Oscillating tank reactor

On/off control 96 Operating line equation 595 Optimisation 108 Order of reaction 53, 323 Oscillating tank reactor 350 Oscillations 507, 518, 663... 

OSCIL - Oscillating Tank Reactor Behaviour System... 

Continuous Multicomponent Distillation Column 501 Gas Separation by Membrane Permeation 475 Transport of Heavy Metals in Water and Sediment 565 Residence Time Distribution Studies 381 Nitrification in a Fluidised Bed Reactor 547 Conversion of Nitrobenzene to Aniline 329 Non-Ideal Stirred-Tank Reactor 374 Oscillating Tank Reactor Behaviour 290 Oxidation Reaction in an Aerated Tank 250 Classic Streeter-Phelps Oxygen Sag Curves 569 Auto-Refrigerated Reactor 295 Batch Reactor of Luyben 253 Reversible Reaction with Temperature Effects 305 Reversible Reaction with Variable Heat Capacities 299 Reaction with Integrated Extraction of Inhibitory Product 280... 

Achieving steady-state operation in a continuous tank reactor system can be difficult. Particle nucleation phenomena and the decrease in termination rate caused by high viscosity within the particles (gel effect) can contribute to significant reactor instabilities. Variation in the level of inhibitors in the feed streams can also cause reactor control problems. Conversion oscillations have been observed with many different monomers. These oscillations often result from a limit cycle behavior of the particle nucleation mechanism. Such oscillations are difficult to tolerate in commercial systems. They can cause uneven heat loads and significant transients in free emulsifier concentration thus potentially causing flocculation and the formation of wall polymer. This problem may be one of the most difficult to handle in the development of commercial continuous processes. 

This set of first-order ODEs is easier to solve than the algebraic equations where all the time derivatives are zero. The initial conditions are that a ut = no, bout = bo,... at t = 0. The long-time solution to these ODEs will satisfy Equations (4.1) provided that a steady-state solution exists and is accessible from the assumed initial conditions. There may be no steady state. Recall the chemical oscillators of Chapter 2. Stirred tank reactors can also exhibit oscillations or more complex behavior known as chaos. It is also possible that the reactor has multiple steady states, some of which are unstable. Multiple steady states are fairly common in stirred tank reactors when the reaction exotherm is large. The method of false transients will go to a steady state that is stable but may not be desirable. Stirred tank reactors sometimes have one steady state where there is no reaction and another steady state where the reaction runs away. Think of the reaction A B —> C. The stable steady states may give all A or all C, and a control system is needed to stabilize operation at a middle steady state that gives reasonable amounts of B. This situation arises mainly in nonisothermal systems and is discussed in Chapter 5. 

Thus it is possible for continuous stirred-tank reactor systems to be stable, or unstable, and also to form continuous oscillations in output, depending upon the system, constant and parameter, values. 

This analysis is limited, since it is based on a steady-state criterion. The linearisation approach, outlined above, also fails in that its analysis is restricted to variations, which are very close to the steady state. While this provides excellent information on the dynamic stability, it cannot predict the actual trajectory of the reaction, once this departs from the near steady state. A full dynamic analysis is, therefore, best considered in terms of the full dynamic model equations and this is easily effected, using digital simulation. The above case of the single CSTR, with a single exothermic reaction, is covered by the simulation examples, THERMPLOT and THERM. Other simulation examples, covering aspects of stirred-tank reactor stability are COOL, OSCIL, REFRIG and STABIL. 

A continuous stirred tank reactor has been reported for the hydrolysis of the triglycerides existing in vegetable oil in the presence of the aqueous phase and for synthesis reactions (Table 5). A microfilter can be used to prevent the immobilized enzyme from leaving the reactor. Kawano et al. [115] investigated the hydrolysis of olive oil in octane with Candida cylindracea lipase in aqueous solution in a Vibro Mixer reactor containing vibration plates connected to the crankshaft of a motor and oscillated with fixed rates. 

The APP technique, recently introduced [50, 51], uses a continuous stirring tank reactor (CSTR) and relies on the sequential perturbation of an oscillating... 

Figure 10 Experimental setup for implementation of CL oscillating reaction-based de terminations. CSTR, continuous stirring tank reactor. (From Ref. 52.)...

The main features of the copper catalyzed autoxidation of ascorbic acid were summarized in detail in Section III. Recently, Strizhak and coworkers demonstrated that in a continuously stirred tank reactor (CSTR) as well as in a batch reactor, the reaction shows various non-linear phenomena, such as bi-stability, oscillations and stochastic resonance (161). The results from the batch experiments can be suitably illustrated with a two-dimensional parameter diagram shown in Pig. 5. 

M. Perez, R. Font, and M.A. Montava. Regular self-oscillating and chaotic dynamics of a continuos stirred tank reactor. Comput. Chem. Eng., 26 889-901, 2002. 

P. Aroca, Jr., and R. Aroca, Chemical Oscillations A Microcomputer-Controlled Experiment, J. Chem. Ed. 1987,64, 1017 J. Amrehn, P. Resch, and F. W. Schneider, Oscillating Chemiluminescence with Luminol in the Continuous Flow Stirred Tank Reactor, J. Phys. Chem. 1988,92, 3318 D. Avnir, Chemically Induced Pulsations of Interfaces The Mercury Beating Heart, ... 

P. Gray and S. K. Scott. Autocatalytic reactions in the isothermal continuous stirred tank reactor Isolas and other forms of multiplicity. Chem. Eng. ScL 38, 29-43 (1983) Autocatalytic reactions in the isothermal continuous stirred tank reactor Oscillations and instabilities in the system A + 2B —> 3B, B —> C. Chem Eng. ScL 34, 1087-1097 (1984). 

The classical problem of multiple solutions and undamped oscillations occurring in a continuous stirred-tank reactor, dealt with in the papers by Aris and Amundson (39), involved a single homogeneous exothermic reaction. Their theoretical analysis was extended in a number of subsequent theoretical papers (40, 41, 42). The present paragraph does not intend to report the theoretical work on multiplicity and oscillatory activity developed from analysis of governing equations, for a detailed review the reader is referred to the excellent text by Schmitz (3). To understand the problem of oscillations and multiplicity in a continuous stirred-tank reactor the necessary and sufficient conditions for existence of these phenomena will be presented. For a detailed development of these conditions the papers by Aris and Amundson (39) and others (40) should be consulted. 

Emulsion polymerization is usually carried out isothermally in batch or continuous stirred-tank reactors. Temperature control is much easier than for bulk or solution polymerization because the small ( 0.5 fim) polymer particles, which are the locus of the reaction, are suspended in a continuous aqueous medium. This complex, multiphase reactor also shows multiple steady states under isothermal conditions. In industrial practice, such a reactor often shows sustained oscillations. Solid-catalyzed olefin polymerization in a slurry batch reactor is a classic example of a slurry reactor where the solid particles change size and characteristics with time during the reaction process. 

Example 4.8 Chemical reactions and reacting flows The extension of the theory of linear nonequilibrium thermodynamics to nonlinear systems can describe systems far from equilibrium, such as open chemical reactions. Some chemical reactions may include multiple stationary states, periodic and nonperiodic oscillations, chemical waves, and spatial patterns. The determination of entropy of stationary states in a continuously stirred tank reactor may provide insight into the thermodynamics of open nonlinear systems and the optimum operating conditions of multiphase combustion. These conditions may be achieved by minimizing entropy production and the lost available work, which may lead to the maximum net energy output per unit mass of the flow at the reactor exit. 

In Table I the high-vacuum (HV) range means a pressure of 10 to 10 Torr entries designated by Torr mean pressures between 0.1 and 10 Torr flow refers to an unspecified steady-state flow pattern. It is apparent from Table I that there is a great diversity in the different oscillation conditions and catalytic systems. The pressures under which oscillations have been observed vary from 10 Torr for the CO/NO reaction on Pt(lOO) 141, 142) to atmospheric pressure for a large number of systems. The reactors used in these studies include ultrahigh-vacuum (UHV) systems, continuous stirred tank reactors (CSTRs), flow reactors, and reactors designed as infrared (IR) cells, calorimeters, and ellipsometric systems. 

The simulations discussed above are focused on the behavior of single catalytic oscillators at fixed reactant pressures. In the full-scale analysis of reactions on nm-supported particles, the reactant pressures should be calculated self-consistently with the reaction kinetics. At present, due to computational limitations, the self-consistent treatment can, however, be done only by using the MF equations (see, e.g., recent simulations [57] of oscillations in CO oxidation in a continuously stirred tank reactor). The MF approach does not, however, make it possible to scrutinize the reaction kinetics on the nm scale. Under such circumstances, the MC and MF treatments are complementary. In particular, the MC results may be employed in order to understand the limits of applicability of the MF approximation. 

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