Kinetic model identification and parameters estimation from TGA experiments

The presented work is a part of an ongoing research effort on the development of a general methodology for the determination of kinetic models of solid thermal decomposition under pyrolysis conditions with thermogravimetric analysis (TGA) devices. The goal is to determine a simple and robust kinetic model for a given solid with the minimum of TGA experiments. From the latter point of view, this work can be seen as the optimal design of TGA experiments for pyrolysis kinetic modelling. In this paper, a general procedure is presented and more precise results are given about the influence of the sensitivity matrix on the estimation of the kinetic parameters and about the important influence of the specific TGA runs used for parameter estimation on the precision of the fitted parameters. The first results are shown for simulated applications; in the final part, the presented results concern cellulose pyrolysis in a Setaram TGA device

Evaluation of an intensified continuous heat-exchanger reactor for inherently safer characteristics

The present paper deals with the establishment of a new methodology in order to evaluate the inherently safer characteristics of a continuous intensified reactor in the case of an exothermic reaction. The transposition of the propionic anhydride esterification by 2-butanol into a new prototype of ‘‘heatexchanger/ reactor’’, called open plate reactor (OPR), designed by Alfa Laval Vicarb has been chosen as a case study. Previous studies have shown that this exothermic reaction is relatively simple to carry out in a homogeneous liquid phase, and a kinetic model is available. A dedicated software model is then used not only to assess the feasibility of the reaction in the ‘‘heat-exchanger/reactor’’ but also to estimate the temperature and concentration profiles during synthesis and to determine optimal operating conditions for safe control. Afterwards the reaction was performed in the reactor. Good agreement between experimental results and the simulation validates the model to describe the behavior of the process during standard runs. A hazard and operability study (HAZOP) was then applied to the intensified process in order to identify the potential hazards and to provide a number of runaway scenarios. Three of them are highlighted as the most dangerous: no utility flow, no reactant flows, both stop at the same time. The behavior of the process is simulated following the stoppage of both the process and utility fluid. The consequence on the evolution of temperature profiles is then estimated for a different hypothesis taking into account the thermal inertia of the OPR. This approach reveals an intrinsically safer behavior of the OPR

Corrigendum to "Hydrodynamic and mass transfer in inertial gas-liquid flow regimes through straight and meandering millimetric square channels" [Chem. Eng. Sci. 66 (2011) 2974-2990]

Heat-exchanger reactors are an important part of process intensification technology. For plate geometries, one solution for intensifying transfer and increasing residence times is to construct two-dimensional meandering channels. Supported by this scientific context, the present work aims at characterising gas-liquid mass transfer in the same square millimetric meandering channel, as in Anxionnaz (2009), this constituted the preliminary step required for performing exothermic gas-liquid reactions. Firstly, the gas-liquid hydrodynamics were characterised for a water/air system. When compared to a straight channel of identical compactness and sectional-area (2×2 mm²), the meandering channel induced (i) a delay in the transition from Taylor to annular-slug regimes, (ii) a rise of 10-20% in bubble lengths while conserving almost identical slug lengths, (iii) higher deformations of bubble nose and rear due to centrifugal forces (bends). Secondly, an original method for verifying the relevancy of the plug flow model and accurately determining kla was used (measurements of concentrations in dissolved oxygen along the channel length). For the Taylor flow regime, kla increased coherently when increasing jg, and the meandering geometry had a small influence. On the contrary, this effect was found no more negligible for the slug-annular flow regime. Whatever the channels, the NTUl remained low, thus showing that, even if millimetric channels allowed to intensify kla, a special attention should be paid for generating sufficient residence times. At identical compactness, the meandering channel was found to be the most competitive. Finally, results on gas-liquid interfacial areas and mass transfer coefficients were confronted and discussed with respect to the predictions issued from the model developed by Van Baten and Krishna (2004)

Predictive functional control for the temperature control of a chemical batch reactor

A predictive functional control (PFC) technique is applied to the temperature control of a pilot-plant batch reactor equipped with a mono-fluid heating/cooling system. A cascade control structure has been implemented according to the process sub-units reactor and heating/cooling system. Hereby differences in the sub-units dynamics are taken into consideration. PFC technique is described and its main differences with a standard model predictive control (MPC) technique are discussed. To evaluate its robustness, PFC has been applied to the temperature control of an exothermic chemical reaction. Experimental results show that PFC enables a precise tracking of the set-point temperature and that the PFC performances are mainly determined by its internal dynamic process model. Finally, results show the performance of the cascade control structure to handle different dynamics of the heating/cooling system

Hydrodynamic and mass transfer in inertial gas–liquid flow regimes through straight and meandering millimetric square channels

Heat-exchanger reactors are an important part of process intensification technology. For plate geometries, one solution for intensifying transfer and increasing residence times is to construct two-dimensional meandering channels. Supported by this scientific context, the present work aims at characterising gas–liquid mass transfer in the same square millimetric meandering channel, as in Anxionnaz (2009), this constituted the preliminary step required for performing exothermic gas–liquid reactions. Firstly, the gas–liquid hydrodynamics were characterised for a water/air system. When compared to a straight channel of identical compactness and sectional-area (2×2 mm2), the meandering channel induced (i) a delay in the transition from Taylor to annular-slug regimes, (ii) a rise of 10–20% in bubble lengths while conserving almost identical slug lengths, (iii) higher deformations of bubble nose and rear due to centrifugal forces (bends). Secondly, an original method for verifying the relevancy of the plug flow model and accurately determining kla was used (measurements of concentrations in dissolved oxygen along the channel length). For the Taylor flow regime, kla increased coherently when increasing jg, and the meandering geometry had a small influence. On the contrary, this effect was found no more negligible for the slug-annular flow regime. Whatever the channels, the NTUl remained low, thus showing that, even if millimetric channels allowed to intensify kla, a special attention should be paid for generating sufficient residence times. At identical compactness, the meandering channel was found to be the most competitive. Finally, results on gas–liquid interfacial areas and mass transfer coefficients were confronted and discussed with respect to the predictions issued from the model developed by Van Baten and Krishna (2004)

Optimisation of solvent replacement procedures according to economic and environmental criteria in pharmaceutical industry

During pharmaceutical syntheses, the reaction solvent has often to be switched off from one reaction step to the following one. Because of the standard industrial practices, solvent replacement generally constitutes a slow and high solvent-consuming operation. In this paper, a specific methodology, based on a batch processes optimisation framework, is proposed for the optimisation of solvent replacement procedures. Optimisation may be performed at different levels according to economic and environmental criteria and satisfying safety and waste treatment constraints. In fact, the proposed methodology allows both to design new procedures of solvent replacement and to improve existing industrial processes. Two industrial applications are detailed to emphasize the benefits related to this methodology. In each case, the proposed methodology leads to the suitable recipe from comparison of traditional and empirical replacement procedures generally used in the pharmaceutical industry

Dynamic Behaviour of a Continuous Heat Exchanger/Reactor after Flow Failure

The intensified technologies offer new prospects for the development of hazardous chemical syntheses in safer conditions: the idea is to reduce the reaction volume by increasing the thermal performances and preferring the continuous mode to the batch one. In particular, the Open Plate Reactor (OPR) type “reactor/ exchanger” also including a modular block structure, matches these characteristics perfectly. The aim of this paper is to study the OPR behaviour during a normal operation, that is to say, after a stoppage of the circulation of the cooling fluid. So, an experiment was carried out, taking the oxidation of sodium thiosulfate with hydrogen peroxide as an example. The results obtained, in particular with regard to the evolution of the temperature profiles of the reaction medium as a function of time along the apparatus, are compared with those predicted by a dynamic simulator of the OPR. So, the average heat transfer coefficient regarding the “utility” fluid is evaluated in conductive and natural convection modes, and then integrated in the simulator. The conclusion of this study is that, during a cooling failure, a heat transfer by natural convection would be added to the conduction, which contributes to the intrinsically safer character of the apparatus

Influence of the meandering channel geometry on the thermo-hydraulic performances of an intensified heatexchanger/reactor

In the global context of process intensification, heat exchanger/reactors are promising apparatuses to implement exothermic chemical syntheses. However, unlike heat exchange processes, the implementation of chemical syntheses requires to control the residence time to complete the chemistry. A way to combine the laminar regime (i.e. enough residence time) with a plug flow and the intensification of both heat and mass transfers is the corrugation of the reaction path. In this work, the experimental set-up is based on plate heat exchanger/reactor technology. 7 milli channel corrugated geometries varying the corrugation angle, the curvature radius, the developed length, the hydraulic diameter and the aspect ratio have been designed and experimentally characterized (heat transfer, mixing times, pressure drops, RTD). The objectives were to assess their respective performances to derive some correlations depending on the channel design. The results confirmed the benefits of the reaction channel corrugation. Heat and mass transfers have been intensified while maintaining a plug flow behavior in the usually laminar flow regime. Moreover, whatever the meandering channel’s curvature radius, the results highlighted the relevance of considering the Dean number as the scale-up parameter. This dimension less number, more than the Reynolds number, seems to govern the flow in the wavy channels

Calcium phosphate precipitation modeling in a pellet reactor

The calcium phosphate precipitation in a pellet reactor can be evaluated by two main parameters: the phosphate conversion ratio and the phosphate removal efficiency. The conversion ratio depends mainly on the pH. The pellet reactor efficiency depends not only on pH but also on the hydrodynamical conditions. An efficiency model based on a thermochemical precipitation approach and an orthokinetic aggregation model is presented. In this paper, the results show that optimal conditions for pellet reactor efficiency can be obtained

Transposition from a batch to a continuous process for microencapsulation by interfacial polycondensation

A novel continuous process is proposed and investigated to produce microcapsules by interfacial polycondensation. Polymeric microcapsules are obtained via a two-step process including an initial emulsification of two immiscible fluids in static mixers and a subsequent interfacial polycondensation reaction performed in two different continuous reactors, the Deanhex heat exchanger/reactor or a classical coiledtube. This study is carried out through a step by step approach. A model system involving polyurea as the polymeric membrane and cyclohexane as the encapsulated species is chosen. A semi-batch reaction kinetic study is first performed in order to obtain kinetics data of the polycondensation reaction and to highlight hydrodynamic issues that can happen when running the encapsulation reaction in classical stirred tank. Parameters influencing droplets size obtained when carrying out emulsification in static mixers are then investigated. The hydrodynamic of the Deanhex reactor used is also characterized in terms of mixing time and residence time distribution. To validate the innovative continuous process, the emulsion droplets obtained at the static mixer outlet are encapsulated firstly in the Deanhex reactor and secondly in the coiled-tube. The apparent reaction kinetics and microcapsules characteristics corresponding to different operating conditions are discussed