CL5005 REACTION

ENGINEERING

MODULE

II
Lecture Notes:
DESIGN OF
Debasree Ghosh IDEAL
Assistant Professor,
REACTORS
Department of Chemical Engineering,
Birla Institute of Technology, Mesra
Introduction To Reactor Design
• In reactor design we want to know what size and type of reactor and
method of operation are best for a given job. Because this may require that
the conditions in the reactor vary with position as well as time, this
question can only be answered by a proper integration of the rate equation
for the operation. This may pose difficulties because the temperature and
composition of the reacting fluid may vary from point to point within the
reactor, depending on the endothermic or exothermic character of the
reaction, the rate of heat addition or removal from the system, and the flow
pattern of fluid through the vessel. In effect, then, many factors must be
accounted for in predicting the performance of a reactor. How best to treat
these factors is the main problem of reactor design.
• In this module, several ideal types of reactors are discussed based on two
modes of operation (batch and continuous), and ideal flow patterns (back-
mix and tubular) for the continuous mode.
• four types of ideal reactors are : (1) Batch reactor (BR), based on complete
mixing; (2) Continuous-flow stirred tank reactor (CSTR), based on back-
mix flow; (3) Plug-flow reactor (PFR), based on plug flow; and (4)
Laminar-flow reactor (LFR), based on laminar flow.
Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Introduction To Reactor Design

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Batch Reactor (BR)
• A batch reactor (BR) is sometimes used for investigation of the
kinetics of a chemical reaction in the laboratory, and also for
larger-scale (commercial) operations in which a number of
different products are made by different reactions on an
intermittent basis.

Batch reactor (schematic, liquid-phase reaction)

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
• Characteristics of BR
1. Each batch is a closed system.
2. The total mass of each batch is fixed.
3. The volume or density of each batch may vary (as reaction
proceeds).
4. The energy of each batch may vary (as reaction proceeds); for
example, a heat exchanger may be provided to control
temperature, as indicated in above Figure .
5. The reaction (residence) time t for all elements of fluid is the
same.
6. The operation of the reactor is inherently unsteady-state; for
example, batch composition changes with respect to time.
7. Point (6) notwithstanding, it is assumed that, at any time, the
batch is uniform (e.g., in composition, temperature, etc.), because
of efficient stirring.
Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Performance equation of BR
• In a batch reactor, since the composition is uniform throughout at any
instant of time, we may make the accounting about the whole reactor.
Noting that no fluid enters or leaves the reaction mixture during reaction,
• Material balance with respect to reactant A(say) is as follows:

or

Or there fore

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
• The performance equation of BR with constant density system
is

• For all reactions in which the volume of reacting mixture

changes proportionately with conversion, such as in single gas-
phase reactions with significant density changes, above
equation becomes

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Space-Time and Space-Velocity
• SPACE-TIME

• SPACE-VELOCITY

• Again

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continuous-flow stirred tank reactor (CSTR)
• A continuous stirred-tank reactor (CSTR) is normally used for liquid-
phase reactions, both in a laboratory and on a large scale. It may also be
used, however, for the laboratory investigation of gas-phase reactions,
particularly when solid catalysts are involved, in which case the operation
is batch-wise for the catalyst.
• Stirred tanks may also be used in a series arrangement (e.g., for the
continuous copolymerization of styrene and butadiene to make synthetic
rubber).

Single CSTR 2 CSTR in series

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
• Characteristics of CSTR
1. The flow through the vessel(s), both input and output streams,
is continuous but not necessarily at a constant rate.
2. The system mass inside each vessel is not necessarily fixed.
3. The fluid inside each vessel is perfectly mixed (back-mix flow,
BMF), and hence its properties are uniform at any time,
because of efficient stirring.
4. The density of the flowing system is not necessarily constant;
that is, the density of the output stream may differ from that of
the input stream.
5. The system may operate at steady-state or at unsteady-state.
6. A heat exchanger may be provided in each vessel to control
temperature

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Performance equation of CSTR
• The fluid inside the vessel is uniformly mixed (and hence
elements of fluid are uniformly distributed), all fluid elements
have equal probability of leaving the vessel in the output stream
at any time. Therefore, the output stream has the same
properties as the fluid inside the vessel. If there is a step-change
across the inlet in any property of the system that changes from
inlet to outlet;
• Material balance:

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
• As referred to the above figure

Or

Therefore

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued….

Order of reaction A Performance equation

1st order 0

1st order Any value

2nd order 0

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
example

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Plug-flow reactor (PFR)
 steady-state
 maintenance of constant throughput
 turbulent flow with plug flow velocity
profile
 L/D ratio is sufficiently large
 D/Dp ratio is sufficiently large
 low pressure drop
 well-defined axial T-profile
 negligible radial T-profile
 prevention of further reaction following
sampling

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Plug-flow reactor (PFR)
• A plug-flow reactor (PFR) may be used for both liquid-phase and gas-
phase reactions, and for both laboratory-scale investigations of kinetics
and large-scale production. The reactor itself may consist of an empty
tube or vessel, or it may contain packing or a tied bed of particles (e.g.,
catalyst particles).
• A PFR is similar to a CSTR in being a flow reactor, but is different in
its mixing characteristics. It is different from a BR in being a flow
reactor, but is similar in the progressive change of properties, with
position replacing time. These features are explored further in this
section, but first we elaborate the characteristics of a PFR, as follows:
1. The flow through the vessel, both input and output streams, is
continuous, but not necessarily at constant rate; the flow in the vessel
is PF.
2. The system mass inside the vessel is not necessarily fixed.
3. There is no axial mixing of fluid inside the vessel (i.e., in the direction
of flow).

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…..
4. There is complete radial mixing of fluid inside the vessel (i.e., in the plane
perpendicular to the direction of flow); thus, the properties of the fluid,
including its velocity, are uniform in this plane.
5. The density of the flowing system may vary in the direction of flow.
6. The system may operate at steady-state or at unsteady-state.
7. There may be heat transfer through the walls of the vessel between the
system and the surroundings.
• MATERIAL BALANCE:
• In a plug flow reactor the composition of the fluid varies from point to
point along a flow path; consequently, the material balance for a reaction
component must be made for a differential element of volume dV. Thus
for reactant A, the balance equation becomes

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Performance equation of PFR
• from the figure

• Therefore the overall balance equation

• is
theas follows:

or

or

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
• This, then, is the equation which accounts for A in the
differential section of reactor of volume dV. For the reactor as a
whole the expression must be integrated. Now FA,, the feed
rate, is constant, but r, is certainly dependent on the
concentration or conversion of materials. Grouping the terms
accordingly, we obtain

• Thus

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
SOME SPECIAL CASES
• For constant-density systems ( )

• Zero-order homogeneous reaction, any constant

• First-order irreversible reaction

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
• First-order reversible reaction,
and
therefore the performance equation is

where is the equilibrium conversion.

• Second-order irreversible reaction

And the performance equation is

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Holding Time and Space Time for Flow Reactors
• Space time is

• Holding time is

• Therefore for constant density systems

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Laminar-flow reactor (LFR)
• A laminar-flow reactor (LFR) is rarely used for kinetic studies, since it
involves a flow pattern that is relatively difficult to attain experimentally.
However, the model based on laminar flow, a type of tubular flow, may be
useful in certain situations, both in the laboratory and on a large scale, in
which flow approaches this extreme (at low Re). Such a situation would
involve low fluid flow rate, small tube size, and high fluid viscosity, either
separately or in combination, as, for example, in the extrusion of high-
molecular-weight polymers.

LAMINAR FLOW REACTOR

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Characteristics of LFR
• The general characteristics of the simplest model of a
continuous LFR, illustrated schematically in above Figure , are
as follows:
1. The flow through the vessel is laminar (LF) and continuous, but
not necessarily at constant rate.
2. The system mass inside the vessel is not necessarily fixed.
3. There is no axial mixing of fluid inside the vessel.
4. There is no radial mixing of fluid inside the vessel.
5. The density of the flowing system is not necessarily constant.
6. The system may operate at steady-state or at unsteady-state.
7. There may be heat transfer through the walls of the vessel
between the system and the surroundings.

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Size comparison of single reactors
• The batch reactor has the advantage of small instrumentation cost and
flexibility of operation (may be shut down easily and quickly).
• It has the disadvantage of high labor and handling cost, often considerable
shutdown time to empty, clean out, and refill, and poorer quality control of
the product.
• Hence we may generalize to state that the batch reactor is well suited to
produce small amounts of material and to produce many different products
from one piece of equipment.
• On the other hand, for the chemical treatment of materials in large amounts
the continuous process is nearly always found to be more economical.
• Regarding reactor sizes, a comparison for a given duty and for  = 0 shows
that an element of fluid reacts for the same length of time in the batch and in
the plug flow reactor have the same volume.
• Of course, on a long-term production basis we must correct the size
requirement estimate to account for the shutdown time between batches. Still,
it is easy to relate the performance capabilities of the batch reactor with the
plug flow reactor.

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
• Mixed Versus Plug Flow Reactors
• For a given duty the ratio of sizes of mixed and plug flow reactors will
depend on the extent of reaction, the stoichiometry, and the form of the
rate equation.
• Let us make this comparison for the large class of reactions approximated
by the simple nth-order rate law

• For mixed flow reactor the space time calculated is as follows:

• For plug flow reactor the space time calculated is as follows:

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
• Therefore

• With constant density, or  = 0, this expression integrates to

• or

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Comparison of performance of single mixed flow and
plug flow reactors for the nth-order reactions

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
• From the above figure we can conclude that:
1. For any particular duty and for all positive reaction orders the mixed
reactor is always larger than the plug flow reactor. The ratio of volumes
increases with reaction order.
2. When conversion is small, the reactor performance is only slightly
affected by flow type. The performance ratio increases very rapidly at
high conversion; consequently, a proper representation of the flow
becomes very important in this range of conversion.
3. Density variation during reaction affects design; however, it is normally
of secondary importance compared to the difference in flow type.
• Variation of Reactant Ratio for Second-Order Reactions
• Second-order reactions of two components and of the type

• For M =1, the order of reaction is two and for M > 1, the order of reaction
is one.
Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
General Graphical Comparison

Comparison of performance of mixed flow and plug flow reactors for any
reaction kinetics.
• For reactions with arbitrary but known rate the performance capabilities of
mixed and plug flow reactors are best illustrated in Fig. The ratio of
shaded and of hatched areas gives the ratio of space-times needed in these
two reactors.
• The rate curve drawn in Fig. 6.2 is typical of the large class of reactions
whose rate decreases continually on approach to equilibrium (this includes
all nth-order reactions, n > 0). For such reactions it can be seen that mixed
flow always needs a larger volume than does plug flow for any given duty.

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Multiple-reactor systems
• Plug Flow Reactors in Series and/or in Parallel
• Consider N plug flow reactors connected in series, and let X1, X2, . . . , XN,
be the fractional conversion of component A leaving reactor 1, 2, . . . , N.
Basing the material balance on the feed rate of A to the first reactor, we
find for the ith reactor from

• For N numbers of reactors in series

• Hence, N plug flow reactors in series with a total volume V gives the same
conversion as a single plug flow reactor of volume V.

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
• For the optimum hook up of plug flow reactors connected in
parallel or in any parallel-series combination, we can treat the
whole system as a single plug flow reactor of volume equal to
the total volume of the individual units if the feed is distributed
in such a manner that fluid streams that meet have the same
composition. Thus, for reactors in parallel V/F or  must be the
same for each parallel line. Any other way of feeding is less
efficient.

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Equal-Size Mixed Flow Reactors in Series
• In plug flow, the concentration of reactant decreases
progressively through the system; in mixed flow, the
concentration drops immediately to a low value. Because of this
fact, a plug flow reactor is more efficient than a mixed flow
reactor for reactions whose rates increase with reactant
concentration, such as nth-order irreversible reactions, n > 0.
• Consider a system of N mixed flow reactors connected in series.
Though the concentration is uniform in each reactor, there is,
nevertheless, a change in concentration as fluid moves from
reactor to reactor. This stepwise drop in concentration,
illustrated in Fig. below, suggests that the larger the number of
units in series, the closer should the behavior of the system
approach plug flow.

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…

Concentration profile through an N-

stage mixed flow reactor system
compared with single flow reactors.
Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…

Notation for a system of N equal-size mixed reactors in series.

• Let us now quantitatively evaluate the behavior of a series of N equal-size
mixed flow reactors. Density changes will be assumed to be negligible;
hence  = 0 and t =  . As a rule, with mixed flow reactors it is more
convenient to develop the necessary equations in terms of concentrations
rather than fractional conversions; therefore, we use this approach. The
nomenclature used is shown in Fig. above with subscript i referring to the
ith vessel.

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
• So the performance equation becomes

• For 1st order reaction in constant density system

Or

• Now the space-time (or mean residence time t) is the same in all the equal
size reactors of volume Vi. Therefore,

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
• Rearranging, we find for the system as a whole

• In the limit, for N  , this equation reduces to the plug flow

equation

• This comparison is shown in Fig. below for first-order reactions

in which density variations are negligible.

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
Continued…
• Comparison of performance of a series of N equal-size mixed flow
reactors with a plug flow reactor for the first-order reaction

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors
PFR and CSTR Combinations in Series
• To this point it has been shown, mainly by illustration, that the
performance of a reactor depends on three factors:
1. The kinetics of reaction, as described by the rate law; thus, the fractional
conversion depends on the order of reaction.
2. The characteristics of flow through the vessel as described by the RTD;
thus, for given kinetics, the fractional conversion in a reactor with PF (a
PFR) is different from that in one with BMF (a CSTR).
3. The nature of mixing of fluid elements during flow through the vessel as
characterized, so far, by the degree of segregation; thus, in a CSTR (i.e., a
given RTD) with given kinetics, the fractional conversion is different for
the extremes of non-segregated flow and completely segregated flow,
except for a first-order reaction, which is a linear process. Reactions of
other orders are examples of nonlinear processes

Debasree Ghosh, Lecture notes on Polymer Reaction Engineering, Module II: Design of Ideal Reactors