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
 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 =


 =  0 (1 + X )
T P0
Gas Phase Flow System:
T0 P

FA FA0 (1 − X ) C (1 − X ) T0 P
CA = = = A0
 0 (1 + X )
T P0 (1 + X ) T P0
T0 P
 b   b 
FA0   B − X  C A0   B − X 
CB =
FB
=  a 
=  a  T0 P
  (1 + X ) T P0 (1 + X ) 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:
A→B
Mole Balances
Must use the differential form of the mole balance to
separate variables: dX
FA0 = −rA
dW
Rate Laws
Second order in A and irreversible: − rA = kC A2

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

(1 − X ) P
Isothermal, T=T0 CA = CA 0
 (1+ X ) P0
dX kC (1 − X )  P 
2 2
2
Combine: = A0
 
2 
dW FA0 (1 + X )  P0 

Need to find (P/P0) as a function of W (or V if you have a PFR)
(Pressure change along the length of reactor)
Two steps:
• Find dp due to dz
5 • Find W correllate with z
 Pressure Drop in PBRs
 
dP − G  1 −   150(1 −  ) 
Ergun Equation: =  3   + 1
.75
G 
dz g c D p    
p TURBULENT 
D
 LAMINAR 
Only gas density, ,
varies with pressure

6
 Pressure Drop in PBRs
 
Ergun Equation: dP − G  1 −   150(1 −  ) 
=  3   + 1
.75
G 
dz g c D p    
 TURBULENT 
Dp
 LAMINAR 
Reactor operate at steady state → Constant mass flow:
m = m 0
 =  00
0
 = 0

FT P0 T
 = 0
FT 0 P T0
P0 T
 = 0 (1 + X )
7 P T0
 Pressure Drop in PBRs
P T0 FT 0
Variable Density  = 0
P0 T FT

dP −G  1 −   150(1 −  )  P0 T FT
=  3   + 1.75G 
dz  0 g c D p     Dp  P T0 FT 0

G  1 −   150(1 −  ) 
Let 0 =  3   + 1.75G 
0 gc Dp     Dp 

dP P0 T FT
= 0
8 dz P T0 FT 0
Pressure For PBR, W is of more interest than z
Drop in
PBRs
Catalyst Weight W = zAc  b = zAc (1 −  ) c

Where b = bulk density

c = solid catalyst density
 = porosity (a.k.a., void fraction)
(1 −  ) = solid fraction

 dW = Ac  b dz = Ac (1 −  ) c dz

dP P0 T FT dP − 0 P0 T FT
= 0 =
dz P T0 FT 0 dW Ac (1 −  ) c P T0 FT 0
2 0 1
Let =
9 Ac (1 −  ) c P0
 Pressure Drop in PBRs

d (P P0 )  1 T
=− (1 + X )
dW 2 (P P0 ) T0
P
Let: p=
P0

dp a T FT This Equation used when multiple reactions

=- occurring (ex: pressure drop in a
dW 2 p T0 FT 0 membrane reactor)

(Ergun equation)
10
Pressure Drop in PBRs
 For single reactions → more convenient to express Ergun
equation the in terns of the conversion X.:
dp a T FT
=-
dW 2 p T0 FT 0

dp a T
=- (1+ e X )
dW 2 p T0

dp a
= - (1+ e X )
Isothermal
case
dW 2p

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 Pressure Drop in PBRs
dX kC (1- X ) 2
2 2

= A0
p
dW FA 0 (1+ e X ) 2

dp
= f ( X , P ) and = f ( X , P ) or
dX dP
= 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
12 and Stoichiometry.
 Packed Bed Reactors
𝐹𝑜𝑟 𝜀 = 0
𝑑𝑝 −𝛼
= (1 + 𝜀𝑋)
𝑑𝑊 2𝑝
2𝑝𝑑𝑝
= −𝛼
𝑑𝑊

2𝑝𝑑𝑝 = −𝛼𝑑𝑊
Integrating with p = 1 (P=P0) at W = 0
p 2 = 1 − W
p = (1 − W )1/ 2

13
 1 Pressure Drop in a PBR
P  = 0; p = (1 − W )
1/ 2

W
14
 2 Concentration Profile in a PBR
CA P
CA = CA 0 (1 − X )
P0

No P
P

W 
15
 3 Reaction Rate in a PBR

-rA
2
P
−rA = kC = k (1 − X )  
2
A
2

 P0 

No P

P

W
16
 4 Conversion in a PBR
X

No P
P




W
17
  = 0 (1 + X )
P0 T
5 Flow Rate in a PBR P T0
P
For  = 0 :

  P0 
 = 0  
f = P 
0
1 No P

W
18
Example 1: Gas Phase Reaction in PBR for =0
 = y A0 = 0
Gas Phase reaction in PBR with δ = 0 (Analytical
Solution)
A + B → 2C
Repeat the previous one with equimolar feed of A
and B and:

kA = 1.5dm6/mol/kg/min C A0 = C B 0
α = 0.0099 kg-1
Find X at 100 kg
C A0 X =?
CB 0
19
 Example 1:
Gas Phase Reaction in PBR for =0
dX − r ' A
1) Mole Balance =
dW FA0

2) Rate Law − r ' A = kC AC B

3) Stoichiometry CA = CA0 (1- X ) p

CB = CA0 (1- X ) p

20
 Example 1:
Gas Phase Reaction in PBR for =0
dp a 2 pdp = -a dW
=-
dW 2p
W =0 , p =1 p2 =1- aW

p = (1- aW )
12

4) Combine
-rA = kCA0 (1- X ) p = kCA0 (1- X ) (1- aW )
2 2 2 2 2

dX kC A2 0 (1 − X ) (1 − W )
2
=
dW FA0
21
 Example 1:
Gas Phase Reaction in PBR for =0
kC A2 0
dX
= (1 − W )dW
(1 − X ) FA0
2

X kC A2 0  W 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.  = 0 )

22
 Example 2:
Gas Phase Reaction in PBR for ≠0
The reaction
A + 2B → 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
23
 Example 2:
Gas Phase Reaction in PBR for ≠0
A + 2B → C
dX − rA
1) Mole Balance =
dW FA0

2) Rate Law − rA = kC AC B2

3) Stoichiometry: Gas, Isothermal

 = 0 (1 + X )
P0
P

CA = CA0
(1- X )
p
24 (1+ e X )
 Example 2:
Gas Phase Reaction in PBR for ≠0
( QB - 2X )
4) CB = CA0 p
(1+ e X )
dp a
5) = - (1+ e X )
dW 2p

6) f =
u
=
(1+ e X )
u0 p
1 2
7) 𝜀 = 𝑦𝐴0 [1 − 1 − 2] = 3 [−2] = − 3
𝐶𝐴0 = 0.2, 𝐹𝐴0 = 2, 𝑘 = 6, 𝛼 = 0.02

Initial values: W=0, X=0, p=1

Final values: W=100
Combine with Polymath.
25 If δ≠0, polymath must be used to solve.
 Example 2:
Gas Phase Reaction in PBR for ≠0

26
 Example 2:
Gas Phase Reaction in PBR for ≠0

27
 T = T0

28
  http://www.umich.edu/~elements/5e/software/polymath
.html

29
Robert the Worrier wonders: What if we increase
the catalyst size by a factor of 2?
 Pressure Drop
Engineering Analysis

𝑀𝑊 ∗ 𝑃0
𝜌0 = 𝑀𝑊 ∗ 𝐶𝑇0 =
𝑅𝑇0

2𝑅𝑇0 150 1 − 𝜙 𝜇
𝛼= 𝐺 + 1.75𝐺
𝐴𝐶 𝜌𝐶 𝑔𝐶 𝑃02 𝐷𝑃 𝜙 3 𝑀𝑊 𝐷𝑃

2
1
𝛼≈
𝑃0

31
 Pressure Drop
Engineering Analysis

32
 Pressure Drop
Engineering Analysis

33
 Heat Effects

Isothermal Design

Stoichiometry

Rate Laws

Mole Balance

34
 End of Lecture 8

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