CN110813373A - Titanium-silicon molecular sieve catalyst, preparation method and application thereof in olefin epoxidation reaction - Google Patents
Titanium-silicon molecular sieve catalyst, preparation method and application thereof in olefin epoxidation reaction Download PDFInfo
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Abstract
A titanium silicon (TS-1) molecular sieve catalyst synthesized by an additive in an auxiliary way, a preparation method and application thereof in olefin epoxidation reaction belong to the technical field of heterogeneous catalysts. The high-performance TS-1 molecular sieve catalyst is synthesized by adopting tetrapropylammonium hydroxide as a structure directing agent, polyethylene glycol or L-carnitine as an additive, adding a titanium source and a silicon source into the additive and adopting a traditional hydrothermal or solvothermal method. And crystallizing for 12-48 hours in a static oven or a rotary oven, sufficiently washing the product by using deionized water and absolute ethyl alcohol, drying, and then calcining at high temperature to remove the structure directing agent and the solvent to obtain the molecular sieve product, wherein the product has an ellipsoidal shape or a hexagonal shape. In a catalytic evaluation system, the TS-1 molecular sieve catalyst shows better catalytic performance in olefin epoxidation reaction and has better circulation stability.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysts, and particularly relates to a titanium silicalite (TS-1) molecular sieve catalyst synthesized by an additive in an auxiliary manner, a preparation method and application thereof in olefin epoxidation.
Background
Epoxy compounds represented by propylene oxide are an important chemical intermediate. Because the traditional production processes for preparing epoxy compounds by chlorohydrination and the like have the problems of serious equipment corrosion, high three wastes and the like, the current research focuses mainly on developing an olefin epoxidation process taking hydrogen peroxide as an oxidant and a titanium silicalite molecular sieve catalyst as a catalyst. The process has the advantages of mild reaction conditions, environmental friendliness and the like, and is the main direction of the development of the olefin epoxidation industrial production at present and even in the future.
The TS-1 molecular sieve catalyst with the MFI structure is formed by isomorphously replacing a pure silicon molecular sieve catalyst S-1 with heteroatom Ti, has the characteristics of regular pore channel structure, high stability, large specific surface area and the like, and shows higher catalytic activity and selectivity for various olefin epoxidation reactions. Currently, several chemical enterprises at home and abroad have successively developed olefin epoxidation production processes based on TS-1 molecular sieve catalysts, and have gradually realized industrialization. However, the preparation process of the TS-1 molecular sieve catalyst is relatively complex and has poor repeatability, and the indexes of epoxy selectivity, hydrogen peroxide utilization rate, catalyst life and the like are also in need of improvement. In addition, due to the limitation of the pore size of the microporous molecular sieve catalyst, the activity of the TS-1 microporous molecular sieve catalyst is relatively low, and the epoxidation performance is not ideal particularly for some of the larger sized cycloolefins. These problems severely restrict the application and popularization of the olefin epoxidation production process based on hydrogen peroxide.
In order to solve the problems, domestic and foreign scholars report a plurality of new strategies and methods for synthesizing the TS-1 molecular sieve catalyst in succession, so that the performance of the catalyst is improved by adjusting parameters such as the state (coordination environment) of Ti species, a pore structure, the crystal morphology, the particle size and the like. For example: bear, etc. forms hierarchical pores and reduces grain size by post-treating traditional TS-1, and improves selectivity of propylene oxide and utilization rate of hydrogen peroxide (G.Xiong, D.Hu, Z.Guo, Q.Meng, L.Liu, Microporous.MeOporous.Mater.2018, 268, 93-99). However, this post-treatment method results in a large loss of the molecular sieve catalyst sample and reduces the structural stability of the molecular sieve catalyst after the formation of hierarchical pores. Recently, the addition of additives (polymer, protein, amino acid and the like) and alcohols in a molecular sieve catalyst synthesis system is tried to regulate the crystal grain size of the TS-1 molecular sieve catalyst, disperse Ti species and form multi-level pores, and certain progress is made. For example, chapters and the like have synthesized anatase-free hierarchical pore TS-1(t.zhang, x.chen, g.chen, m.chen, r.bai, m.jia, j.yu, j.mater.chem.a.2018,6,9473) under dynamic crystallization conditions by adding an additive triton x-100 (triton-100), which shows high catalytic performance for olefin epoxidation. Left, etc. by post-treating TS-1, additives SBA-15 or silicon carbide (Y.Zuo, M.Liu, M.Ma, C.Song, X.Guo, Ind.Eng.chem.Res.2017,56,26,7462-7467) are added to prevent catalyst deactivation and improve the catalytic performance of olefin epoxidation reaction. Although the additive method has the problems of higher cost of using additives, more complicated synthesis steps and the like, the results clearly show that by introducing proper additives and adjusting synthesis parameters, a TS-1 molecular sieve catalyst for olefin epoxidation with more excellent performance is probably obtained.
In the invention, the TS-1 molecular sieve catalyst with different shapes and particle sizes can be synthesized in one step by adopting environment-friendly polyethylene glycol (PEG) or L-carnitine (L-carnitine) as an additive and combining with the adjustment of synthesis parameters (the dosage of the additive, the type and dosage of a solvent, crystallization temperature, crystallization time and the like). Polyethylene glycol (PEG) is a water-soluble linear polymer and has the characteristics of low toxicity, low cost and the like. As an additive, a series of molecular sieve catalysts such as layered SPAOs molecular sieve catalyst, FAU molecular sieve catalyst, ZSM-5 and the like have been synthesized in an auxiliary manner. L-carnitine (L-carnitine) is an amino acid, and is used as an additive to assist in synthesizing a layered Y molecular sieve catalyst and the like. The method used by the invention has the characteristics of simple operation, controllable morphology, crystal face orientation and particle size of the titanium silicalite molecular sieve catalyst in a certain range, uniform distribution of titanium species and the like, and the synthesized TS-1 molecular sieve catalyst shows high catalytic activity, selectivity and hydrogen peroxide utilization rate for epoxidation of various types of olefins (propylene, cyclopentene, 1-hexene and the like), and has good application and development prospects.
Disclosure of Invention
The invention aims to provide a titanium silicon (TS-1) molecular sieve catalyst synthesized by an additive in an auxiliary way, a preparation method and application thereof in olefin epoxidation reaction.
The invention provides a strategy for introducing a proper amount of additives into a sol-gel system for synthesizing a TS-1 molecular sieve catalyst so as to achieve the aim of realizing the aim. The high-performance TS-1 molecular sieve catalyst is synthesized in one step by adding an environment-friendly polyethylene glycol (PEG) or L-carnitine (L-carnitine) additive in the synthesis process, and has higher catalytic performance in olefin epoxidation reaction.
The invention relates to a preparation method of a TS-1 molecular sieve catalyst synthesized by an additive in an auxiliary way, which comprises the following steps:
1) uniformly mixing a structure directing agent tetrapropylammonium hydroxide (TPAOH) with a solvent, and stirring for 1-3 hours at 20-50 ℃ to obtain a uniformly mixed structure directing agent solution;
2) fully and uniformly mixing a silicon source and a titanium source, and stirring for 1-3 hours at 20-50 ℃ to obtain a uniformly mixed silicon source and titanium source solution;
3) mixing the structure directing agent solution obtained in the step 1) and the silicon source and titanium source solution obtained in the step 2), stirring for 3-6 hours at 20-50 ℃ to obtain an initial sol-gel mixture of the TS-1 molecular sieve catalyst, wherein the silicon source is SiO2The titanium source is calculated as TiO2The molar ratio of each component is SiO2：(0.020～0.033)TiO2: (0.20-0.50) structure directing agent: (30-150) a solvent;
4) adding an additive PEG (molecular weight is 300-20000) or L-carnitine (L-carnitine) into the initial sol of the TS-1 molecular sieve catalyst obtained in the step 3)In gel mixture, PEG and SiO2The molar ratio of the used amount of the compound is 0.001-0.02: 1, L-carnitine and SiO2The molar ratio of the used amount of the compound is 0.2-0.8: 1; then, continuously stirring for 4-8 hours under the condition of water bath to obtain a reaction sol-gel mixture; putting the reaction sol-gel mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and crystallizing for 12-48 hours at the temperature of 150-200 ℃ under a static or rotating condition; cooling to room temperature after the reaction is finished, fully washing the product with deionized water and absolute ethyl alcohol for a plurality of times in sequence, and drying at the temperature of 60-80 ℃ to obtain TS-1 molecular sieve catalyst raw powder;
5) calcining the TS-1 molecular sieve catalyst raw powder obtained in the step 5) at 500-600 ℃ for 3-12 hours, and removing the structure directing agent and the solvent contained in the raw powder to obtain the TS-1 molecular sieve catalyst.
The solvent in the step 1) is one or a mixture of water, anhydrous methanol, anhydrous ethanol and anhydrous isopropanol;
the silicon source in the step 2) is one of silica sol, water glass, white carbon black, ethyl orthosilicate or butyl orthosilicate; the titanium source is one of tetraethyl titanate, tetraisopropyl titanate or tetrabutyl titanate.
The TS-1 molecular sieve catalyst synthesized by the aid of the additive prepared by the invention has better catalytic activity in olefin epoxidation reaction.
The TS-1 molecular sieve catalyst applied to olefin epoxidation reaction has the dosage of 50mg, the molar dosages of an olefin substrate and an oxide reagent are respectively 10mmol and 10mmol, the reaction temperature is 50-80 ℃, and the reaction time is 1-3 h. Experimental procedure for the epoxidation of specific olefins: adding a TS-1 molecular sieve catalyst, an olefin substrate, an oxide reagent and methanol into a round-bottom flask (provided with a condenser tube), and magnetically stirring; after the reaction was completed, the reaction solution was taken out and analyzed for the conversion of the olefin substrate by gas chromatography. In the application, the olefin substrate is one of 1-hexene, cyclopentene and propylene; the oxide reagent is one of hydrogen peroxide and tert-butyl hydroperoxide.
The innovation points of the invention are as follows:
the high-performance TS-1 molecular sieve catalyst is synthesized in one step by adopting environment-friendly polyethylene glycol or L-carnitine (L-carnitine) as an additive. The addition of polyethylene glycol or L-carnitine effectively improves the conversion rate of olefin and the selectivity of olefin epoxidation products, and compared with other types of multi-level pore TS-1 catalysts, the catalyst provided by the invention has the following remarkable advantages:
1) the catalyst has simple synthesis steps, short crystallization time and one-step synthesis;
2) the used additive is green and friendly, and the improvement of the catalytic performance is promoted;
3) in the liquid phase catalytic reaction, the catalyst has higher catalytic activity;
4) in the liquid phase catalytic reaction, the circulation is relatively good;
drawings
FIG. 1 is XRD diffraction patterns of the products of examples 1 to 6, from which it can be seen that the crystallinity of 6 samples is high;
FIG. 2 is a Scanning Electron Micrograph (SEM) of the products of examples 1 to 6, from which it can be seen that the samples of examples 1 to 4 have a particle size of 350nm to 500nm and an ellipsoidal morphology. The samples of examples 5 to 6 had particle sizes of 2.5 μm to 5.0. mu.m, and had hexagonal morphologies.
FIG. 3 is a plot of the conversion of olefin substrate in an olefin epoxidation reaction for the samples synthesized in examples 1 through 6; as can be seen from the conversion rate curve, the titanium silicalite molecular sieves synthesized in the examples 1-6 have obviously improved catalytic performance compared with the titanium silicalite molecular sieves synthesized in the comparative example 1.
Table 1: data on catalytic stability in olefin epoxidation reactions for the samples synthesized in examples 1-6
| Products of the examples | T0 | T1 | T2 | T3 | T4 | T5 | T6 |
| Conversion (%) | 30.1 | 47.8 | 52.1 | 48.3 | 47.4 | 45.2 | 55.1 |
| Conversion (%) after 1 cycle | — | 47.7 | 51.7 | 48.4 | 47.1 | 44.9 | 54.8 |
| Conversion (%) after 2 cycles | — | 47.6 | 51.8 | 48.2 | 47.3 | 44.7 | 55.0 |
Detailed Description
In order to clearly illustrate the present invention, the following are only some examples of the present invention, which are convenient for understanding the specific technical solutions of the present invention, but the present invention is not limited to the scope of the present invention, and all equivalent changes and modifications made by the present invention are covered by the scope of the present invention.
The conversions mentioned in the examples are the conversions of 1-hexene (2h catalytic reaction) calculated by chromatographic analysis as follows:
comparative example 1
Fully stirring and mixing 14.34g of deionized water and 4.88g of tetrapropyl ammonium hydroxide aqueous solution with the mass fraction of 25% at 25 ℃ for 2 hours, and marking as solution A; 224.0mg of tetrabutyl titanate and 4.28g of ethyl orthosilicate are mixed and stirred for 2 hours, and the mixture is marked as a solution B; mixing the two solutions, and stirring for 4 hours to obtain a clear solution, namely a TS-1 molecular sieve catalyst sol-gel mixture; the mol ratio of the oxide, tetrapropylammonium hydroxide and water of each component of the sol-gel mixture is SiO2：0.033TiO2：0.3TPAOH：50H2And O. And (3) putting the finally obtained mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, heating to 170 ℃, and carrying out static crystallization at constant temperature (170 ℃) for 24 hours under the autogenous pressure and hydrothermal condition. And then, centrifugally separating the solid product, repeatedly washing the solid product to be neutral by using deionized water and absolute ethyl alcohol, drying the solid product in an oven at 70 ℃ to obtain TS-1 molecular sieve catalyst raw powder, calcining the raw powder at 550 ℃ for 6 hours, and removing the structure directing agent and the solvent contained in the raw powder to obtain a TS-1 molecular sieve catalyst sample (No. T0). The simultaneous catalyst evaluationPerformance: the conversion of 1-hexene was 30% (fig. 3).
Example 1
Fully stirring and mixing 14.34g of deionized water and 4.88g of tetrapropyl ammonium hydroxide aqueous solution with the mass fraction of 25% at 25 ℃ for 2 hours, and marking as solution A; 224.0mg of tetrabutyl titanate and 4.28g of ethyl orthosilicate are mixed and stirred for 2 hours, and the mixture is marked as a solution B; mixing the two solutions, and stirring for 4 hours to obtain a clear solution, namely an initial sol-gel mixture of the TS-1 molecular sieve catalyst; adding 0.14g of PEG (1000) into the initial sol-gel mixture, and stirring for 4 hours to obtain a mixture with the molar ratio of SiO to the oxide, tetrapropylammonium hydroxide and water of each component2：0.033TiO2：0.3TPAOH：50H2O: 0.007 PEG. And (3) filling the finally obtained sol-gel mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, heating to 170 ℃, and carrying out static crystallization at constant temperature (170 ℃) for 24 hours under the autogenous pressure and hydrothermal condition. And then, centrifugally separating the solid product, repeatedly washing the solid product to be neutral by using deionized water and absolute ethyl alcohol, drying the solid product in an oven at 70 ℃ to obtain TS-1 molecular sieve catalyst raw powder, calcining the raw powder at 550 ℃ for 6 hours, and removing a template agent and a solvent contained in the raw powder to obtain a TS-1 molecular sieve catalyst sample (the number of T1) with an ellipsoidal shape. The XRD spectrogram of the sample is shown in figure 1, and the sample can be proved to be in an MFI phase, and the baseline of the spectrogram is relatively flat, which shows that the crystallization degree of the sample is relatively high; scanning electron micrographs (figure 2) can prove that the obtained TS-1 molecular sieve catalyst with an ellipsoidal morphology is uniform in size and morphology and very good in dispersibility. Meanwhile, the evaluation performance of the catalyst is as follows: the 1-hexene conversion was 47.8% (fig. 3) and the catalyst was better worked 2 times (table 1).
Example 2
Fully stirring and uniformly mixing 14.34g of deionized water, 3g of anhydrous Isopropanol (IPA) and 4.88g of 25 mass percent tetrapropyl ammonium hydroxide aqueous solution at 25 ℃ for 2 hours, and marking as solution A; 224.0mg of tetrabutyl titanate and 4.28g of ethyl orthosilicate are mixed and stirred for 2 hours, and the mixture is marked as a solution B; mixing the above two solutions, stirring for 2 hr to obtain clear solutionThe solution is the initial sol-gel mixture of the TS-1 molecular sieve catalyst; adding 0.21g of PEG (1000) into the initial sol-gel mixture, and stirring for 4 hours to obtain a TS-1 molecular sieve catalyst sol-gel mixture; the mol ratio of the oxide, tetrapropylammonium hydroxide, water and the like of each component in the gel mixture is SiO2：0.033TiO2：0.3TPAOH：50H2O: 5 IPA: 0.01 PEG. And (3) putting the finally obtained sol-gel mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, heating to 170 ℃, and carrying out static crystallization at constant temperature (170 ℃) for 36 hours under the autogenous pressure and hydrothermal condition. And then, centrifugally separating the solid product, repeatedly washing the solid product to be neutral by using deionized water and absolute ethyl alcohol, drying the solid product in an oven at 70 ℃ to obtain nano TS-1 molecular sieve catalyst raw powder, and calcining the raw powder at 550 ℃ for 6 hours to remove a template agent and a solvent contained in the raw powder to obtain a TS-1 molecular sieve catalyst sample (the number of T2) with an ellipsoidal shape. The XRD spectrogram of the sample is shown in figure 1, and the sample can be proved to be in an MFI phase, and the baseline of the spectrogram is relatively flat, which shows that the crystallization degree of the sample is relatively high; scanning electron micrographs (figure 2) can prove that the obtained TS-1 molecular sieve catalyst with an ellipsoidal morphology is uniform in size and morphology and very good in dispersibility. Meanwhile, the evaluation performance of the catalyst is as follows: the 1-hexene conversion was 52.1% (fig. 3) and the catalyst was better worked 2 times (table 1).
Example 3
Fully stirring and mixing 10.13g of deionized water and 5.69g of 25 mass percent tetrapropyl ammonium hydroxide aqueous solution at 25 ℃ for 2 hours, and marking as a solution A; 224.0mg of tetrabutyl titanate and 1.2g of fumed silica are mixed and stirred for 2 hours, and the mixture is marked as solution B; mixing the two solutions, stirring for 4 hours, adding 0.3g of PEG (6000), and stirring for 4 hours to obtain a sol-gel mixture of the TS-1 molecular sieve catalyst; the mol ratio of the oxide, the tetrapropylammonium hydroxide and the water of each component is SiO2：0.033TiO2：0.35TPAOH：40H2O: 0.0025 PEG. Loading the sol-gel mixture into stainless steel reactor with polytetrafluoroethylene lining, heating to 170 deg.CAnd then the mixture is subjected to static crystallization for 36 hours at a constant temperature (170 ℃) under the autogenous pressure and hydrothermal condition. And then, centrifugally separating the solid product, repeatedly washing the solid product to be neutral by using deionized water and absolute ethyl alcohol, drying the solid product in an oven at 70 ℃ to obtain TS-1 molecular sieve catalyst raw powder, and calcining the raw powder at 550 ℃ for 6 hours to remove a template agent and a solvent contained in the raw powder to obtain a TS-1 molecular sieve catalyst sample (the number of T3) with an ellipsoidal shape. The XRD spectrogram of the sample is shown in figure 1, and the sample can be proved to be in an MFI phase, and the baseline of the spectrogram is relatively flat, which shows that the crystallization degree of the sample is relatively high; scanning electron micrographs (figure 2) can prove that the obtained TS-1 molecular sieve catalyst with an ellipsoidal morphology is uniform in size and morphology and very good in dispersibility. Meanwhile, the evaluation performance of the catalyst is as follows: the 1-hexene conversion was 48.3% (fig. 3) and the catalyst was better worked 2 times (table 1).
Example 4
Fully stirring and mixing 8.33g of deionized water and 5.69g of 25 mass percent tetrapropylammonium hydroxide aqueous solution at 25 ℃ for 2 hours, and marking as a solution A; 224.0mg of tetrabutyl titanate is mixed with 3g of silica hydrosol with the mass fraction of 40 percent, and the mixture is stirred for 2 hours and is marked as solution B; mixing the two solutions, stirring for 4 hours, adding 0.3g of PEG (2000), and stirring for 4 hours to obtain a clear solution, namely an initial sol-gel mixture of the TS-1 molecular sieve catalyst; the molar ratio of each component oxide, tetrapropylammonium hydroxide and water in the initial sol-gel mixture is SiO2：0.033TiO2：0.35TPAOH：40H2O: 0.0075 PEG. And (3) filling the finally obtained sol-gel mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, heating to 170 ℃, and carrying out constant-temperature (170 ℃) dynamic crystallization for 36 hours under the autogenous pressure and hydrothermal condition. And then, centrifugally separating the solid product, repeatedly washing the solid product to be neutral by using deionized water, drying the solid product in an oven at 70 ℃ to obtain TS-1 molecular sieve catalyst raw powder, and calcining the raw powder at 550 ℃ for 6 hours to remove a template agent and a solvent contained in the raw powder to obtain a TS-1 molecular sieve catalyst sample (No. T4) with an ellipsoidal shape. The XRD pattern of the sample as shown in figure 1 can confirm that the sample exhibits an MFI phase,the base line of the spectrogram is relatively flat, which indicates that the crystallization degree of the sample is relatively high; scanning electron microscope photo (figure 2) can obtain the TS-1 molecular sieve catalyst with ellipsoidal morphology, uniform size and morphology, and very good dispersibility. Meanwhile, the evaluation performance of the catalyst is as follows: the 1-hexene conversion was 47.4% (fig. 3) and the catalyst was better worked 2 times (table 1).
Example 5
40.98g of deionized water, 13.8g of absolute ethanol (C)2H5OH) and 4.88g of tetrapropylammonium hydroxide aqueous solution with the mass fraction of 25 percent are fully stirred and mixed for 2 hours at 25 ℃, and the solution A is marked; 224.0mg of tetrabutyl titanate and 4.28g of ethyl orthosilicate are mixed and stirred for 2 hours, and the mixture is marked as a solution B; mixing the two solutions, stirring for 4 hours, adding 1.29g of L-carnitine (LC), and stirring for 4 hours to obtain a clear solution, namely an initial sol-gel mixture of the TS-1 molecular sieve catalyst; the molar ratio of the oxide, tetrapropylammonium hydroxide and water of each component in the mixture is SiO2：0.033TiO2：0.30TPAOH：124H2O：15C2H5OH: 0.4 LC. And (3) putting the finally obtained sol-gel mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, heating to 170 ℃, and crystallizing for 36 hours at constant temperature (170 ℃) under the conditions of autogenous pressure and hydrothermal reaction. And then, centrifugally separating the solid product, repeatedly washing the solid product to be neutral by using deionized water and absolute ethyl alcohol, drying the solid product in an oven at 70 ℃ to obtain TS-1 molecular sieve catalyst raw powder, and calcining the raw powder at 550 ℃ for 6 hours to remove a template agent and a solvent contained in the raw powder to obtain a TS-1 molecular sieve catalyst sample (No. T5). The XRD spectrogram of the sample is shown in figure 1, which can prove that the sample presents MFI phase, and the baseline of the spectrogram is relatively flat, which shows that the crystallization degree of the sample is relatively high; scanning electron microscope photo (figure 2) can obtain the TS-1 molecular sieve catalyst with the morphology of a long hexagon body, the size and the morphology are uniform, and the dispersity is very good. Meanwhile, the evaluation performance of the catalyst is as follows: the 1-hexene conversion was 45.2% (fig. 3) and the catalyst was better worked 2 times (table 1).
Example 6
40.98g of deionized water, 13.8g ofWater ethanol (C)2H5OH) and 4.88g of tetrapropylammonium hydroxide aqueous solution with the mass fraction of 25 percent are fully stirred and mixed for 2 hours at 25 ℃, and the solution A is marked; 224.0mg of tetrabutyl titanate and 4.28g of ethyl orthosilicate are mixed and stirred for 2 hours, and the mixture is marked as a solution B; mixing the two solutions, stirring for 4 hours, adding 1.94g of L-carnitine (LC), and stirring for 4 hours to obtain a clear solution, namely an initial sol-gel mixture of the TS-1 molecular sieve catalyst; the molar ratio of each component oxide, tetrapropylammonium hydroxide and water in the initial sol-gel mixture is SiO2：0.033TiO2：0.30TPAOH：124H2O：15C2H5OH: 0.6 LC. And (3) putting the finally obtained gel mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, putting the reaction kettle into an oven, heating to 170 ℃, and crystallizing for 36 hours at constant temperature (170 ℃) under the autogenous pressure and hydrothermal condition. And then, centrifugally separating the solid product, repeatedly washing the solid product to be neutral by using deionized water and absolute ethyl alcohol, drying the solid product in an oven at 70 ℃ to obtain TS-1 molecular sieve catalyst raw powder, and calcining the raw powder at 550 ℃ for 6 hours to remove a template agent and a solvent contained in the raw powder to obtain a TS-1 molecular sieve catalyst sample (No. T6). The XRD spectrogram of the sample is shown in figure 1, which can prove that the sample presents MFI phase, and the baseline of the spectrogram is relatively flat, which shows that the crystallization degree of the sample is relatively high; scanning electron microscope photo (figure 2) can obtain the TS-1 molecular sieve catalyst with the morphology of a long hexagon body, the size and the morphology are uniform, and the dispersity is very good. Meanwhile, the evaluation performance of the catalyst is as follows: the 1-hexene conversion was 55.1% (fig. 3) and the catalyst was better worked 2 times (table 1).
The above description is only a preferred embodiment of the present invention, and the above examples are provided to illustrate the detailed synthesis and application of the catalyst of the present invention in olefin epoxidation reaction, but the scope of the present invention is not limited thereto, and the selection of the raw materials, the ratio of the components, and the preparation method of the catalyst of the present invention are all within the scope of the present invention. Any person skilled in the art should be able to substitute or change the technical solution of the present invention and its inventive concept within the technical scope of the present invention.
Claims (5)
1. A preparation method of a titanium silicalite molecular sieve catalyst synthesized by the aid of additives comprises the following steps:
1) uniformly mixing a structure directing agent tetrapropylammonium hydroxide with a solvent, and stirring for 1-3 hours at 20-50 ℃ to obtain a uniformly mixed structure directing agent solution;
2) fully and uniformly mixing a silicon source and a titanium source, and stirring for 1-3 hours at 20-50 ℃ to obtain a uniformly mixed silicon source and titanium source solution;
3) mixing the structure directing agent solution obtained in the step 1) and the silicon source and titanium source solution obtained in the step 2), stirring for 3-6 hours at 20-50 ℃ to obtain an initial gel mixture of the titanium-silicon molecular sieve catalyst, wherein the silicon source is SiO2The titanium source is calculated as TiO2The molar ratio of each component is SiO2：(0.020～0.033)TiO2: (0.20-0.50) structure directing agent: (30-150) a solvent;
4) adding additive polyethylene glycol or L-carnitine into the initial sol-gel mixture of the titanium silicalite molecular sieve catalyst obtained in the step 3), wherein the polyethylene glycol and SiO2The molar ratio of the used amount of the compound is 0.001-0.02: 1, L-carnitine and SiO2The molar ratio of the used amount of the compound is 0.2-0.8: 1; then, continuously stirring for 4-8 hours under the condition of water bath to obtain a reaction sol-gel mixture; putting the reaction sol-gel mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, and performing static or rotary crystallization for 12-48 hours at the temperature of 150-200 ℃; cooling to room temperature after the reaction is finished, fully washing the product with deionized water and absolute ethyl alcohol for a plurality of times in sequence, and drying at the temperature of 60-80 ℃ to obtain the titanium silicalite molecular sieve catalyst raw powder;
5) calcining the raw powder of the titanium silicalite molecular sieve catalyst obtained in the step 5) at 500-600 ℃ for 3-12 hours, and removing the structure directing agent and the solvent contained in the raw powder to obtain the titanium silicalite molecular sieve catalyst.
2. The method of claim 1, wherein the method comprises the following steps: the solvent in the step 1) is one or a mixture of water, anhydrous methanol, anhydrous ethanol and anhydrous isopropanol.
3. The method of claim 1, wherein the method comprises the following steps: the silicon source in the step 2) is one of silica sol, water glass, white carbon black, ethyl orthosilicate or butyl orthosilicate; the titanium source is one of tetraethyl titanate, tetraisopropyl titanate or tetrabutyl titanate.
4. An additive-assisted synthesized titanium silicalite molecular sieve catalyst is characterized in that: is prepared by the method of any one of claims 1 to 3.
5. The use of an additive-assisted synthesized titanium silicalite molecular sieve catalyst of claim 4 in olefin epoxidation reactions.
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| CN113731485A (en) * | 2021-09-29 | 2021-12-03 | 江西师范大学 | Preparation method of supported hierarchical pore titanium silicalite molecular sieve |
| CN115845916A (en) * | 2022-12-23 | 2023-03-28 | 大连理工大学 | Preparation method and application of Au/TS-1 nano microsphere catalyst for propylene gas phase epoxidation |
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