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# Chapter 3

Ideal Reactors

LEARNING OBJECTIVES

After completing this chapter, you should be able to

1. explain the differences between the three ideal reactors: batch, continuous stirred

tank, and plug ﬂow;

2. explain how the reactant and product concentrations vary spatially in ideal batch,

ideal continuous stirred tank, and ideal plug-ﬂow reactors;

3. derive ‘‘design equations’’ for the three ideal reactors, for both homogeneous

and heterogeneous catalytic reactions, by performing component material balances;

4. calculate reaction rates using the ‘‘design equation’’ for an ideal continuous

stirred-tank reactor;

5. simplify the most general forms of the ‘‘design equations’’ for the case of constant

mass density.

The next few chapters will illustrate how the behavior of chemical reactors can be

predicted, and how the size of reactor required for a given ‘‘job,’’ can be determined.

These calculations will make use of the principles of reaction stoichiometry and reaction

kinetics that were developed in Chapters 1 and 2.

There are many different types of reactor. One of the most important features that

differentiates one kind of reactor from another is the nature of mixing in the reactor. The

inﬂuence of mixing is easiest to understand through the material balance(s) on the reactor.

These material balances are the starting point for the discussion of reactor performance.

3.1 GENERALIZED MATERIAL BALANCE

The reaction rate r

i

is an intensive variable. It describes the rate of formation of species

‘‘i’’ at any point in a chemical reactor. However, as we learned in Chapter 2, the rate of

any reaction depends on variables such as temperature and the species concentrations. If

these variables change from point to point in the reactor, r

i

also will change from point

to point.

For the time being, to emphasize that r

i

depends on temperature and on the various

species concentrations, let’s use the nomenclature

r

i

= r

i

(T; all C

i

)

The term‘‘all C

i

’’ reminds us that the reaction rate may be inﬂuenced by the concentration of

each and every species in the system.

Consider an arbitrary volume (V) in which the temperature and the species concen-

trations vary from point to point, as shown below.

36

T

1

, all C

i,1

(Point 1)

T

2

, all C

i,2

(Point 2)

T

3

, all C

i,3

(Point 3)

The rate at which ‘‘i’’ is formed in this control volume by a chemical reaction or reactions is

designated G

i

, the generation rate of ‘‘i’’. The units of G

i

are moles/time. For a homogeneous

reaction, G

i

is related to r

i

by

Generation rate÷÷

homogeneous reaction

G

i

=

Z Z Z

V

r

i

dV

(3-1)

For a heterogeneous catalytic reaction, where r

i

has units of moles/time-weight of catalyst,

G

i

is given by

Generation rate÷÷

heterogenous catalytic

reaction

G

i

=

Z Z Z

W

r

i

dW =

Z Z Z

V

r

i

r

B

dV (3-2)

Here, r

B

is the bulk density of the catalyst (weight/volume of reactor). In Eqns. (3-1) and

(3-2), r

i

is the net rate at which ‘‘i’’ is formed by all of the reactions taking place, as given by

Eqn. (1-17).

Although they are formally correct, Eqns. (3-1) and (3-2) are not very useful in practice.

This is because the reaction rate r

i

is never known as an explicit function of position.

Therefore, the indicated integrations cannot be performed directly. The means of resolving

this apparent dilemma will become evident as we treat some speciﬁc cases.

Generalized component material balance

Consider the control volume shown below, with chemical reactions taking place that result

in the formation of species ‘‘i’’ at a rate, G

i

. Species ‘‘i’’ ﬂows into the systemat a molar ﬂow

rate of F

i0

(moles i/time), and ﬂows out of the system at a molar ﬂow rate of F

i

.

F

i0

F

i

T

1

, all C

i,1

(Point 1)

T

2

, all C

i,2

(Point 2)

T

3

, all C

i,3

(Point 3)

3.1 Generalized Material Balance 37

The molar material balance for species ‘‘i’’ for this control volume is

rate in ÷ rate out ÷ rate of generation by chemical reactions = rate of accumulation

Generalized material balance

on component ‘‘i’’

F

i0

÷ F

i

÷ G

i

=

dN

i

dt

(3-3)

Here ‘‘t’’ is the time and N

i

is the number of moles of ‘‘i’’ in the system at any time.

Now let’s consider three special cases that are of practical signiﬁcance, and allow Eqn.

(3-3) to be simpliﬁed to a point that it is useful.

3.2 IDEAL BATCH REACTOR

A batch reactor is deﬁned as a reactor in which there is no ﬂow of mass across the system

boundaries, once the reactants have been charged. The reaction is assumed to begin at some

precise point in time, usually taken as t = 0. This time may correspond, for example, to

when a catalyst or initiator is added to the batch, or to when the last reactant is added.

As the reaction proceeds, the number of moles of each reactant decreases and the

number of moles of each product increases. Therefore, the concentrations of the species in

the reactor will change with time. The temperature of the reactor contents may also change

with time. The reaction continues until it reaches chemical equilibrium, or until the limiting

reactant is consumed completely, or until some action is taken to stop the reaction, e.g.,

cooling, removing the catalyst, adding a chemical inhibitor, etc.

Figure 3-1a Overall view of a

nominal 7000 gallon batch reactor

(in a plant of Syngenta Crop

Protection, Inc.). This reactor is used

to produce several different products.

The reactor has a jacket around it to

permit heat to be transferred into or

out of the reactor contents via a

heating or cooling ﬂuid that

circulates through the jacket. The

hoists are used for lifting raw

materials to higher levels of the

structure. (Photo used with

permission of Syngenta Crop

Protection, Inc.)

38 Chapter 3 Ideal Reactors

Batch reactors are used extensively throughout the chemical and pharmaceutical

industries to manufacture products on a relatively small scale. Properly equipped, these

reactors are very ﬂexible. Asingle reactor may be used to produce many different products.

Batch reactors usually are mechanically agitated to ensure that the contents are well

mixed. Agitation also increases the heat-transfer coefﬁcient between the reactor contents

and any heat-transfer surface in the reactor. In multiphase reactors, agitation may also keep a

solid catalyst suspended, or may create surface area between two liquid phases or between a

gas phase and a liquid phase.

Very few reactions are thermally neutral (DH

R

= 0), so it frequently is necessary to

either supply heat or remove heat as the reaction proceeds. The most common means to

transfer heat is to circulate a hot or cold ﬂuid, either through a coil that is immersed in the

reactor, or through a jacket that is attached to the wall of the reactor, or both.

For a batch reactor, F

i0

= F

i

= 0. Therefore, for a homogeneous reaction, Eqn. (3-3)

becomes

G

i

=

Z Z Z

V

r

i

dV =

dN

i

dt

(3-4)

Ideal batch reactor

Now, consider a limiting case of batch-reactor behavior. Suppose that agitation of the reactor

contents is vigorous, i.e., mixing of ﬂuid elements in the reactor is very intense. Then the

temperature and the species concentrations will be the same at every point in the reactor, at

every point in time. A batch reactor that satisﬁes this condition is called an ideal batch

reactor. Many laboratory and commercial reactors can be treated as ideal batch reactors, at

least as a ﬁrst approximation.

For an ideal batch reactor, r

i

is not a function of position. Therefore,

RRR

V

r

i

dV = r

i

V

and Eqn. (3-4) becomes

r

i

V =

dN

i

dt

Figure 3-1b The top of the reactor in Figure 3-1a. The view port in the left front of the picture

permits the contents of the reactor to be observed, and can be opened to permit solids to be charged to

the reactor. Amotor that drives an agitator is located in the top center of the picture, and a charging line

and valve actuator connected to a valve are on the left. (Photo used with permission of Syngenta Crop

Protection, Inc.)

3.2 Ideal Batch Reactor 39

Rearranging

Design equation÷÷

ideal batch reactor÷÷

homogeneous reaction

(moles)

1

V

dN

i

dt

= r

i

(3-5)

Equation (3-5) is referred to as the design equation for an ideal batch reactor, in

differential form. This equation is valid no matter how many reactions are taking place,

provided that Eqn. (1-17) is used to express r

i

, and provided that all of the reactions are

homogeneous.

The subject of multiple reactions is treated inChapter 7. Until then, wewill be concerned

with the behavior of one, stoichiometrically simple reaction. For that case, r

i

in Eqn. (3-5) is

just the rate equation for the formation of species ‘‘i’’ in the reaction of concern.

The variable that describes composition in Eqn. (3-5) is N

i

, the total moles of species

‘‘i’’. It sometimes is more convenient to work problems in terms of either the extent of

reaction j or the fractional conversion of a reactant, usually the limiting reactant. Extent of

reaction is very convenient for problems where more than one reaction takes place.

Fractional conversion is convenient for single-reaction problems, but can be a source of

confusion in problems that involve multiple reactions. The use of all three compositional

variables, moles (or molar ﬂow rates), fractional conversion, and extent of reaction, will be

illustrated in this chapter, and in Chapter 4.

If ‘‘i’’ is a reactant, say A, then the number of moles of Ain the reactor at anytime can be

written in terms of the fractional conversion of A.

x

A

=

N

A0

÷ N

A

N

A0

; N

A

= N

A0

(1 ÷ x

A

)

In terms of fractional conversion, Eqn. (3-5) is

Design equation÷÷

ideal batch reactor÷÷

homogeneous reaction

(fractional conversion)

N

A0

V

dx

A

dt

= ÷r

A

(3-6)

If ‘‘A’’ is the limiting reactant, the value of x

A

that is stoichiometrically attainable will lie

between 0 and 1. However, as discussed in Chapter 1, chemical equilibrium may limit the

value of x

A

that can actually be achieved to something less than 1.

Equation (3-6) should not be applied to a product. First, N

A

will be greater than N

A0

if

‘‘A’’ is a product. Moreover, if N

A0

= 0; x

A

is inﬁnite. However, Eqn. (3-5) can be used for

either a product or a reactant.

The design equation can also be written in terms of the extent of reaction. If only one

stoichiometrically simple reaction is taking place

j =

DN

i

n

i

=

N

i

÷ N

i0

n

i

(1-4)

Design equation÷÷

ideal batch reactor÷÷

homogeneous reaction

(extent of reaction)

n

i

V

dj

dt

= r

i

(3-7)

40 Chapter 3 Ideal Reactors

Equations (3-5)–(3-7) are alternative forms of the design equation for an ideal batch

reactor with a homogeneous reaction taking place. Despite the somewhat pretentious name,

design equations are nothing more than component material balances, i.e., molar balances

on ‘‘i’’, ‘‘A’’, etc.

The volume V in Eqns. (3-5)–(3-7) is that portion of the overall reactor volume in which

the reaction actually takes place. This is not necessarily the whole geometrical volume of

the reactor. For example, consider a reaction that takes place in a liquid that partially ﬁlls a

vessel. If no reaction takes place in the gas-ﬁlled ‘‘headspace’’ above the liquid, then Vis the

volume of liquid, not the geometrical volume of thevessel, which includes the ‘‘headspace.’’

Equations (3-5)–(3-7) apply to a homogeneous reaction. For a reaction that is catalyzed

by a solid, the design equation that is equivalent to Eqn. (3-5) is

Design equation÷÷

ideal batch reactor÷÷

heterogeneous catalytic reaction

(moles)

1

W

dN

i

dt

= r

i

(3-5a)

EXERCISE 3-1

Derive this equation.

The equivalents to Eqns. (3-6) and (3-7) for heterogeneously catalyzed reactions are givenin

Appendix 3 at the end of this chapter, and are labeled Eqns. (3-6a) and (3-7a). Be sure that

you can derive them.

Temperature variation with time

In developing Eqns. (3-5)–(3-7), we did not assume that the temperature of the reactor contents

was constant, independent of time. Only one assumption was made concerning temperature,

i.e., there are no spatial variations in the temperature at any time. An ideal batch reactor is said

to be isothermal when the temperature does not vary with time. The design equations for an

ideal batch reactor are valid for both isothermal and nonisothermal operation.

Constant volume

If Vis constant, independent of time, Eqn. (3-5) can be written in terms of concentration as

dC

i

dt

= r

i

(3-8)

where C

i

is the concentration of species i. Similarly, if V is constant, Eqn. (3-6) can be

written as

C

A0

dx

A

dt

= ÷r

A

(3-9)

where C

A0

is the initial concentration of A. Equations (3-8) and (3-9) are alternative forms of

the design equations for an ideal, constant-volume batch reactor, in differential form. The

lighter boxes around these equations indicate that they are not as general as Eqns. (3-5) and

(3-6) because they contain the assumption of constant volume.

If the volume V is constant, then the mass density of the system, r (mass/volume), must

also be constant, since the mass of material in a batch reactor does not change with time. We

could have speciﬁed that the mass density was constant instead of specifying that the reactor

volume was constant. These two statements are equivalent. However, for a batch reactor,

3.2 Ideal Batch Reactor 41

constant volume probably is easier to visualize than constant mass density. For constant-

volume (constant mass density) systems, the design equations can be written directly in

terms of concentrations, which can easily be measured. For systems where the mass density

is not constant, we must work with the most general forms of the design equations, using

moles, fractional conversion, or extent of reaction.

For a heterogeneous catalytic reaction, derivation of the constant-volume version of

Eqn. (3-5a) requires a bit of manipulation.

1

W

dN

i

dt

= r

i

(3-5a)

Dividing by the reactor volume V and multiplying by W

1

V

dN

i

dt

=

W

V

r

i

If V is constant,

Design equation÷÷

ideal batch reactor÷÷

heterogeneous catalytic reaction

(constant volume)

dC

i

dt

= C

cat

r

i

(3-8a)

Equation (3-8a) is the design equation for an ideal, constant-volume, batch reactor for a

reaction that is catalyzed by a solid catalyst. The symbol C

cat

represents the mass

concentration (mass/volume) of the catalyst. The catalyst concentration does not change

with time if V is constant.

The equivalent of Eqn. (3-9) for a heterogeneous catalytic reaction is given in Appendix

3.I at the end of this chapter and is labeled Eqn. (3-9a).

The assumption of constant volume is valid for most industrial batch reactors. The mass

density is approximately constant for a large majority of liquids, even if the temperature

changes moderately as the reaction proceeds. Therefore, the assumption of constant volume

is reasonable for batch reactions that take place in the liquid phase. Moreover, if a rigid

vessel is ﬁlled with gas, the gas volume will be constant because the dimensions of the vessel

are ﬁxed and do not vary with time.

Variable volume

If V changes with time, Eqn. (3-5) must be written

1

V

dN

i

dt

=

1

V

d(C

i

V)

dt

=

dC

i

dt

÷

C

i

V

dV

dt

= r

i

Clearly, this equation is more complex, and harder to work with, than Eqn. (3-8).

EXERCISE 3-2

There are a few batch reactors where the assumption of constant

volume is not appropriate. Can you think of one? Hint: You

probably come within 10 ft of this reactor at least once a week,

perhaps even every day.

Integrated forms of the design equation

The design equation must be integrated in order to solve problems in reactor design and

analysis. In order to actually perform the integration, the temperature must be known as a

function of either time or composition. This is because the rate equation r

i

contains one or

more constants that depend on temperature.

42 Chapter 3 Ideal Reactors

As we shall see in Chapter 8, the energy balance determines how the reactor temper-

ature changes as the reaction proceeds. Broadly, there are three possibilities:

1. The energy balance is so complexthat the design equation and the energy balance must be

solved simultaneously. We shall leave this case for Chapter 8.

2. The reactor can be heated or cooled such that the temperature changes, but is known as a

function of time. An example of this case is treated in Chapter 4.

3. The reactor is adiabatic, or is heated or cooled so that it is isothermal. If the reactor is

isothermal, the parameters in the rate equation are constant, i.e., they do not depend on

either time or composition. In the adiabatic case, the temperature can be expressed as a

function of composition. Therefore, the parameters in the rate equation can also be

written as functions of composition. This will be illustrated in Chapter 8.

For the third case, i.e., an isothermal or adiabatic reactor, r

i

depends only on concen-

tration. If Vis constant, or can be expressed as a function of concentration, Eqn. (3-5) can be

symbolically integrated from t = 0; N

i

= N

i0

to t = t; N

i

= N

i

. The result is

Z

N

i

Ni0

1

V

dN

i

r

i

=

Z

t

0

dt = t (3-10)

When the reactor temperature varies with time in a known manner, then r

i

depends on

time as well as concentration. In such a case, Eqn. (3-5) must be used as a starting point

instead of Eqn. (3-10). This will be illustrated in the next chapter.

The integrated forms of Eqns. (3-5) through (3-9) for Case 3 above are given in

Appendix 3.I, and are labeledas Eqns. (3-10) through (3-14), respectively. Appendix 3.I also

contains the integrated forms of Eqns. (3-5a) through (3-9a) for Case 3.

Once the integrations of the design equations have been performed, the time required

to reach a concentration C

A

, or a fractional conversion x

A

, or an extent of reaction j can be

calculated. Conversely, the value of C

A

; x

A

, or j that results for a speciﬁed reaction time can

also be calculated. Chapter 4 illustrates the solution of some batch-reactor problems where the

reactor is isothermal, or where the temperature is knownas a function of time. The simultaneous

solution of the design equation and the energy balance is considered in Chapter 8.

3.3 CONTINUOUS REACTORS

When the demand for a single chemical product reaches a high level, in the region of tens of

million pounds per year, there generally will be an economic incentive to manufacture the

product continuously, using a reactor that is dedicated to that product. The reactor may

operate at steady state for a year or more, with planned shutdowns only for regular

maintenance, catalyst changes, etc.

Almost all of the reactors in a petroleum reﬁnery operate continuously because of the

tremendous annual production rates of the various fuels, lubricants, and chemical inter-

mediates that are manufactured in a reﬁnery. Many well-known polymers such as poly-

ethylene and polystyrene are also produced in continuous reactors, as are many large-

volume chemicals such as styrene, ethylene, ammonia, and methanol.

Figure 3-3 is a simpliﬁed ﬂowsheet showing some of the auxiliary equipment that may be

associated with a continuous reactor. In this example, the feed stream is heated to the desired

inlet temperature, ﬁrst in a feed/product heat exchanger and then in a ﬁred heater. The stream

leavingthe reactor contains the product(s), the unconvertedreactants, andanyinert components.

3.3 Continuous Reactors 43

This streamis cooled in the feed/product heat exchanger and then is cooled further to condense

some of its components. The gas and liquid phases are separated. The liquid phase is sent to a

separations section (fractionation unit), where the product is recovered. A purge is taken from

the gas that leaves the separator, in part to prevent buildup of impurities in the recycle loop. The

remainder of the gas is recycled.

Most of the unconverted reactants from a continuous reactor will be recycled back into

the feed stream, unless the fractional conversion of the reactants is very high. Some of the

product and/or inert components also may be recycled, to aid in control of the reactor

temperature, for example.

Continuous reactors normally operate at steady state. The ﬂowrate and composition of

the feed stream do not vary with time, and the reactor operating conditions do not vary with

time. We will assume steady state in developing the design equations for the two ideal

Figure 3-2 A continuous reactor,

with associated equipment, for the

catalytic isomerization of heavy

normal parafﬁns, containing about 35

carbon atoms, to branched parafﬁns.

The catalyst is comprised of platinum

on an acidic zeolite that has relatively

large pores. The reaction produces

lubricants that have a high viscosity at

high temperatures, but retain the

characteristics of a liquid at low

temperatures. Without the

isomerization reaction, the lubricant

would become ‘‘waxy’’ and would not

ﬂow at low temperatures. This unit is

located at the ExxonMobil reﬁnery in

Fawley, UK. (Photo, ExxonMobil

2003 Summary Annual Report.)

44 Chapter 3 Ideal Reactors

continuous reactors, the ideal continuous stirred-tank reactor (CSTR), and the ideal plug-

ﬂow reactor (PFR).

3.3.1 Ideal Continuous Stirred-Tank Reactor (CSTR)

Like the ideal batch reactor, the ideal CSTR is characterized by intense mixing. The

temperature and the various concentrations are the same at every point in the reactor. The

feed stream entering the reactor is mixed instantaneously into the contents of the reactor,

immediately destroying the identity of the feed. Since the composition and the temperature

are the same everywhere in the CSTR, it follows that the efﬂuent stream must have exactly

the same composition and temperature as the contents of the reactor.

Feed

Composition and

temperature are the

same everywhere in

the reactor

Composition and

temperature are the

same in the effluent as

in the reactor

Effluent

Charge heater

Reactor

Combined

feed-reactor

effluent exchanger

Effluent condenser

Separator liquid

to fractionation

Separator

Net

separator

gas

Recycle

compressor

Charge

Figure 3-3 A typical ﬂow scheme for

the reactor section of a continuous plant.

1

Several items of heat exchange

equipment, a recycle compressor, and a

phase separator are required to support

the steady-state operation of the reactor.

(Figure Copyright 2004 UOP LLC. All

rights reserved. Used with permission.)

1

Stine, M. A., Petroleum Reﬁning, presented at the North Carolina State University AIChE Student Chapter

Meeting, November 15, 2002.

3.3 Continuous Reactors 45

On a small scale, e.g., a laboratory reactor, mechanical agitation is usually required to

achieve the necessary high intensity of mixing. On a commercial scale, the required mixing

sometimes can be obtained by introducing the feed streaminto the reactor at a high velocity,

such that the resulting turbulence produces intense mixing. A bed of catalyst powder that is

ﬂuidized by an incoming gas or liquid stream, i.e., a ﬂuidized-bed reactor, might be treated

as a CSTR, at least as a ﬁrst approximation. Another reactor conﬁguration that can

approximate a CSTR is a slurry bubble column reactor, in which a gas feed stream is

sparged through a suspension of catalyst powder in a liquid. Slurry bubble column reactors

are used in some versions of the Fischer–Tropsch process for converting synthesis gas, a

mixture of H

2

and CO, into liquid fuels.

The continuous stirred-tank reactor is also known as a continuous backmix, backmixed,

or mixed ﬂow reactor. In addition to the catalytic reactors mentioned in the preceding

paragraph, the reactors that are used for certain continuous polymerizations, e.g., the

polymerization of styrene monomer to polystyrene, closely approximate CSTRs.

Because of the intense mixing in a CSTR, temperature and concentration are the same

at every point in the reactor. Therefore, as with the ideal batch reactor, r

i

does not depend on

position. For a homogeneous reaction, Eqns. (3-1) and (3-3) simplify to

F

i0

÷ F

i

÷ r

i

V =

dN

i

dt

(3-15)

Equation (3-15) describes the unsteady-state behavior of a CSTR. This is the equation that

must be solved to explore strategies for starting up the reactor, or shutting it down, or

switching from one set of operating conditions to another.

At steady state, the concentrations and the temperature of the CSTR do not vary with

time. The exact temperature of operation is determined by the energy balance, as we shall

see in Chapter 8. At steady state, the right-hand side of Eqn. (3-15) is zero.

F

i0

÷ F

i

÷ r

i

V = 0

Design equation÷÷

ideal CSTR÷÷

homogeneous reaction

(molar flowrates)

V =

F

i0

÷ F

i

÷r

i

(3-16)

Equation (3-16) is the designequation for an ideal CSTR. It can be applied to a reactor where

more than one reaction is taking place, if Eqn. (1-17) is used to express r

i

.

For a single reaction, it frequently is convenient to write Eqn. (3-16) in terms of either

extent of reaction or fractional conversion of a reactant. If ‘‘i’’ is a reactant, say A,

F

A

= F

A0

(1 ÷ x

A

)

and Eqn. (3-16) becomes

Design equation÷÷

ideal CSTR÷÷

homogeneous reaction

(molar flowrates)

V

F

A0

=

x

A

÷r

A

(3-17)

Alternatively, if only one, stoichiometrically simple reaction is taking place,

j =

F

i

÷ F

i0

n

i

46 Chapter 3 Ideal Reactors

and Eqn. (3-16) becomes

Design equation÷÷

ideal CSTR÷÷

homogeneous reaction

(extent of reaction)

V =

n

i

j

r

i

(3-18)

Equations (3-16)–(3-18) are equivalent forms of the design equation for an ideal CSTR.

In these equations, ÷r

A

(or r

i

) is always evaluated at the exit conditions of the reactor, i.e., at

the temperature and concentrations that exist in the efﬂuent stream, and therefore in the

whole reactor volume. Once again, the design equation is simply a molar component

material balance.

For a heterogeneous catalytic reaction, the equivalent form of Eqn. (3-16) is

Design equation÷÷

ideal CSTR÷÷

heterogeneous catalytic reaction

(molar flowrates)

W =

F

i0

÷ F

i

÷r

i

(3-16a)

EXERCISE 3-3

Derive this equation.

Appendix 3.II gives the forms of the design equation for a heterogeneous catalytic

reaction that are equivalent to Eqns. (3-17) and (3-18). These equations are labeled Eqns.

(3-17a) and (3-18a).

Space time and space velocity

The molar feed rate, F

A0

, is the product of the inlet concentration C

A0

and the inlet

volumetric ﬂow rate y

0

, i.e.,

F

A0

= y

0

C

A0

(3-19)

For a homogeneous reaction, the space time at inlet conditions t

0

is deﬁned as

t

0

=V=y

0

(3-20)

This deﬁnition of space time applies to any continuous reactor, whether it is a CSTR or not.

For a homogeneous reaction, space time has the dimension of time. It is related to the

average time that the ﬂuid spends in the reactor, although it is not necessarily exactly equal

to the average time. However, the space time and the average residence time behave in a

similar manner. If the reactor volume V increases and the volumetric ﬂow rate y

0

stays

constant, both the space time and the average residence time increase. Conversely, if the

volumetric ﬂowrate y

0

increases and the reactor volume stays constant, both the space time

and the average residence time decrease.

Space time inﬂuences reaction behavior in a continuous reactor in the same way that

real time inﬂuences reaction behavior in a batch reactor. In a batch reactor, if the time that the

reactants spend in the reactor increases, the fractional conversion and the extent of reaction

will increase, and the concentrations of the reactants will decrease. The same is true for

space time and a continuous reactor. If a continuous reactor is at steady state, the conversion

and the extent of reaction will increase, and the reactant concentrations will decrease, when

the space time is increased.

3.3 Continuous Reactors 47

Using Eqns. (3-19) and (3-20), Eqn. (3-17) can be written as

Design equation÷÷

ideal CSTR÷÷

homogeneous reaction

(in terms of space time)

t

0

=

C

A0

x

A

÷r

A

(3-21)

The concept of space time is also applicable to heterogeneously catalyzed reactions. In

this case, t

0

is deﬁned by

t

0

=W=y

0

(3-22)

Here, the units of t

0

are (wt. catalyst-time/volume of ﬂuid). With this deﬁnition, Eqn. (3-21)

applies to both homogeneous reactions and reactions catalyzed by solids.

The inverse of space time is known as space velocity. Space velocity is designated in

various ways, e.g., SV, GHSV(gas hourly space velocity), and WHSV(weight hourly space

velocity). ‘‘Space velocity’’ is commonly used in the ﬁeld of heterogeneous catalysis, and

there can be considerable ambiguity in the deﬁnitions that appear in the literature. For

example, GHSV may be deﬁned as the volumetric ﬂowrate of gas entering the catalyst

divided by the weight of catalyst. In this case, the units of space velocity are (volume of ﬂuid/

time-wt. catalyst). The volumetric ﬂowrate may correspond to inlet conditions or to STP.

However, it is not uncommon to ﬁnd space velocity deﬁned as the volumetric ﬂowrate of gas

divided by the volume of catalyst bed, or by the volume of catalyst particles. With either of

these deﬁnitions, the units of space time are inverse time, even though the reaction is

catalytic.

When the term ‘‘space velocity’’ is encountered in the literature, it is important to

pay very careful attention to how this parameter is deﬁned! Analysis of the units may

help.

This book will emphasize the use of space time, since it is analogous to real time in a

batch reactor. Space velocity can be a bit counterintuitive. Conversion increases as space

time increases, but conversion decreases as space velocity increases.

Constant ﬂuid density

If the mass density (mass/volume) of the ﬂuid ﬂowing through the reactor is constant, i.e., if

it is the same in the feed, in the efﬂuent, and at every point in the reactor, then the subscript

‘‘0’’ can be dropped from both t and y. In this case Eqn. (3-21) can be written as

t =

C

A0

x

A

÷r

A

(3-23)

When the ﬂuid density is constant, then t(=V=y) is the average residence time that the

ﬂuid spends in the reactor. This is true for the CSTR, and for any other continuous reactor

operating at steady state.

If (and only if ) the ﬂuid density is constant,

x

A

=

F

A0

÷ F

A

F

A0

=

yC

A0

÷ yC

A

yC

A0

=

C

A0

÷ C

A

C

A0

48 Chapter 3 Ideal Reactors

so that Eqn. (3-23) becomes

t =

C

A0

÷ C

A

÷r

A

(3-24)

Equations (3-23) and (3-24) are design equations for an ideal CSTR with a constant-

density ﬂuid. The lighter box around these equations indicates that they are not as

general as Eqn. (3-21), which is not restricted to a constant-density ﬂuid. Equations

(3-23) and (3-24) apply to both homogeneous and heterogeneously catalyzed reactions,

provided that t is calculated from the appropriate equation, either Eqn. (3-20) or Eqn.

(3-22).

Calculating the reaction rate

The various forms of the design equation for an ideal CSTR (Eqns. (3-16) through (3-18),

(3-21), (3-23), and (3-24)) can be used to calculate a numerical value of the rate of reaction,

if all of the other parameters in the equation are known. The following example illustrates

this use of the CSTR design equation.

EXAMPLE 3-1

Calculation of Rate

of Disappearance

of Thiophene

The catalytic hydrogenolysis of thiophene was carried out in a reactor that behaved as an ideal CSTR.

The reactor contained 8.16 g of ‘‘cobalt molybdate’’ catalyst. In one experiment, the feed rate of

thiophene to the reactor was 6:53 × 10

÷5

mol/min. The fractional conversion of thiophene in the

reactor efﬂuent was measured and found to be 0.71. Calculate the value of the rate of disappearance

of thiophene for this experiment.

APPROACH Equation (3-16a) is the most fundamental form of the design equation for a heterogeneous catalytic

reaction in an ideal CSTR.

W =

F

i0

÷ F

i

÷r

i

(3-16a)

Using the subscript ‘‘T’’ for thiophene and rearranging,

÷r

T

=

F

T0

÷ F

T

W

From the deﬁnition of fractional conversion, F

T0

÷ F

T

= F

T0

x

T

. Therefore, all of the param-

eters on the right-hand side of the above equation are known and ÷r

T

can be calculated.

SOLUTION

÷r

T

=

F

T0

x

T

W

=

6:53 × 10

÷5

(mol/min) × 0:71

8:16(g)

= 0:57 × 10

÷5

(mol/min-g)

3.3.2 Ideal Continuous Plug-Flow Reactor (PFR)

The plug-ﬂow reactor is the third and last of the so-called ‘‘ideal’’ reactors. It is frequently

represented as a tubular reactor, as shown below.

3.3 Continuous Reactors 49

z

Little “plugs” of fluid flow single file

through reactor:

• no mixing in direction of flow, i.e.,

one fluid element cannot pass or mix

with another;

• no temperature or concentration

variations normal to flow.

F

i0

F

i

The ideal plug-ﬂow reactor has two deﬁning characteristics:

1. There is no mixing in the direction of ﬂow. Therefore, the concentrations of the

reactants decrease in the direction of ﬂow, from the reactor inlet to the reactor outlet. In

addition, the temperature may vary in the direction of ﬂow, depending on the magnitude of

the heat of reaction, and on what, if any, heat transfer takes place through the walls of the

reactor. Because of the variation of concentration, and possibly temperature, the reaction

rate, r

i

, varies in the direction of ﬂow;

2. There is no variation of temperature or concentration normal to the direction of ﬂow.

For a tubular reactor, this means that there is no radial or angular variation of temperature or

of any species concentration at a given axial position z. As a consequence, the reaction rate r

i

does not vary normal to the direction of ﬂow, at any cross section in the direction of ﬂow.

The plug-ﬂowreactor may be thought of as a series of miniature batch reactors that ﬂow

through the reactor in single ﬁle. Each miniature batch reactor maintains its integrity as it

ﬂows from the reactor inlet to the outlet. There is no exchange of mass or energy between

adjacent ‘‘plugs’’ of ﬂuid.

In order for a real reactor to approximate this ideal condition, the ﬂuid velocity cannot

vary normal to the direction of ﬂow. For a tubular reactor, this requires a ﬂat velocity proﬁle

in the radial and angular directions, as illustrated below.

50 Chapter 3 Ideal Reactors

For ﬂow through a tube, this ﬂat velocity proﬁle is approached when the ﬂow is highly

turbulent, i.e., at high Reynolds numbers.

Let’s analyze the behavior of an ideal plug-ﬂowreactor. We might be tempted to choose

the whole reactor as a control volume as we did with the ideal batch reactor and the ideal

CSTR and apply Eqn. (3-3),

F

i0

÷ F

i

÷ G

i

=

dN

i

dt

(3-3)

Assuming a homogeneous reaction, setting the right-hand side equal to 0 to reﬂect steady

state, and substituting Eqn. (3-1),

F

i0

÷ F

i

÷

Z Z Z

V

r

i

dV = 0 (3-25)

For a PFR, the reaction rate varies with position in the direction of ﬂow. Therefore, r

i

is a

function of V and the above integral cannot be evaluated directly.

We can solve this problem in two ways, the easy way and the hard way.

3.3.2.1 The Easy Way—Choose a Different Control Volume

Let’s choose a different control volume over which towrite the component material balance.

More speciﬁcally, let’s choose the control volume such that r

i

does not depend on V.

From the above discussion, it should be clear that the new control volume must be

differential in the direction of ﬂow, since r

i

varies in this direction. However, the control volume

can span the whole cross section of the reactor, normal to ﬂow, since there are no temperature or

concentrationgradients normal toﬂow. Therefore, r

i

will beconstant over anysuchcross section.

For a tubular reactor, the control volume is a slice through the reactor perpendicular to

the axis (z direction), with a differential thickness dz, as shown below.

dz

F

i

+ dF

i

F

i

z = z

The inlet face of the control volume is located at an axial position, z. The molar ﬂowrate

of ‘‘i’’ into the element is F

i

and the molar ﬂow rate of ‘‘i’’ leaving the element is F

i

÷ dF

i

.

For this element, the steady-state material balance on ‘‘i’’ is

F

i

÷ (F

i

÷ dF

i

) ÷ r

i

dV = 0

Design equation÷÷

ideal PFR÷÷

homogeneous reaction

(molar flowrate)

dV =

dF

i

r

i

(3-26)

3.3 Continuous Reactors 51

Equation (3-26) is the design equation for an ideal PFR, in differential form. This equation

applies to a PFR where more than one reaction is taking place, provided that r

i

is expressed

using Eqn. (1-17).

For a single reaction, it may be convenient to write Eqn. (3-26) in terms of either

extent of reaction or fractional conversion. If ‘‘i’’ is a reactant, say A, the molar ﬂow rates

may be written in terms of the fractional conversion x

A

, i.e., F

A

= F

A0

(1 ÷ x

A

), and

dF

A

= ÷F

A0

dx

A

. With these transformations, Eqn. (3-26) becomes

Design equation÷÷

ideal PFR÷÷

homogeneous reaction

(fractional conversion)

dV

F

A0

=

dx

A

÷r

A

(3-27)

If only one, stoichiometrically simple reaction takes place,

j =

F

i

÷ F

i0

n

i

; dF

i

= n

i

dj

Design equation÷÷

ideal PFR÷÷

homogeneous reaction

(extent of reaction)

dV =

n

i

dj

r

i

(3-28)

Equations (3-26)–(3-28) are various forms of the design equation for a homogeneous

reaction in an ideal, plug-ﬂowreactor, in differential form. The equivalents of Eqns. (3-26)–

(3-28) for a heterogeneous catalytic reaction are given in Appendix 3.IIIAas Eqns. (3-26a),

(3-27a), and (3-28a). Be sure that you can derive them.

Temperature variation with position

In developing Eqns. (3-26)–(3-28), we assumed that the temperature was constant in any

cross section normal to the direction of ﬂow. We did not assume that the temperature was

constant in the direction of ﬂow. For a PFR, the reactor is said to be isothermal if the

temperature does not vary with position in the direction of ﬂow, e.g., with axial position in

a tubular reactor. On the other hand, for nonisothermal operation, the temperature will

vary with axial position. Consequently, the rate constant and perhaps other parameters in

the rate equation such as an equilibrium constant will also vary with axial position. The

design equations for an ideal PFR are valid for both isothermal and nonisothermal

operation.

Space time and space velocity

As notedinthediscussionof theideal CSTR, thespace time at inlet conditions, t

0

, is deﬁnedby

t

0

=

V

y

0

(3-20)

Using Eqn. (3-20), Eqn. (3-27) can be written in terms of C

A0

and t

0

as

dt

0

= C

A0

dx

A

(÷r

A

)

(3-29)

52 Chapter 3 Ideal Reactors

This equation is also valid for a heterogeneous catalytic reaction, if Eqn. (3-22) is used to

deﬁne t

0

.

The concept of ‘‘space velocity,’’ discussed in connection with the ideal CSTR, also

applies to ideal PFRs.

Constant density

If the mass density of the ﬂowing ﬂuid is the same at every position in the reactor, the

subscript ‘‘0’’ can be dropped fromt and y. As noted in the discussion of the ideal CSTR, for

the case of constant density, t(=V=y) is the average residence time of the ﬂuid in the reactor.

This is true for any continuous reactor operating at steady state. However, for the ideal PFR, t

has an even more exact meaning. Not only is t the average residence time of the ﬂuid in the

reactor, it is also the exact residence time that each and every ﬂuid element spends in the

reactor. For an ideal PFR, there is no mixing in the direction of ﬂow, i.e., adjacent ﬂuid

elements cannot mix with or pass each other. Therefore, every element of ﬂuid must spend

exactly the same time in the reactor. That time is t, when the mass density is constant.

For the case of constant density, Eqn. (3-29) becomes

dt = C

A0

dx

A

(÷r

A

)

(3-30)

For constant density, x

A

= (C

A0

÷ C

A

)=C

A0

and dx

A

= ÷dC

A

=C

A0

, so that Eqn. (3-30) can

be written as

dt =

÷dC

A

(÷r

A

)

(3-31)

Equations (3-30) and (3-31) are also valid for a PFR with a heterogeneous catalytic

reaction taking place, provided that Eqn. (3-22) is used to deﬁne t.

Integrated forms of the design equation

As with the batch reactor, the design equations in differential form for the PFR must be

integrated to solve engineering problems. The same three possibilities that were discussed

for the batch reactor also exist here, except that the variable of time for the batch reactor is

replaced by position in the direction of ﬂowfor the ideal PFR. For Case 3, where the reactor

is either isothermal or adiabatic, Eqns. (3-26) and (3-27) can be integrated symbolically to

give

V =

Z

Fi

F

i0

dF

i

r

i

(3-32)

V

F

A0

=

Z

x

A

0

dx

A

÷r

A

(3-33)

The initial conditions for these integrations are V = 0, F

i

= F

i0

, x

A

= 0.

Appendix 3.III contains the equivalents of these equations for different variables (e.g., j

and t), for heterogeneous catalytic reactions, and for the constant-density case. The

numbering of the equations in Appendix 3.IIIA continues from Eqn. (3-33) above.

3.3 Continuous Reactors 53

3.3.2.2 The Hard Way—Do the Triple Integration

Let’s return to Eqn. (3-25) and again focus on a tubular reactor, with ﬂow in the axial

direction.

F

i0

÷ F

i

÷

Z Z Z

V

r

i

dV = 0 (3-25)

The triple integral may be written in terms of three coordinates z (axial position), u (angular

position), and R (radial position).

F

i0

÷ F

i

÷

Z

2p

0

Z

R0

0

Z

L

0

r

i

du RdRdz = 0 (3-38)

In this equation, R

0

is the inside radius of the tube and L is its length. Since there are no

temperature or concentration gradients normal to the direction of ﬂow, r

i

does not depend on

either u or R. Since

R

2p

0

R

R

0

0

du RdR = A, where A is the cross-sectional area of the tube

(A = pR

2

0

), Equation (3-38) may be written as

F

i0

÷ F

i

÷ A

Z

L

0

r

i

dz = 0

Differentiating this equation with respect to z gives dF

i

=dz = Ar

i

, which can be rearranged

to

Adz = dV =

dF

i

r

i

(3-26)

Equation (3-26) has been recaptured. Therefore, all of the equations derived from it can be

obtained via the triple integration in Eqn. (3-38).

3.4 GRAPHICAL INTERPRETATION OF THE DESIGN EQUATIONS

Figure 3-4 is a plot of (1= ÷ r

A

), the inverse of the rate of disappearance of Reactant A,

versus the fractional conversion of reactant A (x

A

). The shape of the curve in Figure 3-4 is

based on the assumption that ÷r

A

decreases as x

A

increases. In this case, (1=÷r

A

) will

increase as x

A

increases. We will refer to this situation as ‘‘normal kinetics.’’

1/(–r

A

)

Fractional conversion (x

A

)

Figure 3-4 Inverse of reaction rate (rate

of disappearance of reactant A) versus

fractional conversion of A.

54 Chapter 3 Ideal Reactors

‘‘Normal kinetics’’ will be observed in a number of situations, e.g., if the reactor is

isothermal and the concentration-dependent term in the rate equation obeys Generalization III

fromChapter 2. Recall that GeneralizationIII statedthat theconcentration-dependent termF(all

C

i

) decreases as the concentrations of the reactants decrease, i.e., as the reactants are consumed.

In the discussion of graphs of

À

1=÷r

A

Á

versus x

A

, the term‘‘isothermal’’ will be used to

mean that the temperature does not change as x

A

changes. This deﬁnition is consistent with

the deﬁnitions, given previously, for isothermal ideal batch reactors and isothermal ideal

plug-ﬂow reactors. However, this deﬁnition of ‘‘isothermal’’ is more general and can apply

to a CSTR or to a series of reactors.

‘‘Normal kinetics’’ will also be observed if Generalization III applies and the reaction

temperature decreases as x

A

increases. The temperature will decrease as x

A

increases, for

example, when an endothermic reaction is carried out in an adiabatic reactor.

The shape of the (÷1=r

A

) versus x

A

curve is not always ‘‘normal.’’ This curve can be

very different if the reaction is exothermic and the reactor is adiabatic, or if the rate equation

does not obey Generalization III.

Now, let’s reexamine one form of the design equation for an ideal CSTR:

V

F

A0

=

x

A

÷r

A

(3-17)

In order to discriminate between the variable x

A

and the outlet conversion from the CSTR,

let’s call the latter x

A,e

(‘‘e’’ for ‘‘efﬂuent’’), and write the design equation as

V

F

A0

=

x

A;e

÷r

A

(x

A;e

)

This equation tells us that (V=F

A0

) for an ideal CSTR is the product of the fractional

conversion of A in the reactor outlet stream (x

A,e

) and the inverse of the reaction rate,

evaluated at the outlet conditions [1=÷r

A

(x

A;e

)[. This product is shown graphically in

Figure 3-5. The length of the shaded area is equal to x

A,e

, and the height is equal to

1=÷r

A

(x

A;e

). The area is equal to V=F

A0

, according to the above equation.

Now, let’s examine the comparable design equation for an ideal PFR:

V

F

A0

=

Z

xA;e

0

dx

A

÷r

A

(3-33)

Area = V/F

A0

x

A,e

1/(–r

A

)

1/[–r

A

(x

A,e

)]

Fractional conversion (x

A

)

Figure 3-5 Graphical representation of the design equation for an ideal CSTR.

3.4 Graphical Interpretation of the Design Equations 55

This equation tells us that (V=F

A0

) for an ideal PFR is the area under the curve of (1=÷r

A

)

versus x

A

, between the inlet fractional conversion (x

A

= 0) and the outlet fractional

conversion (x

A,e

). This area is shown graphically in Figure 3-6.

Now we can compare the volumes (or weights of catalyst) required to achieve a

speciﬁed conversion in each of the two ideal, continuous reactors. Suppose we have an ideal

CSTRand an ideal PFR. The same reaction is being carried out in both reactors. The PFRis

isothermal and operates at the same temperature as the CSTR. The molar feed rate of

Reactant A to both reactors is F

A0

. If the kinetics are ‘‘normal,’’ which reactor will require

the smaller volume to produce a speciﬁed conversion, x

A,e

, in the efﬂuent stream?

Figure 3-7 shows the graphical answer to this question. For a given F

A0

, the required

volume for an ideal CSTRis proportional to the entire shaded area (both types of shading). The

required volume for an ideal PFR is proportional to the area under the curve. Clearly, the

required volume for the PFRis substantially less than the required volume for the ideal CSTR.

Area = V/F

A0

x

A,e

1/(–r

A

)

Fractional conversion (x

A

)

Figure 3-6 Graphical representation of the design equation for an ideal PFR.

1/(–r

A

)

Fractional conversion (x

A

)

x

A,e

1/[–r

A

(x

A,e

)]

Figure 3-7 Comparison of the volumes required to achieve a given conversion in an ideal PFR

and an ideal CSTR, for a given feed rate, F

A0

. The required volume for a PFRis proportional to the area

under the curve. The required volume for a CSTRis proportional to the area of the rectangle (the sum

of the two cross-hatched areas).

56 Chapter 3 Ideal Reactors

EXERCISE 3-4

Explain this result qualitatively. What is there about the oper-

ation of an ideal CSTR with ‘‘normal kinetics’’ that causes it to

need a larger volume than an ideal PFR to achieve a speciﬁed

outlet conversion for a ﬁxed F

A0

?

Hint: Using the above ﬁgure, compare the average reaction

rate in the PFR with the rate in the CSTR. Why are these rates

different?

The graphical interpretation of the design equations for the two ideal continuous

reactors has been illustrated using fractional conversion to measure the progress of the

reaction. The analysis could have been carried out using the extent of reaction j with Eqns.

(3-18) and (3-34). Moreover, for a constant-density system, the analysis could have been

carried out using the concentration of Reactant A, C

A

, with Eqns. (3-24) and (3-37).

Plots suchas those inFigures 3-5–3-7are oftenreferredtoas ‘‘Levenspiel’’ plots. Octave

Levenspiel, a pioneering ﬁgure in the ﬁeld of chemical reaction engineering, popularized the

use of this type of plot as a pedagogical tool more that 40 years ago.

2

‘‘Levenspiel plots’’ will

recur in Chapter 4, as a means of analyzing the behavior of ‘‘systems’’ of ideal reactors.

SUMMARY OF IMPORTANT CONCEPTS

v

Design equations are nothing more than component material

balances.

v

There are no spatial variations of temperature or concentration

in an ideal batch reactor or in an ideal continuous stirred-tank

reactor (CSTR).

v

There are no spatial variations of temperature or concentration

normal to ﬂow in an ideal plug-ﬂow reactor (PFR). However,

the concentrations, and perhaps the temperature, do vary in the

direction of ﬂow;

v

If (and only if ) the mass density is constant, the design

equations can be simpliﬁed and written in terms of concen-

tration.

PROBLEMS

Problem 3-1 (Level 1) Radial reactors are sometimes used in

catalytic processes where pressure drop through the reactor is an

important economic parameter, for example, in ammonia syn-

thesis and in naphtha reforming to produce high-octane gasoline.

Top and cross-sectional views of a simpliﬁed radial cata-

lytic reactor are shown below.

In this conﬁguration, the feed to the reactor, a gas, is

introduced through a pipe into an outer annulus. The gas dis-

tributes evenly throughout the annulus, i.e., the total pressure is

essentially constant at every position in the annulus. The gas then

ﬂows radially inward through a uniformly packed catalyst bed, in

the shape of a hollow cylinder with outer radius R

o

and inner

radius R

i

. The total pressure is essentially constant along the

length of the central pipe. There is no ﬂuid mixing in the radial

direction. There are no temperature or concentration gradients in

the vertical or angular directions. The catalyst bed contains a

total of W pounds of catalyst.

Reactant A is fed to the reactor at a molar feed rate F

A0

(moles A/time), and the average ﬁnal fractional conversion of A

in the product stream is x

A

.

Derive the ‘‘design equation,’’ i.e., a relationship among F

A0

,

x

A

, and W, for a radial reactor operating at steady state.

A more detailed design of a radial ﬁxed-bed reactor is

shown below.

1

Gas in

Reactor

wall

Reactor

wall

Central

pipe

Retaining

screen

Gas

out

Catalyst

bed

Inlet

pipe

Annulus

1

Stine, M. A., Petroleum Reﬁning, presented at the North Carolina

State University AIChE Student Chapter Meeting, November 15,

2002.

2

Levenspiel, O., Chemical Reaction Engineering, 1st edition, John

Wiley & Sons, Inc., New York (1962).

Problems 57

Conventional radial flow reactor

Catalyst bed cover plate

Scallop shield

Centerpipe shroud

Scallops (or outer screen)

Catalyst bed (concentrically loaded

around centerpipe)

Centerpipe (punched plate

wrapped with screen material)

(Figure Copyright 2004 UOP LLC. All rights reserved.

Used with permission.)

Problem 3-2 (Level 2) Rate equations of the form

÷r

A

=

kC

A

C

B

(1 ÷ K

A

C

A

)

2

are requiredto describe the rates of some heterogeneous catalytic

reactions. Suppose that the reaction A ÷ B!products occurs in

the liquid phase. Reactant B is present in substantial excess, so

that C

B

does not change appreciably as reactant A is consumed.

1. Thevalue of ÷r

A

goes through a maximumas C

A

is increased.

At what value of C

A

does this maximum occur?

2. The concentration of A in the feed to a continuous reactor is

C

A0

= 1:5=K

A

. The concentration of A in the efﬂuent is

0:50=K

A

. Make a sketch of (1=÷r

A

) versus C

A

that covers

this range of concentration. One ideal continuous reactor will

be used to carry out this reaction. Should it be a CSTR or

PFR? Explain your answer.

3. Would your answer to Part b be different if the inlet concen-

tration was C

A0

= 1:5=K

A

and the outlet concentration was

C

A

= 1:0=K

A

? Explain your answer.

Problem3-3 (Level 2) In an ideal, semi-batch reactor, some of

the reactants are charged initially. The remainder of the reactants

are fed, either continuously or in ‘‘slugs,’’ over time. The

contents of the reactor are mixed vigorously, so that there are

no spatial gradients of temperature or concentration in the

reactor at any time.

Consider the single liquid-phase reaction

A ÷ B!products

which takes place in an ideal, semi-batch reactor. The initial

volume of liquid in the reactor is V

0

and the initial concentrations

of A and B in this liquid are C

A0

and C

B0

respectively. Liquid

is fed continuously to the reactor at a volumetric ﬂow rate y.

The concentrations of A and B in this feed are C

Af

and C

Bf

,

respectively.

1. Derive a design equation for this system by carrying out a

material balance on ‘‘A’’. Work in terms of C

A

, not x

A

or j.

2. Ultimately, we would like to determine C

A

as a function of

time. Under what conditions is the design equation that you

derived sufﬁcient to do this? Assume that the rate equation for

the disappearance of A is known.

Problem 3-4 (Level 1) Plot (1=÷r

A

) versus x

A

for an iso-

thermal, zero-order reaction with a rate constant of k. If the

desired outlet conversion is x

A

= 0:50, which of the two ideal

continuous reactors requires the smaller volume, for a ﬁxed

value of F

A0

?

What is the outlet conversion from a PFR when

V=F

A0

= 2=k?

Problem 3-5 (Level 1) Develop a graphical interpretation of

the design equation for an ideal batch reactor.

Problem 3-6 (Level 1) The kinetics of the catalytic reaction

3

SO

2

÷ 2H

2

S!3S ÷ 2H

2

O

are being studied in an ideal CSTR. Hydrogen sulﬁde (H

2

S) is

fed to the reactor at a rate of 1000 mol/h. The rate at which H

2

S

leaves the reactor is measured and found to be 115 mol/h. The

feed to the reactor is a mixture of SO

2

; H

2

S, and N

2

in the molar

ratio 1/2/7.5. The total pressure and temperature in the reactor

are 1.1 atmand 250 8C, respectively. The reactor contains 3.5 kg

of catalyst.

What is the rate of disappearance of H

2

S? What are the

corresponding concentrations of H

2

S; SO

2

, S, and H

2

O?

Problem 3-7 (Level 2) The homogeneous decomposition of

the free-radical polymerization initiator diethyl peroxydicarbon-

ate (DEPDC) has been studied in supercritical carbon dioxide

using an ideal, continuous, stirred-tank reactor (CSTR).

4

The

concentration of DEPDC in the feed to the CSTR was

0.30 mmol. Because of this very low concentration, constant

ﬂuid density can be assumed. At 70 8C and a space time of

10 min, the fractional conversion of DEPDC was 0.21. At 70 8C

and a space time of 30 min, the fractional conversion of DEPDC

was 0.44.

The rate equation for DEPDC decomposition is believed to

have the form

÷r

DEPDC

= k[DEPDC[

n

1. What is the value of n, and what is the value of k, at 70 8C?

2. The activation energy of the decomposition reaction is

132 kJ/mol. What is the value of the rate constant k at 85 8C?

3

This reaction is the catalytic portion of the well-known Claus

process for converting H

2

S in waste gas streams into elemental sulfur.

4

Adapted from Charpentier, P. A., DeSimone, J. M., and Roberts,

G. W. Decomposition of polymerization initiators in supercritical

CO

2

: a novel approach to reaction kinetics in a CSTR, Chem. Eng.

Sci., 55, 5341–5349 (2000).

58 Chapter 3 Ideal Reactors

Problem3-8 (Level 1) An early study of the dehydrogenation

of ethylbenzene to styrene

5

contains the following comments

concerning the behavior of a palladium-black catalyst:

‘‘A fair yield (of styrene) was obtained at 400 8C. A 12-g

sample of catalyst produced no greater yield than the 8-g sample.

By passing air with the ethylbenzene vapor, the dehydrogenation

occurred at even lower temperatures and water was produced.’’

The Pd-black catalyst was contained in a quartz tube and the

ﬂow rate of ethylbenzene through the tube was 5 cc (liquid) per

hour for all experiments. The measured styrene yields (moles

styrene formed/mole ethylbenzene fed) were about 0.2 with both

8 and 12 g of catalyst. For the purposes of this problem, assume

that ‘‘yield’’ of styrene is the same as the conversion of ethyl-

benzene, andassume that the dehydrogenation of ethylbenzene is

stoichiometrically simple. Also assume that the reaction took

place at 1 atm total pressure. In answering the questions below,

assume that the experimental reactor was an ideal PFR.

1. In view of the design equation for an ideal PFR in which a

heterogeneously catalyzed reaction takes place, how would

you expect the yield of styrene to have changed when the

amount of catalyst was increased from 8 to 12 g?

2. How do you explain the fact that the yield of styrene did not

change when the catalyst weight was increased from8 to 12 g?

3. Howdo you explain the behavior of the reaction when air was

added to the feed?

Problem 3-9 (Level 1) The hydrogenolysis of thiophene

(C

4

H

4

S) has been studied at 235–265 8C over a cobalt–molyb-

date catalyst, using a CSTR containing 8.16 g of catalyst. The

stoichiometry of the system can be represented by

C

4

H

4

S ÷ 3H

2

!C

4

H

8

÷ H

2

S Reaction 1

C

4

H

8

÷ H

2

!C

4

H

10

Reaction 2

All species are gaseous at reaction conditions.

The feed to the CSTR consisted of a mixture of thiophene,

hydrogen, and hydrogen sulﬁde. The mole fractions of butene

(C

4

H

8

), butane (C

4

H

10

), and hydrogen sulﬁde in the reactor

efﬂuent were measured. The mole fractions of hydrogen and

thiophene were not measured.

The data from one particular experimental run are given

below:

Total pressure in reactor = 832 mmHg

Feed rate

Thiophene = 0:653 × 10

÷4

gmol/min

Hydrogen = 4:933 × 10

÷4

gmol/min

Hydrogen sulfide = 0

Mole fractions in efﬂuent

H

2

S = 0:0719

Butenes (total) = 0:0178

Butane = 0:0541

Calculate ÷r

T

(the rate of disappearance of thiophene) and

the partial pressures of thiophene, hydrogen, hydrogen sulﬁde,

butenes (total), and butane in the efﬂuent. You may assume that

the ideal gas laws are valid.

Problem 3-10 (Level 2) The hydrolysis of esters, i.e.,

C

O

OR'

(E) (W) (A)

+ H

2

O + R'OH

R

C

O

OH R

frequently is catalyzed by acids. As the above hydrolysis

reaction proceeds, more acid is produced and the concentration

of catalyst increases. This phenomenon, known as ‘‘autocatal-

ysis,’’ is captured by the rate equation

÷r

E

= (k

0

÷ k

1

[A[)[E[[H

2

O[

Here k

0

is the rate constant in the absence of the organic acid that

is produced by the reaction.

To illustrate the behavior of autocatalytic reactions, let’s

arbitrarily assumed the following values:

E

0

(ester concentration in feed) = 1:0 mol/l

W

0

(water concentration in feed) = 1:0 mol/l

A

0

(acid concentration in feed) = 0

The concentration of the alcohol (R

0

OH) in the feed also is

zero. The rate constants are

k

0

= 0:01 l/mol-h

k

1

= 0:20 l

2

/mol

2

-h

In answering the following questions, assume that the

reaction takes place in the liquid phase.

1. Calculate values of ÷r

E

at fractional conversions of ester

(x

E

) = 0; 0:10; 0:20; 0:30; 0:40; 0:50; 0:60; and 0:70:

2. Plot 1=÷r

E

versus x

E

.

3. What kind of continuous reactor system would you use if a

ﬁnal ester conversion of 0.60 were desired, and if the reaction

were to take place isothermally. Choose the reactor or

combination of reactors that has the smallest volume. Justify

your answer.

Problem 3-11 As pointed out in Chapter 2, kinetics are not

always ‘‘normal’’ (e.g., see Figure 2-3). Consider a liquid-phase

reaction that obeys the rate equation: ÷r

A

= kC

÷1

A

, over some

range of concentration. Suppose this reaction was to be carried out

in a continuous, isothermal reactor, with feed and outlet concen-

trations within the range where the rate equation is valid.

1. Make a sketch of (1=÷r

A

) versus C

A

for the range of

concentration where the rate equation is valid.

2. What kind of continuous reactor (or system of continuous

reactors) would you use for this job, in order to minimize the

volume required? Explain your answer.

5

Taylor, H. S. and McKinney, P. V., Adsorption and activation of carbon

monoxide at palladium surfaces, J. Am. Chem. Soc., 53, 3604 (1931).

Problems 59

I. Ideal batch reactor

A. General—differential form Design equation

Variable

Homogeneous

reaction

Heterogeneous

catalytic reaction

Moles of species ‘‘i’’, N

i

1

V

dN

i

dt

= r

i

(3-5)

1

W

dN

i

dt

= r

i

(3-5a)

Fractional conversion of reactant A, x

A

N

A0

V

dx

A

dt

= ÷r

A

(3-6)

N

A0

W

dx

A

dt

= ÷r

A

(3-6a)

Extent of reaction, j

n

i

V

dj

dt

= r

i

(3-7)

n

i

W

dj

dt

= r

i

(3-7a)

B. Constant volume—differential

form

Homogeneous

reaction

Heterogeneous

catalytic reaction

Concentration of species ‘‘i’’, C

i

dC

i

dt

= r

i

(3-8)

dC

i

dt

= C

cat

(r

i

) (3-8a)

Fractional conversion of reactant A, x

A

C

A0

dx

A

dt

= ÷r

A

(3-9) C

A0

dx

A

dt

= C

cat

(÷r

A

) (3-9a)

C. General—integrated form (see

Note 1)

Homogeneous

reaction

Heterogeneous

catalytic reaction

Moles of species ‘‘i’’, N

i

Z

N

i

N

i0

1

V

dN

i

r

i

= t (3-10)

1

W

Z

N

i

N

i0

dN

i

r

i

= t (3-10a)

Fractional conversion of reactant A, x

A

N

A0

Z

1

V

dx

A

(÷r

A

)

= t (3-11)

N

A0

W

Z

x

A

0

dx

A

(÷r

A

)

= t (3-11a)

Extent of reaction, j n

i

Z

j

0

1

V

dj

r

i

= t (3-12)

n

i

W

Z

j

0

dj

r

i

= t (3-12a)

D. Constant volume—integrated form

(see Note 1)

Homogeneous

reaction

Heterogeneous

catalytic reaction

Concentration of species ‘‘i’’, C

i

Z

C

i

C

i0

dC

i

r

i

= t (3-13)

Z

C

i

C

i0

dC

i

r

i

= C

cat

t (3-13a)

Fractional conversion of reactant A, x

A

C

A0

Z

x

A

0

dx

A

(÷r

A

)

= t (3-14) C

A0

Z

x

A

0

dx

A

(÷r

A

)

= C

cat

t (3-14a)

Note 1: For Case 3 (p. 43).

3.5 APPENDIX 3 SUMMARY OF DESIGN EQUATIONS

Warning: Careless use of the equations in this appendix can be damaging to per-

fomance. In extreme cases, improper use of these materials can be academically fatal.

Always carry out a careful analysis of the problem being solved before using this

appendix.

When in doubt, ﬁrst carefully choose the type of reactor for which calculations are to be

performed. Then decide whether the reaction is homogeneous or heterogeneous. Finally,

begin with the most general form of the appropriate design equation and make any

simpliﬁcations that are warranted.

60 Chapter 3 Ideal Reactors

II. Ideal continuous stirred-tank reactor (CSTR)

A. General—in terms of V or W Homogeneous

reaction

Heterogeneous

catalytic reaction

Molar ﬂow rate of species ‘‘i’’, F

i

V =

F

i0

÷ F

i

÷r

i

(3-16) W =

F

i0

÷ F

i

÷r

i

(3-16a)

Fractional conversion of reactant A, x

A

V

F

A0

=

x

A

(÷r

A

)

(3-17)

W

F

A0

=

x

A

(÷r

A

)

(3-17a)

Extent of reaction, j V =

n

i

j

r

i

(3-18) W =

n

i

j

r

i

(3-18a)

B. General—in terms of t

0

(see Note 1)

Homogeneous

reaction

Heterogeneous

catalytic reaction

Fractional conversion of reactant A, x

A

t

0

=

C

A0

x

A

÷r

A

(3-21) t

0

=

C

A0

x

A

÷r

A

(3-21)

C. Constant density—in terms of t

(see Note 2)

Homogeneous

reaction

Heterogeneous

catalytic reaction

Fractional conversion of reactant A, x

A

t =

C

A0

x

A

÷r

A

(3-23) t =

C

A0

x

A

÷r

A

(3-23)

Concentration of reactant A, C

A

t =

C

A0

÷ C

A

÷r

A

(3-24) t =

C

A0

÷ C

A

÷r

A

(3-24)

Note 1:

For a homogeneous reaction, t

0

= V=y

0

= VC

A0

=F

A0

.

For a heterogeneous reaction, t

0

= W=y

0

= WC

A0

=F

A0

.

Note 2:

For a homogeneous reaction, t = V=y = VC

A0

=F

A0

.

For a heterogeneous reaction, t = W=y = WC

A0

=F

A0

.

III. Ideal continuous plug-ﬂow reactor (PFR)

A. General—differential form—in

terms of V or W

Homogeneous

reaction

Heterogeneous

catalytic reaction

Molar ﬂow rate of species ‘‘i’’, F

i

dV =

dF

i

r

i

(3-26) dW =

dF

i

r

i

(3-26a)

Fractional conversion of reactant A, x

A

dV

F

A0

=

dx

A

÷r

A

(3-27)

dW

F

A0

=

dx

A

÷r

A

(3-27a)

Extent of reaction, j dV =

n

i

dj

r

i

(3-28) dW =

n

i

dj

r

i

(3-28a)

B. General—differential form–in

terms of t

0

(see Note 1)

Homogeneous

reaction

Heterogeneous

catalytic reaction

Fractional conversion of reactant A, x

A

dt

0

= C

A0

dx

A

(÷r

A

)

(3-29) dt

0

= C

A0

dx

A

(÷r

A

)

(3-29)

C. Constant density—differential

form in terms of t (see Note 2)

Homogeneous

reaction

Heterogeneous catalytic

reaction

Fractional conversion of reactant A, x

A

dt = C

A0

dx

A

(÷r

A

)

(3-30) dt = C

A0

dx

A

(÷r

A

)

(3-30)

Concentration of reactant A, C

A

dt =

÷dC

A

(÷r

A

)

(3-31) dt =

÷dC

A

(÷r

A

)

(3-31)

Appendix 3 Summary of Design Equations 61

D. General—integrated form (see

Note 3)

Homogeneous

reaction

Heterogeneous

catalytic reaction

Molar ﬂow rate of species ‘‘i’’, F

i

V =

Z

F

i

F

i0

dF

i

r

i

(3-32) W =

Z

F

i

F

i0

dF

i

r

i

(3-32a)

Fractional conversion of reactant A, x

A

V

F

A0

=

Z

x

A

0

dx

A

(÷r

A

)

(3-33)

W

F

A0

=

Z

x

A

0

dx

A

(÷r

A

)

(3-33a)

Extent of reaction, j V =

Z

j

0

n

i

dj

r

i

(3-34) W =

Z

j

0

n

i

dj

r

i

(3-34a)

Fractional conversion of reactant A,

x

A

—in terms of t

0

(see Note 1)

t

0

= C

A0

Z

x

A

0

dx

A

(÷r

A

)

(3-35) t

0

= C

A0

Z

x

A

0

dx

A

(÷r

A

)

(3-35)

E. Integrated form—constant

density—in terms of t (see Note 2

and 3)

Homogeneous

reaction

Heterogeneous

catalytic reaction

Fractional conversion of reactant A, x

A

t = C

A0

Z

x

A

0

dx

A

(÷r

A

)

(3-36) t = C

A0

Z

x

A

0

dx

A

(÷r

A

)

(3-36)

Concentration of reactant A, C

A

t = ÷

Z

C

A

C

A0

dC

A

(÷r

A

)

(3-37) t = ÷

Z

C

A

C

A0

dC

A

(÷r

A

)

(3-37)

Note 1:

For a homogeneous reaction, t

0

= V=y

0

= VC

A0

=F

A0

.

For a heterogeneous reaction, t

0

= W=y

0

= WC

A0

=F

A0

.

Note 2:

For a homogeneous reaction, t = V=y = VC

A0

=F

A0

.

For a heterogeneous reaction, t = W=y = WC

A0

=F

A0

.

Note 3:

For the PFR equivalent of Case 3 (p. 43). See the discussion on p. 53.

62 Chapter 3 Ideal Reactors