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Conversion Fouglr
Conversion Fouglr
Overview. In the first chapter, the general mole balance equation was
detived and then applied to the four most common types of industrial
reactors. A balance equation was developed for each reactor type and
these equations are summarized in TabIe S-I. In Chapter 2, we will eval-
uate these equations to size CSTRs and PFRs. To size these reactors we
first define conversion, which is a measure of the reaction's progress
toward completion, and then rewrite all the balance equations in terms of
conversion. These equations are ofren referred to as the design equations.
Next, we show how one may size a reactor line., determine the reactor
volume necessary to achieve a specified conversion) once the relationship
, conversion, X,is known. In addition
between the reaction rate, - r ~ and
to being abIe to size C S R s and PFRs once given -r, =Am, another
goal of this chapter is to compare CSTRs and PFRs and the overall con-
versions far reactors arranged in series. It is also important to arrive at
the best arrangement of reactors in series.
After completing this chapter you will be able to size CSTRs and
PFRs given the rate of reaction as a function of conversion and to calcu-
late the overall conversion and reactor volumes for reactors arranged in
series.
38 Conversion and Reactor Sizing Chap. 2
The uppercase letters represent chemical species and the lowercase letters rep-
resent stoichiometric coefficients. Taking species A as our basis of c~lcularion,
we divide the reaction expression through by the stoichiometric coefficient of
species A. in order to arrange the reaction expression in the form
Definition of X
x* = Moles of A reacted
Moles af A fed
Because we arre defining conversion with respect to our basis of calculation [A in
Equation (2-211, we eliminate the subscript A for the sake of brevity and let X = X, .
For irreversible reactions, the maximum conversion is 1.O, i.e., complete conversion.
For reversible reactions, the maximum conversion is the equilibrium conversion &
(i.e., X,, = X,).
Moles of A reacted
r 7
Moles of A I
I (2-3)
Now, the number of moles of A that remain in the reactor after a time r,
N,, can be expressed in terms of NAOand X:
Moles of A that
When no spatial variations in reaction rate exist, the mole balance on spe-
cies A for a batch system is given by the following equation [cf. Equation (1-5)J:
This equation is valid whether or not the reactor volunle is constant. In the
general reaction, Equation (2-2). reactant A is disappearing: therefore, we rnul-
tiply both sides of Equation (2-5) by -1 to obtain the mole balance for the
hatch reactor in the form
We call Equation (2-6) the differential form of the design equation for
batch reactor because we have written the mole balance in terms of conversior
The differential forms of the batch reactor mole balances. Equations (2-5) an1
(2-6). are often used in the interpretation of reaction rate data (Chapter 5 ) ant
for reactors with heat effects (Chapter 9), respectiveIy. Batch reactors are fre
quently used in industry for both gas-phase and liquid-phase reactions. Thl
laboratory bomb calorimeter reactor is widely used for obtaining reaction rat1
data (see Section 9.3). Liquid-phase reactions are frequently carried out ii
batch reactors when small-scale productton is desired or operating difficuftie,
mle out the use of continuous flow systems.
For a constant-volume batch reactor. V = V,,, Equation (2-5) can bc
arranged into the form
Constant-volume
batch reactor
As previously mentioned. the differential form of the mole balance, e.g.. Equa
tion (2-7). is used for analyzing rate data jn a batch reactor as we will see ir
Chapters 5 and 9.
To determine the time to achieve a specified conversion X, we first sepa-
rate the variables in Equation (2-6) as follows
Batch time t This equation is now integrated with the limits that the reaction begins at
to achieve e time equal zero where there is no conversion initially (i.e., t = 0,X = 0). Car-
conversion X rying out the inteption, we obtain the time t necessary to achieve a conver-
sion X in a batch reactor
u Batch
The longer the reactants are left in the reactor, the greater will be h e conver-
sion. Equation (2-6) is the differential Form of the design equation. and Equa-
Design
Equation
tion (2-9) is the integral form of the design equation for a batch reactor.
reactor volume. e.,a.. the biggert'lonper the reactor, the more time it will take
the reactant5 to Row conipleteIy through the reactor and thus, the more time to
react. Consequently, the conversion X is a Function of reactor volume V. If FA,,
i s the molar flnw rate of specres A fed to a system operated at steady state. the
molar rate at which species A is reacting rr3ithirrthe entire system will be F,d.
The molar feed rate of A ro the system minus the rate of reaction of A within
the system eqltnls the moIar flow rate of A leaving the system FA. The preced-
ing sentence can be written in the form of the following mathematical state-
ment:
Molar rate at
Molar flow rate Molar flow rate
consumed within
fed to the system
the system
Rearranging gives
The entering molar flow rate of species A. FA, (mol/s), is just the product of
the entering concentration, CAo(mol/dmf ), and the entering volumetric flow
rate, u, (drn31s):
Gas phase
42 Conversion and Reactor Sizing Chap. 2
Exumpk 2-1 U~ittgthe Ideal Gas Law to Caicuhfe CAl and FA*
A gas of pure A at 830 kPa (8.2 atm) enters a reactor with a volumetric flow rate,
v* of 2 dm% at 500 K. Calculate the enterlng concentration of A, C,,, and the
entertng molar Bow rate. rho.
Solurioil
U'e again recall that for an ideal pas:
However, since pure A enters, the total pressure and partial pressure entering are the
same. The entering molar flowrate, FA,, is just the p d u c t of the entering concen-
tration, C,,, and the entering volumetric flow rate, vo:
This feed rate (FA, = 0.4 moYs) is in the range o f that which is necessary to form
several million pounds of product per year. We will use this value of FA, together
with either Table 2-2 or Figure 2-1 to size and evaluate a number of reactor schemes
in Examples 2-2 through 2-5.
Recall that the CSTR is modeled as being we11 mixed such that there are no
spatial variations in the reactor. The CSTR mole balaoce, Equation ( I -7), when
applied to species A in the reaction
can he arranged to
v= 5 0 - (50
- r*
- F,d
Evalrlate -r, at Because the reactor is perfprrk mixer/, the exit composition from the reactor i
CSTR exit. identical to the composition inside the reactor, and the rate of reaction is eval
uated at the exir conditions.
We model the tubular reactor as having the fluid flowing in plug flow. i.e.. nr
radial gradients in concentration, temperature, or reaction rate.' As the reac
[ant$ enter and flow axially down the reactor, [hey are consumed and the con
version increases along the length of the reactor. To develop the PFR desigr
equation we first multiply both sides of the tubular reactor design equatior
(1- 123 by - I . We then express the mole balance equation for species A in tht
reaction as
For a flow system, FA has previously been given in terms of the entering molat
Row rare FM and the conversion X
differentiating
dFA= - F A d X
and substituting into (7-141, gives the differential form of the design equation
for a plug-flow reactor (PFR):
blgn
4 PFR b, We now separate the variables and integrate with the limits V = 0 when X = 0
cquntlon
to obtain the plug-flow reactor voluine necessary to achieve a specified conver-
sion X:
To carry out the integrations in the batch and plug-Row reactor design
equations (2-9) and (2-16). as welI as to evaluate the CSTR design equation
(2-23), we need to know how the reaction rate - r ~varies with the concentra-
tion (hence conversion) of the reacting species. This relationship between reac-
tion rate and concentration is developed in Chapter 3.
This constraint will be removed when we extend our analysis to nonideal (industrial)
reactors in Chapters 13 rind Id.
Sm. 2.4 Apolicatiors cl ths Design Equaticns for Continuous-Flow Fleactors 45
Packed-bed reactors are tubular reactors filled with catalyst particles. The drr-
ivation of the differential and integral forms of the design equations For
packed-bed reactors are analogous 10 those for a PFR {cf. Equations ( 2 - 15) and
(2- 1611. That is, substituting Equation (2- 12) for FA in Equation ( 1 - 15) gives
PBR design
equation
The differential Form o f the design equation [i.e., Equation (2-17)J must be
used when analyzing reactors that have a pressure drop along the length of the
reactor. We discuss pressure drop in packed-bed reactors in Chapter 4.
I n the abserlce of pressure drop, i.e., AP = 0. we can integrate (2- 17)
with Iimits X = 0 at W = 0 to obtain
Here. k is the specific reaction rate and is a function only of temperature, and
CA0is the entering concentration. We note in Equations (2-13) and (2-16) the
reactor volume in a function of the reciprocal of -r,. For this first-order depen-
dence, a plot of the reciprocal rate of reaction (I/-r,) as a function of conver-
sion yields a curve similar to the one shown in Figure 2-1, where
46 Conversion and Reactor Sizing Chap. 2
If we know -r, as a
function of X,we
can size any
isothermal
mcrion system.
Recalling the CSTR and PFR design equations, (2-13) and (2-I&},
we see that the reactor volume varies with the reciprocal of -r,, (I/-r,4f. e.g.,
reaction is carried out isothermally, the rate is usually greatest at the start of
the reaction when the concentration of reactant is greatest (i.e., when there is
negligible conversion SX E 03). Hence I 1/-rAf will be small. Near the end of
the reaction, when the reactant has been mostly used up and thus the concen-
tration of A is small (i.e., the conversion is large), the reaction rate will be
small. Consequently. (I/-rA)is large.
For all irreversible reactions of greater than zero order (see Chapter 3 for
zero-order reactions), as we approach complete conversion where all the limit-
ing reactant is used up. i.e., X = 1. the reciprocal rate approaches infinity as
does the reactor volume. i.e.
A+BtC As X I +x
+ I . - I : , + 0 , thus, - therefore If -+
-rA
"To infinity Consequently, we see that an infinite reactor volume is necessary to reach
and beyond"
--Buzz Lightyear complete conversion, X = 1.0
For reversible reactions (e.~.,
- A B), the maximum conversion is the
equilibrium conversion X,. At equilibrium. the reaction rate is zero ( r , s 0).
Therefore.
-r,
and we see that an infinite reactor volume would also be necessary to obtain
the exact equilibrium conversion, X = X,.
To size a number of reactors for the reaction we have been considering,
uRewill use FA, = 0.4 moI/s (calculated in Example 2- 1) to add another row to
the processed data shown in Table 2-2 to obtain Table 1-3.
Sec. 2.4 Apal~caltronsof the Design Equat~onsfor Cont~nuous-FfowReactors 49
I
(8) Quation (2-13) gives the volume o f a CSTR as a function of FA,,.X,and -r,,:
I n a CSTR, the composition, temperature, and conversion of the effluent stream an:
rdentical ta that of the Ruid within the reactor, because perfect mixing is assumed.
Therefore, we need to hiid the value of -rA (or reciprocal thereof) at X = 0.8. From
either Table 2-2 or Figure 1-I , we see that when X = 0.8, then
Substitution into Equation (2-13) for an entering molar flow rate. FA* of 0.4 mol A/s
and X = 0.8 gives
(b) Shade the area in Figure 2-2 that yields the CSTR vocllume. Rearnnging Equa-
tion (2- 13) gives
In Figwe E2-2.1, the volume is equal to the area of a rectangle with a height
= 8 rn3) and a base
(FAIj-rA (X= 0.81. This rectangle is shaded in the figure.
(E2-2.2)
The CSTR volume necessary to achieve 80% conversion is 6.4 m7when oper-
ated at 500 K. 830 kPa (8.2 am), and with an entering molar flow rate ~f A of 0.4
rnolh. This volume corresponds to a reactor about 1.5 rn in diametervand 3.6 rn
high. It's a large CSTR, but this is a pas-phase reaction, and CSTRs ate normally
not used for gas-phase reactions. CSTRs are used primarily for liquid-phase reactions.
Conversion and Reactor Siting Chap. 2
I4 ILf M 06 Od Id
Conversion. X
figure EZ-2.1 Levenspiel CSTR plot.
The reaction described by the data in Tables 2-1 and 2-2 is to k carried out In a
PI%. The entering molar flow rate of A is 0.4 rnofls.
(a) First. use one of the integration formulas given in Appendix A.4 to determine the
PER reactor volume necessary to achieve 80% conversion.
(b) Next. shade the area in Figure 2-2 that would give the PFR the volume neces-
sary to achieve 80% conversion.
(c) Finally, make a qualitative sketch of the conversion. X, and the rate of reaction.
-rA, down the length (volume) of the reactor.
Solution
We start by repeating rows ( I ) and (4) of Table 2-3.
We shall use the jive poin~quadrature formula (A-23) given in Appendix A.4 to
numerically evaluate Equation 12-16), For the five-point formula with a final conver-
siw of 0.8, gives for four equal segments between X = 0 and X = 0.8 with a
I segment length of AX = - 0.8 = 0.2. The function inside the integral is evaluated at
4
The PFR reactor volume necessary to achieve 80% conversion is 2165 dm3. T h i s
*
100 P f Rs
volume could result from a bank of 100 PERs that are each 0.1 m in diameter with
a length of 2.8 m (e-g.. see Figures 1-8(a) and {b)).
(b) The integral in Equation (2-16) can also be evaluated from the area under the
in parallel curve of a plot of (FAd-vA)versus X.
PFR
Conversion, X
The area under the curve ail1 gibe the tubular reactor volume necessary to achiex
the specified conversion of A . For 80% conversion. the shaded area is roughly equ,
to 2165 dm'(2.165 m").
(c) Sketch the pmf l
a of -r, and X down the length of the reactor.
We know that as we proceed down the reactor and more and more of the reactant i
consumed. the concentration of reactant decreases, as does the rate of disappearanc
of A. However, the conversron increases as more and more reactant 1 s converted t
product. For X = 0.2. we calculate the corresponding reactor volume using S i m ~
?on's rule (given in Appendix A.4 as Equation [A-211) with AX = 0. I and the dat
in rows 1 and 4 in Table 2-3,
For X = 0.4. we can again use Simpson's rule wirh A X = 0.2 to find the react01
volume necessary for a conversion of 40%.
The data in Table E1-3.1are plotted in Figures E2-3.2 la) and (b).
One observes that the reaction rate, -XA, decrease^ as we move down the
reactor while the conversion increases. These plots are typical for reactors operated
isothomally.
Sec. 2.4 Apal~catjonsof The D~srgnEauatlons b r Cont~nuous-Flav~
Reactors 53
1 For isnthcr~nnl
reacllons. lhs
C ~ ~ ~ ~ eIncrease<
r~ion
and the nte derrta<e<
v,e miwe down the
118
PFR.
X
01 -- - .-. . --- -1
02 - - - . .
00
a HXI IWO 1% ZODD ~m o 5m IWO 1 4 ~ 2wo 2 5 ~
V (dm? V (dm3)
It to compare the volumer of a CSTR and a PFR required for the same
E S interesting
job. To make thls comparison. we shall use the data in Figure 2-2 to learn which
reactor would require the smaller volume to achieve a conversion of 80%: a CSTR
or a PFR.The entering molar Row rate FAo = 0.4 molls, and the feed conditions are
the same in both cases.
The CSTR volume was 6+4m" and the PI% voluine was 2. I65 m3. When we com-
bine Figures El-2.1 and E2-3. I on the same graph. we see that the crosshatched
area above the curve is the difference in the CSTR and PFR reactor volumes.
For isothermal reactions greater than zero order (see Chapter 3 for zem
order), the CSTR volume will urually be greater than the PFR volume for the same
conversion and reaction conditions (temperature, Bow rate, etc.).
We see that the reason the isotherma[ CSTR volume is usually greater than
the PFR volume is that the CSTR is always operating at the Iowest reaction rate
(e-g.. -rA = 0.05 in Figure E2-4.IIb)).The PFR on the other hand stans at a high
rate at the entrance and gradually decreases to the exit rate, thereby requiring less
volume because the volume is inversely proportional to the rate. However, for auto-
catalytic reactions. product-inhibited reactions. and nonisothermal exothermic reac-
tions. these trends will not always be the case. as we will see in Chapten 7 and 8.
54 Conversion and Reactor Sizing Chap. 2
: between
CSTR & PFR
For the first reactor, the rate of disappearance of A is -r,, at conversion XI.
A mole balance on reactor 1 gives
In - Out + Generation = 0
Reactor 1: FAo-FAl + r,,V, =O (2- 19)
The molar flow rate of A at point 1 is
FA,=EAo-FAOXI (2-20)
Combining Equations (2- 19) and (2-20) or rearranging
Reactor I
Reactor 2
For the second CSTR recall that -r,: is evaluated at Xz and then use (X2-X,
to calculate V2 at X2.
In the examples that follow, we shall use the molar Row rate of A we cal
culated in Example 2-1 (0.4 ma1 Ms) and the reaction conditions given it
Table 2-3.
For the two CSTRs in series, 40% convenion is achieved in the first reactor. Wha
is the volume of each of the two reactors necessary to achieve RO% overall conver
sion of the entering species A?
Snlrtlion
Fur reactor 1, we observe from either Table 2-3 or Figure E2-5.1 that when X = 0.4.
then
then
To achreve the
same over~ll
convenlon, the
tr~tal.olume fur
two CSTRs In
series is l e ~ than
s
{hat required
for one CSTR.
0.0 0.2 0.4 0.8 0.i 1.0
Conversion X
Figure EZ-5.1 Two CSTRs in .series.
Note again that for CSTRs in series the rate - r ~ ,i s evaIuared at a conversion
of 0.4 and rate -r+ is evaluated at a conversion of 0.8. The rota1 volume for these
two reactors i n senes i s
We need only
-r.4 = Jk)
and
FA" 10 size
reactors.
By comparison. the volume necessary to achieve 80% conversion in one CSTR is
Notice in Example 2-5 that the sum of the two CSTR reactor volumes (4.02 m3)
in series is less than the volume of one CSTR (6.4 m3) to achieve the same
conversion.
uuuuu
Figure 2.5 Modeling a PFR with CSTRs in series.