CN115007139A - Manganese-based VOCs catalytic combustion catalyst rich in oxygen vacancies and preparation method thereof - Google Patents
Manganese-based VOCs catalytic combustion catalyst rich in oxygen vacancies and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of chemical catalysts, and particularly relates to a manganese-based VOCs catalytic combustion catalyst rich in oxygen vacancies and a preparation method thereof. The molecular formula of the catalyst is shown as follows: MnZn X O Y Wherein X is 0-0.20 and Y is 2-2.2. The invention adopts a solvothermal reduction method, manganese acetate and zinc acetate are taken as precursor salts, polyoxyethylene polyoxypropylene ether block copolymer is taken as a dispersing agent and a template agent, urea is taken as a precipitating agent, diethylene glycol is taken as a reducing agent, and MnZn rich in oxygen vacancies and with a porous structure is prepared through a solvothermal self-assembly process and roasting X O Y A nanoflake catalyst. The catalyst does not need to load noble metal, has high activity, good stability and strong water resistance, can reduce the production cost and meet the actual industrial requirements.
Description
Technical Field
The invention belongs to the technical field of chemical catalysts, and particularly relates to a manganese-based VOCs catalytic combustion catalyst rich in oxygen vacancies and a preparation method thereof.
Background
Volatile Organic Compounds (VOCs) which are the main sources of industrial emissions and automobile exhaust are a major atmospheric pollutant. If directly discharged into the external environment, the waste water is not only seriously polluted, but also seriously threatens the life and health of human beings. In addition, in the face of stringent environmental laws and regulations, the abatement of VOCs is at hand and is of particular importance. Over the past several decades, numerous technologies for the control of VOCs have been developed, with catalytic combustion methods being widely recognized as one of the most effective and widely used technologies currently for the elimination of various pollutants of VOCs. Compared with the traditional thermal incineration method, the catalytic combustion technology can be carried out at relatively low temperature, and generates carbon dioxide and water which are harmless to the environment without secondary pollution. However, the discharged VOCs are various in kind and complicated in structure. Wherein, the saturated alkane has stable molecular structure and challenges of deep catalytic oxidation because of containing stronger C-H bonds. Propane is a representative lower alkane, and the emission amount of propane is large, and is mainly generated in oil refineries, various industrial processes and automobile exhaust emission. In catalytic combustion of VOCs, although noble metal-based catalysts exhibit excellent catalytic performance, their disadvantages of high price, susceptibility to poisoning, susceptibility to sintering, etc. limit their large-scale application. Therefore, the development of the high-efficiency non-noble metal VOCs catalytic combustion catalyst has higher value and significance.
In transition metal oxide catalysts, the manganese oxide has multiple Mn states δ+ The catalyst has the advantages of low cost, easy obtaining, safety and no toxicity, is widely concerned by researchers, has better catalytic performance in various oxidation-reduction reactions, and is generally considered to be a non-noble metal oxidation catalyst with great development prospect. However, the deep catalytic activity of oxides of manganese during the catalytic combustion of propane is still insufficient. According to the literature concerned, it is reported that the catalytic combustion of propane on manganese-based oxides follows the MVK mechanism, i.e. the redox mechanism, and then the transport capacity of lattice oxygen and the activation capacity of oxygen, i.e. the oxygen vacancies, are of crucial importance. However, in the limited reports, some disadvantages still exist, such as: (1) the catalytic activity is low; (2) complex appearance and crystal face control method. In addition, in the actual industrial production process,the water resistance of the catalyst is also particularly important since the exhaust gas often contains water, which is itself one of the products of catalytic combustion. However, the method reported so far has no obvious profit, and cannot completely meet the water resistance requirement of the VOCs catalytic combustion catalyst in practical application.
Disclosure of Invention
The invention aims to provide a propane catalytic combustion catalyst with high activity, good stability and strong water resistance and a preparation method thereof aiming at the defects of the existing propane catalytic combustion catalyst.
The high-efficiency catalytic combustion catalyst provided by the invention is a manganese-based VOCs catalytic combustion catalyst rich in oxygen vacancies, and the molecular formula of the catalyst is MnZn X O Y X is 0-0.20, Y is 2-2.2; preferably, X is 0.01 to 0.20. The catalyst is of a one-dimensional porous sheet structure, can expose more catalytic active sites, and effectively improves the catalytic activity of the catalyst.
In order to obtain a compound of this formula, the skilled person can adjust the molar ratio among the starting materials used according to the number of atoms in the formula.
Preferably, the catalyst comprises a support on which the compound is supported. The carrier can be various types of common carrier materials for catalysts, such as alumina, titanium dioxide, zirconium oxide and various types of common molecular sieves. To widen the application range of the catalyst.
The invention also provides a preparation method of the high-efficiency propane catalytic combustion catalyst, which comprises the following specific steps:
(1) adding a certain amount of surfactant into deionized water, and ultrasonically stirring until the surfactant is fully dissolved; then adding a reducing agent into the solution, and continuing to stir by ultrasound until the mixture is uniformly mixed;
(2) adding manganese precursor salt and zinc precursor salt into the mixed solution according to a certain proportion, carrying out ultrasonic stirring until the manganese precursor salt and the zinc precursor salt are fully dissolved, then adding a certain amount of precipitator, and continuing to carry out ultrasonic stirring until the manganese precursor salt and the zinc precursor salt are uniformly mixed;
(3) placing the mixed solution in a reaction kettle, and carrying out solvothermal reaction to carry out a self-assembly process; wherein the reaction temperature is controlled to be 160-220 ℃, and the reaction time is 4-10 h;
(4) naturally cooling to room temperature, carrying out suction filtration and washing on the obtained slurry, drying and roasting the obtained filter cake to obtain the MnZn rich in oxygen vacancies X O Y A porous nano-flake VOCs catalytic combustion catalyst; wherein the drying temperature is 80-120 ℃, the drying time is 8-18 h, the roasting temperature is 400-600 ℃, and the roasting time is 4-8 h.
In the step (1), the surfactant is polyvinylpyrrolidone (PVP), or a polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer (P123), or a polyoxyethylene polyoxypropylene ether block copolymer (F127), and the adding mass of the surfactant is 0.75-1.5 g/100g relative to the mass of deionized water; the ultrasonic stirring time is 0.5-1 h; the reducing agent is ethanol, or ethylene glycol, or diethylene glycol, wherein the volume ratio of the reducing agent to the deionized water is 0.5-2, and the preferential ratio is 0.5-1.
In the step (2), the manganese precursor salt is manganese nitrate or manganese acetate, and the zinc precursor salt is zinc nitrate or zinc acetate; in the raw materials, the molar ratio of zinc to manganese is 0-0.20, and the preferred molar ratio of zinc to manganese is 0.01-0.20; the precipitator is urea or sodium hydroxide, the addition amount of the precipitator is 80-200 mmol, and the preferable addition amount is 100-150 mmol; the ultrasonic stirring time is 0.5-1 h respectively.
The surfactant is added in the synthesis process, so that not only can the metal particles be stabilized and dispersed, but also the morphological growth can be controlled, and the concentration of oxygen vacancies of the catalyst can be greatly improved by adding the reducing agent, thereby greatly improving the catalytic oxidation capability of the catalyst. The catalytic performance equal to or even better than that of part of the noble metal-containing catalyst is realized without using noble metal.
The catalyst prepared by the invention can be used for propane catalytic combustion.
The steps of the propane catalytic combustion reaction are as follows: the MnZn rich in oxygen vacancies X O Y Carrying out a propane catalytic combustion reaction on the catalyst, propane/oxygen/nitrogen mixed gas and water vapor at the temperature of 100-350 ℃.
Compared with the prior art, the invention has the following advantages:
(1) the catalyst synthesis method is simple and easy to operate;
(2) the catalyst has a porous flaky morphology structure, is beneficial to the adsorption of reactants and the contact of reaction molecules and active sites, thereby obviously improving the catalytic performance of the catalyst;
(3) the catalyst has abundant acid sites on the surface, and is beneficial to the activation of C-H bonds and C-C bonds;
(4) the catalyst has abundant oxygen vacancy defect sites and has stronger oxygen adsorption capacity and dissociation capacity, thereby accelerating the oxidation-reduction cycle of the whole catalytic reaction;
(5) compared with the reported transition metal oxide catalyst, the catalyst has the advantages of high catalytic activity, strong water resistance, good stability and the like, can be applied to the catalytic combustion scene of VOCs in the presence of water vapor on a large scale, and greatly reduces the production cost.
Detailed Description
In order to more clearly illustrate the present invention, the following examples are given, but the present invention is not limited to the scope of the examples.
Materials and instruments used in the following examples were all obtained from commercial sources, unless otherwise specified.
Propane conversion calculation formula:
example 1
Adding 0.3g of polyoxyethylene polyoxypropylene ether block copolymer (F127) into 80mL of deionized water, ultrasonically stirring for 0.5 h, then dropwise adding 20mL of diethylene glycol (the volume ratio of a reducing agent to the deionized water is 0.5), ultrasonically stirring for 0.5 h, then adding a certain amount of manganese acetate (the molar ratio of zinc to manganese in the raw material is 0), further ultrasonically stirring for 0.5 h, then adding 80mmol of urea, continuously ultrasonically stirring the mixed solution for 0.5 h, then placing the mixed solution into a reaction kettle, and thermally self-assembling the solvent for 4 h at 200 ℃. After cooling to room temperature, the resulting slurryThe material is filtered with suction and treated with a large amount of hot deionized water (>Washing the filter cake at 90 ℃ until the pH of the filtrate is neutral, drying the obtained filter cake at 80 ℃ for 18h, and then roasting at 400 ℃ for 4 h in an air atmosphere to obtain a catalyst marked as MnO 2 。
The catalyst is used for propane catalytic combustion reaction in a fixed bed reactor: tabletting and sieving (40-60 meshes) the obtained catalyst, weighing 0.2g of the catalyst, putting the weighed catalyst into a fixed bed reactor for activity test, wherein the simulated reaction gas comprises the following components: 5vol.% water vapor, 0.2 vol.% propane, 2.4vol.% balance gas of oxygen and nitrogen. The total flow rate of the gas is 100 mL/min, and the corresponding mass space velocity (WHSV) is 30000mL -1 •h -1 . Carrying out a propane catalytic combustion reaction at 100-350 ℃, and carrying out on-line analysis on the conversion rate of propane by adopting gas chromatography. Specific reaction properties are shown in Table 1.
Example 2
0.3g of polyvinylpyrrolidone (PVP) is added into 40 mL of deionized water, after ultrasonic stirring is carried out for 0.5 h, 80mL of ethanol (the volume ratio of the reducing agent to the deionized water is 2) is added dropwise, after ultrasonic stirring is carried out for 0.5 h, a certain amount of manganese acetate and zinc nitrate (the molar ratio of zinc to manganese in the raw material is 0.01) are added, after ultrasonic stirring is carried out for 0.5 h, 80mmol of sodium hydroxide is added, after ultrasonic stirring is carried out on the mixed solution for 0.5 h, the mixed solution is placed in a reaction kettle, and solvent thermal self-assembly is carried out for 4 h at 160 ℃. After cooling to room temperature, the resulting slurry is suction filtered and treated with a large amount of hot deionized water (c) (ii)>Washing the filter cake at 90 ℃ until the pH of the filtrate is neutral, drying the obtained filter cake at 80 ℃ for 18h, then roasting the filter cake at 400 ℃ for 4 h in an air atmosphere, and marking the obtained catalyst as MnZn 0.01 O 2.01 。
The catalyst was used in a fixed bed reactor for propane catalytic combustion reactions under the same reaction conditions and analysis as in example 1. Specific reaction properties are shown in Table 1.
Example 3
0.3g of polyoxyethylene polyoxypropylene ether block copolymer (F127) is added into 60mL of deionized water, after ultrasonic stirring is carried out for 0.5 h, 60mL of glycol is dropwise added (the volume ratio of reducing agent to deionized water is 1), after ultrasonic stirring is carried out for 0.5 h, a certain amount of manganese nitrate and zinc acetate (zinc in raw materials) are addedManganese molar ratio of 0.05), continuing to perform ultrasonic stirring for 0.5 h, adding 200 mmol of urea, continuing to perform ultrasonic stirring on the mixed solution for 0.5 h, placing the mixed solution in a reaction kettle, and performing solvothermal self-assembly for 4 h at 180 ℃. After cooling to room temperature, the resulting slurry is suction filtered and treated with a large amount of hot deionized water (c) (ii)>Washing the filter cake at 90 ℃ until the pH of the filtrate is neutral, drying the obtained filter cake at 80 ℃ for 18h, then roasting the filter cake at 400 ℃ for 4 h in an air atmosphere, and marking the obtained catalyst as MnZn 0.05 O 2.05 。
The catalyst was used in a fixed bed reactor for the catalytic combustion of propane under the same reaction conditions and analysis as in example 1. Specific reaction properties are shown in Table 1.
Example 4
0.3g of polyvinylpyrrolidone (PVP) is added into 60mL of deionized water, 60mL of diethylene glycol (the volume ratio of a reducing agent to the deionized water is 1) is added dropwise after ultrasonic stirring is carried out for 0.5 h, a certain amount of manganese acetate and zinc acetate (the molar ratio of zinc to manganese in the raw material is 0.10) are added after ultrasonic stirring is carried out for 0.5 h, 120 mmol of urea is added after ultrasonic stirring is carried out for 0.5 h, the mixed solution is placed in a reaction kettle and is subjected to solvothermal self-assembly for 6h at 200 ℃. After cooling to room temperature, the resulting slurry is suction filtered and treated with a large amount of hot deionized water (c) (ii)>Washing the filter cake at 90 ℃ until the pH of the filtrate is neutral, drying the obtained filter cake at 80 ℃ for 18h, then roasting the filter cake at 400 ℃ for 4 h in an air atmosphere, and marking the obtained catalyst as MnZn 0.10 O 2.10 。
The catalyst was used in a fixed bed reactor for propane catalytic combustion reactions under the same reaction conditions and analysis as in example 1. Specific reaction properties are shown in Table 1.
Example 5
0.3g of polyvinylpyrrolidone (PVP) is added into 60mL of deionized water, 60mL of diethylene glycol (the volume ratio of a reducing agent to the deionized water is 1) is added dropwise after ultrasonic stirring is carried out for 0.5 h, a certain amount of manganese nitrate and zinc nitrate (the molar ratio of zinc to manganese in the raw material is 0.20) are added after ultrasonic stirring is carried out for 0.5 h, 120 mmol of urea is added after ultrasonic stirring is carried out for 0.5 h, the mixed solution is placed in a reaction kettle and is subjected to solvothermal self-assembly for 6h at 200 ℃.After cooling to room temperature, the resulting slurry is suction filtered and treated with a large amount of hot deionized water (c) (ii)>Washing the filter cake at 90 ℃ until the pH of the filtrate is neutral, drying the obtained filter cake at 120 ℃ for 8h, then roasting the filter cake at 400 ℃ for 4 h in an air atmosphere, and marking the obtained catalyst as MnZn 0.20 O 2.20 。
The catalyst was used in a fixed bed reactor for propane catalytic combustion reactions under the same reaction conditions and analysis as in example 1. Specific reaction properties are shown in Table 1.
Comparative example 1
The comparative example was prepared using a coprecipitation method. Adding a certain amount of manganese acetate and zinc acetate (the molar ratio of zinc to manganese is 0.10) into a beaker containing 120 mL of deionized water, fully dissolving the manganese acetate and the zinc acetate under the condition of magnetic stirring, then dropwise adding 0.5mol/LNaOH solution until the pH value of the solution is about 9, keeping the stirring condition unchanged, aging the solution at the temperature of 70 ℃ for 15 hours, filtering and washing the solution, drying the solution at the temperature of 120 ℃ for 8 hours, and finally roasting the solution at the temperature of 400 ℃ for 4 hours in an air atmosphere to obtain a manganese-cobalt composite oxide catalyst prepared by a coprecipitation method, wherein the manganese-cobalt composite oxide catalyst is marked as MnZn 0.10 O 2.10 −CP。
The above catalyst was used in a fixed bed reactor for propane catalytic combustion reaction under the same reaction conditions and analysis method as in example 1. Specific reaction properties are shown in Table 1.
Table 1: the catalytic performance data of the samples of examples and comparative examples, respectively, count the temperature at which the conversion of propane reaches 50: (T 50 ) And the temperature at which the conversion reaches 90: (T 90 ）
Claims (6)
1. The oxygen vacancy-rich VOCs catalytic combustion catalyst is characterized in that the molecular formula is MnZn X O Y X is 0-0.20, Y is 2-2.2; is in a one-dimensional porous sheet structure.
2. The oxygen vacancy rich VOCs catalytic combustion catalyst of claim 1,characterized in that the molecular formula is MnZn X O Y Wherein X is 0.01 to 0.20.
3. The method for preparing a catalyst for catalytic combustion of oxygen vacancy rich VOCs as claimed in claim 1 or 2, comprising the steps of:
(1) adding a surfactant into deionized water, carrying out ultrasonic stirring until the surfactant is fully dissolved, then adding a reducing agent into the solution, and continuing ultrasonic stirring until the surfactant is uniformly mixed;
(2) weighing manganese precursor salt and zinc precursor salt according to a proportion, adding the manganese precursor salt and the zinc precursor salt into the mixed solution, carrying out ultrasonic stirring until the manganese precursor salt and the zinc precursor salt are fully dissolved, then adding a precipitator, and continuing the ultrasonic stirring until the manganese precursor salt and the zinc precursor salt are uniformly mixed;
(3) placing the mixed solution in a reaction kettle, and carrying out solvothermal reaction to carry out a self-assembly process; wherein the reaction temperature is controlled to be 160-220 ℃, and the reaction time is 4-10 h;
(4) naturally cooling to room temperature, carrying out suction filtration and washing on the obtained slurry, drying and roasting the obtained filter cake to obtain the MnZn rich in oxygen vacancies X O Y A porous nano-flake VOCs catalytic combustion catalyst; wherein the drying temperature is 80-120 ℃, the drying time is 8-18 h, the roasting temperature is 400-600 ℃, and the roasting time is 4-8 h.
4. The preparation method according to claim 3, wherein the surfactant in step (1) is polyvinylpyrrolidone, polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer or polyoxyethylene polyoxypropylene ether block copolymer, and the addition amount thereof is (0.75-1.5)% by mass of deionized water; the reducing agent is ethanol, ethylene glycol or diethylene glycol, and the volume ratio of the reducing agent to the deionized water is 0.5-2.
5. The method according to claim 3, wherein the manganese precursor salt in the step (2) is manganese nitrate or manganese acetate, and the zinc precursor salt is zinc nitrate or zinc acetate; the precipitator is urea or sodium hydroxide, and the addition amount of the precipitator is 80-200 mmol.
6. Use of the oxygen vacancy-rich VOCs catalytic combustion catalyst of claim 1 or 2 in propane catalytic combustion, in particular to use the oxygen vacancy-rich MnZn X O Y Carrying out a propane catalytic combustion reaction on the catalyst, propane/oxygen/nitrogen mixed gas and water vapor at the temperature of 100-350 ℃.
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| CN115849449A (en) * | 2022-11-24 | 2023-03-28 | 中国人民解放军军事科学院军事医学研究院 | N-type semiconductor photo-anode and preparation method and application thereof |
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