Fogler_Ch08_web_excerpt.

fm Page 1 Tuesday, February 10, 2015 4:47 PM

Chapter 8 Multiple Reactions W8-1

Web Solved Problems

Web Example SP-8.1 Hydrodealkylation of Mesitylene in a PFR

The production of m-xylene by the hydrodealkylation of mesitylene over a Houdry

Detrol catalyst1 involves the following reactions:

CH3 CH3

 H2  CH4 (WESP-8.1.1)
CH3 CH3 CH3

m-Xylene can also undergo hydrodealkylation to form toluene:

CH3 CH3

 H2  CH4 (WESP-8.1.2)
CH3
A significant The second reaction is undesirable, because m-xylene sells for a higher price than
economic incentive toluene ($1.32/lbm vs. $0.30/lbm).2 Thus we see that there is a significant incentive
to maximize the production of m-xylene.
The hydrodealkylation of mesitylene is to be carried out isothermally at
1500R and 35 atm in a packed-bed reactor in which the feed is 66.7 mol% hydro-
gen and 33.3 mol% mesitylene. The volumetric feed rate is 476 ft3/h and the reactor
volume (i.e., V = W ⁄ ρb ) is 238 ft3.
The rate laws for reactions 1 and 2 are, respectively,
0.5
–r 1M = k 1C MC H (WESP-8.1.3)

0.5
r 2T = k 2C XC H (WESP-8.1.4)

where the subscripts are: M  mesitylene, X  m-xylene, T  toluene, Me 

methane, and H  hydrogen (H2 ).
At 1500R, the specific reaction rates are

Reaction 1: k 1  55.20 ( ft3 ⁄ lb mol )0.5 ⁄ h

Reaction 2: k 2  30.20 ( ft3 ⁄ lb mol )0.5 ⁄ h

The bulk density of the catalyst has been included in the specific reaction rate (i.e.,
k 1 = k′1 ρb ).
Plot the concentrations of hydrogen, mesitylene, and xylene as a function of
PFR space time. Calculate the space time where the production of xylene is a max-
imum (i.e., τopt ).

1 Ind. Eng. Chem. Process Des. Dev., 4, 92 (1965); 5, 146 (1966).

2 November 2004 prices, from Chemical Market Reporter (Schnell Publishing Co.),
265, 23 (May 17, 2004). Also see www.chemweek.com/ and www.icislor.com
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W8-2 Multiple Reactions Chapter 8

Solution
Reaction 1: M + H ⎯⎯→ X + Me (WESP-8.1.1)

Reaction 2: X + H ⎯⎯→ T + Me (WESP-8.1.2)

Mole balance on 1. Mole balances:
each and every
species dFH
Hydrogen: ---------  r H (WESP-8.1.5)
dV

dF
Mesitylene: ---------M-  r M (WESP-8.1.6)
dV

dFX
Xylene: ---------  r X (WESP-8.1.7)
dV

dF
Toluene: --------T-  r T (WESP-8.1.8)
dV

dFMe
Methane: ------------  r Me (WESP-8.1.9)
dV
2. Rate laws and net rates: Given
1⁄2
Reaction 1: –r 1M = k 1C H C M (WESP-8.1.3)
1⁄2
Reaction 2: r 2T = k 2C H C X (WESP-8.1.4)

Relative rates:
(1) –r1H = –r1M = r1Me = r1X (WESP-8.1.10)
(2) r2T = r2Me = –r2H = –r2X (WESP-8.1.11)
Net rates:
1/2
r M = r 1M = –k 1C H C M (WESP-8.1.12)
1/2 1/2
r H = r 1H + r 2H = r 1H – r 2T = –k 1C H C M –k 2C H C X (WESP-8.1.13)
1/2 1/2
r X = r 1X + r 2X = –r 1H – r 2T = k 1C H C M – k 2C H C X (WESP-8.1.14)
1/2 1/2
r Me = r 1Me + r 2Me = –r 1H + r 2T = k 1C H C M + k 2C H C X (WESP-8.1.15)
1/2
r T = r 2T = k 2C H C X (WESP-8.1.16)

3. Stoichiometry
The volumetric flow rate is
F P T
v = v0 -------T- -----0 -----
FT 0 P T 0
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Chapter 8 Multiple Reactions W8-3

Because there is no pressure drop P = P0 (i.e., y = 1), the reaction is carried

out isothermally, T = T0, and there is no change in the total number of moles;
consequently,
v = v0
Flow rates:

FH  v 0 C H (WESP-8.1.17)

FM  v 0 C M (WESP-8.1.18)

FX  v 0 C X (WESP-8.1.19)

FMe  v0C Me = FH0 – FH = v0 ( C H0 – C H ) (WESP-8.1.20)

FT  F M0– FM – FX = v0 ( C M0 – C M – C X ) (WESP-8.1.21)

4. Combining and substituting in terms of the space-time yields

V
τ = ----
v0

If we know C M , C H , and C X , then C Me and C T can be calculated from the reaction

stoichiometry. Consequently, we need only to solve the following three equations:

dC H 1⁄2 1⁄2
----------  – k 1C H C M – k 2C XC H (WESP-8.1.22)
The emergence of dτ
user-friendly ODE
solvers favors this dC M 1⁄2
approach over -----------  –k 1C MC H (WESP-8.1.23)
dτ
fractional
conversion.
dC X 1⁄2 1⁄2
----------  k 1C MC H – k 2C XC H (WESP-8.1.24)
dτ

5. Parameter evaluation:
At T0 = 1,500º R and P0 = 35 atm, the total concentration is
P0 35 atm 3
C T 0 = --------- = ----------------------------------------------------------------- = 0.032 lb mol/ft
RT 0 ⎛ atm ft ⎞
3
0.73 ------------------------- ( 1,500°R )
⎝ lb mol ⋅ °R⎠
3
C H0 = yH0C T 0 = ( 0.667 )( 0.032 lb mol/ft )
3
= 0.021 lb mol/ft

1
C M0 = --- C H0 = 0.0105 lb mol/ft3
2
C X0 = 0
V 238 ft3
t = ---- = ---------------------
- = 0.5 h
v0 476 ft3 ⁄ h
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W8-4 Multiple Reactions Chapter 8

3
F T 0 = C T 0v0 = ⎛ 0.032 --------------
lb mol⎞ ⎛
- 476 -----⎞
ft
⎝ ft
3 ⎠⎝ h⎠
F T 0 = 15.23 lb mol/h
We now solve these three equations, (WESP-8.1.22) to (WESP-8.1.24), simulta-
neously using Polymath. The program and output in graphical form are shown in
Table WESP-8.1.1 and Figure WESP-8.1.1, respectively. However, I hasten to point
out that these equations can be solved analytically and the solution was given in the
first edition of this text.

Figure WESP-8.1.1 Concentration profiles in a PFR.

TABLE WESP-8.1.1. POLYMATH PROGRAM

Web Example SP-8.2 Hydrodealkylation of Mesitylene in a CSTR

For the multiple reactions and conditions described in Web Example SP-8.1, calcu-
late the conversion of hydrogen and mesitylene along with the exiting concentra-
tions of mesitylene, hydrogen, and xylene in a CSTR.