CN110152722B - Method for assisting in synthesizing zeolite molecular sieve supported composite catalyst by utilizing polyvinylpyrrolidone - Google Patents
Method for assisting in synthesizing zeolite molecular sieve supported composite catalyst by utilizing polyvinylpyrrolidone Download PDFInfo
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- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
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Abstract
The invention discloses a method for assisting in synthesizing a zeolite molecular sieve supported composite catalyst by utilizing polyvinylpyrrolidone, which comprises the following steps: preparing zeolite molecular sieve suspension; mixing the zeolite molecular sieve suspension with polyvinylpyrrolidone to prepare a zeolite molecular sieve mixed solution; mixing the zeolite molecular sieve mixed solution, the n-butyl titanate solution and the ammonium heptamolybdate solution to prepare a precursor mixture; and roasting the precursor mixture to obtain the composite catalyst. The preparation method has the advantages of simple process, convenient operation, cheap and easily-obtained raw materials, low preparation cost, short preparation period and the like, can realize large-scale batch preparation, is beneficial to industrial utilization, and the prepared composite catalyst has the advantages of economy, practicability, good stability, good catalytic oxidation performance, good recycling performance and the like, can realize ultrahigh-efficiency and ultra-deep oxidative desulfurization, and has excellent economic benefit and application prospect.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysis and petrochemical engineering thereof, and relates to a method for synthesizing a zeolite molecular sieve supported composite catalyst by using polyvinylpyrrolidone.
Background
In recent years, the problem of air pollution caused by organic sulfur compounds in fuels has become increasingly serious. These organosulfur compounds react with oxygen during combustion in automotive engines, directly resulting in SOx emissions, which is one of the major sources of air pollution and acid rain. In addition, organic sulfur compounds in the fuel have a corrosive effect on parts of the internal combustion engine of the motor vehicle. To address these challenges, many countries have developed new specifications for fuel sulfur content. For example, in the United states, sulfur concentrations in diesel and gasoline are limited to less than 15ppmw and 30ppmw, respectively. Therefore, deep and rapid desulfurization is an urgent research issue at present.
Oxidative desulfurization is considered to be the most promising desulfurization method for removing organic sulfides in petroleum compared to other desulfurization methods. The oxidative desulfurization method has the advantages of mild operating conditions, simple operation, high-efficiency removal of sulfur-containing heterocyclic compounds such as Dibenzothiophene (DBT) and derivatives thereof and the like, under the existence of a proper catalyst, an oxidant can convert refractory organic sulfides into sulfoxide or sulfone, and then the products are removed through polar extraction to obtain the ultra-low sulfur fuel. Therefore, efficient and fast catalysts have been the focus of research. In recent years, many researchers seek to prepare an oxidative desulfurization catalyst with excellent performance. There have been many reports on catalysts for catalytically oxidizing organic sulfides in petroleum. Such as: solid-phase supported catalysts such as metal oxides and Metal Organic Framework (MOF) supported catalysts are widely used for catalytic oxidation of petroleum desulfurization. However, most of the existing preparation methods of solid-phase supported catalysts have the problems of complicated preparation process, long preparation period, high preparation cost and the like, and many transition metals are not easy to be successfully loaded on a carrier, which seriously limits the practical application of the solid-phase supported catalysts. In addition, in order to successfully support the transition metal on the carrier, a catalyst is synthesized by hydrothermal reaction under high temperature and high pressure conditions in the conventional synthesis methods, but the synthesis methods have the defects of harsh conditions, high cost and the like. In addition, the existing solid-phase supported catalyst still has the problems of high cost, insufficient catalytic oxidation performance, poor regeneration performance and the like when being used for catalytic oxidation petroleum desulfurization, so that the wide application of the solid-phase supported catalyst is limited.
Disclosure of Invention
The technical problem to be solved by the invention is to overcome the defects of the prior art and provide a method for synthesizing the zeolite molecular sieve supported composite catalyst by using polyvinylpyrrolidone, which has the advantages of simple process, convenient operation, cheap and easily available raw materials, low preparation cost and short preparation period.
In order to solve the technical problems, the invention adopts the technical scheme that:
a method for assisting in synthesizing a zeolite molecular sieve supported composite catalyst by utilizing polyvinylpyrrolidone comprises the following steps:
s1, preparing the zeolite molecular sieve into zeolite molecular sieve suspension;
s2, mixing the zeolite molecular sieve suspension obtained in the step S1 with polyvinylpyrrolidone, and stirring to obtain a zeolite molecular sieve mixed solution;
s3, mixing the zeolite molecular sieve mixed solution obtained in the step S2, the n-butyl titanate solution and the ammonium heptamolybdate solution, stirring, centrifuging and drying to obtain a precursor mixture;
s4, roasting the precursor mixture obtained in the step S3 to obtain the zeolite molecular sieve supported composite catalyst.
In the step S2, the mass ratio of the zeolite molecular sieve to the polyvinylpyrrolidone in the zeolite molecular sieve suspension is 5: 3 to 5: 5.
In the above method, further improvement, in the step S2, the rotation speed of the stirring is 1000r/min to 2000 r/min; the stirring time is 30-60 min.
In the method, in a further improvement, in step S3, the n-butyl titanate solution and the ammonium heptamolybdate solution are simultaneously added dropwise to the zeolite molecular sieve mixed solution; the dropping rate of the n-butyl titanate solution is 1.5mL/min to 2.5 mL/min; the dropping speed of the ammonium heptamolybdate solution is 1.5 mL/min-2.5 mL/min.
In the above method, further improvement, in the step S3, the rotation speed of the stirring is 1000r/min to 2000 r/min; the stirring time is 2-4 h; the rotating speed of the centrifugation is 5000 r/min-6000 r/min.
In the above method, further improvement, in the step S1, the preparation method of the zeolite molecular sieve suspension comprises the following steps:
(1) mixing a zeolite molecular sieve with an ammonium nitrate solution, stirring, cleaning, drying, and repeating the operation for 2-3 times;
(2) roasting the zeolite molecular sieve dried in the step (1);
(3) and (3) mixing the calcined zeolite molecular sieve in the step (2) with water, and performing ultrasonic treatment and stirring to obtain a zeolite molecular sieve suspension.
In the method, in a further improvement, in the step (1), the ratio of the zeolite molecular sieve to the ammonium nitrate solution is 0.5 g: 50 mL; the concentration of the ammonium nitrate solution is 1 mol/L; the stirring is carried out at a temperature of 80 ℃; the stirring time is 2 hours; the drying is carried out under the vacuum condition; the drying temperature is 80 ℃;
in the step (2), the heating rate in the roasting process is 5 ℃/min; the roasting is carried out at the temperature of 550 ℃; the roasting time is 3 hours;
in the step (3), the ratio of the calcined zeolite molecular sieve to water is 0.5 g: 50 mL; the ultrasonic time is 30 min.
In the above method, further improvement, in the step S4, the temperature rise rate during the roasting process is 5 ℃/min; the roasting is carried out at the temperature of 550 ℃; the roasting time is 3 hours.
In the method, the zeolite molecular sieve is used as a carrier, and molybdenum trioxide and titanium dioxide are loaded on the zeolite molecular sieve.
In the method, the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst is further improved to be 1-4: 4-1; the total mass of molybdenum and titanium in the zeolite molecular sieve supported composite catalyst is 20-25% of that of the zeolite molecular sieve; the zeolite molecular sieve is MCM-22.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a method for assisting in synthesizing a zeolite molecular sieve supported composite catalyst by utilizing polyvinylpyrrolidone. In the invention, the polyvinylpyrrolidone used as a high molecular surfactant plays a role of a binder, and can more efficiently load molybdenum and titanium on the MCM-22 carrier, thereby greatly shortening the preparation time of the catalyst. The preparation method has the advantages of simple process, convenient operation, cheap and easily-obtained raw materials, low preparation cost, short preparation period and the like, can realize large-scale batch preparation, and is beneficial to industrial utilization.
(2) The zeolite molecular sieve supported composite catalyst prepared by the invention takes the zeolite molecular sieve as a carrier, and molybdenum trioxide and titanium dioxide are loaded on the zeolite molecular sieve. In the invention, the zeolite molecular sieve is a very suitable carrier due to the advantages of large specific surface area, good stability, abundant acid sites and the like. In addition, because the molybdenum trioxide and the titanium dioxide have the advantages of low price, no toxicity, no harm, high thermal stability, high chemical stability and the like, the molybdenum trioxide and the titanium dioxide are loaded on the zeolite molecular sieve, so that the composite catalyst integrates the advantages of the molybdenum trioxide and the titanium dioxide, and has the advantages of low cost, no toxicity, no harm, high thermal stability, high chemical stability and the like. In addition, the molybdenum trioxide and the titanium dioxide are loaded on the zeolite molecular sieve, so that the composite catalyst shows better regeneration performance, and the molybdenum trioxide and the titanium dioxide are loaded on the zeolite molecular sieve under the action of polyvinylpyrrolidone, so that the structure of the composite catalyst is more stable, and the cyclic utilization performance of the composite catalyst is improved. The zeolite molecular sieve supported composite catalyst has the advantages of economy, practicability, good stability, good catalytic oxidation performance, good recycling performance and the like, can quickly and efficiently realize the effective conversion of sulfur-containing organic pollutants when being used for removing the sulfur-containing organic pollutants in petroleum products, achieves the ultrahigh-efficiency and ultra-deep oxidative desulfurization, and has excellent economic benefit and application prospect.
(3) The mass ratio of molybdenum to titanium in the prepared zeolite molecular sieve supported composite catalyst is 1-4: 4-1, and the total mass of molybdenum and titanium is 20-25% of that of the zeolite molecular sieve, wherein the mass ratio of molybdenum to titanium is 1-4: 4-1 and is a ratio of molybdenum to titanium between two active centers, and the total mass of molybdenum and titanium is a ratio of the active centers to a carrier between 20-25% of that of the zeolite molecular sieve.
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In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
Fig. 1 is a schematic diagram of a synthetic process flow of the zeolite molecular sieve supported composite catalyst in example 1 of the present invention.
FIG. 2 is an SEM image of a zeolite molecular sieve-supported composite catalyst prepared in example 1 of the present invention.
FIG. 3 is a graph showing the effect of different catalysts on the conversion of sulfur in dibenzothiophene in example 6 of the present invention under different reaction time conditions.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The materials and equipment used in the following examples are commercially available.
Example 1
A method for synthesizing a zeolite molecular sieve supported composite catalyst by utilizing polyvinylpyrrolidone, wherein the schematic flow diagram of the synthesis process is shown in figure 1, and the method comprises the following steps:
(1) preparation of MCM-22 suspension:
(1.1) adding MCM-22 into 50mL of 1mol/L ammonium nitrate solution, stirring for 2h at 80 ℃, washing with deionized water for three times, drying at 80 ℃ under a vacuum condition, and repeating the operation twice.
And (1.2) grinding the MCM-22 dried in the step (1.1), and placing the ground MCM-22 in a temperature-programmed muffle furnace to be heated to 550 ℃ at the heating rate of 5 ℃/min for roasting for 3 hours. In the invention, the zeolite molecular sieve can obtain better stability by roasting.
(1.3) adding 0.5g of the MCM-22(H-MCM-22) roasted in the step (1.2) into 50mL of deionized water, carrying out ultrasonic treatment for 30min, and stirring to obtain an MCM-22 suspension. In the invention, deionized water is used as a solvent, so that the cost is lower.
(2) Preparing MCM-22 mixed solution:
and (2) adding polyvinylpyrrolidone into the MCM-22 suspension obtained in the step (1) according to the mass ratio of the zeolite molecular sieve to the polyvinylpyrrolidone in the zeolite molecular sieve suspension of 5: 4, and stirring at the stirring speed of 1500r/min for 30min to obtain the MCM-22 mixed solution.
(3) Preparing a precursor mixture:
(3.1) adding 1.42mL of n-butyl titanate into 5mL of anhydrous ethanol, and carrying out ultrasonic treatment for 30min to obtain a n-butyl titanate solution. 0.092g of ammonium heptamolybdate was added to 5mL of deionized water, and the mixture was sonicated for 30min to obtain an ammonium heptamolybdate solution. In the invention, the method for preparing the titanium-containing catalyst by using the n-butyl titanate as the titanium source has the advantages of moderate hydrolysis speed, controllable hydrolysis process, no impurity sulfur element and the like, the problem that the preparation process is not suitable to control due to the overhigh hydrolysis speed of the isopropyl titanate exists, and the sulfur element is introduced into the titanium sulfate to finally influence the use effect of the catalyst. In the invention, the ammonium heptamolybdate is used as the molybdenum source, so that the method has the advantages of low cost, high preparation efficiency and the like.
And (3.2) simultaneously dripping the n-butyl titanate solution and the ammonium heptamolybdate solution prepared in the step (3.1) into the MCM-22 mixed solution prepared in the step (2) under the condition of stirring (the rotating speed is 1500r/min), wherein the dripping speed of the n-butyl titanate solution and the ammonium heptamolybdate solution is 2.0mL/min, continuously stirring for 4 hours under the stirring rotating speed of 1500r/min after dripping is finished, centrifuging at the rotating speed of 5000r/min, and drying to obtain a precursor mixture. According to the method, the dropping rate of the n-butyl titanate solution and the ammonium heptamolybdate solution is optimized, so that the n-butyl titanate and the ammonium heptamolybdate can be uniformly distributed on the MCM-22 carrier, and the composite catalyst with molybdenum trioxide and titanium dioxide uniformly distributed on the MCM-22 carrier is prepared through subsequent roasting treatment, because the n-butyl titanate solution is hydrolyzed due to too slow dropping rate, and the n-butyl titanate solution and the ammonium heptamolybdate solution are unevenly distributed and finally gathered on the MCM-22 carrier due to too fast dropping rate, so that the molybdenum trioxide and the titanium dioxide generated in the subsequent roasting treatment process are difficult to be uniformly distributed on the MCM-22 carrier.
(4) Preparing a zeolite molecular sieve supported composite catalyst:
heating the precursor mixture prepared in the step (3) to 550 ℃ according to the heating rate of 5 ℃/min, and roasting for 3h to obtain the zeolite molecular sieve supported composite catalyst, namely MoO3-TiO2/MCM-22, numbering MT-1: 4. In the invention, on one hand, excessive moisture and unstable substances are removed by roasting, namely, the titanium source and the molybdenum source are respectively converted into titanium dioxide and molybdenum trioxide products with catalytic action under the high-temperature condition, and on the other hand, the structural stability of the catalyst is improved by roasting at high temperature, so that the catalyst is more stable under the condition of carrying out an oxidation desulfurization test subsequently.
The zeolite molecular sieve supported composite catalyst prepared in this example uses a zeolite molecular sieve as a carrier, and molybdenum trioxide and titanium dioxide are supported on the zeolite molecular sieve, wherein the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst is 1: 4, and the total mass of molybdenum and titanium is 23.19% of that of the zeolite molecular sieve.
FIG. 2 is an SEM image of a zeolite molecular sieve-supported composite catalyst prepared in example 1 of the present invention. As can be seen from fig. 2, the MCM-22 carrier is lamellar, titanium dioxide is a large-particle substance, molybdenum trioxide is a small particle, and the molybdenum trioxide particles and titanium dioxide particles are supported on the lamellar MCM-22 carrier.
Example 2
A preparation method of a zeolite molecular sieve supported composite catalyst, which is basically the same as the preparation method of the example 1, and is different from the preparation method of the zeolite molecular sieve supported composite catalyst in that: the preparation of example 2 was carried out using different amounts of n-butyl titanate and ammonium heptamolybdate. In this example, the specific amounts of tetrabutyl titanate and ammonium heptamolybdate are obtained by those skilled in the art without any doubt and exclusively according to the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst of 2: 3.
The zeolite molecular sieve supported composite catalyst prepared in example 2 was numbered MT-2: 3.
The zeolite molecular sieve supported composite catalyst (MT-2: 3) prepared in this example is substantially the same as the zeolite molecular sieve supported composite catalyst (MT-1: 4) of example 1, except that: the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst of example 2 was 2: 3.
Example 3
A preparation method of a zeolite molecular sieve supported composite catalyst, which is basically the same as the preparation method of the example 1, and is different from the preparation method of the zeolite molecular sieve supported composite catalyst in that: the preparation of example 3 was carried out with different amounts of n-butyl titanate and ammonium heptamolybdate. In this example, the specific amounts of tetrabutyl titanate and ammonium heptamolybdate are obtained by those skilled in the art without any doubt and exclusively according to the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst of 1: 1.
The zeolite molecular sieve supported composite catalyst prepared in example 3 was numbered MT-1: 1.
The zeolite molecular sieve supported composite catalyst (MT-1: 1) prepared in this example is substantially the same as the zeolite molecular sieve supported composite catalyst (MT-1: 4) of example 1, except that: the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst of example 3 was 1: 1.
Example 4
A preparation method of a zeolite molecular sieve supported composite catalyst, which is basically the same as the preparation method of the example 1, and is different from the preparation method of the zeolite molecular sieve supported composite catalyst in that: the preparation of example 4 was carried out using different amounts of n-butyl titanate and ammonium heptamolybdate. In this example, the specific amounts of tetrabutyl titanate and ammonium heptamolybdate are obtained by those skilled in the art without any doubt and exclusively according to the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst of 3: 2.
The zeolite molecular sieve supported composite catalyst prepared in example 4 was numbered MT-3: 2.
The zeolite molecular sieve supported composite catalyst (MT-3: 2) prepared in this example is substantially the same as the zeolite molecular sieve supported composite catalyst (MT-1: 4) of example 1, except that: the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst of example 4 was 3: 2.
Example 5
A preparation method of a zeolite molecular sieve supported composite catalyst, which is basically the same as the preparation method of the example 1, and is different from the preparation method of the zeolite molecular sieve supported composite catalyst in that: the preparation of example 5 varied the amounts of n-butyl titanate and ammonium heptamolybdate. In this example, the specific amounts of tetrabutyl titanate and ammonium heptamolybdate are obtained by those skilled in the art without any doubt and exclusively according to the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst of 4: 1.
The zeolite molecular sieve supported composite catalyst prepared in example 5 was numbered MT-4: 1.
The zeolite molecular sieve supported composite catalyst (MT-4: 1) prepared in this example is substantially the same as the zeolite molecular sieve supported composite catalyst (MT-1: 4) of example 1, except that: the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst of example 5 was 4: 1.
Comparative example 1
A preparation method of a titanium dioxide/zeolite molecular sieve composite catalyst comprises the following steps: adding 1.78mL of n-butyl titanate into 5mL of absolute ethanol, and carrying out ultrasonic treatment for 30min to obtain a n-butyl titanate solution. The solution of n-butyl titanate was added dropwise to the MCM-22 suspension obtained in example 1 at a rate of 2.0mL/min with stirring (1500r/min), and the mixture was further stirred at 1500r/min for 4 hours, centrifuged at 5000r/min, dried, and the mixture was baked at 550 deg.CBurning for 3h to obtain the titanium dioxide/zeolite molecular sieve composite catalyst, namely TiO2/MCM-22, numbering MT-0: 5.
Comparative example 2
A preparation method of a molybdenum trioxide/zeolite molecular sieve composite catalyst comprises the following steps: 0.4601g of ammonium heptamolybdate was added to 5mL of deionized water and sonicated for 30min to obtain an ammonium heptamolybdate solution. Dropwise adding an ammonium heptamolybdate solution into the MCM-22 mixed solution prepared in the embodiment 1 at the speed of 2.0mL/min under the condition of stirring (1500r/min), stirring for 4h at the stirring speed of 1500r/min, centrifuging at the rotating speed of 5000r/min, drying, roasting the mixture for 3h at 550 ℃ to obtain the molybdenum trioxide/zeolite molecular sieve composite catalyst, namely the MoO3/MCM-22, numbering MT-5: 0.
Example 6
The method for investigating the influence of different catalysts on the removal effect of dibenzothiophene in petroleum products comprises the following steps:
0.10g of each of the zeolite molecular sieve-supported composite catalysts (MT-1: 4, MT-2: 3, MT-1: 1, MT-3: 2 and MT-4: 1) prepared in examples 1 to 5, the titanium dioxide/zeolite molecular sieve composite catalyst (MT-0: 5) prepared in comparative example 1 and the molybdenum trioxide/zeolite molecular sieve composite catalyst (MT-5: 0) prepared in comparative example 2 was added to 20mL of a Dibenzothiophene (DBT) -n-octane solution (i.e., a simulated petroleum oil containing dibenzothiophene) having a sulfur concentration of 500ppmw, adding 280 mul of cyclohexanone peroxide (oxidant, O/S is 2) solution with the mass fraction of 50 percent respectively, and (3) reacting for 30min in an oil bath kettle at the temperature of 100 ℃ under magnetic stirring to finish the removal of dibenzothiophene in the petroleum product.
After the reaction is finished, cooling to room temperature, measuring the content of sulfur in dibenzothiophene in the product solution obtained by the reaction, and calculating to obtain the conversion rate of sulfur in dibenzothiophene, wherein the result is shown in fig. 3; meanwhile, filtering and separating the catalyst in the product solution obtained by the fixed reaction from simulated petroleum (N-octane), further transferring the simulated petroleum obtained by separation into a separating funnel, adding 10mL of N, N-dimethylacetamide to extract once, and taking an upper oil phase after layering is obvious; and detecting the content of sulfur in the upper oil phase by using gas chromatography.
FIG. 3 is a graph showing the effect of different catalysts on the conversion of sulfur in dibenzothiophene in example 6 of the present invention under different reaction time conditions. As can be seen from FIG. 3, the zeolite molecular sieve supported composite catalyst (MT-1: 4, MT-2: 3, MT-1: 1, MT-3: 2, MT-4: 1) prepared by the present invention can effectively convert dibenzothiophene in petroleum products, wherein the conversion rates of the zeolite molecular sieve supported composite catalyst (MT-1: 4, MT-2: 3, MT-1: 1, MT-3: 2, MT-4: 1) to sulfur in dibenzothiophene at 10min are 98.14%, 81.54%, 75.46%, 73.38%, 69.95%, respectively, the conversion rates to sulfur in dibenzothiophene at 30min are 100%, 99.73%, 99.2%, 98.18%, respectively, while the titanium dioxide/zeolite molecular sieve composite catalyst (MT-0: 5) prepared in comparative example 1 has conversion rates to sulfur in dibenzothiophene of 45.51% and 67.43% at 10min and 30min, the molybdenum trioxide/zeolite molecular sieve composite catalyst (MT-5: 0) prepared in comparative example 2 had 23.9% and 54.31% conversion rates of sulfur in dibenzothiophene at 10min and 30min, respectively. The results show that the zeolite molecular sieve supported composite catalyst obtained by simultaneously loading molybdenum trioxide and titanium dioxide on a zeolite molecular sieve (MCM-22) has better catalytic oxidation performance and is obviously superior to a pure molybdenum catalyst and a pure titanium catalyst. Therefore, for oxidative desulfurization, the invention has synergistic effect between the molybdenum trioxide loaded on the zeolite molecular sieve and the titanium dioxide. Particularly, the synergistic effect is best when the mass ratio of the molybdenum to the titanium is 1: 4, so that the zeolite molecular sieve supported composite catalyst (MT-1: 4) achieves the best catalytic oxidation effect. In addition, the results of gas chromatography for sulfur content show that: the total sulfur content of dibenzothiophene and its product is 0, i.e. the total sulfur content in the petroleum product obtained by said invention is less than 10ppmw, and is in accordance with European five standard, and its total desulfurization rate is up to 100%.
The above description is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above-described embodiments. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.
Claims (8)
1. A method for assisting in synthesizing a zeolite molecular sieve supported composite oxidation desulfurization catalyst by utilizing polyvinylpyrrolidone is characterized by comprising the following steps:
s1, preparing the zeolite molecular sieve into zeolite molecular sieve suspension;
s2, mixing the zeolite molecular sieve suspension obtained in the step S1 with polyvinylpyrrolidone, and stirring to obtain a zeolite molecular sieve mixed solution;
s3, simultaneously dripping the n-butyl titanate solution and the ammonium heptamolybdate solution into the zeolite molecular sieve mixed solution obtained in the step S2 according to the dripping speed of the n-butyl titanate solution being 1.5 mL/min-2.5 mL/min and the dripping speed of the ammonium heptamolybdate solution being 1.5 mL/min-2.5 mL/min, stirring, centrifuging and drying to obtain a precursor mixture;
s4, roasting the precursor mixture obtained in the step S3 to obtain the zeolite molecular sieve supported composite catalyst;
the zeolite molecular sieve supported composite catalyst prepared by the method takes a zeolite molecular sieve as a carrier, and molybdenum trioxide and titanium dioxide are loaded on the zeolite molecular sieve; the zeolite molecular sieve is MCM-22.
2. The method of claim 1, wherein in the step S2, the mass ratio of the zeolite molecular sieve in the zeolite molecular sieve suspension to the polyvinylpyrrolidone is 5: 3-5: 5.
3. The method according to claim 2, wherein in the step S2, the stirring speed is 1000r/min to 2000 r/min; the stirring time is 30-60 min.
4. The method according to claim 1, wherein in the step S3, the stirring speed is 1000r/min to 2000 r/min; the stirring time is 2-4 h; the rotating speed of the centrifugation is 5000 r/min-6000 r/min.
5. The method of any one of claims 1 to 3, wherein in the step S1, the preparation method of the zeolite molecular sieve suspension comprises the following steps:
(1) mixing a zeolite molecular sieve with an ammonium nitrate solution, stirring, cleaning, drying, and repeating the operation for 2-3 times;
(2) roasting the zeolite molecular sieve dried in the step (1);
(3) and (3) mixing the calcined zeolite molecular sieve in the step (2) with water, and performing ultrasonic treatment and stirring to obtain a zeolite molecular sieve suspension.
6. The method according to claim 5, wherein in the step (1), the ratio of the zeolite molecular sieve to the ammonium nitrate solution is 0.5 g: 50 mL; the concentration of the ammonium nitrate solution is 1 mol/L; the stirring is carried out at a temperature of 80 ℃; the stirring time is 2 hours; the drying is carried out under the vacuum condition; the drying temperature is 80 ℃;
in the step (2), the heating rate in the roasting process is 5 ℃/min; the roasting is carried out at the temperature of 550 ℃; the roasting time is 3 hours;
in the step (3), the ratio of the calcined zeolite molecular sieve to water is 0.5 g: 50 mL; the ultrasonic time is 30 min.
7. The method according to any one of claims 1 to 3, wherein in the step S4, the temperature rise rate during the roasting process is 5 ℃/min; the roasting is carried out at the temperature of 550 ℃; the roasting time is 3 hours.
8. The method according to claim 1, wherein the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst is 1-4: 4-1; the total mass of molybdenum and titanium in the zeolite molecular sieve supported composite catalyst is 20-25% of that of the zeolite molecular sieve.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101069850A (en) * | 2006-05-12 | 2007-11-14 | 中国科学院大连化学物理研究所 | Loaded and non-loaded catalyst and preparing method |
| CN101219383A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Amorphous, high-efficiency, high carbon deposition resistance, deep desulfurization catalyst |
| CN101543787A (en) * | 2008-03-26 | 2009-09-30 | 中国科学院大连化学物理研究所 | Method for preparing MCM-22molecular sieve catalyst for alkylation desulfurization of gasoline |
| CN103012366A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for oxidizing thiophene sulfides |
| CN105664998A (en) * | 2015-12-28 | 2016-06-15 | 哈尔滨工业大学 | Preparation method for Ti/MCM-41 molecular sieve having catalytically oxidizing activity and application thereof |
-
2019
- 2019-05-30 CN CN201910463782.5A patent/CN110152722B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101069850A (en) * | 2006-05-12 | 2007-11-14 | 中国科学院大连化学物理研究所 | Loaded and non-loaded catalyst and preparing method |
| CN101219383A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Amorphous, high-efficiency, high carbon deposition resistance, deep desulfurization catalyst |
| CN101543787A (en) * | 2008-03-26 | 2009-09-30 | 中国科学院大连化学物理研究所 | Method for preparing MCM-22molecular sieve catalyst for alkylation desulfurization of gasoline |
| CN103012366A (en) * | 2011-09-28 | 2013-04-03 | 中国石油化工股份有限公司 | Method for oxidizing thiophene sulfides |
| CN105664998A (en) * | 2015-12-28 | 2016-06-15 | 哈尔滨工业大学 | Preparation method for Ti/MCM-41 molecular sieve having catalytically oxidizing activity and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| "The Role of Molybdenum Oxide Based Catalysts on Oxidative Desulfurization of Diesel Fuel";Wan Azelee Wan Abu Bakar等;《Mod Chem app》;20151231;第3卷(第2期);第1-4页 * |
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