Broeckhoven K, Desmet G
Vrije Universiteit Brussel, Department of Chemical Engineering, Pleinlaan 2, 1050 Brussels, Belgium.
Vrije Universiteit Brussel, Department of Chemical Engineering, Pleinlaan 2, 1050 Brussels, Belgium.
J Chromatogr A. 2017 Nov 10;1523:183-192. doi: 10.1016/j.chroma.2017.07.040. Epub 2017 Jul 12.
The current contribution investigates the effects of viscous heat dissipation in chromatographic columns (with an emphasis on so-called narrow bore columns with an inner diameter of 2.1mm) using numerical simulations of the temperature and velocity profiles and the resulting band broadening, for the first time at operating pressures up to 2000bar. When operating columns under well-thermostatted conditions to maintain a constant temperature of the mobile phase, a dramatic increase in plate heights can be observed that voids any advantage one could expect from the possibility to use smaller particles offered by the increased pressure limit. It is also clearly demonstrated that, even when the column is not temperature controlled, the backflow of heat along the wall can causes a significant loss in performance under standard operating conditions in a still air oven. It is found that for operating pressure above 1250bar, a significant (relative to the typical column performance) contribution to the observed plate height will be caused by viscous heating effects, which increases with increasing temperature dependency of the retention factor. In addition, unprecedented experimental measurements of the temperature effects at an operating pressure up to 2600bar were performed on a 10cm long, 2.1mm ID column showing a dramatic temperature increase up to 60°C relative to the inlet temperature when using methanol as a mobile phase.
本研究首次通过对温度和速度分布以及由此产生的谱带展宽进行数值模拟,研究了色谱柱中粘性热耗散的影响(重点是内径为2.1mm的所谓窄径柱),操作压力高达2000bar。在恒温条件下操作色谱柱以保持流动相温度恒定时,可以观察到板高急剧增加,这抵消了人们因压力上限提高而能够使用更小颗粒所期望获得的任何优势。还清楚地表明,即使色谱柱没有温度控制,在静止空气烘箱的标准操作条件下,沿壁的热回流也会导致性能显著下降。研究发现,对于高于1250bar的操作压力,粘性加热效应将对观察到的板高产生显著(相对于典型色谱柱性能)贡献,且该贡献随保留因子温度依赖性的增加而增大。此外,在一根10cm长、内径2.1mm的色谱柱上,在高达2600bar的操作压力下进行了前所未有的温度效应实验测量,结果表明,当使用甲醇作为流动相时,相对于入口温度,温度会急剧升高至60°C。