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CN-121988312-A - TiO (titanium dioxide)2Supported manganese cerium oxide catalyst and preparation method and application thereof

CN121988312ACN 121988312 ACN121988312 ACN 121988312ACN-121988312-A

Abstract

The invention discloses a TiO 2 -loaded manganese-cerium oxide catalyst, and a preparation method and application thereof, and aims to solve the technical problem that the oxidation efficiency of a manganese-cerium-based catalyst is not ideal at low temperature in the prior art. The catalyst takes TiO 2 modified by ammonium sulfate as a matrix, and manganese cerium oxide with the load content of 0.1% -20% is taken as an active component. The preparation method comprises the steps of firstly preparing an ammonium sulfate modified TiO 2 carrier, then mixing a manganese cerium precursor solution with the carrier, and loading active components after treatment. The scheme improves the low-temperature catalytic oxidation performance by enhancing the synergism of the acidity of the carrier and the active components.

Inventors

  • LI SHUN
  • WANG JIANYANG
  • DU HAORAN
  • HE JINLIANG
  • ZHOU JIAN
  • CHEN SONGTAO

Assignees

  • 苏州西热节能环保技术有限公司
  • 西安热工研究院有限公司

Dates

Publication Date
20260508
Application Date
20260122

Claims (10)

  1. 1. A TiO 2 -supported manganese cerium oxide catalyst characterized by comprising a matrix and an active component: the matrix is TiO 2 modified based on ammonium sulfate; The active component is manganese cerium oxide; And the content of the manganese cerium oxide is 0.1% -20% based on 100% of the total mass of the matrix.
  2. 2. The preparation method of the TiO 2 -loaded manganese cerium oxide catalyst is characterized by comprising the following steps of: s1, preparing an ammonium sulfate modified TiO 2 carrier; s2, mixing the manganese cerium precursor solution with the ammonium sulfate modified TiO 2 carrier, and carrying out treatment to load manganese cerium oxide on the carrier.
  3. 3. The method for preparing a TiO 2 supported manganese cerium oxide catalyst according to claim 2, wherein the step of S1, preparing an ammonium sulfate modified TiO 2 support, comprises the steps of: dissolving ammonium sulfate in deionized water to obtain an ammonium sulfate solution; mixing an ammonium sulfate solution with a TiO 2 matrix to obtain a first suspension; removing the solvent in the first suspension to obtain a first block; The first mass was dried, ground and calcined to give an ammonium sulfate modified TiO 2 support.
  4. 4. The method for preparing a TiO 2 -supported manganese cerium oxide catalyst according to claim 3, wherein the solvent in the first suspension is removed by heating in a water bath to obtain a first block; The temperature of the water bath heating is 60-100 ℃; and/or drying the first block, grinding and calcining to obtain the ammonium sulfate modified TiO 2 carrier, wherein the drying temperature is 80-110 ℃, the drying time is 12-48h, and the calcining comprises heating to 150-500 ℃ and calcining for 5-24h under the condition that the heating rate is 1-20 ℃ per minute.
  5. 5. The method for preparing a TiO 2 -supported manganese cerium oxide catalyst according to claim 3, wherein the concentration of sulfate radical in the ammonium sulfate solution is 0-2M.
  6. 6. The method for preparing a TiO 2 supported manganese cerium oxide catalyst according to claim 2, wherein the step S2 of mixing a manganese cerium precursor solution with the ammonium sulfate modified TiO 2 carrier, and carrying out treatment to support a manganese cerium oxide on the carrier comprises the following steps: dissolving inorganic salts of manganese and inorganic salts of cerium in deionized water to obtain manganese-cerium precursor solution; Mixing a manganese cerium precursor solution with the ammonium sulfate modified TiO 2 carrier to obtain a second suspension; removing the solvent in the second suspension to obtain a second block; and drying, grinding and calcining the second block to obtain the TiO 2 -loaded manganese-cerium oxide catalyst.
  7. 7. A method for preparing a TiO 2 -supported manganese cerium oxide catalyst according to claim 3, wherein the inorganic salt of manganese is selected from one or more of manganese nitrate, manganese sulfate and manganese chloride; and/or the inorganic salt of cerium is selected from one or more of cerium nitrate, cerium sulfate and cerium chloride.
  8. 8. The method for preparing a TiO 2 -supported manganese-cerium oxide catalyst according to claim 6, wherein the total oxide loading amount of manganese and cerium elements in the manganese-cerium precursor solution is 0.1% -20% based on 100% of the total mass of the ammonium sulfate-modified TiO 2 carrier.
  9. 9. The method for preparing a TiO 2 supported manganese cerium oxide catalyst according to claim 6, characterized in that the solvent in the second suspension is removed by heating in a water bath to obtain a second block; The temperature of the water bath heating is 60-100 ℃; And/or drying the second block, grinding and calcining to obtain the TiO 2 -loaded manganese cerium oxide catalyst, wherein the drying temperature is 80-110 ℃, the drying time is 12-48h, and the calcining comprises heating to 150-500 ℃ and calcining for 5-24h under the condition that the heating rate is 1-20 ℃ per min.
  10. 10. The use of a TiO 2 -supported ceria oxide catalyst according to claim 1 for catalytic oxidation of volatile organics in industrial flue gas.

Description

TiO 2 -loaded manganese cerium oxide catalyst and preparation method and application thereof Technical Field The invention relates to the field of catalysts, in particular to a TiO 2 -loaded manganese cerium oxide catalyst, a preparation method and application thereof. Background The catalytic oxidation technology is a key means for realizing efficient and thorough removal of Volatile Organic Compounds (VOCs) in industrial flue gas, and the core of the catalytic oxidation technology is development of high-performance catalysts. Among the numerous catalytic materials, manganese cerium composite oxides are considered to be extremely potential VOCs oxidation catalysts due to their excellent redox capability and relatively low cost. For example, published literature studies have shown that by controlling the ratio of Cu/Mn/Ce, etc., the catalytic performance of the catalyst, VOCs such as p-toluene, etc., can be optimized, but the optimum operating temperature window for such catalysts is typically high (e.g., T90 exceeds 280 ℃). However, in practical industrial flue gas environments, the flue gas temperature tends to be low and fluctuates widely, which makes it difficult for many highly active catalysts to perform their ideal performance at low temperatures, limiting their industrial application potential. In order to enhance the oxidation activity of VOCs of catalysts, particularly manganese cerium based catalysts, at low temperatures, current research has employed strategies to support them on high surface area supports. Titanium dioxide (TiO 2) is often used as a catalyst support due to its good stability and surface properties. Although the simple TiO 2 carrier can provide dispersing sites, the surface acidity is usually limited, and the adsorption activation capability of VOCs molecules is insufficient, so that the overall low-temperature catalytic efficiency is affected. Therefore, how to effectively modify the TiO 2 carrier to enhance the surface acidity and optimize the synergistic effect of the TiO 2 carrier and the manganese-cerium active component, so as to significantly reduce the complete oxidation temperature of VOCs is a technical problem to be solved in the art. Disclosure of Invention The invention aims to provide a TiO 2 -loaded manganese-cerium oxide catalyst, and a preparation method and application thereof, so as to solve the technical problem that the oxidation efficiency of a manganese-cerium-based catalyst is not ideal at low temperature in the prior art. In order to achieve the above purpose, the present invention adopts the following technical scheme: The invention provides a TiO 2 -loaded manganese cerium oxide catalyst, which comprises a matrix and active components: the matrix is TiO 2 modified based on ammonium sulfate; The active component is manganese cerium oxide, and the content of the manganese cerium oxide is 0.1% -20% based on 100% of the total mass of the matrix. The invention also provides a preparation method of the TiO 2 -loaded manganese cerium oxide catalyst, which comprises the following steps: s1, preparing an ammonium sulfate modified TiO 2 carrier; s2, mixing the manganese cerium precursor solution with the ammonium sulfate modified TiO 2 carrier, and carrying out treatment to load manganese cerium oxide on the carrier. According to one embodiment of the invention, the S1, the preparation of the ammonium sulfate modified TiO 2 carrier comprises the following steps: Dissolving ammonium sulfate in deionized water to obtain an ammonium sulfate solution, mixing the ammonium sulfate solution with a TiO 2 matrix to obtain a first suspension; removing the solvent in the first suspension to obtain a first block; The first mass was dried, ground and calcined to give an ammonium sulfate modified TiO 2 support. According to one embodiment of the invention, the solvent in the first suspension is removed by heating in a water bath to obtain a first block; The temperature of the water bath heating is 60-100 ℃; and/or drying the first block, grinding and calcining to obtain the ammonium sulfate modified TiO 2 carrier, wherein the drying temperature is 80-110 ℃, the drying time is 12-48h, and the calcining comprises heating to 150-500 ℃ and calcining for 5-24h under the condition that the heating rate is 1-20 ℃ per minute. According to one embodiment of the present invention, the concentration of sulfate radical in the ammonium sulfate solution is 0 to 2M. According to one embodiment of the present invention, the step S2 of mixing a manganese cerium precursor solution with the ammonium sulfate modified TiO 2 carrier, and carrying out treatment to load manganese cerium oxide on the carrier comprises the following steps: dissolving inorganic salts of manganese and inorganic salts of cerium in deionized water to obtain manganese-cerium precursor solution; Mixing a manganese cerium precursor solution with the ammonium sulfate modified TiO 2 carrier to obtain a second suspension; remov