ChBE 424 - HW #8 Solution Set

P8-5. Given: The endothermic liquid-phase elementary reaction:

A+B 2C

A B C
Feed Fi0 (lbmol/hr) 10.0 10.0 0.0
Feed Ti0, (°F) 80 80 ---
Specific heat CPi, (Btu/lbmol⋅°F) 51.0 44.0 47.5
MW (lb/lbmol) 128 94 222
Density ρi, (lb/ft3) 63.0 67.2 65.0
ΔH Rx = 20,000 Btu/lbmol A, independent of temperature
o

Calculate the steady-state reactor temperature assuming that the reaction goes to completion in a
single steam-jacketed continuously-stirred tank reactor.
Solution: The steady-state energy balance for a well-mixed system is:
Q − Ws − FA0 ∑ Θi CPi (T − Ti 0 ) − ΔH Rx
o
FA0 X A,final = 0 Eq. (8-27)
where
FB0 10
Θ A = 1, Θ B = = = 1, X A,final = 1
FA0 10
Q = UA(TS − T )
⎛ 2545 Btu ⎞ Btu
−Ws = ( 25 hp ) ⎜ ⎟ = 63,525
⎝ hp-hr ⎠ hr
Substituting into the energy balance gives
UA(TS − T ) − Ws − FA0 (CPA + CPB )(T − T0 ) − ΔH Rx
o
FA0 = 0
or
UA(TS − T0 ) − Ws − ( FA0 (CPA + CPB ) + UA ) (T − T0 ) − ΔH Rx
o
FA0 = 0
Solving for the temperature T gives
UA(TS − T0 ) − Ws − ΔH Rox FA0
T = T0 +
FA0 (CPA + CPB ) + UA
(150 Btu/hr ⋅ ft 2 ⋅ o F)(10 ft 2 )(365.9 o F − 80 o F) + (63,525 Btu/hr) − (20, 000 Btu/lbmol)(10 lbmol/hr)
T = 80 o F +
(10 lbmol/hr)((51 + 44) Btu/lbmol ⋅ o F) + (150 Btu/hr ⋅ ft 2 ⋅ o F)(10 ft 2 )
T = 199 o F
P8-8(a) Using POLYMATH and following the example in Fogler on pages 506-507 for adiabatic
operation gives:

Calculated values of the DEQ variables

Variable initial value minimal value maximal value final value

W 0 0 50 50 (kg)
X 0 0 0.9060474 0.9060474
T 450 450 903.02371 903.02371 (K)
Po 10 10 10 10 (atm)
R 0.0083144 0.0083144 0.0083144 0.0083144 (kJ/mol-K)
E 31.4 31.4 31.4 31.4 (kJ/mol)
k 0.133 0.133 8.9606698 8.9606698 (L/kg-s)
To 450 450 450 450 (K)
R2 0.082 0.082 0.082 0.082 (L-atm/mol-K)
P 10 10 10 10 (atm)
Cao 0.2710027 0.2710027 0.2710027 0.2710027 (mol/L)
Ca 0.2710027 0.0066567 0.2710027 0.0066567 (mol/L)
ra -0.0360434 -0.1566938 -0.0360434 -0.0596489 (mol/kg-s)
vo 20 20 20 20 (L/s)
Fao 5.4200542 5.4200542 5.4200542 5.4200542 (mol/s)
HCr -40 -40 -40 -40 (kJ/mol)
HAr -70 -70 -70 -70 (kJ/mol)
HBr -50 -50 -50 -50 (kJ/mol)
DHr -20 -20 -20 -20 (kJ/mol)
Tr 273 273 273 273 (K)
Cpa 0.04 0.04 0.04 0.04 (kJ/mol-K)

ODE Report (RKF45)

Differential equations as entered by the user

[1] d(X)/d(W) = -ra/Fao
[2] d(T)/d(W) = (-ra)*(-DHr)/(Fao*Cpa) (DCp = 25 + 15 - 40 = 0)

Explicit equations as entered by the user

[1] Po = 10 (atm)
[2] R = 0.0083144 (kJ/mol-K)
[3] E = 31.4 (kJ/mol)
[4] k = 0.133*exp(E/R*((1/450)-(1/T))) (L/kg-s)
[5] To = 450 (K)
[6] R2 = 0.082 (L-atm/mol-K)
[7] P = Po (atm)
[8] Cao = Po/(R2*To) (mol/L)
[9] Ca = Cao*(1-X)/(1+X)*(P/Po)*(To/T) (mol/L)
[10] ra = -k*Ca (mol/kg-s)
[11] vo = 20 (L/s)
[12] Fao = Cao*vo (mol/s)
[13] HCr = -40 (kJ/mol)
[14] HAr = -70 (kJ/mol)
[15] HBr = -50 (kJ/mol)
[16] DHr = HBr+HCr-HAr (kJ/mol)
[17] Tr = 273 (K)
[18] Cpa = 40/1000 (kJ/mol-K)

Comments
[3] ra = -k*Ca
mol/(kg cat*s)
[4] k = 0.133*exp(E/R*((1/450)-(1/T)))
dm3/(kg cat*s)
[5] E = 31.4
kJ/mol
[6] R = 0.0083144
kJ/(mol*K)
[7] Ca = Cao*(1-X)/(1+X)*(P/Po)*(To/T)
mol/L
[8] Cao = Po/(R2*To)
mol/L
[9] Po = 10
atm
[10] To = 450
K
[11] P = Po
atm
[12] R2 = 0.082
L*atm/(mol*K)
[13] Fao = Cao*vo
mol/s
[14] vo = 20
L/s
[15] DHr = HBr+HCr-HAr
kJ/mol
[16] HAr = -70
kJ/mol
[17] HBr = -50
kJ/mol
[18] HCr = -40
kJ/mol
[19] Tr = 273
K
[20] Cpa = 40/1000
kJ/(mol*K)
P8-8(b) Following the example on page 494;
F X FA 0 X
WCSTR = A0 =
− rA ⎛ 1 − X ⎞⎛ P ⎞⎛ T0 ⎞
kC A0 ⎜ ⎟⎜⎜ ⎟⎟⎜ ⎟
⎝ 1 + X ⎠⎝ P0 ⎠⎝ T ⎠
From the total energy balance, we have:
Q − W S − F A 0 ∑ Θ i C Pi ( T − Ti 0 ) − F A 0 X [ Δ H Rx
o
( T R ) + Δ C P ( T − T R )] = 0
From the problem statement,
Adiabatic: Q = 0
Negligible stirring work: W = 0 S

ΔC P = C PB + C PC − C PA = 25 + 15 − 40 = 0
ΔH Rx
o
(TR ) = H Bo + H Co − H Ao = −50 − 40 + 70 = −20 kJ/mol
P 10 atm mol
C A0 = A0 = = 0.271
RT0 ⎛ L ⋅ atm ⎞ L
⎜ 0.082 mol ⋅ K ⎟ ( 450 K )
⎝ ⎠
⎛ mol ⎞⎛ L ⎞ mol
FA0 = C A0 v0 = ⎜ 0.271 ⎟⎜ 20 ⎟ = 5.42
⎝ L ⎠⎝ s ⎠ s
Insert into the total energy balance, rearranging, & inserting into the CSTR design equation to give:
( − ΔH Rx
o
)X ( − ΔH Rx
o
)X − ( −20 kJ/mol)(0.8)
T = T0 + = T0 + = 450 K + = 850 K
ΣΘi C Pi C PA (0.04 kJ/mol ⋅ K )
 ⎡ kJ ⎤
⎡E ⎛ 1 1 ⎞⎤ ⎢ 31.4 ⎛ 1 1 ⎞⎥ L
k = 0.133exp ⎢ ⎜ − ⎟ ⎥ = 0.133exp ⎢ mol
⎜ 450 K − 850 K ⎟ ⎥ = 6.903 kg cat ⋅ s
⎣ ⎝
R 450 T ⎠⎦ ⎢ 0.0083144
kJ ⎝ ⎠⎥
⎣ mol ⋅ K ⎦
⎛ mol ⎞
⎜ 5.42
s ⎟⎠
( 0.8)
WCSTR =
FA0 X
= ⎝ = 39.4 kg cat
⎛ 1 − X ⎞ ⎛ P ⎞ ⎛ T0 ⎞ ⎛ L ⎞⎛ mol ⎞⎛ 1 − 0.8 ⎞ ⎛ 10 atm ⎞ ⎛ 450 K ⎞
kC A0 ⎜ ⎟⎜ ⎟ ⎜ ⎟ ⎜ 6.903 kg cat ⋅ s ⎟ ⎜ 0.271 L ⎟⎜ 1 + 0.8 ⎟ ⎜ 10 atm ⎟⎜ 850 K ⎟
⎝ 1 + X ⎠⎝ P0 ⎠ ⎝ T ⎠ ⎝ ⎠⎝ ⎠⎝ ⎠⎝ ⎠⎝ ⎠

P8-8(c) An example question is “How would your answer in part (a) change if pressure drop was
taken into account?” This question requires critical thinking since it is the fifth type of Socratic
question listed in Table P-1 on page xx.

P8-8d) Repeat P8-8a using POLYMATH, this time including the pressure differential equation and
appropriate alpha value. For alpha = 0.0075/kg cat for particle diameter D2:

Calculated values of the DEQ variables

Variable initial value minimal value maximal value final value

W 0 0 50 50
X 0 0 0.7751552 0.7751552
T 450 450 837.57761 837.57761
P 10 5.3620913 10 5.3620913
Po 10 10 10 10
R 0.0083144 0.0083144 0.0083144 0.0083144
E 31.4 31.4 31.4 31.4
k 0.133 0.133 6.462801 6.462801
To 450 450 450 450
R2 0.082 0.082 0.082 0.082
Cao 0.2710027 0.2710027 0.2710027 0.2710027
Ca 0.2710027 0.0098888 0.2710027 0.0098888
ra -0.0360434 -0.1212363 -0.0360434 -0.0639091
vo 20 20 20 20
Fao 5.4200542 5.4200542 5.4200542 5.4200542
HCr -40 -40 -40 -40
HAr -70 -70 -70 -70
HBr -50 -50 -50 -50
DHr -20 -20 -20 -20
Cpa 0.04 0.04 0.04 0.04
alpha 0.0075 0.0075 0.0075 0.0075

ODE Report (RKF45)

Differential equations as entered by the user

[1] d(X)/d(W) = -ra/Fao
[2] d(T)/d(W) = (-ra)*(-DHr)/(Fao*Cpa)
[3] d(P)/d(W) = -(alpha/2)*(T/To)*(Po/(P/Po))*(1+X)

Explicit equations as entered by the user

[1] Po = 10
[2] R = 0.0083144
[3] E = 31.4
[4] k = 0.133*exp(E/R*((1/450)-(1/T)))
[5] To = 450
[6] R2 = 0.082
[7] Cao = Po/(R2*To)
[8] Ca = Cao*(1-X)/(1+X)*(P/Po)*(To/T)
[9] ra = -k*Ca
[10] vo = 20
[11] Fao = Cao*vo
[12] HCr = -40
[13] HAr = -70
[14] HBr = -50
[15] DHr = HBr+HCr-HAr
[16] Cpa = 40/1000
[17] alpha = 0.0075

Comments
[1] d(X)/d(W) = -ra/Fao
1/kg cat
[2] d(T)/d(W) = (-ra)*(-DHr)/(Fao*Cpa)
K/kg cat
[3] d(P)/d(W) = -alpha/2*(T/To)*(Po/(P/Po))*(1+X)
atm/kg cat
[4] ra = -k*Ca
mol/(kg cat*s)
[5] k = 0.133*exp(E/R*((1/450)-(1/T)))
dm3/(kg cat*s)
[6] E = 31.4
kJ/mol
[7] R = 0.0083144
kJ/(mol*K)
[8] Ca = Cao*(1-X)/(1+X)*(P/Po)*(To/T)
mol/L
[9] Cao = Po/(R2*To)
mol/L
[10] Po = 10
atm
[11] To = 450
K
[12] R2 = 0.082
L*atm/(mol*K)
[13] Fao = Cao*vo
mol/s
[14] vo = 20
L/s
[15] DHr = HBr+HCr-HAr
kJ/mol
[16] HAr = -70
kJ/mol
[17] HBr = -50
kJ/mol
[18] HCr = -40
kJ/mol
[19] Cpa = 40/1000
kJ/(mol*K)
[20] alpha = 0.0075
1/kg cat
The conversion is lower for a reactor with 50 kg of catalyst when pressure drop is taken into
account, which makes sense, since the lower pressure results in lower concentration of reactant A,
and lower reaction rate. For the range of alpha between 0.0075 and 0.0123, decreasing the alpha
value increases the conversion X, whereas increasing the alpha value lowers the pressure P which
lowers the concentration of reactant A, which lowers the reaction rate which lowers the conversion.

A value of alpha > 0.0123 results in pressure P reaching zero before the end of the reactor, in which
case an inlet pressure of 10 atm is not large enough to force flow through the reactor. Such a reactor
would need a higher inlet pressure, or a more loosely packed catalyst bed (which would result in a
lower value for alpha). In POLYMATH, entering a value of alpha larger than 0.0123 results in
numerical problems when the pressure P reaches zero in the reactor with 50 kg of catalyst, which is
not unexpected since the model equations make no physical sense when the pressure becomes
negative. Hence the listed value of alpha of 0.019 for a particle diameter of D1 leads to POLYMATH
convergence problems, unless the catalyst weight W is reduced so that P > 0 throughout the reactor.