Graft-modified polystyrene primary amine resin adsorption material and preparation method thereof
Graft-modified polystyrene primary amine resin adsorbent materials were prepared by acylation and nucleophilic substitution reactions of acyl halides with polystyrene primary amine resins. This solved the problems of limited active sites on the support and poor controllability of the grafting process, achieving high CO2 adsorption capacity and good cycling stability, making it suitable for industrial-grade carbon capture.
Patent Information
- Application Number
- CN202511016697.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-23
- Publication Date
- 2025-11-04
AI Technical Summary
Existing chemical grafting technology suffers from limitations on the active sites on the carrier surface, poor controllability of the grafting process, contradictions between environmental friendliness and scale-up production, and an imbalance in overall performance, resulting in insufficient CO2 adsorption capacity and cycle stability of solid amine adsorbent materials.
Acylation reaction of acyl halides with polystyrene primary amine resin was carried out to form a high-density amine network through nucleophilic substitution reaction. Combined with mild reaction conditions and a suitable solvent system, graft-modified polystyrene primary amine resin adsorbent materials were prepared.
It significantly improves CO2 adsorption capacity and cycling stability, with an amine loading of over 9 mmol/g, a CO2 saturation adsorption loss rate of ≤2.0%, and excellent water resistance, with a CO2 saturation adsorption loss rate of ≤3.0%.
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Figure CN120888019A_ABST
Abstract
Description
TECHNICAL FIELD
[0001] The present application relates to the technical field of solid amine adsorption materials, and particularly relates to a grafted modified polystyrene primary amine resin adsorption material and a preparation method thereof. BACKGROUND
[0002] Under the background of global climate change, efficient capture and storage (CCS) of greenhouse gases such as carbon dioxide has become a key technical path to achieve the "double carbon" goal. Industrial emission sources (such as coal-fired power plants, steel plants, and cement plants) are the main anthropogenic CO2 emission sources, and their emission control is of strategic significance to global climate governance. Although the traditional liquid amine absorption method (such as monoethanolamine MEA solution) has been commercialized and applied, it has inherent defects such as high energy consumption for regeneration (accounting for 50-70% of the capture cost), severe equipment corrosion, solvent volatilization degradation, and entrainment loss, which makes it difficult to meet the cost reduction and efficiency improvement needs of large-scale industrial carbon capture.
[0003] Solid amine adsorption materials are considered as the core direction of the next generation of carbon capture technology due to their low energy consumption for regeneration (such as temperature / pressure swing adsorption), non-corrosive, no solvent volatilization, and easy operation. The core design principle is to fix high CO2 affinity amine groups (primary amine, secondary amine, tertiary amine, etc.) on the surface of a porous solid carrier (mesoporous silica, alumina, activated carbon, polymer, etc.) through physical loading or chemical bonding, and to realize efficient adsorption by using the reversible reaction of amine groups and CO2. Among them, the chemical grafting method anchors the amine groups on the surface of the carrier through covalent bonds, which can effectively solve the problems of poor cycle stability caused by amine molecule leaching, migration, and aggregation, significantly prolonging the service life of the material, and becoming a key modification means to improve the practical performance of solid amine materials.
[0004] However, the existing chemical grafting technology still faces the following core bottlenecks: Limitation of active sites on the surface of the carrier: the low and uneven distribution of hydroxyl groups on the surface of traditional carriers (such as commercial silica) limits the theoretical amine loading (usually <2.0 mmol / g), and the actual CO2 adsorption capacity is difficult to break through 4.0 mmol / g (dry basis), which is far lower than the adsorption level of liquid amine solution; Poor controllability of the grafting process: existing methods mostly rely on pretreatment of the carrier with silane coupling agents, but the reaction conditions are harsh (high temperature, strong acid / strong base), which easily leads to collapse of the carrier structure or side reactions (such as excessive crosslinking of amine groups), making it difficult to precisely control the type (primary / secondary / tertiary amine ratio) and spatial distribution of amine groups; Conflict between environmental friendliness and scale-up production: traditional grafting processes use toxic organic solvents (such as toluene, DMF) or corrosive reagents (such as hydrochloric acid, ammonia), which not only increase the environmental burden, but also easily cause equipment corrosion and solvent recovery problems in large-scale production; Performance imbalance: Although the existing materials have certain cycle stability (usually > 50 times), the balance between adsorption capacity and regeneration energy consumption has not been broken through, and it is difficult to meet the requirements of industrial level capture efficiency (> 90%) and economy (regeneration energy consumption < 2.5 MJ / kg CO2).
[0005] In summary, developing a new solid amine adsorption material grafting modification method with mild conditions, high grafting efficiency, few side reactions, controllable amine group type and distribution, environmental friendliness and easy amplification is the key to breaking through the bottleneck of existing technology and promoting the industrial application of solid amine materials. The present invention is just aimed at the above core needs, and proposes an innovative chemical grafting technology route, which aims to significantly improve the comprehensive performance (high capacity and high stability) of solid amine adsorption materials and reduce the preparation cost, providing an efficient, economical and environmentally friendly solution for industrial carbon capture. SUMMARY
[0006] The problem existing in the prior art is that the CO2 adsorption capacity of the conventional chemically grafted and modified solid amine adsorption material is difficult to break through 4.0 mmol / g. In view of the above technical problems, the present invention provides a grafted and modified polystyrene primary amine resin adsorption material, which is obtained by acylation reaction of the primary amine group of polystyrene primary amine resin with an acylating agent to obtain an intermediate, and then by nucleophilic substitution reaction of the intermediate with an amine compound to obtain a product. The acylating agent is acyl halide, and the chemical formula of the acyl halide is XCH2COX', X and X' are both halogen. The amine compound is one or more of ethylenediamine and polyethylene polyamine.
[0007] Preferably, the polystyrene primary amine resin includes one or more of Purolite A110, Suqing D309 and Lewatit VP OC1065.
[0008] Preferably, the acyl halide includes bromoacetyl bromide, bromoacetyl chloride or chloroacetyl chloride.
[0009] Preferably, the polyethylene polyamine includes one or more of diethylene triamine, triethylene tetramine, tetraethylene pentamine and pentaethylene hexamine.
[0010] Preferably, the acid binding agent used in the acylation reaction is one of sodium carbonate, sodium acetate, triethylamine, N,N-diisopropyl ethylamine and potassium carbonate.
[0011] Preferably, the amount ratio of polystyrene primary amine resin to acylating agent in the acylation reaction is 1g:6-12mmol.
[0012] Preferably, the preparation method of the grafted and modified polystyrene primary amine resin adsorption material includes the following steps: (1) adding polystyrene primary amine resin and an acid binding agent into organic solvent I, stirring and mixing uniformly, and cooling to-5℃ to 5℃, then adding an acylation reagent, and stirring and reacting at constant temperature under low temperature, after the reaction is completed, an intermediate is obtained; (2) adding the intermediate and an amine compound into organic solvent II, stirring and reacting at constant temperature under low temperature, after the reaction is completed, removing the filtrate, and obtaining a crude product of the adsorption material; (3) washing the crude product of the adsorption material with ethanol, deionized water, hydrochloric acid, deionized water, sodium hydroxide aqueous solution and deionized water in sequence until the filtrate is neutral, and then drying to obtain the grafted modified polystyrene primary amine resin adsorption material.
[0013] Preferably, the reaction temperature in step (1) is 0-10℃.
[0014] Preferably, the reaction temperature in step (2) is 10-20℃.
[0015] The present application has the following beneficial effects: The grafted modified polystyrene primary amine resin adsorption material and the CO2 adsorption method thereof provided by the present application realize a breakthrough in adsorption performance through precisely controlled grafting chemistry and process design, and the specific effects are as follows: (1) CO2 adsorption capacity is significantly improved The long-chain polyamine (such as pentaethylenehexamine) grafted on the resin surface forms a high-density amine group network (primary amine / secondary amine / tertiary amine synergistically), and the amine group loading of the unit resin reaches 9mmol / g or more, which is much higher than that of the unmodified resin (6mmol / g); (2) CO2 adsorption cycle stability is excellent The covalent grafting structure avoids amine loss, and after 20 adsorption-regeneration cycles, the loss rate of CO2 saturated adsorption capacity is ≤2.0%, which is significantly better than liquid amine which is easy to degrade or physically loaded solid amine; (3) The grafted modified polystyrene primary amine resin adsorption material obtained by the present application has excellent water resistance, and after being soaked in boiling water for 24 h, the loss rate of CO2 saturated adsorption capacity is ≤3.0%. BRIEF DESCRIPTION OF DRAWINGS
[0016] Figure 1 : is the infrared (FTIR) spectrum of Purolite A110, the intermediate and the grafted modified polystyrene primary amine resin adsorption material in Example 1 of the present application.
[0017] Figure 2 : is the CO2 adsorption process curve of MZBJ-1 obtained in Example 1 of the present application. DETAILED DESCRIPTION
[0018] The application will be described in detail below with reference to the examples. However, it should be understood that the examples below are only illustrative of the embodiments of the application and are not intended to limit the scope of the application.
[0019] Example 1
[0020] A preparation method of the grafted modified polystyrene primary amine resin adsorbent material is as follows: (1) 1.0 g of Purolite A110 and 0.64 g of sodium carbonate (6 mmol) were taken in 5 mL of dichloromethane, stirred uniformly, cooled to -5°C, and then 1.82 g of bromoacetyl bromide (9 mmol) was added to the reaction system, the temperature of the reaction system was controlled at 0°C, and stirred for 4 h. After removing the filtrate, an intermediate was obtained; (2) 5 mL of dichloromethane was added to 1.4 g of the intermediate, stirred uniformly, cooled to 10°C, and then 9.29 g of pentaethylenehexamine (40 mmol) was added. The reaction was stirred at 20°C for 15 h, and the filtrate was removed to obtain a crude adsorbent material; (3) The crude adsorbent material was washed with ethanol, deionized water, 1 mol / L hydrochloric acid, deionized water, 1 mol / L sodium hydroxide aqueous solution, and deionized water in sequence until the filtrate after washing was neutral. Then, the product was dried at 65°C to obtain 1.61 g of the grafted modified polystyrene primary amine resin adsorbent material, which was recorded as MZBJ-1. The infrared (FTIR) spectra of Purolite A110, the intermediate, and the grafted modified polystyrene primary amine resin adsorbent material in Example 1 of the application are shown in the accompanying drawings of the specification, wherein A110 refers to Purolite A110 and the product refers to MZBJ-1. The CO2 adsorption process curve of MZBJ-1 obtained in Example 1 of the application is shown in the accompanying drawings of the specification. Figure 1 Figure 2
[0021] Example 2
[0022] A preparation method of the grafted modified polystyrene primary amine resin adsorbent material is as follows: (1) 1.0 g of Suqing D309 and 1.11 g of potassium carbonate (8 mmol) were taken in 6 mL of chloroform, stirred uniformly, cooled to 0°C, and then 1.42 g of bromoacetyl chloride (9 mmol) was added to the reaction system, the temperature of the reaction system was controlled at 5°C, and stirred for 4 h. After removing the filtrate, an intermediate was obtained; (2) 6 mL of chloroform was added to 1.2 g of the intermediate, stirred uniformly, cooled to 8°C, and then 5.68 g of tetraethylenepentamine (30 mmol) was added. The reaction was stirred at 18°C for 12 h, and the filtrate was removed to obtain a crude adsorbent material; (3) The crude adsorbent material is washed with ethanol, deionized water, 1 mol / L hydrochloric acid, deionized water, 1 mol / L sodium hydroxide solution and deionized water in sequence until the filtrate after washing is neutral, and then dried at 65°C to obtain 1.58 g of the grafted modified polystyrene primary amine resin adsorbent material, which is recorded as MZBJ-2.
[0023] Example 3
[0024] A preparation method of a grafted modified polystyrene primary amine resin adsorbent material is as follows: (1) 1.0 g of Purolite A110 and 1.29 g of N,N-diisopropylethylamine (10 mmol) are taken in 5 mL of cyclohexane, uniformly stirred, cooled to 0°C, and then 2.42 g of bromoacetyl bromide (12 mmol) is added to the reaction system, the temperature of the reaction system is controlled to be 5°C, and stirring is performed for 1 h. After removing the filtrate, an intermediate is obtained; (2) 5 mL of cyclohexane is added to 1.3 g of the intermediate, uniformly stirred, cooled to 5°C, and then 4.39 g of triethylenetetramine (30 mmol) is added. Stirring is performed at 15°C for 10 h, the filtrate is removed, and a crude adsorbent material is obtained; (3) The crude adsorbent material is washed with ethanol, deionized water, 1 mol / L hydrochloric acid, deionized water, 1 mol / L sodium hydroxide solution and deionized water in sequence until the filtrate after washing is neutral, and then dried at 65°C to obtain 1.58 g of the grafted modified polystyrene primary amine resin adsorbent material, which is recorded as MZBJ-2.
[0025] Example 4
[0026] A preparation method of a grafted modified polystyrene primary amine resin adsorbent material is as follows: (1) 1.0 g of Lewatit VP OC 1065 and 1.01 g of triethylamine (10 mmol) are taken in 8 mL of toluene, uniformly stirred, cooled to 5°C, and then 1.36 g of chloroacetyl chloride (12 mmol) is added to the reaction system. The temperature of the reaction system is controlled to be 10°C, and stirring is performed for 2 h. After removing the filtrate, an intermediate is obtained; (2) 8 mL of toluene is added to 1.1 g of the intermediate, uniformly stirred, cooled to 5°C, and then 4.13 g of diethylenetriamine (40 mmol) is added. Stirring is performed at 15°C for 8 h, the filtrate is removed, and a crude adsorbent material is obtained; (3) The crude adsorbent material is sequentially washed with ethanol, deionized water, 1 mol / L hydrochloric acid, deionized water, 1 mol / L sodium hydroxide solution, and deionized water until the filtrate after washing is neutral, and then dried at 65°C to obtain 1.45 g of the grafted modified polystyrene primary amine resin adsorbent material, which is denoted as MZBJ-4.
[0027] Example 5
[0028] A preparation method of a grafted modified polystyrene primary amine resin adsorbent material is as follows: (1) 1.0 g of Sartomer D309 and 0.98 g of sodium acetate (12 mmol) are added to 5 mL of dichloromethane, stirred uniformly, and then cooled to -5°C. Then, 0.94 g of bromoacetyl chloride (6 mmol) is added to the reaction system, the temperature of the reaction system is controlled to be 0°C, and stirring is performed for 2 h. After removing the filtrate, an intermediate is obtained; (2) 5 mL of dichloromethane is added to 1.2 g of the intermediate, stirred uniformly, and then cooled to 0°C. Then, 3.60 g of ethylenediamine (60 mmol) is added, stirring is performed at 10°C for 5 h, and the filtrate is removed to obtain a crude adsorbent material; (3) The crude adsorbent material is sequentially washed with ethanol, deionized water, 1 mol / L hydrochloric acid, deionized water, 1 mol / L sodium hydroxide solution, and deionized water until the filtrate after washing is neutral, and then dried at 65°C to obtain 1.45 g of the grafted modified polystyrene primary amine resin adsorbent material, which is denoted as MZBJ-4.
[0029] Example 6
[0030] A preparation method of a grafted modified polystyrene primary amine resin adsorbent material is as follows: (1) 1.0 g of Lewatit VP OC 1065 and 1.59 g of sodium carbonate (15 mmol) are added to 10 mL of toluene, stirred uniformly, and then cooled to 0°C. Then, 0.68 g of chloroacetyl chloride (6 mmol) is added to the reaction system, the temperature of the reaction system is controlled to be 5°C, and stirring is performed for 2 h. After removing the filtrate, an intermediate is obtained; (2) 10 mL of toluene is added to 1.2 g of the intermediate, stirred uniformly, and then cooled to 5°C. Then, 4.65 g of pentaethylenehexamine (20 mmol) is added, stirring is performed at 15°C for 15 h, and the filtrate is removed to obtain a crude adsorbent material; (3) The crude adsorbent material was washed successively with ethanol, deionized water, 1 mol / L hydrochloric acid, deionized water, 1 mol / L sodium hydroxide solution, and deionized water until the filtrate after washing was neutral. Then, 1.56 g of the grafted polystyrene primary amine resin adsorbent material was obtained by drying at 65°C, and was recorded as MZBJ-6.
[0031] Comparative Example 1 was pure Purolite A110.
[0032] Comparative Example 2 was pure Suqing D309.
[0033] Comparative Example 3 was Lewatit VP OC 1065.
[0034] Comparative Example 4 was the same as Example 4, except that the amount of chloroacetyl chloride used in the preparation of the intermediate in Comparative Example 4 was 3 mmol.
[0035] Comparative Example 5 was the same as Example 4, except that the amount of chloroacetyl chloride used in the preparation of the intermediate in Comparative Example 5 was 15 mmol.
[0036] Comparative Example 6 was the same as Example 4, except that sodium hydroxide was used as the acid-binding agent in the preparation of the intermediate in Comparative Example 6.
[0037] Performance test
[0038] (1) Amine loading (E): 0.1 g of the grafted polystyrene primary amine resin adsorbent material was weighed into a 100 mL conical flask, 50 mL of a 0.10 mol / L HCl solution was added, and the mixture was shaken in a water bath at 25°C for 12 h. Then, 10 mL of the supernatant was removed, and titrated with a 0.05 mol / L NaOH solution until a faint red color was obtained, which persisted for 15 s. The volume of the NaOH solution consumed was V (mL). The test was repeated three times, and the amine loading was calculated according to the following formula:
[0039] Adsorption capacity (Q): refers to the saturated adsorption capacity of the grafted polystyrene primary amine resin adsorbent material for carbon dioxide, and is measured in mmol / g. The DVS constant-pressure dynamic weight method was used, and the test was performed as follows: about 30 mg of the material sample was weighed into a crucible, and was purged with high-purity nitrogen at a flow rate of 400 SCCM while being heated at a rate of 10°C / min to 105°C. The temperature and the high-purity nitrogen flow rate were maintained for 60 min or more until the sample weight was constant. Then, the sample was cooled to 25°C, and the weight was measured as G0. The high-purity nitrogen was switched to carbon dioxide (M A ), the sample was continuously purged at a flow rate of 400 SCCM until the sample was saturated with adsorption again, and the weight of the sample was measured as G1. The saturated adsorption amount was calculated according to the formula Q = [(G1-G0) / M A ] / G0, with the unit of mmol / g.
[0040] (3) Cycle stability: the adsorption amount of the grafted modified polystyrene primary amine resin adsorption material after 20 adsorption-desorption cycles and the loss rate compared with the initial adsorption amount were represented.
[0041] (4) Water loss rate: 0.3 g of the grafted modified polystyrene primary amine resin adsorption material was weighed in a reaction bottle, deionized water was added to submerge it, and after heating at 100°C for 24 h, the material was taken out and vacuum dried at 60 C to constant weight, and the CO2 adsorption amount was measured by DVS constant pressure dynamic weight method. The loss rate was calculated by comparing the adsorption amount of the material after water with the adsorption amount of the fresh material.
[0042] According to the above test method, the test results are shown in Table 1: Table 1
[0043] According to the data in Table 1, it can be seen that the grafted modified polystyrene primary amine resin adsorption material obtained by the present application has an amine loading of 9.0 mmol / g or more, and the CO2 saturated adsorption capacity is 4.4 mmol / g or more. The grafted modified polystyrene primary amine resin adsorption material obtained by the present application has good cycle stability (the CO2 saturated adsorption amount loss rate is ≤2.0% after 20 cycles of adsorption-desorption) and water resistance (the CO2 saturated adsorption amount loss rate is ≤3.0% after being immersed in boiling water for 24 h). Compared with pure polystyrene primary amine resin, it has better adsorption effect.
[0044] Based on the above ideal embodiments according to the present application, through the above description, relevant personnel can make various changes and modifications without deviating from the technical idea of the present application. The technical scope of the present application is not limited to the contents in the specification, and the technical scope must be determined according to the scope of claims.
Claims
1. A grafted and modified polystyrene primary amine resin adsorbent material, characterized in that, The product is obtained by acylation of the primary amine group of polystyrene primary amine resin with an acylation reagent to obtain an intermediate, followed by nucleophilic substitution reaction of the intermediate with an amine compound. The acylation reagent is an acyl halide with the general chemical formula XC. COX', X, and X' are all halogens, and the amine compound is one or more of ethylenediamine and polyethylenepolyamine.
2. The grafted modified polystyrene primary amine resin adsorbent material according to claim 1, characterized in that, The polystyrene primary amine resin includes one or more of Purolite A110, Suqing D309, and Lewatit VP OC 1065.
3. The grafted modified polystyrene primary amine resin adsorbent material according to claim 1, characterized in that, The acyl halide includes bromoacetyl bromide, bromoacetyl chloride, or chloroacetyl chloride.
4. The grafted modified polystyrene primary amine resin adsorbent material according to claim 1, characterized in that, The polyethylene polyamine includes one or more of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, and pentaethylenehexamine.
5. The grafted modified polystyrene primary amine resin adsorbent material according to claim 1, characterized in that, The acid-binding agent used in the acylation reaction is one of sodium carbonate, sodium acetate, triethylamine, N,N-diisopropylethylamine, or potassium carbonate.
6. The grafted modified polystyrene primary amine resin adsorbent material according to claim 1, characterized in that, In the acylation reaction, the ratio of polystyrene primary amine resin to acylation reagent is 1 g: 6-12 mmol.
7. The grafted modified polystyrene primary amine resin adsorbent material according to claim 1, characterized in that, The preparation method includes the following steps: (1) Add polystyrene primary amine resin and acid-binding agent to organic solvent I, stir and mix evenly, and cool to -5℃ to 5℃. Then add acylation reagent, and stir the reaction at a constant temperature at low temperature. After the reaction is completed, the intermediate is obtained. (2) The intermediate and amine compound were added to organic solvent II and stirred at a constant temperature at low temperature. After the reaction was completed, the filtrate was removed to obtain crude adsorbent material. (3) The crude adsorbent material is washed thoroughly with ethanol, deionized water, hydrochloric acid, deionized water, sodium hydroxide aqueous solution and deionized water in sequence until the filtrate is neutral. After drying, the grafted modified polystyrene primary amine resin adsorbent material is obtained.
8. The grafted modified polystyrene primary amine resin adsorbent material according to claim 7, characterized in that, The reaction temperature in step (1) is 0-10℃.
9. The grafted modified polystyrene primary amine resin adsorbent material according to claim 7, characterized in that, The reaction temperature in step (2) is 10-20℃.
10. A method for CO2 adsorption, characterized in that, The grafted modified polystyrene primary amine resin adsorbent material according to any one of claims 1-9 is used as a solid amine adsorbent.