Mechanically agitated calorimetric cells working under pressure at macro and micro scale: application to gas hydrates

Abstract

Originally applied to fields related to oil and gas production and flow assurance, high pressure differential scanning calorimetry (HP-DSC) has now been involved in several new studies such as carbon dioxide sequestration by CO2/CH4 exchange in naturally occurring gas hydrates or CO2 hydrate reversible formation/dissociation for refrigeration loops. However, the technique still has some limitations, which are linked to the fact that the gas hydrate formation occurs at the gas/liquid interface, and because the hydrate nucleation can be rather difficult in small volumes especially in quiescent conditions. It leads to several problems such as inefficient gas dissolution, long induction times, formation of a hydrate crust covering the gas/liquid interface, low hydrate to water conversion, etc. As a result, it is very difficult to determine accurately the heat capacities and the kinetics of formation/dissociation of several systems involving gas hydrates. This study presents two prototypes of calorimetric cells equipped with an in-situ mechanical agitation system, which allow performing experiments under pressure (150 bar maximum for the cells used in this work). The first system presented, called MIXCEL®, was developed for macro-calorimetry analysis (experiments carried out with a BT 2.15 Calvet Calorimeter from SETARAM Instrumentation). Very recently, we have developed a novel prototype of micro-calorimetric agitated cell (called MICROMIXCEL®) for microDSC analyses (experiments carried out using a microDSC7 evo from SETARAM Instrumentation). Both technical aspects, and results obtained at macro and micro scales with gas hydrate systems are presented and discussed.