited a typical type IV isotherm at P/P0The high-pressure area with the diameter of 0.7-1.0 has an obvious hysteresis loop, and the aperture is intensively distributed at 16.4nm, which shows that the sample has uniform mesopores and is beneficial to mass transfer of reactants and products; as can be seen from FIG. 5, the sample has a large number of three-dimensionally connected pores, and the pore size is 10-20 nm.
Example 2
This example prepares amorphous mesoporous TiO according to example 12-SiO2The catalyst is characterized in that the silicon source B is methyl triethoxysilane, and the mole fraction of the methyl triethoxysilane in the silicon source is 20%. The catalyst obtained in this example has two different mesoporous pore sizes.
Example 3
This example prepares amorphous mesoporous TiO according to example 12-SiO2The catalyst is characterized in that the silicon source B is ethyl triethoxysilane, and the mole fraction of the ethyl triethoxysilane in the silicon source is 7.5%.
Example 4
This example prepares amorphous mesoporous TiO according to example 12-SiO2The catalyst is characterized in that the silicon source B is vinyl triethoxysilane, the titanium source is TiCl4The alkali source is ammonia water, and the molar ratio of the ammonia water to the silicon source is 0.8.
Example 5
This example prepares amorphous mesoporous TiO according to example 12-SiO2The catalyst is characterized in that the silicon source B is hexyltriethoxysilane, and the molar ratio of the titanium source to the silicon source is 0.05.
Example 6
This example prepares amorphous mesoporous TiO according to example 12-SiO2The catalyst is characterized in that the silicon source B is octyl triethoxysilane, the molar ratio of the titanium source to the silicon source is 0.01, and the molar ratio of the alcohol to the silicon source isIs 1.11.
Example 7
This example prepares amorphous mesoporous TiO according to example 12-SiO2The catalyst is characterized in that the silicon source B is phenyl triethoxysilane, and the alcohol is ethanol.
Example 8
This example prepares amorphous mesoporous TiO according to example 12-SiO2The catalyst is characterized in that the silicon source B is isobutyl triethoxy silane, and the molar ratio of deionized water to the silicon source is 20.
Example 9
This example prepares amorphous mesoporous TiO according to example 12-SiO2The catalyst is characterized in that the silicon source B is pentyltriethoxysilane, and the molar ratio of the deionized water to the silicon source is 50.
Example 10
This example prepares amorphous mesoporous TiO according to example 12-SiO2The catalyst is prepared by hydrothermal crystallization of dodecyl triethoxy silane at 140 deg.c for 48 hr.
Example 11
This example prepares amorphous mesoporous TiO according to example 12-SiO2The catalyst is characterized in that the organic silicon source is hexadecyl triethoxy silane, and the molar ratio of alcohol to the silicon source is 13.32.
Example 12
This example prepares amorphous mesoporous TiO according to example 12-SiO2The catalyst is characterized in that the silicon source B is dimethyl diethoxy silane, and the catalyst is hydrothermally crystallized for 24 hours at 180 ℃.
Example 13
This example prepares amorphous mesoporous TiO according to example 12-SiO2The catalyst is characterized in that the silicon source B is diethyl diethoxysilane, the alkali source is methylamine, and the molar ratio of the methylamine to the silicon source is 0.2
Example 14
This example was prepared as in example 1Amorphous mesoporous TiO2-SiO2The catalyst is characterized in that the silicon source B is trimethyl methoxy silane, and the mole fraction of the trimethyl methoxy silane in the silicon source is 20%.
Comparative example 1
This comparative example was prepared as in example 1, except that the silicon source was only silicon source a and silicon source a was tetraethyl silicate during the preparation.
Comparative example 2
This comparative example was prepared as in example 1, except that the silicon source was silicon source B alone and silicon source B was n-propyltriethoxysilane during the preparation.
Comparative example 3
Comparative example preparation of amorphous mesoporous TiO according to example 12-SiO2Catalyst except that the molar ratio of the titanium source to the silicon source was 0.2.
Preparing simulation oil: dissolving DBT and 4,6-DMDBT in n-octane to respectively prepare simulated oil containing DBT and simulated oil containing 4, 6-DMDBT; the mass concentration of sulfur contained in the DBT-containing simulated oil is 1000ppm, and the mass concentration of sulfur contained in the 4, 6-DMDBT-containing simulated oil is 500 ppm.
Evaluation of catalytic Oxidation Effect: respectively adding the catalyst prepared in the examples 1-14 and the comparative examples 1-3 and 10mL of simulated oil into a 50mL two-neck flask connected with a condenser tube, and heating to 333K; then, t-butyl hydroperoxide (TBHP, TBHP/S ═ 2) was added to start the reaction (DBT reaction 30min, 4,6-DMDBT reaction 15 min); finally, the reaction mixture was cooled and centrifuged; the centrifuged supernatant was analyzed by GC126N (FPD detector, HP-5 capillary column) and the residual DBT and 4,6-DMDBT in the mock oil were quantified by peak area normalization. The conversion of DBT and 4,6-DMDBT is defined as the amount of sulfide reacted divided by the initial amount of sulfide.
TABLE 1 pore structure parameters and oxidative desulfurization performance of catalysts prepared in each example and comparative example
As can be seen from Table 1, the pore diameter of the catalyst obtained by the invention can be controlled to be 8-35 nm and can be adjusted, and the BET specific surface area is 500-650 m2(g) the external surface area is 300-550 m2The catalyst has high catalytic oxidation activity in the probe reaction simulating the oxidative desulfurization reaction of the fuel oil.
In comparison with example 1, the silicon source of comparative example 1 is only silicon source a, which loses the function of silicon source B as a pore former, resulting in smaller mesopore volume and specific surface area, resulting in a lower selective oxidation activity of the resulting catalyst.
Compared with the example 1, in the comparative example 2, the silicon source B is used as the only silicon source, and a large amount of alkyl groups existing in the synthesis system obstruct the formation of a three-dimensional Si-O-Si framework and are not beneficial to Ti atoms entering the Si-O-Si framework to form active sites, so that the obtained catalyst has no selective oxidation activity.
Comparative example 3, where more titanium source was added as compared to example 1, resulted in the formation of a larger amount of anatase TiO2It can decompose peroxide in the course of desulfurization reaction, and can reduce catalytic oxidation activity.
Referring to FIG. 6, FIG. 6 shows amorphous mesoporous TiO obtained in example 1 of the present invention2-SiO2The repeated application times of the catalyst-desulfurization rate curve. As can be seen from FIG. 6, after recycling 15 times, the catalyst obtained in example 1 was usedThe conversion rate of DBT and 4,6-DMDBT is kept above 97%, which shows that the catalyst obtained by the invention has higher catalytic stability.
Compared with the prior art, the invention has the beneficial effects that:
the method has the advantages of simple adopted raw materials, easily controlled conditions and good preparation repeatability;
the amorphous mesoporous TiO prepared by the invention2-SiO2The catalyst has high catalytic activity and catalytic stability to DBT and 4,6-DMDBT, and catalytic products and the catalyst are easy to separate from an oil phase.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. Amorphous mesoporous TiO2-SiO2The preparation method of the catalyst is characterized by comprising the following steps:
mixing a silicon source, a titanium source, an alkali source, alcohol and water to prepare a mixed solution;
carrying out hydrothermal crystallization on the mixed solution to obtain a crystallization product;
roasting the crystallized product to obtain amorphous mesoporous TiO2-SiO2A catalyst;
wherein the silicon source comprises a silicon source A and a silicon source B;
the silicon source A is one or a mixture of more of silica sol, silica gel, tetraethyl silicate and tetramethyl silicate;
the silicon source B is represented by the general formula (R)1)nSi(OR2)4-nOne or a mixture of more than one of alkyl siloxane in the general formula1Is C1-C16Alkyl of R2Is C1-C4N is more than or equal to 1 and less than or equal to 3.
2. The amorphous mesoporous TiO of claim 12-SiO2Preparation of catalystThe preparation method is characterized in that the silicon source B is methyltrimethoxysilane, methyltriethoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isobutyltrimethoxysilane, isobutyltriethoxysilane, pentyltrimethoxysilane, pentyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltrimethoxysilane, octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, dodecyltrimethoxysilane, dodecyltriethoxysilane, hexadecyltrimethoxysilane, hexadecyltriethoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, dimethyldimethoxysilane, One or a mixture of several of diethyldiethoxysilane, trimethylmethoxysilane, triethylmethoxysilane, triethylethoxysilane and trimethylethoxysilane.
3. The amorphous mesoporous TiO of claim 12-SiO2The preparation method of the catalyst is characterized in that the mole fraction of the silicon source B in the silicon source is 1-40%.
4. The amorphous mesoporous TiO of claim 12-SiO2The preparation method of the catalyst is characterized in that the titanium source is TiCl3、TiCl4One or a mixture of more of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl titanate and tetramethyl titanate; the molar ratio of the silicon source to the titanium source is 1: (0.01-0.15).
5. The amorphous mesoporous TiO of claim 12-SiO2The preparation method of the catalyst is characterized in that the alkali source is one or a mixture of more of tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropyl ammonium hydroxide, tetrabutyl ammonium hydroxide, ammonia water, methylamine, dimethylamine, trimethylamine, ethylamine, n-propylamine and n-butylamine(ii) a The molar ratio of the silicon source to the alkali source is 1: (0.1-1.0).
6. The amorphous mesoporous TiO of claim 12-SiO2The preparation method of the catalyst is characterized in that the alcohol is one or a mixture of more of methanol, ethanol, n-propanol, isopropanol, n-butanol and 2-butanol; the molar ratio of the silicon source to the alcohol is 1: (1.11-17.76).
7. The amorphous mesoporous TiO of claim 12-SiO2The preparation method of the catalyst is characterized in that the molar ratio of the silicon source to the water is 1: (15-100).
8. The amorphous mesoporous TiO of claim 12-SiO2The preparation method of the catalyst is characterized in that the temperature of the hydrothermal crystallization is 120-200 ℃, and the time of the hydrothermal crystallization is 12-72 hours.
9. The amorphous mesoporous TiO of claim 12-SiO2The preparation method of the catalyst is characterized in that the roasting temperature is 500-700 ℃, and the roasting time is 5-12 h.
10. Amorphous mesoporous TiO2-SiO2Catalyst, characterized in that the amorphous mesoporous TiO2-SiO2Passing the catalyst through the amorphous mesoporous TiO of any one of claims 1-92-SiO2The catalyst is prepared by the preparation method.
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Citations (7)
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| CN101115561A (en) * | 2004-12-06 | 2008-01-30 | 住友化学株式会社 | Method for manufacturing titanium-containing silicon oxide catalyst and catalyst |
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