496 Nonisothermal Reactor Design Chapter 11

Example 11-3 Adiabatic Liquid-Phase Isomerization of Normal Butane

Normal butane, C 4 H 10 , is to be isomerized to isobutane in a plug-flow reactor. Isobutane

is a valuable product that is used in the manufacture of gasoline additives. For example,
isobutane can be further reacted to form iso-octane. The 20 I 0 selling price of n-butane
Living Example Problem was $0.44/kg, while the trading price of isobutane was $0.68/kg.
This elementary reversible reaction is to be carried out adiabatically in the liquid
phase under high pressure using essentially trace amounts of a liquid catalyst which
gives a specific reaction rate of 31.1 h- 1 at 360 K. The feed enters at 330 K.
(a) Calculate the PFR volume necessary to process I00,000 gallday (163 krnol/h)
at 70% conversion of a mixture 90 mol % n-butane and lO mol % i-pentane,
which is considered an inert.
(b) Plot and analyze X, X, T, and -rA down the length of the reactor.
{c) Calculate the CSTR volume for 40% conversion.

Additional information:

The economic t:..H~. = -6900 J/ mol n-butane , Activation energy= 65.7 kJ/mol
incentive
$ = 0.68/kg Kc = 3.03 at 60C , CAo= 9.3 mol / dm 3= 9.3 krnol/m 3
vs. 0.44/kg
i-Pentane
Cp = 141 J/ mol K Cp = 161 J/ mol K
n-8 i-P

Cp = 141 J/ mol K = 141 kJ/kmol K

i-B

Solution
n-C 4H 10 i-C 4 H 10
A B
(a) PFR algorithm
dX (E11 -3.1)
1. Mole Balance: FAo dV = -rA

The algorithm 2. Rate Law: -rA=k(cA- ~:} Ell-3.2)

with

(Ell-3.3)

{Ell-3.4)

3. Stoichiometry (liquid phase, v = v0):

CA = CAO ( 1 -X) (EJ 1-3.5)

C8 = CAoX {Ell -3.6)

,.,~ ~'-' 4. Combine:

(Eil-3 .7)
Following the Algorithm
Section 11.4 Adiabatic Operation 497

5. Energy Balance: Recalling Equation ( 11-27), we have

(11-27)

From the problem statement

Adiabatic: Q= 0
No work: W= 0
/lCp = Cp - Cp = 141 - 141 = 0
B A

Applying the preceding conditions to Equation (11-27) and rearranging

gives

Nomenclalllre Note T = T. + ( -llH~,JX (E11-3.8)

o 2- I.Cpj
llHRx<n = MRx
llHRx(TR) = llH~x 6. Parameter Evaluation:
llHRx=
FAO = 0.9FTO = (0.9)(163 ~o)) = 146.7 ~
01
llH~ + /lCp(T- TR)

2-;Cp = Cp +ICP =(14l+QJ161JJ / molK

i A I 0.9
= 159 J/ mol K

T = 330 + -( - 6900 ) X
159

I T= 330+43.4X I (EII-3.9)

where T is in degrees Kelvin.

Substituting for the activation energy, TI , and ki in Equation (Ell-3.3), we
obtain

k = 3 1.1 ex [65,700 (-'-_!)]<h - I)

p 8.31 360 T

k= 31.1 exp[7906 (~ J]<h - I) (El1-3.10)

Substituting for llH~, T2 , and Kc (T2 ) in Equation (E11-3.4) yields

-6900
Kc = 3.03 exp - - [ -I - -I)]
[ 8.31 333 T

Kc = 3.03 exp -830.3 T- 333)]

T (Ell-3.11)
[ ( 333
498 Nonisothermal Reactor Design Chapter 11

Recalling the rate law gives us

(E ll-3.7)

7. Equilibrium Conversion:
At equilibrium
-rA =0
and therefore we can solve Equation (Ell-3.7) for the equilibrium conver-
sion

X=~ (E il-3. 12)

e I +Kc
Because we know Kc (1), we can find X, as a function of temperature.

PFR Solution
It's risky business to
ask for 70% conver- (a) Find the PFR volume necessary to achieve 70% conversion. This prob-
sion in a reversible lem statement is risky. Why? Because the adiabatic equilibrium conver-
reaction. sion may be less than 70%! Fortunately, it's not for the conditions here
0.7 <X,. In general, we should ask for the reactor volume to obtain 95%
of the equilibrium conversion, X1 = 0.95 X,.
(b) Plot and analyze X, X,, -rA, and T down the length (volume) of the reactor.
We will solve the preceding set of equations to find the PFR reactor volume using
both hand calculations and an ODE computer solution. We carry out the hand calcula-
tion to help give an intuitive understanding of how the parameters X, and -rA vary
with conversion and temperature. The computer solution allows us to readily plot the
reaction variables along the length of the reactor and also to study the reaction and
reactor by varying the system parameters such as CAo and T0 .

Part (a) [Solution by Hand Cakulation to perhaps give greater insight and to
build on techniques in Chapter 2.]
We will now integrate Equation (Ell-3.8) using Simpson 's rule after forming a
table (Ell-3.1) to calculate (FA 0/-rA) as a function of X. This procedure is similar
We are only going
to do this once! ! to that described in Chapter 2. We now carry out a sample calculation to show how
Table Ell-3.1 was constructed.
For example, at X= 0.2 .
(a) T = 330 + 43.4(0.2) = 338.6 K

(b) k = 31.1 exp[7906 (

338 6 360
-
(360)(338.6)
J] = 31.1 exp ( -1.388) = 7.76 h- 1

Sample calculation
for Table Ell-3 .1 (c) K
c
= 3.03 exp[-830.3 (
338 6 333
-
(333)(338.6)
J] = 3.03e-0.04l2 = 2.9

(d) X = _22_ = 0.74

e l + 2.9

(e) -r
A
= (7 76 J(9.3) mol
h dm 3
[1- (1 _!_J(0.2)] = 52.8 ~ = 52.8
+ 2.9 dm3 h
kmol
m3 h
Section 11 .4 Adiabatic Operation 499

FAo = (0.9 mol butane/ mol total)(l63 . kmol total / h) =

2 .78 m 3
- rA 52.8 kmol
m3 h

TABLE Ell-3.1 HAND CALCULATION

X T(K) k (h- 1) Kc X, - r A( kmol!m3. h) FAo (ml)

-rA

0 330 4.22 3.1 0.76 39.2 3.74

0.2 338.7 7.76 2.9 0.74 52.8 2.78
0.4 347.3 14.02 2.73 0.73 58.6 2.50
0.6 356.0 24.27 2.57 0.72 37.7 3.88
0.65 358.1 27.74 2.54 0.718 24.5 5.99
0.7 360.3 31.67 2.5 0.715 6.2 23.29

Continuing in this manner for other conversions, we can complete Table Ell-3.1.
Use the data in Table E 11-3.1 to make a Levenspiel plot, as in Chapter 2.

30
FAo 2 0 L l
-rA 10
(m3) 0
0 0.2 0.4 0 .6 0 .8
X

The reactor volume for 70% conversion will be evaluated using the quadrature
formulas. Because (FA 0!-rA) increases rapidly as we approach the adiabatic
equilibrium conversion, 0.71, we will break the integral into two parts.

V=
o.7F
~dX=
Jo.6 ~dX+
F Jo.1 F
~dX (Ell-3.13)
Jo -rA o -rA 0.6 - rA

Using Equations (A-24) and (A-22) in Appendix A, we obtain

Why are we V= ~X 0 6 [3.74 + 3 X 2.78 + 3 X 2.50 + 3.88)m 3 + ! X Ql[3 .88 + 4 X 5.99 + 23.29)m
3
doing this hand 8 3 3 2
calculation? If it
3 3
isn't helpful, send V = 1.75 m + 0.85 m
me an email and you
won't see this again.

You probably will never ever carry out a hand calculation similar to the one shown
above. So why did we do it? Hopefully, we have given the reader a more intuitive
feel of the magnitude of each of the terms and how they change as one moves
down the reactor (i.e., what the computer solution is doing) , as well as to show
how the Levenspiel Plots of (FAof-rA) vs. X in Chapter 2 were constructed. At the
exit, V = 2.6 m\ X= 0.7, X, = 0.715, and T= 360 K.
Part (b) PFR computer solution and variable profiles
We could have also solved this problem using Polymath or some other ODE solver.
The Polymath program using Equations (Ell-3.1), (Ell-3.7), (Ell-3.9), (Ell-3.10),
(Ell-3.11), and (Ell-3.12) is shown in Table Ell-3 .2.
500 Nonisothermal Reactor Design Chapter 11

TABLE Ell -3.2 POLYMATH PROGRAM ADIAB ATIC ISOMERIZATION

Differential equations POLYMATH Report

Ordinary Differential Equations
1 d(X)/d(V) = -ra/FaO
Calculated values of DEQ variables
Explicit equations
1 cao = 9.3 Variable Initial value Final value
2 FaO = .9*163 6 rate 39.28165 0.0029845
Living Example Problem 3 T = 330+43.3*X 7 T 330. 360.9227
4 Kc = 3.03*exp(-830.3*((T-333)/(T*333))) 8 v 0 5.
5 k = 31.1*exp(7906*(T-360)/(T*360)) 9 X 0 0.7141504
6 Xe = Kc/(1+Kc) 10 Xe 0.7560658 0.7141573
7 ra = -k*cao*(1-(1 + 1/Kc)*X)
8 rate= -ra

(a) (b) (c)

l70.0 Exam 11 -3 Adiabatic Isomerization of Normal Butane

.....
362.0

358.0

3540 Fxl
~
3500

....o
342.0

1.5 20 2.5 30 35 AO 45 50
2.5 3.0 3.5 4.0 4.5 5.0 v
v

Figure Ell-3.1 Adiabadic PFR temperature, reaction rate, and conversion profiles.

Analysis: The graphical output is shown in Figure E 11-3.1. We see from Figure
Ell-3. l (c) that 1.15 m3 is required for 40% conversion. The temperature and reac-
Look at the shape tion rate profiles are also shown. Notice anything strange? One observes that the
of the curves in rate of reaction
Figure E 11 -3. 1.
Why do they look
the way they do?
(Ell-3.14)

goes through a maximum. Near the entrance to the reactor, T increases as does k,
causing term A to increase more rapidly than term B decreases, and thus the rate
increases. Near the end of the reactor, term B is decreasing more rapidly than term A
is increasing. Consequently, because of these two competing effects, we have a maxi-
mum in the rate of reaction.
AspenTecb: Example 11-3 has also been formulated in AspenTech and can be loaded
on your computer directly from the DVD-ROM.
Section 11 .4 Adiabatic Operation 501

Part (c) CSTR Solution

Let's now calculate the adiabatic CSTR volume necessary to achieve 40% conversion .
Do you think the CSTR will be larger or smaller than the PFR? The mole balance is

Using Equation (El1-3.7) in the mole balance, we obtain

Is
VPFR > VcsTR V= FAoX
or (El1-3 .15)
VpfR < VcsTR?
kCAO [ 1 - ( 1 + ~J] X
From the energy balance, we have Equation (E11-3.10):

T = 330 + 43.4X
For 40% conversion
T = 330 + 43.4(0.4) = 347.3K
Using Equations (E11-3 .11) and (E11-3 .12) orfrom Table El1-3.1,
k = 14.02 h- I
Kc = 2.73
Then
- r A = 58.6 kmol/m 3 h
V = ( 146.7 kmol butane/ h)(0.4)
58.6 kmol f m3 h
V= 1.0 m3
We see that the CSTR volume ( 1 m3) to achieve 40% conversion in this adiabatic
reaction is less than the PFR volume (1.15 m 3).
One can readily see why the reactor volume for 40% conversion is smaller for a
CSTR than a PFR by recalling the Levenspiel plots from Chapter 2. Plotting (FA0/- rA)
as a function of X from the data in Table E 11-3 .I is shown here.

6 6
The adiabatic CSTR 5 5
volume is less ~ 4
FAo
than the PFR -fA -fA
3
volume.
(m3) 2 (m3)
0.6 0 .2 0.6
X X

The PFR area (volume) is greater than the CSTR area (volume).

Analvsis: In this example we applied the CRE algorithm to a reversible-first-order

reaction carried out adiabatically in a PFR and in a CSTR. We note that at the
CSTR volume necessary to achieve 40% conversion is smaller than that to achieve
the same conversion in a PFR. In Figure E 11-3.l(c) we also see that at a PFR vol-
ume of three m3, equilibrium is essentially reached about half way through the reac-
tor, and no further changes in temperature, reaction rate, equilibrium conversion, or
conversion take place further down the reactor.