Tubular reactors stability problems

The time relaxation corresponds to the change in the initial entropy state. As it has been established by one of the present authors (6), it is possible to derive generalized thermodynamic forces and fluxes in the sense of Onsager s theory and to study e.g. stability problems of tubular reactors. 

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Chapter 1 reviews the concepts necessary for treating the problems associated with the design of industrial reactions. These include the essentials of kinetics, thermodynamics, and basic mass, heat and momentum transfer. Ideal reactor types are treated in Chapter 2 and the most important of these are the batch reactor, the tubular reactor and the continuous stirred tank. Reactor stability is considered. Chapter 3 describes the effect of complex homogeneous kinetics on reactor performance. The special case of gas—solid reactions is discussed in Chapter 4 and Chapter 5 deals with other heterogeneous systems namely those involving gas—liquid, liquid—solid and liquid—liquid interfaces. Finally, Chapter 6 considers how real reactors may differ from the ideal reactors considered in earlier chapters. 

Of the various methods of weighted residuals, the collocation method and, in particular, the orthogonal collocation technique have proved to be quite effective in the solution of complex, nonlinear problems of the type typically encountered in chemical reactors. The basic procedure was used by Stewart and Villadsen (1969) for the prediction of multiple steady states in catalyst particles, by Ferguson and Finlayson (1970) for the study of the transient heat and mass transfer in a catalyst pellet, and by McGowin and Perlmutter (1971) for local stability analysis of a nonadiabatic tubular reactor with axial mixing. Finlayson (1971, 1972, 1974) showed the importance of the orthogonal collocation technique for packed bed reactors. 

Another type of stability problem arises in reactors containing reactive solid or catalyst particles. During chemical reaction the particles themselves pass through various states of thermal equilibrium, and regions of instability will exist along the reactor bed. Consider, for example, a first-order catalytic reaction in an adiabatic tubular reactor and further suppose that the reactor operates in a region where there is no diffusion limitation within the particles. The steady state condition for reaction in the particle may then be expressed by equating the rate of chemical reaction to the rate of mass transfer. The rate of chemical reaction per unit reactor volume will be (1 - e)kCAi since the effectiveness factor rj is considered to be unity. From equation 3.66 the rate of mass transfer per unit volume is (1 - e) (Sx/Vp)hD(CAG CAl) so the steady state condition is ... 

The steam reforming of methane cycle suffers from the problem of coke deposition on the catalyst bed. The primary objective of this project was to study the stability of a commercial nickel oxide catalyst for the steam reforming of methane. The theoretical minimum ratios of steam to methane that are required to avoid deposition of coke on the catalyst at various temperatures were calculated, based on equilibrium considerations. Coking experiments were conducted in a tubular reactor at atmospheric pressure in the range of 740-915°C. 

In all these cases, the correct design must grow from the equations of mass, energy, and momentum balance to which we now turn in the next few sections. From these we proceed to the design problem (Sec. 9.5) and hence to elementary considerations of optimal design (Sec. 9.6). The stability and sensitivity of a tubular reactor is a vast and fascinating subject. Since the steady state equations are ordinary differential equations, the equations describing the transient behavior are partial differential equations. This... 

The averaging technique characteristic of the second approach may apply to the case of a tubular reactor where the ratio of the characteristic catalyst particle size to the diameter of a single tube is close to unity, but it is invalid, as will be shown, in the general case of fixed-bed reactors. This approach keeps out of a researcher s field of vision the problem of the reactor stability to local perturbations. At the same time, the technologist is often faced with hot spots in the catalyst bed of a fixed-bed reactor, which make its operation imperfect and even lead to an emergency situation in a number of cases, Until recently, nonuniformity of the fields of external parameters (e.g., nonuniform packing of the catalyst bed or nonuniformity of reactant stream velocity ) was considered the only cause of these phenomena. The question naturally arises whether the provision for uniformity of external conditions guarantees the uniformity of temperature and concentration profiles at the reactor cross-section. The present paper seeks to answer this question, which, as a matter of fact, has not yet been posed in such a form in the theory of chemical reactors. 

The problems of simultaneously treating spatial distributions of both temperature and concentration are currently the concern of the chemical engineer in his treatment of catalyst particles, catalyst beds, and tubular reactors. These treatments are still concerned with systems that are kineticaliy simple. The need for a unified theory of ignition has been highlighted by contemporary studies of gas-phase oxidations, many features being revealed that neither thermal theory, nor branched-chain theory for that matter, can resolve alone. A successful theoretical basis for such reactions necessarily involves the treatment of both the enorgy balance and mass balance equations. Such equations are invariably coupled and cannot be solved independently of each other. However, much information is offered by the phase-plane analj s of the syst (e.g. stability of equilibrium solutions, existence of oscillations) without the need for a formal solution of the balance equations. 

For most polsrmerizations starting from monomer, tubular reactors have been avoided because of the various stability problems. They can he used in recycle loops where the per-pass conversion is low, in solution polymerizations with large amounts of solvent, and in post- or finishing reactors intended to drive a polymerization to completion. Shell-and-tube designs with as many as 1000 tubes are used in polystyrene processes where they also serve as devolatilization preheaters. The entering polymer solution has a concentration of about 70%, and its viscosity is high enough to avoid tube-to-tube instabilities. 

We employ a method of numerical continuation which has been earlier developed into a software tool for analysis of spatiotemporal patterns emerging in systems with simultaneous reaction, diffusion and convection. As an example, we take a catalytic cross-flow tubular reactor with first order exothermic reaction kinetics. The analysis begins with determining stability and bifurcations of steady states and periodic oscillations in the corresponding homogeneous system. This information is then used to infer the existence of travelling waves which occur due to reaction and diffusion. We focus on waves with constant velocity and examine in some detail the effects of convection on the fiiont waves which are associated with bistability in the reaction-diffusion system. A numerical method for accurate location and continuation of front and pulse waves via a boundary value problem for homo/heteroclinic orbits is used to determine variation of the front waves with convection velocity and some other system parameters. We find that two different front waves can coexist and move in opposite directions in the reactor. Also, the waves can be reflected and switched on the boundaries which leads to zig-zag spatiotemporal patterns. 

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