CN101456562A - Method for preparing mesoporous titanium silicate molecular sieve - Google Patents
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Abstract
The invention relates to a method for preparing mesoporous titanium silicon molecular sieves, which belongs to the technical field of preparation of mesoporous molecular sieve catalytic materials. The method comprises: adopting a cationic surfactant as a template agent, dispersing the cationic surfactant into deionized water, adding ammonia water to adjust the pH value of the solution, and adding silicon sources after the template agent is completely dissolved; making the materials undergo filtration, washing, drying and roasting, removing the organic template agent, and obtaining silicon dioxide mesoporous materials; and dispersing the obtained silicon dioxide mesoporous materials into ethanol, slowly adding titanium sources, loading titanium ions after hydrolysis of the titanium sources on the silicon dioxide mesoporous molecular sieves to form an active center, and obtaining titanium-loaded mesoporous molecular sieves. The reaction is easy to control, and the product has good repeatability and is suitable for mass production. By adoption of the prepared titanium silicon molecular sieves as a catalyst and hydrogen peroxide as an oxygen source to catalyze olefin epoxidation and alcohol oxidation, the reaction conditions are mild and the reaction has good selectivity and conversion rate.
Description
Technical field
The invention belongs to mesopore molecular sieve catalytic material preparing technical field, the preparation method and the catalysis epoxidation thereof that are specifically related to a kind of mesoporous titanium-silicon molecular screen are used.
Background technology
In production fields such as fine chemicals, agrochemicals and medicine intermediate, selective catalytic oxidation is a kind of important synthetic method.Adopting solid catalyst efficiently, is that oxygenant realizes that the new catalytic process in these fields more meets the requirement of " Green Chemistry chemical industry " with the aqueous hydrogen peroxide solution of dilute concentration.Therefore, the exploitation of high-performance solid catalyzer becomes one of the matter of utmost importance that realizes these friendly process and core technology.
Since synthetic first Ti-MCM-41 such as Corma in 1994, the extensive concern that mesoporous titanium-silicon molecular screen particular structure, big specific surface area and catalytic performance obtain academia, the research and development of mesoporous material is all significant for theoretical investigation and actual production.Titanium-containing meso-porous molecular sieve is because of the variable valence performance and the surface acidity of titanium, in catalysis, has very big advantage, and research is many, but the synthetic main problem that has two aspects of titanium-containing meso-porous molecular sieve, the one, the introducing experiment condition of titanium atom is relatively harsher, and not every titanium atom can become the active centre, because the performance of appraising at the current rate of titanium atom, some titanium atom loses catalytic activity.Generate active little anatase octahedrite easily.The 2nd, different titaniums source is different to the catalytic performance influence of synthetic HTS.
Synthesizing of mesoporous titanium-silicon molecular screen adopted hydrothermal synthesis method usually at present, for example: a kind of synthetic method of mesoporous titanium-silicon molecular screen material (CN101190794A).Hydro-thermal synthetic basic step is the back to be mixed in titanium source and silicon source add and contain in the alkalescence or acidic mixed solution of template, after reaction is finished solution is transferred to crystallization in the reactor, and crystallization time does not wait from one day by seven days, dry then, calcining.This is a kind of more traditional synthetic method, because synthesis condition is relatively harsher, causes product repeatability very poor, even adopt identical reagent and preparation method, the titanium molecular sieve catalysis performance that obtains also often differs greatly.And the synthetic mesoporous titanium-silicon molecular screen causes the formation of extra-framework titanium easily, and the existence of extra-framework titanium can cause the hydrolysis of hydrogen peroxide, reduces catalyzed reaction efficient.
The catalysis epoxidation performance of mesoporous titanium-silicon molecular screen is lower than traditional TS-1 type molecular sieve, but TS-1 type molecular sieve only is applicable to the catalysis small molecules because of its smaller aperture, and mesoporous titanium-silicon molecular screen has bigger aperture because of it and surface-area has shown special advantages in macromolecular catalysis.Therefore, improve the catalytic performance of mesoporous titanium-silicon molecular screen, seek a kind of simple and feasible synthetic method and prepare worth further research of mesoporous titanium-silicon molecular screen and exploration.
Summary of the invention
The objective of the invention is to: adopt the synthesising mesoporous HTS of two-step approach, at first synthesizing mesoporous silicon dioxide is carried on the titanium active centre on the molecular sieve again, and a kind of short-cut method of synthesising mesoporous HTS is provided.And handle to improve the catalytic performance of mesopore molecular sieve by silanization.
The objective of the invention is to be achieved through the following technical solutions:
It is template that the present invention adopts cats product, and it is scattered in the deionized water, adds the pH value of ammoniacal liquor regulator solution, treat that template is dissolved fully after, adding silicon source.Have hydrophilic and tensio-active agent hydrophobic grouping and in water, form spherical micelle, the micellar outside surface is made up of the water-wet side of tensio-active agent, be dissolved in inorganic monomer molecule in the solvent or oligopolymer because of and water-wet side exist gravitation to be deposited on hole between the micella rod, polymerizing curable constitutes hole wall, forms organic-inorganic hybrid material.This material through filtration, washing, dry, roasting process, is removed organic formwork agent, obtain SiO 2 mesoporous materials.The SiO 2 mesoporous materials that obtains is distributed in the ethanol, slowly adds the titanium source, the titanium ion after the hydrolysis of titanium source is carried on and forms the active centre on the silica mesoporous zeolite, obtains the mesopore molecular sieve of load titanium.
The concrete preparation process of mesoporous titanium-silicon molecular screen is:
Cats product is dissolved in is made into the homogeneous solution that mass percent concentration is 0.5%-5% in the deionized water, add between the ammoniacal liquor regulator solution pH value 9-11, the silicon source is joined in the above-mentioned solution, and the mol ratio of silicon source and cats product is 2-10, magnetic agitation 2-24h.Product is filtered, use deionized water wash, dry down at 30 ℃-70 ℃ then.At 450 ℃ of-550 ℃ of following roasting 4-8h, obtain white silica mesoporous zeolite.
Get silica mesoporous zeolite and be added in the ethanol and disperse, the mass percent concentration of silica mesoporous zeolite is 0.5%-12%; The titanium source is dissolved in the solvent, press the mol ratio 0.01-0.5 of titanium/silicon, be added in the silica mesoporous zeolite ethanolic soln, 10 ℃ of-60 ℃ of following stirring reaction 2-10h, product filters, and obtains white powder with washing with alcohol, and is dry down at 90 ℃-110 ℃, 300 ℃-550 ℃ calcining 4h-8h obtain mesoporous titanium-silicon molecular screen.
Described cats product comprises: Trimethyllaurylammonium bromide or cetyl trimethylammonium bromide.
Described silicon source comprises: tetraethoxy, sodium orthosilicate, dimethoxydiphenylsilane, select wherein one or more.
Described titanium source comprises: tetraethyl titanate, titanous chloride or titanium tetrachloride.
Described solvent comprises: ethanol or Virahol.
The invention has the advantages that: a kind of method for preparing mesoporous titanium-silicon molecular screen is provided, synthesis material is easy to get, reaction can at room temperature be carried out, and does not need long crystallization process, the titanium-silicone metapore molecular sieve that makes to have high specific surface area and high porosity.Because easy control of reaction conditions, product repeated fine is applicable to mass production.With the HTS that makes is catalyzer, is oxygen source with the hydrogen peroxide, the oxidation of catalyzing expoxidation of olefines and alcohol, and the reaction conditions gentleness, reaction has good selectivity and transformation efficiency.
Description of drawings
Fig. 1 is the SEM photo of the silica mesoporous zeolite that obtains among the embodiment 1.
Fig. 2 is the high resolution TEM photo of mesoporous titanium-silicon molecular screen among the embodiment 1.
Embodiment
Embodiment 1
Trimethyllaurylammonium bromide is dissolved in to be made into mass percent concentration in the deionized water be 0.7% homogeneous solution, adding ammoniacal liquor regulator solution pH value is 10, tetraethoxy is joined (mol ratio of silicon source and Trimethyllaurylammonium bromide is 7) in the solution, magnetic agitation 4h.Product is filtered, use deionized water wash, dry down at 30 ℃ then.At 550 ℃ of following roasting 6h, obtain white silica mesoporous zeolite (see figure 1).
Get silica mesoporous zeolite and join dispersion (mass percent concentration is 3%) in the ethanol, tetraethyl titanate is dissolved in (mol ratio of titanium/silicon is 0.15) is added in the silica mesoporous zeolite ethanolic soln in the ethanol, 30 ℃ of following stirring reaction 4h, product filters, obtain white powder with washing with alcohol, dry under 90 ℃, 300 ℃ of calcining 6h obtain the mesoporous titanium-silicon molecular screen (see figure 2).
Take by weighing mesoporous titanium-silicon molecular screen 28.5mg, 0.46ml cyclooctene, 5ml acetonitrile and join in the round-bottomed flask, be heated to 60 ℃ under the magnetic agitation, add 2.5ml hydrogen peroxide (30%) reaction, the timesharing sampling detects.The transformation efficiency of finding reaction 6h sample reaches 78%, and selectivity is 99%.
Embodiment 2
Cetyl trimethylammonium bromide is dissolved in to be made into mass percent concentration in the deionized water be 0.7% homogeneous solution, adding ammoniacal liquor regulator solution pH value is 10, tetraethoxy and dimethoxydiphenylsilane are joined (mol ratio of silicon source and cetyl trimethylammonium bromide is 7) in the solution, magnetic agitation 6h.Product is filtered, use deionized water wash, dry down at 30 ℃ then.At 550 ℃ of following roasting 6h, obtain white silica mesoporous zeolite.
Get silica mesoporous zeolite and join dispersion (mass percent concentration is 3%) in the ethanol, tetraethyl titanate is dissolved in (mol ratio of titanium/silicon is 0.15) is added in the silica mesoporous zeolite ethanolic soln in the ethanol, 30 ℃ of following stirring reaction 4h, product filters, obtain white powder with washing with alcohol, dry under 90 ℃, 300 ℃ of calcining 6h obtain mesoporous titanium-silicon molecular screen.
Take by weighing mesoporous titanium-silicon molecular screen 28.5mg, 0.46ml cyclooctene, 5ml acetonitrile and join in the round-bottomed flask, be heated to 60 ℃ under the magnetic agitation, add 2.5ml hydrogen peroxide (30%) reaction, the timesharing sampling detects.The transformation efficiency of finding reaction 6h sample reaches 76%, and selectivity is 99%.
Embodiment 3
The hexadecyl trimethylammonium bromide is dissolved in to be made into mass percent concentration in the deionized water be 1.7% homogeneous solution, adding ammoniacal liquor regulator solution pH value is 10, sodium orthosilicate is joined (mol ratio of silicon source and hexadecyl trimethylammonium bromide is 7) in the solution, magnetic agitation 6h.Product is filtered, use deionized water wash, dry down at 30 ℃ then.At 550 ℃ of following roasting 6h, obtain white silica mesoporous zeolite.
Get silica mesoporous zeolite and join dispersion (mass percent concentration is 3%) in the ethanol, titanous chloride is dissolved in (mol ratio of titanium/silicon is 0.15) is added in the silica mesoporous zeolite ethanolic soln in the Virahol, 30 ℃ of following stirring reaction 4h, product filters, obtain white powder with washing with alcohol, dry under 90 ℃, 300 ℃ of calcining 6h obtain mesoporous titanium-silicon molecular screen.
Take by weighing mesoporous titanium-silicon molecular screen 28.5mg, 0.46ml cyclooctene, 5ml acetonitrile and join in the round-bottomed flask, be heated to 60 ℃ under the magnetic agitation, add 2.5ml hydrogen peroxide (30%) reaction, the timesharing sampling detects.The transformation efficiency of finding reaction 6h sample reaches 80%, and selectivity is 99%.
Embodiment 4
Cetyl trimethylammonium bromide is dissolved in to be made into mass percent concentration in the deionized water be 4.6% homogeneous solution, adding ammoniacal liquor regulator solution pH value is 10, tetraethoxy is joined (mol ratio of silicon source and cetyl trimethylammonium bromide is 2.5:1) in the solution, magnetic agitation 2h.Product is filtered, use deionized water wash, dry down at 30 ℃ then.At 550 ℃ of following roasting 6h, obtain white silica mesoporous zeolite.
Get silica mesoporous zeolite and join dispersion (mass percent concentration is 3%) in the ethanol, titanium tetrachloride is dissolved in (mol ratio of titanium/silicon is 0.026) is added in the silica mesoporous zeolite ethanolic soln in the Virahol, 30 ℃ of following stirring reaction 4h, product filters, obtain white powder with washing with alcohol, dry under 90 ℃, 300 ℃ of calcining 6h obtain mesoporous titanium-silicon molecular screen.
Take by weighing mesoporous titanium-silicon molecular screen 28.5mg, 0.46ml cyclooctene, 5ml acetonitrile and join in the round-bottomed flask, be heated to 60 ℃ under the magnetic agitation, add 2.5ml hydrogen peroxide (30%) reaction, the timesharing sampling detects.The transformation efficiency of finding reaction 6h sample reaches 85.2%, and selectivity is 99%.
Claims (5)
1, a kind of preparation method of mesoporous titanium-silicon molecular screen, it is characterized in that, cats product is dissolved in is made into the homogeneous solution that mass percent concentration is 0.5%-5% in the deionized water, add ammoniacal liquor regulator solution pH value between the 9-11, the silicon source is joined in the above-mentioned solution, the mol ratio of silicon source and tensio-active agent is 2-10, magnetic agitation 2-24h, product is filtered, use deionized water wash, dry down at 30 ℃-70 ℃ then.At 450 ℃ of-550 ℃ of following roasting 4-8h, obtain white silica mesoporous zeolite; Getting silica mesoporous zeolite is added in the ethanol and disperses, mass percent concentration is 0.5%-12%, the titanium source is dissolved in the solvent, mol ratio by titanium/silicon is that 0.01-0.5 is added in the silica mesoporous zeolite ethanolic soln, 10 ℃ of-60 ℃ of following stirring reaction 2-10h, and product filters, obtain white powder with washing with alcohol, dry under 90 ℃-110 ℃, 300 ℃-550 ℃ calcining 4h-8h obtain mesoporous titanium-silicon molecular screen.
2, preparation method as claimed in claim 1 is characterized in that, described cats product is Trimethyllaurylammonium bromide or cetyl trimethylammonium bromide.
3, preparation method as claimed in claim 1 is characterized in that, described silicon source is one or more in tetraethoxy, sodium orthosilicate, the dimethoxydiphenylsilane.
4, preparation method as claimed in claim 1 is characterized in that, described titanium source is tetraethyl titanate or titanous chloride or titanium tetrachloride.
5, preparation method as claimed in claim 1 is characterized in that, described solvent is ethanol or Virahol.
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