CN111889099A - Catalyst for propane low-temperature catalytic combustion and preparation method and application thereof - Google Patents

Catalyst for propane low-temperature catalytic combustion and preparation method and application thereof Download PDF

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CN111889099A
CN111889099A CN202010435373.7A CN202010435373A CN111889099A CN 111889099 A CN111889099 A CN 111889099A CN 202010435373 A CN202010435373 A CN 202010435373A CN 111889099 A CN111889099 A CN 111889099A
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propane
temperature
catalyst
mno
catalytic combustion
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CN111889099B (en
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刘晓
胡浩露
张礼知
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Central China Normal University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
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    • F23G2209/141—Explosive gases

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Abstract

The invention discloses a catalyst for propane low-temperature catalytic combustion and a preparation method and application thereof, wherein the catalyst is alpha-MnO with oxygen vacancy concentration of 0.7-1.52(100) The crystal face is prepared by taking manganese nitrate and potassium permanganate as raw materials and carrying out hydrothermal reaction to obtain alpha-MnO with oxygen vacancy concentration of 0.7-1.52(100) The catalyst is used for propane catalytic combustion and is completely oxidized into carbon dioxide, the propane is catalytically combusted and oxidized into carbon dioxide at low temperature, the combustion temperature is low, and the stability is high.

Description

Catalyst for propane low-temperature catalytic combustion and preparation method and application thereof
Technical Field
The invention relates to the field of tail gas treatment, in particular to a catalyst for low-temperature catalytic combustion of propane, and a preparation method and application thereof.
Background
Since the 21 st century, rapid urbanization and industrialization have led to a dramatic increase in the emission of Volatile Organic Compounds (VOCs). Volatile Organic Compounds (VOCs) generally refer to organic compounds having a boiling point below 250 ℃ at atmospheric pressure (101.325 kPa). Volatile Organic Compounds (VOCs) are mostly composed of alkanes, alkenes, alkynes, aromatics, and the like. Among the compounds classified as VOCs, linear short-chain alkanes are the most difficult class to eliminate, mainly produced by automobile exhaust emissions. The control of harmful emissions from automobiles is one of the most pressing problems facing countries around the world. It is reported that during cold start, a significant amount (50-80%) of CO and Hydrocarbons (HCs) are released into the air despite the use of Three Way Catalysts (TWCs).
A representative alkane of linear short-chain alkanes is propane. Due to the stability of the molecular structure, the removal difficulty is high, and propane molecules are not easy to absorb, so that a large amount of propane is discharged into the air, and the atmosphere is polluted.
In the prior art, propane is catalytically oxidized by using a noble metal catalyst, 75% of the catalyst is a noble metal catalyst such as palladium, platinum and the like, for example, Chinese patent with publication number CN109395734A discloses a preparation method of a high-activity cobalt-based catalyst for propane low-temperature catalytic combustion, a product and an application thereof, and although the catalyst has good activity, the catalyst has the defects of high sintering rate caused by high combustion temperature, easiness in volatilization, easiness in poisoning, high price and the like, so that the development of the catalyst with good low-temperature catalytic combustion activity for removing propane is strongly suggested.
Disclosure of Invention
In order to solve the problems, the invention provides a catalyst for propane low-temperature catalytic combustion, a preparation method and application thereof, which realize the low-temperature catalytic combustion oxidation of propane into carbon dioxide, and have low combustion temperature and high stability.
The technical scheme of the invention is to provide a catalyst for propane low-temperature catalytic combustion, which is characterized in that the catalyst is alpha-MnO with oxygen vacancy concentration of 0.7-1.52(100) A crystal plane.
Also provides a preparation method of the catalyst for propane low-temperature catalytic combustion, which comprises the following steps: manganese nitrate and potassium permanganate are used as raw materials, and alpha-MnO with oxygen vacancy concentration of 0.7-1.5 is obtained through hydrothermal reaction2(100) And (4) obtaining a crystal face, namely the catalyst.
Preferably, the reaction temperature of the hydrothermal reaction is 70 to 180 ℃, preferably, the reaction temperature of the hydrothermal reaction is 70 ℃, in which case, α -MnO2(100) The oxygen vacancy concentration of the crystal plane is highest.
Preferably, the mass ratio of the manganese nitrate to the potassium permanganate is 1: 1.
Preferably, the method further comprises the steps of centrifuging, washing with water, washing with alcohol, and drying to remove impurities from the hydrothermal reaction product.
Preferably, the drying temperature is 105 ℃.
Further, the application of the catalyst for propane low-temperature combustion for propane catalytic combustion complete oxidation to carbon dioxide is provided, wherein the propane catalytic combustion temperature is 260-340 ℃, and preferably the propane catalytic combustion temperature is 260 ℃.
The scheme uses manganese nitrate and potassium permanganate as raw materials to obtain alpha-MnO with high oxygen vacancy concentration by hydrothermal reaction at the temperature of 70-180 DEG C2(100) Crystal face with oxygen vacancy concentration of 0.7-1.5 and crystal face number of 100, and temperature is not easy to be too high, otherwise, alpha-MnO obtained by reaction2(100) The oxygen vacancy concentration of the crystal plane is low because: the hydrothermal time and temperature can influence the appearance and crystal form of the catalyst, the hydrothermal time is short or the hydrothermal temperature is low, the crystal form of the catalyst is incomplete to grow, and the surface defects of the catalyst are increased; generally, the surface defects of the oxide produce corresponding active sites, and the sites are usually supplemented and quenched by external oxygen atoms due to high activity, especially in an oxygen-rich environment, but the alpha-MnO prepared by the method2(100) The crystal face has high activity and high stability, and the alpha-MnO with high oxygen vacancy concentration (0.7-1.5) prepared by the scheme2(100) When the catalyst is used in a system for completely oxidizing propane, the catalyst can complete the catalytic combustion and complete oxidation of propane at a lower temperature (260 ℃ C. and 340 ℃ C.), and alpha-MnO prepared at an over-high temperature, such as more than 200 ℃ C2(100) alpha-MnO in the case of a system for complete oxidation of propane having an excessively low oxygen vacancy concentration2(100) T of90The temperature is higher due to: 1. the oxygen vacancy concentration is high, namely, the oxygen defect is more, the reaction sites are more, thus being more beneficial to the adsorption of reactants, namely propane, oxygen (surface adsorbed oxygen) and the like, and the oxygen passes through O2Characterization by-TPD and the like demonstrates that alpha-MnO at high oxygen vacancy concentrations (0.7-1.5)2(100) The reactants, i.e., propane and oxygen, are also more readily desorbed so that the reactants have a high oxygen vacancy concentration of alpha-MnO2(100) Is easier to suckAnd adsorption and desorption, which can make propane and oxygen quickly and fully react so as to obtain alpha-MnO with high oxygen vacancy concentration2(100) Has good activity, then T is reached90Lower temperature of (a); 2. propane catalytic combustion is a typical oxidation reaction, and the mechanism is a classical MvK redox mechanism, namely propane and oxygen are adsorbed on different sites, propane reacts with active lattice oxygen, oxygen vacancies left after the lattice oxygen reaction are rapidly filled by surface adsorbed oxygen, oxygen and the like, so that the oxidation rate of propane is accelerated, the surface adsorbed oxygen plays a more important role here, the higher the oxygen vacancy concentration is, the more beneficial the surface adsorbed oxygen adsorption is, and the higher the oxygen vacancy concentration is, the more the surface adsorbed oxygen adsorption is, the side explanation can also be made on the high-oxygen vacancy concentration alpha-MnO2(100) The reason for good activity; while VOCs catalytic combustion is generally T90The lower the catalyst activity, the better the catalyst activity, so that the alpha-MnO can be prepared according to the scheme2(100) The crystal face oxygen vacancy concentration is high, and the propane can be completely oxidized after catalytic combustion at low temperature, so that the catalytic activity is high and the stability is strong.
Specifically, the preparation method and application of the catalyst for propane low-temperature catalytic combustion are as follows: weighing manganese nitrate and dissolving the manganese nitrate in deionized water at room temperature, then quickly adding potassium permanganate into the solution, stirring the potassium permanganate under a magnetic stirrer to completely dissolve the potassium permanganate, transferring the mixed solution into a polytetrafluoroethylene inner container, placing the inner container into a reaction kettle, heating the reaction kettle in a constant-temperature oven at the temperature of 70-180 ℃, after the reaction is finished, naturally cooling the reaction kettle to room temperature, ultrasonically treating solid solution in the reaction kettle in an ultrasonic machine until the solid is uniformly dispersed, centrifugally collecting the reacted solid product, centrifugally washing the solid product with distilled water and absolute ethyl alcohol for three times respectively, collecting the washed solid product into a culture dish, and drying the solid product in an oven at the temperature of 105 ℃ for 12 hours to obtain the rodlike alpha-MnO with the oxygen vacancy concentration of 0.7-1.52(100) The obtained rod-shaped alpha-MnO is2(100) And (4) carrying out a propane oxidation activity test, controlling the temperature by using a temperature control type tubular furnace, and monitoring the concentration of propane at an inlet and an outlet by using a chromatograph to obtain the conversion rate of propane oxidation.
The invention has the beneficial effects that:
1. the catalyst prepared by the scheme is used for completely oxidizing propane into carbon dioxide and water by catalytic combustion, the combustion temperature is lower, the carbon dioxide is easier to absorb, the environment is friendly, and the tail gas emission is reduced at lower temperature.
2. The alpha-MnO prepared by the scheme2(100) High crystal face oxygen vacancy concentration, high catalytic activity, strong stability, can complete the catalytic combustion of propane at low temperature, alpha-MnO2(100) The crystal face is not easy to sinter and the toxicity is low.
3. The synthesis raw materials are cheap and easy to obtain, the synthesis conditions are easy to realize, complex devices are not needed, the operation is simple, no danger is caused, and no professional is required to be employed for operation.
4. The alpha-MnO in the scheme2(100) Crystal face as catalyst in T90(conversion rate is 90%) and has good effect of completely oxidizing propane.
Drawings
FIG. 1 shows the preparation of alpha-MnO with different oxygen vacancy concentrations in the present scheme2(100) XRD pattern of crystal face;
FIG. 2 shows the preparation of alpha-MnO with different oxygen vacancy concentrations according to the present embodiment2(100) TEM image of crystal plane;
FIG. 3 shows the preparation of alpha-MnO with different oxygen vacancy concentrations according to the present embodiment2(100) (iii) crystal plane XPS plot;
FIG. 4 shows the preparation of alpha-MnO with different oxygen vacancy concentrations according to the present embodiment2(100) Crystal plane XPS map corresponding data;
FIG. 5 shows the preparation of alpha-MnO with different oxygen vacancy concentrations according to the present embodiment2(100) EPR map of crystal plane;
FIG. 6 shows the preparation of alpha-MnO with different oxygen vacancy concentrations according to the present embodiment2(100) Activity comparison graph of crystal face propane catalytic combustion;
FIG. 7 shows the preparation of alpha-MnO with different oxygen vacancy concentrations according to the present embodiment2(100) T of crystal face90Stability profile for the lower 24 h;
FIG. 8 is a graph of α -MnO of different oxygen vacancy concentrations2(100) A kinetic data plot of a crystal plane;
Detailed Description
In order to more clearly illustrate the embodiments of the present invention and the technical solutions in the prior art, the following will describe the specific embodiments of the present invention with reference to the accompanying drawings.
It is obvious that the drawings in the following description are only some examples of the invention, and it is obvious to a person skilled in the art that other drawings and other embodiments can be obtained from these drawings without inventive effort, and the invention is not limited to this example.
Example 1
The catalyst for low temperature catalytic combustion of propane is alpha-MnO with oxygen vacancy concentration of 0.7-1.52(100) A crystal plane.
Example 2
At room temperature, three parts of manganese nitrate, about 3 g, are weighed and respectively added into three 100 mL small beakers, then, 40 mL of Wahaha water is respectively measured by a 50mL measuring cylinder and added into the small beaker, then about 3 g of potassium permanganate is rapidly added into the solution, stirring the mixture under a magnetic stirrer to ensure that the potassium permanganate is completely dissolved, transferring the mixed solution into a 100 mL polytetrafluoroethylene inner container, and the inner container is put into a reaction kettle, and is put into a constant temperature oven to be heated for 24 hours at 70 ℃, after the reaction is finished, after the reaction kettle is naturally cooled to the room temperature, pouring the solid solution in the reaction kettle into a 500 mL beaker, then the solid is evenly dispersed by ultrasonic in an ultrasonic machine, the solid product after reaction is collected by centrifugation, the solid product is washed by the distilled water and the absolute ethyl alcohol by centrifugation for three times respectively, the solid product after washing is collected to a culture dish, drying in a 105 ℃ oven for 12 h to obtain the alpha-MnO with the oxygen vacancy concentration of 1.5.2(100) Crystal face, namely a catalyst for low-temperature catalytic combustion of propane.
Example 3
At room temperature, weighing three parts of manganese nitrate, namely 3 g and about 3 g, respectively adding the three parts of manganese nitrate into three 100 mL small beakers, then respectively weighing 40 mL of Waahaha water by using a 50mL measuring cylinder, adding the small beakers into the small beakers, then quickly adding the potassium permanganate, namely 3 g and about 3 g of potassium permanganate into the solution, stirring the solution under a magnetic stirrer until the potassium permanganate is completely dissolved, then transferring the mixed solution into a 100 mL polytetrafluoroethylene inner container, putting the inner container into a reaction kettle, putting the reaction kettle into a constant-temperature oven, heating the reaction kettle, and keeping the temperature at 1Heating at 30 ℃ for 26h, after the reaction is finished, naturally cooling the reaction kettle to room temperature, pouring the solid solution in the reaction kettle into a 500 mL beaker, then performing ultrasonic treatment in an ultrasonic machine until the solid is uniformly dispersed, centrifugally collecting the reacted solid product, centrifugally washing the solid product for three times by using distilled water and absolute ethyl alcohol respectively, collecting the washed solid product into a culture dish, and drying the solid product in a 105 ℃ oven for 12 h to obtain the alpha-MnO with the oxygen vacancy concentration of 0.92(100) Crystal face, namely a catalyst for low-temperature catalytic combustion of propane.
Example 4
At room temperature, three parts of manganese nitrate, about 3 g, are weighed and respectively added into three 100 mL small beakers, then, 40 mL of Wahaha water is respectively measured by a 50mL measuring cylinder and added into the small beaker, then about 3 g of potassium permanganate is rapidly added into the solution, stirring the mixture under a magnetic stirrer to ensure that the potassium permanganate is completely dissolved, transferring the mixed solution into a 100 mL polytetrafluoroethylene inner container, and the inner container is put into a reaction kettle, and is put into a constant-temperature oven to be heated for 25 hours at 180 ℃, after the reaction is finished, after the reaction kettle is naturally cooled to the room temperature, pouring the solid solution in the reaction kettle into a 500 mL beaker, then the solid is evenly dispersed by ultrasonic in an ultrasonic machine, the solid product after reaction is collected by centrifugation, the solid product is washed by the distilled water and the absolute ethyl alcohol by centrifugation for three times respectively, the solid product after washing is collected to a culture dish, drying in a 105 ℃ oven for 12 h to obtain the alpha-MnO with the oxygen vacancy concentration of 0.7.2(100) Crystal face, namely a catalyst for low-temperature catalytic combustion of propane.
Example 5
Application of catalyst for propane low-temperature combustion in catalytic combustion and complete oxidation of propane into carbon dioxide
The first step is as follows: at room temperature, weighing three parts of manganese nitrate, namely about 3 g, into three small beakers of 100 mL respectively, then weighing 40 mL of Wahaha water into the small beakers by using a 50mL measuring cylinder respectively, then quickly adding about 3 g of potassium permanganate into the solution, stirring the solution under a magnetic stirrer until the potassium permanganate is completely dissolved, transferring the mixed solution into a liner of 100 mL of polytetrafluoroethylene, putting the liner into a reaction kettle, putting the reaction kettle into a constant-temperature oven, heating, controlling the temperature and the reaction time to be 70 ℃ and 1 ℃ respectivelyReacting at 30 ℃ and 180 ℃ for 24 hours, and synthesizing the alpha-MnO with different oxygen vacancy concentrations by a low-temperature hydrothermal method2（100）。
The second step is that: after the reaction is finished, after the reaction kettle is naturally cooled to room temperature, respectively pouring the solid solution in the reaction kettle into 3 500 mL beakers, and then carrying out ultrasonic treatment in an ultrasonic machine until the solid is uniformly dispersed.
The third step: centrifugally collecting the reacted solid product, centrifugally washing the solid product with distilled water and absolute ethyl alcohol for three times respectively, collecting the washed solid product to a culture dish, and drying the solid product in a drying oven at 105 ℃ for 12 hours to obtain three rodlike alpha-MnO with different oxygen vacancy concentrations2(100) Respectively named as alpha-MnO2-70，α-MnO2-130，α-MnO2-180, said α -MnO2-70，α-MnO2-130，α-MnO2alpha-MnO with the crystal face number of 100 is-1802The results of the identification are shown in FIGS. 1 and 2.
The fourth step: taking 200 mg of alpha-MnO 270, oxygen vacancy concentration of 1.5, placing the reaction tube, plugging quartz wool on two sides of a reaction tube catalyst, setting a temperature-raising program through a tube furnace, setting gas flow through a flowmeter, monitoring the change of propane concentration through gas chromatography, and obtaining the conversion rate of propane catalytic combustion-1h-1The total gas flow is 100 mL/min, and the gas flows are respectively as follows: 4 mL/min of propane, 10 mL/min of oxygen and 86mL/min of nitrogen, wherein the nitrogen is used as a carrier gas and does not participate in the reaction, the temperature program is set to be 160-400 ℃, points are taken at every 20 ℃, each temperature is reacted for 30 min after the temperature is stabilized, and the conversion rate of each temperature point is obtained by taking the average value. alpha-MnO2-130 and alpha-MnO2The-180 test method is as above, as can be taken from FIG. 6, alpha-MnO2-70 of T50(T50Lower indicates better light-off characteristics of the catalyst) is 230 ℃ T90(T90Lower indicates better activity of the catalyst) is 260 ℃, T90Temperature of 90% conversion of propane, alpha-MnO2-130 of T90alpha-MnO at 300 DEG C2-180 of T90340 ℃ from EPR (FIG. 5) and XPS: (FIG. 3,4) data show that α -MnO2Oxygen vacancy concentration of-70, maximum, alpha-MnO2-130，α-MnO2Oxygen vacancy concentration of-180 decreases sequentially from T for three catalysts90It can also be obtained that the higher the oxygen vacancy concentration is, the lower the temperature of propane catalytic combustion is, the alpha-MnO prepared by the scheme2(100) The crystal face can catalyze and combust propane to be completely oxidized into carbon dioxide at the low temperature of 260-340 ℃.
Performance testing
The alpha-MnO prepared by the scheme2(100) Stability as catalyst for low temperature catalytic combustion of propane
The first step is as follows: at room temperature, weighing three parts of manganese nitrate, namely about 3 g, into three 100 mL small beakers respectively, then weighing 40 mL of Wahaha water into the small beakers respectively by using a 50mL measuring cylinder, then quickly adding about 3 g of potassium permanganate into the solution, stirring the solution under a magnetic stirrer until the potassium permanganate is completely dissolved, transferring the mixed solution into a 100 mL polytetrafluoroethylene inner container, putting the inner container into a reaction kettle, and heating the reaction kettle in a constant-temperature oven. The temperature and the reaction time are respectively controlled at 70 ℃, 130 ℃ and 180 ℃ for 26 hours. Synthesis of alpha-MnO of different oxygen vacancy concentrations by low temperature hydrothermal method2（100）。
The second step is that: after the reaction is finished, after the reaction kettle is naturally cooled to room temperature, respectively pouring the solid solution in the reaction kettle into 3 500 mL beakers, and then carrying out ultrasonic treatment in an ultrasonic machine until the solid is uniformly dispersed.
The third step: centrifugally collecting the reacted solid product, centrifugally washing the solid product with distilled water and absolute ethyl alcohol for three times respectively, collecting the washed solid product to a culture dish, and drying the solid product in a drying oven at 105 ℃ for 12 hours to obtain three rodlike alpha-MnO with different oxygen vacancy concentrations2(100) Respectively named as alpha-MnO2-70，α-MnO2-130，α-MnO2-180。
The fourth step: consistent with the activity test conditions, 200 mg of alpha-MnO is still taken2-70 placing in a quartz tube, loading quartz wool at two ends of the catalyst, and setting the temperature of the tube furnace at 260 ℃ (T)90) Time is set to 24h, space velocity and gasThe flow rate was kept consistent with the activity test conditions at T90The reaction was continued for 24h at temperature and it was found that the conversion of propane remained around 90% with time as shown in FIG. 7, indicating that no significant deactivation of the catalyst occurred and that alpha-MnO was present2-130 and alpha-MnO2Stability test conditions of-180 with alpha-MnO2The method of-70 was consistent and the continuous reaction was found for 24h, as shown in FIG. 7 for alpha-MnO2-130 and alpha-MnO2The stability of-180 is also better.
The alpha-MnO prepared by the scheme2(100) Kinetic data of
The first step is as follows: at room temperature, weighing three parts of manganese nitrate, namely about 3 g, into three 100 mL small beakers respectively, then weighing 40 mL of Wahaha water into the small beakers respectively by using a 50mL measuring cylinder, then quickly adding about 3 g of potassium permanganate into the solution, stirring the solution under a magnetic stirrer until the potassium permanganate is completely dissolved, transferring the mixed solution into a 100 mL polytetrafluoroethylene inner container, putting the inner container into a reaction kettle, and heating the reaction kettle in a constant-temperature oven. The temperature and the reaction time are respectively controlled to be 70 ℃, 130 ℃ and 180 ℃ for 25h, and alpha-MnO with different oxygen vacancy concentrations is synthesized by a low-temperature hydrothermal method2(100) And after the reaction is finished, naturally cooling the reaction kettle to room temperature, respectively pouring the solid solution in the reaction kettle into 3 500 mL beakers, and then carrying out ultrasonic treatment in an ultrasonic machine until the solid is uniformly dispersed.
The second step is that: centrifugally collecting the reacted solid product, centrifugally washing the solid product with distilled water and absolute ethyl alcohol for three times respectively, collecting the washed solid product to a culture dish, and drying the solid product in a drying oven at 105 ℃ for 12 hours to obtain three rodlike alpha-MnO with different oxygen vacancy concentrations2(100) Respectively named as alpha-MnO2-70，α-MnO2-130，α-MnO2-180。
The third step: consistent with the activity test conditions, 200 mg of alpha-MnO is still taken2-70, placing the catalyst in a quartz tube, installing quartz wool at two ends of the catalyst, setting a temperature rise program through a tube furnace, setting the flow rate of each gas through a flowmeter, and monitoring the change of the concentration of propane through gas chromatography so as to obtain the conversion rate of the catalytic combustion of the propane. The experiment and most workersThe industrial conditions are consistent in airspeed, and the set airspeed is 30000 mL/g-1h-1The total gas flow is 100 mL/min, and the gas flows are respectively as follows: 4 mL/min of propane, 10 mL/min of oxygen and 86mL/min of nitrogen, wherein the nitrogen is used as a carrier gas and does not participate in the reaction, the temperature program is set to be 40-160 ℃, points are taken at every 20 ℃, each temperature reacts for 30 min after the temperature is stabilized, and then the average value is taken to obtain the conversion rate of each temperature point. The calculation of kinetic data requires that the data of the complete oxidation conversion rate of the propane is less than 15 percent, 5 points are taken to make a linear equation of the reaction rate r and the temperature T, then a linear equation of lnr and 1/T is obtained, the apparent activation energy of the catalytic combustion reaction of the propane is obtained according to the slope, and alpha-MnO is obtained by calculation as shown in figure 82Ea (apparent activation energy) of-70 is 35.5 KJ/mol, alpha-MnO2Ea of-130 is 52.9 KJ/mol, alpha-MnO2Ea of-180 was 59.8 KJ/mol, and alpha-MnO was found from the activation energy data2-70，α-MnO2-130，α-MnO2The activity of-180 is low, wherein alpha-MnO is2Activation energy of-70 was the lowest, demonstrating high oxygen vacancy concentration (0.7-1.5) of alpha-MnO2(100) The rate of catalytic reaction can be greatly increased while the activation energy of the reaction process is reduced.
Specific embodiments of the present invention have been described above in detail.
It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, any technical solutions that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments in the prior art based on the inventive concept should be within the scope of protection defined by the claims.

Claims (8)

1. The catalyst for propane low-temperature catalytic combustion is characterized by being alpha-MnO with oxygen vacancy concentration of 0.7-1.52(100) A crystal plane.
2. The preparation method of the catalyst for propane low-temperature catalytic combustion is characterized by comprising the following steps of: manganese nitrate and potassium permanganate are taken as raw materialsPerforming hydrothermal reaction, and removing impurities from the product to obtain alpha-MnO with oxygen vacancy concentration of 0.7-1.52(100) And (4) obtaining a crystal face, namely the catalyst.
3. The method for preparing a catalyst for low-temperature catalytic combustion of propane according to claim 2, wherein the reaction temperature of the hydrothermal reaction is 70-180 ℃.
4. The method for preparing the catalyst for propane low-temperature catalytic combustion according to claim 2, wherein the mass ratio of the manganese nitrate to the potassium permanganate is 1: 1.
5. The method for preparing the catalyst for propane low-temperature catalytic combustion according to claim 2, wherein the step of removing impurities from the product comprises the steps of centrifuging the product, washing with water and alcohol, and drying.
6. The method for preparing a catalyst for low-temperature catalytic combustion of propane according to claim 3, wherein the drying temperature is 105 ℃.
7. The method for preparing a catalyst for low-temperature catalytic combustion of propane according to claim 5, wherein the reaction time of the hydrothermal reaction is 24-26 h.
8. Use of a catalyst for the low-temperature combustion of propane according to claim 1 for the catalytic combustion of propane for the complete oxidation to carbon dioxide, the catalytic combustion temperature of propane being 260-340 ℃.
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Cited By (3)

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