Porous organic polymer CIGS thin film battery tail gas purifying agent and preparation method thereof

Abstract

The invention provides a porous organic polymer CIGS thin film battery tail gas purifying agent and a preparation method thereof, and is characterized in that the tail gas purifying agent is prepared from the following raw materials in parts by weight: 50-75 parts of a porous organic polymer and 10-35 parts of an active component, the active component is copper hydroxide and / or permanganate, and in addition, the active component is a porous organic polymer. The tail gas purifying agent also contains 5-10 parts of a modifier. The tail gas purifying agent can be used at normal temperature, is high in desulfurization efficiency, can be used for removing tail gas discharged in the production process of the CIGS thin-film solar cell module, can also be used for other desulfurization scenes, and is good in market prospect.

Description

Technical Field

[0001] The invention belongs to the technical field of composite materials, and in particular relates to a porous organic polymer CIGS thin film battery tail gas purifier and a preparation method thereof. Background Art

[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 are considered to be the future development direction of solar cell technology due to their high light absorption coefficient, high conversion efficiency, high stability and low temperature coefficient. However, CIGS thin-film solar cells produce highly toxic gases containing H2S and H2Se during the production process, and the treatment of these gases has become an urgent problem to be solved.

[0003] Among the existing desulfurization technologies, wet method and dry method are the two main treatment methods. Although the wet method is easy to operate and has wide adaptability, it has problems such as high energy consumption, serious equipment corrosion and difficulty in waste liquid treatment. The dry method is mainly based on the Claus method and the activated carbon method, but these methods usually require higher reaction temperatures and have problems such as low desulfurization efficiency and residual tail gas. Especially in the production process of CIGS thin-film solar cells, since the tail gas temperature is at room temperature, traditional metal oxide-based desulfurizers cannot work effectively under such conditions and require additional heating equipment, which increases energy consumption and costs.

[0004] In this context, porous organic polymers, as a new type of adsorption material, have begun to attract the attention of researchers due to their unique structure and properties. Porous organic polymers have the advantages of high specific surface area, adjustable pore structure, good chemical stability and thermal stability, and the ability to introduce specific active sites through functional modification. These characteristics make porous organic polymers show great potential in the fields of gas adsorption, separation and catalysis.

[0005] For the tail gas generated in CIGS thin-film solar cell production lines, researchers are exploring the possibility of using porous organic polymers as desulfurizers. Compared with traditional metal oxide desulfurizers, porous organic polymers can work at room temperature without the need for additional heating equipment, which greatly reduces energy consumption. In addition, by precisely controlling the pore structure of porous organic polymers and the introduction of functional groups, their selective adsorption capacity for H2S and H2Se can be improved, thereby achieving efficient desulfurization.

[0006] Patent publication number CN 116474745 B discloses an iron oxide desulfurizer based on a porous polymer and a preparation method thereof. The desulfurizer is prepared by designing and synthesizing a porous polymer and then loading iron oxide on the porous polymer. The porous polymer prepared by this invention has a large specific surface area, and the pores contain pyridine alkaline heterocyclic compounds. On the one hand, the porosity allows the gas to pass smoothly while allowing the alkaline heterocyclic groups to react with hydrogen sulfide; on the other hand, the loaded iron oxide can react with hydrogen sulfide to desulfurize; however, the desulfurizer may experience structural collapse during the exhaust gas purification process, which affects the service life of the desulfurizer. Summary of the invention

[0007] In view of the shortcomings of the prior art, the present invention proposes a porous organic polymer CIGS thin film battery tail gas purifier and a preparation method thereof, aiming to solve the problems of low efficiency and high cost of the existing desulfurization technology at room temperature, and to contribute to the sustainable development of the photovoltaic industry. The tail gas purifier of the present invention can be used at room temperature, has high desulfurization efficiency, can be used to remove tail gas emitted during the production process of copper indium gallium selenide thin film solar cell modules, and can also be used in other desulfurization scenarios, with good market prospects.

[0008] In order to achieve the above object, the technical solution adopted by the present invention is as follows: On the one hand, the present invention provides a porous organic polymer CIGS thin film battery exhaust gas purifier, which is characterized in that it is made of the following raw materials: in parts by weight, the exhaust gas purifier contains the following raw materials: 50-75 parts of porous organic polymer and 10-35 parts of active components; wherein the active components are copper hydroxide and / or permanganate.

[0009] In some embodiments, the method for preparing the porous organic polymer comprises the following steps: S1. Add 2-tributylstannylthiophene, tetrakis(triphenylphosphine)palladium, 2,4,6-tribromobenzene-1,3,5-triol and toluene into a reaction kettle, heat to 100-120°C under an inert gas atmosphere, stir and react for 20-28h, cool, extract and obtain an organic layer; S2. The organic layer obtained in step S1 was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by chromatography to obtain an intermediate product; S3. The intermediate product obtained in step S2, triethylamine and anhydrous N,N-dimethylacetamide are added to a reactor, stirred in an ice-water bath for 20-40 minutes, and then 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine is added, and stirring is continued in an ice-water bath for 20-40 minutes. The mixture is heated to 20-25°C and reacted for 20-30 minutes, and then heated to 100-120°C and reacted for 20-28 hours. The mixture is cooled to room temperature, filtered, washed, and dried to obtain a porous organic polymer.

[0010] In some embodiments, the molar ratio of 2-tributylstannylthiophene to 2,4,6-tribromobenzene-1,3,5-triol in step S1 is (3.2-3.8):1.

[0011] Furthermore, in step S1, the molar ratio of 2-tributylstannylthiophene to 2,4,6-tribromobenzene-1,3,5-triol is 3.5:1.

[0012] In some embodiments, the molar ratio of the intermediate product to 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine in step S3 is 1:(1.05-1.2).

[0013] Furthermore, in step S3, the molar ratio of the intermediate product to 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine is 1:1.1.

[0014] Preferably, the temperature of the ice water bath in step S3 is 0°C.

[0015] Furthermore, the structural formula of the intermediate product in step S2 is as follows:

[0016] The present invention synthesizes a novel porous organic polymer. During the synthesis process, the folding of the polymer chain is effectively avoided through cross-linking, thereby forming a rich porous structure. This ultra-high cross-linked porous polymer has excellent micropore volume and specific surface area characteristics, giving it excellent hydrogen sulfide adsorption capacity and significantly increasing the sites of active components, thereby improving the desulfurization efficiency.

[0017] In addition, the porous polymer synthesized by the present invention contains s-triazine and thiophene functional groups, which, as groups with high electron density, 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 s-triazine and thiophene groups can adjust 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 desulfurizer.

[0018] The present invention adopts porous organic polymer as a carrier, which not only has high sulfur capacity and desulfurization efficiency, but also has a rapid desulfurization process. It can be used to treat tail gas in the production process of CIGS thin-film batteries at room temperature and has broad application prospects.

[0019] In some embodiments, the exhaust gas purifier further contains 5-10 parts of a modifier by weight.

[0020] In some embodiments, the method for preparing the modifier comprises the following steps: Add stearic acid and acetone into the reaction kettle, stir, cool to 0-5°C, add chlorosulfonic acid dropwise, keep warm for 1-2h, filter, wash, and dry to obtain a modifier.

[0021] In some embodiments, the molar ratio of stearic acid to chlorosulfonic acid is 1:(1.1-1.5).

[0022] Furthermore, the molar ratio of stearic acid to chlorosulfonic acid is 1:1.25.

[0023] The modifier of the present invention uses modified stearic acid. On the one hand, stearic acid can be used as a lubricant, which can significantly improve the strength of the original purifier, avoid the phenomenon of structural collapse of the desulfurizer during the tail gas purification process, and is beneficial to improving the service life and penetration sulfur capacity of the desulfurizer; on the other hand, polar sulfonic acid groups are added to the modifier, which enhances its compatibility and dispersibility in the raw material system. At the same time, it can form a stable chemical bond with sulfide, thereby effectively removing sulfide in the gas.

[0024] Another aspect of the present invention is to provide a method for preparing a porous organic polymer CIGS thin film battery tail gas purifier, comprising the following steps: The porous organic polymer, active component and modifier are added into a kneading machine, kneaded evenly, extruded and formed, and dried to obtain the tail gas purifier.

[0025] In some embodiments, the drying temperature is 110-150° C., and the drying time is 10-20 hours.

[0026] In the process of preparing the exhaust gas purifier, the applicant controls the drying temperature to maintain the structural integrity of the material to avoid excessive heat treatment that would lead to a decrease in the mechanical strength and stability of the material; at the same time, the pore structure of the porous organic polymer will be optimized, the pore size distribution will become more uniform, and the porosity will increase, 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.

[0027] In some embodiments, the H2S conversion rate is not less than 90%, and the H2Se conversion rate is not less than 89%.

[0028] Compared with the prior art, the present invention has the following beneficial effects: 1. The tail gas purifier of the present invention can be used at room temperature, has high desulfurization efficiency, can be used to remove tail gas emitted during the production process of copper indium gallium selenide thin-film solar cell modules, and can also be used in other desulfurization scenarios, with good market prospects.

[0029] 2. The present invention synthesizes a new type of porous organic polymer with excellent micropore volume and specific surface area characteristics, which gives it excellent hydrogen sulfide adsorption capacity and significantly increases the sites of active components, thereby improving the efficiency of desulfurization. In addition, 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 the chemical adsorption capacity of hydrogen sulfide; at the same time, the pore structure of the porous organic polymer can be adjusted to improve the adsorption capacity and desulfurization efficiency of the desulfurizer.

[0030] 3. The present invention adopts a special modifier, which can significantly improve the strength of the original purifier on the one hand, which is beneficial to improve the service life and sulfur penetration capacity of the desulfurizer; on the other hand, the polar sulfonic acid group in the modifier can form a stable chemical bond with the sulfide, thereby effectively removing the sulfide.

[0031] 4. In the process of preparing the exhaust gas purifier, the present invention controls the drying temperature to maintain the structural integrity of the material, optimizes the pore structure and distribution of the porous organic polymer, and thus improves the working efficiency and service life of the desulfurizer. DETAILED DESCRIPTION

[0032] The present invention will be described below in conjunction with specific embodiments. It should be noted that the following embodiments are examples of the present invention and are only used to illustrate the present invention, rather than to limit the present invention. Other combinations and various modifications within the concept of the present invention may be performed without departing from the spirit or scope of the present invention.

[0033] According to the ratios of the raw materials and the preparation methods specified in the following examples and comparative examples, various tail gas purifiers were prepared.

[0034] In order to facilitate those skilled in the art to implement the present invention, some raw material manufacturers of the embodiments and comparative examples are described as follows: Hydrotalcite: purchased from Kaisima (Dandong) High-tech Materials Technology Co., Ltd.

[0035] Other raw materials are not specially specified and can be purchased from the market.

[0036] Preparation Example 1 The method for preparing the porous organic polymer A comprises the following steps: S1. Add 35 mmol of 2-tributylstannylthiophene, 1.35 mmol of tetrakis(triphenylphosphine)palladium, 10 mmol of 2,4,6-tribromobenzene-1,3,5-triol, and 75 ml of toluene into a reaction kettle, heat to 110°C under a nitrogen atmosphere, stir and react for 24 hours, cool to room temperature, extract, and obtain an organic layer; S2. The organic layer obtained in step S1 was dried over 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 an intermediate product; 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 reactor, 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, continue stirring in an ice-water bath at 0°C for 30 min, heat to 25°C to react for 30 min, then heat to 110°C to react for 24 h, cool to room temperature, filter, wash with distilled water and tetrahydrofuran 3 times each, and dry at 105°C for 12 h to obtain a porous organic polymer A.

[0037] Preparation Example 2 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.

[0038] Preparation Example 3 The preparation method of porous organic polymer C is the same as that of Preparation Example 1, except that the amount of 2-tributylstannylthiophene added in step S1 is 10 mmol.

[0039] Preparation Example 4 The preparation method of modifier A comprises the following steps: 10 mmol of stearic acid and 30 ml of acetone were added to the reactor, stirred for 30 min, cooled to 2°C, 12.5 mmol of chlorosulfonic acid was slowly added dropwise at a rate of 1 / s, the mixture was kept warm for 2 h, filtered, washed with 30 ml of acetone, and dried at 60°C for 8 h to obtain modifier A.

[0040] Preparation Example 5 The preparation method of modifier B is the same as that of Preparation Example 4, except that the amount of chlorosulfonic acid added is 5 mmol. Example

[0041] A porous organic polymer CIGS thin film battery tail gas purifier comprises 62.5 parts of porous organic polymer A, 22.5 parts of copper hydroxide and 7.5 parts of modifier A by weight.

[0042] The preparation method of the exhaust gas purifier of this embodiment comprises the following steps: adding porous organic polymer A, copper hydroxide and modifier A into a kneader, kneading them evenly and then extruding them into shapes, and drying them at 130° C. for 12 hours to obtain the exhaust gas purifier. Example

[0043] A porous organic polymer CIGS thin film battery tail gas purifier comprises, by weight, 62.5 parts of porous organic polymer A and 22.5 parts of copper hydroxide.

[0044] The preparation method of the exhaust gas purifier of this embodiment comprises the following steps: adding a porous organic polymer and copper hydroxide into a kneader, kneading them evenly and then extruding them into shapes, and drying them at 130° C. for 12 hours to obtain the exhaust gas purifier. Example

[0045] A porous organic polymer CIGS thin film battery tail gas purifier comprises 50 parts of porous organic polymer A, 10 parts of copper hydroxide and 5 parts of modifier A by weight.

[0046] The preparation method of the exhaust gas purifier of this embodiment comprises the following steps: adding porous organic polymer A, copper hydroxide and modifier A into a kneader, kneading them evenly and then extruding them into shapes, and drying them at 110° C. for 16 hours to obtain the exhaust gas purifier. Example

[0047] A porous organic polymer CIGS thin film battery tail gas purifier comprises 75 parts of porous organic polymer A, 35 parts of copper hydroxide and 10 parts of modifier A by weight.

[0048] The preparation method of the exhaust gas purifier of this embodiment comprises the following steps: adding porous organic polymer A, copper hydroxide and modifier A into a kneader, kneading them evenly and then extruding them into shapes, and drying them at 150° C. for 10 hours to obtain the exhaust gas purifier. Example

[0049] A porous organic polymer CIGS thin film battery tail gas purifier and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that an equal amount of porous organic polymer B is used to replace porous organic polymer A. Example

[0050] A porous organic polymer CIGS thin film battery tail gas purifier and a preparation method thereof, wherein the specific implementation manner is the same as that of Example 1, except that an equal amount of porous organic polymer C is used to replace porous organic polymer A. Example

[0051] A porous organic polymer CIGS thin film battery tail gas purifier and a preparation method thereof, the specific implementation manner is the same as that of Example 1, except that an equal amount of modifier B is used to replace modifier A.

[0052] Comparative Example 1 A porous organic polymer CIGS thin film battery tail gas purifier and a preparation method thereof, the specific implementation manner is the same as that of Example 1, except that an equal amount of commercially available hydrotalcite is used to replace the porous organic polymer A.

[0053] Effect evaluation: The exhaust gas purifiers prepared in the above Examples 1-7 and Comparative Example 1 were tested and analyzed, and the specific results are shown in Table 1.

[0054] Performance test: The exhaust gas purifier obtained by drying is crushed and ground to obtain a 100-mesh powder, and then the powder is placed in the mold of a tablet press and pressed into a sheet material at 1MPa. The sheet material is briefly cut into smaller flakes, mixed evenly with 100-mesh quartz sand, and then placed in the experimental area of ​​the reaction tube; CIGS industrial simulated exhaust gas (N2 / H2S / H2Se mixed gas, H2S=3000ppm, H2Se=500ppm, and the rest is N2) is directly introduced into the reaction tube for purification at 500ml / min, and finally the hose at the outlet of the reaction tube is introduced into the exhaust gas absorption device (NaOH solution), the main gas valve is closed and the flowmeter is adjusted to zero.

[0055]

[0056] From the results in Table 1, it can be seen that the tail gas purifiers prepared in Examples 1-4 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 is added to Examples 1, 3, and 4, which is beneficial to improving the service life and penetration sulfur capacity of the desulfurizer, and the conversion rate of sulfides is higher. In addition, the conversion rate at 60 min in Examples 1, 3, and 4 decreases less than that at 30 min.

[0057] In Example 5, compared with Example 1, an equal amount of porous organic polymer B is used to replace porous organic polymer A, which changes the molar ratio of the intermediate product and 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine, thereby reducing the s-triazine group and affecting the sulfide conversion rate.

[0058] In Example 6, compared with Example 1, an equal amount of porous organic polymer C is used to replace porous organic polymer A, and the molar ratio of 2-tributylstannylthiophene and 2,4,6-tribromobenzene-1,3,5-triol is changed, so that the thiophene group is reduced, thereby affecting the sulfide conversion rate.

[0059] Compared with 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, thereby reducing the compatibility and dispersibility of the modifier in the raw material system, thereby affecting the sulfide conversion rate.

[0060] Compared with Example 1, Comparative Example 1 uses an equal amount of commercially available hydrotalcite to replace the porous organic polymer A, resulting in a smaller specific surface area, which in turn affects the sulfide conversion rate.

[0061] The above is only a preferred embodiment of the present invention and does not constitute any form of limitation to the present application. Although the present application is disclosed as above in the preferred embodiment, it is not intended to limit the present application. Any technician familiar with the profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases. However, 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 content 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 battery tail gas purifier, characterized in that The tail gas purifier is made of the following raw materials: in parts by weight, the tail gas purifier comprises the following raw materials: 50-75 parts of porous organic polymer and 10-35 parts of active components; wherein the active components are copper hydroxide and / or permanganate.

2. The porous organic polymer CIGS thin film battery tail gas purifier according to claim 1, characterized in that: The method for preparing the porous organic polymer comprises the following steps: S1. Add 2-tributylstannylthiophene, tetrakis(triphenylphosphine)palladium, 2,4,6-tribromobenzene-1,3,5-triol and toluene into a reaction kettle, heat to 100-120°C under an inert gas atmosphere, stir and react for 20-28h, cool, extract and obtain an organic layer; S2. The organic layer obtained in step S1 was dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by chromatography to obtain an intermediate product; S3. The intermediate product obtained in step S2, triethylamine and anhydrous N,N-dimethylacetamide are added to a reactor, stirred in an ice-water bath for 20-40 minutes, and then 2,4,6-tris(4-(bromomethyl)phenyl)-1,3,5-triazine is added, and stirring is continued in an ice-water bath for 20-40 minutes. The mixture is heated to 20-25°C and reacted for 20-30 minutes, and then heated to 100-120°C and reacted for 20-28 hours. The mixture is cooled to room temperature, filtered, washed, and dried to obtain a porous organic polymer.

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

1.

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

5. The porous organic polymer CIGS thin film battery tail gas purifier according to claim 1, characterized in that: The tail gas purifier further contains 5-10 parts of a modifier by weight.

6. The porous organic polymer CIGS thin film battery tail gas purifier according to claim 5, characterized in that: The preparation method of the modifier comprises the following steps: Add stearic acid and acetone into the reaction kettle, stir, cool to 0-5°C, add chlorosulfonic acid dropwise, keep warm for 1-2h, filter, wash, and dry to obtain a modifier.

7. The porous organic polymer CIGS thin film battery tail gas purifier according to claim 6, characterized in that: The molar ratio of stearic acid to chlorosulfonic acid is 1:(1.1-1.5).

8. A method for preparing a porous organic polymer CIGS thin film battery tail gas purifier according to any one of claims 5 to 7, characterized in that The preparation steps include: The porous organic polymer, active component and modifier are added into a kneading machine, kneaded evenly, extruded and formed, and dried to obtain the tail gas purifier.

9. The method for preparing a porous organic polymer CIGS thin film battery tail gas purifier according to claim 8, characterized in that: The drying temperature is 110-150° C., and the drying time is 10-20 hours.

10. The method for preparing a porous organic polymer CIGS thin film battery tail gas purifier according to claim 8, characterized in that: The H2S conversion rate is not less than 90%, and the H2Se conversion rate is not less than 89%.

Images