Periodic feed reactor

A related oscillatory phenomenon is that in which the concentration of one or more reactants, fed to a flow reactor, is varied in time. Such forced periodic feed oscillations during oxidation reactions have now been studied by a number of authors. It is found that not only can conversion be increased but the selectivity of certain parallel reactions can be improved, which may be of value in industrial applications. Cutlip and Abdul-Karem and Jain ... 

The example with periodic feed is relevant in chemical reactors. Further, it is the starting point for the kinetics of drug administration. However, in real live the... 

Figure 1.7 shows one such application to polymerization carried out in a constant volume stirred tank reactor or CSTR fed by liquid streams of initiator and monomer. The feed streams react to form polymer, which is discharged in the output stream. It is desired to find periodic feed flow rates versus time that would produce a polymer of specified polydispersity index (PI), a measure of polymer MWD. 

Figure 1.7 A constant volume stirred tank reactor with periodic feed flow rates...

Optimal periodic control involves a periodic process, which is characterized by a repetition of its state over a fixed time period. Examples from nature include the circadian rhythm of the core body temperature of mammals and the cycle of seasons. Man-made processes are run periodically by enforcing periodic control inputs such as periodic feed rate to a chemical reactor or cyclical injection of steam to heavy oil reservoirs inside the earth s crust. The motivation is to obtain performance that would be better than that imder optimal steady state conditions. 

ProCGdures. From a technological point of view heterophase polymerizations can be carried out either batchwise, semicontinuous (or semibatch), or continuous. In the batchwise case the reactor is filled with all ingredients before the polymerization is started and the reactor content is removed at the end of the polymerization. In a semibatch procedure, at the start of the poljunerization the reactor is filled only partially and a stream of either neat monomers or monomer emulsion with constant or deliberately changed composition is fed continuously until the reactor is filled. After a final post-feeding batch reaction period, the reactor is emptied. A continuous procedure means that all necessary ingredients are fed and final latex is removed continuously. In all three cases the poljunerization can be carried out in the absence or presence of preformed particles (so-called seed particles). Reactions in the absence of seed particles are frequently called ab initio polymerizations and require that particle nucleation takes place. Table 7 is an... 

It is now well established that, in the most active and selective catalysts used in fixed- or fluidized-bed reactors, only a few layers of VPO participate in the reaction. One may think that the Mars-van Krevelen redox mechanism is ruled out, or at least that it is confined to the outermost layers. The question arises as to how this picture holds when working deliberately in the transient state using alternate pulses or periodic feed, with the idea of separately optimizing the two steps of the redox mechanism, or when alternative reactors in which the redox system is physically separated by decoupling. The next paragraphs address this question, as well as show some important differences in using the same DuPont catalyst in different reactor configurations. 

In the second model (Fig. 2.16) the continuous well-stirred model, feed and product takeoff are continuous, and the reactor contents are assumed to he perfectly mixed. This leads to uniform composition and temperature throughout. Because of the perfect mixing, a fluid element can leave at the instant it enters the reactor or stay for an extended period. The residence time of individual fluid elements in the reactor varies. 

The gas leaving the heat recovery equipment contains soot and ash some ash is deposited in the bottom of the reactor for removal during periodic inspection shutdowns. The gas passes to a quench vessel containing multiple water-sprays which scmb most of the soot from the gas. Additional heat recovery can be accompHshed downstream of the quench vessel by heat exchange of the gas with cold feed water. Product gas contains less than 5 ppm soot. 

Unsteady-State Direct Oxidation Process. Periodic iatermption of the feeds can be used to reduce the sharp temperature gradients associated with the conventional oxidation of ethylene over a silver catalyst (209). Steady and periodic operation of a packed-bed reactor has been iavestigated for the production of ethylene oxide (210). By periodically varyiag the inlet feed concentration of ethylene or oxygen, or both, considerable improvements ia the selectivity to ethylene oxide were claimed. 

The rate of polymerization with styrene-type monomers is directly proportional to the number of particles formed. In batch reactors most of the particles are nucleated early in the reaction and the number formed depends on the emulsifier available to stabilize these small particles. In a CSTR operating at steady-state the rate of nucleation of new particles depends on the concentration of free emulsifier, i.e. the emulsifier not adsorbed on other surfaces. Since the average particle size in a CSTR is larger than the average size at the end of the batch nucleation period, fewer particles are formed in a CSTR than if the same recipe were used in a batch reactor. Since rate is proportional to the number of particles for styrene-type monomers, the rate per unit volume in a CSTR will be less than the interval-two rate in a batch reactor. In fact, the maximum CSTR rate will be about 60 to 70 percent the batch rate for such monomers. Monomers for which the rate is not as strongly dependent on the number of particles will display less of a difference between batch and continuous reactors. Also, continuous reactors with a particle seed in the feed may be capable of higher rates. 

One of the few attempts to examine a polymerization reactor in periodic operation experimentally is the work of Spitz, Laurence and Chappelear (X6)who reported the influence of periodicity in the initiator feed to the bulk polymerization of styrene in a CSTR. To induce periodicity the initiator feed was pulsed on-and-off and the reactor output compared with steady-state operation with the same time-averaged initiator input. 

There are many variations on this theme. Fed-batch and continuous emulsion polymerizations are common. Continuous polymerization in a CSTR is dynamically unstable when free emulsifier is present. Oscillations with periods of several hours will result, but these can be avoided by feeding the CSTR with seed particles made in a batch or tubular reactor. 

Fig. 8 Dependence of catalytic activity measured by TOP (rate of reaction per Rh atom) (squares) and IR intensity of hydride (2020-cm mode) (diamonds) during the induction period for ethene hydrogenation catalyzed by Rhg supported on La203 at 298 K and atmospheric pressure in a flow reactor (partial pressures in feed H2, 348 Torr C2H4, 75Torr He, 337 Torr) [37]...

The experiments were performed in a CINC V-02 separator also known as the CS-50 (15). Two Verder VL 500 control peristaltic tube pumps equipped with a double pump head (3,2 x 1,6 x 8R) were used to feed the CCS. In case of the enzymatic reaction, the low mix bottom plate was applied. To operate the reactor at a desired temperature, it was equipped with a jacket which was coimected to a temperature controlled water bath with an accuracy of 0.01°C. The CCS was fed with pure heptane and pure water, both with a flow rate of 6 mL/min. Subsequently, the centrifuge was started (40 Hz, which corresponds to 2400 rpm) and the set-up was allowed to equilibrate for a period of 1 h. At this point, the heptane feed stream was replaced by the organic feed stream (oleic acid (0.6M) and 1-bntanol (0.9M) in heptane). After equilibration for 10 minutes, the reaction in the CCS was started by replacing the water stream with the aqueous feed stream (0.1 M phosphate buffer pH 5.6 containing 1 g/1 of the lipase form Rhizomucor miehei). Samples were taken at regular intervals and analysed by GC. 

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