阅读说明：本技术 太阳能光热催化快速处理有机气体的方法 (Method for quickly treating organic gas by solar photo-thermal catalysis ) 是由 吴梁鹏 李新军 李娟� 于 2020-04-21 设计创作，主要内容包括：本发明公开了一种太阳能光热催化快速处理有机气体的方法,该方法包括以下步骤：将复合光热协同催化剂装载在石英管反应器中,将石英管反应器放置于槽式太阳能聚光装置上,在太阳光照射条件下,光热温度为70～180℃下,有机气体通过复合光热协同催化剂生成无害的二氧化碳和水。本发明借助于复合光热协同催化剂中光催化活性组元的强氧化性,首先将有机气体分子活化,起燃温度降低,经过催化燃烧快速转化为二氧化碳和水,这样大大缩短了处理时间,降低了能耗,大幅度提高了降解有机气体的效率,解决了传统光催化和催化燃烧技术在处理有机气体方面的实际应用中所存在的难点,可应用于化工生产车间有机废气的处理。(The invention discloses a method for quickly treating organic gas by solar photo-thermal catalysis, which comprises the following steps: loading the composite photo-thermal synergistic catalyst in a quartz tube reactor, placing the quartz tube reactor on a groove type solar light gathering device, and under the condition of sunlight irradiation, wherein the photo-thermal temperature is 70-180 ℃, organic gas generates harmless carbon dioxide and water through the composite photo-thermal synergistic catalyst. By means of the strong oxidizing property of the photocatalytic active component in the composite photo-thermal synergistic catalyst, organic gas molecules are activated, the ignition temperature is reduced, and the organic gas molecules are quickly converted into carbon dioxide and water through catalytic combustion, so that the treatment time is greatly shortened, the energy consumption is reduced, the efficiency of degrading the organic gas is greatly improved, the difficulty existing in the practical application of the traditional photocatalytic and catalytic combustion technology in the aspect of treating the organic gas is solved, and the composite photo-thermal synergistic catalyst can be applied to the treatment of organic waste gas in a chemical production workshop.)

1. A method for rapidly processing organic gas by solar photo-thermal catalysis is characterized by comprising the following steps: the composite photo-thermal synergistic catalyst is carried in glass microspheres, glass fibers, carbon microspheres and zeoliteOne or more of the organic gases are loaded in a quartz tube reactor, the quartz tube reactor is placed on a groove type solar light gathering device, and under the condition of sunlight irradiation, the photo-thermal temperature is 70-180 ℃, the organic gases generate harmless carbon dioxide and water through a composite photo-thermal synergistic catalyst; the organic gas comprises one or more of methanol, formaldehyde, methyl ether, acetaldehyde, diethyl ether, ethylene, acetone, benzene, toluene and xylene; the composite photo-thermal synergistic catalyst comprises a limited domain carrier, a thermal catalytic combustion component and a photocatalytic activity component, wherein the limited domain carrier comprises one or more of a nano tube, a molecular sieve, an MOF (metal-organic framework) and a COF (chip on film), and the photocatalytic component comprises TiO₂、ZnO、CoO、Co₃O₄、Bi₂O₃、Cu₂O、CuO、Fe₂O₃、VO₂、MTiO₃One or more of the components are mixed; wherein M is selected from any one of Sr, Mg and Mn; the thermal catalytic component comprises Pt, Pd, Au, Ru and MnO₂、CeO、CuO、Co₃O₄、Fe₂O₃、Fe₃O₄Or NiO; the photocatalytic active component is loaded on the outer surface of the limited area carrier, and the thermocatalytic combustion component is embedded in the pore channel of the limited area carrier; the weight percentage of the photocatalytic active component is 10-30%, and the weight percentage of the thermocatalytic combustion component is 0.1-5%, calculated by taking the total weight of the catalyst as 100%.

The technical field is as follows:

the invention relates to the technical field of organic gas treatment, in particular to a method for quickly treating organic gas through solar photo-thermal catalysis.

Background art:

along with the rapid development of the world economic society, the emission of volatile organic gases (VOCs) in the environment is increasing. Emissions of VOCs outdoors are mainly from the combustion of fossil fuels and industrial waste gases, etc., and VOCs have been recognized as one of the major environmental hazards in air that is a serious hazard to the environment and human health. At present, the common treatment modes of VOCs mainly comprise a plurality of modes, such as a washing absorption technology, a catalytic combustion technology, a recycling technology, an adsorption method, a low-temperature plasma technology, a photocatalysis technology and the like, and various methods have the characteristics under specific environments. The photocatalytic oxidation and catalytic oxygen combustion technology is one of the most promising treatment technologies at present. However, the main problems of photocatalytic degradation of organic gases are slow degradation rate and low light energy utilization efficiency. The catalytic combustion technology has higher ignition temperature and higher process energy consumption cost.

The invention content is as follows:

the invention aims to provide a method for rapidly treating organic gas by solar photo-thermal catalysis, which utilizes a composite photo-thermal synergistic catalyst to generate a hole-electron pair with strong reduction and oxidation effects under the assistance of visible light, enhances the oxidation reduction capability, effectively reduces the reaction temperature, and solves the problems of single treatment way of VOCs, high energy consumption of catalytic oxygen combustion technology and low reaction efficiency of photocatalysis technology in the prior art.

The invention is realized by the following technical scheme:

a method for quickly treating organic gas by solar photo-thermal catalysis comprises the following steps:

the method comprises the following steps of (1) loading a composite photo-thermal synergistic catalyst on one or more of glass microspheres, glass fibers, carbon microspheres and zeolite, loading the catalyst into a quartz tube reactor, placing the quartz tube reactor on a groove type solar light gathering device, and under the condition of sunlight irradiation, wherein the photo-thermal temperature is 70-180 ℃, organic gas generates harmless carbon dioxide and water through the composite photo-thermal synergistic catalyst; the organic gas comprises one or more of methanol, formaldehyde, methyl ether, acetaldehyde, diethyl ether, ethylene, acetone, benzene, toluene and xylene; the composite photo-thermal synergistic catalyst comprises a limited domain carrier, a thermal catalytic combustion component and a photocatalytic activity component, wherein the limited domain carrier comprises one or more of a nano tube, a molecular sieve, an MOF (metal-organic framework) and a COF (chip on film), and the photocatalytic component comprises TiO₂、ZnO、CoO、Co₃O₄、Bi₂O₃、Cu₂O、CuO、Fe₂O₃、VO₂、MTiO₃One or more of the components are mixed; wherein M is selected from any one of Sr, Mg and Mn; the thermal catalytic component comprises one or more of Pt, Pd and Au; the photocatalytic active component is loaded on the outer surface of the limited area carrier, and the thermocatalytic combustion component is embedded in the pore channel of the limited area carrier; the weight percentage of the photocatalytic active component is 10-30%, and the weight percentage of the thermocatalytic combustion component is 0.1-5%, calculated by taking the total weight of the catalyst as 100%.

The preparation method of the composite photo-thermal synergistic catalyst comprises the following steps: 1) preparing nanotubes, molecular sieves, MOFs, COFs carriers (Liangpen Wu, Xu Yang, Juan Li, Yanjin Huang, Xinjun Li, catalysis of titanium dioxide nanotubes with good morphology at high calcium temperature and photocatalytic activity, Materials Chemistry and Physics,2017,202, 136-); 2) embedding thermal catalytic combustion components Pt, Pd and Au into a carrier pipeline (xuYang, XiangYu, Lizhen Long, Tiejun Wang, Long Ma, Liangpeng Wu, Yu Bai, Xinjun Li, Shijun Liao, Pt nanoparticles impregnated in Titanium Nanoparticles (TNT) for phenol hydrogenation) by adopting a vacuum-assisted isometric impregnation method, wherein the component Pt, Pd and Au are contained in the carrier pipeline (XuYang, XiangYu, Lizhen Long, Tiejun Wang, Long Ma, Liangpeng Wu, Yu Bai, Xinjun Li, Shijun Liao, Pt nanoparticles impregnated in Titanium Nanoparticles (TNT) for phenol hydrogenation: the final effect of TNT, chem.Commun.,2014,50, 2794); 3) and (3) depositing a photocatalytic component (Quanming Pen, guiding Pen, Liangpeng Wu, Juan Li, Xiaooyang Wang, Mingwei Liu, Xinjun Li, Fe2O3 modification precursors of the photocatalytic performance of TiO2 nanotube defined Pd nanoparticles, Journal of Photochemistry & Photobiology A: Chemistry 380(2019)111865) on the surface of the catalyst in the step 2) by adopting a surface chemical deposition method, and finally obtaining the composite photothermal synergistic catalyst.

The invention has the following beneficial effects:

by means of the strong oxidizing property of the photocatalytic active component in the composite photo-thermal synergistic catalyst, organic gas molecules are activated to generate activated molecules, the ignition temperature of the activated molecules is reduced, and the activated molecules are quickly converted into carbon dioxide and water through catalytic combustion, so that the treatment time is greatly shortened, the energy consumption is reduced, the efficiency of degrading organic gas is greatly improved, the difficulty existing in the practical application of the traditional photocatalytic and catalytic combustion technology in the aspect of treating organic gas is solved, and the method can be applied to the treatment of organic waste gas in a chemical production workshop.

Description of the drawings:

FIG. 1 is a schematic diagram of the solar photo-thermal catalytic rapid treatment of organic gases according to the present invention.

The specific implementation mode is as follows:

the following is a further description of the invention and is not intended to be limiting.

Example 1:

preparing Pt @ TiO by adopting hydrothermal synthesis method, ultrasonic-assisted impregnation method and surface chemical deposition method₂Nanotube @ Bi₂O₃Photo-thermal catalytic material. The method comprises the following steps:

preparing a titanium dioxide nanotube by a hydrothermal method: 6g P25 titanium dioxide nanopowder was added to a 500mL polytetrafluoroethylene bottle. Then preparing 10mol/L sodium hydroxide solution, measuring 360mL solution by using a measuring cylinder, adding the solution into a polytetrafluoroethylene bottle filled with P25 titanium dioxide nanometer, violently stirring for half an hour, placing the polytetrafluoroethylene bottle in an oil bath, heating to 120 ℃, and carrying out reflux reaction for 48 hours. Naturally cooling to room temperature, filtering, washing the prepared powder with deionized water to be nearly neutral, soaking for 8 hours with 0.1mol/L hydrochloric acid, then washing with deionized water until the pH value is equal to 7, drying the obtained powder for 24 hours at 60 ℃ after filtering, then roasting in a muffle furnace at the heating rate of 1 ℃/min, heating to 400 ℃, and preserving heat for 2 hours to obtain the titanium dioxide nanotube.

Embedding the active component noble metal into the titanium dioxide nanotube by a vacuum-assisted ultrasonic equal-volume impregnation method: weighing 300mg of titanium dioxide nanotube, dropwise adding 0.005g/mL of chloroplatinic acid ethanol solution for multiple times until the powder is just soaked, placing the powder in an ultrasonic environment, pumping the powder under negative pressure by using a vacuum pump, transferring the powder into a crucible, annealing the powder in a tubular furnace at 300 ℃ for 2 hours in a mixed atmosphere containing 8% of hydrogen and 92% of argon to obtain a product of the titanium dioxide nanotube with a catalytic oxidation active component noble metal embedded in a reduction, and recording Pt @ TiO₂A nanotube;

chemical deposition method for loading metal oxide Bi on surface₂O₃Surface modification of the catalytic promoter: weighing Pt @ TiO₂Adding 5-15 mL0.01-0.1mol/L of metal salt aqueous solution into a nanotube, stirring for 15-40 min under the condition of water bath at the temperature of 60-80 ℃, dropwise adding 0.5 wt% of ammonia water, stirring for 60min, settling, filtering, drying in an oven, transferring into a crucible, annealing in a tube furnace at the temperature of 300 ℃ for 2h in an argon atmosphere to obtain a target catalyst, namely Pt @ TiO₂Nanotube @ Bi₂O₃Photo-thermal catalytic material. The weight percentage of the photocatalytic active component is 15 percent and the weight percentage of the thermal catalytic combustion component is 1 percent, calculated by taking the total weight of the catalyst as 100 percent, and the photo-thermal catalyst is loaded on glass fiber and loaded in a quartz reactor. Placing a quartz tube on a groove type solar light-gathering device, under the condition of 120W simulated sunlight irradiation, the photothermal temperature is 70 ℃, the concentration of formaldehyde is 500ppm, the flow rate of gas is 60mL/min, and detecting by chromatographyThe immediate removal rate of the organic gas formaldehyde is up to more than 98 percent.

Comparative example 1:

reference example 1 preparation of Pt @ TiO by hydrothermal Synthesis method and ultrasonic assisted impregnation method₂A nanotube thermocatalytic material. The weight percentage of the thermal catalytic combustion component was 1% calculated on the total weight of the catalyst as 100%, and the thermal catalyst was loaded on glass fibers and loaded in a quartz reactor. The quartz tube is placed on a groove type solar light gathering device, under the condition of 120W simulated sunlight irradiation, the photothermal temperature is 70 ℃, the concentration of formaldehyde is 500ppm, the flow rate of gas is 60mL/min, and the instant removal rate of organic gas formaldehyde is up to about 70% through chromatographic detection.

Example 2:

reference example 1 Pt-Pd @ molecular sieve @ Fe was prepared by hydrothermal synthesis, ultrasonic-assisted impregnation, and surface chemical deposition₂O₃Photo-thermal catalytic material. The photo-thermal catalyst is loaded on glass microspheres and loaded in a quartz reactor. The quartz tube is placed on a groove type solar energy light gathering device, under the condition of 300W simulated sunlight irradiation, the photo-thermal temperature is 120 ℃, the concentration of toluene is 300ppm, and the flow rate of gas is 30 mL/min. The real-time removal rate of the organic gas toluene is up to more than 95 percent through chromatographic detection.

Comparative example 2:

reference example 1 a Pt-Pd @ molecular sieve thermo-catalytic material was prepared using a hydrothermal synthesis method and an ultrasonic assisted impregnation method. The thermal catalyst was loaded on glass microspheres in a quartz reactor. The quartz tube is placed on a groove type solar energy light gathering device, under the condition of 300W simulated sunlight irradiation, the photo-thermal temperature is 120 ℃, the concentration of toluene is 300ppm, and the flow rate of gas is 30 mL/min. The real-time removal rate of the organic gas toluene is up to about 75 percent through chromatographic detection.