Tail gas treatment device suitable for preparation of high-purity triethylamine and manufacturing method thereof

Abstract

The application discloses a tail gas treatment device suitable for preparation of high-purity triethylamine and a manufacturing method thereof. The tail gas treatment device is arranged after a discharge end of a preparation device and before a tail gas exhaust port. An oil-water double-layer absorption device, a composite electrochemical degradation device and a tail gas combustion exhaust device are integrated in the tail gas treatment device. The composite electrochemical degradation device specifically comprises an alternating current pulse power supply with a voltage of 10kV-15kV, a wire, a ceramic frame and a sheet-shaped substrate fixed in the ceramic frame in a louver blade distribution. The closely arranged hexagonal holes have a grid gap of 0.3mm-0.5mm and a grid aperture of 0.8mm-1.2mm. The tail gas treatment device has the characteristics of composite degradation of toxic gas, adsorption of toxic emissions and physical filtration of toxic waste solid particles.

Description

Technical Field

[0001] This invention relates to the field of semiconductor materials technology, and in particular to a tail gas treatment device and its manufacturing method suitable for the preparation of high-purity triethylamine. Background Technology

[0002] The industrial production of high-purity triethylamine generates toxic and harmful gases. If not properly handled, these gases can pollute the environment and harm human health. In particular, the production process produces harmful gases such as nitrogen oxides and ammonia. These gases are highly irritating to the human body; inhaling small amounts can cause various discomforts such as runny nose and coughing, while inhaling large amounts can lead to poisoning, directly endangering human life. The environmental pollution and toxic effects on humans from volatile organic compounds and other related toxic waste products generated during the production process are also significant.

[0003] In existing technologies, the exhaust gas treatment after the preparation of high-purity triethylamine is still a very crude exhaust gas combustion treatment, which has several problems: 1. The purification, absorption, and degradation of exhaust gases are incomplete, and a certain proportion of toxic waste gases are still emitted into the environment. 2. Difficult to remove non-combustible and flame-retardant materials; 3. It does not specifically target water-soluble and oil-soluble substances; 4. The removal effect on solid particles is not good.

[0004] Therefore, there is an urgent need in the market for a tail gas treatment device and its manufacturing method that can combine the degradation of toxic gases, adsorption of toxic emissions, and physical filtration of toxic waste solid particles, suitable for the preparation of high-purity triethylamine. Summary of the Invention

[0005] The present invention aims to provide a tail gas treatment device and its manufacturing method suitable for the preparation of high-purity triethylamine, which combines the degradation of toxic gases, adsorption of toxic emissions, and physical filtration of toxic waste solid particles.

[0006] To achieve the above objectives, the present invention adopts the following technical solution: a tail gas treatment device suitable for the preparation of high-purity triethylamine. This tail gas treatment device is located after the emission end of the preparation equipment and before the tail gas exhaust port. Within this tail gas treatment device, according to the tail gas flow sequence, an oil-water double-layer absorption device, a composite electrochemical degradation device, and a tail gas combustion exhaust device are integrated. Specifically, the composite electrochemical degradation device consists of a 10kV-15kV AC pulse power supply, wires, a ceramic frame, and a sheet-like substrate fixed within the ceramic frame in a louvered arrangement. The thickness of the sheet-like substrate is 1mm-1.5mm. The device is a cuboid with a fixed tilt angle. The plane of the sheet substrate forms a 30°-60° angle with the plane of the ceramic frame, and the vertical projection of the sheet substrate onto the plane of the frame completely covers the plane of the frame. The sheet substrates are distributed parallel to each other under the ceramic frame, and both ends of the sheet substrates are connected to the two ends of the power supply via wires. The sheet substrates are connected in parallel in the circuit. The sheet substrates include a loosely porous silicon dioxide matrix with hexagonal pores arranged in a honeycomb pattern and a functional material fixed to the matrix. The hexagonal pores arranged in a honeycomb pattern have a grid spacing of 0.3mm-0.5mm and a grid pore diameter of 0.8mm-1.2mm. The method for manufacturing the above-mentioned device includes the following stages: S1: Raw Material Preparation ① Raw material preparation: Prepare sufficient tap water, mineral oil, ceramic frame, silica, boric acid, sodium carbonate, InCl3·4H2O, SnCl4·5H2O, triblock copolymer polyethylene glycol-polyglycerol-polyethylene glycol, graphite powder with a particle size of 1μm-2μm, tetraethyl orthosilicate, titanium oxysulfate powder, urea, deionized water, 10% hydrochloric acid aqueous solution, 10% sodium hydroxide aqueous solution, saturated hydrochloric acid, and a quartz container with an inlet at the bottom and an outlet at the top; S2: Matrix Preparation ① Mix the silica, boric acid and sodium carbonate prepared in step ① of stage S1 evenly in a mass ratio of 85: (7-8): (7-8). Then, under nitrogen protection, heat to 1500℃ to melt. Pour into a mold with closely spaced hexagonal holes as required by the design. After cooling and forming, anneal to obtain the glass to be processed. ②The glass to be processed obtained in step ① is trimmed and cut to the required size and shape to obtain a glass substrate; ③ After mechanically polishing the surface of the prepared glass substrate, the polished glass substrate is placed in a nitrogen-protected environment and then heated to 660℃-680℃ for 35h-38h. After that, it is taken out and naturally cooled to room temperature. Then, the treated glass substrate is successively immersed and etched with deionized water, hydrochloric acid solution, and sodium hydroxide solution heated to 90℃-95℃. The deionized water and hydrochloric acid solution are used to clean the glass substrate until the weight no longer changes, and the sodium hydroxide solution is used to clean it for 80min-90min. After etching, the glass substrate is cleaned with deionized water and then naturally dried to obtain the desired loose and porous silica matrix with hexagonal pores arranged in a honeycomb pattern. S3: Functional Ingredient Integration ① Mix InCl3·4H2O and SnCl4·5H2O in a mass ratio of (28-30):(34-36) until homogeneous, then immerse the mixture completely in 11-13 times its weight of deionized water and stir until homogeneous to obtain wetting solution A; ② Immerse the silica substrate obtained in step ③ of stage S2 completely in the wetting solution A for 1-2 days and protect it with ultrasonic treatment; after immersion, place it in a sealed space under nitrogen protection and let it dry naturally until it is completely dry; then heat the dried silica substrate in an air resistance furnace at a temperature of 970℃-990℃ for 6-7 hours to obtain a conductive substrate. ③ After mixing the triblock copolymer polyethylene glycol-polyglycerol-polyethylene glycol and graphite powder at a mass ratio of 5:(2-3) to obtain mixture A, mix mixture A with 23-25 ​​times its mass of hydrochloric acid aqueous solution and stir until homogeneous. Maintain stirring and heat to 45℃-50℃. Then slowly add 1.5-1.7 times its mass of tetraethyl orthosilicate to the hydrochloric acid aqueous solution while maintaining stirring and heating for 20-21 hours to obtain mixture B. ④ Immerse the conductive substrate obtained in step ② completely in the mixture B obtained in step ③, maintain stirring and heating, and soak for 15-20 minutes. Then, transfer the soaked conductive substrate into a resistance furnace at 105℃-110℃ under nitrogen protection and keep it at that temperature for 1-1.5 days. Afterward, cool it to room temperature under nitrogen protection and clean the surface with deionized water. Then, place the conductive substrate in an air resistance furnace, heat it to 550℃-560℃, and keep it at that temperature for 4-5 hours to obtain a pretreated sheet substrate. ⑤ Dissolve titanium oxysulfate in 4-5 times its mass of deionized water and stir until completely melted; add 1.5%-2% urea by mass of the solution to the solution, then add the pretreated sheet substrate obtained in step ④ into the mixture, heat to 105℃-110℃, and stir for 11-12 hours; then remove the pretreated sheet substrate and wash it thoroughly with deionized water; then place the pretreated sheet substrate in an air resistance furnace, heat to 510℃-520℃, and hold for 4-5 hours to obtain the desired sheet substrate; S4: Assembly ① After mixing tap water and mineral oil in a volume ratio of 1:(0.1-5), the mixture is injected into the first quartz container. The bottom inlet of the first quartz container is connected to the discharge end of the preparation equipment through a quartz tube, and the top outlet is connected to the composite electrochemical degradation device through a quartz tube. ② Assemble and fix the sheet substrate obtained in step ⑤ of stage S3 to the ceramic frame, so that the sheet substrate is fixed in the ceramic frame in the form of louver blades, and the plane of the sheet substrate is at an angle of 30°-60° with the plane of the ceramic frame; connect the two ends of the sheet substrate to the two ends of the power supply through wires, and the sheet substrate is connected in parallel in the circuit. Place the frame part in the second quartz container, so that the outer contour of the frame is sealed and matched with the inner contour of the second quartz container, and obtain the composite electrochemical degradation device. The top outlet of the second quartz container is matched with the exhaust gas combustion device through a quartz tube, thus obtaining the exhaust gas treatment device suitable for the preparation of high-purity triethylamine.

[0007] Compared with the prior art, the present invention, by adopting the above technical solutions, has the following advantages: (1) In the composite electrochemical degradation device of the present invention, the sheet substrate is based on nanoporous quartz glass, and indium tin oxide semiconductor oxide nanocrystal doped glass is prepared by solution doping method, which makes the sheet substrate possible to exist as a conductive medium. This possibility gives the present invention a large space for skill expansion, and is also the basis for the implementation of the present invention (structural basis and material basis).

[0008] (2) The material and porous structure of the sheet substrate in this invention determine that this invention can generate plasma through dielectric barrier discharge, thus enabling this invention to purify toxic waste gas using plasma technology based on dielectric barrier discharge.

[0009] (3) Some of the materials solidified in the sheet substrate of the present invention have strong electro-catalytic properties. Some of the functional materials, after being electro-stimulated, have a strong catalytic oxidation effect on cyanide, carbon monoxide and organic matter, so that most oxidizable substances can be disposed of in this process.

[0010] (4) The material solidified in the sheet substrate of the present invention has strong nitrogen-based and nitro-based electro-catalytic properties and solidification and degradation function for solid particles, so that most nitrogen-based and nitro-based toxic waste gases and solid particles that were not blocked in the previous stages can be disposed of in this stage.

[0011] (5) The present invention uses a simple oil-water double-layer self-stratified absorption and filtration device to first absorb and remove most of the water-soluble and oil-soluble substances and some solid particles in the exhaust gas in the pre-stage, which reduces the burden on the subsequent fine detoxification waste device, greatly extends the service life of the subsequent device, and improves the stability.

[0012] Therefore, the present invention has the characteristics of compound degradation of toxic gases, adsorption of toxic emissions, and physical filtration of toxic waste solid particles. Detailed Implementation Example 1

[0013] The method for manufacturing the tail gas treatment device applicable to the preparation of high-purity triethylamine in this embodiment includes the following stages: ① Raw material preparation: Prepare sufficient tap water, mineral oil, ceramic frame, silica, boric acid, sodium carbonate, InCl3·4H2O, SnCl4·5H2O, triblock copolymer polyethylene glycol-polyglycerol-polyethylene glycol, graphite powder with a particle size of 1μm-2μm, tetraethyl orthosilicate, titanium oxysulfate powder, urea, deionized water, 10% hydrochloric acid aqueous solution, 10% sodium hydroxide aqueous solution, saturated hydrochloric acid, and a quartz container with an inlet at the bottom and an outlet at the top; ② Mix silica, boric acid and sodium carbonate in a mass ratio of 85:(7-8):(7-8), then heat to 1500℃ under nitrogen protection to melt, then pour into a mold with closely spaced hexagonal holes as required by the design, cool and solidify, and then anneal to obtain the glass to be treated; trim and cut the obtained glass to be treated to process it into the size and shape required by the design to obtain a glass substrate; ③ After mechanically polishing the surface of the prepared glass substrate, the polished glass substrate is placed in a nitrogen-protected environment and then heated to 660℃-680℃ for 35h-38h. After that, it is taken out and naturally cooled to room temperature. Then, the treated glass substrate is successively immersed and etched with deionized water, hydrochloric acid solution, and sodium hydroxide solution heated to 90℃-95℃. The deionized water and hydrochloric acid solution are used to clean the glass substrate until the weight no longer changes, and the sodium hydroxide solution is used to clean it for 80min-90min. After etching, the glass substrate is cleaned with deionized water and then naturally dried to obtain the desired loose and porous silica matrix with hexagonal pores arranged in a honeycomb pattern. S3: Functional Ingredient Integration ④ Mix InCl3·4H2O and SnCl4·5H2O at a mass ratio of (28-30):(34-36) until homogeneous, then immerse the mixture completely in 11-13 times its weight of deionized water and stir until homogeneous to obtain impregnation solution A; completely immerse the silica substrate in impregnation solution A for 1-2 days and protect it with ultrasonic treatment; after immersion, place it in a sealed space under nitrogen protection and allow it to dry naturally until completely dry; then heat the dried silica substrate in an air resistance furnace at a temperature of 9... The conductive matrix is ​​obtained by heating at 70℃-990℃ for 6-7 hours. Triblock copolymer polyethylene glycol-polyglycerol-polyethylene glycol and graphite powder are mixed evenly at a mass ratio of 5:(2-3) to obtain mixture A. Mixture A is mixed and stirred evenly with 23-25 ​​times its mass of hydrochloric acid aqueous solution, and the mixture is stirred and heated to 45℃-50℃. Then, 1.5-1.7 times its mass of tetraethyl orthosilicate is slowly added dropwise to the hydrochloric acid aqueous solution while stirring and heating for 20-21 hours to obtain mixture B. ⑤ Immerse the conductive substrate completely in mixture B, maintaining stirring and heating. After immersion for 15-20 minutes, transfer the immersed conductive substrate to a nitrogen-protected resistance furnace at 105℃-110℃ and hold for 1-1.5 days. Then, cool to room temperature under nitrogen protection and clean the surface with deionized water. Subsequently, place the conductive substrate in an air resistance furnace, heat to 550℃-560℃, and hold for 4-5 hours to obtain a pretreated sheet substrate. Then, apply sulfuric acid oxygen... Titanium is dissolved in 4-5 times its mass of deionized water and stirred until completely melted. 1.5%-2% urea is added to the solution by mass, and then the pretreated sheet substrate is added to the mixture. The temperature is raised to 105℃-110℃ and stirred for 11-12 hours. The pretreated sheet substrate is then removed and thoroughly washed with deionized water. The pretreated sheet substrate is then placed in an air resistance furnace and heated to 510℃-520℃, held for 4-5 hours to obtain the desired sheet substrate. ⑥ After mixing tap water and mineral oil in a volume ratio of 1:(0.1-5), the mixture is injected into the first quartz container. The bottom inlet of the first quartz container is connected to the discharge end of the preparation equipment through a quartz tube, and the top outlet is connected to the composite electrochemical degradation device through a quartz tube. The obtained sheet substrate is assembled and fixed with the ceramic frame, so that the sheet substrate is fixed in the ceramic frame in a louvered arrangement, and the plane of the sheet substrate is at an angle of 30°-60° with the plane of the ceramic frame. The two ends of the sheet substrate are connected to the two ends of the power supply through wires, and the sheet substrate is connected in parallel in the circuit. The frame part is placed in the second quartz container, so that the outer contour of the frame is sealed and matched with the inner contour of the second quartz container to obtain the composite electrochemical degradation device. The top outlet of the second quartz container is matched with the exhaust gas combustion device through a quartz tube. After the above steps are completed, an exhaust gas treatment device is obtained. This device is located after the emission end of the preparation equipment and before the exhaust gas outlet. Within this device, according to the exhaust gas flow sequence, an oil-water dual-layer absorption device, a composite electrochemical degradation device, and an exhaust gas combustion device are integrated. Specifically, the composite electrochemical degradation device consists of a 10kV-15kV AC pulse power supply, wires, a ceramic frame, and sheet-like substrates fixed within the ceramic frame in a louvered arrangement. The sheet-like substrates are 1mm-1.5mm thick, rectangular, and have a fixed tilt angle. The plane of the substrate forms an angle of 30°-60° with the plane of the ceramic frame, and the vertical projection of the sheet substrate onto the plane of the frame completely covers the plane of the frame; the sheet substrates are distributed parallel to each other under the ceramic frame, and the two ends of the sheet substrates are respectively connected to the two ends of the power supply through wires, and the sheet substrates are connected in parallel in the circuit; the sheet substrates include a loose and porous silicon dioxide substrate with hexagonal holes arranged in a honeycomb pattern, and a functional material fixed to the substrate; the hexagonal holes arranged in a honeycomb pattern have a grid gap of 0.3mm-0.5mm and a grid hole diameter of 0.8mm-1.2mm.

[0014] The exhaust gas recovery device manufactured according to the method of this embodiment has a low rate of toxic waste emission (the mass fraction of toxic waste substances in the exhaust gas does not exceed 0.01%), a high disposal rate, and good stability, which is superior to the prior art.

[0015] The above description of the disclosed embodiments is merely intended to enable those skilled in the art to make or use the invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the general principles defined herein may be implemented in other embodiments without departing from the spirit or scope of the invention. Therefore, the invention is not to be limited to the embodiments shown herein, but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.

Claims

1. A tail gas treatment device suitable for the preparation of high-purity triethylamine, wherein the tail gas treatment device is installed after the emission end of the preparation equipment and before the tail gas exhaust port, characterized in that: This exhaust gas treatment device integrates an oil-water dual-layer absorption device, a composite electrochemical degradation device, and an exhaust gas combustion and venting device, according to the exhaust gas flow sequence. The composite electrochemical degradation device specifically comprises a 10kV-15kV AC pulse power supply, wires, a ceramic frame, and sheet-like substrates arranged in a louvered pattern within the ceramic frame. The sheet-like substrates are 1mm-1.5mm thick, cuboid in shape, with a fixed tilt angle. The plane of the sheet-like substrate forms a 30°-60° angle with the plane of the ceramic frame, and the vertical projection of the sheet-like substrate onto the plane of the frame completely covers the plane of the frame. The sheet-like substrates are distributed parallel to each other under the ceramic frame, with both ends connected to the two ends of the power supply via wires, forming a parallel connection in the circuit. The sheet-like substrates include a loosely porous silica matrix with hexagonal pores arranged in a honeycomb pattern, and a functional material fixed to the matrix. The densely arranged hexagonal pores have a grid spacing of 0.3mm-0.5mm and a grid aperture of 0.8mm-1.2mm. The method for manufacturing the above-mentioned exhaust gas treatment device includes the following stages: S1: Raw Material Preparation ① Raw material preparation: Prepare sufficient tap water, mineral oil, ceramic frame, silica, boric acid, sodium carbonate, InCl3·4H2O, SnCl4·5H2O, triblock copolymer polyethylene glycol-polyglycerol-polyethylene glycol, graphite powder with a particle size of 1μm-2μm, tetraethyl orthosilicate, titanium oxysulfate powder, urea, deionized water, 10% hydrochloric acid aqueous solution, 10% sodium hydroxide aqueous solution, and a quartz container with an inlet at the bottom and an outlet at the top; S2: Matrix Preparation ① Mix the silica, boric acid and sodium carbonate prepared in step ① of stage S1 evenly in a mass ratio of 85: (7-8): (7-8). Then, under nitrogen protection, heat to 1500℃ and melt. Pour into a mold with closely spaced hexagonal holes as required by the design. After cooling and forming, anneal to obtain the glass to be processed. ②The glass to be processed obtained in step ① is trimmed and cut to the required size and shape to obtain a glass substrate; ③ After mechanically polishing the surface of the prepared glass substrate, the polished glass substrate is placed in a nitrogen-protected environment and then heated to 660℃-680℃ for 35h-38h. After that, it is taken out and naturally cooled to room temperature. Then, the treated glass substrate is successively immersed and etched with deionized water, hydrochloric acid solution, and sodium hydroxide solution heated to 90℃-95℃. The deionized water and hydrochloric acid solution are used to clean the glass substrate until the weight no longer changes, and the sodium hydroxide solution is used to clean it for 80min-90min. After etching, the glass substrate is cleaned with deionized water and then naturally dried to obtain the desired loose and porous silica matrix with hexagonal pores arranged in a honeycomb pattern. S3: Functional Ingredient Integration ① Mix InCl3·4H2O and SnCl4·5H2O evenly in a mass ratio of (28-30):(34-36), then completely immerse them in 11-13 times the weight of the mixture in deionized water, stir evenly, and obtain immersion solution A; ② Immerse the silica substrate obtained in step ③ of stage S2 completely in the wetting solution A for 1-2 days and protect it with ultrasonic treatment; after immersion, place it in a sealed space under nitrogen protection and let it dry naturally until it is completely dry; then heat the dried silica substrate in an air resistance furnace at a temperature of 970℃-990℃ for 6-7 hours to obtain a conductive substrate. ③ After mixing the triblock copolymer polyethylene glycol-polyglycerol-polyethylene glycol and graphite powder at a mass ratio of 5:(2-3) to obtain mixture A, mix mixture A with 23-25 ​​times its mass of hydrochloric acid aqueous solution and stir until homogeneous. Maintain stirring and heat to 45℃-50℃. Then slowly add 1.5-1.7 times its mass of tetraethyl orthosilicate to the hydrochloric acid aqueous solution while maintaining stirring and heating for 20-21 hours to obtain mixture B. ④ Immerse the conductive substrate obtained in step ② completely in the mixture B obtained in step ③, maintain stirring and heating, and soak for 15-20 minutes. Then, transfer the soaked conductive substrate into a resistance furnace at 105℃-110℃ under nitrogen protection and keep it at that temperature for 1-1.5 days. Afterward, cool it to room temperature under nitrogen protection and clean the surface with deionized water. Then, place the conductive substrate in an air resistance furnace, heat it to 550℃-560℃, and keep it at that temperature for 4-5 hours to obtain a pretreated sheet substrate. ⑤ Dissolve titanium oxysulfate in 4-5 times its mass of deionized water and stir until completely melted; add 1.5%-2% urea by mass of the solution to the solution, then add the pretreated sheet substrate obtained in step ④ into the mixture, heat to 105℃-110℃, and stir for 11-12 hours; then remove the pretreated sheet substrate and wash it thoroughly with deionized water; then place the pretreated sheet substrate in an air resistance furnace, heat to 510℃-520℃, and hold for 4-5 hours to obtain the desired sheet substrate; S4: Assembly ① After mixing tap water and mineral oil in a volume ratio of 1:(0.1-5), the mixture is injected into the first quartz container. The bottom inlet of the first quartz container is connected to the discharge end of the preparation equipment through a quartz tube, and the top outlet is connected to the composite electrochemical degradation device through a quartz tube. ② Assemble and fix the sheet substrate obtained in step ⑤ of stage S3 to the ceramic frame, so that the sheet substrate is fixed in the ceramic frame in the form of louver blades, and the plane of the sheet substrate is at an angle of 30°-60° with the plane of the ceramic frame; connect the two ends of the sheet substrate to the two ends of the power supply through wires, and the sheet substrate is connected in parallel in the circuit. Place the frame part in the second quartz container, so that the outer contour of the frame is sealed and matched with the inner contour of the second quartz container, and obtain the composite electrochemical degradation device. The top outlet of the second quartz container is matched with the exhaust gas combustion device through a quartz tube, thus obtaining the exhaust gas treatment device suitable for the preparation of high-purity triethylamine.