CN112978754B - Preparation method and application of basic titanium silicalite TS-1 - Google Patents

Preparation method and application of basic titanium silicalite TS-1 Download PDF

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CN112978754B
CN112978754B CN201911282431.0A CN201911282431A CN112978754B CN 112978754 B CN112978754 B CN 112978754B CN 201911282431 A CN201911282431 A CN 201911282431A CN 112978754 B CN112978754 B CN 112978754B
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张晓敏
许磊
陈磊
赵晓炜
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Dalian Institute of Chemical Physics of CAS
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Abstract

The application discloses a preparation method of a basic titanium silicalite TS-1, which comprises the following steps: 1) Reacting a silicon source and a titanium source in an alkaline system to obtain a titanium dioxide/silicon composite material containing amino; 2) Adding the titanium dioxide/silicon composite material containing amino in the step 1) into a solution containing a structure directing agent II, and drying to obtain an initial synthesis mixture; 3) Carrying out crystallization reaction on the initial synthesis mixture in the step 2) by adopting a dry glue method; 4) Separating and roasting the reaction product obtained in the step 3) to obtain the basic titanium silicalite TS-1. The method can effectively utilize raw materials, saves production cost, is simple and feasible in the prior art, and the prepared TS-1 molecular sieve crystal has high crystallinity, contains an alkaline center and a framework titanium oxidation active center, and can adjust the content of framework titanium and amino in a wider range.

Description

Preparation method and application of basic titanium silicalite TS-1
Technical Field
The application relates to a preparation method and application of an alkaline titanium silicalite TS-1, belonging to the technical field of catalyst synthesis.
Background
Propylene oxide is an important basic organic chemical raw material, and the largest application is to produce polyether polyol and further serve as a polyurethane raw material; secondly, the method is used for producing propylene glycol, propylene glycol ether, isopropanolamine, allyl alcohol, 1,4-butanediol and the like with wide application, and the epoxypropane can also be used for producing a large amount of nonionic surfactants, oil field demulsifiers, pesticide emulsifiers, developers and the like. The derivative of the propylene oxide is widely applied to industries and daily lives of people, such as industries of automobiles, buildings, foods, medicines, cosmetics and the like, and has important significance for improving the quality of life of human beings.
At present, the chlorohydrin method and the co-oxidation method are mainly adopted for industrial production of the propylene oxide. The chlorohydrin method has obvious defects, large water resource consumption, and large amount of wastewater and waste residues, wherein 40-50 tons of saponified wastewater containing chloride and more than 2 tons of waste residues are generated when 1 ton of propylene oxide is produced, and the three wastes are difficult to treat. The co-oxidation method comprises 2 kinds of iso-butane co-oxidation methods and ethyl benzene co-oxidation methods, wherein iso-butane or ethyl benzene and propylene are subjected to co-oxidation reaction respectively to generate tert-butyl alcohol or styrene, and PO is co-produced at the same time. The co-oxidation method overcomes the defects of large corrosion, more three wastes and the like of the chlorohydrin method, and has the advantages of low product cost (co-product apportionment cost), less environmental pollution and the like. The co-oxidation method has the disadvantages of long process flow, various raw materials, high propylene purity requirement, high process operation requirement under high pressure, high equipment cost and high construction investment due to the adoption of alloy steel as the equipment material.
As can be seen from the above, the existing process for producing propylene oxide has various disadvantages, and particularly does not meet the requirements of green chemistry and chemical engineering. Therefore, there is an urgent need to develop an economical and also environmentally friendly production process. The discovery of the titanium silicalite molecular sieve and the application thereof in the field of selective catalytic oxidation open up a new way for the production of propylene oxide.
Until now, researchers have made a lot of research on the synthesis of propylene oxide by catalyzing the epoxidation reaction of propylene and hydrogen peroxide with TS-1 as a catalyst. Researches show that when TS-1 is used as a catalyst to catalyze propylene epoxidation reaction, alkaline additives such as ammonia water and sodium bicarbonate are required to be added into both a fixed bed reactor and a kettle reactor to adjust the pH value of reaction raw materials so as to inhibit side reactions in the propylene epoxidation reaction process, and further improve the selectivity of propylene oxide. The addition of the alkaline additive not only increases the cost of the separation process of the product, but also influences the service life of the TS-1 molecular sieve catalyst in practical application. Therefore, the novel TS-1 molecular sieve catalyst is further developed, the selectivity of propylene oxide in the reaction process is improved, and the use of an alkaline additive is avoided, so that the method has important practical application value.
Disclosure of Invention
According to one aspect of the application, a preparation method of a basic titanium silicalite TS-1 is provided, which solves the problem that a basic additive is required to be used in the existing propylene epoxidation reaction process.
The preparation method of the basic titanium silicalite TS-1 comprises the following steps: 1) Reacting a silicon source and a titanium source in an alkaline system to obtain a titanium dioxide/silicon composite material containing amino; 2) Adding the titanium dioxide/silicon composite material containing amino in the step 1) into a solution containing a structure directing agent II, and drying to obtain an initial synthesis mixture; 3) Carrying out crystallization reaction on the initial synthesis mixture in the step 2) by adopting a dry glue method; 4) Separating and roasting the reaction product obtained in the step 3) to obtain the basic titanium silicalite TS-1.
Optionally, the silicon source comprises a component I and a component II; the component I is a silane coupling agent containing amino; the component II is a silicon source without amino; the molar ratio of the component I to the component II is 0.001-0.3.
Alternatively, the molar ratio of the component i to the component ii is 0.001.
Optionally, the component I is selected from at least one of aminopropyltrimethoxysilane, aminopropyltriethoxysilane and anilinomethyltriethoxysilane; the component II is at least one selected from methyl orthosilicate, ethyl orthosilicate, silica sol and sodium silicate.
Optionally, the alkaline system in the step 1) contains a structure directing agent I, wherein the structure directing agent I is a cationic surfactant.
Optionally, the structural formula of the cationic surfactant is shown as formula I;
Figure BDA0002317128100000031
wherein R is 1 ，R 2 ，R 3 Independently selected from C 1 ～C 5 Alkyl groups of (a); r 4 Is selected from C 8 ～C 20 Alkyl groups of (a); x - Is selected from Br - 、Cl - Or OH - 。
Optionally, the structure directing agent i is selected from at least one of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide or octadecyl trimethyl ammonium bromide.
Optionally, the alkaline system in step 1) is selected from at least one of ammonia or sodium hydroxide solution; the pH value of the alkaline system is between 9 and 12.
Optionally, the titanium source is at least one selected from the group consisting of tetraethyl titanate, tetrabutyl titanate, isopropyl titanate, titanium trichloride and titanium tetrachloride.
Alternatively, the structure directing agent i: silicon source: titanium source = 0.005-1.0;
preferably, the structure directing agent i: silicon source: titanium source = 0.005-1.0.
Alternatively, structure directing agent i: the molar ratio of the silicon source is 0.005.0, 0.006, 1.0, 0.007.
Optionally, the silicon source: the molar ratio of the titanium source is 1.001, 1.002, 1.003, 1.004, 1.
Optionally, the reaction in step 1) is a stirred reaction; wherein the reaction temperature is 30-100 ℃, and the stirring time is 2-12h.
Optionally, the titanium dioxide/silicon composite material containing amino groups is spherical in shape and has an average particle size of 50 to 1000nm.
Optionally, the titanium dioxide/silicon composite material containing amino groups has an average particle size of 100 to 500nm.
Optionally, the structure directing agent ii is selected from at least one of tetraethylammonium hydroxide, tetrapropylammonium bromide and tetrapropylammonium chloride.
Optionally, the molar ratio of silicon in the titanium dioxide/silicon composite material in the step 2) to the structure directing agent II is 1:0.05-0.5.
Alternatively, the molar ratio of silicon in the titanium dioxide/silicon composite material in step 2) to the structure directing agent ii is in the range of 1.
Optionally, the crystallization reaction in step 3) comprises: placing the initial synthesis mixture in the step 2) into a closed reactor, and carrying out crystallization reaction on the initial synthesis mixture in the presence of water vapor.
Optionally, the temperature of the crystallization reaction is 100-200 ℃, and the time of the crystallization reaction is 12-100h.
Optionally, the temperature of the crystallization reaction is 100 ℃, 110 ℃, 120 ℃, 130 ℃, 140 ℃, 150 ℃, 160 ℃, 170 ℃, 180 ℃, 190 ℃, 200 ℃ and a range between any two values.
Alternatively, the crystallization reaction time is 12h, 20h, 24h, 30h, 40h, 50h, 60h, 70h, 72h, 80h, 90h, 96h, 100h, and ranges between any two values.
Optionally, the basic TS-1 molecular sieve has a particle size of between 0.08 and 5 μm.
As a specific embodiment, the preparation method of the basic titanium silicalite TS-1 comprises the following steps:
step 1, in an alkaline system with PH of 9-12, taking a cationic surfactant as a structure directing agent, adding a silicon source and a titanium source, stirring for 2-12h at 30-100 ℃, and then filtering, washing and drying to obtain amorphous titanium dioxide/silicon composite materials with different amino and titanium contents;
step 2, impregnating the material obtained in the step 1 with an organic structure directing agent, and drying and concentrating at room temperature to obtain an initial synthetic mixture;
and 3, placing the mixture obtained in the step 2 on the upper part of a stainless steel high-pressure reaction kettle, adding deionized water into the lower part of the reaction kettle, and carrying out reaction crystallization for 12-100h at the temperature of 100-200 ℃. Finally cooling the reaction kettle after the reaction is finished to room temperature;
and 4, centrifuging, washing and drying the reaction product obtained in the step 3 to obtain the alkaline TS-1 molecular sieve.
According to another aspect of the application, the application of the basic titanium silicalite TS-1 prepared by the preparation method as a catalyst in the epoxidation reaction of olefin is also provided.
In the present application, the silicon source is in terms of the number of moles of silicon element contained therein, the titanium source is in terms of the number of moles of titanium element contained therein, and the structure-directing agent I and the structure-directing agent II are in terms of the number of moles thereof.
In the present application, the titanium dioxide/silicon composite material containing amino groups refers to homogeneous titanium silicon spheres.
The beneficial effect that this application can produce includes:
1) The alkaline titanium silicalite TS-1 provided by the application solves the problem that an alkaline additive is needed in the existing propylene epoxidation reaction process.
2) According to the preparation method provided by the application, the amorphous titanium dioxide/silicon nanospheres are firstly synthesized in an alkaline system, the problems that the introduction of framework titanium is difficult and the content of titanium is low are solved, and meanwhile, alkaline amino groups are introduced to provide alkaline active centers. In the synthesis method, the introduction amount of titanium and amino can be adjusted in a wider range, and a foundation is laid for synthesizing TS-1 molecular sieves with different amino and titanium contents.
3) The preparation method adopts a dry glue method as a crystallization process, the titanium silicon precursor is not directly contacted with the aqueous solution in the crystallization process, and the TS-1 molecular sieve is generated by performing crystallization reaction on steam generated by the aqueous solution and the titanium silicon precursor in a crystallization kettle. The method can effectively utilize raw materials, saves production cost, is simple and feasible in the prior art, and the prepared TS-1 molecular sieve crystal has high crystallinity, contains an alkaline center and a framework titanium oxidation active center, and can adjust the content of framework titanium and amino in a wider range.
4) The alkaline TS-1 molecular sieve synthesized by the preparation method provided by the application shows excellent catalytic performance in propylene epoxidation reaction, the activity of the catalyst is improved, the catalyst has excellent catalytic performance on propylene epoxidation reaction, and the selectivity of propylene oxide is high.
Drawings
FIG. 1 is an SEM photograph of MTS-I to MTS-IV samples prepared in example 1.
FIG. 2 is an XRD spectrum of samples TS-1-1 to TS-1-6 prepared in example 2.
FIG. 3 is an SEM photograph of samples TS-1-1 to TS-1-6 prepared in example 2.
Detailed Description
The present invention is further illustrated by the following examples and drawings, but the present invention is not limited to the following examples, and all similar structures and similar variations of the present invention are included in the scope of the present invention.
The raw material reagents used in the examples were all obtained commercially and used without any special treatment.
The analysis method in the examples of the present application is as follows:
performing morphology analysis on the product by using a scanning electron microscope (model: JSM-7800F);
the product was subjected to diffraction analysis using an X-ray diffractometer (model: PANalytical X' Pert Pro).
Example 1: preparation of amino modified amorphous mesoporous titanium dioxide/silicon spheres
Dissolving a structure directing agent I (R) in 60mL of deionized water and ethanol solution under the stirring condition of 30-100 ℃, adding ammonia water into the solution to adjust the pH value of the solution, adding a silicon source (component II) without amino, an aminosilane coupling agent (component I) and a titanium source after stirring, and continuing stirring for 2-12h. The product was filtered, washed and dried, and the structure directing agent I was removed by refluxing in an acidic ethanol solution to give a white powder, which was designated as samples MTS-I to MTS-VI. The types and proportions of the raw materials, the reaction temperatures and the reaction times of the prepared samples MTS-I to MTS-VI are respectively shown in Table 1.
TABLE 1 mesoporous Titania/Si Synthesis conditions and Performance parameter Table
Figure BDA0002317128100000061
Figure BDA0002317128100000071
SEM characterization of the samples was performed, and is typically shown in FIG. 1, where FIG. 1 is a SEM image of samples MTS-I through MTS-IV prepared in example 1. SEM results show that the obtained product has uniform particle size and good dispersibility, and is a spherical material with the size between 50nm and 500nm. Considering that the SEM pictures of the samples MTS-V, MTS-VI are substantially similar to that of MTS-I, the sizes are all between 50nm and 500nm and thus are not shown.
Example 2: preparation of samples TS-1-1 to TS-1-8
Preparation of sample TS-1-1:
firstly, adding tetrapropylammonium hydroxide (structure directing agent II) into deionized water, and stirring and dissolving to obtain a mixed solution. A certain amount of the above solution was taken to impregnate the amino-modified amorphous titanium oxide/silicon spheres prepared in example 1, and after drying at room temperature for a period of time, a solid mixture was obtained. And transferring the solid mixture to a flat disc at the upper part of a stainless steel high-pressure reaction kettle, and adding water into the bottom of the reaction kettle. Sealing the stainless steel reaction kettle, putting the stainless steel reaction kettle into an oven, and crystallizing the stainless steel reaction kettle for 12 to 100 hours at the temperature of between 100 and 200 ℃. And after the reaction is finished, quickly cooling, separating a solid product, washing with deionized water, drying for 12 hours at 110 ℃ in an air atmosphere, stirring and washing for 6 hours in an ethanol solution, and centrifugally drying to obtain the alkaline TS-1 molecular sieve, wherein the sample is marked as TS-1-1.
Preparation of samples TS-1-2 to TS-1-8:
samples TS-1-2 to TS-1-8 were prepared according to the conditions listed in Table 2 below, respectively, in a manner substantially similar to that of sample TS-1-1, except as listed in Table 2, and otherwise identical to the conditions for the preparation of sample TS-1-1.
The correspondence between the sample numbers and the preparation conditions is shown in Table 2.
XRD characterization of the prepared samples was performed, and since the XRD patterns of TS-1-7 and TS-1-8 were similar to that of TS-1-1, the main diffraction peak positions and shapes were the same, and the relative peak intensities varied within + -5% depending on the synthesis conditions, they were not shown. Typically, the results are shown in FIG. 2, where FIG. 2 is an XRD spectrum of samples TS-1-1 to TS-1-6 prepared in example 2. As can be seen from FIG. 2, the XRD pattern of the samples TS-1-1 to TS-1-6 is consistent with the characteristic pattern of the standard MFI molecular sieve, the diffraction peak intensity is high, the crystallization is good, and the obtained sample is the titanium silicalite TS-1.
And performing scanning electron microscope characterization on the prepared typical samples TS-1-1 to TS-1-6 by using a JSM-7800F type high-resolution scanning electron microscope, wherein SEM images of the TS-1-7 and the TS-1-8 are similar to the SEM image of the TS-1-1 and are not shown. As shown in FIG. 3, the sample is a crystal grain with uniform distribution of nanometer to micrometer size, and the grain diameter is between 0.08 and 5 μm.
TABLE 2 table of TS-1 molecular sieve compounding ingredients, crystallization conditions and particle size of the product
Figure BDA0002317128100000081
Example 3: evaluation of epoxidation reaction of propylene
The experiment adopts the traditional hydrothermal method to synthesize the TS-1 sample, and the proportion of the synthesized gel is 1SiO 2 :0.25TPAOH:0.02TiO 2 :35H 2 And O. The preparation method comprises the following specific gel preparation steps: firstly, adding tetrapropylammonium hydroxide (TPAOH) into deionized water at room temperature and stirring; slowly adding a certain amount of ethyl orthosilicate and butyl titanate after the materials are fully dissolved; stirring at room temperature for 24 hr, transferring the material to a stainless steel synthesis kettle, and crystallizing at 150 deg.C for 24 hr. The solid product obtained is centrifuged, washed and then dried at 110 ℃And finally roasting at 550 ℃ for 6h to remove the organic template, and naming the template as conv-TS-1.
The prepared conv-TS-1 and the basic TS-1 molecular sieve prepared in example 2 were subjected to propylene epoxidation evaluation, and propylene epoxidation evaluation was performed using a fixed bed reactor and a high pressure reactor, respectively.
The fixed bed reaction evaluation comprises the following specific steps: tabletting and crushing the TS-1 molecular sieve into 20-40 meshes, and loading the 20-40 meshes into the middle section of a fixed bed reactor; methanol and hydrogen peroxide (30 percent) are mixed according to a proportion to prepare reaction mixed liquid, and the reaction mixed liquid is pumped into a fixed bed reactor by a feed pump. Before the reaction, nitrogen is pressurized to 3.0Mpa, and the reaction temperature is controlled to be 50 ℃ by adopting a circulating water bath. Propylene enters from the lower end of the reactor through a feed pump, and a product flows out from the upper end and enters a cold trap for storage. The reaction products were analyzed by gas chromatography and iodometry, respectively.
The high-pressure reaction kettle type evaluation comprises the following specific steps: 0.10g of sample, 10mL of methanol solvent, 1.5g H are weighed 2 O 2 Was charged into a 100mL autoclave, to which propylene was then introduced under a pressure of 0.6MPa. The reaction is carried out for 1h at 50 ℃. After the reaction was stopped, the solid catalyst was filtered off, and the reaction solution was subjected to gas chromatography and iodometry. The conversion of propylene and the selectivity to cyclohexene oxide are shown in Table 3. Comparing the conv-TS-1 sample with the TS-1-TS-1-8 samples, the results show that the catalytic activity of the nano TS-1 molecular sieve prepared by the preparation method disclosed by the application for catalyzing the propylene epoxidation reaction is obviously higher than that of the TS-1 molecular sieve synthesized by the traditional hydrothermal method.
TABLE 3 results of propylene epoxidation reaction catalyzed by TS-1 molecular sieve
Figure BDA0002317128100000091
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.

Claims (17)

1. A preparation method of a basic titanium silicalite TS-1 is characterized by comprising the following steps:
1) Reacting a silicon source and a titanium source in an alkaline system to obtain a titanium dioxide/silicon composite material containing amino;
2) Adding the titanium dioxide/silicon composite material containing amino in the step 1) into a solution containing a structure directing agent II, and drying to obtain an initial synthesis mixture;
3) Carrying out crystallization reaction on the initial synthesis mixture in the step 2) by adopting a dry glue method;
4) Separating and roasting the reaction product obtained in the step 3) to obtain the basic titanium silicalite TS-1;
the silicon source comprises a component I and a component II;
the component I is a silane coupling agent containing amino;
the component II is a silicon source without amino;
the molar ratio of the component I to the component II is 0.001-0.3;
the alkaline system in the step 1) is at least one selected from ammonia water or sodium hydroxide solution;
the pH value of the alkaline system is between 9 and 12.
2. The method according to claim 1, wherein the component I is at least one selected from aminopropyltrimethoxysilane, aminopropyltriethoxysilane, and anilinomethyltriethoxysilane;
the component II is at least one selected from methyl orthosilicate, ethyl orthosilicate, silica sol and sodium silicate.
3. The process according to claim 1, wherein the basic system of step 1) contains a structure-directing agent I,
wherein, the structure directing agent I is a cationic surfactant.
4. The method according to claim 3, wherein the cationic surfactant has a formula represented by formula I;
Figure FDA0003830292450000021
wherein R is 1 ，R 2 ，R 3 Independently selected from C 1 ～C 5 Alkyl groups of (a); r 4 Is selected from C 8 ～C 20 Alkyl groups of (a); x - Is selected from Br - 、Cl - Or OH - 。
5. The method according to claim 3, wherein the structure-directing agent I is at least one selected from the group consisting of dodecyltrimethylammonium chloride, hexadecyltrimethylammonium bromide and octadecyltrimethylammonium bromide.
6. The method according to claim 1, wherein the titanium source is at least one selected from the group consisting of tetraethyl titanate, tetrabutyl titanate, isopropyl titanate, titanium trichloride and titanium tetrachloride.
7. The method of claim 3, wherein the structure directing agent I: silicon source: titanium source = 0.005-1.0.
8. The method of claim 7, wherein the structure directing agent I: silicon source: titanium source = 0.005-1.0.
9. The production method according to claim 1, wherein the reaction in step 1) is a stirring reaction;
wherein the reaction temperature is 30-100 ℃, and the stirring time is 2-12h.
10. The production method according to claim 1, wherein the titanium dioxide/silicon composite material containing an amino group has a spherical shape and an average particle diameter of 50 to 1000nm.
11. The production method according to claim 10, wherein the titanium dioxide/silicon composite material containing an amino group has an average particle diameter of 100 to 500nm.
12. The preparation method according to claim 1, wherein the structure directing agent II is at least one selected from tetraethylammonium hydroxide, tetrapropylammonium bromide and tetrapropylammonium chloride.
13. The preparation method according to claim 1, wherein the molar ratio of silicon in the titanium dioxide/silicon composite material to the structure directing agent II in step 2) is 1:0.05-0.5.
14. The method of claim 1, wherein the crystallization reaction in step 3) comprises: placing the initial synthesis mixture in the step 2) into a closed reactor, and carrying out crystallization reaction on the initial synthesis mixture in the presence of water vapor.
15. The method according to claim 1, wherein the temperature of the crystallization reaction is 100-200 ℃ and the time of the crystallization reaction is 12-100h.
16. The method of claim 1, wherein the basic TS-1 molecular sieve has a particle size of between 0.08 and 5 μm.
17. The use of the basic titanium silicalite TS-1 prepared by the preparation method of any one of claims 1 to 16 as a catalyst in the epoxidation of olefins.
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