Determining the best reaction calorimetry technique: theoretical development

Reaction calorimetry is a powerful technique for process monitoring as it allows the estimation of the heat of reaction Q˙R, which can be used to determine conversion. In addition, under some circumstances, the overall heat transfer coefficient k, which is useful for maximizing production and for safety analysis, can be estimated. Currently, there is no single technique to estimate both the heat of reaction Q˙R and the overall heat transfer coefficient k for the whole range of reactor sizes simultaneously. For small reactors, oscillation calorimetry is a method to estimate Q˙R and k simultaneously, whereas the solution of the heat balance equations or state estimators such as an Extended Kalman Filter (EKF), which use the heat balance model, perform better for large reactors. However, the reactor size limit of each technique is unknown, and perhaps more importantly, it is not known if the application ranges of the two techniques overlap. This article addresses this problem by comparing the performance of oscillation calorimetry and heat balance calorimetry using a state estimator in simulation studies for reactors of intermediate size. Additionally, guidelines for the use of oscillation calorimetry are presented.