WO2021000672A1 - High-efficiency anti-chlorine poisoning catalyst for catalytic oxidation of volatile organic compound and preparation method therefor - Google Patents

Abstract

The present invention relates to a high-efficiency anti-chlorine poisoning catalyst for the catalytic oxidation of a volatile organic compound and a preparation method therefor. The catalyst uses RuO ₂ as the active component and a mixed metal oxide, Sn _yTi _1-yO ₂ or MO _x-Sn _yTi _1-yO ₂, as the carrier. In the present invention, the doping of TiO₂ using Sn realizes the control of the crystal form of a carrier oxide, so that a tin-titanium-based catalyst carrier having a high-efficiency activation performance is created while the dispersion of RuO ₂ on the surface of the carrier is greatly improved. The catalyst of the present invention has the characteristics such as high catalytic activity for chlorine-containing volatile organic compounds, high anti-chlorine poisoning capability, and high selectivity of the product to CO₂; in addition, the catalyst also has a good removal effect on common volatile organic compounds and can be widely used in the treatment of chlorine-containing organic waste gas in the fields of pharmacy, organic synthesis, painting, etc.

Description

High-efficiency anti-chlorine poisoning catalyst for catalytic oxidation of volatile organic compounds and preparation method thereof Technical field

The invention belongs to the technical field of catalyst and its preparation technology and industrial source volatile organic matter catalytic combustion treatment technology, and specifically relates to a highly effective chlorine poisoning volatile organic matter catalytic oxidation catalyst and a preparation method thereof.

Background technique

Volatile organic compounds (VOCs) are a common type of air pollutants, and chlorinated volatile organic compounds (CVOCs) are one of the more important types, such as methylene chloride, 1,2-dichloroethane, trichloroethylene , Chlorobenzene, etc. are widely used in pharmaceutical, coating, rubber and organic synthesis industries. For the environment, the chlorine in CVOCs will destroy the ozone layer through the chlorine catalytic cycle, and will also lead to the formation of photochemical smog; for the human body, most of the CVOCs will harm the respiratory system, reproductive system and nervous system, etc., and some have been listed as A clear carcinogen. Therefore, the research and development of CVOCs processing technology is particularly important.

The current CVOCs treatment technology is mainly divided into recycling technology and destruction technology. The former includes adsorption method, absorption method, condensation method and membrane separation method, and the latter mainly includes biodegradation method, photocatalysis method, plasma method and direct combustion method. , Catalytic hydrodeoxygenation method and catalytic combustion method, etc. Considering various factors such as the scope of application, cost, and thoroughness of treatment, the catalytic combustion method is considered to be the most promising treatment method.

The core of catalytic combustion technology is the development of catalysts, and the current research is mainly focused on precious metal catalysts, molecular sieve catalysts and transition metal oxide catalysts. The deactivation of the catalyst in the catalytic oxidation process of CVOCs is mainly reflected in two aspects. One is that Cl easily reacts with the active components during the catalytic combustion process to produce metal chlorides and oxychlorides with lower boiling points, which leads to the loss of active components; Strong adsorption on the catalyst causes the active sites to be occupied. In previous studies, the use of RuO ₂ /TiO ₂ system catalysts for the catalytic oxidation of CVOCs has attracted some attention, but for RuO ₂ on the surface of the anatase TiO ₂ support with higher activity for CVOCs activation, it is caused by lattice mismatch. The agglomeration phenomenon of RuO ₂ has not been effectively resolved.

Summary of the invention

In order to overcome the shortcomings of the prior art, the present invention provides a volatile organic compound catalytic oxidation catalyst with high efficiency and anti-chlorine poisoning, suitable for chlorine-containing gas conditions, and a preparation method thereof. The prepared catalyst has the advantages of high catalytic activity, strong resistance to chlorine poisoning, long catalytic life, and few by-products.

A highly effective anti-chlorine poisoning catalyst for the catalytic oxidation of volatile organic compounds. The catalyst uses RuO ₂ as an active component and Sn _y Ti _1-y O ₂ or MO _x -Sn _y Ti _1-y O ₂ as a carrier.

The invention adopts a simple preparation process, through the doping of TiO ₂ with Sn, realizes the control of the crystal form of the carrier oxide during the preparation process, and constructs a tin-titanium-based catalyst carrier with high-efficiency activation performance for chlorine-containing volatile organic compounds At the same time, the dispersion of RuO ₂ on the surface of the carrier is greatly improved.

The invention can fully catalyze and oxidize various volatile organic compounds and chlorine-containing volatile organic compounds at a temperature below 300°C and maintain long-term stable activity and CO ₂ product selectivity.

Preferably, the MO _x -Sn _y Ti _1-y O ₂ support is a mixed metal oxide obtained by supporting Sn _y Ti _1-y O ₂ with an acidic metal oxide MO _x .

Preferably, the acidic metal oxide MOx includes one or any combination of two or more of tungsten, molybdenum, vanadium, niobium, and antimony transition metal oxides.

Preferably, the precursor of the acidic metal oxide includes one or any combination of tungsten, molybdenum, vanadium, niobium, antimony transition metal nitrate, acetate, chloride, sulfate, or oxalate.

Preferably, the active component uses ruthenium trichloride or ruthenium nitrate as a precursor and is prepared by a H ₂ O ₂ pre-oxidation process to obtain a RuO ₂ nanoparticle solution for active component loading.

The present invention also provides a method for preparing the above-mentioned highly effective chlorine poisoning-resistant volatile organic compound catalytic oxidation catalyst. When Sn _y Ti _1-y O ₂ is used as a carrier, the method includes the following steps: firstly, Sn _y Ti ₁ with rutile crystal form is prepared _-y O ₂ support; then the RuO ₂ nanoparticles are loaded by dipping and pulling method; when MO _x -Sn _y Ti _1-y O ₂ is used as the support, the following steps are also included before the RuO ₂ nanoparticles are loaded: through acid metal Oxide MO _x impregnation load. When preparing the Sn _y Ti _1-y O ₂ support with rutile crystal form, it can be prepared by co-precipitation, sol-gel mechanical grinding and other processes combined with high-temperature calcination; the impregnated support of acidic metal oxides greatly improves the catalyst Low temperature removal efficiency of chlorine volatile organic compounds.

By adjusting the doping ratio of the Sn element, the prepared Sn _y Ti _1-y O ₂ carrier is rutile crystal type, thereby improving the dispersion of RuO ₂ on the series of rutile carriers.

Preferably, the preparation method of the highly effective anti-chlorine poisoning catalyst for catalytic oxidation of volatile organic compounds specifically includes the following steps:

(1) Prepare a mixed solution of tin source and titanium source, and make precipitation with ammonia water titration;

(2) After washing the precipitate several times, dry it at 110°C for 12-24 hours;

(3) The precipitate is calcined at a high temperature at 400°C to 600°C for 3 to 6 hours to obtain a Sn _y Ti _1-y O ₂ carrier;

(4) The active component is wet-impregnated and loaded with ruthenium chloride, and after the impregnated and loaded, the resulting solution is rotary evaporated and dried to obtain a catalyst precursor;

(5) After washing several times, dry it at 110℃ for 12-24h;

(6) The precursor is calcined at 400-600°C for 3-6h to obtain RuO ₂ /Sn _y Ti _1-y O ₂ catalyst.

Preferably, the preparation method of the high-efficiency anti-chlorine poisoning volatile organic compound catalytic oxidation catalyst, and the preparation method of the high-efficiency anti-chlorine poisoning volatile organic compound catalytic oxidation catalyst further specifically include the following steps:

(i) Take the Sn _y Ti _1-y O ₂ carrier prepared in step (3), load the acidic metal oxide precursor solution by wet impregnation, and after drying and calcining, the carrier MO _x -modified with MOx heteropoly acid is obtained. Sn _y Ti _1-y O ₂ ;

(ii) Take the above-mentioned MO _x -Sn _y Ti _1-y O ₂ carrier and proceed to steps (4) to (6) to obtain the catalyst RuO ₂ /MO _x -Sn _y Ti _1-y O ₂ modified by heteropoly acid .

Preferably, the titanium source includes one of butyl titanate, tetraisopropyl titanate, titanium sulfate, titanium nitrate or titanium oxide; the tin source is tin tetrachloride, stannous chloride or tin oxide; acid metal oxidation The precursors of the substances include tungsten, molybdenum, vanadium, niobium, antimony transition metal nitrates, acetates, chlorides, sulfates or oxalates, or any combination of two or more; the active component is trichloro Ruthenium or ruthenium nitrate is the precursor and the RuO ₂ nanoparticle solution is prepared by the H ₂ O ₂ pre-oxidation process for active component loading.

Preferably, the mass fraction of RuO ₂ loading is between 0.1% and 5%, the mass fraction of MO _x doping is 0% to 20%, and the doping ratio of Sn and Ti is in the range of 1:1-9. .

The beneficial effects of the present invention are:

(1) The present invention prepares a Sn _y Ti _1-y O ₂ mixed metal oxide carrier with rutile crystal form by doping the carrier titanium dioxide with tin through a simple preparation process. This carrier is compared with the traditional anatase TiO _{2 The} carrier has stronger CVOCs activation performance;

(2) The preparation method of the present invention can realize the epitaxial growth of RuO ₂ active components on the surface of the carrier, greatly improve the dispersion of RuO ₂ on the surface of the carrier, and thus is more conducive to the improvement of catalytic performance and chlorine poisoning resistance;

(3) The catalyst RuO ₂ /Sn _y Ti _1-y O _{2 of the} present invention is tested under 1000 ppm dichloromethane, 20% O ₂ , N ₂ balance, and 30000/h space velocity, when the temperature is lower than 300°C, Dichloromethane has been completely converted, and the product has a selectivity to CO _{2 of} more than 95%; in addition, it has high catalytic activity for the catalytic oxidation of acetone, propane, toluene and other VOCs;

(4) The catalyst RuO ₂ /MO _x -Sn _y Ti _1-y O _{2 of the} present invention is tested at 1000 ppm dichloromethane, 20% O ₂ , N ₂ balance, and space velocity of 50000/h at a temperature lower than 275 At ℃, dichloromethane has been completely converted, and the selectivity of the product to CO ₂ can be as high as 95% or more;

(5) The preparation method of the catalyst of the present invention is simple and easy to implement. The catalyst has the characteristics of high catalytic activity for chlorine-containing volatile organic compounds, strong resistance to chlorine poisoning, and high selectivity for CO _{2 of the} product. It has good removal effect and can be widely used in the treatment of chlorine-containing organic waste gas in the fields of pharmacy, organic synthesis, painting, petrochemical industry, etc.

Description of the drawings

Figure 1 is a diagram showing the catalytic oxidation of methylene chloride by the catalyst of the present invention;

Figure 2 is a diagram showing the selectivity of the catalyst of the present invention for the catalytic oxidation of methylene chloride;

Figure 3 is a diagram of the catalytic oxidation activity of the catalyst of the present invention on acetone and propane;

Figure 4 is a graph showing the results of the operation stability of the catalyst RuO ₂ /Sn _0.2 Ti _0.8 O ₂ of the present invention;

Figure 5 is an XRD crystal structure diagram of the Sn _y Ti _1-y O ₂ series of samples of the present invention;

Figure 6 is a STEM-Mapping diagram of RuO ₂ /anatase-TiO ₂ of the present invention;

Figure 7 is a STEM-Mapping diagram of RuO ₂ /Sn _0.2 Ti _0.8 O ₂ of the present invention;

Fig. 8 is an XRD crystal structure diagram of anatase-TiO ₂ , RuO ₂ /anatase-TiO ₂ , RuO ₂ /Rutile-TiO ₂ , Sn _0.2 Ti _0.8 O ₂ , and RuO ₂ /Sn _0.2 Ti _0.8 O ₂ of the present invention;

Fig. 9 is a graph showing the activity results of RuO ₂ /MO _x -Sn _y Ti _1-y O ₂ of the present invention.

Detailed ways

The present invention will be further described below in conjunction with specific embodiments, but the scope of protection of the present invention is not limited to this.

The rutile titanium dioxide, anatase titanium dioxide and P25 titanium dioxide used in the present invention are all purchased in Aladdin.

Example 1

Preparation of RuO ₂ /Sn _y Ti _1-y O ₂ catalyst for catalytic oxidation of CVOCs

Dissolve an appropriate amount of tin chloride in deionized water and stir for 30 minutes to completely dissolve. Then, according to the different doping ratios of Sn and Ti, the corresponding chemical equivalent of tetrabutyl titanate was slowly added dropwise to the aqueous solution of tin chloride (in the preparation process of Sn _y Ti _1-y O ₂ , the tin chloride used The molar ratio to tetrabutyl titanate is y:1-y), and the dripping process is carried out with vigorous stirring. After the dripping is completed, vigorous stirring is continued for 30 minutes to ensure that the solution is fully mixed. Finally, ammonia water was added dropwise to the resulting mixed solution at a rate of 60 drops per minute until the pH of the solution was 10. After suction filtration, the obtained sediment was allowed to stand for 12 hours and then washed with deionized water and ethanol solution for 3 times. The cleaned deposits were dried at 110°C for 12 hours, and calcined in a muffle furnace at 550°C for 5 hours, and fully ground to obtain Sn _y Ti _1-y O ₂ carrier powder.

The active component RuO ₂ uses ruthenium chloride as a precursor. After pre-oxidation with a volume concentration of 15% H ₂ O ₂ solution, a suspension of RuO ₂ nanoparticles is obtained. Take the carrier Sn _y Ti _1- prepared in the previous step. _y O _{2 is} subjected to wet immersion loading; after immersion and loading, the resulting solution is rotary evaporated and dried, and the resulting powder is dried at 150°C for 16 hours, and then the dried powder is washed three times with deionized water and ethanol, and finally Drying at 110°C for 12-24 hours; calcining the dry powder obtained in the previous step at 400-600°C for 3-6 hours to obtain RuO ₂ /Sn _y Ti _1-y O ₂ catalyst.

The above-mentioned CVOCs catalytic oxidation catalyst RuO ₂ /Sn _y Ti _1-y O _{2 was} pressed into tablets, ground and sieved, and a 40-60 mesh catalyst was taken for catalytic activity and stability test.

Take the above-mentioned CVOCs catalytic oxidation catalyst 200mg, test conditions: 1000ppm dichloromethane, 20% O ₂ , N ₂ balance, 30000/h space velocity, test its catalytic activity and CO ₂ selectivity by gasmet, the test activity results are shown in Figure 1. The result of product selectivity is shown in Figure 2. The results show that RuO ₂ /Sn _y Ti _1-y O ₂ catalyst has stronger catalytic activity and CO ₂ product selectivity than RuO ₂ /TiO ₂ catalyst, and under the reaction conditions of this example, RuO ₂ /Sn _0.2 Ti _0.8 O ₂ showed the best catalytic activity.

Example 2:

Take 200 mg of the RuO ₂ /Sn _0.2 Ti _0.8 O ₂ catalytic oxidation catalyst described in Example 1. The test conditions are: 1000 ppm acetone, 20% O ₂ , N ₂ balance, 30000/h space velocity, and its catalytic activity and CO by gasmet ₂ Selectively carry out the test, the activity result is shown in Figure 3.

Take 200 mg of the RuO ₂ /Sn _0.2 Ti _0.8 O ₂ catalytic oxidation catalyst described in Example 1, and the test conditions are: 1000 ppm propane, 20% O ₂ , N ₂ balance, 30000/h space velocity, and test its catalytic activity by gasmet , The activity results are shown in Figure 3.

It can be seen from Figure 3 that the highly effective chlorine-resistant CVOCs catalytic oxidation catalyst of the present invention also has higher catalytic activity for the catalytic oxidation of acetone, propane and other VOCs. When the temperature is lower than 300°C, both acetone and propane are Fully converted.

Example 3

Take 200 mg of the CVOCs catalytic oxidation catalyst (RuO ₂ /Sn _0.2 Ti _0.8 O ₂ ) described in Example 1, and the test conditions are: 1000 ppm dichloromethane, 20% O ₂ , N ₂ balance, 30000/h space velocity, at temperature The stability test was performed at 250°C, and the stability test result is shown in Figure 4.

Example 4

Preparation of catalyst carrier Sn _y Ti _1-y O ₂ :

Dissolve an appropriate amount of tin chloride in deionized water and stir for 30 minutes to completely dissolve. Then, according to the different doping ratios of Sn and Ti, the corresponding chemical equivalent of tetrabutyl titanate was slowly added dropwise to the aqueous solution of tin chloride (in the preparation process of Sn _y Ti _1-y O ₂ , the tin chloride used The molar ratio to tetrabutyl titanate is y:1-y), and the dripping process is carried out with vigorous stirring. After the dripping is completed, vigorous stirring is continued for 30 minutes to ensure that the solution is fully mixed. Finally, ammonia water was added dropwise to the resulting mixed solution at a rate of 60 drops per minute until the pH of the solution was 10. After suction filtration, the obtained sediment was allowed to stand for 12 hours and then washed with deionized water and ethanol solution for 3 times. The cleaned deposits were dried at 110°C for 12 hours, and calcined in a muffle furnace at 550°C for 5 hours, and fully ground to obtain Sn _y Ti _1-y O ₂ carrier powder.

Take the powdered catalyst carrier Sn _y Ti _1-y O ₂ and anatase-TiO ₂ samples, and observe the XRD (X-ray diffraction patterns) crystal structure of the series of samples by APEXII powder diffractometer. The results are shown in Figure 5. Figure 5 shows that a certain amount of Sn doping can adjust the crystal form of TiO ₂ during the preparation process.

Example 5

Take the powdered catalyst RuO ₂ /Sn _0.2 Ti _0.8 O ₂ and RuO ₂ /anatase-TiO ₂ samples, and after sample preparation, they were characterized by JEOL 2100F TEM/STEM transmission electron microscope equipped with INCA x-sight (Oxford Instruments) detector The distribution of RuO ₂ on the surface of these two groups of catalysts. The results are shown in Figures 6 and 7. It can be seen from Figures 6 and 7 that RuO ₂ has a relatively high dispersion on the surface of Sn _0.2 Ti _0.8 O ₂ while agglomerated growth has occurred on the surface of anatase TiO ₂ .

Example 6

Take powdered catalysts RuO ₂ /Sn _0.2 Ti _0.8 O ₂ and RuO ₂ /anatase-TiO ₂ samples, and after sample preparation, the APEXII powder diffractometer observes the XRD (X-ray diffraction patterns) crystal structure of the series of samples. The result is shown in Figure 8. It can be seen from Fig. 8 that RuO ₂ has a high degree of dispersion on the surface of Sn _0.2 Ti _0.8 O ₂ and there is no obvious signal peak belonging to RuO _{2. On} the surface of anatase TiO ₂ , agglomerated growth occurs, and rutile RuO appears. _2. Signal peaks of (110) and (101) crystal planes. It is further proved that Sn doping and regulating the growth of TiO ₂ from anatase to rutile crystal can increase the dispersion of RuO ₂ on its surface.

Example 7

Preparation of CVOCs catalytic oxidation catalyst RuO ₂ /MO _x -Sn _y Ti _1-y O ₂

Dissolve an appropriate amount of tin chloride in deionized water and stir for 30 minutes to completely dissolve. Then, according to the different doping ratios of Sn and Ti, the corresponding chemical equivalent of tetrabutyl titanate was slowly added dropwise to the aqueous solution of tin chloride (in the preparation process of Sn _y Ti _1-y O ₂ , the tin chloride used The molar ratio to tetrabutyl titanate is y:1-y), and the dripping process is carried out with vigorous stirring. After the dripping is completed, vigorous stirring is continued for 30 minutes to ensure that the solution is fully mixed. Finally, ammonia water was added dropwise to the resulting mixed solution at a rate of 60 drops per minute until the pH of the solution was 10. After suction filtration, the obtained sediment was allowed to stand for 12 hours and then washed with deionized water and ethanol solution for 3 times. The cleaned deposits were dried at 110°C for 12 hours, and calcined in a muffle furnace at 550°C for 5 hours, and fully ground to obtain Sn _y Ti _1-y O ₂ carrier powder.

Take the Sn _y Ti _1-y O ₂ carrier prepared above and load the precursor solution such as ammonium metatungstate/ammonium molybdate/niobium oxalate/ammonium metavanadate through wet impregnation, and then dry and calcinate to obtain MOx heteropoly Acid-modified carrier MO _x -Sn _y Ti _1-y O ₂ ; by adjusting the number of dipping and the concentration of the precursor solution, the MOx loading can be controlled. According to actual needs, the loading can be controlled at 0wt.%～ Within 20wt.%.

The active component RuO ₂ uses ruthenium chloride as a precursor. After pre-oxidation with a volume concentration of 15% H ₂ O ₂ solution, a RuO ₂ nanoparticle suspension is obtained. Take the carrier MO _x -Sn _y prepared in the previous step. Ti _1-y O _{2 is} subjected to wet immersion loading; after immersion and loading, the obtained solution is dried by rotary evaporation, and the obtained powder is dried at 150°C for 16 hours, and then the dried powder is washed three times with deionized water and ethanol respectively Finally, it is dried at 110℃ for 12-24h; the dry powder obtained in the previous step is calcined at 400-600℃ for 3-6h to obtain a heteropolyacid modified catalyst RuO ₂ /MO _x -Sn _y Ti _1-y O ₂ .

The above-mentioned CVOCs catalytic oxidation catalyst RuO ₂ /MO _x -Sn _y Ti _1-y O _{2 was} pressed into tablets, ground and sieved, and a 40-60 mesh catalyst was taken for catalytic activity and stability test.

Take the above-mentioned CVOCs catalytic oxidation catalyst RuO ₂ /MO _x -Sn _y Ti _1-y O ₂ 200 mg, take RuO ₂ /WO ₃ -Sn _y Ti _1-y O ₂ as an example, and the test conditions are: 1000 ppm dichloromethane, 20 %O ₂ , N ₂ balance, 50,000/h space velocity, its catalytic activity was tested by gasmet. The test activity result is shown in Figure 9. The activity result shows that the RuO ₂ /WO ₃ -Sn _y Ti _1-y O ₂ catalyst is more The RuO ₂ /Sn _y Ti _1-y O ₂ catalyst has stronger catalytic activity.

The present invention regulates the growth crystal form of TiO ₂ through Sn doping, and develops a rutile Sn _y Ti _1-y O ₂ based catalytic carrier with higher catalytic activity than anatase TiO ₂ . The results show that the epitaxial growth of RuO ₂ on the surface of the support greatly increases the dispersion of RuO ₂ on the surface of the support. Compared with the traditional RuO ₂ /TiO ₂ system catalyst, the catalyst exhibits higher catalytic activity for CVOCs. And the product selectivity to CO ₂ . At the same time, long-term stability test results prove that the catalyst also has excellent anti-poisoning performance. In addition, the catalyst also shows good catalytic activity for a variety of common VOCs, and has a certain universality.

Claims (10)

1. A highly effective anti-chlorine poisoning catalyst for catalytic oxidation of volatile organic compounds, characterized in that: the catalyst uses RuO ₂ as the active component, and uses Sn _y Ti _1-y O ₂ or MO _x -Sn _y Ti _1-y O ₂ For the carrier.
2. The highly effective anti-chlorine poisoning catalyst for catalytic oxidation of volatile organic compounds according to claim 1, wherein the MO _x -Sn _y Ti _1-y O ₂ carrier is Sn _y Ti _1-y O ₂ through acidic metal oxides. MO _x supports the obtained mixed metal oxide.
3. The high-efficiency anti-chlorine poisoning volatile organic compound catalytic oxidation catalyst according to claim 2, wherein the acidic metal oxide MO _x includes one or two of tungsten, molybdenum, vanadium, niobium, and antimony transition metal oxides Any combination of the above.
4. The highly effective anti-chlorine poisoning catalyst for catalytic oxidation of volatile organic compounds according to claim 3, characterized in that the precursors of acidic metal oxides include tungsten, molybdenum, vanadium, niobium, antimony transition metal nitrates, acetates, and chlorine One kind or any combination of two or more kinds of salt, sulfate or oxalate.
5. The high-efficiency anti-chlorine poisoning catalyst for catalytic oxidation of volatile organic compounds according to claim 1, wherein the active component uses ruthenium trichloride or ruthenium nitrate as a precursor and is prepared by H ₂ O ₂ pre-oxidation process to obtain RuO ₂ nano The particle solution is used for active component loading.
6. A method for preparing a highly effective anti-chlorine poisoning catalyst for the catalytic oxidation of volatile organic compounds according to claim 1, characterized in that: when Sn _y Ti _1-y O ₂ is used as a carrier, the method comprises the following steps: firstly preparing a rutile crystal form The Sn _y Ti _1-y O ₂ support; then the RuO ₂ nanoparticles are loaded by dipping and pulling method; when the MO _x -Sn _y Ti _1-y O ₂ is used as the support, the following is also included before the RuO ₂ nanoparticles are loaded Step: Impregnation loading by acidic metal oxide MO _x .
7. The preparation method of the highly effective anti-chlorine poisoning catalyst for the catalytic oxidation of volatile organic compounds according to claim 6, characterized in that it specifically comprises the following steps:

   (1) Prepare a mixed solution of tin source and titanium source, and make precipitation with ammonia water titration;

   (2) After washing the precipitate several times, dry it at 110°C for 12-24 hours;

   (3) The precipitate is calcined at a high temperature at 400°C to 600°C for 3 to 6 hours to obtain a Sn _y Ti _1-y O ₂ carrier;

   (4) The active component is wet-impregnated and loaded with ruthenium chloride, and after the impregnated and loaded, the obtained solution is rotary evaporated and dried to obtain a catalyst precursor;

   (5) After washing several times, dry it at 110℃ for 12-24h;

   (6) The precursor is calcined at 400-600°C for 3-6h to obtain RuO ₂ /Sn _y Ti _1-y O ₂ catalyst.
8. The method for preparing a highly effective anti-chlorine poisoning catalyst for the catalytic oxidation of volatile organic compounds according to claim 7, characterized in that it further specifically comprises the following steps:

   (i) Take the Sn _y Ti _1-y O ₂ carrier prepared in step (3), load the acidic metal oxide precursor solution by wet immersion, and obtain a carrier MO _x modified with MO _x heteropoly acid after drying and calcining -Sn _y Ti _1-y O ₂ ;

   (ii) Take the above-mentioned MO _x -Sn _y Ti _1-y O ₂ carrier and proceed to steps (4) to (6) to obtain the catalyst RuO ₂ /MO _x -Sn _y Ti _1-y O ₂ modified by heteropoly acid .
9. The method for preparing a highly effective anti-chlorine poisoning catalyst for the catalytic oxidation of volatile organic compounds according to claim 7 or 8, wherein the titanium source comprises butyl titanate, tetraisopropyl titanate, titanium sulfate, titanium nitrate or titanium oxide One of the tin sources: tin tetrachloride, stannous chloride or tin oxide; precursors of acidic metal oxides include tungsten, molybdenum, vanadium, niobium, antimony transition metal nitrates, acetates, and chlorides Salt, sulfate, or oxalate, or any combination of two or more; the active component is ruthenium trichloride or ruthenium nitrate as the precursor, and the RuO ₂ nanoparticle solution is prepared by H ₂ O ₂ pre-oxidation process. Active component load.
10. The method for preparing highly effective anti-chlorine poisoning catalyst for catalytic oxidation of volatile organic compounds according to claim 7 or 8, characterized in that the mass fraction of RuO ₂ loading is between 0.1% and 5%, and the mass fraction of MO _x doped It is 0%-20%, and the doping ratio of Sn and Ti substances is in the range of 1:1-9.

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