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Engineering Reactors for Catalytic Reactions

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Engineering Reactors for Catalytic Reactions J. Chem. Sci. Vol. 126, No. 2, March 2014, pp. 341–351. c Indian Academy of Sciences. Engineering reactors for catalytic reactions VIVEK V RANADE∗ Chemical Engineering and Process Development Division, CSIR - National Chemical Laboratory, Pune 411 008, India e-mail: [email protected] MS received 2 July 2013; revised 26 December 2013; accepted 30 December 2013 Abstract. Catalytic reactions are ubiquitous in chemical and allied industries. A homogeneous or heteroge- neous catalyst which provides an alternative route of reaction with lower activation energy and better control on selectivity can make substantial impact on process viability and economics. Extensive studies have been conducted to establish sound basis for design and engineering of reactors for practising such catalytic reactions and for realizing improvements in reactor performance. In this article, application of recent (and not so recent) developments in engineering reactors for catalytic reactions is discussed. Some examples where performance enhancement was realized by catalyst design, appropriate choice of reactor, better injection and dispersion strategies and recent advances in process intensification/ multifunctional reactors are discussed to illustrate the approach. Keywords. Catalyst; reactors; effectiveness; hydrodynamics; engineering. 1. Introduction several functions such as bringing reactants into inti- mate contact with active sites on catalyst (to allow Chemicals and allied industries manufacture products chemical reactions to occur), providing an appropri- which are essential for realizing and sustaining modern ate environment (temperature and concentration fields) societies. Chemical (and biological) transformations for adequate time and allowing for removal of prod- necessary to make these essential products often involve ucts from catalyst surface. A reactor engineer has to use of catalysts. A catalyst (can be homogeneous or het- ensure that the evolved reactor hardware and operat- erogeneous) reduces activation energy barrier to trans- ing protocol satisfy various process demands without formations and facilitates better control on selectivity. compromising safety, environment and economics. Nat- Development and selection of the right catalyst there- urally, successful reactor engineering requires bringing fore can make substantial impact on process viability together better chemistry (thermodynamics, catalysis and economics. Besides the right catalyst, it is essential (replace reagent-based processes), improved solvents to develop the right reactor type and process intensifi- (supercritical media, ionic liquids), improved atom effi- cation strategies for effective translation of laboratory ciency, prevent wasters — leave no waste to treat) and process to practise. Reaction and reactor engineering better engineering (fluid dynamics, mixing and heat and which deal with these aspects therefore play a crucial mass transfer, new ways of process intensification, com- role in chemical and allied process industries. In this putational models and real-time process monitoring and article, application of recent (and not so recent) devel- control). opments in engineering reactors for catalytic reactions Several tools for modelling of chemical kinetics and is discussed. reactions are already well-developed and routinely used Engineering of reactors includes all the activities in practice for facilitating engineering of reactors. Sev- necessary to evolve best possible hardware and operat- eral excellent textbooks discussing these classical reac- ing protocol of reactor to carry out the desired trans- tion engineering tools and practices are available.1–4 formation of raw materials (or reactants) into value- In this article, we have used these classical texts as a added products. Any catalytic reactor has to carry out starting point and discuss some of the recent advances in reaction/reactor engineering practices for optimiz- ing catalytic reactors. The scope is restricted to discus- sion of catalytic reactors. The vast field of catalysts and ∗For correspondence catalysis is briefly discussed in the following section. 341 342 Vivek V Ranade Key issues in and approach for engineering of catalytic In contrast to this, in heterogeneous catalyst, several reactors are then discussed. Some examples where per- additional steps are involved along with reaction occur- formance enhancement was realized by catalyst design, ring on catalyst surface such as (see figure 2): appropriate choice of reactor, better injection and dis- • External diffusion towards catalyst pellet persion strategies and recent advances in process inten- • Internal diffusion towards catalyst surface sification/multifunctional reactors which were used for • Molecular adsorption on catalyst surface performance enhancement are discussed to illustrate the • Surface reaction approach. • Desorption from catalyst surface • Internal diffusion away from catalyst surface • External diffusion away from catalyst pellet. 2. Catalyst and catalytic reactions It will be prudent to briefly summarize and recapitulate key aspects of catalyst and catalytic reactions before other engineering aspects are discussed. A catalyst is a substance which provides an alternative route of reac- tion where the activation energy is lower without actu- ally taking part in the reaction (see figure 1). Catalysts do not affect chemical equilibrium associated with a reaction. They merely change the rate of reactions. Cat- alysts are classified in a variety of ways. The commonly used classification by reaction engineers is based on number of phases as: • Homogenous catalysis (catalyst and substrate in same phase) • Heterogeneous catalysis (solid catalysis and sub- strate is a gas and/or liquid). Homogeneous catalyst typically forms a complex with one of the reactants which eventually transforms it into the product after interacting with other reactants. The process is essentially similar to homogeneous reactions in absence of catalyst and is often controlled by mix- ing of reactants and catalyst species at molecular level. Figure 1. Role of catalyst.4 Figure 2. Steps in heterogeneous catalysis. Engineering reactors for catalytic reactions 343 These steps need to be understood in order to select applications. Broadly, these reactors may be classified appropriate reactor and operating strategy. This will be based on presence of phases as follows. discussed later in this article. • Gas–liquid reactors: Stirred reactors, bubble column Another important aspect of the catalyst is possi- reactors, packed columns, loop reactors ble catalyst deactivation. The most typical causes of • Gas–liquid–solids reactors: Stirred slurry reactors, deactivation of heterogeneous catalyst are: three-phase fluidized bed reactors (bubble column • Ageing: deactivation resulting from changes in struc- slurry reactors), packed bubble column reactors, ture trickle bed reactors, loop reactors • Sintering: increase in average size of the crystallites • Gas–solid reactors: Fluidized bed reactors, fixed bed due to coalescence of small solids on continued usage reactors, moving bed reactors of catalyst Existence of multiple phases opens up a variety of • Coking: deposition of high molecular weight choices in bringing these phases together to react. Carbon–Hydrogen compounds on catalyst surface Krishna and Sie10 have discussed a three-level approach • Poisoning: inhibitory substances bind to the active for reactor design and selection (see figure 4). sites on catalytic surface. • Strategy level I: Catalyst design strategy Catalytically active complex in homogeneous catalysis may similarly get deactivated due to structural changes ◦ gas–solid systems: catalyst particle size, in the active complex as well as poisoning because of shape, porous structure, distribution of active binding with inhibitory substances. A reactor engineer material has to account for activation as well as deactivation of ◦ gas–liquid systems: choice of gas-dispersed catalyst while designing suitable reactor for carrying or liquid-dispersed systems, ratio between out catalytic reactions. Basic aspects of practical reactor liquid-phase bulk volume and liquid-phase engineering are briefly discussed here. diffusion layer volume • Strategy level II: Injection and dispersion strategies ◦ 3. Practical reactor engineering reactant and energy injection: batch, continu- ous, pulsed, staged... Reactor engineering involves establishing a relationship ◦ state of mixedness of concentrations and tem- between reactor hardware and operating protocols with perature various performance issues as listed in table 1. ◦ separation of product or energy in situ A general reactor engineering methodology is shown ◦ contacting flow pattern: co-, counter-, cross- in figure 3. Based on the available information about current the chemistry and catalysis of the process under con- • Strategy level III: Choice of hydrodynamic flow sideration, the first step of reactor engineering is to regime select a suitable reactor type. In catalytic reactors, mul- tiple phases are almost always involved (see exam- ◦ packed bed, bubbly flow, churn-turbulent ples cited in earlier studies.5–9 There are several types regime, dense-phase or dilute-phase riser of reactors used for such catalytic and multiphase transport Table 1. Reactor engineering. 344 Vivek V Ranade Figure 3. Reactor engineering methodology.17 Besides these considerations for selecting appropriate key issues are shown schematically in figure 5. reactor and mode of operation, there are several other
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