Catalyst for removing methanol by catalytic oxidation method as well as preparation method and application of catalyst
Through the coordinated cooperation of ZSM-5 molecular sieve and Ce active components, a catalyst for removing methanol was developed for catalytic oxidation, which solved the problem of high cost of traditional precious metal catalysts, achieved high efficiency, low temperature, long-life methanol removal effect, and was environmentally friendly and free of secondary pollution.
Patent Information
- Application Number
- CN202510339701.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-03-21
- Publication Date
- 2025-06-24
AI Technical Summary
In the prior art, although traditional platinum (Pt) and palladium (Pd) precious metal catalysts have high activity and long life in removing methanol, they have cost problems due to their high prices and are difficult to widely use.
By cooperating with the specific ZSM-5 molecular sieve with the Ce active components supported therein, a catalyst for the removal of methanol was developed. The high specific surface area and abundant pore structure of ZSM-5 molecular sieve combine the dispersion of Ce active components and the increase of oxygen vacancies to promote the generation of reactive oxygen species, thereby improving catalytic activity and life.
It achieves the effect of efficient methanol removal, high catalytic activity, low catalytic temperature, long catalytic life, and is environmentally friendly, and is not prone to secondary pollution.
Smart Images
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Abstract
Description
Technical Field
[0001] The technical field of the present invention is the removal of methanol, and relates to a catalyst for catalytic oxidation of methanol, a preparation method thereof and uses thereof. Background Art
[0002] Methanol is an oxygen-containing volatile organic compound, which has direct harm to human health and is also a precursor for the formation of ozone and haze, resulting in atmospheric environmental pollution. Methanol often comes from industrial production, etc. As a renewable energy source, the emission sources of methanol also involve transportation fields such as vehicles and ships fueled by methanol. Catalytic technology is one of the commonly used technologies for catalytic oxidation to remove methanol, which has the advantages of high efficiency and being less likely to produce secondary pollution. Compared with other catalysts, traditional noble metal catalysts such as platinum (Pt) and palladium (Pd) have excellent activity, better selectivity and longer service life, and at the same time, the noble metal loading is relatively lower, but there are still problems such as high prices.
[0003] Therefore, it is of great significance to develop non-noble metal catalysts for efficient removal of methanol. Summary of the Invention
[0004] Aiming at the deficiencies of the existing technology, the purpose of the present invention is to provide a catalyst for catalytic oxidation of methanol, a preparation method thereof and uses thereof. The catalyst provided by the present invention, through the synergistic cooperation of a specific ZSM-5 molecular sieve and a specific Ce active component loaded therein, can efficiently catalytically oxidize and remove methanol. During the process of catalytic oxidation to remove methanol, the catalyst has high catalytic activity, low catalytic temperature and long catalytic life.
[0005] To achieve the purpose of this invention, the following technical solutions are adopted in the present invention:
[0006] In the first aspect, the present invention provides a catalyst for catalytic oxidation of methanol, and the catalyst comprises a ZSM-5 molecular sieve and a Ce active component loaded in the ZSM-5 molecular sieve.
[0007] For the catalyst provided by the present invention, through the synergistic cooperation of a specific ZSM-5 molecular sieve and a specific Ce active component loaded therein, when it is used for catalytic oxidation to remove methanol, the ZSM-5 molecular sieve has a high specific surface area, a rich pore structure and adjustable acidity, which is beneficial to methanol adsorption and the dispersion of the Ce active component, increases oxygen vacancies and promotes the generation of active oxygen species. Therefore, during the catalytic process, it has high catalytic activity, low catalytic temperature and long catalytic life, and can efficiently remove methanol; at the same time, it is environmentally friendly and less likely to produce secondary pollution.
[0008] In the present invention, the ZSM-5 molecular sieve and the Ce active component must exist simultaneously and cooperate synergistically to achieve the effect of efficient catalytic oxidation to remove methanol.
[0009] The following are the preferred technical solutions of the present invention, but do not limit the technical solutions provided by the present invention. Through the following preferred technical solutions, the technical objectives and beneficial effects of the present invention can be better achieved and realized.
[0010] Preferably, the ZSM-5 molecular sieve includes a modified ZSM-5 molecular sieve, and the modified ZSM-5 molecular sieve includes an ammonia-type ZSM-5 molecular sieve and / or a hydrogen-type ZSM-5 molecular sieve.
[0011] In the present invention, a modified molecular sieve, especially an ammonia-type ZSM-5 molecular sieve and / or a hydrogen-type ZSM-5 molecular sieve, is selected, which is more conducive to the loading of the Ce active component, thus playing a role in promoting the dispersion of Ce.
[0012] It should be noted that the present invention does not make special limitations on the specific modification method of the ZSM-5 molecular sieve, and the modification methods that can be known within a reasonable range by those skilled in the art are applicable to the present invention.
[0013] Exemplarily, the present invention provides a method for obtaining an ammonia-type ZSM-5 molecular sieve from a ZSM-5 molecular sieve to be modified, and the method includes:
[0014] Pre-treat the ZSM-5 molecular sieve to be modified with an ammonium salt aqueous solution to obtain an ammonia-type ZSM-5 molecular sieve.
[0015] Optionally, the concentration of the ammonium salt in the ammonium salt aqueous solution can be 0.05 - 0.5 mol / L, such as 0.05 mol / L, 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L or 0.5 mol / L, etc., but is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.
[0016] Optionally, the temperature of the pre-treatment is 30 - 100 °C, such as 30 °C, 40 °C, 50 °C, 60 °C, 70 °C, 80 °C, 90 °C or 100 °C, etc., but is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.
[0017] Optionally, the time of the pre-treatment is 1 - 10 h, such as 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h, etc., but is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.
[0018] Optionally, the ammonium salt aqueous solution and the ZSM-5 molecular sieve to be modified are mixed at a mass ratio of 1:1 to 10:1 for the pretreatment, such as 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9 or 1:10, etc., but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.
[0019] Optionally, the ammonium salt includes but is not limited to at least one of ammonium nitrate, ammonium chloride, ammonium acetate or ammonium sulfate.
[0020] Exemplarily, the present invention provides a method for obtaining a hydrogen-type ZSM-5 molecular sieve from a ZSM-5 molecular sieve to be modified:
[0021] The ZSM-5 molecular sieve to be modified is modified by an ion exchange method to obtain a hydrogen-type molecular sieve.
[0022] Optionally, the ZSM-5 molecular sieve to be modified is subjected to ion exchange with an inorganic acid and / or a solution containing ammonium ions, and the material after ion exchange is successively subjected to solid-liquid separation, drying and first calcination.
[0023] Furthermore, the inorganic acid includes but is not limited to nitric acid and / or hydrochloric acid; the solution containing ammonium ions includes but is not limited to at least one of ammonium nitrate solution, ammonium chloride solution and ammonium acetate solution; the concentration of the inorganic acid or ammonium ions is independently 0.05 to 0.15 mol / L, such as 0.05 mol / L, 0.1 mol / L or 0.15 mol / L, etc., but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.
[0024] Optionally, during the process of obtaining the hydrogen-type ZSM-5 molecular sieve from the ZSM-5 molecular sieve to be modified, the temperature of the first calcination is 300 to 800 °C, such as 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 650 °C, 700 °C, 750 °C or 800 °C, etc., but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.
[0025] Optionally, during the process of obtaining the hydrogen-type ZSM-5 molecular sieve from the ZSM-5 molecular sieve to be modified, the time of the first calcination is 1 to 20 h, such as 1 h, 3 h, 5 h, 8 h, 10 h, 12 h, 15 h, 18 h or 20 h, etc., but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.
[0026] Preferably, the loading amount of the Ce active component in the ZSM-5 molecular sieve is 1 wt% to 20 wt%, such as 1 wt%, 2 wt%, 3 wt%, 4 wt%, 5 wt%, 6 wt%, 7 wt%, 8 wt%, 9 wt%, 10 wt%, 11 wt%, 12 wt%, 13 wt%, 14 wt%, 15 wt%, 16 wt%, 17 wt%, 18 wt%, 19 wt% or 20 wt%, etc., but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.
[0027] In a second aspect, the present invention provides a preparation method for a catalyst used for removing methanol by catalytic oxidation as described in the first aspect, and the preparation method includes the following steps:
[0028] Loading a cerium salt onto the ZSM-5 molecular sieve and calcining to obtain the catalyst for removing methanol by catalytic oxidation.
[0029] The preparation method provided by the present invention can obtain a catalyst with excellent performance for removing methanol by catalytic oxidation without a complex treatment process, and the performance of the catalyst is stable, the preparation process is simple, and it is suitable for large-scale production.
[0030] Preferably, the method for loading the cerium salt includes an impregnation method and / or an ion exchange method.
[0031] It can be understood that any method that can achieve the loading of the cerium salt and is conducive to obtaining the Ce active component loaded on the ZSM-5 molecular sieve is applicable to the present invention; by selecting the above two loading methods and further regulating the loading conditions, the activity effect is more excellent.
[0032] It should be noted that the present invention does not make special limitations on the specific type of the cerium salt and the specific operation process of loading. Any technical solutions that can be known within a reasonable range by those skilled in the art are applicable to the present invention.
[0033] For example, the cerium salt includes but is not limited to cerium nitrate and / or cerium acetate.
[0034] Preferably, the impregnation method includes: dissolving the cerium salt in the ZSM-5 molecular sieve suspension, stirring and impregnating, and rotary evaporating to dryness.
[0035] Or, the impregnation method includes: dissolving the cerium salt in deionized water, preparing an impregnation solution equal to the pore volume of the ZSM-5 molecular sieve, dropping it into the ZSM-5 molecular sieve in a dropping form, grinding, and drying.
[0036] Preferably, the ion exchange method includes: dissolving the cerium salt in the ZSM-5 molecular sieve suspension, stirring, filtering and washing by suction, and drying.
[0037] Preferably, when the method for cerium salt loading includes the impregnation method, the calcination temperature is 300 - 750 °C, such as 300 °C, 325 °C, 350 °C, 375 °C, 400 °C, 425 °C, 450 °C, 475 °C, 500 °C, 550 °C, 600 °C, 650 °C, 700 °C or 750 °C, etc., preferably 300 - 500 °C, but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.
[0038] In the present invention, when using the impregnation method for cerium salt loading, when the calcination temperature is relatively low, it is preferably up to 300 - 500 °C, which is more conducive to the dispersion of Ce and the generation of oxygen vacancies, and better improves the catalytic activity and effect.
[0039] Preferably, when the method for cerium salt loading includes the impregnation method, the calcination time is 1 - 10 h, such as 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h, etc., but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.
[0040] Preferably, when the method for cerium salt loading includes the impregnation method, the silica-alumina ratio of the ZSM-5 molecular sieve is 10 - 500, such as 10, 50, 100, 150, 200, 225, 250, 275, 300, 325, 350, 375, 400, 425, 450, 475 or 500, etc., preferably 200 - 500.
[0041] In the present invention, during the process of loading Ce by the impregnation method, ZSM-5 molecular sieves with a higher silica-alumina ratio are selected, especially ZSM-5 molecular sieves with a silica-alumina ratio of 200 - 500, which further increases the Ce 3+ / Ce 4+ ratio and the oxygen vacancy content, and better improves the oxygen activation and methanol oxidation performance.
[0042] Preferably, when the method for cerium salt loading includes the ion exchange method, the calcination temperature is 300 - 750 °C, such as 300 °C, 350 °C, 400 °C, 450 °C, 500 °C, 550 °C, 600 °C, 610 °C, 620 °C, 630 °C, 640 °C, 650 °C, 660 °C, 670 °C, 680 °C, 690 °C, 700 °C, 710 °C, 720 °C, 730 °C, 740 °C or 750 °C, etc., preferably 600 - 750 °C, but not limited to the listed values, and other unlisted values within this numerical range are equally applicable.
[0043] In the present invention, when using the ion exchange method for cerium salt loading, the calcination temperature is adjusted to 600 - 750 °C, which can better play the anchoring role of the Al site (Al-OH), promote the dispersion of Ce, and improve the catalytic activity for oxidizing methanol.
[0044] Preferably, when the method for loading the cerium salt includes the ion exchange method, the calcination time is 1 to 10 h, such as 1 h, 2 h, 3 h, 4 h, 5 h, 6 h, 7 h, 8 h, 9 h or 10 h, etc., but is not limited to the listed values, and other unlisted values within this numerical range are equally applicable.
[0045] Preferably, when the method for loading the cerium salt includes the ion exchange method, the silica-alumina ratio of the ZSM-5 molecular sieve is 10 to 500, for example, preferably 10 to 50.
[0046] In the present invention, during the process of loading Ce by the ion exchange method, a ZSM-5 molecular sieve with a lower silica-alumina ratio is selected, especially a ZSM-5 molecular sieve with a silica-alumina ratio of 10 to 50, which better promotes the dispersion of Ce and the generation of active oxygen species, and further improves the catalytic activity for oxidizing methanol.
[0047] As a preferred technical solution, the preparation method includes the following steps:
[0048] Loading the cerium salt into a ZSM-5 molecular sieve with a silica-alumina ratio of 10 to 50 by the ion exchange method, and calcining at 600 to 750 °C for 1 to 10 h to obtain the catalyst for removing methanol by the catalytic oxidation method.
[0049] It should be noted that in the present invention, the ZSM-5 molecular sieve before any modification treatment can be directly purchased or can be prepared by conventional known preparation methods by those skilled in the art, and can be adaptively selected and adjusted according to actual needs.
[0050] In the third aspect, the present invention also provides a use of the catalyst, and the use includes using the catalyst as described in the first aspect or the catalyst prepared by the preparation method as described in the second aspect for removing methanol by the catalytic oxidation method.
[0051] In the process of removing methanol by the catalytic oxidation method in the present invention, the catalyst provided in the first aspect or the second aspect is selected, which has excellent catalytic activity, high catalytic stability, low catalytic temperature and long service life, thereby achieving the purpose of efficiently removing methanol.
[0052] Preferably, the method for removing methanol includes: obtaining carbon dioxide by the catalytic oxidation method of methanol under the action of the catalyst as described in the first aspect or the catalyst prepared by the preparation method as described in the second aspect.
[0053] In the present invention, methanol is catalytically oxidized to obtain carbon dioxide, and the catalytic process is simple and easy to handle, and will not cause secondary pollution.
[0054] Compared with the prior art, the present invention has the following beneficial effects:
[0055] The catalyst provided by the present invention, through the synergistic cooperation of a specific ZSM-5 molecular sieve and a specific Ce active component loaded therein, when used in the catalytic oxidation method for removing methanol, the ZSM-5 molecular sieve has a high specific surface area, a rich pore structure, adjustable acidity, which is beneficial to the adsorption of methanol and the dispersion of the Ce active component, increases oxygen vacancies, promotes the generation of active oxygen species, so that in the catalytic process, it has high catalytic activity, low catalytic temperature, and long catalytic life, and can efficiently remove methanol; at the same time, it is environmentally friendly and not easy to produce secondary pollution. Specific Embodiments
[0056] The technical solution of the present invention will be further described below through specific embodiments. Those skilled in the art should understand that the embodiments are only for helping to understand the present invention and should not be regarded as specific limitations on the present invention.
[0057] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those skilled in the technical field to which this application belongs; the terms used herein are only for the purpose of describing specific embodiments and are not intended to limit this application; the terms "including" and "having" and any variations thereof in this application are intended to cover non-exclusive inclusion.
[0058] In a specific embodiment, the present invention provides a method for obtaining an ammonia-type ZSM-5 molecular sieve from a ZSM-5 molecular sieve to be modified, and the method includes:
[0059] The ZSM-5 molecular sieve to be modified is pretreated with an ammonium nitrate aqueous solution with a concentration of 0.1 mol / L at 80 °C for 5 h, and the ammonium nitrate aqueous solution and the ZSM-5 molecular sieve to be modified are mixed according to a mass ratio of 1:5 to obtain an ammonia-type ZSM-5 molecular sieve.
[0060] In another specific embodiment, the present invention provides a method for obtaining a hydrogen-type ZSM-5 molecular sieve from a ZSM-5 molecular sieve to be modified, and the method includes:
[0061] The ZSM-5 molecular sieve to be modified is subjected to ion exchange with a nitric acid ammonium solution with a concentration of 0.1 mol / L, and the ion-exchanged material is successively subjected to solid-liquid separation, drying, and then calcined at 400 °C for 10 h to obtain a hydrogen-type ZSM-5 molecular sieve.
[0062] The ammonia-type ZSM-5 molecular sieve or hydrogen-type ZSM-5 molecular sieve used in the following examples and comparative examples is modified by the method provided in the above specific embodiments.
[0063] Example 1
[0064] This embodiment provides a catalyst for removing methanol by catalytic oxidation. The catalyst comprises an ammonia-type ZSM-5 molecular sieve and a Ce active component supported in the ammonia-type ZSM-5 molecular sieve. The loading amount of the Ce active component in the ammonia-type ZSM-5 molecular sieve is 3 wt%.
[0065] The preparation method of the catalyst is as follows:
[0066] Dissolve cerium nitrate in a suspension of ammonia-type ZSM-5 molecular sieve with a silica-alumina ratio of 30, stir at 80 °C for 12 h, then filter and wash with 2000 mL of deionized water. After the filtration and washing are completed, perform a drying treatment at 100 °C, and then calcine at a calcination temperature of 750 °C for 4 h to obtain the catalyst for removing methanol by catalytic oxidation.
[0067] Example 2
[0068] The difference between this embodiment and Example 1 is that in this embodiment, the loading amount of the Ce active component is 5 wt%.
[0069] In the preparation method, just adjust the addition amount of cerium nitrate accordingly, and the calcination temperature is 700 °C.
[0070] The rest of the preparation methods and parameters are the same as those in Example 1.
[0071] Example 3
[0072] The difference between this embodiment and Example 1 is that in this embodiment, the silica-alumina ratio of the ammonia-type ZSM-5 molecular sieve is 10.
[0073] The rest of the preparation methods and parameters are the same as those in Example 1.
[0074] Example 4
[0075] The difference between this embodiment and Example 1 is that in this embodiment, the silica-alumina ratio of the ammonia-type ZSM-5 molecular sieve is 50.
[0076] The rest of the preparation methods and parameters are the same as those in Example 1.
[0077] Example 5
[0078] The difference between this embodiment and Example 1 is that in this embodiment, the silica-alumina ratio of the ammonia-type ZSM-5 molecular sieve is 100.
[0079] The rest of the preparation methods and parameters are the same as those in Example 1.
[0080] Example 6
[0081] The difference between this embodiment and Example 1 is that in this embodiment, the calcination temperature is 600 °C.
[0082] The remaining preparation methods and parameters are the same as those in Example 1.
[0083] Example 7
[0084] The difference between this example and Example 1 is that the calcination temperature in this example is 500 °C.
[0085] The remaining preparation methods and parameters are the same as those in Example 1.
[0086] Example 8
[0087] The difference between this example and Example 1 is that the ZSM-5 molecular sieve in this example is not subjected to any modification treatment.
[0088] The remaining preparation methods and parameters are the same as those in Example 1.
[0089] Comparative Example 1
[0090] The difference between this comparative example and Example 3 is that in the catalyst of this comparative example, the molecular sieve in this comparative example is a Beta molecular sieve with the same silicon-aluminum ratio.
[0091] In the preparation method, it is adaptively replaced with the corresponding Beta molecular sieve.
[0092] The remaining preparation methods and parameters are the same as those in Example 3.
[0093] Comparative Example 2
[0094] The difference between this comparative example and Example 3 is that in the catalyst of this comparative example, the active component is the Cu active component.
[0095] In the preparation method, cerium nitrate is adaptively replaced with copper nitrate.
[0096] The remaining preparation methods and parameters are the same as those in Example 3.
[0097] The catalysts provided in Examples 1-8 and Comparative Examples 1-2 are used for the catalytic oxidation removal process of methanol.
[0098] Application Example 1
[0099] This application example provides a method for removing methanol, and the removal method is as follows:
[0100] A quartz tube flow reactor with an inner diameter of 4 mm and filled with 100 mg of the catalyst provided in Example 1 is used. Methanol to be removed is introduced, with an initial methanol concentration of 200 ppm and an air flow rate of 50 mL / min, and catalytic oxidation is carried out.
[0101] Application Examples 2-8 and Comparative Application Examples 1-2
[0102] The differences between Application Example 2-8, Comparative Application Example 1-2 and Application Example 1 are that the catalysts of Examples 2-8 and Comparative Examples 1-2 are used respectively.
[0103] The remaining application methods and parameters are the same as those in Application Example 1.
[0104] Performance characterization: The concentrations of methanol and CO2 were detected by gas chromatography, and the specific results are shown in Table 1.
[0105] Table 1
[0106]
[0107] Example 9
[0108] This example provides a catalyst for removing methanol by catalytic oxidation. The catalyst includes ammonia-type ZSM-5 molecular sieve and Ce active component loaded in the ammonia-type ZSM-5 molecular sieve. The loading amount of Ce active component in the ammonia-type ZSM-5 molecular sieve is 3wt%.
[0109] The preparation method of the catalyst is as follows:
[0110] Cerium nitrate was dissolved in the suspension of ammonia-type ZSM-5 molecular sieve with a silica-alumina ratio of 200, stirred at 25°C for 6 h, the powder obtained after rotary evaporation was dried at 100°C, and calcined at 500°C for 4 h to obtain the catalyst for removing methanol by catalytic oxidation.
[0111] Example 10
[0112] This example provides a catalyst for removing methanol by catalytic oxidation. The catalyst includes hydrogen-type ZSM-5 molecular sieve and Ce active component loaded in the hydrogen-type ZSM-5 molecular sieve. The loading amount of Ce active component in the hydrogen-type ZSM-5 molecular sieve is 10wt%.
[0113] The preparation method of the catalyst is as follows:
[0114] Cerium nitrate was dissolved in deionized water, formulated into an impregnation solution equal to the pore volume of the molecular sieve, dropped into the hydrogen-type ZSM-5 molecular sieve with a silica-alumina ratio of 300, ground with a mortar for 30 min, dried at 100°C, and calcined at 500°C for 4 h to obtain the catalyst for removing methanol by catalytic oxidation.
[0115] Example 11
[0116] The difference between this example and Example 9 is that in this example, the loading amount of Ce active component is 10wt%.
[0117] In the preparation method, the addition amount of cerium nitrate can be adjusted adaptively.
[0118] The remaining preparation methods and parameters are the same as those in Example 9.
[0119] Example 12
[0120] The difference between this example and Example 9 is that in this example, the loading amount of the Ce active component is 20 wt%.
[0121] In the preparation method, the addition amount of cerium nitrate can be adjusted adaptively, and the calcination temperature is 400 °C.
[0122] The remaining preparation methods and parameters are the same as those in Example 9.
[0123] Example 13
[0124] The difference between this example and Example 9 is that in this example, the silica-alumina ratio of the ammonia-type ZSM-5 molecular sieve is 500.
[0125] The remaining preparation methods and parameters are the same as those in Example 9.
[0126] Example 14
[0127] The difference between this example and Example 9 is that in this example, the silica-alumina ratio of the ammonia-type ZSM-5 molecular sieve is 150.
[0128] The remaining preparation methods and parameters are the same as those in Example 9.
[0129] Example 15
[0130] The difference between this example and Example 9 is that in this example, the calcination temperature is 300 °C.
[0131] The remaining preparation methods and parameters are the same as those in Example 9.
[0132] Example 16
[0133] The difference between this example and Example 9 is that in this example, the calcination temperature is 200 °C.
[0134] The remaining preparation methods and parameters are the same as those in Example 9.
[0135] Example 17
[0136] The difference between this example and Example 9 is that in this example, the calcination temperature is 750 °C.
[0137] The remaining preparation methods and parameters are the same as those in Example 9.
[0138] Comparative Example 3
[0139] The difference between this comparative example and Example 11 is that in the catalyst of this comparative example, the molecular sieve in this comparative example is a Beta molecular sieve with the same silica-alumina ratio.
[0140] In the preparation method, it is adaptively replaced with the corresponding Beta zeolite.
[0141] The remaining preparation methods and parameters are the same as those in Example 11.
[0142] Comparative Example 4
[0143] The difference between this comparative example and Example 11 is that in the catalyst of this comparative example, the active component is the Cu active component.
[0144] In the preparation method, cerium nitrate is adaptively replaced with copper nitrate.
[0145] The remaining preparation methods and parameters are the same as those in Example 11.
[0146] The catalysts provided in Examples 9 - 17 and Comparative Examples 3 - 4 were used for the catalytic oxidation removal process of methanol.
[0147] Application Examples 9 - 17 and Comparative Application Examples 3 - 4
[0148] The differences between Application Examples 9 - 17 and Comparative Application Examples 3 - 4 and Application Example 1 are that the catalysts of Examples 9 - 17 and Comparative Examples 3 - 4 were used respectively.
[0149] The remaining application methods and parameters are the same as those in Application Example 1.
[0150] Performance characterization: The concentrations of methanol and CO2 were detected by gas chromatography, and the specific results are shown in Table 2.
[0151] Table 2
[0152]
[0153]
[0154] In summary, for the catalyst provided by the present invention, through the synergistic cooperation of the specific ZSM - 5 zeolite and the specific Ce active component loaded therein, when it is used for the catalytic oxidation method to remove methanol, the ZSM - 5 zeolite has a high specific surface area, a rich pore structure, adjustable acidity, which is beneficial to the adsorption of methanol and the dispersion of the Ce active component, increases oxygen vacancies, promotes the generation of active oxygen species, so that during the catalytic process, it has high catalytic activity, low catalytic temperature, and long catalytic life, and can efficiently remove methanol; at the same time, it is environmentally friendly and not easy to produce secondary pollution.
[0155] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.
Claims
1. A catalyst for removing methanol by catalytic oxidation, characterized in that: The catalyst comprises a ZSM-5 molecular sieve and a Ce active component loaded in the ZSM-5 molecular sieve.
2. The catalyst for removing methanol by catalytic oxidation according to claim 1, characterized in that: The ZSM-5 molecular sieve includes a modified ZSM-5 molecular sieve, and the modified ZSM-5 molecular sieve includes an ammonia-type ZSM-5 molecular sieve and / or a hydrogen-type ZSM-5 molecular sieve.
3. The catalyst for removing methanol by catalytic oxidation according to claim 1, characterized in that: The loading amount of the Ce active component in the ZSM-5 molecular sieve is 1 wt% to 20 wt%.
4. A preparation method for removing methanol by catalytic oxidation as claimed in any one of claims 1 to 3, characterized in that: The preparation method comprises the following steps: The cerium salt is loaded on the ZSM-5 molecular sieve and calcined to obtain the catalyst for removing methanol by catalytic oxidation.
5. The preparation method according to claim 4, characterized in that: The cerium salt loading method includes an impregnation method and / or an ion exchange method.
6. The preparation method according to claim 5, characterized in that: When the cerium salt loading method includes an impregnation method, the calcination temperature is 300 to 750° C., preferably 300 to 500° C.; Preferably, when the cerium salt loading method includes an impregnation method, the calcination time is 1 to 10 hours; Preferably, when the cerium salt loading method comprises an impregnation method, the silicon-aluminum ratio of the ZSM-5 molecular sieve is 10-500, preferably 200-500.
7. The preparation method according to claim 5, characterized in that: When the cerium salt loading method includes an ion exchange method, the calcination temperature is 300 to 750° C., preferably 600 to 750° C.; Preferably, when the cerium salt loading method includes an ion exchange method, the calcination time is 1 to 10 hours; Preferably, when the method for loading the cerium salt comprises an ion exchange method, the silicon-aluminum ratio of the ZSM-5 molecular sieve is 10-500, preferably 10-50.
8. The preparation method according to claim 4, characterized in that: The preparation method comprises the following steps: The cerium salt is loaded into a ZSM-5 molecular sieve with a silicon-aluminum ratio of 10 to 50 by an ion exchange method, and calcined at 600 to 750° C. for 1 to 10 hours to obtain the catalyst for removing methanol by catalytic oxidation.
9. A use of a catalyst, characterized in that: The use includes using the catalyst described in any one of claims 1 to 3 or the catalyst prepared by the preparation method described in any one of claims 4 to 8 to remove methanol by catalytic oxidation.
10. The use according to claim 9, characterized in that The method for removing methanol comprises: obtaining carbon dioxide by catalytic oxidation of methanol under the action of the catalyst described in any one of claims 1 to 3 or the catalyst prepared by the preparation method described in any one of claims 4 to 8.