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针对CO2作为天然工质优越的制冷特性以及水合物技术在多领域的发展前景,利用水合物相平衡转折温度下压力急剧上升的特点,通过流程的创新设计,提出了一种利用CO2水合物交替生成与分解的过程来实现增压的循环系统。基于CO2复叠制冷低温级的热力学分析,结合对相平衡转折温度的考虑,通过实验表明,在套管式反应器中,0.3%(质量分数)SDS的动力学添加剂较之4%(质量分数)THF热力学添加剂更能促进CO2水合物的生成,在-2℃、1.4MPa的前提下,合成时间为60min;在0.3%SDS的溶液中,温度越低越易于水合物生成,其临界温度接近于-2℃,低于-2℃时,溶液结冰会堵塞管道;两套管式反应器交替运行,得到了-2℃合成、10℃分解的最佳循环温度,55min的最短循环时间,分解后的高压CO2气体经冷凝节流后达到了-36℃的低温。
Aiming at the superior refrigeration characteristics of CO2 as a natural working fluid and the development prospects of hydrate technology in various fields, by utilizing the characteristics that the pressure rises sharply at the equilibrium temperature of hydrate phase, an innovative design of the process is proposed to use CO2 hydrates alternately Generation and decomposition of the process to achieve pressurized circulation system. Based on the thermodynamic analysis of CO2 cascade cryogenic stage and the consideration of the transition temperature of phase equilibrium, experiments show that 0.3% (mass fraction) SDS kinetic additive has a better performance than 4% (mass fraction) ) THF thermodynamic additives can promote the formation of CO2 hydrate. Under the premise of -2 ℃ and 1.4MPa, the synthesis time is 60min. In the solution of 0.3% SDS, the hydrate is easy to form when the temperature is lower and the critical temperature is close to At -2 ℃ and below -2 ℃, solution icing could block the pipeline. The two tubular reactors were operated alternately and the optimal cycle temperature at -2 ℃ and decomposition at 10 ℃, the shortest cycle time at 55min, After the decomposition of high-pressure CO2 gas condensate throttling reached -36 ℃ low temperature.