A porous organic polymer CIGS thin film cell tail gas purifier and a preparation method thereof

Abstract

The application provides a porous organic polymer CIGS thin film battery tail gas purification agent and a preparation method thereof, and is characterized by being prepared from the following raw materials: the tail gas purification agent comprises 50-75 parts of a porous organic polymer, 10-35 parts of an active component, and 5-10 parts of a modifier in terms of weight parts, wherein the active component is copper hydroxide and / or permanganate. The tail gas purification agent of the application can be used at room temperature, has high desulfurization efficiency, can be used for removing tail gas discharged in the production process of copper indium gallium selenide thin film solar cell modules, can also be used for other desulfurization scenes, and has a good market prospect.

Description

Technical Field

[0001] This invention belongs to the field of composite material technology, specifically relating to a porous organic polymer CIGS thin-film battery exhaust gas purifier and its preparation method. Background Technology

[0002] Photovoltaic power generation, as a clean and renewable energy technology, has developed rapidly in recent years. In particular, copper indium gallium selenide (CIGS) thin-film solar cells, due to their high light absorption coefficient, high conversion efficiency, high stability, and low temperature coefficient, are considered the future direction of solar cell technology. However, the production process of CIGS thin-film solar cells generates highly toxic gases containing H2S and H2Se, and the treatment of these gases has become an urgent problem to be solved.

[0003] Among existing desulfurization technologies, wet and dry methods are the two main treatment methods. While wet methods are simple to operate and widely adaptable, they suffer from high energy consumption, severe equipment corrosion, and difficulties in wastewater treatment. Dry methods primarily utilize the Claus process and activated carbon process, but these methods typically require high reaction temperatures and suffer from low desulfurization efficiency and residual tail gas. Especially in the production process of CIGS thin-film solar cells, where the tail gas temperature is ambient, traditional metal oxide-based desulfurizers cannot work effectively under these conditions, requiring additional heating equipment, which increases energy consumption and cost.

[0004] Against this backdrop, porous organic polymers, as a novel type of adsorbent material, have begun to attract researchers' attention due to their unique structure and properties. Porous organic polymers possess advantages such as high specific surface area, tunable pore structure, good chemical and thermal stability, and the ability to introduce specific active sites through functionalization modification. These characteristics make porous organic polymers demonstrate great potential in fields such as gas adsorption, separation, and catalysis.

[0005] Researchers are exploring the use of porous organic polymers as desulfurizing agents to address the exhaust gases generated in CIGS thin-film solar cell production lines. Compared to traditional metal oxide desulfurizers, porous organic polymers can operate at room temperature without the need for additional heating equipment, significantly reducing energy consumption. Furthermore, by precisely controlling the pore structure and the introduction of functional groups into the porous organic polymers, their selective adsorption capacity for H2S and H2Se can be improved, thereby achieving highly efficient desulfurization.

[0006] Patent publication number CN 116474745 B discloses an iron oxide desulfurizer based on a porous polymer and its preparation method. The invention involves designing and synthesizing a porous polymer, then loading iron oxide onto the polymer to prepare the desulfurizer. The porous polymer prepared in this invention has a large specific surface area, and the pores contain pyridine basic heterocyclic compounds. On the one hand, the porosity allows gas to pass through smoothly while enabling the basic heterocyclic groups to react with hydrogen sulfide; on the other hand, the loaded iron oxide can react with hydrogen sulfide to desulfurize. However, this desulfurizer may experience structural collapse during the exhaust gas purification process, affecting its service life. Summary of the Invention

[0007] To address the shortcomings of existing technologies, this invention proposes a porous organic polymer CIGS thin-film solar cell exhaust gas purifier and its preparation method. It aims to solve the problems of low efficiency and high cost of existing desulfurization technologies at room temperature, contributing to the sustainable development of the photovoltaic industry. The exhaust gas purifier of this invention can be used at room temperature, has high desulfurization efficiency, and can be used to remove exhaust gases emitted during the production of copper indium gallium selenide (CIGS) thin-film solar cell modules. It can also be used in other desulfurization scenarios, showing promising market prospects.

[0008] To achieve the above objectives, the technical solution adopted by the present invention is as follows:

[0009] One aspect of this invention is to provide a porous organic polymer CIGS thin-film battery exhaust gas purifier, characterized in that it is made from the following raw materials: by weight, the exhaust gas purifier comprises the following raw materials: 50-75 parts of porous organic polymer and 10-35 parts of active component; wherein, the active component is copper hydroxide and / or permanganate.

[0010] In some embodiments, the method for preparing the porous organic polymer includes the following steps:

[0011] S1. 2-Tributyltinylthiophene, tetra(triphenylphosphine)palladium, 2,4,6-tribromobenzene-1,3,5-triol, and toluene were added to a reaction vessel. Under an inert gas atmosphere, the mixture was heated to 100-120°C and stirred for 20-28 hours. After cooling, the mixture was extracted to obtain the organic layer.

[0012] S2. The organic layer obtained in step S1 is dried with anhydrous sodium sulfate, concentrated under reduced pressure, and purified by chromatography to obtain the intermediate product.

[0013] S3. Add the intermediate product obtained in step S2, triethylamine, and anhydrous N,N-dimethylacetamide to a reaction vessel, stir in an ice-water bath for 20-40 min, then add 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine, continue stirring in an ice-water bath for 20-40 min, heat to 20-25℃ and react for 20-30 min, then heat to 100-120℃ and react for 20-28 h, cool to room temperature, filter, wash, and dry to obtain a porous organic polymer.

[0014] In some embodiments, the molar ratio of 2-tributyltinylthiophene and 2,4,6-tribromobenzene-1,3,5-triol in step S1 is (3.2-3.8):1.

[0015] Further, the molar ratio of 2-tributyltinylthiophene and 2,4,6-tribromobenzene-1,3,5-triol in step S1 is 3.5:1.

[0016] In some embodiments, the molar ratio of the intermediate product in step S3 to 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine is 1:(1.05-1.2).

[0017] Further, the molar ratio of the intermediate product and 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine in step S3 is 1:1.1.

[0018] Preferably, the temperature of the ice-water bath in step S3 is 0°C.

[0019] Furthermore, the structural formula of the intermediate product described in step S2 is as follows:

[0020] .

[0021] This invention synthesizes a novel porous organic polymer. During the synthesis process, cross-linking effectively avoids the folding of polymer chains, thereby forming a rich porous structure. This highly cross-linked porous polymer has excellent micropore volume and specific surface area characteristics, endowing it with outstanding hydrogen sulfide adsorption capacity and significantly increasing the sites of active components, thereby improving desulfurization efficiency.

[0022] Furthermore, the porous polymer synthesized in this invention contains triazine and thiophene functional groups. As groups with high electron density, these groups can effectively increase the active sites on the surface of the porous organic polymer, thereby improving the chemical adsorption capacity for hydrogen sulfide. At the same time, the introduction of triazine and thiophene groups can regulate the pore structure of the porous organic polymer, including pore size and pore distribution, which helps to optimize the diffusion path of gas molecules and improve the adsorption capacity and desulfurization efficiency of the desulfurizing agent.

[0023] This invention uses porous organic polymers as a carrier, which not only has high sulfur capacity and desulfurization efficiency, but also a rapid desulfurization process. It can be used to treat the exhaust gas in the production process of CIGS thin-film batteries at room temperature, and has broad application prospects.

[0024] In some embodiments, the exhaust gas purifier further contains 5-10 parts by weight of a modifier.

[0025] In some embodiments, the method for preparing the modifier includes the following steps:

[0026] Stearic acid and acetone were added to the reaction vessel, stirred, cooled to 0-5℃, and chlorosulfonic acid was added dropwise. The reaction was kept at this temperature for 1-2 hours, filtered, washed, and dried to obtain the modifier.

[0027] In some embodiments, the molar ratio of stearic acid to chlorosulfonic acid is 1:(1.1-1.5).

[0028] Furthermore, the molar ratio of stearic acid to chlorosulfonic acid is 1:1.25.

[0029] The modifier of this invention uses modified stearic acid. On the one hand, stearic acid can act as a lubricant, which can significantly improve the strength of the original purifier and avoid the structural collapse of the desulfurizer during the exhaust gas purification process, thus improving the service life and sulfur penetration capacity of the desulfurizer. On the other hand, the modifier adds polar sulfonic acid groups, which enhances its compatibility and dispersibility in the raw material system. At the same time, it can form stable chemical bonds with sulfides, thereby effectively removing sulfides from the gas.

[0030] Another aspect of the present invention provides a method for preparing a porous organic polymer CIGS thin-film battery exhaust gas purifier, comprising the following steps:

[0031] Porous organic polymer, active components, and modifiers are added to a kneader, kneaded evenly, extruded into shape, and dried to obtain an exhaust gas purifier.

[0032] In some embodiments, the drying temperature is 110-150°C and the drying time is 10-20 hours.

[0033] In the process of preparing the exhaust gas purifier, the applicant maintains the structural integrity of the material by controlling the drying temperature, avoiding excessive heat treatment that would reduce the mechanical strength and stability of the material. At the same time, the pore structure of the porous organic polymer is optimized, the pore size distribution becomes more uniform, and the porosity increases, which is conducive to the diffusion and adsorption of gas molecules, thereby improving the working efficiency of the desulfurizer and ensuring the long-term stability and service life of the material.

[0034] In some implementations, the H2S conversion rate is not less than 90%, and the H2Se conversion rate is not less than 89%.

[0035] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0036] 1. The exhaust gas purifier of the present invention can be used at room temperature, has high desulfurization efficiency, and can be used to remove exhaust gas emitted during the production of copper indium gallium selenide thin-film solar cell modules. It can also be used in other desulfurization scenarios and has good market prospects.

[0037] 2. This invention synthesizes a novel porous organic polymer with excellent micropore volume and specific surface area characteristics, endowing it with outstanding hydrogen sulfide adsorption capacity and significantly increasing the sites of active components, thereby improving desulfurization efficiency. Furthermore, the porous polymer contains triazine and thiophene functional groups, which can effectively increase the active sites on the surface of the porous organic polymer, thereby improving its chemisorption capacity for hydrogen sulfide; simultaneously, the pore structure of the porous organic polymer can be adjusted to improve the adsorption capacity and desulfurization efficiency of the desulfurizing agent.

[0038] 3. The present invention uses a special modifier that can significantly improve the strength of the original purifying agent, which is beneficial to improving the service life and sulfur penetration capacity of the desulfurizing agent; on the other hand, the polar sulfonic acid group in the modifier can form a stable chemical bond with sulfides, thereby effectively removing sulfides.

[0039] 4. In the process of preparing the exhaust gas purifier, this invention maintains the structural integrity of the material by controlling the drying temperature, optimizes the pore structure and distribution of the porous organic polymer, thereby improving the working efficiency and service life of the desulfurizer. Detailed Implementation

[0040] The present invention will be described below with reference to specific embodiments. It should be noted that the following embodiments are examples of the present invention and are used only to illustrate the invention, not to limit it. Other combinations and various modifications within the scope of the present invention can be made without departing from its spirit or scope.

[0041] Each exhaust gas purifier was prepared according to the proportions and preparation methods of the raw materials specified in the following examples and comparative examples.

[0042] To facilitate implementation of this invention by those skilled in the art, the manufacturers of some raw materials for the embodiments and comparative examples are described below:

[0043] Hydrotalcite: Purchased from KESMA (Dandong) High-Tech Materials Technology Co., Ltd.

[0044] Unless otherwise specified, all other raw materials can be purchased from the market.

[0045] Preparation Example 1

[0046] The preparation method of porous organic polymer A includes the following steps:

[0047] S1. 35 mmol of 2-tributyltinylthiophene, 1.35 mmol of tetra(triphenylphosphine)palladium, 10 mmol of 2,4,6-tribromobenzene-1,3,5-triol, and 75 ml of toluene were added to a reaction vessel. Under a nitrogen atmosphere, the mixture was heated to 110 °C and stirred for 24 h. After cooling to room temperature, the mixture was extracted to obtain the organic layer.

[0048] S2. The organic layer obtained in step S1 is dried with anhydrous sodium sulfate, concentrated under reduced pressure, and purified by chromatography (ethyl acetate and petroleum ether in a volume ratio of 1:20) to obtain the intermediate product.

[0049] S3. Add 4 mmol of the intermediate product obtained in step S2, 8 mmol of triethylamine, and 200 mmol of anhydrous N,N-dimethylacetamide to a reaction vessel and stir in an ice-water bath at 0°C for 30 min. Then add 4.4 mmol of 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine and continue stirring in an ice-water bath at 0°C for 30 min. Heat to 25°C and react for 30 min, then heat to 110°C and react for 24 h. Cool to room temperature, filter, wash three times each with distilled water and tetrahydrofuran, and dry at 105°C for 12 h to obtain porous organic polymer A.

[0050] Preparation Example 2

[0051] The preparation method of porous organic polymer B is the same as that of preparation example 1, except that the amount of 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine added in step S3 is 2 mmol.

[0052] Preparation Example 3

[0053] The preparation method of porous organic polymer C is the same as that of preparation example 1, except that the amount of 2-tributyltinylthiophene added in step S1 is 10 mmol.

[0054] Preparation Example 4

[0055] The preparation method of modifier A includes the following steps:

[0056] 10 mmol stearic acid and 30 ml acetone were added to the reaction vessel and stirred for 30 min. The mixture was cooled to 2 °C and 12.5 mmol chlorosulfonic acid was slowly added dropwise at a rate of 1 / s. The mixture was kept at this temperature for 2 h, filtered, washed with 30 ml acetone, and dried at 60 °C for 8 h to obtain modifier A.

[0057] Preparation Example 5

[0058] Modifier B was prepared in the same way as in Preparation Example 4, except that the amount of chlorosulfonic acid added was 5 mmol. Example 1

[0059] A porous organic polymer CIGS thin-film battery exhaust gas purifier, by weight, comprises 62.5 parts of porous organic polymer A, 22.5 parts of copper hydroxide, and 7.5 parts of modifier A.

[0060] The preparation method of the exhaust gas purifier in this embodiment includes the following steps: adding porous organic polymer A, copper hydroxide and modifier A into a kneader, kneading evenly and then extruding and molding, drying at 130°C for 12 hours to obtain the exhaust gas purifier. Example 2

[0061] A porous organic polymer CIGS thin-film battery exhaust gas purifier, comprising, by weight, 62.5 parts of porous organic polymer A and 22.5 parts of copper hydroxide.

[0062] The preparation method of the exhaust gas purifier in this embodiment includes the following steps: adding porous organic polymer and copper hydroxide into a kneader, kneading evenly, extruding and molding, and drying at 130°C for 12 hours to obtain the exhaust gas purifier. Example 3

[0063] A porous organic polymer CIGS thin-film battery exhaust gas purifier, by weight, comprises 50 parts of porous organic polymer A, 10 parts of copper hydroxide, and 5 parts of modifier A.

[0064] The preparation method of the exhaust gas purifier in this embodiment includes the following steps: adding porous organic polymer A, copper hydroxide and modifier A into a kneader, kneading evenly and then extruding and molding, drying at 110°C for 16 hours to obtain the exhaust gas purifier. Example 4

[0065] A porous organic polymer CIGS thin-film battery exhaust gas purifier, by weight, comprises 75 parts of porous organic polymer A, 35 parts of copper hydroxide, and 10 parts of modifier A.

[0066] The preparation method of the exhaust gas purifier in this embodiment includes the following steps: adding porous organic polymer A, copper hydroxide and modifier A into a kneader, kneading evenly and then extruding and molding, drying at 150°C for 10 hours to obtain the exhaust gas purifier. Example 5

[0067] A porous organic polymer CIGS thin-film battery exhaust gas purifier and its preparation method are disclosed. The specific implementation method is the same as in Example 1, except that an equal amount of porous organic polymer B is used to replace porous organic polymer A. Example 6

[0068] A porous organic polymer CIGS thin-film battery exhaust gas purifier and its preparation method are disclosed. The specific implementation method is the same as in Example 1, except that an equal amount of porous organic polymer C is used to replace porous organic polymer A. Example 7

[0069] A porous organic polymer CIGS thin-film battery exhaust gas purifier and its preparation method are disclosed. The specific implementation method is the same as in Example 1, except that an equal amount of modifier B is used to replace modifier A.

[0070] Comparative Example 1

[0071] A porous organic polymer CIGS thin-film battery exhaust gas purifier and its preparation method are disclosed. The specific implementation method is the same as in Example 1, except that an equal amount of commercially available hydrotalcite is used to replace the porous organic polymer A.

[0072] Effect evaluation:

[0073] The exhaust gas purifiers prepared in Examples 1-7 and Comparative Example 1 were tested and analyzed. The specific results are shown in Table 1.

[0074] Performance Testing: The dried exhaust gas purifier was pulverized and ground to obtain 100-mesh powder. The powder was then placed in the mold of a tablet press and pressed into a sheet material at 1 MPa. The sheet material was briefly cut into smaller thin slices and mixed evenly with 100-mesh quartz sand, then placed in the experimental area of ​​the reaction tube. CIGS industrial simulated exhaust gas (a mixture of N2 / H2S / H2Se, H2S=3000ppm, H2Se=500ppm, with the remainder being N2) was directly introduced into the reaction tube at a rate of 500 ml / min for purification. Finally, the hose at the outlet of the reaction tube was introduced into the exhaust gas absorption device (NaOH solution), the main gas valve was closed, and the flow meter was adjusted to zero.

[0075]

[0076] As shown in Table 1, the tail gas purifiers prepared in Examples 1-4 all have high conversion rates for H2S and H2Se. The conversion rates of H2S and H2Se in Examples 1, 3, and 4 are higher than those in Example 2. This is because Modifier A was added in Examples 1, 3, and 4, which helps to improve the service life and sulfur penetration capacity of the desulfurizer and has a higher conversion rate for sulfides. In addition, the conversion rate at 60 min in Examples 1, 3, and 4 decreased less than that at 30 min.

[0077] Compared to Example 1, Example 5 replaced porous organic polymer A with an equal amount of porous organic polymer B, which changed the molar ratio of the intermediate product and 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine, resulting in a reduction of mesityrazine groups and thus affecting the sulfide conversion rate.

[0078] Compared to Example 1, Example 6 replaced porous organic polymer A with an equal amount of porous organic polymer C, which changed the molar ratio of 2-tributyltinylthiophene and 2,4,6-tribromobenzene-1,3,5-triol, resulting in a reduction of thiophene groups and thus affecting the sulfide conversion rate.

[0079] Compared to Example 1, Example 7 uses an equal amount of modifier B to replace modifier A, which changes the molar ratio of stearic acid and chlorosulfonic acid. This reduces the compatibility and dispersibility of the modifier in the raw material system, thereby affecting the sulfide conversion rate.

[0080] Compared to Example 1, Comparative Example 1 used an equal amount of commercially available hydrotalcite to replace porous organic polymer A, resulting in a smaller specific surface area, which in turn affected the sulfide conversion rate.

[0081] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present application in any way. Although the present application discloses the preferred embodiment as described above, it is not intended to limit the present application. Any changes or modifications made by those skilled in the art without departing from the scope of the technical solution of the present application using the disclosed technical content are equivalent to equivalent implementation cases. Any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the scope of the technical solution of the present invention are still within the scope of the technical solution.

Claims

1. A porous organic polymer CIGS thin film cell tail gas scavenger characterized by Made from the following raw materials: by weight: 50-75 parts porous organic polymer, 10-35 parts active component, and 5-10 parts modifier; wherein, the active component is copper hydroxide and / or permanganate; The method for preparing the porous organic polymer includes the following steps: S1. 2-Tributyltinylthiophene, tetra(triphenylphosphine)palladium, 2,4,6-tribromobenzene-1,3,5-triol, and toluene were added to a reaction vessel. Under an inert gas atmosphere, the mixture was heated to 100-120°C and stirred for 20-28 hours. After cooling, the mixture was extracted to obtain the organic layer. S2. The organic layer obtained in step S1 is dried with anhydrous sodium sulfate, concentrated under reduced pressure, and purified by chromatography to obtain the intermediate product. S3. Add the intermediate product obtained in step S2, triethylamine, and anhydrous N,N-dimethylacetamide to a reaction vessel, stir in an ice-water bath for 20-40 min, then add 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine, continue stirring in an ice-water bath for 20-40 min, heat to 20-25℃ and react for 20-30 min, then heat to 100-120℃ and react for 20-28 h, cool to room temperature, filter, wash, and dry to obtain a porous organic polymer; The preparation method of the modifier includes the following steps: Stearic acid and acetone were added to the reaction vessel, stirred, cooled to 0-5℃, and chlorosulfonic acid was added dropwise. The reaction was kept at this temperature for 1-2 hours, filtered, washed, and dried to obtain the modifier.

2. A porous organic polymer CIGS thin film cell tail gas scavenger according to claim 1, characterized in that: The molar ratio of 2-tributyltinylthiophene and 2,4,6-tribromobenzene-1,3,5-triol in step S1 is (3.2-3.8):

1.

3. A porous organic polymer CIGS thin film cell tail gas scavenger according to claim 1, characterized in that: The molar ratio of the intermediate product and 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine in step S3 is 1:(1.05-1.2).

4. The porous organic polymer CIGS thin film cell tail gas purifier of claim 1, wherein: The molar ratio of stearic acid to chlorosulfonic acid is 1:(1.1-1.5).

5. The preparation method of a porous organic polymer CIGS thin-film battery exhaust gas purifier according to claim 1 or 4, characterized in that... The preparation steps include the following: Porous organic polymer, active components, and modifiers are added to a kneader, kneaded evenly, extruded into shape, and dried to obtain an exhaust gas purifier.

6. The method for preparing a porous organic polymer CIGS thin-film battery exhaust gas purifier according to claim 5, characterized in that: The drying temperature is 110-150℃, and the drying time is 10-20 hours.

7. The method for preparing a porous organic polymer CIGS thin-film battery exhaust gas purifier according to claim 5, characterized in that: The porous organic polymer CIGS thin-film battery exhaust gas purifier has an H2S conversion rate of not less than 90% and an H2Se conversion rate of not less than 89%.

Images