Lecture 8

Chemical Reaction Engineering (CRE) is the

field that studies the rates and mechanisms of
chemical reactions and the design of the reactors in
which they take place.
 Lecture 8 – Tuesday 2/5/2013
—  Block 1: Mole Balances
—  Block 2: Rate Laws
—  Block 3: Stoichiometry
—  Block 4: Combine

—  Pressure Drop

—  Liquid Phase Reactions
—  Gas Phase Reactions

—  Engineering Analysis of Pressure Drop

2
 Pressure Drop in PBRs
FA
Concentration Flow System: CA =
υ
T P0
Gas Phase Flow System: υ = υ 0 (1 + εX )
T0 P

FA FA0 (1 − X ) C (1 − X ) T0 P
CA = = = A0
υ T P0 (1 + εX ) T P0
υ0 (1 + εX )
T0 P
⎛ b ⎞ ⎛ b ⎞
FA0 ⎜ Θ B − X ⎟ C A0 ⎜ Θ B − X ⎟
FB ⎝ a ⎠ ⎝ a ⎠ T0 P
CB = = =
υ υ (1 + εX ) T P0 (1 + εX ) T P0
0
3 T0 P
 Pressure Drop in PBRs
Note: Pressure Drop does NOT affect liquid phase reactions

Sample Question:
Analyze the following second order gas phase reaction
that occurs isothermally in a PBR:
AàB
Mole Balances
Must use the differential form of the mole balance to
separate variables: dX ʹ′
FA0 = −rA
dW
Rate Laws
Second order in A and irreversible: − rAʹ′ = kCA2

4
 Pressure Drop in PBRs
Stoichiometry FA (1 − X ) P T0
CA = = CA 0
υ (1+ εX ) P0 T

Isothermal, T=T0 (1 − X ) P
CA = CA 0
€ (1+ εX ) P0

2 2
2
Combine: dX kC (1 − X ) ⎛ P ⎞
A0
€ = ⎜ ⎟⎟
2 ⎜
dW FA0 (1 + εX ) ⎝ P0 ⎠

Need to find (P/P0) as a function of W (or V if you have a PFR)

5
 Pressure Drop in PBRs
⎡ ⎤
Ergun Equation: dP − G ⎛ 1 − φ ⎞ ⎢150(1 − φ )µ ⎥
= ⎜⎜ 3 ⎟⎟ ⎢ + 1#
.75
"!G ⎥
dz ρg c D p ⎝ φ ⎠ ⎢ Dp
#$"$! TURBULENT ⎥
⎢⎣ LAMINAR ⎥⎦
Constant mass flow: m! = m! 0
ρυ = ρ 0υ 0
υ0
ρ = ρ0
υ
FT P0 T
υ = υ0
FT 0 P T0
P0 T
υ = υ0 (1 + εX )
6 P T0
 Pressure Drop in PBRs
P T0 FT 0
Variable Density ρ = ρ0
P0 T FT

dP − G ⎛ 1 − φ ⎞⎡150(1 − φ )µ ⎤ P0 T FT
= ⎜⎜ 3 ⎟⎟⎢ + 1.75G ⎥
dz ρ0 g c Dp ⎝ φ ⎠⎢⎣ Dp ⎥⎦ P T0 FT 0

G ⎛ 1 − φ ⎞⎡150(1 − φ )µ ⎤
Let β0 = ⎜⎜ 3 ⎟⎟⎢ + 1.75G ⎥
ρ0 g c Dp ⎝ φ ⎠⎢⎣ Dp ⎥⎦

7
 Pressure Drop in PBRs
Catalyst Weight W = zAc ρb = zAc (1 − φ )ρc

Where ρb = bulk density

ρc = solid catalyst density
φ = porosity (a.k.a., void fraction)
(1 − φ ) = solid fraction
€
€ dP − β0 P0 T FT
€ =
dW Ac (1 − φ )ρ c P T0 FT 0

2β 0 1
Let α=
Ac (1 − φ )ρ c P0
8
 Pressure Drop in PBRs
dp α T FT P
=− p=
dW 2 p T0 FT 0 P0
We will use this form for single reactions:

d (P P0 ) α 1 T
=− (1 + εX )
dW 2 (P P0 ) T0

dp α T
=− (1+ ε X )
dW 2 p T0

dp α
= − (1+ ε X ) Isothermal case
9
dW 2p
 Pressure Drop in PBRs
2 2
dX kC (1− X ) 2
A0
= 2
p
dW FA0 (1+ ε X )

dX dP dp
= f ( X , P ) and = f ( X , P ) or = f ( p, X )
dW dW dW
The two expressions are coupled ordinary differential
equations. We can only solve them simultaneously using
an ODE solver such as Polymath. For the special case of
isothermal operation and epsilon = 0, we can obtain an
analytical solution.
Polymath will combine the Mole Balances, Rate Laws
10 and Stoichiometry.
 Packed Bed Reactors
For ε = 0
dp −α
= (1+ ε X)
dW 2 p
When W = 0 p = 1
2
dp = −α dW
2
p = (1− αW )
1/2
p = (1− αW )
11
 1 Pressure Drop in a PBR
P

W
12
 2 Concentration Profile in a PBR
CA P
CA = CA 0 (1 − X )
P0

No ΔP
ΔP

W €
13
 3 Reaction Rate in a PBR

-rA
2
2 ⎛ P ⎞
2
−rA = kC = k (1 − X ) ⎜ ⎟
A
⎝ P0 ⎠

No ΔP

ΔP
€
W
14
 4 Conversion in a PBR
X

No ΔP
ΔP

€
€

W
15
 5 Flow Rate in a PBR
ΔP
For ε = 0 :

υ ⎛ P0 ⎞
υ = υ0 ⎜ ⎟
f = ⎝ P ⎠ €
υ0
1
No ΔP

W
16
 P0 T
υ = υ0 (1 + εX )
P T0
P0
T = T0 p=
P
υ0 1
f = =
υ (1+ ε X ) p

17
 Example 1:
Gas Phase Reaction in PBR for =0
Gas Phase reaction in PBR with δ = 0 (Analytical
Solution)
A + B à 2C
Repeat the previous one with equimolar feed of A
and B and:

kA = 1.5dm6/mol/kg/min C A0 = CB 0
α = 0.0099 kg-1
Find X at 100 kg
C A0 X =?
CB0
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 Example 1:
Gas Phase Reaction in PBR for =0

1) Mole Balance dX − r ' A

=
dW FA0

2) Rate Law − r ' A = kCACB

3) Stoichiometry CA = CA0 (1− X ) p

CB = CA0 (1− X ) p

19
 Example 1:
Gas Phase Reaction in PBR for =0
dp α 2 pdp = −α dW
=−
dW 2p

W =0 , p =1 p 2 = 1− αW

12
p = (1− αW )
4) Combine
2 2 2 2 2
−rA = kC A0 (1− X ) p = kC A0 (1− X ) (1− αW )
2
dX kC A2 0 (1 − X ) (1 − αW )
=
dW FA0
20
 Example 1:
Gas Phase Reaction in PBR for =0
dX kC A2 0
2
= (1 − αW )dW
(1 − X ) FA0
X kC A2 0 ⎛ αW 2 ⎞
= ⎜⎜W − ⎟⎟
1− X FA0 ⎝ 2 ⎠

W = 0, X = 0, W = W , X = X

X = 0.6 (with pressure drop )

X = 0.75 (without pressure drop, i.e. α = 0)
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 Example 2:
Gas Phase Reaction in PBR for ≠0
The reaction
A + 2B à C
is carried out in a packed bed reactor in which there is
pressure drop. The feed is stoichiometric in A and B.

Plot the conversion and pressure ratio y = P/P0 as a

function of catalyst weight up to 100 kg.
Additional Information
kA = 6 dm9/mol2/kg/min
α = 0.02 kg-1
22
 Example 2:
Gas Phase Reaction in PBR for ≠0
A + 2B à C

1) Mole Balance dX − rAʹ′

=
dW FA0

2) Rate Law − rAʹ′ = kC ACB2

3) Stoichiometry: Gas, Isothermal

P0
υ = υ0 (1 + εX )
P

CA = CA0
(1− X )
p
23 (1+ ε X )
 Example 2:
Gas Phase Reaction in PBR for ≠0
( Θ B − 2X )
4) CB = CA0 1+ ε X p
( )
dp α
5) = − (1+ ε X )
dW 2p
υ (1+ ε X )
6) f = =
υ0 p
1 2
7) ε = y A0 [1 − 1 − 2] = [−2] = −
3 3
C A0 = 2, FA0 = 2, k = 6, α = 0.02
Initial values: W=0, X=0, p=1
Final values: W=100
Combine with Polymath.
24 If δ≠0, polymath must be used to solve.
 Example 2:
Gas Phase Reaction in PBR for ≠0

25
 Example 2:
Gas Phase Reaction in PBR for ≠0

26
 T = T0

27
Robert the Worrier wonders: What if we increase
the catalyst size by a factor of 2?
 Pressure Drop
Engineering Analysis

​𝜌↓0 =𝑀𝑊∗​𝐶↓𝑇0 =​𝑀𝑊∗​  𝑃↓0 /𝑅​𝑇↓0  

𝛼=​2𝑅​𝑇↓0 /​𝐴↓𝐶 ​𝜌↓𝐶 ​𝑔↓𝐶 ​𝑃↓0↑2 ​𝐷↓𝑃 ​𝜙↑3 𝑀𝑊 𝐺[​150(1−𝜙)𝜇/​𝐷↓𝑃  +1.75𝐺]

𝛼≈​(​1/​𝑃↓0  )↑2 

29
 Pressure Drop
Engineering Analysis

30
 Pressure Drop
Engineering Analysis

31
 Heat Effects

Isothermal Design

Stoichiometry

Rate Laws

Mole Balance

32
 End of Lecture 8

33
 Pressure Drop - Summary
—  Pressure Drop
—  Liquid Phase Reactions
—  Pressure Drop does not affect concentrations in liquid
phase reactions.
—  Gas Phase Reactions
—  Epsilon does not equal to zero
d(P)/d(W)=…
Polymath will combine with d(X)/d(W) =… for you
—  Epsilon = 0 and isothermal
P=f(W)
Combine then separate variables (X,W) and integrate
—  Engineering Analysis of Pressure Drop

34
 Pressure Change – Molar Flow Rate
FT P0 T
β0
dP FT 0 P T0
=−
dW ρA c (1 − ϕ)ρc
FT T
β0 2β0
dp FT 0 T0 α=
=− P0 A C (1 − ϕ)ρC
dW pP0 Ac (1− φ ) ρc

dy α FT T Use for heat effects,

=−
dW 2 p FT 0 T0 multiple rxns
FT dX α
= (1 + εX ) Isothermal: T = T0 = − (1+ ε X )
FT 0 dW 2p
35
 Example 1:
Gas Phase Reaction in PBR for =0
A + B à 2C
dm 6
k = 1.5 , α = 0.0099kg −1 , C B 0 = C A0
mol ⋅ kg ⋅ min
Case 1: W = 100kg , X = ? , P = ?
1
Case 2: DP = 2 DP1 , P02 = P01 , X = ? , P = ?
2

C A0 X =?
CB0 P=?
36
 PBR

dX
FA0 = −r ' A
dW
rA = −kC AC B
FA
CA = p
FT
C A = CB
δ = 0 and T = T0 ∴ p = (1− αW )1/2

37