Carbendazim production waste gas treatment process based on catalytic membrane
By employing a catalytic membrane-based process for treating waste gas from carbendazim production, a copper-cobalt-titanium carbide composite modified ceramic catalytic membrane is used in conjunction with ozone oxidation and catalytic decomposition. This process solves the problems of low efficiency and equipment blockage in the treatment of waste gas from carbendazim production, achieving a highly efficient, stable, and environmentally friendly purification effect.
Patent Information
- Application Number
- CN202512028331.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-30
- Publication Date
- 2026-03-06
AI Technical Summary
Existing alkaline absorption methods for treating carbendazim production waste gas suffer from low efficiency, easy equipment crystallization and blockage, and the generation of secondary wastewater.
The process employs a catalytic membrane-based treatment, including dust removal pretreatment, ozone-co-catalytic decomposition, and intelligent detection. It utilizes a copper-cobalt-titanium carbide composite modified ceramic catalytic membrane, which is a cylindrical membrane module composed of a catalytic layer and a substrate ceramic layer, combining ozone oxidation and efficient catalytic decomposition of organic matter.
It achieves efficient and stable purification of waste gas, avoids equipment blockage, reduces operating costs, and is environmentally friendly and highly integrated.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of waste gas treatment technology, specifically relating to a process for treating waste gas from the production of carbendazim based on a catalytic membrane. Background Technology
[0002] Carbendazim, also known as cotton wilt fungicide, carbendazim, benzimidazole 44, is a highly effective, low-toxicity, systemic, broad-spectrum fungicide. Benzimidazole compounds are chemically stable and have systemic therapeutic and protective effects. It has low toxicity to humans and animals; the acute oral LD50 in rats is >2000 mg / kg, and it also has low toxicity to fish. It is effective against many diseases of the Ascomycota, Basidiomycota, and Deuteromycota. Seed treatment, foliar spraying, and soil treatment can control various diseases in rice, cotton, vegetables, fruit trees, and wheat.
[0003] There are several methods for synthesizing carbendazim. Currently, the calcium cyanamide method is widely used. This method involves producing calcium cyanamide (calcium cyanamide) from calcium cyanamide (calcium cyanamide) and water. The calcium hydroxide and residue are then separated by filtration (or, filtration can be skipped, and the calcium hydroxide can be used as a deacidifying agent in subsequent processes, followed by filtration after the synthesis of methyl cyanamide; this is called the post-filtration method; however, the residue separated by this method contains toxic organic impurities). The calcium cyanamide solution is then reacted with methyl chloroformate in the presence of sodium hydroxide to produce a methyl cyanamide solution, which is then condensed with o-phenylenediamine to obtain carbendazim. However, this process generates a large amount of waste gas, which mainly consists of unreacted raw materials (such as methyl chloroformate and ammonia), byproducts (such as carbon dioxide and cyanamide), and small amounts of toxic and harmful substances (such as cyanide). For these exhaust gases, alkaline solutions such as sodium hydroxide solution are usually used as absorbents. However, the solubility of the exhaust gas is limited due to factors such as temperature, resulting in poor treatment effects. Alternatively, the reaction between the exhaust gas and the alkaline solution can lead to excessive crystal formation in the absorption tower, clogging equipment and pipelines and reducing the efficiency of exhaust gas treatment.
[0004] Ceramic membranes possess excellent thermal stability, chemical stability, mechanical strength, and durability, making them promising for use in harsh environments. Catalytic membranes can be formed by loading a catalytic layer onto the surface of ceramic membranes. However, existing catalytic membrane technologies are mostly focused on single-gas purification or model reactions. For the complex waste gas system generated during the production of carbendazim, which is multi-component, highly toxic, and prone to crystallization, there is still a lack of efficient, stable, and dedicated catalytic membrane treatment processes that can fundamentally avoid equipment blockage. Summary of the Invention
[0005] The purpose of this invention is to provide a process for treating carbendazim production waste gas based on a catalytic membrane, which solves the technical defects of the existing alkaline absorption method for treating carbendazim production waste gas, such as low treatment efficiency, easy crystallization and clogging of equipment, and generation of secondary wastewater.
[0006] The objective of this invention can be achieved through the following technical solutions: The process for treating waste gas from carbendazim production based on catalytic membranes includes the following steps: S1. Carbendazim production waste gas is transported to the dust removal tower through the exhaust gas collection pipeline; S2. The exhaust gas from the dust removal tower is transported to the purifier, which is equipped with a cylindrical membrane module. A ceramic catalytic membrane is installed in the cylindrical membrane module. The ceramic catalytic membrane includes a catalytic layer and a base ceramic layer arranged in sequence. The catalytic layer side is connected to the air inlet of the membrane module, and the base ceramic layer side is connected to the air outlet of the membrane module. Oxygen flowing out from the oxygen source tank passes through a pressure reducing valve and an oxygen flow controller, and is oxidized into ozone gas by an ozone generator. It enters the air inlet of the membrane module along with the dust removal exhaust gas. After catalytic decomposition, the purified gas is discharged from the air outlet of the membrane module. S3. The gas discharged from the membrane module is detected by a detection device to determine the composition of the waste gas. If it meets the standards, it is discharged; otherwise, it is recycled into the purifier for secondary treatment.
[0007] Furthermore, the exhaust gas collection pipe is made of stainless steel and is equipped with a flow regulating valve.
[0008] Furthermore, the dust removal tower is equipped with a cooling device and a dust removal filter. The cooling device is used to reduce the temperature of the exhaust gas to room temperature, and the dust removal filter uses a 50-300 mesh screen to capture solid particles in the exhaust gas.
[0009] Furthermore, the raw materials for preparing the ceramic catalytic membrane include a tubular ceramic membrane and a gel solution, wherein the gel solution includes magnesium nitrate, manganese nitrate, citric acid, deionized water, and a copper-cobalt-titanium carbide composite material.
[0010] Furthermore, the preparation steps of the copper-cobalt-titanium carbide composite material are as follows: Sodium fluoride, hydrochloric acid solution, and deionized water were mixed evenly, and Ti3AlC2 was added. The mixture was reacted at 60℃ for 48 hours. After centrifugation, the precipitate was collected as titanium carbide. The titanium carbide was ultrasonically dispersed in deionized water to obtain a titanium carbide dispersion. Cobalt nitrate hexahydrate, copper nitrate trihydrate, hexadecyltrimethylammonium bromide, and urea were added to the titanium carbide dispersion. After stirring for 0.5-1 hours, the mixture was reacted at 120℃ for 24 hours. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, and the precipitate was dried to obtain a copper-cobalt titanium carbide composite material.
[0011] Furthermore, the ratio of sodium fluoride, hydrochloric acid solution, deionized water, and Ti3AlC2 is 2g:20mL:20mL:2g, and the concentration of hydrochloric acid solution is 1mol / L.
[0012] Furthermore, the ratio of titanium carbide, deionized water, cobalt nitrate hexahydrate, copper nitrate trihydrate, hexadecyltrimethylammonium bromide, and urea is 1-2g: 30-40mL: 1mmol: 1mmol: 0.8-1.2g: 10-14mmol.
[0013] Furthermore, the ceramic catalytic membrane is prepared in the following steps: Magnesium nitrate, manganese nitrate, and citric acid were added to deionized water and stirred until homogeneous. Then, copper-cobalt-titanium carbide composite material was added, and ammonia was added dropwise to adjust the pH to 4.5-5.0. The mixture was heated to 80°C and stirred for 2-4 hours to obtain a gel solution. After cleaning, the tubular ceramic membrane is immersed in the gel solution for 5-10 seconds, then removed and treated in a vacuum drying oven for 0.5 hours, dried at 120°C for 3 hours, and finally calcined in a muffle furnace at 450°C in air for 4 hours to obtain the ceramic catalytic membrane.
[0014] Furthermore, the mass ratio of magnesium nitrate, manganese nitrate, citric acid, deionized water, and copper-cobalt-titanium carbide composite material is 0.3-0.6 mol: 0.3-0.6 mol: 0.4-0.7 mol: 1 L: 10.2-11.5 g.
[0015] Furthermore, the ammonia content of the water is 28%.
[0016] Furthermore, the tubular ceramic membrane is an alumina tubular ceramic membrane with an outer diameter of 12 mm, an inner diameter of 8 mm, a length of 80 mm, and a porosity of 32-35%.
[0017] Furthermore, the tubular ceramic membrane is cleaned with 0.1 mol / L sodium hydroxide solution for 1 hour, rinsed with ultrapure water, and then dried at 120°C for 12 hours.
[0018] Furthermore, the detection device includes two gas sensors, one for detecting toxic gases and the other for detecting combustible gases in the exhaust gas, and also includes a temperature sensor and a humidity sensor to detect the temperature and humidity of the exhaust gas in real time.
[0019] The beneficial effects of this invention are: 1. The carbendazim production waste gas treatment process based on a catalytic membrane provided by this invention solves the three major problems of traditional alkaline absorption methods: low efficiency, easy clogging, and secondary wastewater production. This process integrates dust pretreatment, ozone synergy, deep purification via catalytic membrane, and intelligent detection, and incorporates a copper-cobalt-titanium carbide composite modified ceramic catalytic membrane as the core. This invention not only achieves efficient, stable, and thorough purification of waste gas but also possesses comprehensive advantages such as high process integration, low operating costs, and environmental friendliness.
[0020] 2. The copper-cobalt-titanium carbide composite modified ceramic catalytic membrane provided by this invention has the advantages of high waste gas purification efficiency and thoroughness. It uses a "copper-cobalt-titanium carbide composite material" as the catalytic activity enhancement phase, anchored within a magnesium-manganese oxide gel framework formed by magnesium nitrate and manganese nitrate, and then firmly loaded onto the ceramic membrane surface. This structure effectively prevents the loss and sintering agglomeration of active components during high-temperature calcination and use, ensuring the activity and long lifespan of the catalytic membrane.
[0021] 3. The ceramic catalytic membrane of this application can efficiently catalyze the decomposition of ozone to generate a large number of highly active substances such as hydroxyl radicals (·OH). It can non-selectively oxidize and decompose structurally stable organic matter such as methyl chloroformate and cyanamide in the waste gas into CO2, H2O and inorganic salts, fundamentally avoiding the transfer of pollutants. In addition, there is an electronic synergistic effect between copper and cobalt bimetals, which can significantly improve the catalyst's utilization efficiency of ozone and the oxidation rate of organic matter. The high conductivity of the titanium carbide substrate promotes electron transport and further accelerates the catalytic oxidation reaction kinetics. Detailed Implementation
[0022] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.
[0023] The following is a detailed description with reference to specific examples.
[0024] Example 1
[0025] A ceramic catalytic membrane is prepared from tubular ceramic membranes and a gel solution, wherein the gel solution comprises magnesium nitrate, manganese nitrate, citric acid, deionized water, and a copper-cobalt-titanium carbide composite material.
[0026] The preparation steps of copper-cobalt-titanium carbide composite material are as follows: 2g of sodium fluoride, 20mL of 1mol / L hydrochloric acid solution and 20mL of deionized water were mixed evenly, and 2g of Ti3AlC2 was added. The mixture was reacted at 60℃ for 48h, centrifuged, and the precipitate was collected as titanium carbide. 1g of titanium carbide was ultrasonically dispersed in 30mL of deionized water to obtain a titanium carbide dispersion. 1mmol of cobalt nitrate hexahydrate, 1mmol of copper nitrate trihydrate, 0.8g of hexadecyltrimethylammonium bromide and 10mmol of urea were added to the titanium carbide dispersion. After stirring for 0.5h, the mixture was reacted at 120℃ for 24h. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, and the precipitate was dried to obtain copper cobalt titanium carbide composite material.
[0027] The steps for preparing the ceramic catalytic membrane are as follows: Add 0.3 mol magnesium nitrate, 0.3 mol manganese nitrate and 0.4 mol citric acid to 1 L of deionized water, stir well, then add 10.2 g of copper cobalt titanium carbide composite material, add 28 wt% ammonia dropwise to adjust the pH to 4.5, heat to 80 ℃ and stir for 2 h to obtain gel solution. After cleaning, the tubular ceramic membrane was immersed in the gel solution for 5 seconds, then removed and treated in a vacuum drying oven for 0.5 hours, dried at 120°C for 3 hours, and finally calcined in a muffle furnace at 450°C in air for 4 hours to obtain the ceramic catalytic membrane.
[0028] The tubular ceramic membrane is an alumina tubular ceramic membrane with an outer diameter of 12 mm, an inner diameter of 8 mm, a length of 80 mm, and a porosity of 32%.
[0029] The tubular ceramic membrane was cleaned with 0.1 mol / L sodium hydroxide solution for 1 hour, rinsed with ultrapure water, and then dried at 120°C for 12 hours.
[0030] Example 2
[0031] A ceramic catalytic membrane is prepared from tubular ceramic membranes and a gel solution, wherein the gel solution comprises magnesium nitrate, manganese nitrate, citric acid, deionized water, and a copper-cobalt-titanium carbide composite material.
[0032] The preparation steps of copper-cobalt-titanium carbide composite material are as follows: 2g of sodium fluoride, 20mL of 1mol / L hydrochloric acid solution, and 20mL of deionized water were mixed evenly. 2g of Ti3AlC2 was added, and the mixture was reacted at 60℃ for 48h. After centrifugation, the precipitate was collected as titanium carbide. 1.5g of titanium carbide was ultrasonically dispersed in 35mL of deionized water to obtain a titanium carbide dispersion. 1mmol of cobalt nitrate hexahydrate, 1mmol of copper nitrate trihydrate, 0.8-1.2g of hexadecyltrimethylammonium bromide, and 12mmol of urea were added to the titanium carbide dispersion. After stirring for 0.8h, the mixture was reacted at 120℃ for 24h. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, and the precipitate was dried to obtain a copper-cobalt titanium carbide composite material.
[0033] The steps for preparing the ceramic catalytic membrane are as follows: Add 0.5 mol magnesium nitrate, 0.5 mol manganese nitrate and 0.6 mol citric acid to 1 L of deionized water, stir well, then add 10.5 g of copper cobalt titanium carbide composite material, add 28 wt% ammonia dropwise to adjust the pH to 5.0, heat to 80 ℃ and stir for 3 h to obtain gel solution. After cleaning, the tubular ceramic membrane was immersed in the gel solution for 8 seconds, then removed and treated in a vacuum drying oven for 0.5 hours, dried at 120°C for 3 hours, and finally calcined in a muffle furnace at 450°C in air for 4 hours to obtain the ceramic catalytic membrane.
[0034] The tubular ceramic membrane is an alumina tubular ceramic membrane with an outer diameter of 12 mm, an inner diameter of 8 mm, a length of 80 mm, and a porosity of 35%.
[0035] The tubular ceramic membrane was cleaned with 0.1 mol / L sodium hydroxide solution for 1 hour, rinsed with ultrapure water, and then dried at 120°C for 12 hours.
[0036] Example 3
[0037] A ceramic catalytic membrane is prepared from tubular ceramic membranes and a gel solution, wherein the gel solution comprises magnesium nitrate, manganese nitrate, citric acid, deionized water, and a copper-cobalt-titanium carbide composite material.
[0038] The preparation steps of copper-cobalt-titanium carbide composite material are as follows: 2g of sodium fluoride, 20mL of 1mol / L hydrochloric acid solution and 20mL of deionized water were mixed evenly, and 2g of Ti3AlC2 was added. The mixture was reacted at 60℃ for 48h, centrifuged, and the precipitate was collected as titanium carbide. 2g of titanium carbide was ultrasonically dispersed in 40mL of deionized water to obtain a titanium carbide dispersion. 1mmol of cobalt nitrate hexahydrate, 1mmol of copper nitrate trihydrate, 1.2g of hexadecyltrimethylammonium bromide and 14mmol of urea were added to the titanium carbide dispersion. After stirring for 1h, the mixture was reacted at 120℃ for 24h. After the reaction was completed, the mixture was cooled to room temperature, centrifuged, and the precipitate was dried to obtain copper cobalt titanium carbide composite material.
[0039] The steps for preparing the ceramic catalytic membrane are as follows: Add 0.6 mol magnesium nitrate, 0.6 mol manganese nitrate and 0.7 mol citric acid to 1 L of deionized water, stir well, then add 11.5 g of copper cobalt titanium carbide composite material, add 28 wt% ammonia dropwise to adjust the pH to 5.0, heat to 80 ℃ and stir for 4 h to obtain gel solution. After cleaning, the tubular ceramic membrane was immersed in the gel solution for 10 seconds, then removed and treated in a vacuum drying oven for 0.5 hours, dried at 120°C for 3 hours, and finally calcined in a muffle furnace at 450°C in air for 4 hours to obtain the ceramic catalytic membrane.
[0040] The tubular ceramic membrane is an alumina tubular ceramic membrane with an outer diameter of 12 mm, an inner diameter of 8 mm, a length of 80 mm, and a porosity of 35%.
[0041] The tubular ceramic membrane was cleaned with 0.1 mol / L sodium hydroxide solution for 1 hour, rinsed with ultrapure water, and then dried at 120°C for 12 hours.
[0042] Compare with Example 1
[0043] A ceramic catalytic membrane, which differs from Example 1 only in that the copper-cobalt-titanium carbide composite material in Example 1 is removed.
[0044] Compare with Example 2
[0045] A ceramic catalytic membrane, which differs from Example 1 only in that magnesium nitrate is removed from Example 1.
[0046] Compare with Example 3
[0047] A ceramic catalytic membrane, which differs from Example 1 only in that manganese nitrate is removed from Example 1.
[0048] Compare with Example 4
[0049] A ceramic catalytic membrane, which differs from Example 1 only in that both manganese nitrate and magnesium nitrate are removed in Example 1.
[0050] Example 4
[0051] The process for treating waste gas from carbendazim production based on catalytic membranes includes the following steps: S1. Carbendazim production waste gas is transported to the dust removal tower through the exhaust gas collection pipeline; S2. The exhaust gas from the dust removal tower is transported to the purifier, which is equipped with a cylindrical membrane module. The cylindrical membrane module is equipped with the ceramic catalytic membrane prepared in Example 1. The ceramic catalytic membrane includes a catalytic layer and a substrate ceramic layer arranged in sequence. The catalytic layer side is connected to the air inlet end of the membrane module, and the substrate ceramic layer side is connected to the air outlet end of the membrane module. The oxygen flowing out from the oxygen source tank passes through the pressure reducing valve and the oxygen flow controller, and is oxidized into ozone gas by the ozone generator. It enters the air inlet end of the membrane module along with the dust removal exhaust gas. After catalytic decomposition, the purified gas is discharged from the air outlet end of the membrane module. S3. The gas discharged from the membrane module is detected by a detection device to determine the composition of the waste gas. If it meets the standards, it is discharged; otherwise, it is recycled into the purifier for secondary treatment.
[0052] The exhaust gas collection pipe is made of stainless steel and is equipped with a flow regulating valve.
[0053] The dust removal tower is equipped with a cooling device and a dust filter. The cooling device is used to reduce the temperature of the exhaust gas to room temperature, and the dust filter uses a 50-300 mesh screen to capture solid particles in the exhaust gas.
[0054] The detection device includes two types of gas sensors, one for detecting toxic gases and the other for detecting combustible gases in the exhaust gas. It also includes a temperature sensor and a humidity sensor to detect the temperature and humidity of the exhaust gas in real time.
[0055] Example 5
[0056] The process for treating waste gas from carbendazim production based on a catalytic membrane differs from Example 4 only in that the ceramic catalytic membrane in Example 4 is replaced with the product obtained in Example 2.
[0057] Example 6
[0058] The process for treating waste gas from carbendazim production based on a catalytic membrane differs from Example 4 only in that the ceramic catalytic membrane in Example 4 is replaced with the product obtained in Example 3.
[0059] Comparative Example 1
[0060] The process for treating waste gas from carbendazim production based on a catalytic membrane differs from Example 4 only in that the ceramic catalytic membrane in Example 4 is replaced with the product obtained in Comparative Example 1.
[0061] Comparative Example 2
[0062] The process for treating waste gas from carbendazim production based on a catalytic membrane differs from Example 4 only in that the ceramic catalytic membrane in Example 4 is replaced with the product obtained in Comparative Example 2.
[0063] Comparative Example 3
[0064] The process for treating waste gas from carbendazim production based on a catalytic membrane differs from Example 4 only in that the ceramic catalytic membrane in Example 4 is replaced with the product obtained in Comparative Example 3.
[0065] Comparative Example 4
[0066] The process for treating waste gas from carbendazim production based on a catalytic membrane differs from Example 4 only in that the ceramic catalytic membrane in Example 4 is replaced with the product obtained in Comparative Example 4.
[0067] The catalytic membrane-based carbendazim production waste gas treatment processes provided in Examples 4-6 and Comparative Examples 1-4 were used to treat waste gas discharged from a carbendazim production plant in Anhui Province. The plant generates 0.0187 tons of waste gas daily, with the following original composition: methyl chloroformate 4.02%, cyanamide 0.65%, and methyl cyanamide 5.57%. The composition of the discharged waste gas was tested, and the removal rates of methyl chloroformate, cyanamide, and methyl cyanamide were calculated. The results are shown in Table 1. Table 1
[0068] As can be seen from the data recorded in Table 1, the processing technology provided in Examples 4-6 has a better processing effect compared with Comparative Examples 1, 2, 3 and 4.
[0069] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.
[0070] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A catalytic membrane based process for the treatment of carbendazim production off-gas, characterized in that, The method comprises the following steps: S1, delivering the carbendazim production waste gas to a dust removal tower through a tail gas collection pipeline; S2, delivering the tail gas through the dust removal tower to a purifier, wherein the purifier is provided with a cylindrical membrane assembly, the cylindrical membrane assembly is provided with a ceramic catalytic membrane, the ceramic catalytic membrane comprises a catalytic layer and a base ceramic layer arranged in sequence, the side of the catalytic layer is communicated with the gas inlet end of the membrane assembly, the side of the base ceramic layer is communicated with the gas outlet end of the membrane assembly, the oxygen gas from an oxygen gas source tank is oxidized into ozone gas by an ozone generator after passing through a pressure reducing valve and an oxygen flow controller, and then the ozone gas enters the gas inlet end of the membrane assembly together with the dust removal waste gas, the ozone gas is catalytically decomposed, and the purified gas is discharged from the gas outlet end of the membrane assembly; S3, the membrane assembly discharged gas is detected by a detection device, the composition of the waste gas is detected, the waste gas meeting the standard is discharged, otherwise, the waste gas is recycled into the purifier for secondary treatment.
2. The catalytic membrane based carbendazim production off-gas treatment process as claimed in claim 1 wherein, The tail gas collection pipeline is made of stainless steel, and a flow regulating valve is arranged on the pipeline.
3. The catalytic membrane based carbendazim production off-gas treatment process as claimed in claim 1 wherein, The dust removal tower is provided with a cooling device and a dust removal filter screen, the cooling device is used for reducing the temperature of the tail gas to room temperature, and the dust removal filter screen is a 50-300 mesh screen for capturing solid particles in the tail gas.
4. The catalytic membrane based carbendazim production off-gas treatment process as claimed in claim 1 wherein, The ceramic catalytic membrane is prepared from a tubular ceramic membrane and a gel solution, and the gel solution comprises magnesium nitrate, manganese nitrate, citric acid, deionized water and a copper-cobalt-titanium carbide composite material.
5. The catalytic membrane based carbendazim production off-gas treatment process as claimed in claim 4 wherein, The copper-cobalt-titanium carbide composite material is prepared by the following steps: Sodium fluoride, hydrochloric acid solution and deionized water are uniformly mixed, Ti3AlC2 is reacted at 60 DEG C for 48 hours, centrifuged, and the collected precipitate is titanium carbide, the titanium carbide is ultrasonically dispersed in deionized water to obtain a titanium carbide dispersion liquid, and the titanium carbide dispersion liquid is added with cobalt nitrate hexahydrate, copper nitrate trihydrate, cetyltrimethylammonium bromide and urea, stirred for 0.5-1 hours, reacted at 120 DEG C for 24 hours, cooled to room temperature after the reaction, centrifuged, and the precipitate is dried to obtain the copper-cobalt-titanium carbide composite material.
6. The catalytic membrane based carbendazim production off-gas treatment process as claimed in claim 5 wherein, The amount ratio of sodium fluoride, hydrochloric acid solution, deionized water and Ti3AlC2 is 2g:20mL:20mL:2g, and the concentration of the hydrochloric acid solution is 1mol / L.
7. The catalytic membrane based carbendazim production off-gas treatment process as claimed in claim 5 wherein, The amount ratio of titanium carbide, deionized water, cobalt nitrate hexahydrate, copper nitrate trihydrate, cetyltrimethylammonium bromide and urea is 1-2g:30-40mL:1mmol:1mmol:0.8-1.2g:10-14mmol.
8. The catalytic membrane based carbendazim production off-gas treatment process as claimed in claim 1 or 4 wherein, The ceramic catalytic membrane is prepared by the following steps: Magnesium nitrate, manganese nitrate and citric acid are added to deionized water, stirred uniformly, and then the copper-cobalt-titanium carbide composite material is added, ammonia water is added dropwise to adjust the pH value to 4.5-5.0, and the temperature is raised to 80 DEG C for stirring reaction for 2-4 hours to obtain the gel solution; The cleaned tubular ceramic membrane is immersed in the gel solution for 5-10 seconds, taken out and treated in a vacuum drying box for 0.5 hours, dried at 120 DEG C for 3 hours, and finally calcined in a muffle furnace at 450 DEG C in an air environment for 4 hours to obtain the ceramic catalytic membrane.
9. The catalytic membrane based carbendazim production off-gas treatment process as claimed in claim 8 wherein, The mass ratio of magnesium nitrate, manganese nitrate, citric acid, deionized water and copper-cobalt-titanium carbide composite material is 0.3-0.6mol:0.3-0.6mol:0.4-0.7mol:1L:10.2-11.5g.
10. The catalytic membrane based carbendazim production off-gas treatment process as claimed in claim 1 wherein, The detection device includes two kinds of gas sensors for detecting toxic gas and combustible gas in tail gas respectively, and also contains a temperature sensor and a humidity sensor for detecting the temperature and humidity of the exhaust gas in real time.