MODELS OF IMPERFECTLY MIXED REACTORS

Not all tank reactors are perfectly mixed nor do all tubular reactors exhibit plug-flow behavior.
In these situations, some means must be used to allow for deviations from ideal behavior.

When constructing a flow model for a given chemical reactor, one starts by knowledge of the
pattern of fluid passage through the reactor. This flow behaviour could be determined by finding the
complete history of each fluid element. It was poited out that instead of this complexity of flow
patterns, it is enough to know how long the fluid element stays in the reactor, in other words, to
determine the residence time distribution (RTD) of the fluid particles in the exit streams.

The residence time of a fluid element is the time that elapses from the time the element enters
the vessel to the time it leaves. The age of the fluid element at a given instant is the time that elapses
between the elements entrance into the vessel and the given instant. The residence distribution time
(RDT) is the age distribution frequency of the fluid elements leaving the vessel.

RTD is sufficient if the reaction is first order or if the fluid is either in a state of complete
segregation or maximum mixedness. We use the segregation and maximum mixedness models to bound
the conversion when no adjustable parameters are use. For non-first-order reactions in a fluid with good
micromixing, more than just the RTD is needed. These situations compose a number of reactor analysis
problems and cannot be ignored. For example, we may have an existing reactor in storage and want to
carry out a new reaction in the reactor. To predict conversions and product distribution for such
systems, a model of reactor flow patterns and/or RTD is necessary.

Using the models, we will first measure the RTD to characterize the reactor at the new operating
conditions of temperature and flow rate. After selecting a model for the reactor, we use the RTD to
evaluate the parameter(s) in the model after which we calculate the conversion.

GUIDELINES FOR DEVELOPING MODELS

The choice of the particular model to be used depends largely on the engineering judgment of
the person carrying out the analysis. It is this person’s job to choose the model that best combines the
conflicting goals of mathematical simplicity and physical realism.

For a given real reactor, it is not uncommon to use all the models to predict conversion and then make
comparisons. Usually, the real conversion will be bounded by the model calculations.

The following guidelines are suggested when developing models for non-ideal reactors:

1. The model must be mathematically tractable. The equations used to describe a chemical reactor
should be able to be solved without an inordinate expenditure of human or computer time.

2. The model must realistically describe the characteristics of the non-ideal reactor. The phenomena
occurring in the nonideal reactor must be reasonably described physically, chemically, and
mathematically.
3. The model should not have more than two adjustable parameters. This constraint is often used
because an expression with more than two adjustable parameters can be fitted to a great variety of
experimental data, and the modeling process in this circumstance is nothing more than an exercise in
curve fitting. A one-parameter model is, of course, superior to a two-parameter model if the one-
parameter model is sufficiently realistic. To be fair, however, in complex systems (e.g., internal diffusion
and conduction, mass transfer limitations) where other parameters may be measured independently,
then more than two parameters are quite acceptable.

The reactors treated thus far—the perfectly mixed batch, the plug-flow tubular, the packed bed,
and the perfectly mixed continuous tank reactors have been modeled as ideal reactors. Unfortunately,
in the real world we often observe behavior very different from that expected from the exemplar; this
behavior is true of students, engineers, college professors, and chemical reactors. Just as we must learn
to work with people who are not perfect, so the reactor analyst must learn to diagnose and handle
chemical reactors whose performance deviates from the ideal. Non-ideal reactors and the principles
behind their analysis form the subject of this chapter and the next.

Two types of ideal flow are commonly used as limits of flow patterns in process vessels; these
are the "plug flow" and the "perfectly mixed" flow.

The conditions for the physical realization of the plug flow are fulfilled in a piston-type flow,
when it is assumed that there is no mixing takes place in the direction of the flow. The model is
employed to describe tubular apparatus with a large length to diameter ratio. At the other extremes,
perfect mixing assumes that the vessel contents are completely homogeneous and the outlet stream
properties are identical to the vessel-fluid properties. In chemical engineering, the usual tendency is to
come closer to conditions of perfect mixing by fitting apparatus with special mixers, baffles, etc.

Non-idealities of flow in industrial apparatus can be traced to the following most important reasons:

 Presence of dead spaces

Stagnant fluids or dead spaces - represents regions with extremely poor contacting. A dead space will
contain fluid elements for interval of time with an order of magnitude over the mean residence time.

Bypassing or channeling - is when some of the fluids slip or pass through the vessel considerably faster
than others do. Bypassing may be found in flow through poorly packed vessels, through heat exchanger
in two-phase operations etc.

Recycling - a certain amount of fluid is recirculated or returned to the vessel inlet. This type of flow may
be desirable for example in auto-thermal reactions.
Overall three somewhat interrelated factors make up the contacting or flow pattern:

 the RTD or residence time distribution of material which is flowing through the vessel
 the state of aggregation of the flowing material, its tendency to clump and for a group of
molecules to move about together
 the earliness and lateness of mixing of material in the vessel.

The Residence Time Distribution, RTD

Deviation from the two ideal flow patterns can be caused by channeling of fluid, by recycling of
fluid, or by creation of stagnant regions in the vessel. Figure 11.1 shows this behavior. In all types of
process equipment, such as heat exchangers, packed columns, and reactors, this type of flow should be
avoided since it always lowers the performance of the unit. If we know precisely what is happening
within the vessel, thus if we have a complete velocity distribution map for the fluid in the vessel, then
we should, in principle, be able to predict the behavior of a vessel as a reactor. Unfortunately, this
approach is impractical, even in today's computer age.

Setting aside this goal of complete knowledge about the flow, let us be less ambitious and see
what it is that we actually need to know. In many cases we really do not need to know very much, simply
how long the individual molecules stay in the vessel, or more precisely, the distribution of residence
times of the flowing fluid. This information can be determined easily and directly by a widely used
method of inquiry, the stimulus-response experiment.

State of Aggregation of the Flowing Stream

Single-Phase Systems. These lie somewhere between the extremes of macro- and microfluids.

Two-Phase Systems. A stream of solids always behaves as a macrofluid, but for gas reacting with liquid,
either phase can be a macro- or microfluid depending on the contacting scheme being used. The
sketches of Fig. 11.3 show completely opposite behavior. We treat these two phase reactors in later
chapters.

Earliness of Mixing

The fluid elements of a single flowing stream can mix with each other either early or late in their flow
through the vessel. For example, see Fig. 11.4. Usually this factor has little effect on overall behavior for
a single flowing fluid. However, for a system with two entering reactant streams it can be very
important. For example, see Fig. 11.5.
17.2 Zero-Adjustable-Parameter Models

17.2.1 Segregation Model

In a “perfectly mixed” CSTR, the entering fluid is assumed to be distributed immediately and
evenly throughout the reacting mixture. This mixing is assumed to take place even on the microscale,
and elements of different ages mix together thoroughly to form a completely micromixed fluid (see
Figure 17-1(b)). However, if fluid elements of different ages do not mix together at all, the elements
remain segregated from each other, and the fluid is termed completely segregated (see Figure 17-1(a)).
The extremes of complete micromixing and complete segregation are the limits of the micromixing of a
reacting mixture.
17.2.2 Maximum Mixedness Model

In a reactor with a segregated fluid, mixing between particles of fluid does not occur until the
fluid leaves the reactor. The reactor exit is, of course, the latest possible point where mixing can occur,
and any effect of mixing is postponed until after all reaction has taken place. We can also think of a
completely segregated flow as being in a state of minimum mixedness. We now want to consider the
other extreme, that of maximum mixedness consistent with a given residence time distribution. As soon
as the fluid enters the reactor, it is completely mixed radially (but not longitudinally) with the other fluid
already in the reactor. The entering fluid is fed into the reactor through the side entrances in such a
manner that the RTD of the plug-flow reactor with side entrances is identical to the RTD of the real
reactor.

In the reactor with side entrances, mixing occurs at the earliest possible moment consistent with
the RTD. This situation is termed the condition of maximum mixedness.

18.1.1 One-Parameter Models

Here, we use a single parameter to account for the non-ideality of our reactor. This parameter is
most always evaluated by analyzing the RTD determined from a tracer test. Examples of one-parameter
models for non-ideal CSTRs include either a reactor dead volume, VD, where no reaction takes place, or
volumetric flow rate with part of the fluid bypassing the reactor, υb, thereby exiting unreacted.
Examples of one-parameter models for tubular reactors include the tanks-in-series model and the
dispersion model. For the tanks-in-series model, the one parameter is the number of tanks, n, and for
the dispersion model, the one parameter is the dispersion coefficient, Da. Knowing the parameter
values, we then proceed to determine the conversion and/or effluent concentrations for the reactor.

18.1.1.1 The Tanks-in-Series (T-I-S) One-Parameter Model

The T-I-S model is a one-parameter model. We will analyze the RTD to determine the number of ideal
tanks, n, in series that will give approximately the same RTD as the non- ideal reactor.

The number of tank in series is

This expression represents the number of tanks necessary to model the real reactor as n ideal tanks in
series. If the number of reactors, n, turns out to be small, the reactor characteristics turn out to be those
of a single CSTR or perhaps two CSTRs in series. At the other extreme, when n turns out to be large, the
reactor characteristics approach those of a PFR.
18.1.1.2 Dispersion One-Parameter Model

The dispersion model is also often used to describe non-ideal tubular reactors. In this model, there is an
axial dispersion of the material, which is governed by an analogy to Fick’s law of diffusion, superimposed
on the flow as shown in Figure 18-4. So in addition to transport by bulk flow, UAcC, every component in
the mixture is transported through any cross section of the reactor at a rate equal to [–DaAc(dC/dz)]
resulting from molecular and convective diffusion. By convective diffusion (i.e., dispersion), we mean
either Aris-Taylor dispersion in laminar-flow reactors or turbulent diffusion resulting from turbulent
eddies. Radial concentration profiles for plug flow (a) and a representative axial and radial profile for
dispersive flow (b) are shown in Figure 18-4. Some molecules will diffuse forward ahead of the molar
average velocity, while others will lag behind.

18.1.2 Two-Parameter Models

The premise for the two-parameter model is that we can use a combination of ideal reactors to model
the real reactor. For example, consider a packed bed reactor with channeling. Here, the response to a
pulse tracer input would show two dispersed pulses in the output as shown in Figure 16-1 and Figure 18-
1.

Here, we could model the real reactor as two ideal PBRs in parallel, with the two parameters being the
volumetric flow rate that channels or by passes, υb , and the reactor dead volume, VD. The real reactor
volume is V = VD + VS with entering volumetric flow rate υ0 = υb + υS.