Sulfur-resistant and moisture-resistant industrial organic waste gas purification composite adsorption material and preparation method thereof
Patent Information
- Application Number
- CN202611295608.0
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-08-25
- Publication Date
- 2026-09-29
AI Technical Summary
[0006]为了克服现有吸附材料在高湿度及含硫工业有机废气环境中易发生吸附容量下降、活性位点失活、循环稳定性差以及对多种污染物协同净化能力不足技术问题，本发明的目的在于提供一种耐硫抗湿型工业有机废气净化复合吸附材料及其制备方法
本发明通过构建KH550-氧化铈协同接枝改性13X分子筛与组氨酸协同作用的复合吸附体系，实现了对工业有机废气中含硫污染物和挥发性有机污染物的高效协同净化。其中，KH550接枝于13X分子筛表面后，可有效提高分子筛表面的稳定性和抗湿性能，减少水蒸气对吸附位点的竞争吸附作用；氧化铈负载于分子筛表面及孔道内部后，可提供丰富的活性位点，增强材料对硫化氢、硫醇等含硫污染物的捕获能力，并有效减缓含硫物质对吸附材料活性位点的毒化作用；组氨酸分子中含有咪唑基、氨基等活性官能团，能够与含硫污染物及极性有机分子产生协同作用，进一步提升材料对复杂工业有机废气的吸附容量和选择性。与此同时，活性炭与介孔二氧化硅构建的多级孔道结构有利于污染物的快速传质与富集，氧化镁则进一步提高材料对酸性含硫气体的吸附能力，从而形成兼具物理吸附与化学吸附作用的复合吸附体系。
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Figure CN122828690A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of industrial waste gas treatment technology, specifically relating to a sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas and its preparation method. Background Technology
[0002] Industrial organic waste gas is a significant air pollutant generated during the production processes of industries such as chemical, pharmaceutical, coating, printing, rubber, waste disposal, and wastewater treatment. Its main components include benzene compounds, alcohols, ketones, esters, and sulfur-containing volatile organic compounds such as hydrogen sulfide, thiols, and sulfides. These pollutants not only have irritating odors and are toxic, but they also participate in atmospheric photochemical reactions, forming ozone and fine particulate matter, adversely affecting the ecological environment and human health. Therefore, the development of efficient and stable industrial organic waste gas purification materials is of great importance.
[0003] Currently, adsorption is one of the most widely used technologies in the treatment of industrial organic waste gas due to its advantages such as simple equipment, high treatment efficiency, low operating cost, and wide applicability. Existing adsorption materials mainly include activated carbon, molecular sieves, activated alumina, and their composite materials. Among them, 13X molecular sieves have a large specific surface area and abundant pore structure, exhibiting good adsorption capacity for organic waste gas; activated carbon has a well-developed pore structure, enabling efficient enrichment of various organic pollutants. However, in actual industrial applications, waste gas often contains a certain concentration of water vapor and sulfides, leading to problems such as competitive occupation of adsorption sites, pore blockage, and deactivation of active centers in traditional adsorption materials. This results in decreased adsorption capacity, shortened service life, and poor regeneration performance.
[0004] To improve the moisture and sulfur resistance of adsorbent materials, existing technologies typically employ methods such as metal oxide loading, silane coupling agent modification, or multi-component composites. While these measures can improve the overall performance of adsorbent materials to some extent, they still have the following shortcomings: Firstly, the selective adsorption capacity of some adsorbent materials for organic pollutants decreases significantly under high humidity environments, making it difficult to maintain stable purification effects over the long term. Secondly, sulfur-containing pollutants such as hydrogen sulfide and thiols easily undergo irreversible reactions with the active sites on the surface of the adsorbent material, leading to gradual deactivation and affecting its recyclability. Furthermore, existing adsorbent materials have limited synergistic removal capabilities for sulfur-containing pollutants and volatile organic pollutants, making it difficult to meet the practical needs of long-term stable purification of complex industrial waste gases.
[0005] Therefore, developing a composite adsorption material that combines excellent sulfur resistance, moisture resistance, and organic waste gas adsorption performance to improve the stability and service life of the adsorption material in complex industrial waste gas environments has become an urgent technical problem to be solved in this field. Summary of the Invention
[0006] To overcome the technical problems of existing adsorbent materials, such as decreased adsorption capacity, deactivation of active sites, poor cycle stability, and insufficient synergistic purification ability for multiple pollutants in high humidity and sulfur-containing industrial organic waste gas environments, the present invention aims to provide a sulfur-resistant and moisture-resistant composite adsorbent material for purifying industrial organic waste gas and its preparation method. This invention uses KH550-cerium oxide synergistic grafting modified 13X molecular sieve as the main adsorbent component, and combines it with histidine, activated carbon, magnesium oxide, and mesoporous silica to construct a multi-level pore and multi-active-site synergistic adsorption system. KH550 is used to improve the surface stability and hydrophobic properties of the molecular sieve, cerium oxide is used to enhance the material's tolerance to sulfur-containing pollutants, and histidine is used to improve the material's synergistic adsorption performance for sulfur-containing compounds and polar organic pollutants. Combined with activated carbon, magnesium oxide, mesoporous silica, polytetrafluoroethylene micropowder, and a binder, a composite adsorbent material with sulfur resistance, moisture resistance, and high adsorption performance is obtained. The preparation process of this invention is simple and the raw materials are widely available. The resulting composite adsorbent material has excellent sulfur resistance, moisture resistance, industrial organic waste gas purification performance and recycling stability.
[0007] The objective of this invention can be achieved through the following technical solutions: A sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas comprises the following raw materials in parts by weight: 80-150 parts of KH550-cerium oxide synergistic grafted modified 13X molecular sieve; 1-15 parts of histidine; 20-80 parts of activated carbon; 2-20 parts of magnesium oxide; 10-50 parts of mesoporous silica; 0.5-8 parts of polytetrafluoroethylene micro powder; and 2-15 parts of binder. The KH550-cerium oxide synergistic grafted modified 13X molecular sieve is a composite modified molecular sieve obtained by silanizing and grafting 13X molecular sieve with KH550, followed by cerium oxide loading treatment.
[0008] Optionally, the KH550-cerium oxide synergistic graft modification of 13X molecular sieve comprises the following raw materials in parts by weight: 100 parts of 13X molecular sieve; 3-12 parts of KH550; 5-15 parts of cerium oxide; 50-100 parts of ethanol; and 60-120 parts of deionized water.
[0009] Optionally, the preparation method of KH550-cerium oxide synergistic graft modification of 13X molecular sieve includes the following steps: (1) 13X molecular sieve was mixed with KH550 and grafted to obtain KH550 grafted 13X molecular sieve. (2) KH550 graft-modified 13X molecular sieve was subjected to loading modification treatment with cerium oxide to obtain the loading modified product; (3) The loaded modified product was separated, washed and dried to obtain KH550-cerium oxide synergistic graft modified 13X molecular sieve.
[0010] Optionally, the reaction conditions in step (1) are as follows: ethanol and deionized water are used as a mixed solvent, the mass ratio of the mixed solvent to 13X molecular sieve is 1.5:1 to 3:1, the reaction is carried out at 50 to 80°C for 2 to 6 hours, and the stirring speed is 300 to 800 rpm during the reaction.
[0011] Optionally, the reaction conditions in step (2) are as follows: cerium oxide is dispersed in deionized water and then mixed with the product obtained in step (1), and the reaction is carried out at 50-90°C for 2-8 hours, with a stirring speed of 300-800 rpm during the reaction.
[0012] Optionally, the reaction conditions for step (3) are washing with deionized water and ethanol 1 to 5 times, followed by drying at 80 to 120°C for 4 to 12 hours.
[0013] Optionally, the binder is a mixture of silica sol and sodium carboxymethyl cellulose in a mass ratio of 5:1 to 20:1.
[0014] Optionally, a method for preparing a sulfur-resistant and moisture-resistant composite adsorbent for purifying industrial organic waste gas includes the following steps: S1, Histidine, activated carbon, magnesium oxide and mesoporous silica are mixed evenly to obtain a mixture; S2, add KH550-cerium oxide synergistic grafted modified 13X molecular sieve and polytetrafluoroethylene micro powder to the mixture, mix evenly, add binder, continue mixing, and obtain shaped mixture. S3. The shaped mixture is shaped and dried to obtain a sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas.
[0015] Optionally, the mixing conditions in step S1 are: mixing at room temperature for 20–60 min and mixing speed of 200–800 rpm.
[0016] Optionally, the mixing conditions in step S2 are: after adding the binder, continue mixing for 30 to 120 minutes, and the mixing speed is 300 to 1000 rpm; the molding method in step S3 is one of extrusion molding, sheet molding, or granulation molding, and the drying conditions are: drying at 80 to 120°C for 4 to 12 hours.
[0017] The beneficial effects of this invention are: This invention achieves highly efficient synergistic purification of sulfur-containing pollutants and volatile organic pollutants in industrial organic waste gas by constructing a composite adsorption system of KH550-cerium oxide synergistic grafting modification of 13X molecular sieve and histidine synergistic effect. Specifically, KH550 grafted onto the surface of 13X molecular sieve effectively improves the stability and moisture resistance of the molecular sieve surface, reducing the competitive adsorption effect of water vapor on adsorption sites. Cerium oxide loaded on the surface and inside the pores of the molecular sieve provides abundant active sites, enhancing the material's ability to capture sulfur-containing pollutants such as hydrogen sulfide and thiols, and effectively mitigating the poisoning effect of sulfur-containing substances on the active sites of the adsorption material. Histidine molecules contain active functional groups such as imidazole and amino groups, which can synergistically interact with sulfur-containing pollutants and polar organic molecules, further improving the adsorption capacity and selectivity of the material for complex industrial organic waste gas. Meanwhile, the hierarchical pore structure constructed by activated carbon and mesoporous silica is conducive to the rapid mass transfer and enrichment of pollutants, while magnesium oxide further enhances the material's adsorption capacity for acidic sulfur-containing gases, thus forming a composite adsorption system that combines physical and chemical adsorption.
[0018] Compared with existing adsorption materials, the composite adsorption material obtained by this invention can still maintain high adsorption efficiency and stable purification performance under high humidity and sulfur-containing conditions. It is not prone to pore blockage and active site deactivation. It has excellent sulfur resistance, moisture resistance, recycling performance and long-term operational stability, which can meet the application requirements of continuous and efficient purification of complex industrial organic waste gas. Attached Figure Description
[0019] The invention will now be further described with reference to the accompanying drawings.
[0020] Figure 1 A comparison chart showing the sulfur resistance life test results of samples with different formulation ratios. Detailed Implementation
[0021] The present invention will be further described below with reference to specific embodiments. However, the present invention is not limited to the following embodiments. Equivalent adjustments made without departing from the spirit and essence of the present invention should also be considered to fall within the protection scope of the present invention.
[0022] Example 1: The purpose of this example is to verify the purification effect of the composite adsorbent material obtained under the conditions of using the lower limit ratio of each component and a low reaction intensity on industrial organic waste gas.
[0023] S1. Weigh 100 parts of 13X molecular sieve, 3 parts of KH550, 50 parts of ethanol and 60 parts of deionized water. Add the 13X molecular sieve to a mixed solvent of ethanol and deionized water and stir to disperse at 300 rpm. Then add KH550 and react at 50°C for 2 h to obtain KH550 grafted modified 13X molecular sieve. Disperse 5 parts of cerium oxide in deionized water and mix with the above product. React at 50°C for 2 h. After the reaction, wash once with deionized water and once with ethanol, and dry at 80°C for 4 h to obtain KH550-cerium oxide synergistic grafted modified 13X molecular sieve. S2. Weigh 1 part histidine, 20 parts activated carbon, 2 parts magnesium oxide and 10 parts mesoporous silica, and mix them at 200 rpm for 20 min at room temperature to obtain a mixture; then add 80 parts KH550-cerium oxide synergistic graft modified 13X molecular sieve and 0.5 parts polytetrafluoroethylene micro powder, mix evenly and then add 2 parts binder, which is prepared by mixing silica sol and sodium carboxymethyl cellulose at a mass ratio of 5:1. Continue mixing at 300 rpm for 30 min to obtain a shaped mixture; S3. The shaped mixture is formed by pressing and drying at 80°C for 4 hours to obtain a sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas.
[0024] Example 2: The purpose of this example is to verify the effect of the synergistic effect between the components on improving sulfur resistance, moisture resistance and organic waste gas purification performance when the components are in an intermediate ratio and under appropriate reaction conditions.
[0025] S1. Weigh 100 parts of 13X molecular sieve, 8 parts of KH550, 75 parts of ethanol and 90 parts of deionized water. Add the 13X molecular sieve to a mixed solvent of ethanol and deionized water and stir to disperse at 500 rpm. Then add KH550 and react at 70℃ for 4 h to obtain KH550 grafted modified 13X molecular sieve. Disperse 10 parts of cerium oxide in deionized water and mix with the above product. React at 75℃ for 5 h. After the reaction, wash with deionized water and ethanol 3 times each and dry at 100℃ for 8 h to obtain KH550-cerium oxide synergistic grafted modified 13X molecular sieve. S2. Weigh out 8 parts of histidine, 50 parts of activated carbon, 11 parts of magnesium oxide and 30 parts of mesoporous silica, and mix them at 500 rpm for 40 min at room temperature to obtain a mixture; then add 115 parts of KH550-cerium oxide synergistic graft modified 13X molecular sieve and 4 parts of polytetrafluoroethylene micro powder, mix evenly and then add 8 parts of binder, which is prepared by mixing silica sol and sodium carboxymethyl cellulose at a mass ratio of 10:1. Continue mixing at 600 rpm for 60 min to obtain a shaped mixture. S3. The shaped mixture is formed by extrusion molding and dried at 100℃ for 8 hours to obtain a sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas.
[0026] Example 3: The purpose of this example is to verify the comprehensive purification performance and stability of the composite adsorbent material obtained under the conditions of using the upper limit ratio of each component and a high reaction intensity.
[0027] S1. Weigh 100 parts of 13X molecular sieve, 12 parts of KH550, 100 parts of ethanol, and 120 parts of deionized water. Add the 13X molecular sieve to a mixed solvent of ethanol and deionized water and stir to disperse at 800 rpm. Then add KH550 and react at 80℃ for 6 h to obtain KH550 grafted modified 13X molecular sieve. Disperse 15 parts of cerium oxide in deionized water and mix with the above product. React at 90℃ for 8 h. After the reaction, wash with deionized water and ethanol 5 times each and dry at 120℃ for 12 h to obtain KH550-cerium oxide synergistic grafted modified 13X molecular sieve. S2. Weigh 15 parts of histidine, 80 parts of activated carbon, 20 parts of magnesium oxide and 50 parts of mesoporous silica, and mix them at 800 rpm for 60 min at room temperature to obtain a mixture. Then add 150 parts of KH550-cerium oxide synergistic graft modified 13X molecular sieve and 8 parts of polytetrafluoroethylene micro powder, mix evenly and then add 15 parts of binder. The binder is prepared by mixing silica sol and sodium carboxymethyl cellulose at a mass ratio of 20:1. Continue mixing at 1000 rpm for 120 min to obtain a shaped mixture. S3. The shaped mixture is shaped by granulation and dried at 120℃ for 12 hours to obtain a sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas.
[0028] Comparative Example 1: The purpose of this comparative example is to verify the effect of KH550 graft modification and cerium oxide loading synergistic modification on the performance of composite adsorbent materials.
[0029] S1. Weigh 100 parts of 13X molecular sieve, 8 parts of KH550, 75 parts of ethanol and 90 parts of deionized water. Add the 13X molecular sieve to a mixed solvent of ethanol and deionized water and stir to disperse at 500 rpm. Then add KH550 and react at 70℃ for 4 h to obtain KH550 grafted modified 13X molecular sieve. After the reaction, wash with deionized water and ethanol 3 times each and dry at 100℃ for 8 h to obtain KH550 grafted modified 13X molecular sieve. S2. Weigh out 8 parts of histidine, 50 parts of activated carbon, 11 parts of magnesium oxide and 30 parts of mesoporous silica, and mix them at 500 rpm for 40 min at room temperature to obtain a mixture; then add 115 parts of KH550 grafted modified 13X molecular sieve and 4 parts of polytetrafluoroethylene micro powder, mix evenly and then add 8 parts of binder, which is prepared by mixing silica sol and sodium carboxymethyl cellulose at a mass ratio of 10:1. Continue mixing at 600 rpm for 60 min to obtain a shaped mixture. S3. The mixture is formed by extrusion molding and dried at 100°C for 8 hours to obtain the adsorbent material.
[0030] Comparative Example 2: The purpose of this comparative example is to verify the effect of cerium oxide loading modification and KH550 graft synergistic modification on the performance of composite adsorbent materials.
[0031] S1. Weigh 100 parts of 13X molecular sieve, 10 parts of cerium oxide and 90 parts of deionized water. Disperse the cerium oxide in the deionized water and mix it with the 13X molecular sieve. React at 75℃ for 5 hours. After the reaction, wash with deionized water and ethanol three times each, and dry at 100℃ for 8 hours to obtain cerium oxide-supported modified 13X molecular sieve. S2. Weigh 8 parts of histidine, 50 parts of activated carbon, 11 parts of magnesium oxide and 30 parts of mesoporous silica, and mix them at 500 rpm for 40 min at room temperature to obtain a mixture; then add 115 parts of cerium oxide-supported modified 13X molecular sieve and 4 parts of polytetrafluoroethylene micro powder, mix evenly and then add 8 parts of binder, which is prepared by mixing silica sol and sodium carboxymethyl cellulose at a mass ratio of 10:1. Continue mixing at 600 rpm for 60 min to obtain a shaped mixture. S3. The mixture is formed by extrusion molding and dried at 100°C for 8 hours to obtain the adsorbent material.
[0032] Comparative Example 3: The purpose of this comparative example is to verify the effect of histidine on the sulfur resistance, moisture resistance and organic waste gas purification performance of the composite adsorbent material.
[0033] S1. Weigh 100 parts of 13X molecular sieve, 8 parts of KH550, 75 parts of ethanol and 90 parts of deionized water. Add the 13X molecular sieve to a mixed solvent of ethanol and deionized water and stir to disperse at 500 rpm. Then add KH550 and react at 70℃ for 4 h to obtain KH550 grafted modified 13X molecular sieve. Disperse 10 parts of cerium oxide in deionized water and mix with the above product. React at 75℃ for 5 h. After the reaction, wash with deionized water and ethanol 3 times each and dry at 100℃ for 8 h to obtain KH550-cerium oxide synergistic grafted modified 13X molecular sieve. S2. Weigh 50 parts of activated carbon, 11 parts of magnesium oxide and 30 parts of mesoporous silica, and mix them at 500 rpm for 40 min at room temperature to obtain a mixture. Then add 115 parts of KH550-cerium oxide synergistic graft modified 13X molecular sieve and 4 parts of polytetrafluoroethylene micro powder, mix evenly and then add 8 parts of binder. The binder is prepared by mixing silica sol and sodium carboxymethyl cellulose at a mass ratio of 10:1. Continue mixing at 600 rpm for 60 min to obtain a shaped mixture. S3. The mixture is formed by extrusion molding and dried at 100°C for 8 hours to obtain the adsorbent material.
[0034] Performance testing: 1. Sulfur resistance life test The adsorbent materials prepared in the examples and comparative examples were respectively loaded into fixed-bed adsorption devices, with a loading amount of 50g. Simulated sulfur-containing waste gas containing 1000ppm hydrogen sulfide, 500ppm methanethiol, and nitrogen balance was prepared and continuously introduced into the adsorption bed at a flow rate of 100mL / min, with the test temperature controlled at 25℃. The concentration of hydrogen sulfide in the outlet gas was monitored in real time using a gas chromatograph. When the outlet hydrogen sulfide concentration reached 10% of the inlet concentration, the corresponding operating time was recorded as the sulfur resistance lifetime of the adsorbent material, in hours (h). The longer the sulfur resistance lifetime, the stronger the material's ability to resist poisoning and deactivation by sulfur-containing pollutants.
[0035] 2. VOC adsorption capacity test under high humidity conditions The adsorbent materials prepared in the examples and comparative examples were placed in a dynamic adsorption device and pre-equilibrated for 24 hours with air at a relative humidity of 85%. Subsequently, simulated organic waste gas containing 1000 ppm toluene was introduced, with a flow rate controlled at 100 mL / min and a test temperature of 25°C. The outlet toluene concentration was detected using gas chromatography, and the dynamic adsorption capacity of the adsorbent material per unit mass for toluene was calculated based on the breakthrough curve, expressed in mg / g. A higher adsorption capacity indicates that the material still has a strong adsorption capacity for organic waste gas under high humidity conditions.
[0036] 3. Organic waste gas removal rate test The adsorbent materials prepared in the examples and comparative examples were loaded into a fixed-bed reactor. A mixed organic waste gas containing 1000 ppm toluene, 800 ppm ethyl acetate, and 800 ppm acetone was prepared and continuously introduced into the adsorption bed at a flow rate of 100 mL / min. The test temperature was controlled at 25°C. The inlet and outlet gas concentrations were measured separately, and the removal rate of the mixed organic waste gas was calculated according to the formula: Removal rate = (Inlet gas concentration - Outlet gas concentration) / Inlet gas concentration × 100%. The higher the removal rate, the better the purification effect of the material on complex industrial organic waste gas.
[0037] 4. Cyclic stability test The adsorbent materials prepared in the examples and comparative examples were subjected to adsorption-regeneration cycle tests. First, toluene waste gas was used for adsorption testing. After the adsorption reached the breakthrough condition, desorption and regeneration were performed using hot air at 120°C for 2 hours. After the material cooled to room temperature, the adsorption test was performed again, and this cycle was repeated 5 times. The toluene adsorption capacity of the adsorbent material after the fifth cycle was recorded, and the adsorption capacity retention rate was calculated as the ratio of the adsorption capacity of the fifth cycle to the adsorption capacity of the first cycle, expressed as a percentage. A higher adsorption capacity retention rate indicates better cycle regeneration performance and long-term operational stability of the material.
[0038] Table 1. Performance test results of the examples and comparative examples.
[0039] As shown in Table 1, the examples and comparative examples exhibit significant differences in sulfur resistance lifespan, VOC adsorption capacity under high humidity conditions, organic waste gas removal rate, and cycle stability. Specifically, the performance of Examples 1-3 is superior to that of Comparative Examples 1-3, indicating that the KH550-cerium oxide synergistic grafted modified 13X molecular sieve and histidine synergistic system constructed in this invention can effectively improve the comprehensive purification performance of adsorbent materials for complex industrial organic waste gases.
[0040] The sulfur resistance life test results show that Example 2 achieved a sulfur resistance life of 156 hours, significantly higher than Examples 1 and 3, as well as the comparative examples. Comparative Examples 1 and 2, modified with KH550 and cerium oxide respectively, had sulfur resistance lives of only 84 hours and 90 hours, indicating that the introduction of KH550 or cerium oxide alone can improve the sulfur resistance of the material to some extent, but the improvement effect is limited. When the two work synergistically, they can simultaneously enhance the surface stability of the molecular sieve and the ability to capture sulfur-containing pollutants, thereby significantly improving the material's ability to resist the poisoning and deactivation of sulfur-containing pollutants such as hydrogen sulfide and thiols. Meanwhile, the sulfur resistance life of Comparative Example 3 was 122 hours, lower than that of Example 2, indicating that the imidazole and amino functional groups in histidine can further promote the adsorption and fixation of sulfur-containing pollutants, thereby extending the effective service life of the material.
[0041] The test results of VOC adsorption capacity and organic waste gas removal rate under high humidity conditions show that Example 2 achieved a VOC adsorption capacity of 312 mg / g and an organic waste gas removal rate of 97.8%, both the highest values among all samples. Analysis suggests that KH550 grafting reduced the affinity of the molecular sieve surface for water molecules, decreasing competition for adsorption sites from water vapor under high humidity conditions; the introduction of cerium oxide increased the number of active adsorption centers on the material surface; and histidine further provided polar functional group sites, which is beneficial for enhancing the interaction between the material and polar organic pollutants. Therefore, the synergistic effect of these components enabled the material to maintain high VOC adsorption capacity and purification efficiency under high humidity conditions. In contrast, Comparative Examples 1, 2, and 3, lacking the corresponding key components, showed varying degrees of decrease in adsorption capacity and removal rate.
[0042] The cyclic stability test results show that Example 2 maintained a 95.3% adsorption capacity retention rate after multiple adsorption-regeneration cycles, significantly higher than the comparative examples. This indicates that the composite adsorption system constructed in this invention has good structural stability and regeneration performance. Specifically, the KH550 graft layer helps improve the stability of the material surface, cerium oxide reduces the irreversible poisoning effect of sulfur-containing pollutants on the active sites, and histidine helps improve the utilization efficiency of the active sites, thus jointly ensuring the performance stability of the material during long-term cyclic use. Although the content of active components in Example 3 is further increased, the mass transfer efficiency decreases due to partial pore coverage, therefore its overall performance is slightly lower than that of Example 2.
[0043] In summary, this invention achieves simultaneous improvements in sulfur resistance, moisture resistance, organic waste gas purification performance, and cycle stability by constructing a composite adsorption system with KH550-cerium oxide synergistic grafting modification of 13X molecular sieve and histidine synergistic effect. Example 2, in particular, exhibits optimal comprehensive performance when the component ratios and process conditions are optimally matched, fully demonstrating the effectiveness and superiority of the technical solution of this invention.
Claims
1. A sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas, characterized in that, The raw materials include the following parts by weight: 80-150 parts of KH550-cerium oxide synergistic graft modified 13X molecular sieve; 1-15 parts of histidine; 20-80 parts of activated carbon; 2-20 parts of magnesium oxide; 10-50 parts of mesoporous silica; 0.5-8 parts of polytetrafluoroethylene micro powder; and 2-15 parts of binder. The KH550-cerium oxide synergistic graft modified 13X molecular sieve is a composite modified molecular sieve prepared by silanizing and grafting 13X molecular sieve with KH550, followed by cerium oxide loading treatment.
2. The sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas according to claim 1, characterized in that, The KH550-cerium oxide synergistic grafting modified 13X molecular sieve comprises the following raw materials in parts by weight: 100 parts of 13X molecular sieve; 3-12 parts of KH550; 5-15 parts of cerium oxide; 50-100 parts of ethanol; and 60-120 parts of deionized water.
3. The sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas according to claim 1 or 2, characterized in that, The preparation method of the KH550-cerium oxide synergistic graft modified 13X molecular sieve includes the following steps: (1) 13X molecular sieve was mixed with KH550 and grafted to obtain KH550 grafted 13X molecular sieve. (2) KH550 graft-modified 13X molecular sieve was subjected to loading modification treatment with cerium oxide to obtain the loading modified product; (3) The loaded modified product was separated, washed and dried to obtain KH550-cerium oxide synergistic graft modified 13X molecular sieve.
4. The sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas according to claim 3, characterized in that, The reaction conditions for step (1) are as follows: ethanol and deionized water are used as a mixed solvent, the mass ratio of the mixed solvent to 13X molecular sieve is 1.5:1 to 3:1, the reaction is carried out at 50 to 80°C for 2 to 6 hours, and the stirring speed is 300 to 800 rpm during the reaction.
5. The sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas according to claim 3, characterized in that, The reaction conditions for step (2) are as follows: cerium oxide is dispersed in deionized water and then mixed with the product obtained in step (1), and reacted at 50-90°C for 2-8 hours, with a stirring speed of 300-800 rpm during the reaction.
6. The sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas according to claim 3, characterized in that, The reaction conditions for step (3) are washing with deionized water and ethanol 1 to 5 times, followed by drying at 80 to 120°C for 4 to 12 hours.
7. The sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas according to claim 1, characterized in that, The binder is a mixture of silica sol and sodium carboxymethyl cellulose in a mass ratio of 5:1 to 20:
1.
8. A method for preparing a sulfur-resistant and moisture-resistant composite adsorbent for purifying industrial organic waste gas, characterized in that, The preparation method includes the following steps: S1, Histidine, activated carbon, magnesium oxide and mesoporous silica are mixed evenly to obtain a mixture; S2, add KH550-cerium oxide synergistic grafted modified 13X molecular sieve and polytetrafluoroethylene micro powder to the mixture, mix evenly, add binder, continue mixing, and obtain shaped mixture. S3. The shaped mixture is shaped and dried to obtain a sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas.
9. The preparation method of a sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas according to claim 8, characterized in that, The mixing conditions for step S1 are: mixing at room temperature for 20 to 60 minutes and mixing speed of 200 to 800 rpm.
10. The preparation method of a sulfur-resistant and moisture-resistant composite adsorption material for purifying industrial organic waste gas according to claim 8, characterized in that, The mixing conditions for step S2 are: after adding the binder, continue mixing for 30 to 120 minutes, and the mixing speed is 300 to 1000 rpm; the molding method for step S3 is one of extrusion molding, sheet molding, or granulation molding, and the drying conditions are: drying at 80 to 120°C for 4 to 12 hours.