Industrial reactors, reaction calorimetry

Most accidents in the chemical and related industries occur in batch processing. Therefore, in Chapter 5 much attention is paid to theoretical analysis and experimental techniques for assessing hazards when scaling up a process. Reaction calorimetry, which has become a routine technique to scale up chemical reactors safely, is discussed in much detail. This technique has been proven to be very successful also in the identification of kinetic models suitable for reactor optimization and scale-up. 

For the determination of reaction parameters, as well as for the assessment of thermal safety, several thermokinetic methods have been developed such as differential scanning calorimetry (DSC), differential thermal analysis (DTA), accelerating rate calorimetry (ARC) and reaction calorimetry. Here, the discussion will be restricted to reaction calorimeters which resemble the later production-scale reactors of the corresponding industrial processes (batch or semi-batch reactors). We shall not discuss thermal analysis devices such as DSC or other micro-calorimetric devices which differ significantly from the production-scale reactor. 

This is the most common mode of addition. For safety or selectivity critical reactions, it is important to guarantee the feed rate by a control system. Here instruments such as orifice, volumetric pumps, control valves, and more sophisticated systems based on weight (of the reactor and/or of the feed tank) are commonly used. The feed rate is an essential parameter in the design of a semi-batch reactor. It may affect the chemical selectivity, and certainly affects the temperature control, the safety, and of course the economy of the process. The effect of feed rate on heat release rate and accumulation is shown in the example of an irreversible second-order reaction in Figure 7.8. The measurements made in a reaction calorimeter show the effect of three different feed rates on the heat release rate and on the accumulation of non-converted reactant computed on the basis of the thermal conversion. For such a case, the feed rate may be adapted to both safety constraints the maximum heat release rate must be lower than the cooling capacity of the industrial reactor and the maximum accumulation should remain below the maximum allowed accumulation with respect to MTSR. Thus, reaction calorimetry is a powerful tool for optimizing the feed rate for scale-up purposes [3, 11]. 

Zuflerey, B. (2006) Scale-down Approach Chemical Process Optimisation Using Reaction Calorimetry for the Experimental Simulation of Industrial Reactors Dynamics, EPFL, n°3464, Lausanne. 

In this chapter, the reactor dynamics under adiabatic and isoperibolic conditions is analyzed, while the temperature-controlled case is addressed in Chap. 5. It must be pointed out that these conditions can be easily realized in laboratory investigations, e.g., in reaction calorimetry, but represent mere ideality at the industrial scale. Nevertheless, this classification is useful to recognize the main paths leading to runaway without the burden of a more complex mathematical approach. 

The set-up gives the opportunity to work at larger scale with reaction conditions close to those of industrial reactors. In fact, most of the studies related to SCF chemical reaction applications are reahzed in small-scale batch or tubular reactors (1-60 mL). So far, very few pubhcations deal with calorimetry applied to the supercritical phase. 

Polymerization rate can be measured by several techniques, although calorimetry (the heat of reaction, Qr, is monitored by solving the energy balances of the reactor and the cooling jacket) is often the most convenient one for industrial reactors. 

Reaction calorimetry is probably the cheapest, easiest, and most robust monitoring technique for polymerization reactors, due to the large enthalpy of polymerization of most monomers. The technique is noninvasive (basically, only temperature sensors are required), and it is industrially applicable [151, 152]. It yields continuous information on the heat released by polymerization and hence it is also very useful for safety issues. The main drawback is that only overall polymerization rates can be obtained. Consequently, the determination of the individual rates requires estimation techniques [114, 153-155]. 

The optimization provides the amounts of monomers and CTAs in the reactor at any overall conversion. These profiles are independent of the kinetics of the process and can be regarded as master curves. Once the trajectories of the amounts of monomers and CTAs as a function of the conversion are calculated, the implementation of the closed-loop strategy (Figure 6.14) reduces to tracking these profiles. To do so, on-line measurements of the overall conversion and of the free amount of monomers and CTA are necessary. Reaction calorimetry plus state estimation is probably the easiest, cheapest, and most robust option from an industrial perspective. 

More significantly, when calorimetry is combined with an integral kinetic analysis method, e.g. a spectroscopic technique, we have an expanded and extremely sophisticated method for the characterisation of chemical reactions. And when the calorimetric method is linked to FTIR spectroscopy (in particular, attenuated total reflectance IR spectroscopy, IR-ATR), structural as well as kinetic and thermodynamic information becomes available for the investigation of organic reactions. We devote much of Chapter 8 to this new development, and the discussion will focus on reaction calorimeters of a size able to mimic production-scale reactors of the corresponding industrial processes. 

The heat of reaction and the rate of heat production in a reaction mixture as a function of temperature are important quantities for the design of reactors in chemical industry. Presently, several methods for the determination of these quantities are available, such as Differential Scanning Calorimetry, Differential Thermal Analysis, Bench Scale Calorimetry / / and adiabatic calorimetric methods. 

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