CN110180584B - Zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil product and preparation method thereof - Google Patents
Zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil product and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products and a preparation method thereof. The preparation method comprises the steps of preparing zeolite molecular sieve suspension, and preparing the zeolite molecular sieve suspension, n-butyl titanate solution and ammonium heptamolybdate solution into a precursor mixture; and roasting the precursor mixture to obtain the composite catalyst. The composite catalyst has the advantages of economy, practicality, good catalytic oxidation performance, good recycling performance and the like, can quickly and efficiently realize the effective conversion of the sulfur-containing organic pollutants when being used for removing the sulfur-containing organic pollutants in petroleum products, achieves the ultra-efficient and ultra-deep oxidative desulfurization, has excellent economic benefit and application prospect, has the advantages of simple process, convenient operation, cheap and easily obtained raw materials, low preparation cost and the like, can realize large-scale batch preparation, and is beneficial to industrial utilization.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysis and petrochemical industry, and relates to a zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products and a preparation method thereof.
Background
In recent decades, the emission of sulfur organic compounds in petroleum seriously affects the air quality, harms human health and shortens the service life of various automobile engines. The requirements in the existing rules for clean air highway diesel oil are as follows: the sulphur content in road diesel is 15 mg/l and allows engine manufacturers to use advanced emission control systems capable of further reducing the emission of harmful substances. However, these sulfur-containing organics can cause corrosion to the engine and reduce the service life of the automobile. Therefore, there is a strong need to find a suitable desulfurization process for removing these harmful sulfur-containing organic compounds from crude oil.
Oxidative Desulfurization (ODS) has the advantages of mild operation conditions, simple operation (room temperature and normal pressure), high desulfurization efficiency and the like, and is considered to be a green ultra-deep desulfurization technology with broad prospects. The effectiveness of the oxidation process depends to a large extent on the catalyst efficiency. 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: metal oxides, Metal Organic Framework (MOF) supported catalysts, and other solid phase supported catalysts. The solid-phase supported catalyst can be well separated from petroleum by filtration, so the solid-phase supported catalyst is widely used for catalytic oxidation petroleum desulfurization, however, the problems of high cost, insufficient catalytic oxidation performance, poor regeneration performance and the like still exist when the existing solid-phase supported catalyst is used for catalytic oxidation petroleum desulfurization, and the wide application of the solid-phase supported catalyst is seriously limited. In addition, most of the existing preparation methods of the solid-phase supported catalyst have the problems of complicated preparation process, high preparation cost and the like, and a lot of transition metals are not easy to be successfully loaded on a carrier, so that the practical 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, provide a zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products, which is economical and practical, has good catalytic oxidation performance and recycling performance, and also provide a preparation method of the zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products, which has the advantages of simple process, convenient operation, cheap and easily available raw materials and low preparation cost.
In order to solve the technical problems, the invention adopts the technical scheme that:
a zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products is characterized in that a zeolite molecular sieve is used as a carrier, and molybdenum trioxide and titanium dioxide are loaded on the zeolite molecular sieve.
The zeolite molecular sieve supported composite catalyst is further improved, 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.
The zeolite molecular sieve supported composite catalyst is further improved, and the zeolite molecular sieve is MCM-22.
As a general inventive concept, the invention also provides a preparation method of the zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products, which 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, the n-butyl titanate solution and the ammonium heptamolybdate solution, stirring, dipping, centrifuging and drying to obtain a precursor mixture;
s3, roasting the precursor mixture obtained in the step S2 to obtain the zeolite molecular sieve supported composite catalyst.
In the preparation method, further improvement is provided, in step S2, the n-butyl titanate solution and the ammonium heptamolybdate solution are simultaneously added dropwise to the zeolite molecular sieve suspension; 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 preparation method, further improvement is provided, in the step S2, the rotation speed of the stirring is 1000r/min to 2000 r/min; the stirring time is 2-4 h; the dipping time is 20-30 h; the rotating speed of the centrifugation is 5000 r/min-6000 r/min.
In a further improvement of the above preparation method, in 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 preparation method, the proportion of the zeolite molecular sieve to the ammonium nitrate solution in the step (1) 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 preparation method, further improvement is provided, in step S3, the temperature rise rate in the roasting process is 5 ℃/min; the roasting is carried out at the temperature of 550 ℃; the roasting time is 3 hours.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products, which takes a zeolite molecular sieve as a carrier, wherein 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 recycling performance of the composite catalyst is improved. The zeolite molecular sieve supported composite catalyst has the advantages of economy, practicability, 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.
(2) The mass ratio of molybdenum to titanium in the 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, and the mass ratio of molybdenum to titanium and the total mass ratio of molybdenum to titanium are optimized to further improve the catalytic oxidation performance and the regeneration performance of the catalyst, so that a better catalytic oxidation effect is obtained, lower cost and more efficient catalytic oxidation are realized, and the sulfur-containing organic pollutants in petroleum can be efficiently and locally converted.
(3) The invention provides a preparation method of a zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products. The preparation method has the advantages of simple process, convenient operation, cheap and easily-obtained raw materials, low preparation cost and the like, can realize large-scale batch preparation, and is beneficial to industrial utilization.
Drawings
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 flow chart of the preparation process of the zeolite molecular sieve supported composite catalyst in example 1 of the present invention.
FIG. 2 is a TEM image of the 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 sulfur conversion in dibenzothiophenes in example 6 of the present invention.
FIG. 4 is a graph showing the effect of the zeolite molecular sieve-supported composite catalyst on the cyclic treatment of sulfur in dibenzothiophene in example 7 of the present invention.
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 zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products takes a zeolite molecular sieve as a carrier, and molybdenum trioxide and titanium dioxide are loaded on the zeolite molecular sieve.
In this example, the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst was 1: 4, and the total mass of molybdenum and titanium was 22.10% of that of the zeolite molecular sieve.
In this example, the zeolite molecular sieve is MCM-22; molybdenum trioxide belongs to a 210 crystal plane, and the lattice spacing is 0.345 nm; the titanium dioxide is in anatase type, belongs to a 101 crystal plane, and has a lattice spacing of 0.352 nm.
A schematic flow chart of the preparation process of the preparation method of the zeolite molecular sieve supported composite catalyst in the embodiment of the present invention is shown in fig. 1, and the preparation method includes 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 a precursor mixture:
(2.1) 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 (2.2) simultaneously dripping the n-butyl titanate solution and the ammonium heptamolybdate solution prepared in the step (2.1) into the MCM-22 suspension prepared in the step (1) under the condition of stirring (the rotating speed is 1500r/min), wherein the dripping speed of both the n-butyl titanate solution and the ammonium heptamolybdate solution is 2.0mL/min, continuously stirring for 4h under the stirring rotating speed of 1500r/min after dripping is finished, soaking (the soaking process is to stand the mixed solution) for 24h, 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.
(3) Preparing a zeolite molecular sieve supported composite catalyst:
heating the precursor mixture prepared in the step (2) 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, code A1. 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.
FIG. 2 is a TEM image of the zeolite molecular sieve-supported composite catalyst prepared in example 1 of the present invention. As can be seen from fig. 2, the molybdenum trioxide and the titanium dioxide are successfully loaded on the MCM-22, and the molybdenum trioxide and the titanium dioxide loaded on the MCM-22 have crystal lattices, crystal face types are obtained by the XRD colorimetric card, and lattice spacings are obtained by calculation, which indicates that: molybdenum trioxide belongs to a 210 crystal plane, and the lattice spacing is 0.345 nm; the titanium dioxide is in anatase type, belongs to a 101 crystal plane, and has a lattice spacing of 0.352 nm.
Example 2
A zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products is basically the same as the zeolite molecular sieve supported composite catalyst (A1) in example 1, and the difference is only that: the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst of example 2 was 2: 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 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 zeolitic molecular sieve-supported composite catalyst prepared in example 2 was identified by the reference number a 2.
Example 3
A zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products is basically the same as the zeolite molecular sieve supported composite catalyst (A1) in example 1, and the difference is only that: the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst of example 3 was 1: 1.
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 zeolitic molecular sieve-supported composite catalyst prepared in example 3 was identified by the reference number a 3.
Example 4
A zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products is basically the same as the zeolite molecular sieve supported composite catalyst (A1) in example 1, and the difference is only that: the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst of example 4 was 3: 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 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 zeolitic molecular sieve-supported composite catalyst prepared in example 4 was identified by the reference number a 4.
Example 5
A zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products is basically the same as the zeolite molecular sieve supported composite catalyst (A1) in example 1, and the difference is only that: the mass ratio of molybdenum to titanium in the zeolite molecular sieve supported composite catalyst of example 5 was 4: 1.
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 zeolitic molecular sieve-supported composite catalyst prepared in example 5, code a 5.
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. Dropwise adding the n-butyl titanate solution into the MCM-22 suspension prepared in the example 1 at the speed of 2.0mL/min under the stirring condition (1500r/min), continuously stirring at the stirring speed of 1500r/min for 4h, centrifuging at the rotating speed of 5000r/min, drying, roasting the mixture at 550 ℃ for 3h to obtain the titanium dioxide/zeolite molecular sieve composite catalyst, namely the TiO molecular sieve composite catalyst2/MCM-22, code number B1.
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, code number B2.
Example 6
The method for investigating the influence of different catalysts on the removal effect of dibenzothiophene in petroleum products comprises the following steps:
taking 0.10g of each of the zeolite molecular sieve supported composite catalysts (a1, a2, A3, a4 and a5) prepared in examples 1 to 5, the titanium dioxide/zeolite molecular sieve composite catalyst (B1) prepared in comparative example 1 and the molybdenum trioxide/zeolite molecular sieve composite catalyst (B2) prepared in comparative example 2, adding the mixture into 20mL of Dibenzothiophene (DBT) -n-octane solution (namely simulated petroleum containing dibenzothiophene) with the sulfur concentration of 500ppmw, adding 280 μ L of cyclohexanone peroxide (oxidant, O/S ═ 2) solution with the mass fraction of 50% respectively, and reacting the mixture in an oil bath kettle at the temperature of 100 ℃ for 30min under magnetic stirring to complete the removal of dibenzothiophene in petroleum products.
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 sulfur conversion in dibenzothiophenes in example 6 of the present invention. As can be seen from fig. 3, the zeolite molecular sieve supported composite catalysts (a1, a2, A3, a4, a5) prepared by the present invention can effectively convert dibenzothiophene in petroleum products, wherein the conversion rates of the zeolite molecular sieve supported composite catalysts (a1, a2, A3, a4, a5) to sulfur in dibenzothiophene are 100%, 91.54%, 85.83%, 83.84%, 83.05%, respectively, while the conversion rates of the titanium dioxide/zeolite molecular sieve composite catalyst (B1) prepared in comparative example 1, and the conversion rates of the molybdenum trioxide/zeolite molecular sieve composite catalyst (B2) prepared in comparative example 2 to sulfur in dibenzothiophene are 58.64% and 36.43%, 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, which enables the zeolite molecular sieve supported composite catalyst (A1) to achieve 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%.
Example 7
The cyclic utilization performance of the zeolite molecular sieve supported composite catalyst is inspected, and the method comprises the following steps:
(1) 0.10g of the zeolite molecular sieve-supported composite catalyst (a1) prepared in example 1 was added to 20mL of a dibenzothiophene-n-octane solution (i.e., a simulated petroleum oil containing dibenzothiophene) having a sulfur concentration of 500ppmw, 280 μ L of a 50% cyclohexanone peroxide (oxidant, O/S ═ 2) solution was added, and the mixture was reacted in an oil bath at 100 ℃ for 30 minutes under magnetic stirring.
(2) After the reaction is finished, filtering the reaction product solution, washing and filtering the obtained zeolite molecular sieve supported composite catalyst by using N, N-dimethylacetamide and ethanol respectively, drying, placing in a muffle furnace, raising the temperature to 550 ℃ at the heating rate of 5 ℃/min, and roasting for 3 h. And (3) circularly treating the dibenzothiophene-n-octane solution by using the catalyst obtained after roasting, wherein other conditions are the same as those in the step (1), and circularly treating for 8 times.
After each reaction is completed, the reaction solution is cooled to room temperature, the content of sulfur in dibenzothiophene in the product solution obtained from the reaction is measured, and the conversion rate of sulfur in dibenzothiophene is obtained through calculation, and the result is shown in fig. 4.
FIG. 4 is a graph showing the effect of the zeolite molecular sieve-supported composite catalyst on the cyclic treatment of sulfur in dibenzothiophene in example 7 of the present invention. As can be seen from FIG. 4, the activity of the catalyst is not obviously reduced after 5 times of continuous operation, and the conversion rate of sulfur still reaches 93.16% after 8 times of continuous operation, which indicates that the zeolite molecular sieve supported composite catalyst has better regeneration capability for oxidative desulfurization of dibenzothiophene, and is a novel solid-phase supported catalyst which is economical and practical, good in catalytic oxidation performance and good in recycling performance.
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 (7)
1. A zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products is characterized in that the zeolite molecular sieve supported composite catalyst takes a zeolite molecular sieve as a carrier, and molybdenum trioxide and titanium dioxide are loaded on the zeolite molecular sieve; 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; the zeolite molecular sieve is MCM-22;
the preparation method of the zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products comprises the following steps:
1, preparing zeolite molecular sieve into zeolite molecular sieve suspension;
a2, mixing the zeolite molecular sieve suspension obtained in the step a1, an n-butyl titanate solution and an ammonium heptamolybdate solution, stirring, dipping, centrifuging and drying to obtain a precursor mixture;
a3, roasting the precursor mixture obtained in the step a2 to obtain the zeolite molecular sieve supported composite catalyst;
in the step a1, the preparation method of the zeolite molecular sieve suspension comprises the following steps:
b1, mixing the zeolite molecular sieve with the ammonium nitrate solution, stirring, cleaning, drying, and repeating the operation for 2-3 times;
b2, roasting the dried zeolite molecular sieve in the step b 1;
b3, mixing the zeolite molecular sieve roasted in the step b2 with water, performing ultrasonic treatment, and stirring to obtain a zeolite molecular sieve suspension; the ratio of the calcined zeolite molecular sieve to water is 0.5 g: 50 mL; the ultrasonic time is 30 min.
2. The preparation method of the zeolite molecular sieve supported composite catalyst for removing dibenzothiophene in oil products according to claim 1, which 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, the n-butyl titanate solution and the ammonium heptamolybdate solution, stirring, dipping, centrifuging and drying to obtain a precursor mixture;
s3, roasting the precursor mixture obtained in the step S2 to obtain the zeolite molecular sieve supported composite catalyst.
3. The method according to claim 2, wherein in step S2, the n-butyl titanate solution and the ammonium heptamolybdate solution are simultaneously added dropwise to the zeolite molecular sieve suspension; 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.
4. The method according to claim 3, wherein in the step S2, the rotation speed of the stirring is 1000r/min to 2000 r/min; the stirring time is 2-4 h; the dipping time is 20-30 h; the rotating speed of the centrifugation is 5000 r/min-6000 r/min.
5. The method of any one of claims 2 to 4, wherein in the step S1, the method of preparing 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 preparation 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 production method according to any one of claims 2 to 4, wherein in the step S3, the temperature increase rate during the baking process is 5 ℃/min; the roasting is carried out at the temperature of 550 ℃; the roasting time is 3 hours.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327933A (en) * | 2007-06-21 | 2008-12-24 | 中国石油天然气集团公司 | Silicon based mesoporous composite material loaded with transient metal and preparation thereof |
| 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 |
-
2019
- 2019-05-30 CN CN201910462969.3A patent/CN110180584B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101327933A (en) * | 2007-06-21 | 2008-12-24 | 中国石油天然气集团公司 | Silicon based mesoporous composite material loaded with transient metal and preparation thereof |
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| "The Role of Molybdenum Oxide Based Catalysts on Oxidative Desulfurization of Diesel Fuel";Wan Azelee Wan Abu Bakar等;《Mod Chem appl》;20151231;第3卷(第2期);第1-4页 * |
| "油品氧化脱硫介孔催化剂研究进展";王天星等;《化工科技》;20121231;第20卷(第2期);第72-76页 * |
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