CN112158856B - Method for preparing Ti-MWW molecular sieve - Google Patents
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Abstract
The invention discloses a method for preparing a Ti-MWW molecular sieve, belonging to the technical field of inorganic chemical synthesis. The method comprises the following steps: mixing silica sol, titanium trichloride, tetramethylammonium borohydride, caprolactam and water at room temperature to obtain a gel precursor for synthesizing the molecular sieve; grinding the gel precursor obtained in the step by using a colloid mill, heating to 50-100 ℃, aging for 6-24h to obtain reaction gel, putting the reaction gel into a hydrothermal crystallization synthesis kettle for crystallization, carrying out solid-liquid separation after the reaction is finished, washing the obtained solid by using dilute nitric acid, and drying to obtain the Ti-MWW molecular sieve with the MWW structure. The method for preparing the Ti-MWW molecular sieve can avoid the use of easily prepared toxic chemical piperidine and highly toxic chemical hexamethyleneimine, and the obtained molecular sieve has good catalytic activity.
Description
Technical Field
The invention belongs to the technical field of inorganic chemical synthesis, and particularly relates to a method for preparing a Ti-MWW molecular sieve.
Background
The Ti-MWW type titanium-silicon molecular sieve is a MWW structure molecular sieve containing skeleton titanium atom, and has unique sinusoidal 10-membered ring net pore system, 12-membered ring cavity and super-cage pore system structure of MWW molecular sieve, so that the organic reactant can be easily approached to its active center in the pore channel, and its titanium active site pair H also can be used as active site pair2O2Has unique adsorption and activation performance, thus having high catalytic oxidation activity in the reaction of various organic compounds.
The Ti-MWW molecular sieve is one of a few heteroatom molecular sieves for realizing industrial application, can be used for catalyzing ammoximation reaction of various small molecular ketones, hydrogen peroxide and ammonia, such as preparation of cyclohexanone-oxime by catalyzing cyclohexanone ammoximation, preparation of butanone oxime by catalyzing butanone ammoximation, preparation of butanone oxime by catalyzing acetone ammoximation and the like, and has the advantages of high product selectivity, mild reaction conditions, cleaner whole catalytic oxidation reaction process and good application prospect.
The Ti-MWW synthesis method generally adopts a silicon source, a titanium source, a boron source and a template agent as raw materials to carry out crystallization synthesis, wherein the template agent generally adopts pyridine or hexamethyleneimine, such as CN1686795A, CN101012062A, CN110203947A and the like. However, pyridine is a chemical easy to prepare toxic substances, and hexamethyleneimine is a chemical extremely toxic and high in cost.
Disclosure of Invention
The invention aims to provide a method for preparing a Ti-MWW molecular sieve, which does not directly use pyridine or hexamethyleneimine as a template agent and simultaneously obtains the Ti-MWW molecular sieve with MWW structure and high catalytic activity.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a process for preparing a Ti-MWW molecular sieve comprising the steps of:
(1) mixing silica sol, titanium trichloride, tetramethylammonium borohydride, caprolactam and water at room temperature to obtain a gel precursor for synthesizing the molecular sieve;
(2) grinding the gel precursor obtained in the step (1) by using a colloid mill, heating to 50-100 ℃, aging for 6-24h to obtain reaction gel, putting the reaction gel into a hydrothermal crystallization synthesis kettle for crystallization, performing solid-liquid separation after the reaction is finished, washing the obtained solid with dilute nitric acid, and drying to obtain the Ti-MWW molecular sieve with the MWW structure.
Further, in the step (1), SiO in the gel precursor is calculated by mol2 Ti, tetramethylammonium borohydride, caprolactam and water in a weight ratio of 1: 0.02-0.05: 0.25-1: 0.5-2: 10-50.
Further, in the step (1), SiO in the gel precursor is calculated by mol2 Ti, tetramethylammonium borohydride, caprolactam and water in a weight ratio of 1: 0.03-0.04: 0.4-0.7: 0.8-1.5: 20-30.
Further, the crystallization temperature in the step (2) is 160-.
Further, the crystallization temperature in the step (2) is 165-175 ℃, and the crystallization time is 96 h.
Further, the grinding time of the colloid mill for the gel precursor in the step (2) is 2-12h, and the grinding power is 10-100W/kg of material.
Further, the concentration of the dilute nitric acid used in the step (2) is 2mol/L, and the mass of the dilute nitric acid used is 10 times of that of the washed solid.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the invention, caprolactam is used for replacing hexamethyleneimine or pyridine, tetramethylammonium borohydride is used for replacing crystallization auxiliary agent boric acid, the caprolactam can be reduced by tetramethylammonium borohydride in situ in a gel precursor to generate hexamethyleneimine as a template agent under the catalytic action of titanium trichloride after being fully ground, the tetramethylammonium metaborate as a product of the tetramethylammonium borohydride can provide an alkaline mineralization environment for a crystallization synthesis system, meanwhile, the boric acid as the crystallization auxiliary agent is replaced, and the titanium trichloride simultaneously serves as a titanium source and enters a molecular sieve skeleton structure.
2. The synthesis method of the invention avoids directly using easily toxic chemicals such as pyridine or hexamethyleneimine and highly toxic reagents, reduces the cost and reduces the risk and environmental pollution in the production process.
3. The invention can synthesize the Ti-MWW molecular sieve with high catalytic activity by one-step hydrothermal method, has simple synthesis process and convenient operation, is easy to realize industrial production and application, and the obtained molecular sieve has excellent performance as a catalyst.
Drawings
FIG. 1 is an XRD pattern of the molecular sieve prepared in comparative example 1;
FIG. 2 is an XRD pattern of the molecular sieve prepared in comparative example 2;
FIG. 3 is an XRD pattern of the molecular sieve prepared in example 1;
FIG. 4 is an XRD pattern of the molecular sieve prepared in example 2;
FIG. 5 is an XRD pattern of the molecular sieve prepared in example 3;
figure 6 is an XRD pattern of the molecular sieve prepared in example 4.
Detailed Description
The present invention will be described in further detail with reference to the following examples and the accompanying drawings.
Comparative example 1
At room temperature, a certain amount of silica sol (in SiO)2Calculated) is added into a certain amount of water, and after being evenly stirred, butyl titanate (calculated as TiO) is sequentially added2Metering), tetramethylammonium Borohydride (BHA) and stirring for 12 hours, then adding a certain amount of Hexamethyleneimine (HMI) to prepare reaction gel, wherein the molar composition in the reaction gel is 1.0SiO2 : 0.05TiO2 : 1.0BHA : 1.0HMI : 25.0H2And O, then placing the reaction gel in a closed reaction kettle, fixing the closed reaction kettle on a horizontal rotating shaft of a homogeneous reactor through a connecting rod, adjusting the rotating speed to be 30 r/min, crystallizing for 120 hours at 180 ℃, filtering, washing and drying to obtain the Ti-MWW molecular sieve raw powder. Mixing the obtained Ti-MWW molecular sieve raw powder with a nitric acid aqueous solution with the concentration of 2.0mol/L according to the weight ratio of 1:10, stirring and washing for 10 hours at 80 ℃, filtering, drying, and roasting the obtained solid for 8 hours at 550 ℃ to obtain the product Ti-MWW molecular sieve, wherein the XRD (X-ray diffraction) pattern of the product is shown in figure 1.
The catalytic activity of the synthesized Ti-MWW molecular sieve is evaluated by cyclohexanone ammoximation reaction, and the reaction conditions are as follows: 0.1 g of Ti-MWW molecular sieve serving as a catalyst, 6.0 g of cyclohexanone, 18 g of water, 8.0 g of hydrogen peroxide with the mass concentration of 27.3 percent and 13.9 g of ammonia water. The specific process is as follows: adding a solvent, reactants and a Ti-MWW molecular sieve as a catalyst into a flask in sequence, reacting for 2 hours at 80 ℃ under the condition of stirring, and measuring the reaction result after the reaction as follows: the conversion rate of cyclohexanone is 25 percent, the selectivity of cyclohexanone-oxime is 28 percent, and the yield of cyclohexanone-oxime is 7.0 percent.
Comparative example 2
At room temperature, a certain amount of silica sol (in SiO)2Calculated) is added into a certain amount of water, and after being evenly stirred, butyl titanate (calculated as TiO) is sequentially added2Calculated as B), boric acid (calculated as B)2O3Calculated) and stirred for 12 hours, then a certain amount of Caprolactam (CPL) is added to prepare reaction gel, and the molar composition of the gel is 1.0SiO2 : 0.05TiO2 : 1.0B2O3 : 1.0CPL : 25H2And O. And then placing the reaction gel in a closed reaction kettle, fixing the closed reaction kettle on a horizontal rotating shaft of a homogeneous reactor through a connecting rod, adjusting the rotating speed to be 30 r/min, crystallizing for 120 hours at 180 ℃, and filtering, washing and drying to obtain the Ti-MWW molecular sieve raw powder. Mixing the obtained Ti-MWW molecular sieve raw powder with a nitric acid aqueous solution with the concentration of 2.0mol/L according to the weight ratio of 1:10, stirring and washing for 10 hours at 80 ℃, filtering, drying, and roasting the obtained solid for 8 hours at 550 ℃ to obtain an amorphous product, wherein an XRD (X-ray diffraction) pattern of the amorphous product is shown in figure 2.
The catalytic activity of the obtained product was evaluated by cyclohexanone ammoximation reaction under the same conditions as in comparative example 1, and the reaction results were: the conversion rate of cyclohexanone is 21 percent, the selectivity of cyclohexanone oxime is 0 percent, and the yield of cyclohexanone oxime is 0 percent.
Example 1
At room temperature, a certain amount of silica sol (in SiO)2Calculated) is added into a certain amount of water, after being evenly stirred, titanium trichloride (calculated as Ti), tetramethylammonium Borohydride (BHA) and Caprolactam (CPL) are sequentially added to obtain a gel precursor, and the composition of the gel precursor is 1.0SiO in molar ratio2 : 0.05Ti : 0.5BHA : 1.0CPL : 25H2O; the gel precursor was milled with a colloid mill at 50 watts/kg of material for 2 hours. Then heating the gel precursor to 50 ℃ under stirring for aging for 24 hours; and placing the aged gel precursor into a closed reaction kettle, fixing the closed reaction kettle on a horizontal rotating shaft of a homogeneous reactor through a connecting rod, adjusting the rotating speed to be 30 r/min, crystallizing for 120 hours at 180 ℃, filtering, washing and drying to obtain the Ti-MWW molecular sieve raw powder. Mixing the obtained molecular sieve raw powder with a nitric acid aqueous solution with the concentration of 2.0mol/L according to the weight ratio of 1:10, stirring and washing for 10 hours at 80 ℃, filtering, drying, roasting the obtained solid for 8 hours at 550 ℃, and obtaining the product, namely the Ti-MWW molecular sieve, wherein the XRD (X-ray diffraction) pattern of the product is shown in figure 3.
The catalytic activity of the Ti-MWW molecular sieve is evaluated by cyclohexanone ammoximation reaction, the reaction conditions are the same as the comparative example 1, and the reaction result is as follows: the conversion rate of cyclohexanone is 97%, the selectivity of cyclohexanone oxime is 98%, and the yield of cyclohexanone oxime is 95%.
Example 2
At room temperature, a certain amount of silica sol (in SiO)2Calculated) is added into a certain amount of water, after being evenly stirred, titanium trichloride (calculated as Ti), tetramethylammonium Borohydride (BHA) and Caprolactam (CPL) are sequentially added to obtain a gel precursor, and the composition of the gel precursor is 1.0SiO in molar ratio2 : 0.05Ti : 1.0BHA : 2.0CPL : 50H2O; grinding the gel precursor by using a colloid mill for 6 hours by using 10W/kg of material, and then heating the gel precursor to 100 ℃ under stirring for aging for 6 hours; and placing the aged gel precursor into a closed reaction kettle, fixing the closed reaction kettle on a horizontal rotating shaft of a homogeneous reactor through a connecting rod, adjusting the rotating speed to be 30 r/min, crystallizing for 120 hours at 160 ℃, filtering, washing and drying to obtain the Ti-MWW molecular sieve raw powder. Mixing the obtained molecular sieve raw powder with a nitric acid aqueous solution with the concentration of 2.0mol/L according to the weight ratio of 1:10, stirring and washing for 10 hours at 80 ℃, filtering, drying, roasting the obtained solid for 8 hours at 550 ℃, and obtaining the product, namely the Ti-MWW molecular sieve, wherein the XRD (X-ray diffraction) pattern of the product is shown in figure 4.
The catalytic activity of the Ti-MWW molecular sieve is evaluated by cyclohexanone ammoximation reaction, the reaction conditions are the same as the comparative example 1, and the reaction result is as follows: the conversion rate of cyclohexanone is 83 percent, the selectivity of cyclohexanone-oxime is 78 percent, and the yield of cyclohexanone-oxime is 65 percent.
Example 3
At room temperature, a certain amount of silica sol (in SiO)2Calculated) is added into a certain amount of water, after being evenly stirred, titanium trichloride (calculated as Ti), tetramethylammonium Borohydride (BHA) and Caprolactam (CPL) are sequentially added to obtain a gel precursor, and the composition of the gel precursor is 1.0SiO in molar ratio2 : 0.02Ti : 0.25BHA : 0.5CPL : 10H2O; the gel precursor was ground with a colloid mill at 100 watts/kg gel for 2 hours, and then the gel was allowed to setHeating the precursor to 50 ℃ under stirring for aging for 24 hours; and placing the aged gel precursor into a closed reaction kettle, fixing the closed reaction kettle on a horizontal rotating shaft of a homogeneous reactor through a connecting rod, adjusting the rotating speed to be 30 r/min, crystallizing for 72 hours at 180 ℃, filtering, washing and drying to obtain the Ti-MWW molecular sieve raw powder. Mixing the obtained molecular sieve raw powder with a nitric acid aqueous solution with the concentration of 2.0mol/L according to the weight ratio of 1:10, stirring and washing for 10 hours at 80 ℃, filtering, drying, roasting the obtained solid for 8 hours at 550 ℃, and obtaining the product, namely the Ti-MWW molecular sieve, wherein the XRD (X-ray diffraction) pattern of the product is shown in figure 5.
The catalytic activity of the Ti-MWW molecular sieve is evaluated by cyclohexanone ammoximation reaction, the reaction conditions are the same as the comparative example 1, and the reaction result is as follows: the conversion rate of cyclohexanone is 79 percent, the selectivity of cyclohexanone oxime is 75 percent, and the yield of cyclohexanone oxime is 59 percent.
Example 4
At room temperature, a certain amount of silica sol (in SiO)2Calculated) is added into a certain amount of water, after being evenly stirred, titanium trichloride (calculated as Ti), tetramethylammonium Borohydride (BHA) and Caprolactam (CPL) are sequentially added to obtain a gel precursor, and the composition of the gel precursor is 1.0SiO in molar ratio2 : 0.05Ti : 1.0BHA : 2.0CPL : 50H2O; grinding the gel precursor by using a colloid mill at a power of 100W/kg of gel for 12 hours, grinding the gel precursor by using the colloid mill at a power of 100W/kg of gel for 2 hours, and then heating the gel precursor to 50 ℃ under stirring for aging for 12 hours; and then placing the aged reaction gel in a closed reaction kettle, fixing the closed reaction kettle on a horizontal rotating shaft of a homogeneous reactor through a connecting rod, adjusting the rotating speed to be 30 r/min, crystallizing for 120 hours at 160 ℃, filtering, washing and drying to obtain the Ti-MWW molecular sieve raw powder. Mixing the obtained molecular sieve raw powder with a nitric acid aqueous solution with the concentration of 2.0mol/L according to the weight ratio of 1:10, stirring and washing for 10 hours at 80 ℃, filtering, drying, roasting the obtained solid for 8 hours at 550 ℃, and obtaining the product, namely the Ti-MWW molecular sieve, wherein the XRD (X-ray diffraction) pattern of the product is shown in figure 6.
The catalytic activity of the Ti-MWW molecular sieve is evaluated by cyclohexanone ammoximation reaction, the reaction conditions are the same as the comparative example 1, and the reaction result is as follows: the conversion rate of cyclohexanone is 92%, the selectivity of cyclohexanone oxime is 90%, and the yield of cyclohexanone oxime is 83%.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (5)
1. A process for preparing a Ti-MWW molecular sieve, characterized in that it comprises the steps of:
(1) mixing silica sol, titanium trichloride, tetramethylammonium borohydride, caprolactam and water at room temperature to obtain a gel precursor for synthesizing the molecular sieve;
(2) grinding the gel precursor obtained in the step (1) by using a colloid mill, heating to 50-100 ℃, aging for 6-24h to obtain reaction gel, putting the reaction gel into a hydrothermal crystallization synthesis kettle for crystallization, performing solid-liquid separation after the reaction is finished, washing the obtained solid with dilute nitric acid, and drying to obtain the Ti-MWW molecular sieve with the MWW structure;
in the step (1), SiO in the gel precursor is calculated by mol2 Ti, tetramethylammonium borohydride, caprolactam and water in a weight ratio of 1: 0.02-0.05: 0.25-1: 0.5-2: 10-50;
the crystallization temperature in the step (2) is 160-.
2. The process for preparing a Ti-MWW molecular sieve as claimed in claim 1, wherein in step (1), SiO is present in the gel precursor on a molar basis2 Ti, tetramethylammonium borohydride, caprolactam and water in a weight ratio of 1: 0.03-0.04: 0.4-0.7: 0.8-1.5: 20-30.
3. The method for preparing the Ti-MWW molecular sieve as claimed in claim 1, wherein the crystallization temperature in the step (2) is 165-175 ℃, and the crystallization time is 96 h.
4. The method for preparing the Ti-MWW molecular sieve, according to claim 1, wherein the gel precursor is ground by the colloid mill in the step (2) for 2-12h with a grinding power of 10-100W/kg.
5. The method for preparing the Ti-MWW molecular sieve of claim 1, wherein the concentration of the dilute nitric acid used in the step (2) is 2mol/L, and the mass of the dilute nitric acid used is 10 times of the mass of the washed solid.
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