Heat Effects

CL324

Prof. Swati Bhattacharya

Example -1
Normal butane 𝐶4 𝐻10 is to be isomerized to iso-butane in a plug flow
reactor. The reaction is to be carried out adiabatically in the liquid
phase under high pressure using essentially trace amounts of liquid
catalyst what gives a specific reaction rate of 31.1 ℎ−1 at 360𝐾.
Calculate the PFR and CSTR volumes necessary to process 100,000
gal/day (163 kmol/h) at 70% conversion of a mixture 90 mol% n-
butane and 10 mol % 𝑖 −pentane, which is considered an inert. The
feed enters at 330 K

𝑛 − 𝐶4 𝐻10 ⇄ 𝑖 − 𝐶4 𝐻10
Or 𝐴 ⇄ B
Additional Data
0
𝐽
Δ𝐻𝑅𝑥 = −6900 𝑛 − 𝑏𝑢𝑡𝑎𝑛𝑒
𝑚𝑜𝑙
Activation energy =65.7 𝑘𝐽/𝑚𝑜𝑙
𝐾𝐶 = 3.03 𝑎𝑡 600 𝐶
𝐶𝐴0 = 9.3 𝑘𝑚𝑜𝑙/𝑚3
Butane:
𝐽
𝐶𝑃𝑛−𝐵𝑢𝑡𝑎𝑛𝑒 = 141
𝑚𝑜𝑙 ⋅ 𝐾
𝐽
𝐶𝑃𝑖𝑠𝑜−𝐵𝑢𝑡𝑎𝑛𝑒 = 141
𝑚𝑜𝑙 ⋅ 𝐾
𝐽
Pentane: 𝐶𝑃𝑖𝑠𝑜−𝑃𝑒𝑛𝑡𝑎𝑛𝑒 = 161
𝑚𝑜𝑙⋅𝐾
Nomenclature
Δ𝐻𝑅𝑥 (𝑇) ≡ Δ𝐻𝑅𝑥

0
Δ𝐻𝑅𝑥 𝑇𝑅 ≡ Δ𝐻𝑅𝑥

0
Δ𝐻𝑅𝑥 = Δ𝐻𝑅𝑥 + Δ𝐶𝑃 (𝑇 − 𝑇𝑅 )
Solution
𝑑𝑋
Mole Balance: 𝐹𝐴0 = −𝑟𝐴
𝑑𝑉

𝐶𝐵
Rate Law: −𝑟𝐴 = 𝑘 𝐶𝐴 −
𝐾𝐶

𝐸 1 1
With 𝑘 = 𝑘 𝑇1 exp −
𝑅 𝑇1 𝑇
0
Δ𝐻𝑅𝑥 1 1
And 𝐾𝐶 = 𝐾𝐶 (𝑇2 ) exp −
𝑅 𝑇2 𝑇
Stoichiometry: Liquid 𝜈 = 𝜈0
𝐶𝐴 = 𝐶𝐴0 (1 − 𝑋)
And 𝐶𝐵 = 𝐶𝐴0 𝑋

Combine:
1
−𝑟𝐴 = 𝑘𝐶𝐴0 1− 1+ 𝑋
𝐾𝐶
𝑑𝑋
Integrating mole Balance 𝐹𝐴0 = −𝑟𝐴
𝑑𝑉

𝑋 𝑋
𝐹𝐴0 𝐶𝐴0 𝜈0
𝑉=න 𝑑𝑋 = න 𝑑𝑋
0 −𝑟𝐴 0 𝑘𝐶
1
𝐴0 1− 1+ 𝑋
𝐾𝐶
Energy Balance: Steady State

𝑄ሶ − 𝑊ሶ − 𝐹𝐴0 ∑ Θ𝑖 𝐶𝑃𝑖 𝑇 − 𝑇0 0
− 𝐹𝐴0 𝑋 Δ𝐻𝑅𝑥 𝑇𝑅 + Δ𝐶𝑃 𝑇 − 𝑇𝑅
=0

We know:
Adiabatic: 𝑄ሶ = 0
No shaft work: 𝑊ሶ𝑠 = 0
Δ𝐶𝑃 = ? Δ𝐶𝑃 = 𝐶𝑃𝐵 − 𝐶𝑃𝐴 = 0
0
−Δ𝐻𝑅𝑥 𝑋
So: 𝑇 = 𝑇0 +
∑Θ𝑖 𝐶𝑝𝑖
Calculate parameters:
∑Θ𝑖 𝐶𝑝𝑖 = 𝐶𝑃𝐴 + Θ𝐼 𝐶𝑃𝐼 =?

0.1 𝐽
= 141 + × 161 =
0.9 𝑚𝑜𝑙⋅𝐾
𝐽
159
𝑚𝑜𝑙⋅𝐾

𝑇 =?
− −6900
𝑇 = 330 + 𝑋 = 330 + 43.4𝑋 (in units Kelvin)
159
Rate constant : 𝑘 =?

65700 1 1
31.1 exp − (ℎ−1 )
8.31 360 𝑇
7906 𝑇−360
Simplify to: 𝑘 = 31.1 exp (ℎ−1 )
360𝑇

Equilibrium constant: 𝐾𝐶 =?
6900 1 1
𝐾𝐶 = 3.03 exp − −
8.31 333 𝑇
𝑇−333
Simplify to 𝐾𝐶 = 3.03 exp −830.3
333𝑇
 1
Rate Law gives : −𝑟𝐴 = 𝑘𝐶𝐴0 1 − 1 + 𝑋
𝐾𝐶

Equilibrium Conversion: −𝑟𝐴 = 0

𝐾𝐶
Or, 𝑋𝑒 =
1+𝐾𝐶
Since we know 𝐾𝐶 𝑇 , 𝑦𝑜𝑢 𝑐𝑎𝑛 𝑔𝑒𝑡 𝑋(𝑇)
PFR Solution: Require 70% conversion
Fogler says that it is risky to ask for 70% conversion in a reversible
reaction. Because adiabatic equilibrium conversion may be less than
70%.
In general, ask for 95% of equilibrium conversion!
So, please check what is 𝑋𝑒 .

HA. Use an ODE solver to solve the equations

Hand Solution: Take 𝑋 = 0.2
a. 𝑇 = 330 + 43.4 ∗ 0.2 = 338.68𝐾
7906 338.68−360
b. 𝑘 = 31.1 exp = 7.76 ℎ−1
360∗338.68
338.68−333
c. 𝐾𝐶 = 3.03 exp −830.3
333∗338.68
= 2.9
2.9
d. 𝑋𝑒 =
1+2.9
= 0.74 (We are safe !)
7.76 mol 1 mol
e. −𝑟𝐴 =
h
9.3 3 1 − 1 +
dm 2.9
0.2 = 52.8 3
dm ⋅ℎ
=
kmol
52.8
m3 ⋅ℎ
𝑚𝑜𝑙 𝑏𝑢𝑡𝑎𝑛𝑒 𝑡𝑜𝑡𝑎𝑙
𝐹𝐴0 0.9 163.𝑘𝑚𝑜𝑙
f. = 𝑚𝑜𝑙 𝑇𝑜𝑡𝑎𝑙 ℎ
= 2.78 𝑚3
−𝑟𝐴 52.8 𝑘𝑚𝑜𝑙/(𝑚3 ⋅ℎ )
 𝑿 𝑻 𝒌 𝑲𝑪 𝑿𝒆 −𝒓_𝑨 𝑭𝑨𝟎
−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

3 0.6
Volume : 𝑉 = ∗ ∗ (3.74 + 3 ∗ 2.78 + 3 ∗ 2.50 + 3.88) 𝑚3 =2.60𝑚3
8 3
CSTR solution
Calculate the CSTR volume required to achieve 40% conversion .

𝐹𝐴0 𝑋
𝑉=
−𝑟𝐴

1
𝑉 = 𝐹𝐴0 𝑋/(𝑘𝐶𝐴0 1− 1+
𝐾𝐶

At 40%, 2.50 ∗ 0.4 = 1.0 𝑚3

Which is greater ?
PFR volume or CSTR volume for 40% conversion