Pyrolysis of Benzene

Diphenyl (C 12 H10 ) is an important industrial intermediate. One production scheme involves the
pyrolytic dehydrogenetation of benzene (C 6 H6 ) [1]. During the process, triphenyl (C 18 H14 ) is also
formed by a secondary reaction.

The reactions are as follows:

(1) 2 C 6 H 6 → C12 H 10 + H 2
←
(2) C 6 H 6 + C12H 10 → C18 H 14 + H 2
←

Substituting the symbolic IDs A = C6 H6 , B = C12 H10 , C = C18 H14 and D = H2

(3) 2A → B+D
←
(4) A+ B → C+D
←

Murhpy, Lamb and Watson presented some laboratory data regarding these reactions originally
carried out by Kassell [2]. In these experiments, liquid benzene was vaporized, heated to the
reaction temperature and fed to a plug flow reactor (PFR). The product stream is condensed and
analyzed for various components. The results are tabulated in Table 1.

Table 1 the laboratory data for P = 1 atm.

Temperature Flow rate yA yB yC yD

(°F) (lbmole/hr)
1400 0.0682 0.8410 0.0695 0.00680 0.0830
1265 0.0210 0.8280 0.0737 0.00812 0.0900
1265 0.0105 0.7040 0.1130 0.02297 0.1590
1265 0.0070 0.6220 0.1322 0.03815 0.2085
1265 0.0053 0.5650 0.1400 0.05190 0.2440
1265 0.0035 0.4990 0.1468 0.06910 0.2847
1265 0.0030 0.4820 0.1477 0.07400 0.2960
1265 0.0026 0.4700 0.1477 0.07810 0.3040
1265 0.0007 0.4430 0.1476 0.08700 0.3220
1265 0.0003 0.4430 0.1476 0.08700 0.3220

[1] H.S. Fogler, Elements of Chemical Reaction Engineering, 3rd ed., p.77-79, Prentice
Hall, New Jersey, 1999.
[2] G.B. Murphy, G.G. Lamb, and K.M. Watson, Trans. Am. Inst. Chem. Engrs., (34) 429,
1938.

1
Additional data

Recall A = C6 H6 B = C12 H10 C = C18 H14 D = H2

The reactor tube dimensions :

L = 37.5 in, D = 0.5 in

Rate laws
 p p 
− r1A = k1 A  p 2A − B D 
 K 1A 

 p p 
− r2B = k 2 B  p A p B − C D 
 K2B 

Specific reaction rate constants

E
k 1A = A1 exp( − 1 )
RT

E2
k 2B = A2 exp( − )
RT

Equilibrium constants
B′
ln K1A = A′ + + C ′ ln( T ) + D ′ T + E ′ T 2
T

B′′
ln K 2B = A′′ + + C ′′ ln( T ) + D ′′ T + E ′′ T 2
T

Parameter values

E1 = 30190 cal/mol A1 = 7.4652E6 lbmole/h/ft3 /atm2

E2 = 30190 cal/mol A2 = 8.6630E6 lbmole/h/ft3 /atm2

A’ = -19.76 A’’ = -28.74

B’ = -1692 B’’ = 742
C’ = 3.13 C’’ = 4.32
D’ = -1.63E-3 D’’ = -3.15E-3
E’ = 1.96E-7 E’’ = 5.08E-7

P = 14.69595 psi R = 1.987 cal/mol/K

2
Exercises

a) Follow the instructions during the lab session and use the handouts to replicate the data
presented in Table 1 for T = 1400 °F and P = 1 atm using Aspen Plus™. What is the
percent difference between experimental and simulated mole fractions?

b) Run Aspen Plus™ simulations for different flow rates presented in Table 1 for T = 1265
°F. Compare your results to the experimental values by preparing a graph. The mole
fractions should be graphed as a smooth curve for the simulated data and as hollow
circles for the experimental values. Try to fit everything on one figure.

c) Calculate the number of reactor tubes (L = 219 in and D = 0.5 in) necessary to meet a
production target of 8000 lbmole/day diphenyl. Simulate this case with Aspen Plus™.
(Reactor temperature is kept constant at 1400 °F)

d) A simpler approach to solve this problem would be to ignore the side-reaction that
produces terphenyl. Simulate this simplified case for T = 1400 °F and P = 1 atm using
Aspen Plus™. What is the percent difference between experimental and simulated mole
fractions?

e) Repeat part b for the simplified version.

f) Did the number of tubes change for part c? By how many?

g) Discuss the effects of simplification. Do you recommend it?

Hint:
1) Attached is the solution of the problem in polymath. It might be useful to understand the
solution. Please use Aspen Plus™ to solve it. Due to the round off errors there will be
slight differences in the reported answers from Polymath and Aspen Plus™!
2) In part c, use the new dimensions for one reactor tube to come up with a flow rate that
would reach 60% conversion first.
3) For questions you can use the following email address: [email protected]

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POLYMATH Results
Aspen Plus Workshop - Pyrolysis of Benzene 03-06-2002, Rev5.1.225

Calculated values of the DEQ variables

Variable initial value minimal value maximal value final value

V 0 0 0.004263 0.004263
FA 0.0682 0.0568806 0.0682 0.0568806
FB 0 0 0.0048753 0.0048753
FC 0 0 5.229E-04 5.229E-04
FD 0 0 0.0059211 0.0059211
To 1033 1033 1033 1033
Po 1 1 1 1
T 1033 1033 1033 1033
P 1 1 1 1
Ep 1.96E-07 1.96E-07 1.96E-07 1.96E-07
Epp 5.08E-07 5.08E-07 5.08E-07 5.08E-07
E1 3.019E+04 3.019E+04 3.019E+04 3.019E+04
E2 3.019E+04 3.019E+04 3.019E+04 3.019E+04
Dp -0.00163 -0.00163 -0.00163 -0.00163
Dpp -0.00315 -0.00315 -0.00315 -0.00315
Cpp 4.32 4.32 4.32 4.32
App -28.74 -28.74 -28.74 -28.74
Bpp 742 742 742 742
K2B 0.4715116 0.4715116 0.4715116 0.4715116
F 0.0682 0.0682 0.0682 0.0682
R 1.987 1.987 1.987 1.987
Co 4.872E-04 4.872E-04 4.872E-04 4.872E-04
CA 4.872E-04 4.063E-04 4.872E-04 4.063E-04
CB 0 0 3.483E-05 3.483E-05
CD 0 0 4.23E-05 4.23E-05
CC 0 0 3.736E-06 3.736E-06
pA 1 0.8340269 1 0.8340269
pB 0 0 0.0714852 0.0714852
pC 0 0 0.0076676 0.0076676
A1 7.465E+06 7.465E+06 7.465E+06 7.465E+06
A2 8.663E+06 8.663E+06 8.663E+06 8.663E+06
k1A 3.056827 3.056827 3.056827 3.056827
k2B 3.547288 3.547288 3.547288 3.547288
pD 0 0 0.0868203 0.0868203
Ap -19.76 -19.76 -19.76 -19.76
Bp -1692 -1692 -1692 -1692
Cp 3.13 3.13 3.13 3.13
K1A 0.3167343 0.3167343 0.3167343 0.3167343
r1A -3.056827 -3.056827 -2.0664335 -2.0664335
r2B 0 -0.2064831 0 -0.2064831
rA -3.056827 -3.056827 -2.2729167 -2.2729167
rB 1.5284135 0.8267336 1.5284135 0.8267336
rC 0 0 0.2064831 0.2064831
rD 1.5284135 1.2396999 1.5284135 1.2396999

ODE Report (RKF56)

Differential equations as entered by the user

[1] d(FA)/d(V) = rA
[2] d(FB)/d(V) = rB
[3] d(FC)/d(V) = rC
[4] d(FD)/d(V) = rD

Explicit equations as entered by the user

[1] To = 1033
[2] Po = 1

4
[3] T = To
[4] P = Po
[5] Ep = 1.96e-7
[6] Epp = 5.08e-7
[7] E1 = 30190
[8] E2 = 30190
[9] Dp = -1.63e-3
[10] Dpp = -3.15e-3
[11] Cpp = 4.32
[12] App = -28.74
[13] Bpp = 742
[14] K2B = exp(App + Bpp/T + Cpp*ln(T) + Dpp*T + Epp*T^2)
[15] F = FA + FB + FC + FD
[16] R = 1.987
[17] Co = Po/R/To
[18] CA = Co*(FA/F)*(P/Po)*(To/T)
[19] CB = Co*(FB/F)*(P/Po)*(To/T)
[20] CD = Co*(FD/F)*(P/Po)*(To/T)
[21] CC = Co*(FC/F)*(P/Po)*(To/T)
[22] pA = CA*R*T
[23] pB = CB*R*T
[24] pC = CC*R*T
[25] A1 = 2.68e9/359
[26] A2 = 3.11e9/359
[27] k1A = A1*exp(-E1/R/T)
[28] k2B = A2*exp(-E2/R/T)
[29] pD = CD*R*T
[30] Ap = -19.76
[31] Bp = -1692
[32] Cp = 3.13
[33] K1A = exp(Ap + Bp/T + Cp*ln(T) + Dp*T + Ep*T^2)
[34] r1A = - k1A * (pA^2 - pB*pD/K1A)
[35] r2B = - k2B * (pA*pB - pC*pD/K2B)
[36] rA = r1A+r2B
[37] rB = r2B-r1A/2
[38] rC = -r2B
[39] rD = -r1A/2-r2B

Comments
[1] d(FA)/d(V) = rA
lbmole/h/ft^3
[2] d(FB)/d(V) = rB
lbmole/h/ft^3
[3] d(FC)/d(V) = rC
lbmole/h/ft^3
[4] d(FD)/d(V) = rD
lbmole/h/ft^3
[5] To = 1033
K
[6] Po = 1
atm
[7] T = To
K (isothermal)
[8] P = Po
atm (isobaric, no pressure drop)
[11] k1A = A1*exp(-E1/R/T)
lbmole/h/ft^3/atm^2
[12] k2B = A2*exp(-E2/R/T)
lbmole/h/ft^3/atm^2

5
[13] r1A = - k1A * (pA^2 - pB*pD/K1A)
lbmole/h/ft^3/atm^2
[14] r2B = - k2B * (pA*pB - pC*pD/K2B)
lbmole/h/ft^3/atm^2
[15] rA = r1A+r2B
lbmole/h/ft^3/atm^2
[16] rB = r2B-r1A/2
lbmole/h/ft^3/atm^2
[17] rC = -r2B
lbmole/h/ft^3/atm^2
[18] rD = -r1A/2-r2B
lbmole/h/ft^3/atm^2
[19] F = FA + FB + FC + FD
lbmole/h (Total molar flow rate)
[20] Co = Po/R/To
lbmole/ft^3
[21] CA = Co*(FA/F)*(P/Po)*(To/T)
lbmole/ft^3
[22] CB = Co*(FB/F)*(P/Po)*(To/T)
lbmole/ft^3
[23] CD = Co*(FD/F)*(P/Po)*(To/T)
lbmole/ft^3
[24] CC = Co*(FC/F)*(P/Po)*(To/T)
lbmole/ft^3
[25] pA = CA*R*T
atm
[26] pB = CB*R*T
atm
[27] pC = CC*R*T
atm
[28] pD = CD*R*T
atm
[29] A1 = 2.68e9/359
lbmole/h/ft^3/atm^2
[30] A2 = 3.11e9/359
lbmole/h/ft^3/atm^2
[31] E1 = 30190
cal/gmole
[32] E2 = 30190
cal/gmole
[33] R = 1.987
cal/gmole/K
[34] Ap = -19.76
for the 1st equilibrium constant
[39] App = -28.74
for the 2nd equilibrium constant

Independent variable
variable name : V
initial value : 0
final value : 0.004263

Precision
Step size guess. h = 0.000001
Truncation error tolerance. eps = 0.000001

General
number of differential equations: 4
number of explicit equations: 39

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