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    基于 1,3−丙二胺的少水吸收剂制备及CO2吸收特性

    Preparation and CO2 absorption characteristics of less water absorbent based on 1, 3−propylenediamine

    • 摘要: 化学吸收法作为目前广泛应用的碳捕集技术,仍然存在再生能耗高的问题,前人的研究中可以看到大量关于新型化学吸收剂如两相吸收剂、无水吸收剂的结论,但是关于少水吸收剂的研究鲜有报道。为了解决常规吸收剂吸收速率慢、吸收负荷低、分相比高的缺点,构建了以1,3−丙二胺为反应剂的少水吸收剂。通过添加不同叔胺分相剂、非水溶剂与醇胺以1∶2∶1的质量比分别组成两相吸收剂,在恒温水浴锅中保持40 ℃后,通入二氧化碳吸到溶液中进行吸收,吸收结束后测试吸收液的性能。对比吸收负荷、分相比、黏度等关键性能,筛选出性能优良的1,3−丙二胺/四甲基乙二胺与1,3−丙二胺/二乙二醇二甲醚组成的少水吸收剂,吸收二氧化碳后可以发生液液分相,其中1,3−丙二胺/四甲基乙二胺吸收负荷最高可以达到3.85 mol/kg,富相占比为54%;1,3−丙二胺/四甲基乙二胺吸收负荷最高可以达到3.11 mol/kg,富相占比为75%;再将1,3−丙二胺/四甲基乙二胺中的水替换为非水溶剂进行测试,得到1,3−丙二胺/四甲基乙二胺/二乙二醇二甲醚组成的少水吸收剂,吸收负荷为3.69 mol/kg,是30%MEA化学吸收剂吸收负荷的2.37倍,并且对比不加入非水溶剂的两相吸收剂分相比大幅下降为39%,黏度也降低为83.4 MPa·s,仅是加入前的55%,与目前研究得到的少水吸收剂黏度相当,可以匹配现有的捕集换热系统;分相时间从7 min缩短为1.5 min;分相比和黏度的大幅度降低有利于降低再生能耗。经过5次吸收—解吸循环试验测得,1,3−丙二胺/四甲基乙二胺/二乙二醇二甲醚吸收负荷在第二次吸收后逐步降低,但是降幅较小趋于稳定,循环负荷为2.64 mol/kg,具有良好的重复稳定性。经核磁检测可以推测吸收二氧化碳后的反应机理,1,3−丙二胺/四甲基乙二胺/二乙二醇二甲醚吸收二氧化碳后,1,3−丙二胺与二氧化碳反应会形成中间产物氨基甲酸酯,中间产物与1,3−丙二胺再次结合生成氨基甲酸盐;整个反应中1,3−丙二胺作为主要吸收剂,四甲基乙二胺和非水溶剂不参与吸收反应。

       

      Abstract: As a widely used carbon capture technology at present, chemical absorption method still has the problem of high renewable energy consumption. In previous studies, we can see a lot of conclusions about new chemical absorbents such as two-phase absorbents and anhydrous absorbents, but there are few reports on the research of oligohydrous absorbents. In order to solve the disadvantages of slow absorption rate, low absorption load and high specific ratio of conventional absorbents, a low-water absorbent with 1, 3−propylenediamine as the reaction agent was constructed. Two phase absorbents were formed by adding different tertiary amine phase separators, non-aqueous solvents and alcoholamine respectively. After being kept at 40 ℃ in a constant temperature water bath, carbon dioxide was sucked into the solution for absorption. After absorption, the performance of the absorbent solution was tested. The two-phase absorbent composed of 1, 3−propylenediamine/Tetramethylenediamine and 1, 3−propylenediamine/Diglyme ether with excellent performance was selected by comparing absorption load, fraction ratio and viscosity, etc. After absorbing carbon dioxide, liquid-liquid phase separation can occur, and the absorption load of 1, 3−propylenediamine/tetramethylenediamine can reach up to 3.85 mol/kg. The proportion of rich phase is 54%. The maximum absorption load of 1, 3−propylenediamine/Tetramethylenediamine was 3.11 mol/kg, and the proportion of rich phase was 75%. Then, the water in 1, 3−propylenediamine/Tetramethylenediamine was replaced by a non-aqueous solvent for testing. The absorption load of 1, 3−propylenediamine/Tetramethylenediamine/Diglyme was 3.69 mol/kg. It is 2.37 times the absorption load of 30%MEA chemical absorbent. And the fraction of the two-phase absorbent was significantly reduced to 39% and the viscosity was reduced to 83.4 MPa·s compared with that of the two-phase absorbent without adding non-aqueous solvent. Only 55% of what it was before joining. The phase separation time is reduced from 7 min to 1.5 min. The significant reduction of fraction ratio and viscosity is conducive to the reduction of renewable energy consumption. After 5 absorption−desorption cycles, the absorption load of 1, 3−propylenediamine/tetramethylenediamine/diethylene glycol dimethyl ether gradually decreased after the second absorption, but the decrease was small and tended to be stable, and the cyclic load was 2.64 mol/kg, which had good repetitive stability. The reaction mechanism after absorption of carbon dioxide can be predicted by nuclear magnetic detection. After absorption of carbon dioxide by 1, 3−propylenediamine/Tetramethylenediamine/Diglyme, 1, 3−propylenediamine reacts with carbon dioxide to form an intermediate carbamate, which recombines with 1, 3−propylenediamine to form carbamate. In the whole reaction, 1, 3−propylenediamine is the main absorbent, and tetramethylenediamine and non-aqueous solvents do not participate in the absorption reaction.

       

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