CN110560145B - Preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan - Google Patents

Preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan Download PDF

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CN110560145B
CN110560145B CN201910880545.9A CN201910880545A CN110560145B CN 110560145 B CN110560145 B CN 110560145B CN 201910880545 A CN201910880545 A CN 201910880545A CN 110560145 B CN110560145 B CN 110560145B
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sba
methyl mercaptan
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罗永明
赵雨桐
陆继长
何德东
张黎明
曹小华
黄子君
张哲玮
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Kunming University of Science and Technology
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    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
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    • B01D53/8606—Removing sulfur compounds only one sulfur compound other than sulfur oxides or hydrogen sulfide
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/03—Catalysts comprising molecular sieves not having base-exchange properties
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    • B01J29/0341—Mesoporous materials not having base exchange properties, e.g. Si-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself

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Abstract

The invention discloses a preparation method of a Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan, which comprises the steps of dissolving a template agent in deionized water, and stirring to completely dissolve the template agent; adding a molybdenum source and a silicon source into the solution, adjusting the pH value to be less than 1, and stirring at constant temperature; then crystallizing, filtering, drying and roasting to obtain the Mo-SBA-15 catalyst; the catalyst shows excellent catalytic performance, has no inactivation sign after the service life reaches 400 hours under the reaction conditions of normal pressure and 550 ℃, is far more than the reported stability of the catalyst, has simple synthesis process, not only maintains the structural characteristics of SBA-15, but also enables a large amount of Mo species to be uniformly dispersed on the surface, the framework and the pore channel of the SBA-15, thereby realizing the degradation of the sulfur-containing volatile pollutant methyl mercaptan, and having good application prospect.

Description

Preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan
Technical Field
The invention relates to a preparation method of a Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan, belonging to the technical field of treatment of malodorous organic sulfur pollutants.
Background
Methyl mercaptan, a typical sulfur-containing Volatile Organic Compounds (VOCs), is not only prone to accumulating to form organic aerosol, which leads to atmospheric photochemical smog and acid deposition, but also can be converted into sulfate through a series of chemical processes, which leads to haze formation. Methyl mercaptan widely exists in the processes of petrochemical industry, pesticide production, pollution control facilities and the like, and can cause serious influence on environmental safety and human health if not treated in time. The national standard of the people's republic of China, namely the discharge Standard of malodorous pollutants (GB-14554-93), has very strict regulation on the discharge, namely the first-class factory boundary standard of methyl mercaptan (0.004 mg/m)3) First grade factory boundary standard (0.03 mg/m) for specific hydrogen sulfide3) One order of magnitude lower. In recent years, many serious environmental pollution events are caused by the emission or leakage of mercaptan pollutants, so that the removal work of sulfur-containing volatile organic compounds, particularly methyl mercaptan, is particularly important, and the development of a new methyl mercaptan technology which is difficult to treat and degrade is acceleratedIs very urgent.
At present, the technology for treating methyl mercaptan at home and abroad mainly comprises an alkali liquor absorption method, an adsorption method, a direct combustion method, a catalytic oxidation method, a photocatalytic degradation method, a biological method, a catalytic decomposition method and the like. Among them, the catalytic decomposition method has attracted much attention because of its advantages such as high efficiency, high speed, no need of introducing an additional reactant, and the like. There are three catalysts commonly used today for the catalytic degradation of methyl mercaptan: cerium oxide based, H-ZSM-5 based, and silica based molecular sieves. Although these catalysts have good catalytic activity by improving their acidity-basicity and oxidation-reduction properties, under the atmosphere containing carbon and sulfur, the catalysts are not only vulnerable to sulfur species, but also likely to generate a large amount of carbon deposits to block the pore channels of the molecular sieve, which is also a main cause of catalyst deactivation. For treating malodorous gas methyl mercaptan by a catalytic decomposition method, patent 201510678176.7 discloses a method for catalytically degrading methyl mercaptan by using a rare earth (samarium, europium, gadolinium, erbium, yttrium) modified HZSM-5 molecular sieve, wherein the stability of the modified catalyst is far higher than that of unmodified HZSM-5, and the service life of the series of catalysts is 70-130 h; patent 201510678174.8 discloses a rare earth (lanthanum, cerium, praseodymium, neodymium) modified HZM-5 catalyst, the service life of the modified catalyst is 60-105 h; patent 201710129043.3 discloses a resource utilization method of waste chromium adsorbent, the conversion rate of the catalyst for catalytic decomposition of methyl mercaptan shows deactivation signs after 88 h; patent 201710128182.4 discloses a transition metal chromium modified silica-based supported catalyst in which the stability of Cr/MCM-41 can reach 120 h. Therefore, the key problem is to obtain the catalyst with sulfur resistance and carbon deposition resistance by surface modification and other methods aiming at efficiently removing sulfur-containing volatile organic compound methyl mercaptan.
The SBA-15 mesoporous molecular sieve has the characteristics of adjustable pore diameter, thicker pore wall, larger specific surface area and the like, and has wide application prospect in the fields of macromolecular conversion, catalysis, separation, catalyst carriers and the like. However, pure silicon SBA-15 lacks an acid-base site with no ability to catalytically degrade methyl mercaptan.
Disclosure of Invention
The invention aims to provide a preparation method of a Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan, which can obtain Mo-SBA-15 with different Mo doping amounts, not only preserves the mesoporous structure of SBA-15, but also can be applied to the reaction of catalytic decomposition of sulfur-containing volatile organic matter methyl mercaptan gas, shows a catalyst with excellent activity and stability, and has practical application prospects.
The purpose of the invention is realized by the following technical scheme:
a preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan comprises the following steps:
(1) dissolving a template agent in deionized water, and stirring to completely dissolve the template agent;
(2) adding a molybdenum source into the solution obtained in the step (1), and stirring to completely dissolve the molybdenum source;
(3) adding a silicon source into the solution obtained in the step (2), adjusting the pH value to be less than 1, and stirring in a constant-temperature water bath at 38-42 ℃ for 20-24 hours;
(4) and (4) transferring the solution obtained in the step (3) to a stainless steel reaction kettle containing a polytetrafluoroethylene lining for crystallization, filtering, drying and roasting to obtain the Mo-SBA-15 catalyst.
The template agent in the step (1) is a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) which is a commercial product.
And (3) mixing the molybdenum source in the step (2) with one or more of ammonium molybdate, phosphomolybdic acid hydrate and sodium molybdate in any proportion.
The silicon source in the step (3) is one or a mixture of more of methyl orthosilicate, ethyl orthosilicate and propyl orthosilicate in any proportion; the mole ratio of the template agent to the silicon source to the molybdenum source is 1.6:6: 1-1.6: 48: 1.
And (3) regulating the pH value by adopting commercially available concentrated hydrochloric acid, wherein the mass fraction of the concentrated hydrochloric acid is 36-38%.
The crystallization in the step (4) is carried out for 6-24 hours at 90-100 ℃.
And (4) drying, namely, keeping the temperature of 90-100 ℃ for 24 hours.
And (4) the roasting in the step is carried out for 5-8 h at the temperature of 500-600 ℃ in the air atmosphere.
The Mo-SBA-15 mesoporous prepared by the inventionThe molecular sieve can be applied to degrading methyl mercaptan gas, and specifically comprises the following components: introducing methyl mercaptan to be treated with the concentration of 1-10000 ppm into a fixed bed reactor, sieving the synthesized Mo-SBA-15 catalyst to 40-60 meshes, filling the catalyst into the reactor, wherein the reaction pressure is normal pressure, the reaction temperature is 250-550 ℃, and the airspeed of methyl mercaptan gas is 1000-30000 h-1。
The invention has the beneficial effects that:
1. the one-step method is adopted to prepare the Mo-SBA-15, the synthesis process is simple, the structural characteristics of the SBA-15 are kept, a large number of Mo species are uniformly dispersed on the surface, the framework and the pore channel of the SBA-15, and the specific surface area is 650-1200 m2The pore diameter is 3.5-8.5 nm, so that the high-efficiency catalytic degradation of methyl mercaptan molecules is realized.
2. According to the invention, transition metal molybdenum (Mo) is doped on the premise of not destroying the mesoscopic structure of the SBA-15, and is modified, so that the performance of catalyzing methyl mercaptan is improved, the Mo-SBA-15 catalyst with high activity and high stability is obtained, and an idea is provided for designing a sulfur-resistant catalyst.
3. Compared with the existing catalyst for decomposing methyl mercaptan, the Mo-SBA-15 catalyst prepared by the invention has the following advantages:
(1) high activity. Compared with the cerium oxide-based, H-ZSM-5-type and chromium-based catalysts reported in the existing documents, the catalyst can completely convert methyl mercaptan at the reaction temperature of 375 ℃ and is 100-200 ℃ lower than other reported catalysts.
(2) High stability. At normal pressure and at the reaction temperature of 550 ℃, the catalyst has no sign of deactivation within 400h, and the stability of the catalyst is far higher than that of other catalysts reported in other prior documents.
4. The Mo-SBA-15 catalyst prepared by the invention realizes the directional conversion of methyl mercaptan into H2S、CS2、CH4And small amounts of other simple hydrocarbons, wherein H2The S treatment process is mature, and is mostly treated by the Claus process, and the CS2And CH4Can be used as industrial raw material.
Drawings
FIG. 1 shows preparation of example 1N of the Mo-SBA-15 mesoporous molecular sieve2Adsorption-desorption pattern and pore size distribution;
FIG. 2 is a comparison (450 ℃ C.) of the stability of Mo-SBA-15 prepared in example 1 to the stability of the Mo/SBA-15 catalyst prepared in comparative example 1 in degrading methyl mercaptan;
FIG. 3 is a comparison of the activity of Mo-SBA-15 prepared in example 1 in degrading methyl mercaptan with the catalyst reported in the prior art;
FIG. 4 is a graph showing the stability of Mo-SBA-15 prepared in example 1 compared with the stability of catalyst degrading methyl mercaptan reported in the literature (550 ℃).
Detailed Description
The present invention will be described in further detail with reference to examples, but the scope of the present invention is not limited to the examples.
Example 1
A preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan comprises the following steps:
weighing 1.6mol of template agent polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) and dissolving in 100mL of water, and stirring until the triblock copolymer is completely dissolved; then adding 1mol of phosphomolybdic acid hydrate into the solution and stirring until the phosphomolybdic acid hydrate is completely dissolved; adding 12mol of tetraethyl orthosilicate (TEOS), adjusting the pH value of the mixed solution to be less than 1 by adopting commercially available concentrated hydrochloric acid, and continuously stirring for 24 hours under the condition of water bath at 40 ℃; and finally, transferring the solution into a polytetrafluoroethylene-containing autoclave, carrying out hydrothermal crystallization at 96 ℃ for 24h, filtering a sample after reaction, keeping the temperature at 90 ℃ for 24h, drying, and roasting the obtained solid powder at 550 ℃ for 6h to remove the template agent to obtain the Mo-SBA-15 catalyst.
FIG. 1 shows N in the Mo-SBA-15 mesoporous molecular sieve prepared in example 12Adsorption-desorption pattern and pore size distribution; as can be seen from the figure, the sample presents a typical IV-type adsorption isotherm and an H1-type hysteresis loop, and the steep and narrow adsorption curve hysteresis loop shows that the prepared catalyst has a regular mesoporous structure and an average pore diameter of 6.5 nm.
Sieving the prepared catalyst to 40-60 meshes, and filling the catalyst into a reactor, wherein the filling mass of the catalyst is 0.2g, and the total space velocity of feeding is 4280h-1A reaction bodyThe system pressure is normal pressure, the reaction temperature is 250-550 ℃, and a catalytic activity evaluation experiment for catalytic degradation of methyl mercaptan is carried out, so that the conversion rate of methyl mercaptan at 375 ℃ can reach 100%.
Sieving the prepared catalyst to 40-60 meshes, and filling the catalyst into a reactor, wherein the filling mass of the catalyst is 0.2g, and the total space velocity of feeding is 4280h-1The pressure of a reaction system is normal pressure, the reaction temperature is 450 ℃, a catalytic stability experiment of catalytic degradation of methyl mercaptan is carried out, and the sign of deactivation appears after the service life of the catalyst reaches 250 hours; the reaction temperature is 550 ℃, and a catalytic activity evaluation experiment for catalytic degradation of methyl mercaptan is carried out, so that the catalyst has no sign of inactivation within 400 h.
Comparative example 1
Mo/SBA-15 was prepared by the conventional impregnation method by first weighing phosphomolybdic acid hydrate having the same Mo content as in example 1, dissolving in 8mL of water and stirring until it was completely dissolved, then adding 2g of SBA-15 carrier (Science, 1998, 279, 54) to the above solution and stirring until homogeneous; standing at room temperature for one night, drying at 100 ℃ for 12h, transferring the material to a muffle furnace for roasting at 550 ℃ for 5h, filling the obtained catalyst into a reactor, and evaluating the activity of methyl mercaptan catalytic decomposition and testing the stability of the methyl mercaptan. Activity evaluation experiments showed that complete conversion of methyl mercaptan was achieved at 425 deg.C, but at a temperature 50 deg.C higher than the Mo-SBA-15 catalyst prepared in example 1.
FIG. 2 is a comparison of the stability of Mo-SBA-15 prepared in example 1 to the catalyst prepared in comparative example 1 for the degradation of methyl mercaptan; when two catalysts are used for catalytically decomposing methyl mercaptan under the same conditions, it can be seen from the figure that the Mo/SBA-15 catalyst prepared in comparative example 1 decomposes methyl mercaptan at a reaction temperature of 450 ℃, and the methyl mercaptan decomposition rate is only 42% after 96h, and the conversion rate of the methyl mercaptan is still 94% at a reaction time of 300h, which shows that the preparation method of example 1 has great advantages in stability compared with the conventional impregnation method.
FIG. 3 shows Mo-SBA-15 prepared in example 1 and a catalyst CeO reported in the prior art2H-ZSM-5 (Si/Al = 18) degradation methyl mercaptan activity comparison; in which CeO is present2According to the literature [ Chemical Engineering Journal，2016， 289，161-169 ]Prepared by using H-ZSM-5 (Si/Al = 18) which is a conventional product on the market, and three catalysts are used for catalytically decomposing methyl mercaptan under the same conditions, and the CeO is shown in the figure2The conversion rate of the H-ZSM-5 and Mo-SBA-15 catalysts for catalytic decomposition of methyl mercaptan increases with the increase of temperature, and Mo-SBA-15 shows the highest catalytic activity compared with the other two catalysts under the temperature conditions of 350 ℃ and 400 ℃.
FIG. 4 shows Mo-SBA-15 prepared in example 1 and a catalyst CeO reported in the prior art2H-ZSM-5 (Si/Al = 18) degradation methyl mercaptan stability comparison; in which CeO is present2Is according to the literature [ Chemical Engineering Journal, 2016, 289, 161-]The preparation is carried out, H-ZSM-5 (Si/Al = 18) is a conventional product on the market, three catalysts are used for catalytically decomposing methyl mercaptan under the same conditions, and the CeO is shown in the figure when the reaction temperature is 550 DEG C2The catalyst shows deactivation signs at 6h, and the conversion rate of methyl mercaptan is reduced to 35% after 9h along with the reaction; the H-ZSM-5 catalyst showed signs of deactivation at 8H and only after 15H the conversion dropped to 43%; the Mo-SBA-15 catalyst has no inactivation sign in 400h, and the stability is far higher than that of the two catalysts.
In conclusion, compared with the catalysts reported in comparative example 1 and the literature, the Mo-SBA-15 prepared in example 1 has higher catalytic activity and ultra-long stability.
Example 2
A preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan comprises the following steps:
weighing 1.6mol of template agent polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) and dissolving in 100mL of water, and stirring until the triblock copolymer is completely dissolved; then adding 1mol of phosphomolybdic acid hydrate into the solution and stirring until the phosphomolybdic acid hydrate is completely dissolved; then 6mol of methyl orthosilicate is added, commercial concentrated hydrochloric acid is adopted to adjust the pH value of the mixed solution to be less than 1, and the mixed solution is continuously stirred for 22 hours under the condition of 38 ℃ water bath; finally, the solution was transferred to an autoclave containing Polytetrafluoroethylene (PTFE), 90%oC, performing hydrothermal crystallization for 22 hours, filtering a sample after reaction, and drying the sample at 96 ℃ for 24 hours to obtain a solidThe powder was calcined at 500 ℃ for 8h to remove the template to obtain the Mo-SBA-15 catalyst.
Sieving the prepared catalyst to 40-60 meshes, and filling the catalyst into a reactor, wherein the filling mass of the catalyst is 0.2g, and the total space velocity of feeding is 4280h-1The catalytic activity evaluation experiment of catalytic degradation of methyl mercaptan is carried out at the reaction system pressure of normal pressure and the reaction temperature of 250-550 ℃, and the conversion rate of methyl mercaptan at 400 ℃ can reach 100%.
Example 3
A preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan comprises the following steps:
weighing 1.6mol of template agent polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) and dissolving in 100mL of water, and stirring until the triblock copolymer is completely dissolved; then adding 1mol of phosphomolybdic acid hydrate into the solution and stirring until the phosphomolybdic acid hydrate is completely dissolved; then adding 24mol of propyl orthosilicate, adjusting the pH value of the mixed solution to be less than 1 by adopting commercially available concentrated hydrochloric acid, and continuously stirring for 20 hours under the water bath condition of 42 ℃; and finally, transferring the solution into a polytetrafluoroethylene-containing autoclave, carrying out hydrothermal crystallization at 100 ℃ for 20h, filtering a sample after reaction, keeping the temperature at 100 ℃ for 24h, drying, and roasting the obtained solid powder at 600 ℃ for 5h to remove the template agent to obtain the Mo-SBA-15 catalyst.
Sieving the prepared catalyst to 40-60 meshes, and filling the catalyst into a reactor, wherein the filling mass of the catalyst is 0.2g, and the total space velocity of feeding is 4280h-1The catalytic activity evaluation experiment of catalytic degradation of methyl mercaptan is carried out at the reaction system pressure of normal pressure and the reaction temperature of 250-550 ℃, and the conversion rate of methyl mercaptan at 400 ℃ can reach 100%.
Example 4
A preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan comprises the following steps:
weighing 1.6mol of template agent polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) and dissolving in 100mL of water, and stirring until the triblock copolymer is completely dissolved; then adding 1mol of phosphomolybdic acid hydrate into the solution and stirring until the phosphomolybdic acid hydrate is completely dissolved; adding 36mol of ethyl orthosilicate, adjusting the pH value of the mixed solution to be less than 1 by adopting commercially available concentrated hydrochloric acid, andcontinuously stirring for 24 hours under the condition of water bath at 40 ℃; finally, the solution was transferred to an autoclave containing polytetrafluoroethylene, 96oC, performing hydrothermal crystallization for 24 hours, filtering a sample after reaction, keeping the temperature at 90 ℃ for 24 hours, drying, and roasting the obtained solid powder at 550 ℃ for 6 hours to remove the template agent to obtain the Mo-SBA-15 catalyst.
Sieving the prepared catalyst to 40-60 meshes, and filling the catalyst into a reactor, wherein the filling mass of the catalyst is 0.2g, and the total space velocity of feeding is 4280h-1The catalytic activity evaluation experiment of catalytic degradation of methyl mercaptan is carried out at the reaction system pressure of normal pressure and the reaction temperature of 250-550 ℃, and the conversion rate of methyl mercaptan at 400 ℃ can reach 100%.
Example 5
A preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan comprises the following steps:
weighing 1.6mol of template agent polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) and dissolving in 100mL of water, and stirring until the triblock copolymer is completely dissolved; then adding 1mol of phosphomolybdic acid hydrate into the solution and stirring until the phosphomolybdic acid hydrate is completely dissolved; adding 48mol of tetraethyl orthosilicate (TEOS), adjusting the pH value of the mixed solution to be less than 1 by adopting commercially available concentrated hydrochloric acid, and continuously stirring for 24 hours under the condition of water bath at 40 ℃; and finally, transferring the solution into a polytetrafluoroethylene-containing autoclave, carrying out hydrothermal crystallization at 96 ℃ for 24h, filtering a sample after reaction, keeping the temperature at 90 ℃ for 24h, drying, and roasting the obtained solid powder at 550 ℃ for 6h to remove the template agent to obtain the Mo-SBA-15 catalyst.
Sieving the prepared catalyst to 40-60 meshes, and filling the catalyst into a reactor, wherein the filling mass of the catalyst is 0.2g, and the total space velocity of feeding is 4280h-1The catalytic activity evaluation experiment of catalytic degradation of methyl mercaptan is carried out at the reaction system pressure of normal pressure and the reaction temperature of 250-550 ℃, and the conversion rate of methyl mercaptan at 400 ℃ can reach 100%.
Example 6
A preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan comprises the following steps:
1.6mol of template agent polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) is weighedDissolving in 100mL of water, and stirring until the solution is completely dissolved; then adding 1mol of phosphomolybdic acid hydrate into the solution and stirring until the phosphomolybdic acid hydrate is completely dissolved; adding 12mol of tetraethyl orthosilicate (TEOS), adjusting the pH value of the mixed solution to be less than 1 by adopting commercially available concentrated hydrochloric acid, and continuously stirring for 20 hours under the condition of water bath at 40 ℃; finally, transferring the solution into a high-pressure autoclave containing polytetrafluoroethylene, carrying out hydrothermal crystallization at 100 ℃ for 20h, filtering a sample after reaction, keeping the temperature at 90 ℃ for 24h, and drying the sample to obtain solid powder at 500 DEG CoC, roasting for 8 hours to remove the template agent to obtain the Mo-SBA-15 catalyst.
Sieving the prepared catalyst to 40-60 meshes, and filling the catalyst into a reactor, wherein the filling mass of the catalyst is 0.2g, and the total space velocity of feeding is 4280h-1The catalytic activity evaluation experiment of catalytic degradation of methyl mercaptan is carried out at the reaction system pressure of normal pressure and the reaction temperature of 250-450 ℃, and the conversion rate of methyl mercaptan at 400 ℃ can reach 100%.
Example 7
A preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan comprises the following steps:
weighing 1.6mol of template agent polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) and dissolving in 100mL of water, and stirring until the triblock copolymer is completely dissolved; then adding 1mol of ammonium molybdate into the solution and stirring until the ammonium molybdate is completely dissolved; adding 12mol of tetraethyl orthosilicate (TEOS), adjusting the pH value of the mixed solution to be less than 1 by adopting commercially available concentrated hydrochloric acid, and continuously stirring for 20 hours under the condition of 38 ℃ water bath; finally, the solution was transferred to an autoclave containing Polytetrafluoroethylene (PTFE), 100%oC, carrying out hydrothermal crystallization for 12h, filtering a sample after reaction, keeping the temperature at 96 ℃ for 24h, drying, and roasting the obtained solid powder at 600 ℃ for 5h to remove the template agent to obtain the Mo-SBA-15 catalyst.
Sieving the prepared catalyst to 40-60 meshes, and filling the catalyst into a reactor, wherein the filling mass of the catalyst is 0.2g, and the total space velocity of feeding is 4280h-1The pressure of a reaction system is normal pressure, the reaction temperature is 250-550 ℃, a catalytic activity evaluation experiment of catalytic degradation of methyl mercaptan is carried out, and 400 DEG CoThe conversion rate of methyl mercaptan at C can reach 100%.
Example 8
A preparation method of Mo-SBA-15 mesoporous molecular sieve for catalytic decomposition of methyl mercaptan comprises the following steps:
weighing 1.6mol of template agent polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123) and dissolving in 100mL of water, and stirring until the triblock copolymer is completely dissolved; then adding 1mol of sodium molybdate into the solution and stirring until the sodium molybdate is completely dissolved; then adding 5mol of tetraethyl orthosilicate (TEOS) and 7mol of methyl orthosilicate, adjusting the pH value of the mixed solution to be less than 1 by adopting commercially available concentrated hydrochloric acid, and continuously stirring for 24 hours under the condition of water bath at 40 ℃; and finally, transferring the solution into a polytetrafluoroethylene-containing autoclave, carrying out hydrothermal crystallization for 6h at 100 ℃, filtering a sample after reaction, keeping the temperature at 100 ℃ for 24h, drying, and roasting the obtained solid powder at 550 ℃ for 6h to remove the template agent to obtain the Mo-SBA-15 catalyst.
Sieving the prepared catalyst to 40-60 meshes, and filling the catalyst into a reactor, wherein the filling mass of the catalyst is 0.2g, and the total space velocity of feeding is 4280h-1The catalytic activity evaluation experiment of catalytic degradation of methyl mercaptan is carried out at the reaction system pressure of normal pressure and the reaction temperature of 250-550 ℃, and the conversion rate of methyl mercaptan at 400 ℃ can reach 100%.

Claims (1)

1. A method for catalytic decomposition of methyl mercaptan by a Mo-SBA-15 mesoporous molecular sieve is characterized by comprising the following steps:
weighing 1.6mol of template agent polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, dissolving in 100mL of water, and stirring until the triblock copolymer is completely dissolved; then adding 1mol of phosphomolybdic acid hydrate into the solution and stirring until the phosphomolybdic acid hydrate is completely dissolved; adding 12mol of ethyl orthosilicate, adjusting the pH value of the mixed solution to be less than 1 by adopting commercially available concentrated hydrochloric acid, and continuously stirring for 24 hours under the condition of water bath at 40 ℃; finally, transferring the solution into a polytetrafluoroethylene-containing autoclave, carrying out hydrothermal crystallization at 96 ℃ for 24h, filtering a sample after reaction, keeping the temperature at 90 ℃ for 24h, drying, and roasting the obtained solid powder at 550 ℃ for 6h to obtain a Mo-SBA-15 catalyst;
sieving the prepared catalyst to 40-60 meshes, and filling the catalyst into a reactor, wherein the filling mass of the catalyst is 0.2g, and the total space velocity of feeding is 4280h-1A reaction bodyThe system pressure is normal pressure, and the conversion rate of methyl mercaptan reaches 100% at 375 ℃.
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