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
CA 
Concentration Flow System:


T P0
Gas Phase Flow System:    0 1  X 
T0 P

FA FA0 1  X  C 1  X  T0 P
CA    A0
  1  X  T P0 1  X  T P0
0
T0 P
 b   b 
FA0   B  X  C A0   B  X 
FB  a   a  T0 P
CB   
   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

Isothermal, T=T0 1  X  P
CA  C A 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)

5
 Pressure Drop in PBRs
 
Ergun Equation: dP  G  1    1501     
  3    1.75
 G 
dz g c D p     Dp TURBULENT 
    
 LAMINAR 
Constant mass flow: m  m 0
   0 0
0
  0

FT P0 T
  0
FT 0 P T0
P0 T
   0 (1  X )
6 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 

7
 Pressure 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

 dP  0 P0 T FT
 
dW Ac 1     c P T0 FT 0

2 0 1
Let 
Ac 1     c P0
8
 Pressure Drop in PBRs
dp a T FT P
=- p=
dW 2 p T0 FT 0 P0
We will use this form for single reactions:
d  P P0   1 T
 1  X 
dW 2  P P0  T0

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

dp a
=- ( 1+ eX ) Isothermal case
9
dW 2p
 Pressure Drop in PBRs
2 2
dX kC ( 1- X ) 2
A0
= 2
p
dW FA 0 ( 1+ eX )

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 e =0
dp - a
= (1+ eX)
dW 2 p
When W =0 p =1
dp =- a dW
2

p =(1- a W )
2

p =(1- a W )1/2
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 P
P

W 
13
 3 Reaction Rate in a PBR

-rA
2
P
 rA  kC  k (1  X )  
2
A
2

 P0 

No P

 P

W
14
 4 Conversion in a PBR
X

No P
P




W
15
 5 Flow Rate in a PBR
P
For   0 :

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



W
16
 P0 T
  0 1  X 
P T0
P0
T  T0 p=
P
u0 1
f = =
u (1+ e X ) p

17
 Example 1:
Gas Phase Reaction in PBR for δ=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 ?
CB0
18
 Example 1:
Gas Phase Reaction in PBR for δ=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 =CA 0 ( 1- X ) p

19
 Example 1:
Gas Phase Reaction in PBR for δ=0
dp a 2 pdp =- a dW
=-
dW 2p
W 0 , p =1 p 2 =1- a W
12
p =( 1- a W )
4) Combine
2 2 2 2 2
- rA =kCA 0 ( 1- X ) p =kCA0 ( 1- X ) ( 1- a W )

dX kC A2 0 1  X  1  W 
2

dW FA0
20
 Example 1:
Gas Phase Reaction in PBR for δ=0
dX kC A2 0
 1  W  dW
1  X  2
FA0

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 
21
 Example 2:
Gas Phase Reaction in PBR for δ≠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
22 α = 0.02 kg-1
 Example 2:
Gas Phase Reaction in PBR for δ≠0
A + 2B  C
dX  rA
1) Mole Balance 
dW FA0

2) Rate Law  rA  kC AC B2

3) Stoichiometry: Gas, Isothermal

P0
   0  1  X 
P

CA =CA0
( 1- X ) p
23 ( 1+ eX )
 Example 2:
Gas Phase Reaction in PBR for δ≠0
( Q B - 2X )
4) CB =CA 0 1+ eX p
( )
dp a
5) =- ( 1+ eX )
dW 2p
u ( 1+ eX )
6) f = =
u0 p
1 2
7)   y A0 [1  1  2]  [2]  
3 3
C A0  2, FA0  2, k  6,   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 δ≠0

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

  𝑀𝑊 ∗ 𝑃 0
𝜌0 =𝑀𝑊 ∗𝐶 𝑇 0=
𝑅 𝑇0

  2𝑅𝑇0 150 (1 − 𝜙 ) 𝜇
𝛼= 2 3
𝐴 𝐶 𝜌𝐶 𝑔𝐶 𝑃0 𝐷𝑃 𝜙 𝑀𝑊
𝐺
𝐷[𝑃
+1.75 𝐺
]
2
  1
𝛼≈
( )
𝑃0

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
0
dP FT 0 P T0

dW A c 1   c
FT T
b0 20
dp FT 0 T0 
dW
=-
pP0 Ac ( 1- f ) r c P0 A C 1   C

dy a FT T Use for heat effects,

=-
dW 2 p FT 0 T0 multiple rxns
FT dX a
  1  X  Isothermal: T = T0 =- ( 1+ eX )
FT 0 dW 2p
35
 Example 1:
Gas Phase Reaction in PBR for δ=0
A + B  2C
dm 6
k  1.5 ,   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 =C B
d =0 and T =T0 \ p =(1- a W )1/2

37