CN114733512A - Novel molybdenum-tungsten oxide catalyst, device and method for degrading dimethyl sulfoxide using the same - Google Patents

Abstract

The invention provides a high-efficiency DMSO (dimethyl sulfoxide) degradation method and a continuous DMSO degradation device based on a composite metal molybdenum-tungsten oxide catalyst, which are used for preparing a composite metal molybdenum-tungsten oxide solid phase catalyst (MoO) by a simple process₃‑WO₃The catalyst has excellent DSMO degradation activity and good recycling performance, and the continuous DMSO degradation device designed by the invention can reduce the adding amount of an oxidant in a wastewater treatment process and can tolerate high-concentration DMSO wastewater, so that the harmless discharge of industrial DMSO wastewater is promoted.

Description

Novel molybdenum-tungsten oxide catalyst, device and method for degrading dimethyl sulfoxide using the same

technical field

The invention relates to the technical field of industrial wastewater treatment, in particular to a method for catalytic degradation of dimethyl sulfoxide using novel molybdenum and tungsten oxides.

Background technique

Dimethyl sulfoxide (DMSO) has good thermal stability, chemical stability and excellent solubility, so it is widely used as industrial solvent and laboratory solvent. At present, DMSO solvent is widely used in various industries such as thin film transistor liquid crystal display, pharmaceutical, thin film and polymer manufacturing process, resulting in a large amount of DMSO-containing industrial wastewater. The biodegradation process of DMSO is very slow, and this process can produce pollutants such as toxic and volatile dimethyl sulfide, methyl mercaptan, hydrogen sulfide, etc. Therefore, it is necessary to develop a green and pollution-free DMSO chemical degradation method.

Oxidative degradation of DMSO is an efficient method for DMSO elimination, in which the Fenton reaction degrades DMSO into methylsulfinate (CH ₃ SO ₂ ^- ), mesylate (CH ₃ SO ₃ ^- ) and sulfate (SO ₄ ^2- ), is the most commonly used method to remove DMSO in wastewater. Methods such as UV/H ₂ O ₂ , α-FeOOH/H ₂ O ₂ , TiO ₂ based photocatalyst/UV, etc. have also been used to remove DMSO. In these methods, DMSO is also oxidized to methyl sulfinate, Mesylate and sulfate. However, the efficiency of the above-mentioned DMSO degradation method is relatively low, for example, the concentration of DMSO in the wastewater treated by the above-mentioned method does not exceed 5mmol/L, an excess of oxidant needs to be added (usually H ₂ O ₂ /DMSO>5(mol/mol)), The wastewater needs to be acidified, and iron sludge will be precipitated during the reaction. In addition, mesylate is difficult to further degrade, and methylsulfinate and mesylate are also environmental pollutants. These factors limit the application of the above-mentioned DMSO degradation methods.

Aiming at the shortcomings of the current dimethyl sulfoxide degradation technology, the present invention develops a high-efficiency DMSO degradation method and device based on a composite metal molybdenum-tungsten oxide catalyst. Biochemically degraded dimethyl sulfone (DMSO ₂ ). The device can treat DMSO wastewater with a concentration of up to 180 mmol/L (ie, 1.4 wt%), without the need to adjust the pH of the wastewater, and without the need for excess oxidant.

SUMMARY OF THE INVENTION

The purpose of the present invention is to provide a high-efficiency DMSO degradation method based on composite metal molybdenum-tungsten oxide catalyst and a device for continuous degradation of DMSO, and to prepare composite metal molybdenum-tungsten oxide solid-phase catalyst (MoO ₃ -WO ₃ /X, Wherein X is a carrier), the catalyst has excellent DSMO degradation activity and good recycling performance, the continuous degradation DMSO device designed in the present invention can reduce the amount of oxidant added in the wastewater treatment process, and can tolerate high-concentration DMSO wastewater, thereby Promote the harmless discharge of industrial DMSO wastewater.

In order to solve the above technical problems, the present invention provides a solid-phase supported catalyst for preparing dimethyl sulfone by degrading dimethyl sulfoxide with hydrogen peroxide, which comprises an active metal oxide component and a carrier, and the active metal component adopts impregnation. Impregnated on the carrier by method, dried overnight, ground to below 80 mesh and calcined to obtain catalyst MoO ₃ -WO ₃ /X, where X is the carrier.

The active metal oxide components are molybdenum oxide and tungsten oxide.

The active metal component precursors taken are ammonium molybdate and ammonium metatungstate.

The mass ratio of MoO ₃ and WO ₃ in the catalyst MoO ₃ -WO ₃ /X is preferably 1:2-2:1.

The carrier can be one of ZrO ₂ , TiO ₂ , Al ₂ O ₃ , SiO ₂ , and ZSM-5 molecular sieve, most preferably SiO ₂ .

The present invention also provides a device for treating DMSO-containing wastewater by using hydrogen peroxide, which comprises: a hydrogen peroxide storage tank, a water storage tank, a DMSO wastewater storage tank, a preheater, a mixer, a fixed bed catalytic reactor and a collector .

The DMSO waste water storage tank, the hydrogen peroxide storage tank and the water storage tank are respectively connected to the corresponding pipelines in the preheater through pipelines. The pipelines connecting the above equipment to the preheater are provided with needle valves and constant flow pumps. The three pipelines in the heater are connected to the mixer, a temperature controller is arranged on the preheater, the mixer is connected to the fixed-bed catalytic reactor through pipelines, and the fixed-bed catalytic reactor is connected with a temperature controller, The fixed bed catalyst reactor is connected to the collector through a pipeline, and a needle valve is arranged on the pipeline.

The middle of the fixed bed catalytic reactor is filled with the catalyst particles provided by the present invention, and both ends are sealed with ceramic rings to ensure the stability of the catalyst particles.

The present invention also provides a method for treating industrial wastewater containing DMSO using the above device, comprising:

In the first step, dilution water, DMSO industrial waste water and hydrogen peroxide solution are sent to preheater for preheating;

In the second step, each liquid after the preheating is sent into the mixer to be fully mixed, then sent into the fixed bed catalytic reactor to carry out oxidative degradation reaction, and by controlling the reaction solution in the space of the catalyst bed, DMSO is fully oxidized;

In the third step, the treated wastewater enters the collector.

The molar ratio of DMSO to the added hydrogen peroxide in the industrial wastewater is preferably 1:1.2-2, more preferably 1:1.5.

The beneficial effects of the present invention

1. The present invention prepares a composite metal molybdenum-tungsten oxide solid-phase catalyst (MoO ₃ -WO ₃ /X, wherein X is a carrier) through a simple process, and the catalyst has excellent DSMO degradation activity and good recycling performance;

2. The continuously degrading DMSO device designed in the present invention can reduce the oxidant addition amount in the wastewater treatment process, and can tolerate high-concentration DMSO wastewater, thereby promoting the harmless discharge of industrial DMSO wastewater.

Description of drawings

Fig.1 20%MoO ₃ -20%WO ₃ /SiO ₂ catalyst at 30℃ for DMSO conversion and DMSO ₂ concentration as a function of time; Reaction conditions: 20%MoO ₃ -20%WO ₃ /SiO ₂ ( 2.4g/L), DMSO waste water (178.6mmol/L), H ₂ O ₂ (267.9mmol/L), 30 ℃, reaction time 200min;

Fig. 2 Reuse performance of molybdenum-tungsten composite oxide catalyst; reaction conditions: 20%MoO ₃ -20% WO ₃ /SiO ₂ (2.4g/L), DMSO wastewater (178.6mmol/L), H ₂ O ₂ (267.9 mmol/L), 30 ℃, reaction time 200min;

Figure _3. The best catalyst 20% _MoO3-20 %WO3/ _SiO2 reuse performance at room temperature.

Detailed ways

The invention provides a solid-phase supported catalyst for degrading dimethyl sulfoxide with hydrogen peroxide to prepare dimethyl sulfone, which comprises an active metal component and a carrier. The active metal component is impregnated on the carrier by an impregnation method, and dried overnight. , ground to below 80 mesh and calcined to obtain catalyst MoO ₃ -WO ₃ /X, X is the carrier.

The active metal components are metal molybdenum Mo and metal tungsten W.

The active metal component precursors taken are ammonium molybdate and ammonium metatungstate.

The mass ratio of MoO ₃ and WO ₃ in the catalyst MoO ₃ -WO ₃ /X is preferably 1:2-2:1, more preferably 1:1.

The carrier can be one of ZrO ₂ , TiO ₂ , Al ₂ O ₃ , SiO ₂ , and ZSM-5 molecular sieve, most preferably SiO ₂ .

The drying is preferably performed at 100°C to 120°C overnight, more preferably at 110°C.

The calcination temperature is preferably 450°C-550°C, more preferably 500°C, and the calcination time is preferably 2h-4h, more preferably 3h.

The present invention also provides a device for treating DMSO-containing wastewater by using hydrogen peroxide, which comprises: a hydrogen peroxide storage tank, a water storage tank, a DMSO wastewater storage tank, a preheater, a mixer, a fixed bed catalytic reactor and a collector .

The DMSO waste water storage tank, the hydrogen peroxide storage tank and the water storage tank are respectively connected to the corresponding pipelines in the preheater through pipelines. The pipelines connecting the above equipment to the preheater are provided with needle valves and constant flow pumps. The three pipelines in the heater are connected to the mixer, a temperature controller is arranged on the preheater, the mixer is connected to the fixed-bed catalytic reactor through pipelines, and the fixed-bed catalytic reactor is connected with a temperature controller, The fixed bed catalyst reactor is connected to the collector through a pipeline, and a needle valve is arranged on the pipeline.

The middle of the fixed bed catalytic reactor is filled with the catalyst particles provided by the present invention, and both ends are sealed with ceramic rings to ensure the stability of the catalyst particles.

The present invention also provides a method for treating industrial wastewater containing DMSO using the above device, comprising:

In the first step, dilution water, DMSO industrial waste water and hydrogen peroxide solution are sent to preheater for preheating;

In the second step, each liquid after the preheating is sent into the mixer to be fully mixed, then sent into the fixed bed catalytic reactor to carry out oxidative degradation reaction, and by controlling the reaction solution in the space of the catalyst bed, DMSO is fully oxidized;

In the third step, the treated wastewater enters the collector.

The molar ratio of DMSO to the added hydrogen peroxide in the industrial wastewater is preferably 1:1.2-2, more preferably 1:1.5.

The added amount of the solid supported catalyst is preferably 1-3g/L DMSO waste water, more preferably 2.4g/LDMSO waste water.

The loading amount of molybdenum-tungsten-tungsten oxide in the solid supported catalyst is preferably 20wt%-40wt%, more preferably 40wt%.

The reaction temperature in the second step is preferably 40°C-60°C, more preferably 50°C, and the reaction time is preferably 1h-3h, more preferably 2h.

Embodiments of the present invention are described in detail below by using examples, whereby the present invention can fully understand and implement the implementation process of how to apply technical means to solve technical problems and achieve technical effects.

The present invention uses the equipment shown in FIG. 1 to treat DMSO in industrial wastewater, which includes: hydrogen peroxide storage tank 2, water storage tank 3, DMSO waste water storage tank 1, preheater 10, mixer 12, fixed bed catalytic reactor and Collector 18. Both ends of the fixed bed catalyst reactor are provided with ceramic rings 13, and the inside is filled with catalyst 14. The DMSO waste water storage tank 1, the hydrogen peroxide storage tank 2 and the water storage tank 3 are respectively connected to the corresponding corresponding in the preheater 10 through pipelines. In the pipeline, needle valves 7, 8, 9 and constant flow pumps 4, 5 and 6 are respectively provided on the pipeline connecting the above equipment to the preheater, and the three pipelines in the preheater are connected to the mixer 12. The preheater 10 is provided with a temperature controller 11, the mixer 12 is connected to the fixed-bed catalytic reactor through pipelines, the fixed-bed catalytic reactor is connected with a temperature controller 15, and the fixed-bed catalyst reactor is connected to the fixed-bed catalytic reactor through pipelines. The device 18 is provided with needle valves 16 and 17 on the pipeline.

Example ₁ : Synthesis of MoO3/ _SiO2

Dissolve 0.74 g of ammonium molybdate in a small amount of deionized water (7.3 mL), add 1.4 g of fumed silica to the above solution under stirring, and dry the obtained product at 110 ° C for 12 h, grind it through an 80-mesh sieve, and place it at 500 °C. calcined in a ℃ muffle furnace for 3 hours with a heating rate of 5 ℃/min to obtain 30% MoO ₃ /SiO ₂ powder.

Catalytic Degradation Effect of DMSO on Supported Molybdenum Oxide Catalyst

Taking high-concentration DMSO sewage (178.6mmol/L, 1.4wt%) as the target pollutant, the same preparation method as in Example 1 was used to prepare supported molybdenum oxide catalysts with different supports and different loadings, and the effect of the supported molybdenum oxide catalyst on DMSO was investigated. The catalytic activity of degradation, the results are shown in Table 1.

Table _1. Conversion of DMSO and the concentration of DMSO generated under different reaction conditions

Reaction conditions: catalyst (2.4 g/L), DMSO wastewater (178.6 mmol/L), H ₂ O ₂ (267.9 mmol/L), 50° C., reaction time 2 h.

In the DMSO wastewater treatment experiment, the catalyst was added in an amount of 2.4 g/L, the molar ratio of H ₂ O ₂ to DMSO was 1.5, and the reaction was carried out at 50 °C. GC-MS analysis indicated that dimethyl sulfone was the only product of the DMSO oxidation reaction. In order to determine the most suitable support for molybdenum oxide, MoO ₃ was supported on supports such as SiO ₂ , ZrO ₂ , ZSM-5 molecular sieve , TiO ₂ and Al ₂ O ₃ , and its catalytic effect on DMSO degradation was investigated. As shown in Table ₁ , when MoO3 was supported on different supports, the catalyst activity varied greatly, the conversion of DMSO was between 28.9% and 56.5% after reaction at 50 °C for 2 h, and the activities followed the following order : MoO ₃ /TiO ₂ <MoO ₃ /Al ₂ O ₃ <MoO ₃ /ZSM-5<MoO ₃ /ZrO ₂ <MoO ₃ /SiO ₂ . Therefore, silica is the most suitable support for molybdenum oxide.

Based _on SiO support, the effect _of MoO loading on the degradation reaction of DMSO was further investigated. Limited by the solubility of the catalyst precursor, ammonium molybdate, the loadings of the investigated MoO3/ _SiO2 catalysts _were between 5-30 wt%. As shown in Table 1, as the loading of MoO3 _{on SiO2} increases from 5% to 30%, the conversion of DMSO rapidly increases from 30.3% to 100%, and the reason for the increase in catalyst activity is mainly the number of active sites increases with the increase in load.

In the aforementioned DMSO degradation reaction, with the increase of DMSO conversion rate, the concentration of its degradation product DMSO ₂ also increased.

In addition, in the blank reaction in which DMSO wastewater was reacted with hydrogen peroxide at 50°C for 2 hours without catalyst, the DMSO conversion rate was only 6.1%, which was much lower than 100% of the catalytic reaction, and the reaction did not produce DMSO ₂ . Therefore, a catalyst is necessary for DMSO degradation.

Example 2: Synthesis of WO ₃ /SiO ₂

Dissolve 0.80 g of ammonium metatungstate in a small amount of deionized water (11.75 mL), add 2.25 g of fumed silica to the above solution with stirring, and dry the obtained product at 110 ° C for 12 h, grind and sieve it, and heat it at 500 ° C calcined in a muffle furnace for 3 hours at a heating rate of 5°C/min to obtain 25% WO ₃ /SiO ₂ powder.

Catalytic Degradation Effect of DMSO on Supported Tungsten Catalyst

Taking high-concentration DMSO sewage (178.6mmol/L, i.e. 1.4wt%) as the target pollutant, the same preparation method as Example 2 was used to prepare the supported molybdenum catalysts with different dosages and different loads, and the effect of the supported tungsten oxide catalyst on the degradation of DMSO was investigated. Catalytic activity, the results are shown in Table 2.

Table _2. Conversion of DMSO and the concentration of DMSO generated under different reaction conditions

Reaction conditions: catalyst (2.4g/L), DMSO wastewater (178.6mmol/L), H ₂ O ₂ (267.9mmol/L), 50°C, reaction time 2h.

In the DMSO wastewater treatment experiment, the amount of catalyst added was still 2.4 g/L, the molar ratio of H ₂ O ₂ to DMSO was 1.5, and the reaction was carried out at 50 °C. In this reaction, dimethyl sulfone was still the only product of DMSO oxidative degradation. WO ₃ was supported on different supports such as SiO ₂ , ZrO ₂ , ZSM-5 molecular sieve, TiO ₂ and Al ₂ O ₃ , and the activity of the obtained catalyst for DMSO degradation was investigated. As shown in Table 2, the carrier has a very significant effect on the activity of WO _3. After 2 hours of reaction at 50 °C, the conversion rate of DMSO is between 19.5% and 46.0%, and the activity follows the following order: WO ₃ /TiO ₂ <WO ₃ /ZSM-5<WO ₃ /ZrO ₂ <WO ₃ /Al ₂ O ₃ <WO ₃ /SiO ₂ , this order is different from the activity order of the supported molybdenum oxide catalyst, indicating that the interactions between WO ₃ and MoO ₃ and the support are different . The conversion rates of DMSO wastewater treated by 10wt% WO ₃ /Al ₂ O ₃ and 10wt% WO ₃ /SiO ₂ were 45.7% and 46.0%, respectively, and silica was slightly better than alumina.

Based on the _SiO2 support, the effect _of WO3 loading on the degradation reaction of DMSO was further investigated. Limited by the solubility of the catalyst precursor, ammonium metatungstate, the loading amount of the investigated WO ₃ /SiO ₂ catalysts was between 5-25 wt%. As shown in Table 2, as the loading of WO3 _{on SiO2} increased from 5% to 25%, the conversion of DMSO continued to increase from 44.4% to 72.2%, and the catalyst activity increased mainly due to the number of active sites increases with the increase in load.

In all supported tungsten oxide-catalyzed DMSO degradation reactions, the concentration of its degradation product DMSO ₂ also increased with the increase of DMSO conversion.

Example 3: Synthesis of MoO ₃ -WO ₃ /SiO ₂

0.74g of ammonium molybdate and 0.64g of ammonium metatungstate were dissolved in a small amount of deionized water (9.4mL), and 1.8g of fumed silica was added to the above solution while stirring. The obtained product was dried at 110°C for 12h and ground. 80 mesh sieve, and calcined in a muffle furnace at 500°C for 3 hours with a heating rate of 5°C/min to obtain 20% MoO ₃ -20% WO ₃ /-SiO ₂ powder.

Catalytic degradation of DMSO over molybdenum-tungsten composite oxide catalysts

The combination of different active components can change the geometric and electronic effects of the catalyst, thereby significantly improving the activity of the catalyst. Based on the high catalytic activity of the aforementioned supported molybdenum oxide and tungsten oxide catalysts for DMSO degradation, the reaction performance of the MoO ₃ -WO ₃ two-component catalyst was further studied, and the catalyst was prepared by the same preparation method as in Example 3.

Table _3. Conversion of DMSO and the concentration of DMSO generated under different reaction conditions

serial number catalyst DMSO conversion rate (%) DMSO₂ concentration (mmol/L) 1 30wt%MoO₃/SiO₂ 46.2 68.2 2 25wt%WO₃/SiO₂ 17.2 18.6 3 5%MoO₃-25%WO₃/SiO₂ 40.5 69.2 4 10%MoO₃-20%WO₃/SiO₂ 62.2 109.1 5 15%MoO₃-15%WO₃/SiO₂ 86.3 145.7 6 20%MoO₃-10%WO₃/SiO₂ 78.3 137.4 7 25%MoO₃-5%WO₃/SiO₂ 55.6 90.9 8 5%MoO₃-5%WO₃/SiO₂ 45.4 76.5 9 10%MoO₃-10%WO₃/SiO₂ 70.5 119.7 10 20%MoO₃-20%WO₃/SiO₂ 100 177.1

Reaction conditions: catalyst (2.4 g/L), DMSO wastewater (178.6 mmol/L), H ₂ O ₂ (267.9 mmol/L), 50° C., reaction time 20 min.

Firstly, the influence _of the ratio of MoO3 to WO3 _on the catalyst performance was investigated. By adjusting the ratio of ammonium molybdate to ammonium metatungstate in the solution used in the impregnation method, a composite catalyst with a total loading _of 30wt% _of MoO3 and WO3 was prepared. The above catalyst was applied to DMSO degradation reaction, the amount of catalyst added was 2.4 g/L, the molar ratio of H ₂ O ₂ to DMSO was 1.5, and the reaction was carried out at 50° C. for 20 minutes. It can be seen from Table 3 that when the content of MoO ₃ is increased from 5% to 25% (the content of WO ₃ is correspondingly reduced from 25% to 5%), the conversion rate of DMSO increases from 40.5% to 86.3%, and then continues to decrease to 55.6% . After the _two active components, MoO3 and WO3, _were jointly supported on silica, the activity of the catalyst was significantly higher than that of the single-component catalyst. The optimum ratio of MoO ₃ and WO ₃ was 1:1, the DMSO conversion rate was 86.3%, and the resulting DMSO ₂ concentration was 145.7 mmol/L.

For the optimal ratio of MoO ₃ and WO 3 1:1, catalysts with different contents of active components were prepared, and their activities under the aforementioned reaction conditions were investigated. As shown in Table ₃ , the conversion of DMSO increased rapidly from 45.4% to 100% as the content of MoO3 and WO3 increased from ₅ % to 20%.

In view of the high catalytic activity of 20%MoO ₃ -20%WO ₃ /SiO ₂ catalyst for DMSO degradation reaction, the follow-up continued to investigate its reaction performance and stability at room temperature.

Room temperature activity of molybdenum-tungsten composite oxide catalyst

The aforementioned degradation reaction of DMSO wastewater is carried out at 50 °C. However, the actual situation is that the output of industrial wastewater is very large. Heating a large amount of wastewater from room temperature to 50 °C will not only lead to huge energy consumption but also have potential safety hazards. Therefore, the room temperature activity of the catalyst critical. This part investigates the activity of 20%MoO ₃ -20%WO ₃ /SiO ₂ catalyst at 30℃.

As shown in Fig. 2, the 20%MoO ₃ -20% WO ₃ /SiO ₂ catalyst still has high catalytic activity at 30 °C, and the DMSO conversion rate rises rapidly to 90.1% within 0-80 minutes; after that, the conversion The rate of increase was relatively slow. After 200 minutes, the conversion rate of DMSO reached 99.7%, and DMSO was basically completely degraded. On the other hand, the concentration of DMSO ₂ gradually increased with the reaction time, and its increasing trend was basically consistent with the conversion rate of DMSO, indicating that DMSO was quantitatively degraded to DMSO ₂ .

Reuse effect of molybdenum-tungsten composite oxide catalyst

In addition to high activity, industrial catalysts also require high stability, so the reusability of catalysts is also an important performance indicator.

For the best catalyst 20%MoO ₃ -20% WO ₃ /SiO ₂ screened above, its reusability was investigated at room temperature. The reacted catalyst was filtered and dried directly for subsequent reactions. The results are shown in Figure 3 shown. Under the reaction conditions of 30°C and 200 minutes, the DMSO conversion rate of the catalyst decreased slightly after 8 times of use, from 99.7% in the first time to 96.5% in the eighth time, and the overall change was not large, which could satisfy Industrial use requirements. In addition, the concentration of DMSO degradation product DMSO ₂ decreased slightly accordingly.

All of the aforementioned primary implementations of this intellectual property do not set limits to other forms of implementation of this new product and/or new method. Those skilled in the art will use this important information to modify the above to achieve a similar implementation. However, all modifications or alterations to new products based on the present invention are reserved.

The above are only preferred embodiments of the present invention, and are not intended to limit the present invention in other forms. Any person skilled in the art may use the technical content disclosed above to make changes or modifications to equivalent changes. Example. However, any simple modifications, equivalent changes and modifications made to the above embodiments according to the technical essence of the present invention without departing from the technical solution content of the present invention still belong to the protection scope of the technical solution of the present invention.

Claims (10)

1. a solid-phase supported catalyst that is used for hydrogen peroxide to degrade dimethyl sulfoxide to prepare dimethyl sulfone, it is characterized in that: comprise active metal oxide component and carrier, and active metal oxide component adopts impregnation method to impregnate On the carrier, dried overnight, ground through an 80-mesh sieve, and then calcined to obtain a catalyst MoO ₃ -WO ₃ /X, where X is the carrier. 2. The solid-phase supported catalyst for preparing dimethyl sulfone by degrading dimethyl sulfoxide with hydrogen peroxide as claimed in claim 1, wherein the active metal tungsten oxide component is molybdenum oxide MoO and _oxide Tungsten WO ₃ . 3. The solid-phase supported catalyst for preparing dimethyl sulfone by degrading dimethyl sulfoxide with hydrogen peroxide as claimed in claim 1 or 2, wherein the active metal oxide component precursor taken is molybdenum Ammonium acid and ammonium metatungstate. 4. The solid-phase supported catalyst for degrading dimethyl sulfoxide with hydrogen peroxide to prepare dimethyl sulfone according to claim 1 or 2, characterized in that: MoO ₃ in the catalyst MoO ₃ -WO ₃ /X The mass ratio to WO ₃ is preferably 1:2-2:1. 5. The solid-phase supported catalyst for preparing dimethyl sulfone by degrading dimethyl sulfoxide with hydrogen peroxide according to claim 1 or 2, wherein the carrier can be ZrO ₂ , TiO ₂ , Al ₂ One of O ₃ , SiO ₂ and ZSM-5 molecular sieve, most preferably SiO ₂ . 6. a device utilizing hydrogen peroxide to process waste water containing DMSO, is characterized in that, comprising: hydrogen peroxide storage tank, water storage tank, DMSO waste water storage tank, preheater, mixer, fixed bed catalytic reactor and collection The fixed bed catalytic reactor is equipped with the catalyst described in any one of the above claims 1 to 5. 7. the device that utilizes hydrogen peroxide to process the waste water containing DMSO as claimed in claim 6 is characterized in that: waste water storage tank, hydrogen peroxide storage tank and dilution water storage tank are respectively connected to corresponding in the preheater by pipeline. In the pipeline, the pipeline connecting the above equipment to the preheater is provided with a needle valve and a constant flow pump, the three pipelines in the preheater are connected to the mixer, and a temperature controller is installed on the preheater. The fixed-bed catalytic reactor is connected to the fixed-bed catalytic reactor through a pipeline, a temperature controller is connected to the fixed-bed catalytic reactor, the fixed-bed catalytic reactor is connected to a collector through a pipeline, and a needle valve is arranged on the pipeline. 8 . The device for treating DMSO-containing wastewater by using hydrogen peroxide according to claim 6 , wherein both ends of the fixed-bed catalytic reactor are sealed with ceramic rings. 9 . 9. adopt the method for the described device of claim 7 or 8 to process the industrial wastewater containing DMSO, is characterized in that, comprises: In the first step, the dilution water, DMSO industrial wastewater and hydrogen peroxide solution are sent to the preheater for preheating; In the second step, the preheated liquids are sent into the mixer to be fully mixed, and then sent to the fixed bed catalytic reactor for oxidative degradation reaction, and the DMSO is fully oxidized by controlling the empty time of the reaction liquid in the catalyst bed; In the third step, the treated wastewater enters the collector. 10. The method for treating industrial wastewater containing DMSO according to claim 9, wherein the molar ratio of DMSO and added hydrogen peroxide in the industrial wastewater is preferably 1:1.2-2.

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