Thiophanate-methyl production tail gas treatment process

Abstract

The invention discloses a thiophanate-methyl production tail gas treatment process, and belongs to the technical field of tail gas treatment, and the thiophanate-methyl production tail gas treatment process comprises the following steps: S1, collecting thiophanate-methyl production tail gas, and carrying out dust removal treatment to obtain pretreated tail gas; s2, the pretreated tail gas is subjected to catalytic incineration through a catalytic incineration reactor, and incineration tail gas is obtained; s3, the incineration tail gas is conveyed into an absorption tower after being subjected to heat exchange and cooling, and slurry and primarily-purified tail gas are obtained; introducing the slurry into a regeneration tank, adding limestone into the regeneration tank, stirring for reaction, introducing the slurry into a sedimentation tank, enabling clarified liquor in the sedimentation tank to overflow into a collection tank for recycling, and treating precipitates in the sedimentation tank by a filter press to recover calcium sulfite and calcium sulfate; s4, conveying the primarily purified tail gas into an adsorption tower filled with an adsorption filler, and then discharging the primarily purified tail gas; according to the tail gas treatment process provided by the invention, sulfur element recovery is realized, and the tail gas purification effect is better.

Description

Technical Field

[0001] The invention belongs to the technical field of tail gas treatment, and particularly relates to a tail gas treatment process for the production of thiophanate-methyl. Background Art

[0002] Thiophanate-methyl, chemical formula: C 12 H 14 N4O4S2 is a benzimidazole fungicide, also known as thiophanate-methyl or "thiophanate-methyl" for short. It is a broad-spectrum systemic, low-toxic fungicide with systemic, preventive and therapeutic effects. It is widely used in agriculture.

[0003] The mechanism of action of methyl thiophanate is that when it is sprayed on the surface of crops, it can be quickly absorbed by the crops and converted into carbendazim through a series of biochemical reactions in the crop plants, interfering with the cell division of pathogens, preventing the pathogens from growing normally and thus achieving a bactericidal effect.

[0004] The preparation method of methyl thiophanate is as follows: (1) Methanol and phosgene react at 15°C to produce methyl chloroformate. (2) Methyl chloroformate and sodium thiocyanate react in acetone to produce methyl isothiocyanate. (3) O-phenylenediamine and methyl isothiocyanate undergo addition reaction at 40°C to prepare methyl thiophanate. The process of preparing methyl isothiocyanate produces hydrogen chloride gas, and the raw materials used in the production process of methyl thiophanate contain a small amount of sulfide. During the reaction, the sulfide reacts with hydrochloric acid to produce hydrogen sulfide gas, which makes the tail gas of methyl thiophanate production have a significant odor and the hydrogen sulfide exceeds the standard. The current tail gas treatment process of methyl thiophanate production uses liquid alkali to recover the gas and then transport it to the tail gas treatment device, which consumes a lot of sulfur and cannot be recovered, resulting in a waste of resources. In addition, the exhaust gas still contains a high content of acidic gas, which is harmful to the environment. Summary of the Invention

[0005] The purpose of the present invention is to provide a process for treating tail gas from the production of thiophanate-methyl, so as to solve the problems that the existing process for treating tail gas from the production of thiophanate-methyl cannot recycle sulfur and cannot completely treat harmful gases in the tail gas.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A process for treating tail gas from the production of thiophanate-methyl comprises the following steps:

[0008] S1, collecting thiophanate-methyl production tail gas and performing dust removal treatment to obtain pretreated tail gas;

[0009] S2. catalytically incinerate the pretreated tail gas using a catalytic incineration reactor to obtain incineration tail gas;

[0010] S3, the incineration tail gas is transported to the absorption tower after heat exchange and cooling to obtain slurry and preliminary purified tail gas; the slurry is passed into the regeneration tank, limestone is added to the regeneration tank, and after stirring and reacting, it is passed into the sedimentation tank, and the clarified liquid overflows from the sedimentation tank into the collection tank for recycling, and the precipitate in the sedimentation tank is processed by a filter press to recover calcium sulfite and calcium sulfate;

[0011] S4. The preliminarily purified tail gas is transported to an adsorption tower equipped with adsorption fillers and then discharged.

[0012] Furthermore, the specific operations of S1 are as follows:

[0013] The tail gas produced in the methyl thiophanate production workshop is collected by the negative pressure generated by the high-pressure fan and transported to the dust collector through a pipeline for treatment. The dust collector removes solid particles in the tail gas to obtain pretreated tail gas.

[0014] Furthermore, the specific operations of S2 are as follows:

[0015] The pretreated tail gas is mixed with air and then preheated before entering the catalytic incineration reactor. The catalytic incineration temperature is 150-450℃ and the air velocity is 1000-3500h -1 , the excess oxygen coefficient is 0.5-8.0, and the incineration tail gas is obtained.

[0016] Furthermore, the preparation method of the catalyst used in the catalytic incineration reactor is as follows:

[0017] Titanium dioxide powder, methyl cellulose powder and ammonium metavanadate are mixed and ground in a ball mill for 45 minutes, a silver nitrate solution is added, and grinding is continued for 15 minutes. Distilled water is added to uniformly mix the ground material into a paste, and the paste is placed in a honeycomb mold for extrusion molding, dried at 60°C for 5 hours and at 105°C for 6 hours, calcined at 250°C for 8 hours and at 500°C for 10 hours to obtain the catalyst.

[0018] Furthermore, the dosage ratio of titanium dioxide powder, methylcellulose powder, ammonium metavanadate, silver nitrate solution and deionized water is 300g:5-10g:20g:15mL:500-900mL, and the silver nitrate solution is composed of nitrate and deionized water in a dosage ratio of 5g:15mL.

[0019] Furthermore, the pH value of the absorption liquid in the absorption tower is 7-10, the sodium ion concentration is 0.3-3 mol / L, and the liquid-gas ratio to the flue gas is 1.5-6 L / m 3 .

[0020] Furthermore, the adsorption filler is a MOFs-loaded organic adsorbent, and the organic adsorbent includes polyethyleneimine and imidazole-based ionic liquid. MOFs (metal-organic framework materials) have a large specific surface area and porosity, and have great application potential in the field of gas adsorption, but their adsorption performance is limited. The present invention further improves its gas adsorption performance, especially the adsorption performance of sulfur-containing gases, through loading treatment.

[0021] Furthermore, the preparation method of the adsorption filler comprises the following steps:

[0022] The MOFs material was treated under nitrogen atmosphere and temperature of 180°C for 12 hours to obtain a pretreated MOFs material. Then, polyethyleneimine and imidazole ionic liquid were added to methanol, stirred at room temperature for 30 minutes, and then the pretreated MOFs material was added and stirred at room temperature for 12 hours. Finally, the mixture was vacuum dried at 65°C to constant weight to obtain an adsorption filler.

[0023] Furthermore, the usage ratio of MOFs material, polyethyleneimine, imidazole-based ionic liquid and methanol is 1 g: 0.1-0.3 g: 0.2-0.4 g: 20 mL.

[0024] Furthermore, the MOFs material is MIL-101(Cr) and / or ZI F-8.

[0025] Furthermore, the imidazolium-based ionic liquid is at least one of 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium dimethyl phosphate, 1,3-dimethylimidazolium nitrate and 1-ethyl-3-methylimidazolium ethyl sulfate.

[0026] Furthermore, the preliminarily purified tail gas flows through the adsorption filler in the adsorption tower at a temperature of 10-50°C, preferably 30°C, at a flow rate of 1.8-2.2 m / s.

[0027] Beneficial effects of the present invention:

[0028] The present invention provides a process for treating tail gas from the production of thiophanate-methyl. The process comprises the following steps: firstly, dust is removed by pretreatment, and then catalytic incineration is performed to efficiently convert hydrogen sulfide and organic sulfides (such as carbon disulfide, hydrogen sulfide, etc.) in the pretreated waste gas into sulfur dioxide. An alkaline solution is used to wash the tail gas after catalytic incineration to reduce the content of pollutants in the tail gas and recover the sulfur dioxide. The generated calcium sulfite and calcium sulfate can be used to prepare gypsum, thereby realizing the recovery of sulfur element. Finally, the present invention performs deep treatment on the preliminarily purified tail gas by using an adsorption filler, and further reduces the content of pollutants in the preliminarily purified tail gas by means of physical adsorption, chemical bonding, etc., so that the content of pollutants in the preliminarily purified tail gas meets the emission standard.

[0029] The present invention utilizes a metal-organic framework material to load two organic adsorbents, polyethyleneimine and imidazolyl ionic liquid, to prepare an adsorption filler. The metal-organic framework material has a large specific surface area and has a good adsorption effect on gases such as hydrogen sulfide and sulfur dioxide. The polyethyleneimine contains primary amine, secondary amine, and tertiary amine groups, has stable chemical properties, is not easily oxidized and degraded, and can chemically react with hydrogen sulfide. The imidazolyl ionic liquid is composed of imidazolyl cations and organic / inorganic anions and has acid-base sites. These sites provide reaction active centers for the adsorption of gases such as hydrogen sulfide and sulfur dioxide, and can further reduce the pollutant content in the initially purified tail gas. In addition, there is a synergistic effect between the polyethyleneimine and the imidazolyl ionic liquid, and compared with using them alone, a better purification effect is achieved. DETAILED DESCRIPTION

[0030] In order to make the technical problems, technical solutions and beneficial effects to be solved by this application more clearly understood, the present application is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain this application and are not intended to limit this application.

[0031] In this application, "at least one" means one or more, and "more than one" means two or more. "At least one of the following" or similar expressions refers to any combination of these items, including any combination of single items or plural items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can all mean: a, b, c, a~b (i.e., a and b), a~c, b~c, or a~b~c, where a, b, c can be single or multiple.

[0032] The terms used in the examples of this application are for the purpose of describing specific implementation rules only and are not intended to limit this application. The singular forms "a", "an", "the" and "the" used in the implementation rules of this application and the appended claims are also intended to include the plural forms unless the context clearly indicates otherwise.

[0033] It should be understood that in the various embodiments of the present application, the size of the serial number of each process does not mean the order of execution. Some or all steps can be executed in parallel or sequentially. The execution order of each process should be determined by its function and internal logic, and should not constitute any limitation on the implementation process of the implementation regulations of this application.

[0034] The weights of the relevant components mentioned in the examples of this application may not only refer to the specific content of each component, but also represent the weight ratio between the components. Therefore, as long as the content of the relevant components is proportionally enlarged or reduced according to the examples of this application, it is within the scope disclosed in the examples of this application. Specifically, the mass described in the examples of this application may be a mass unit known in the chemical industry, such as μg, mg, g, kg, etc.

[0035] Unless otherwise defined, all technical terms used hereinafter have the same meanings as those generally understood by those skilled in the art. The technical terms used herein are only for the purpose of describing specific embodiments and are not intended to limit the scope of protection of the present invention.

[0036] Unless otherwise specified, all raw materials, reagents, instruments and equipment used in this application can be purchased from the market or prepared by existing methods.

[0037] Preparation Example 1

[0038] The preparation method of the adsorption filler comprises the following steps:

[0039] 1 g of MIL-101(Cr) was treated under a nitrogen atmosphere at 180°C for 12 h to obtain a pretreated MOFs material. Then, 0.1 g of polyethyleneimine (MW = 600) and 0.4 g of 1-ethyl-3-methylimidazolium chloride were added to 20 mL of methanol, stirred at room temperature for 30 min, and then the pretreated MOFs material was added, stirred at room temperature for 12 h, and finally vacuum dried at 65°C to constant weight to obtain an adsorption filler.

[0040] Preparation Example 2

[0041] The preparation method of the adsorption filler comprises the following steps:

[0042] 1 g of ZIF-8 was treated under nitrogen atmosphere at 180°C for 12 h to obtain a pretreated MOFs material. Then, 0.3 g of polyethyleneimine (MW = 600) and 0.2 g of 1-ethyl-3-methylimidazole dimethyl phosphate were added to 20 mL of methanol, stirred at room temperature for 30 min, and then the pretreated MOFs material was added, stirred at room temperature for 12 h, and finally vacuum dried at 65°C to constant weight to obtain an adsorption filler.

[0043] Comparative Example 1

[0044] The preparation method of the adsorption filler is different from that of Preparation Example 2 in that the medium-weight 1-ethyl-3-methylimidazole dimethyl phosphate in Preparation Example 2 is replaced by an equal-weight polyethyleneimine.

[0045] Comparative Example 2

[0046] The preparation method of the adsorption filler is different from that of Preparation Example 2 in that the medium-weight polyethyleneimine (MW=600) in Preparation Example 2 is replaced by an equal-weight 1-ethyl-3-methylimidazole dimethyl phosphate.

[0047] Example 1

[0048] A process for treating tail gas from the production of thiophanate-methyl comprises the following steps:

[0049] S1, collecting thiophanate-methyl production tail gas and performing dust removal treatment to obtain pretreated tail gas;

[0050] S2. catalytically incinerate the pretreated tail gas using a catalytic incineration reactor to obtain incineration tail gas;

[0051] S3, the incineration tail gas is transported to the absorption tower after heat exchange and cooling to obtain slurry and preliminary purified tail gas; the slurry is passed into the regeneration tank, limestone is added to the regeneration tank, and after stirring and reacting, it is passed into the sedimentation tank, and the clarified liquid overflows from the sedimentation tank into the collection tank for recycling, and the precipitate in the sedimentation tank is processed by a filter press to recover calcium sulfite and calcium sulfate;

[0052] S4. The preliminarily purified tail gas is transported to an adsorption tower equipped with the adsorption filler of Preparation Example 1, at a temperature of 30° C., flows through the adsorption filler in the active adsorption tower at a flow rate of 1.8 m / s, and then discharged.

[0053] The specific operations of S1 are as follows:

[0054] The tail gas produced in the methyl thiophanate production workshop is collected by the negative pressure generated by the high-pressure fan and transported to the dust collector through a pipeline for treatment. The dust collector removes solid particles in the tail gas to obtain pretreated tail gas.

[0055] The specific operations of S2 are as follows:

[0056] The pretreated tail gas is mixed with air and then preheated before entering the catalytic incineration reactor. The catalytic incineration temperature is 250°C and the air velocity is 1500h -1 , the excess oxygen coefficient is 5.0, and the incineration tail gas is obtained.

[0057] The preparation method of the catalyst used in the catalytic incineration reactor is as follows:

[0058] 300 g of titanium dioxide powder, 5 g of methylcellulose powder and 20 g of ammonium metavanadate were mixed and ground in a ball mill for 45 minutes, 15 mL of silver nitrate solution was added, and grinding was continued for 15 minutes. 500 mL of distilled water was added to uniformly mix the ground material into a paste. The paste was placed in a honeycomb mold for extrusion molding, dried at 60° C. for 5 hours and 105° C. for 6 hours, calcined at 250° C. for 8 hours and 500° C. for 10 hours to obtain the catalyst. The silver nitrate solution was composed of nitrate and deionized water in a dosage ratio of 5 g:15 mL.

[0059] The pH value of the absorption liquid in the absorption tower is 7, the sodium ion concentration is 0.3 mol / L, and the liquid-gas ratio to the flue gas is 1.5 L / m 3 .

[0060] Example 2

[0061] A process for treating tail gas from the production of thiophanate-methyl comprises the following steps:

[0062] S1, collecting thiophanate-methyl production tail gas and performing dust removal treatment to obtain pretreated tail gas;

[0063] S2. catalytically incinerate the pretreated tail gas using a catalytic incineration reactor to obtain incineration tail gas;

[0064] S3, the incineration tail gas is transported to the absorption tower after heat exchange and cooling to obtain slurry and preliminary purified tail gas; the slurry is passed into the regeneration tank, limestone is added to the regeneration tank, and after stirring and reacting, it is passed into the sedimentation tank, and the clarified liquid overflows from the sedimentation tank into the collection tank for recycling, and the precipitate in the sedimentation tank is processed by a filter press to recover calcium sulfite and calcium sulfate;

[0065] S4. The preliminarily purified tail gas is transported to an adsorption tower equipped with the adsorption filler of Preparation Example 1 at a temperature of 40° C., flows through the adsorption filler in the active adsorption tower at a flow rate of 2.0 m / s, and then discharged.

[0066] The specific operations of S1 are as follows:

[0067] The tail gas produced in the methyl thiophanate production workshop is collected by the negative pressure generated by the high-pressure fan and transported to the dust collector through a pipeline for treatment. The dust collector removes solid particles in the tail gas to obtain pretreated tail gas.

[0068] The specific operations of S2 are as follows:

[0069] The pretreated tail gas is mixed with air and then preheated before entering the catalytic incineration reactor. The catalytic incineration temperature is 350°C and the air velocity is 2500h -1 , the excess oxygen coefficient is 6.0, and the incineration tail gas is obtained.

[0070] The preparation method of the catalyst used in the catalytic incineration reactor is as follows:

[0071] 300 g of titanium dioxide powder, 8 g of methylcellulose powder and 20 g of ammonium metavanadate were mixed and ground in a ball mill for 45 minutes, 15 mL of silver nitrate solution was added, and grinding was continued for 15 minutes. 800 mL of distilled water was added to uniformly mix the ground material into a paste. The paste was placed in a honeycomb mold for extrusion molding, dried at 60° C. for 5 hours and 105° C. for 6 hours, calcined at 250° C. for 8 hours and 500° C. for 10 hours to obtain the catalyst. The silver nitrate solution was composed of nitrate and deionized water in a dosage ratio of 5 g:15 mL.

[0072] The pH value of the absorption liquid in the absorption tower is 10, the sodium ion concentration is 2 mol / L, and the liquid-gas ratio to the flue gas is 4 L / m 3 .

[0073] Example 3

[0074] A process for treating tail gas from the production of thiophanate-methyl comprises the following steps:

[0075] S1, collecting thiophanate-methyl production tail gas and performing dust removal treatment to obtain pretreated tail gas;

[0076] S2. catalytically incinerate the pretreated tail gas using a catalytic incineration reactor to obtain incineration tail gas;

[0077] S3, the incineration tail gas is transported to the absorption tower after heat exchange and cooling to obtain slurry and preliminary purified tail gas; the slurry is passed into the regeneration tank, limestone is added to the regeneration tank, and after stirring and reacting, it is passed into the sedimentation tank, and the clarified liquid overflows from the sedimentation tank into the collection tank for recycling, and the precipitate in the sedimentation tank is processed by a filter press to recover calcium sulfite and calcium sulfate;

[0078] S4. The preliminarily purified tail gas is transported to an adsorption tower equipped with the adsorption filler of Preparation Example 1, at a temperature of 50° C., flows through the adsorption filler in the active adsorption tower at a flow rate of 2.2 m / s, and then discharged.

[0079] The specific operations of S1 are as follows:

[0080] The tail gas produced in the methyl thiophanate production workshop is collected by the negative pressure generated by the high-pressure fan and transported to the dust collector through a pipeline for treatment. The dust collector removes solid particles in the tail gas to obtain pretreated tail gas.

[0081] The specific operations of S2 are as follows:

[0082] The pretreated tail gas is mixed with air and then preheated before entering the catalytic incineration reactor. The catalytic incineration temperature is 450°C and the air velocity is 3500h -1 , the excess oxygen coefficient is 8.0, and the incineration tail gas is obtained.

[0083] The preparation method of the catalyst used in the catalytic incineration reactor is as follows:

[0084] 300 g of titanium dioxide powder, 10 g of methylcellulose powder and 20 g of ammonium metavanadate were mixed and ground in a ball mill for 45 minutes, 15 mL of silver nitrate solution was added, and grinding was continued for 15 minutes. 900 mL of distilled water was added to uniformly mix the ground material into a paste. The paste was placed in a honeycomb mold for extrusion molding, dried at 60° C. for 5 hours and 105° C. for 6 hours, calcined at 250° C. for 8 hours and 500° C. for 10 hours to obtain the catalyst. The silver nitrate solution was composed of nitrate and deionized water in a dosage ratio of 5 g:15 mL.

[0085] The pH value of the absorption liquid in the absorption tower is 10, the sodium ion concentration is 3 mol / L, and the liquid-gas ratio to the flue gas is 6 L / m 3 .

[0086] Example 4

[0087] A process for treating tail gas from the production of thiophanate-methyl is disclosed. Compared with Example 1, the only difference is that the adsorption filler in Example 1 is replaced by the product in Preparation Example 2.

[0088] Example 5

[0089] A process for treating tail gas from the production of thiophanate-methyl is described. The difference from Example 1 is that the method for preparing the catalyst used in the catalytic incineration reactor is different. The method for preparing the catalyst used in the catalytic incineration reactor in this embodiment is as follows:

[0090] 300 g of titanium dioxide powder, 5-10 g of methyl cellulose powder and 20 g of ammonium metavanadate are mixed and ground in a ball mill for 45 minutes, 15 mL of silver nitrate solution is added, and grinding is continued for 15 minutes. 500-900 mL of distilled water is added to uniformly mix the ground material into a paste, and the paste is placed in a honeycomb mold for extrusion molding, dried at 60° C. for 5 hours and 105° C. for 6 hours, calcined at 250° C. for 8 hours and 500° C. for 10 hours to obtain the catalyst. The silver nitrate solution is composed of nitrate and deionized water in a dosage ratio of 5 g:15 mL.

[0091] Comparative Example 1

[0092] A process for treating tail gas from the production of thiophanate-methyl is disclosed. Compared with Example 1, the only difference is that the adsorption filler in Example 1 is replaced by the product in Control Example 1.

[0093] Comparative Example 2

[0094] A process for treating tail gas from the production of thiophanate-methyl is disclosed. Compared with Example 1, the only difference is that the adsorption filler in Example 1 is replaced by the product in Control Example 2.

[0095] Comparative Example 3

[0096] A process for treating tail gas from the production of thiophanate-methyl is disclosed, which differs from Example 1 only in that the adsorption filler in Example 1 is replaced with ZIF-8.

[0097] The tail gas treatment process described in Examples 1 to 5 and Comparative Examples 1 to 3 was used to treat the tail gas of a thiophanate-methyl manufacturer in Anhui Province. The sulfide content in the tail gas of thiophanate-methyl production was 20.3 mg / m 3 After the treatment, the exhaust gas was tested for sulfide concentration according to GB14554 "Emission Standards for Odor Pollutants". The results are shown in Table 1:

[0098] Table 1

[0099]

[0100] It can be seen from the data recorded in Table 1 that, compared with Comparative Examples 1-3, the sulfide content in the exhaust gas obtained by the treatment process provided by Examples 1-5 is lower, indicating that the treatment process provided by the present invention has a better treatment effect on the tail gas produced by thiophanate-methyl.

[0101] It should be noted that, in this document, relational terms such as first and second, etc., are used only to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the terms "comprises," "comprising," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that includes a list of elements includes not only those elements but also other elements not explicitly listed, or elements inherent to such process, method, article, or apparatus.

[0102] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A process for treating tail gas from the production of thiophanate-methyl, characterized in that: The following steps are involved: S1, collecting thiophanate-methyl production tail gas and performing dust removal treatment to obtain pretreated tail gas; S2. catalytically incinerate the pretreated tail gas using a catalytic incineration reactor to obtain incineration tail gas; S3, the incineration tail gas is transported to the absorption tower after heat exchange and cooling to obtain slurry and preliminary purified tail gas; the slurry is passed into the regeneration tank, limestone is added to the regeneration tank, and after stirring and reacting, it is passed into the sedimentation tank, and the clarified liquid overflows from the sedimentation tank into the collection tank for recycling, and the precipitate in the sedimentation tank is processed by a filter press to recover calcium sulfite and calcium sulfate; S4, the preliminarily purified tail gas is transported to an adsorption tower equipped with adsorption fillers and then discharged; The adsorption filler is an MOFs-loaded organic adsorbent, and the organic adsorbent includes polyethyleneimine and imidazole-based ionic liquid.

2. A process for treating tail gas from the production of thiophanate-methyl according to claim 1, characterized in that: The preparation method of the adsorption filler comprises the following steps: The MOFs material was treated under nitrogen atmosphere and temperature of 180°C for 12 hours to obtain a pretreated MOFs material. Then, polyethyleneimine and imidazole ionic liquid were added to methanol, stirred at room temperature for 30 minutes, and then the pretreated MOFs material was added and stirred at room temperature for 12 hours. Finally, the mixture was vacuum dried at 65°C to constant weight to obtain an adsorption filler.

3. A process for treating tail gas from the production of thiophanate-methyl according to claim 2, characterized in that: The usage ratio of MOFs material, polyethyleneimine, imidazole-based ionic liquid and methanol is 1g:0.1-0.3g:0.2-0.4g:20mL.

4. A process for treating tail gas from the production of thiophanate-methyl according to claim 2, characterized in that: The MOFs material is MIL-101(Cr) and / or ZI F-8.

5. A process for treating tail gas from the production of thiophanate-methyl according to claim 2, characterized in that: The imidazolyl ionic liquid is at least one of 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium dimethyl phosphate, 1,3-dimethylimidazolium nitrate and 1-ethyl-3-methylimidazolium ethyl sulfate.

6. A process for treating tail gas from the production of thiophanate-methyl according to claim 1, characterized in that: The specific operations of S2 are as follows: The pretreated tail gas is mixed with air and then preheated before entering the catalytic incineration reactor. The catalytic incineration temperature is 150-450℃ and the air velocity is 1000-3500h -1 , the excess oxygen coefficient is 0.5-8.0, and the incineration tail gas is obtained.

7. A process for treating tail gas from the production of thiophanate-methyl according to claim 6, characterized in that: The preparation method of the catalyst used in the catalytic incineration reactor is as follows: Titanium dioxide powder, methyl cellulose powder and ammonium metavanadate are mixed and ground in a ball mill for 45 minutes, a silver nitrate solution is added, and grinding is continued for 15 minutes. Distilled water is added to uniformly mix the ground material into a paste, and the paste is placed in a honeycomb mold for extrusion molding, dried at 60°C for 5 hours and at 105°C for 6 hours, calcined at 250°C for 8 hours and at 500°C for 10 hours to obtain the catalyst.

8. A process for treating tail gas from the production of thiophanate-methyl according to claim 7, characterized in that: The dosage ratio of titanium dioxide powder, methylcellulose powder, ammonium metavanadate, silver nitrate solution and deionized water is 300g:5-10g:20g:15mL:500-900mL, and the silver nitrate solution is composed of nitrate and deionized water in a dosage ratio of 5g:15mL.

9. A process for treating tail gas from the production of thiophanate-methyl according to claim 1, characterized in that: The pH value of the absorption liquid in the absorption tower is 7-10, the sodium ion concentration is 0.3-3 mol / L, and the liquid-gas ratio to the flue gas is 1.5-6 L / m 3 .

10. The process for treating tail gas from the production of thiophanate-methyl according to claim 1, characterized in that: The preliminarily purified tail gas flows through the adsorption packing in the adsorption tower at a temperature of 10-50°C and a flow rate of 1.8-2.2m / s.

Images