CN107081169B - Preparation method of renewable catalyst for efficiently catalytically decomposing methyl mercaptan - Google Patents

Preparation method of renewable catalyst for efficiently catalytically decomposing methyl mercaptan Download PDF

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CN107081169B
CN107081169B CN201710128182.4A CN201710128182A CN107081169B CN 107081169 B CN107081169 B CN 107081169B CN 201710128182 A CN201710128182 A CN 201710128182A CN 107081169 B CN107081169 B CN 107081169B
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methyl mercaptan
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chromium
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CN107081169A (en
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罗永明
陈定凯
张黎明
赵雨桐
何德东
陈然
何昱轩
陆继长
钟丽萍
刘峰
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Kunming University of Science and Technology
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Abstract

The invention discloses a preparation method of a reproducible catalyst for efficiently catalytically decomposing methyl mercaptan. The activity and the catalytic life of the prepared catalyst are obviously higher than those of an unmodified mesoporous molecular sieve, the catalyst can be subjected to multiple inactivation and regeneration cycles, and the catalytic decomposition performance of methyl mercaptan can be recovered to the level of a fresh catalyst.

Description

Preparation method of renewable catalyst for efficiently catalytically decomposing methyl mercaptan
Technical Field
The invention relates to a preparation method of a renewable catalyst for efficiently catalytically decomposing methyl mercaptan, belonging to the technical field of malodorous gas treatment.
Background
Methyl mercaptan, as a special Volatile Organic Compound (VOCs), is easy to accumulate in air to form Organic aerosol, which causes serious air pollution problems such as atmospheric photochemical smog and haze. Methyl mercaptan also has the properties of low olfactory threshold, high toxicity and high corrosion, and can cause anesthesia of the nervous system of a human body; if the patient works for a long time or lives in a high-concentration environment, respiratory system problems can be caused, and respiratory paralysis can be caused in severe cases. Meanwhile, the high acidity of the methyl mercaptan corrodes reaction equipment. In addition, methyl mercaptan is extremely widely available, mainly from petroleum processing, natural gas, coke ovens, tanneries, paper mills, pollution control facilities (wastewater treatment systems, sanitary landfill systems). Therefore, the fundamental research on the application of the methyl mercaptan treatment technology is urgent, and the research work aiming at the methyl mercaptan tail gas treatment in the industrial production process and the mercaptan removal in petroleum products has important practical significance.
The method for removing methyl mercaptan at home and abroad mainly comprises an adsorption method, an alkali liquor absorption method, a combustion method, a biological method, a catalytic decomposition method and the like. The adsorption method has high purification efficiency, particularly has high purification degree on low-concentration harmful gas, but the capacity of the adsorbent is limited, the regeneration is troublesome and the secondary pollution problem exists. The absorption method has the advantages of high absorption rate of mercaptan, low treatment cost and simple and convenient operation, and has the defects of long contact reaction time, incomplete gas-liquid contact and incomplete removal, and difficult guarantee of standard emission of tail gas when the absorption method is used for treating low-concentration industrial tail gas. The catalytic combustion method has high purification efficiency, lower operation temperature and less energy consumption, but the catalyst is expensive and easy to be poisoned, and the one-time investment is slightly higher. The microbiological method can be carried out at normal temperature and normal pressure, has low cost and no secondary pollution, but occupies larger area, the screening and the culture of strains are difficult, the effect is slow, and the growth of microorganisms is inhibited and the removal is not thorough for the low-concentration methyl mercaptan waste gas because of the low concentration. The catalytic decomposition method is a key research direction at home and abroad because no reagent is needed to be added and the pollution is less. In the field of catalytic decomposition, the choice of catalyst is critical.
At present, foreign scholars mainly use cerium-based catalysts, HZSM-5 molecular sieves, rare earth modified HZSM-5 and other series of catalysts to decompose methyl mercaptan. However, the first two catalysts generally have the problem of easy deactivation (for example, after the HZSM-5 molecular sieve reacts for 6 hours on line, the catalyst begins to deactivate; nano CeO2The catalytic decomposition life of methyl mercaptan is only 10 h). After the HZSM-5 rare earth is modified, the catalytic life is obviously prolonged, the complete conversion life of the methyl mercaptan can last for more than 60 hours, the reaction activity of the catalyst is not obviously improved, and the methyl mercaptan can be completely reacted at 550 DEG CAnd (4) transformation. Therefore, for efficiently removing the malodorous gas methyl mercaptan, eliminating the pollution of the methyl mercaptan to the environment, and seeking a catalyst with better activity and better stability is the key.
Disclosure of Invention
The invention aims to provide a preparation method of a renewable catalyst for efficiently catalytically decomposing methyl mercaptan, which comprises the following steps:
(1) transferring the mesoporous molecular sieve into a muffle furnace, and roasting at 400-600 ℃ for 1-6 h for later use;
(2) adding the calcined mesoporous molecular sieve into a chromium-containing compound solution by taking the calcined mesoporous molecular sieve as a carrier, wherein the mass ratio of the chromium-containing compound to the mesoporous molecular sieve is 1.5-160: 100, the solution is used for completely impregnating the carrier to a certain degree, so that the carrier is uniformly impregnated, and impregnating for 12 hours at normal temperature;
(3) and drying the impregnated mesoporous molecular sieve at 80-100 ℃ for 2-6 h, then transferring the dried mesoporous molecular sieve into a muffle furnace, and roasting the dried mesoporous molecular sieve at 400-600 ℃ for 1-6 h to obtain the catalyst.
The mesoporous molecular sieve is any one of MCM-41, SBA-15, SBA-16 and KIT, and can be obtained commercially.
The chromium-containing compound is any one of chromium nitrate, chromium sulfate, chromium chloride, dichromate and chromate.
The prepared catalyst comprises the following components in percentage by weight: 74.5 to 99.5 percent of mesoporous molecular sieve and 0.5 to 25.5 percent of chromium element.
The prepared catalyst can be used for catalytically decomposing methyl mercaptan under the following reaction conditions:
Figure DEST_PATH_IMAGE002
the catalytic reaction temperature is 250-600 ℃;
Figure DEST_PATH_IMAGE004
the pressure of the catalytic reaction is normal pressure;
Figure DEST_PATH_IMAGE006
the content of the methyl mercaptan gas in the total gas is 1-100000 ppm;
Figure DEST_PATH_IMAGE008
the gas hourly space velocity range of the methyl mercaptan gas is 500-50000 h-1。
Regeneration of the deactivated catalyst: purging the deactivated Cr/MCM-41, Cr/SBA-15, Cr/SBA-16 and Cr/KIT catalysts for 30min by using inert gas to remove inflammable gases (methyl mercaptan and the like); introducing air at 500 ℃ for regeneration for 20min to obtain the regenerated Cr/MCM-41, Cr/SBA-15, Cr/SBA-16 and Cr/KIT catalysts.
The regeneration method is described in the patent application "RE/HZSM-5 catalyst regeneration method for decomposing methyl mercaptan gas" (application No. 201510678808. X).
The catalyst prepared by the invention has the following advantages:
(1) the activity is high, for example, when the reaction temperature is 400 ℃, the activity of a 7.5wt% Cr/MCM-41 catalyst calcined at 550 ℃ can reach 100%, and the unmodified MCM-41 molecular sieve is basically inactive;
(2) the service life is long, for example, when the reaction temperature is 500 ℃, the 10wt% Cr/MCM-41 catalyst calcined at 550 ℃ can reach 100% complete conversion of methyl mercaptan in 120 hours, and the unmodified MCM-41 molecular sieve has no activity under the same conditions;
(3) the regenerability is good, the regenerated catalyst has the same service life as the original catalyst, and the performance and the structure hardly change after multiple regenerations.
Drawings
FIG. 1 is a graph comparing the catalytic activity of a 7.5wt% Cr/MCM-41 catalyst prepared in example 2 and an unmodified MCM-41 molecular sieve of example 3;
FIG. 2 is a graph of the lifetime of a 10wt% Cr/MCM-41 catalyst prepared in example 13;
FIG. 3 is XRD patterns of an unmodified MCM-41 molecular sieve of example 3, a 10wt% Cr/MCM-41 catalyst prepared in example 13 and a third regenerated 10wt% Cr/MCM-41 catalyst;
FIG. 4 is a graph of the multiple regeneration life of a 10wt% Cr/MCM-41 catalyst prepared in example 13.
Detailed Description
The invention is further illustrated with reference to the following figures and examples, without however restricting the scope of the invention thereto.
Example 1
The MCM-41 molecular sieve sold in the market is put into a muffle furnace and roasted for 5 hours at the temperature of 550 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). 0.2g of roasted MCM-41 is weighed in advance, deionized water is dripped into a watch glass to determine the capacity of the carrier for absorbing solution, 1.25g of water required for completely impregnating the carrier is measured, 0.2697g of analytically pure chromium chloride hexahydrate is dissolved in 6.25g of deionized water, stirring is carried out, after complete dissolution, 1g of roasted MCM-41 is added into the chromium chloride solution, the mixture is uniformly stirred, after the mixture is fully impregnated and absorbed for 12 hours, the mixture is dried for 6 hours at 90 ℃, then the mixture is moved into a muffle furnace, and roasting is carried out for 5 hours at 550 ℃ to obtain the 5wt% Cr/MCM-41 catalyst containing the active component chromium element.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 93.2 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 110 h.
And (3) regenerating the deactivated catalyst, namely purging the deactivated 5wt% Cr/MCM-41 catalyst for 30min by using inert gas-nitrogen (30 m L/min), removing combustible gas such as methyl mercaptan and the like, introducing air (30 m L/min), and regenerating the catalyst for 20min at 500 ℃ to obtain the regenerated catalyst.
The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The service life test is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, the fresh catalyst reacts for 138 hours and is completely inactivated, and the regenerated catalyst reacts for 137 hours and is completely inactivated.
Example 2
The MCM-41 molecular sieve sold in the market is put into a muffle furnace and roasted for 5 hours at the temperature of 550 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). 0.2g of roasted MCM-41 is weighed in advance, deionized water is dripped into a watch glass to determine the capacity of the carrier for absorbing solution, 1.25g of water required for completely impregnating the carrier is measured, 0.4155g of analytically pure chromium chloride hexahydrate is dissolved in 6.25g of deionized water, stirring is carried out, after complete dissolution, 1g of roasted MCM-41 is added into the chromium chloride solution, the mixture is uniformly stirred, the mixture is fully impregnated and absorbed for 12 hours, then the mixture is dried for 6 hours at 90 ℃, then the dried mixture is moved into a muffle furnace, and roasting is carried out for 5 hours at 550 ℃ to obtain the 7.5wt% Cr/MCM-41 catalyst containing an active component chromium element.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, the conversion rate of methyl mercaptan is 100 percent, and the catalytic activity is shown in figure 1; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 130 h.
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out under the condition that the reaction temperature is 500 ℃, 168 hours of reaction of the fresh catalyst is completely deactivated, and the service life (from reaction to complete deactivation) of the regenerated catalyst is 165 hours.
Example 3
0.2g of a commercially available MCM-41 molecular sieve (which was not subjected to any modification treatment) was charged in a reactor, the reaction conditions for the decomposition of methyl mercaptan were the same as those in example 1, the conversion of methyl mercaptan was 0, the catalytic activity was as shown in FIG. 1, and the XRD pattern was as shown in FIG. 3.
Example 4
The commercial SBA-16 molecular sieve is put into a muffle furnace and roasted for 5 hours at 550 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). 0.2g of roasted SBA-16 is weighed in advance, deionized water is dripped into a watch glass to determine the capacity of the carrier for absorbing solution, 0.35g of water required for completely impregnating the carrier is measured, 0.9043g of analytically pure chromium chloride hexahydrate is dissolved in 1.75g of deionized water, stirring is carried out, after complete dissolution, 1g of roasted SBA-16 is added into the chromium chloride solution, the mixture is uniformly stirred, fully impregnated and absorbed for 12 hours, then the mixture is dried for 6 hours at 90 ℃, then the dried mixture is moved into a muffle furnace, and roasting is carried out for 5 hours at 550 ℃ to obtain the 15wt% Cr/SBA-16 catalyst containing an active component chromium element.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 92.1 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 98 h.
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out at the reaction temperature of 500 ℃, the fresh catalyst is reacted for 118 hours and is completely deactivated, and the service life of the regenerated catalyst is 119 hours.
Example 5
The commercial SBA-16 molecular sieve is put into a muffle furnace and roasted for 5 hours at 550 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). 0.2g of roasted SBA-16 is weighed in advance, deionized water is dripped into a watch glass to determine the capacity of the carrier for absorbing solution, 0.35g of water required for completely impregnating the carrier is measured, 1.2811g of analytically pure chromium chloride hexahydrate is dissolved in 1.75g of deionized water, stirring is carried out, after complete dissolution, 1g of roasted SBA-16 is added into the chromium chloride solution, the mixture is uniformly stirred, fully impregnated and absorbed for 12 hours, then the mixture is dried for 6 hours at 90 ℃, then the dried mixture is moved into a muffle furnace, and roasting is carried out for 5 hours at 550 ℃ to obtain the 20wt% Cr/SBA-16 catalyst containing an active component chromium element.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 91.6 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 93 h.
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out at the reaction temperature of 500 ℃, the fresh catalyst reacts for 123 hours and is completely deactivated, and the service life of the regenerated catalyst is 120 hours.
Example 6
0.2g of a commercial SBA-16 molecular sieve (which had not been subjected to any modification treatment) was charged in the reactor, and the reaction conditions for decomposing methyl mercaptan were the same as in example 4, and the conversion of methyl mercaptan was 0.
Example 7
The commercial SBA-15 molecular sieve is put into a muffle furnace and roasted for 5 hours at 550 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). 0.2g of roasted SBA-15 is weighed in advance, deionized water is dripped into a watch glass to determine the capacity of the carrier for absorbing solution, 0.39g of water required for completely impregnating the carrier is measured, 0.2697g of analytically pure chromium chloride hexahydrate is dissolved in 1.95g of deionized water, stirring is carried out, after complete dissolution, 1g of roasted SBA-15 is added into the chromium chloride solution, the mixture is uniformly stirred, fully impregnated and absorbed for 12 hours, then the mixture is dried for 6 hours at 90 ℃, then the dried mixture is moved into a muffle furnace, and roasting is carried out for 5 hours at 550 ℃ to obtain the 5wt% Cr/SBA-15 catalyst containing the active component chromium element.
Sieving the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, wherein the filling mass of the catalyst is 0.2gThe total space velocity of the material is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 89.3 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 100 hours.
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out at the reaction temperature of 500 ℃, the fresh catalyst reacts for 130 hours and is completely deactivated, and the service life of the regenerated catalyst is 127 hours.
Example 8
The commercial SBA-15 molecular sieve is put into a muffle furnace and roasted for 5 hours at 550 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). 0.2g of roasted SBA-15 is weighed in advance, deionized water is dripped into a watch glass to determine the capacity of the carrier for absorbing solution, 0.39g of water required for completely impregnating the carrier is measured, 0.4155g of analytically pure chromium chloride hexahydrate is dissolved in 1.95g of deionized water, stirring is carried out, after complete dissolution, 1g of roasted SBA-15 is added into the chromium chloride solution, the mixture is uniformly stirred, fully impregnated and absorbed for 12 hours, then the mixture is dried for 6 hours at 90 ℃, then the dried mixture is moved into a muffle furnace, and roasting is carried out for 5 hours at 550 ℃ to obtain the 7.5wt% Cr/SBA-15 catalyst containing an active component chromium element.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of methyl mercaptan is 99.3 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 126 h.
Deactivation of the enzymeThe catalyst regeneration procedure was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out at the reaction temperature of 500 ℃, 156 hours of reaction of the fresh catalyst is completely deactivated, and the service life of the regenerated catalyst is 155 hours.
Example 9
0.2g of a commercial SBA-15 molecular sieve (which had not been subjected to any modification treatment) was charged in the reactor, and the reaction conditions for decomposing methyl mercaptan were the same as in example 7, and the conversion of methyl mercaptan was 0.
Example 10
The KIT molecular sieve sold in the market is put into a muffle furnace and roasted for 5h at 550 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). Weighing 0.2g of roasted KIT in advance, dropwise adding deionized water on a surface dish to determine the capacity of the carrier for absorbing a solution, measuring the water required for completely soaking the carrier to be 0.43g, dissolving 0.5694g of analytically pure chromium chloride hexahydrate in 2.15g of deionized water, stirring, after completely dissolving, adding 1g of roasted KIT into the chromium chloride solution, stirring uniformly, fully soaking and absorbing for 12 hours, drying for 6 hours at 90 ℃, then transferring into a muffle furnace, and roasting for 5 hours at 550 ℃, thus obtaining the 10wt% Cr/KIT catalyst containing an active component chromium element.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 88.2 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 113 h.
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The service life test is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and the fresh catalyst reacts for 143 hours and completely losesThe life of the active, regenerated catalyst was 141 h.
Example 11
The KIT molecular sieve sold in the market is put into a muffle furnace and roasted for 5h at 550 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). Weighing 0.2g of roasted KIT in advance, dropwise adding deionized water on a surface dish to determine the capacity of the carrier for absorbing a solution, measuring the water required for completely soaking the carrier to be 0.43g, dissolving 0.9043g of analytically pure chromium chloride hexahydrate in 2.15g of deionized water, stirring, after completely dissolving, adding 1g of roasted KIT into the chromium chloride solution, stirring uniformly, fully soaking and absorbing for 12 hours, drying for 6 hours at 90 ℃, then transferring into a muffle furnace, and roasting for 5 hours at 550 ℃, thus obtaining the 15wt% Cr/KIT catalyst containing an active component chromium element.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 80.6 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 104 h.
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out at the reaction temperature of 500 ℃, the fresh catalyst reacts for 134 hours and is completely deactivated, and the service life of the regenerated catalyst is 132 hours.
Example 12
0.2g of a KIT molecular sieve (which was not subjected to any modification treatment) was charged in the reactor, and the reaction conditions for decomposing methyl mercaptan were the same as in example 10, and the conversion of methyl mercaptan was 0.
Example 13
The MCM-41 molecular sieve sold in the market is put into a muffle furnace and roasted for 5 hours at the temperature of 550 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). Weighing 0.2g of roasted MCM-41 in advance, dropwise adding deionized water on a surface dish to determine the capacity of the carrier for absorbing a solution, measuring that the water required for completely soaking the carrier is 1.25g, dissolving 0.5386g of analytically pure ammonium dichromate in 6.25g of deionized water, stirring, adding 1g of roasted MCM-41 into the ammonium dichromate solution after complete dissolution, uniformly stirring, fully soaking and absorbing for 12 hours, drying for 2 hours at 80 ℃, transferring into a muffle furnace, and roasting for 5 hours at 550 ℃ to obtain the 10wt% Cr/MCM-41 catalyst containing an active component chromium element, wherein an XRD (X-ray diffraction) diagram is shown in figure 3.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 98.4 percent; the prepared catalyst is screened to 40-60 meshes and filled in a reactor, the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure, the stability experiment of catalytic decomposition of the methyl mercaptan is carried out at the reaction temperature of 500 ℃, and the complete conversion life of the catalyst, namely the methyl mercaptan, is 120h, as shown in figure 2.
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out at the reaction temperature of 500 ℃, the fresh catalyst is reacted for 150 hours and is completely deactivated, and the service life of the regenerated catalyst is 149 hours.
The catalyst which is deactivated again is regenerated for the second time, and the regeneration step is not changed. The catalyst after the second regeneration is fed for 4280h at the total space velocity-1The service life test is carried out under the conditions that the pressure of the reaction system is normal pressure and the reaction temperature is 500 ℃, and the service life of the catalyst subjected to secondary regeneration is 150 hours.
And carrying out third regeneration after the inactivation is carried out again, wherein the regeneration step is unchanged. The catalyst regenerated for the third time is added at the total space velocity of the feeding of 4280h-1The service life test is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, the service life of the catalyst regenerated for the third time is 150h, and XR (X-ray fluorescence)Fig. D is shown in fig. 3.
The obtained 10wt% Cr/MCM-41 catalyst and the life span of the catalyst after multiple regenerations are shown in FIG. 4.
Example 14
The SBA-15 molecular sieve sold in the market is put into a muffle furnace and roasted for 2h at 500 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). 0.2g of roasted SBA-15 is weighed in advance, deionized water is dripped into a watch glass to determine the capacity of the carrier for absorbing solution, 0.39g of water required for completely soaking the carrier is measured, 1.0283g of analytically pure ammonium dichromate is dissolved in 1.95g of deionized water, stirring is carried out, after complete dissolution, 1g of roasted SBA-15 is added into the pure ammonium dichromate solution, the mixture is uniformly stirred, fully soaked and absorbed for 12 hours, then the mixture is dried for 5 hours at 95 ℃, then the dried mixture is transferred into a muffle furnace, and roasting is carried out for 2 hours at 500 ℃ to obtain the 17.5wt% Cr/SBA-15 catalyst containing an active component chromium element.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 92.6 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 117 h.
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out at the reaction temperature of 500 ℃, the fresh catalyst reacts for 147 hours and is completely deactivated, and the service life of the regenerated catalyst is 148 hours.
Example 15
Putting a KIT molecular sieve sold in the market into a muffle furnace, and roasting for 1h at 500 ℃ for later use. An isometric immersion method is adopted to load an active component chromium (Cr). Weighing 0.2g of roasted KIT in advance, dropwise adding deionized water on a surface dish to determine the capacity of the carrier for absorbing a solution, measuring the water required for completely soaking the carrier to be 0.43g, dissolving 0.0397g of analytically pure chromium sulfate in 2.15g of deionized water, stirring, after completely dissolving, adding 1g of roasted KIT into the chromium sulfate solution, stirring uniformly, fully soaking and absorbing for 12h, drying at 90 ℃ for 4h, transferring into a muffle furnace, and roasting at 500 ℃ for 2h to obtain the 0.5wt% Cr/KIT catalyst containing an active component chromium element.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 90.3 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 94 hours.
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out at the reaction temperature of 500 ℃, the fresh catalyst reacts for 124 hours and is completely deactivated, and the service life of the regenerated catalyst is 122 hours.
Example 16
The commercial SBA-16 molecular sieve is put into a muffle furnace and roasted for 4h at 450 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). 0.2g of roasted SBA-16 is weighed in advance, deionized water is dripped into a watch glass to determine the capacity of the carrier for absorbing solution, 0.35g of water required for completely impregnating the carrier is measured, 1.0990g of analytically pure chromium nitrate nonahydrate is dissolved in 1.75g of deionized water, stirring is carried out, after complete dissolution, 1g of roasted SBA-16 is added into the chromium nitrate nonahydrate solution, the mixture is uniformly stirred, fully impregnated and absorbed for 12h, the mixture is dried for 5h at 85 ℃, then the dried mixture is moved into a muffle furnace, and roasting is carried out for 4h at 450 ℃ to obtain the 12.5wt% Cr/SBA-16 catalyst containing an active component chromium element.
Screening the prepared catalyst to 40-60 meshes,the catalyst is filled in a reactor, the filling mass of the catalyst is 0.2g, and the total space velocity of the feeding is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 88.9 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 111 h.
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out at the reaction temperature of 500 ℃, the fresh catalyst reacts for 141 hours and is completely deactivated, and the service life of the regenerated catalyst is 140 hours.
Example 17
The commercial SBA-15 molecular sieve is put into a muffle furnace and roasted for 3h at 600 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). 0.2g of roasted SBA-15 is weighed in advance, deionized water is dripped into a watch glass to determine the capacity of the carrier for absorbing solution, 0.39g of water required for completely impregnating the carrier is measured, 1.0011g of analytically pure ammonium chromate is dissolved in 1.95g of deionized water, stirring is carried out, after complete dissolution, 1g of roasted SBA-15 is added into the chromium chloride solution, the mixture is uniformly stirred, and after the mixture is fully impregnated and absorbed for 12 hours, the mixture is dried for 3 hours at 95 ℃, then the dried mixture is moved into a muffle furnace, and roasting is carried out for 3 hours at 550 ℃ to obtain the 25.5wt% Cr/SBA-15 catalyst containing an active component chromium element.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 79.6 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and completely converting the catalyst methyl mercaptan into the catalyst with the service life of 40-60 meshes80h。
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out at the reaction temperature of 500 ℃, the fresh catalyst is reacted for 110 hours and is completely deactivated, and the service life of the regenerated catalyst is 110 hours.
Example 18
The MCM-41 molecular sieve sold in the market is put into a muffle furnace and roasted for 6 hours at 400 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). 0.2g of roasted MCM-41 is weighed in advance, deionized water is dripped into a watch glass to determine the capacity of the carrier for absorbing the solution, 1.25g of water required for completely impregnating the carrier is measured, 0.4590g of analytically pure potassium dichromate is dissolved into 6.25g of deionized water, the mixture is stirred, after the mixture is completely dissolved, 1g of roasted MCM-41 is added into the potassium dichromate solution, the mixture is uniformly stirred, the mixture is fully impregnated and absorbed for 12 hours, the mixture is dried for 6 hours at 100 ℃, then the dried mixture is moved into a muffle furnace, and the dried mixture is roasted for 6 hours at 400 ℃, so that the 7.5wt% Cr/MCM-41 catalyst containing an active component chromium element is obtained.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 100 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 61 hours.
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out at the reaction temperature of 500 ℃, the fresh catalyst is reacted for 91 hours and is completely deactivated, and the service life of the regenerated catalyst is 88 hours.
Example 19
The commercial SBA-16 molecular sieve is put into a muffle furnace and roasted for 5 hours at 600 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). 0.2g of roasted SBA-16 is weighed in advance, deionized water is dripped into a watch glass to determine the capacity of the carrier for absorbing solution, 0.35g of water required for completely soaking the carrier is measured, 0.6591g of analytically pure potassium chromate is dissolved in 1.75g of deionized water, stirring is carried out, after complete dissolution, 1g of roasted SBA-16 is added into the pure potassium chromate solution, the mixture is uniformly stirred, and after the mixture is fully soaked and absorbed for 12 hours, the mixture is dried for 6 hours at 90 ℃, then the dried mixture is moved into a muffle furnace, and roasting is carried out for 5 hours at 600 ℃, thus obtaining the 15wt% Cr/SBA-16 catalyst containing the active component chromium element.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 91.6 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 65 hours.
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out at the reaction temperature of 500 ℃, the fresh catalyst reacts for 95 hours and is completely deactivated, and the service life of the regenerated catalyst is 90 hours.
Example 20
The KIT molecular sieve sold in the market is put into a muffle furnace and roasted for 3h at 450 ℃ for standby. An isometric immersion method is adopted to load an active component chromium (Cr). Weighing 0.2g of roasted KIT in advance, dropwise adding deionized water on a surface dish to determine the capacity of the carrier for absorbing a solution, measuring the water required for completely soaking the carrier to be 0.43g, dissolving 0.7312g of analytically pure ammonium chromate in 2.15g of deionized water, stirring, adding 1g of pretreated KIT into the pure ammonium chromate solution after complete dissolution, uniformly stirring, fully soaking and absorbing for 12 hours, drying for 4 hours at 85 ℃, transferring into a muffle furnace, and roasting for 3 hours at 450 ℃ to obtain the 20wt% Cr/KIT catalyst containing an active component chromium element.
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 feeding airspeed is 4280h-1The catalytic decomposition reaction of methyl mercaptan is carried out under the conditions that the pressure of a reaction system is normal pressure and the reaction temperature is 400 ℃, and the conversion rate of the methyl mercaptan is 85.3 percent; screening the prepared catalyst to 40-60 meshes, filling the catalyst into a reactor, carrying out a stability experiment of catalytic decomposition of methyl mercaptan under the conditions that the filling mass of the catalyst is 0.4g, the pressure of a reaction system is normal pressure and the reaction temperature is 500 ℃, and ensuring that the complete conversion life of the catalyst methyl mercaptan is 117 h.
The regeneration procedure of the deactivated catalyst was the same as in example 1. The regenerated catalyst is added at the total space velocity of the feeding of 4280h-1The pressure of the reaction system is normal pressure, the service life test is carried out at the reaction temperature of 500 ℃, 147 hours of reaction of the fresh catalyst is completely inactivated, and the service life of the regenerated catalyst is 144 hours.

Claims (2)

1. The application of the chromium molecular sieve catalyst in the high-efficiency catalytic decomposition of methyl mercaptan is characterized in that the preparation method of the catalyst comprises the following steps:
(1) roasting the mesoporous molecular sieve at 400-600 ℃ for 1-6 h for later use; the mesoporous molecular sieve is any one of MCM-41, SBA-15, SBA-16 and KIT;
(2) adding the calcined mesoporous molecular sieve into a chromium-containing compound solution, wherein the solution amount is such that the carrier is just completely impregnated to the degree that the carrier is uniformly impregnated, and impregnating for 12 hours at normal temperature; the chromium-containing compound is any one of chromium nitrate, chromium sulfate, chromium chloride, dichromate and chromate; the mass ratio of the chromium-containing compound to the mesoporous molecular sieve is 1.5-160: 100;
(3) drying the impregnated mesoporous molecular sieve at 80-100 ℃ for 2-6 h, and roasting at 400-600 ℃ for 1-6 h to obtain the catalyst;
the prepared catalyst is used for catalytically decomposing methyl mercaptan under the following reaction conditions: the catalytic reaction temperature is 250-600 ℃;the pressure of the catalytic reaction is normal pressure; the content of the methyl mercaptan gas in the total gas is 1-100000 ppm; the gas hourly space velocity range of the methyl mercaptan gas is 500-50000 h-1。
2. The use according to claim 1, wherein the regeneration process after deactivation of the catalyst comprises the following steps: and (3) purging the deactivated catalyst with inert gas for 30min, and introducing air for regeneration for 20min at 500 ℃ to obtain the regenerated catalyst.
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