CN114733512A

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

Info

Publication number: CN114733512A
Application number: CN202111209805.3A
Authority: CN
Inventors: 汪黎东; 闫飞; 郭潇涵; 许勇毅
Original assignee: Clp Huachuang Power Technology Research Co ltd; North China Electric Power University
Current assignee: Clp Huachuang Power Technology Research Co ltd; North China Electric Power University
Priority date: 2021-10-18
Filing date: 2021-10-18
Publication date: 2022-07-12
Anticipated expiration: 2041-10-18
Also published as: CN114733512B

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, and device and method for degrading dimethyl sulfoxide by using same

Technical Field

The invention relates to the technical field of industrial wastewater treatment, in particular to a method for catalyzing and degrading dimethyl sulfoxide by adopting novel molybdenum-tungsten oxide.

Background

Dimethyl sulfoxide (DMSO) has excellent thermal stability, chemical stability, and excellent dissolution properties, and thus is widely used as an industrial solvent and a laboratory solvent. Currently, DMSO solvents are widely used in various industries such as thin film transistor liquid crystal displays, pharmaceuticals, thin film and polymer manufacturing processes, and thus a large amount of industrial wastewater containing DMSO is generated. The biodegradation process of DMSO is very slow, and toxic and volatile pollutants such as dimethyl sulfide, methyl mercaptan, hydrogen sulfide and the like are generated in the process, so that a green pollution-free DMSO chemical degradation method must be developed.

DMSO oxidative degradation is an effective DMSO elimination method, wherein a Fenton reaction degrades DMSO into methylsulfinate (CH)₃SO₂ ^-) Mesylate (CH)₃SO₃ ^-) And Sulfates (SO)₄ ^2-) It is the most common method for removing DMSO from wastewater. UV/H₂O₂、 α-FeOOH/H₂O₂、TiO₂Base photocatalysts/UV, etc. methods have also been used to remove DMSO, which is also oxidized to methylsulfinate, methanesulfonate, and sulfate salts. However, the above-mentioned DMSO degradation method is inefficient, for example, the above method treats wastewater in which DMSO concentration is not more than 5mmol/L, and an excessive amount of oxidizing agent (usually H) is added₂O₂/DMSO>5(mol/mol)), wastewater needs to be acidified, and iron sludge is generated in the reaction. Furthermore, methanesulfonates are difficult to degrade further, and methanesulfonates are also environmental pollutants. These factors limit the application of the above-described DMSO degradation method.

Aiming at the defects of the prior dimethyl sulfoxide degradation technology, the invention develops a high-efficiency DMSO degradation method and a device based on a composite metal molybdenum-tungsten oxide catalyst, and uses hydrogen peroxide as an oxidant to oxidize DMSO into naturally-existing biochemically-degradable dimethyl sulfone (DMSO) in a living body₂). The device can treat DMSO wastewater with the concentration of up to 180mmol/L (namely 1.4wt percent), does not need to adjust the pH of the wastewater, and does not need excessive oxidant.

Disclosure of Invention

The invention aims to provide a molybdenum-tungsten oxide catalyst based on composite metalAn efficient DMSO (dimethyl sulfoxide) degradation method and a device for continuously degrading DMSO (dimethyl sulfoxide) of an agent 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, can tolerate high-concentration DMSO wastewater, and thus promotes harmless discharge of industrial DMSO wastewater.

In order to solve the technical problems, the 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, wherein the active metal component is impregnated on the carrier by adopting an impregnation method, dried overnight, ground to be below 80 meshes and calcined to obtain a catalyst MoO₃-WO₃and/X and X are carriers.

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

The precursors of the active metal components are ammonium molybdate and ammonium metatungstate.

The catalyst MoO₃-WO₃MoO in X₃And WO₃Is preferably 1: 2-2: 1.

the support may be ZrO₂、TiO₂、Al₂O₃、SiO₂ZSM-5 molecular sieve, most preferably SiO₂。

The present invention also provides a device for treating wastewater containing DMSO using hydrogen peroxide, comprising: hydrogen peroxide storage tank, water storage tank, DMSO waste water storage tank, preheater, blender, fixed bed catalytic reactor and collector.

DMSO waste water storage tank, hydrogen peroxide storage tank and water storage tank are respectively through the tube coupling to the interior pipeline that corresponds of pre-heater, be provided with needle valve and constant flow pump on the pipeline that above-mentioned equipment is connected to the pre-heater, on three tube couplings in the pre-heater are provided with the temperature controller on the pre-heater, the mixer passes through the tube coupling to fixed bed catalytic reactor on, be connected with the temperature controller on the fixed bed catalytic reactor, fixed bed catalytic reactor passes through the tube coupling collector, is provided with the needle valve on the pipeline.

The middle of the fixed bed catalytic reactor is filled with the catalyst particles provided by the invention, and two ends of the fixed bed catalytic reactor are sealed by ceramic rings, so that the stability of the catalyst particles is ensured.

The invention also provides a method for treating industrial wastewater containing DMSO by adopting the device, which comprises the following steps:

firstly, feeding diluting water, DMSO industrial wastewater and a hydrogen peroxide solution into a preheater for preheating;

secondly, feeding all preheated liquids into a mixer for fully mixing, then feeding the liquids into a fixed bed catalytic reactor for oxidation degradation reaction, and fully oxidizing the DMSO by controlling the time of reaction liquid in a catalyst bed layer;

and step three, the treated wastewater enters a collector.

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

the invention has the advantages of

1. The invention prepares the composite metal molybdenum tungsten oxide solid phase catalyst (MoO) by a simple process₃-WO₃X, wherein X is a carrier), the catalyst has excellent DSMO degradation activity and good recycling performance;

2. the continuous DMSO degradation device designed by the invention can reduce the adding amount of the oxidant in the wastewater treatment process, and can tolerate high-concentration DMSO wastewater, thereby promoting the harmless discharge of industrial DMSO wastewater.

Drawings

FIG. 120% MoO₃-20％WO₃/SiO₂Catalyst conversion in DMSO at 30 ℃ and DMSO₂The course of concentration change over time; reaction conditions are as follows: 20% MoO₃-20％WO₃/SiO₂(2.4g/L), DMSO wastewater (178.6mmol/L), H₂O₂(267.9mmol/L), reaction time 200min at 30 ℃;

FIG. 2 shows the reusability of the molybdenum-tungsten composite oxide catalyst; reaction conditions are as follows: 20% MoO₃-20％WO₃/SiO₂(2.4g/L), DMSO wastewater (178.6mmol/L), H₂O₂(267.9mmol/L), reaction time 200min at 30 ℃;

FIG. 3 best catalyst 20% MoO₃-20％WO₃/SiO₂The performance is repeated at room temperature.

Detailed Description

The invention provides a solid-phase supported catalyst for preparing dimethyl sulfone by degrading dimethyl sulfoxide with hydrogen peroxide, which comprises an active metal component and a carrier, wherein the active metal component is impregnated on the carrier by adopting an impregnation method, dried overnight, ground to be below 80 meshes and calcined to obtain a catalyst MoO₃-WO₃and/X and X are carriers.

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

The catalyst MoO₃-WO₃MoO in X₃And WO₃Is preferably 1: 2-2: 1, more preferably 1: 1.

The drying is preferably carried out at 100 ℃ to 120 ℃ overnight, and more preferably at 110 ℃.

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

DMSO waste water storage tank, hydrogen peroxide storage tank and water storage tank are respectively through the tube coupling to in the pipeline that corresponds in the pre-heater, be provided with needle valve and constant flow pump on the pipeline that above-mentioned equipment is connected to the pre-heater, three tube couplings in the pre-heater are provided with the temperature controller on the mixer, the mixer passes through the tube coupling to on the fixed bed catalytic reactor, be connected with the temperature controller on the fixed bed catalytic reactor, the fixed bed catalytic reactor passes through the tube coupling collector, be provided with the needle valve on the pipeline.

and step three, the treated wastewater enters a collector.

the addition amount of the solid supported catalyst is preferably 1-3g/L DMSO wastewater, and further preferably 2.4g/L DMSO wastewater.

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

The reaction temperature in the second step is preferably 40 ℃ to 60 ℃, further preferably 50 ℃, and the reaction time is preferably 1h to 3h, further preferably 2 h.

Embodiments of the present invention will be described in detail below with reference to examples, so that how to apply technical means to solve technical problems and achieve technical effects can be fully understood and implemented.

The invention adopts the equipment shown in figure 1 for treating DMSO in industrial wastewater, which comprises: 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. The two ends of the fixed bed catalyst reactor are provided with ceramic rings 13, a catalyst 14 is contained in the fixed bed catalyst reactor, a DMSO wastewater storage tank 1, a hydrogen peroxide storage tank 2 and a water storage tank 3 are respectively connected to corresponding pipelines in a preheater 10 through pipelines, the pipelines connected to the preheater by the equipment are respectively provided with a

needle valve

7, 8, 9 and a

constant flow pump

4, 5 and 6, three pipelines in the preheater are connected to a mixer 12, the preheater 10 is provided with a temperature controller 11, the mixer 12 is connected to the fixed bed catalyst reactor through pipelines, the fixed bed catalyst reactor is connected with a temperature controller 15, the fixed bed catalyst reactor is connected with a collector 18 through pipelines, and the pipelines are provided with

needle valves

16 and 17.

Example 1: MoO₃/SiO₂Synthesis of (2)

Dissolving 0.74g of ammonium molybdate in a small amount of deionized water (7.3mL), adding 1.4g of fumed silica into the solution under stirring, drying the obtained product at 110 ℃ for 12h, grinding the product through a 80-mesh sieve, calcining the product in a muffle furnace at 500 ℃ for 3h at a heating rate of 5 ℃/min to obtain 30% MoO₃/SiO₂And (3) powder.

DMSO (dimethyl sulfoxide) catalytic degradation effect of loaded molybdenum oxide catalyst

The supported molybdenum oxide catalysts with different carriers and different loading amounts were prepared by the same preparation method as in example 1 with high concentration DMSO wastewater (178.6mmol/L, i.e., 1.4 wt%) as the target pollutant, and the catalytic activity of the supported molybdenum oxide catalysts on DMSO degradation was examined, and the results are shown in Table 1.

TABLE 1 conversion of DMSO and DMSO formation under different reaction conditions₂Concentration of (2)

Reaction conditions are as follows: catalyst (2.4g/L), DMSO wastewater (178.6mmol/L), H₂O₂ (267.9mmol/L)，The reaction time is 2h at 50 ℃.

In a DMSO sewage treatment experiment, the adding amount of the catalyst is 2.4g/L, and H is₂O₂The molar ratio to DMSO was 1.5 and the reaction was carried out at 50 ℃. GC-MS analysis indicated dimethyl sulfone to be the only product of the DMSO oxidation reaction. To determine the most suitable support for molybdenum oxide, MoO was added₃Loaded on SiO₂、ZrO₂、ZSM-5Molecular sieves、TiO₂And Al₂O₃And (3) carrying the carrier, and observing the catalytic action of the carrier on the degradation reaction of the DMSO. When MoO, as shown in Table 1₃The activity of the catalysts when supported on different supports varies widely, with DMSO conversions ranging from 28.9% to 56.5% after 2 hours of reaction at 50 ℃ and following the following sequence: MoO₃/TiO₂<MoO₃/Al₂O₃<MoO₃/ZSM-5<MoO₃/ZrO₂<MoO₃/SiO₂. Thus, silica is the most suitable support for molybdenum oxide.

Based on SiO₂Vector, further investigation of MoO₃Effect of loading on DMSO degradation reaction. MoO examined, limited by the solubility of the catalyst precursor ammonium molybdate₃/SiO₂The loading of the catalyst is between 5 and 30 wt%. As shown in Table 1, with MoO₃In SiO₂The loading on the catalyst increased from 5% to 30%, the DMSO conversion increased rapidly from 30.3% to 100%, and the catalyst activity increased primarily because the number of active sites increased with increasing loading.

In the DMSO degradation reaction, as the DMSO conversion rate is increased, the degradation product DMSO is generated₂The concentration of (a) also increases.

In addition, in the blank reaction of DMSO wastewater and hydrogen peroxide at 50 ℃ for 2 hours without a catalyst, the DMSO conversion rate is only 6.1 percent and is far lower than 100 percent of the catalytic reaction, and the reaction does not produce DMSO₂. Therefore, catalysts are necessary for DMSO degradation.

Example 2: WO₃/SiO₂Synthesis of (2)

Bias 0.80g toDissolving ammonium tungstate in a small amount of deionized water (11.75mL), adding 2.25g of fumed silica while stirring, drying the obtained product at 110 deg.C for 12h, grinding, sieving, calcining in 500 deg.C muffle furnace for 3h at a heating rate of 5 deg.C/min to obtain 25% WO₃/SiO₂And (3) powder.

DMSO (dimethyl sulfoxide) catalytic degradation effect of loaded tungsten catalyst

Using high concentration DMSO wastewater (178.6mmol/L, i.e. 1.4 wt%) as the target pollutant, different amounts and different loads of supported molybdenum catalysts were prepared by the same preparation method as in example 2, and the loads were examinedOxidation by oxygenThe results of the catalytic activity of the tungsten catalyst on DMSO degradation are shown in table 2.

TABLE 2 conversion of DMSO and DMSO formation under different reaction conditions₂Concentration of (2)

Reaction conditions are as follows: catalyst (2.4g/L), DMSO wastewater (178.6mmol/L), H₂O₂(267.9mmol/L),50 ℃, reaction time 2 h.

In DMSO sewage treatment experiment, the adding amount of the catalyst is still 2.4g/L, H₂O₂The molar ratio to DMSO was 1.5 and the reaction was carried out at 50 ℃. Dimethyl sulfone is still the only product of the oxidative degradation of DMSO in this reaction. Mixing WO₃Loaded on SiO₂、ZrO₂ZSM-5 molecular sieve, TiO₂And Al₂O₃And (3) waiting on different carriers, and inspecting the activity of the obtained catalyst on the DMSO degradation reaction. Vector pair WO as shown in Table 2₃The effect of the activity of (3) is very significant, the conversion of DMSO is between 19.5% and 46.0% after 2 hours of reaction at 50 ℃, and the activity follows the following sequence: WO₃/TiO₂<WO₃/ZSM-5<WO₃/ZrO₂<WO₃/Al₂O₃<WO₃/SiO₂This sequence differs from the activity sequence of the supported molybdenum oxide catalyst, illustrating WO₃、 MoO₃The interaction with the carrier is different. 10 wt% of WO₃/Al₂O₃With 10% by weight of WO₃/SiO₂The conversion rates of the treated DMSO wastewater are 45.7% and 46.0%, respectively, and the silica is slightly better than the alumina.

Based on SiO₂Vector, further examination of WO₃Effect of loading on DMSO degradation reaction. Limited by the solubility of the catalyst precursor ammonium metatungstate, WO examined₃/SiO₂The loading of the catalyst is between 5 and 25wt percent. As shown in Table 2, following WO₃In SiO₂The loading on was increased from 5% to 25%, the DMSO conversion rate was continuously increased from 44.4% to 72.2%, and the catalyst activity was increased mainly because the number of active sites was increased with the increase in loading.

In all DMSO degradation reactions catalyzed by supported tungsten oxide, as the DMSO conversion rate increases, the degradation product DMSO₂The concentration of (a) also increases.

Example 3: MoO₃-WO₃/SiO₂Synthesis of (2)

Dissolving 0.74g of ammonium molybdate and 0.64g of ammonium metatungstate in a small amount of deionized water (9.4mL), adding 1.8g of fumed silica into the solution while stirring, drying the obtained product at 110 ℃ for 12h, grinding the product through a 80-mesh sieve, calcining the product in a muffle furnace at 500 ℃ for 3h at the heating rate of 5 ℃/min to obtain 20% MoO₃-20％WO₃/-SiO₂And (3) powder.

DMSO (dimethyl sulfoxide) catalytic degradation effect of molybdenum-tungsten composite oxide catalyst

The combination of different active components can change the geometric effect and electronic effect of the catalyst, thereby obviously improving the activity of the catalyst. Based on the high catalytic activity of the supported molybdenum oxide and tungsten oxide catalyst on the DMSO degradation reaction, MoO is further researched₃-WO₃Reactivity of the two-component catalyst, the catalyst was prepared by the same preparation method as in example 3.

TABLE 3 conversion of DMSO and DMSO formation under different reaction conditions₂Concentration of (2)

Serial number	Catalyst and process for preparing same	DMSO conversion (%)	DMSO₂Concentration (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/SiO ₂	100	177.1

Reaction conditions are as follows: a catalyst (2.4g/L),DMSO wastewater (178.6mmol/L), H₂O₂(267.9mmol/L),50 ℃, reaction time 20 min.

First examine the MoO₃With WO₃The MoO is prepared by adjusting the ratio of ammonium molybdate to ammonium metatungstate in the solution used in the impregnation method₃And WO₃The total loading was 30 wt% of the composite catalyst. The catalyst is applied to DMSO degradation reaction, the adding amount of the catalyst is 2.4g/L, and H is₂O₂The molar ratio to DMSO was 1.5, and the reaction was carried out at 50 ℃ for 20 minutes. As can be seen from Table 3, when MoO₃The content of (A) is increased from 5% to 25% (WO)₃The content correspondingly decreased from 25% to 5%), the DMSO conversion increased from 40.5% to 86.3% and then continued to decrease to 55.6%. MoO₃And WO₃After the two active components are jointly supported on silica, the activity of the catalyst is significantly higher than that of the single-component catalyst. MoO₃And WO₃The optimal ratio of (1: 1) and the DMSO conversion rate is 86.3%, and the generated DMSO₂The concentration was 145.7 mmol/L.

For MoO₃And WO3 at an optimum ratio of 1:1, catalysts having different active component contents were prepared and examined for their activity under the aforementioned reaction conditions. As shown in Table 3, with MoO₃And WO₃The content of (c) increased from 5% to 20%, and the conversion rate of DMSO rapidly increased from 45.4% to 100%.

In view of 20% MoO₃-20％WO₃/SiO₂The catalyst has high catalytic activity on DMSO degradation reaction, and the reaction performance and stability at room temperature are continuously investigated subsequently.

Room temperature activity of molybdenum-tungsten composite oxide catalyst

The DMSO wastewater degradation reaction is carried out at 50 ℃, however, the actual situation is that the industrial wastewater yield is large, heating a large amount of wastewater from room temperature to 50 ℃ not only causes huge energy consumption, but also has potential safety hazard, and therefore, the room temperature activity of the catalyst is very important. This section examines 20% MoO₃-20％WO₃/SiO₂Activity of the agent at 30 ℃.

As shown in FIG. 2Show 20% MoO at 30 ℃₃-20％WO₃/SiO₂The catalyst still has high catalytic activity, and the DMSO conversion rate is rapidly increased to 90.1% within 0-80 minutes; then, the conversion rate rises relatively slowly, and after 200 minutes, the DMSO conversion rate reaches 99.7%, and DMSO is almost completely degraded. DMSO, on the other hand₂The concentration of (A) gradually increases along with the reaction time, and the increasing trend of the concentration of (A) is basically consistent with the DMSO conversion rate, which shows that DMSO is quantitatively degraded into DMSO₂。

Reuse effect of molybdenum-tungsten composite oxide catalyst

Industrial catalysts require high stability in addition to high activity, and therefore the reusability of the catalyst is also an important performance indicator.

20% MoO for the optimum catalyst screened above₃-20％WO₃/SiO₂The reusability of the catalyst was examined at room temperature, and the catalyst after reaction was filtered and dried for direct use in the subsequent reaction, the results are shown in fig. 3. Under the reaction conditions of 30 ℃ and 200 minutes, after the catalyst is used for 8 times, the DMSO conversion rate is slightly reduced, and is reduced from 99.7% of the first time to 96.5% of the eighth time, the total change is small, and the industrial use requirement can be met. In addition, DMSO degradation products DMSO₂The concentration of (b) is slightly decreased accordingly.

All of the above mentioned intellectual property rights are not intended to be restrictive to other forms of implementing the new and/or new products. Those skilled in the art will take advantage of this important information, and the foregoing will be modified to achieve similar performance. However, all modifications or alterations are to the reserved rights based on the new products of the present invention.

While the invention has been described with reference to a preferred embodiment, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention. However, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention still belong to the protection scope of the technical solution of the present invention.

Claims

1. A solid-phase supported catalyst for preparing dimethyl sulfone by degrading dimethyl sulfoxide with hydrogen peroxide is characterized in that: comprises an active metal oxide component and a carrier, wherein the active metal oxide component is impregnated on the carrier by adopting an impregnation method, dried and filtered overnight, ground and sieved by a 80-mesh sieve and then calcined to obtain the catalyst MoO₃-WO₃and/X and X are carriers.

2. The solid-phase supported catalyst for preparing dimethyl sulfone by hydrogen peroxide degradation of dimethyl sulfoxide according to claim 1, wherein: the active metal tungsten oxide component is molybdenum oxide MoO₃And tungsten oxide WO₃。

3. The solid-phase supported catalyst for the preparation of dimethyl sulfone by the degradation of dimethyl sulfoxide with hydrogen peroxide according to claim 1 or 2, characterized in that: the precursors of the active metal oxide components are ammonium molybdate and ammonium metatungstate.

4. The solid-phase supported catalyst for the preparation of dimethyl sulfone by the degradation of dimethyl sulfoxide with hydrogen peroxide according to claim 1 or 2, characterized in that: the catalyst MoO₃-WO₃MoO in X₃And WO₃Is preferably 1: 2-2: 1.

5. the solid-phase supported catalyst for the preparation of dimethyl sulfone by the degradation of dimethyl sulfoxide with hydrogen peroxide according to claim 1 or 2, characterized in that: the support may be ZrO₂、TiO₂、Al₂O₃、SiO₂ZSM-5 molecular sieve, most preferably SiO₂。

6. An apparatus for treating wastewater containing DMSO by using hydrogen peroxide, comprising: 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 trap, the fixed bed catalytic reactor being filled with the catalyst of any one of claims 1 to 5 above.

7. The apparatus according to claim 6, wherein the apparatus comprises: waste water storage tank, hydrogen peroxide storage tank and dilution are with in the water storage tank passes through the pipe connection respectively to the pipeline that corresponds in the pre-heater, be provided with needle valve and constant flow pump on the pipeline of above-mentioned equipment connection to pre-heater, three pipe connections in the pre-heater are provided with the temperature controller on the blender, the blender passes through the pipe connection to fixed bed catalytic reactor on, be connected with the temperature controller on the fixed bed catalytic reactor, fixed bed catalytic reactor passes through the pipe connection collector, be provided with the needle valve on the pipeline.

8. The apparatus according to claim 6, wherein the apparatus comprises: two ends of the fixed bed catalytic reactor are sealed by porcelain rings.

9. Method for treating industrial waste water containing DMSO using a device according to claim 7 or 8, characterized in that it comprises:

secondly, feeding all preheated liquids into a mixer for full mixing, then feeding the liquids into a fixed bed catalytic reactor for oxidative degradation reaction, and controlling the reaction liquid to be empty in a catalyst bed layer so as to fully oxidize DMSO;

and step three, the treated wastewater enters a collector.

10. The method according to claim 9 for treating DMSO-containing industrial wastewater, wherein: the mol ratio of DMSO to the added hydrogen peroxide in the industrial wastewater is preferably 1: 1.2-2.