Chapter 5-6

Isothermal Reactor Design-

Heterogeneous Reactions- Pressure Drop

Chemical Reaction Engineering

 Objectives
• Describe the algorithm that allows the reader to solve
chemical reaction engineering problems through logic rather
than memorization.
• Sizing batch reactors, semi-batch reactors, CSTRs, PFRs, and
PBRs for isothermal operation given the rate law and feed
conditions.
• Studying a liquid-phase batch reactor to determine the
specific reaction rate constant needed for the design of a
CSTR.
• Design of a tubular reactor for a gas-phase reaction.
• Account for the effects of pressure drop on
conversion in packed bed tubular reactors and in
packed bed spherical reactors.
• The principles of unsteady operation and semi-batch reactors.
Fig. 5-1
Isothermal
Reaction
Design
Algorithm
for Conversion
 4.1 Design structure for isothermal reactors

Algorithm for isothermal reactor design

1. Mole balance and design equation
2. Rate law
3. Stoichiometry
4. Combine
5. Evaluate
We can solve the equations in the
combine step either
A. Graphically (Chapter 2)
B. Numerical (Appendix A4)
C. Analytical (Appendix A1)
D. Software packages (polymath)
Algorithm for Isothermal Reactors
 Pressure Drop in Reactors
 In liquid-phase reactions
- the concentration of reactants is insignificantly affected by even
relatively large change in the total pressure =>
- Hence, the effect of pressure drop on the rate of reaction can be ignored
when sizing liquid-phase chemical reactors
• In gas-phase reactions,
• the concentration of the reacting species is proportional to the total
pressure
- the effects of pressure drop on the reaction system are a key factor
in the success or failure of the reactor operation
- that is, pressure drop may be very important for gas-phase reactions
 Pressure Drop and Rate Law

• For an ideal gas,

Fi FA0 i  vi X 
Ci  
v v0 (1  X )( P0 / P)(T / T0 )

  i  vi X  P To
(4-18) Ci  C A0  
 1  X  P0 T

- determine the ratio P/P0 as a function of V or W

- combine the concentration, rate law, and design equation
- the differential form of the mole balance (design equation) must be used
 Pressure Drop and Rate Law

• For example, the second order isomerization reaction in a packed-

bed reactor
2A  B + C
-the differential form of the mole balance

dX  gmoles 
FA0  rA  
dW  g catalyst min 
- rate law
 rA  kCA2
-from stoichiometry for gas-phase reactions

 1  X  P T0
C A  C A0  
 1  X  P0 T
 Pressure drop and the rate law
2
• Then, the rate law   1 X  P T0 
 rA  k C A0    (5-20)
  1  X  0 
P T
- the larger the pressure drop from frictional losses, the
smaller the reaction rate
• Combining with the mole balance and assuming isothermal
operation (T=To) in a Packed-bed reactor,
2 2
dX  C A0 (1  X )  P
FA0  k   
  P 
dW  1 X   0
• Dividing by FA0 2
 1  X   P 
2
dX kCA0
    
dW v0  1  X   P0 
 Pressure Drop and Rate Law

• For isothermal operation (T =T0), a function of only conversion

and pressure
dX (5-21)
 f ( X , P)
dW

-Another equation is needed to determine the conversion as a

function of catalyst weight, - that is, we need to relate the
pressure drop to the catalyst weight
P  f (W )
 Flow Through a Packed Bed
• The majority of gas-phase reactions are catalyzed by
passing the reactant through a packed of catalyst particles

• Ergun equation: to calculate pressure drop in a packed

porous bed
dP G  1   150 (1  ) 
  3   1.75G  (4-22)
dz g c D p    Dp 
laminar turbulent
G=u=superficial mass velocity [g/cm2s]; u=superficial velocity [cm/s];
Dp=diameter of particle in the bed [cm]; f=porosity=volume of void/total
bed volume; 1- f =volume of solid/total bed volume
• The gas density is the only parameter that varies with
pressure on the right-hand side. So, calculate the pressure
drop through the bed
 Flow through a Packed Bed
• Equation of continuity
 0  m 
m
m o=m
 0 v0  v

- steady state  the mass flow rate at any point is equal to the entering
mass flow rate
• Gas-phase volumetric flow rate
P  T  FT
v  v0 0   (3-41)
T  F
P  0  T0
• Then,

v0 P  T0  FT 0
  0  0   (4-23)
v P0  T  FT
 Pressure Drop in a Packed Bed Reactor
• then, Ergun equation

dP G(1  ) 150 (1  )  P0  T  FT

   1.75G   
0 g c D p  3 T  F
dz  Dp  P  0  T0

• Simplifying dP P0  T  FT
  0   (4-24)
dz P  T0  FT 0

dP G(1  ) 150 (1  ) 

We need 0    1.75G  (4-25)
dW 0 g c D p  
3
Dp 

• The catalyst weight,

W  (1  ) Ac z  c (4-26)
Volume of Density of
solid solid catalyst

dW  c (1  ) Ac dz
 Pressure Drop in a Packed Bed Reactor
• then, Ergun equation
dP 0 P0  T  FT
  
dW Ac (1  ) c P  T0  FT 0

dP  T P0  FT 
• Simplifying    (4-27)
F 
dW 2 T0 P / P0  T0 

dP
dy  T F P0T
Let y=P/Po  (1  X ) (4-28)
dW 2y
2 T0 PF/ P
To
0

2 0
 (4-29)
Ac  c (1  ) P0

 F  FT FA0
FT  FT 0  FT 0 X  FT 0 1  A0 X   1  X   y A0   
 FT 0  FT 0 FT 0
 Pressure drop in a packed bed reactor
dP
dy  T P0
 (1+X)(1  X ) (4-30)
dW 2y
2 T0 P / P0

ε < 0, the pressure drop (DP) will be less than that for ε = 0
ε > 0, the pressure drop (DP) will be greater than that for ε = 0
• For isothermal operation
dP dX
 f ( X , P) and  f ( X , P) (4-31)
dW dW
• The two expressions are coupled ordinary differential equations. We can
solve them simultaneously using an ODE solver such as Polymath.
• For the special case of isothermal operation and ε = 0, we can obtain an
analytical solution.
• Polymath will combine the mole balance, rate law and stoichiometry
 Pressure Drop in a Packed Bed Reactor
dP
dy  T P0
 (1+X)(1  X ) (4-30)
dW 2y
2 T0 P / P0

Analytical Solution

If ε = 0 or ε X ≪ 1, we can obtain an analytical solution to Eq. (4-30) for isothermal

operation (i.e., T=T0). For isothermal operation with ε = 0, Eq. (4-30) becomes

Isothermal (T=To) dy
dP  P0

with ε = 0 dW 2y
2 ( P / P0 )
dy dy2
dW = -  dW = - 
2y

At W=0, y=1 (P/Po=1) y2= 1- w

 Pressure Drop in a Packed Bed Reactor

If ε = 0 or ε X ≪ 1, we can obtain an analytical solution to Eq. (4-30) for isothermal

operation (i.e., T=T0). For isothermal operation with ε = 0, Eq. (4-30) becomes

P
Pressure ratio y=  1  W (4-33)
only for ε = 0 P0

2 0

Ac (1  ) c P0

W  (1  ) Ac z  c (4-26)

Pressure as a P 2 0 z
function of y=  1 =f (z) (4-34)
P0 P0
reactor length, z
 Pressure Drop in Pipes
Pressure drop along the length of the pipe

dP d 2 fG 2 P dP 2 dP 2 fG 2
 G  0 G  0
dL dL D P0 dL PdL D
Integrating with P=P0 at L=0, and assuming that f = constant
0
P02  P 2 P  L P 
 G 2 0  2 f  ln 0 
2 0  D P

Rearranging, we get
P0 4 fG 2
 1   pV p 
P 0 P0 Ac D

Example 4-4: 1½” schedule 40 x1000-ft L (p=0.018), DP<10%

 Analytical Solution for Reaction with Pressure Drop
Conversion as a function of catalyst weight
2nd-order isothermal reaction Combining

A B
dX kCA2 0
dW

FA0

(1  X ) 2 1  W 1/ 2 
2

Mole balance: Separating variable and Integrating

dX
F A0   r A FA 0 dX
 1  W dW
dW
kCA2 0 (1  X ) 2
Rate law:
at X  0, W  0 and FA0  C A0 v0
 rA  kCA2
v0  X   W 
   W 1  
Stoichiometry: Gas-phase isothermal with =0
kCA0  1  X   2 
P
C A  C A0 (1  X )
P0 kCA0W  W 
1  
P v0  2 
y=  1  W X (4-38)
P0 kC W  W 
1  A0 1  
v0  2 
C A  C A0 (1  X )(1  W )1/ 2
 Reaction with Pressure Drop
Conversion as a function of catalyst weight

kCA0W  W 
1  
v0  2  (4-38)
X
kC W  W 
1  A0 1  
v0  2 

Catalyst weight for 2nd-order isothermal reaction in PFR with DP

1  1  (2v0 ) / kCA0 X /(1  X )1/ 2 (4-39)

W

 Reaction with Pressure Drop
Conversion as a function of catalyst weight
For gas phase reactions, as the pressure drop increases, the concentration
decreases, resulting in a decreased rate of reaction, hence a lower conversion
when compared to a reactor without a pressure drop.
 Spherical Packed-Bed Reactors
Spherical Ultraformer Reactor (Amoco) for dehydrogenation reaction such as

Paraffin Aromatic + 3 H2

 Spherical reactor
- minimize pressure drop
- inexpensive
- the most economical shape for high
pressure
Coordinate system and variables
used with a spherical reactor
 Synthesizing a Chemical Plant

 Always challenge the assumptions, constraints, and

boundaries of the problem
 The profit from a chemical plant will be the difference
between income from sales and the cost to produce the
chemical

Profit = (value of products) – (cost of reactants)

– (operating costs) – (separation costs)
 The operating cost: energy, labor, overhead, and
depreciation of equipment
 Production of Ethylene Glycol
H2, C2H4
402 million
lbC2H6 /yr
1 C2H6  C2H4 + H2 2
separator
V=81 ft3, X=0.8 C2H6
O2, C2H4, N2, C2H4O
Ag
C2H4+ ½ O2  C2H4O C2H4
3
6 5
4 Air
separator
W=45,440 lb, X=0.6
H2O C2H4O
7 8 H2O, 0.9wt% H2SO4

C2H4O(aq)
200 million
9
lb EG/yr
V=197 ft3, X=0.8
absorber
Cat. CH2OH
C2H4O + H2O 
CH2OH
 Synthesizing a Chemical Plant

 Ethylene glycol = $0.38/lb (2x108 lb/yr)

Ethane = $0.04/lb (4x106 lb/yr)
Sulfuric acid = $0.043/lb (2.26x108 lb/yr)
Operating cost = $8x106/yr

 Profit = ($0.38/lb x 2x108 lb/yr) – ($0.04/lb x 4x108 lb/yr)

-($0.043/lb x 2.26x106 lb/yr) – ($8x106/yr)
= $52 million

 How the profit will be affected by conversion, separation, recycle stream,

and operating costs?
 Using CA (liquid) and FA (gas)
in the mole balance and rate laws

 More convenient to work in terms of the number of moles or molar

flow rate rather than conversion.
Membrane reactor, multiple reaction, and unsteady state

 Must write a mole balance on each species when molar flow

rates (Fi) and concentrations (Ci) are used as variables
b c d
A B   C  D
a a a
rA rB rC rD
  
a b c d

 rA  k AC A C B
 Liquid Phase
For liquid-phase reaction with no volume change 
Concentration is the preferred variable
aA  bB  cC  dD
b c d
A B  C D
a a a
Mole balance for liquid-phase reactions
dC A dC B b
Batch  rA  rA
dt dt a
v0 (C A0  C A ) v0 (C B 0  C B )
CSTR V  V 
 rA  (b / a ) rA
dC A dC B b
PFR v0  rA v0  rA
dV dV a
dC A dC B b
PBR v0  rA v0  rA
dW dW a
 Gas Phase
 For gas phase reactions
 need to be expressed in terms of the molar flow rates
dF j
 rj (1-11)
dV y
 Fj  P  T0 
C j  CT 0  
 P
 
 T
(3-42)
 FT  0  
dy - FT
= (4-28, T=To)
dW 2y FTo

 Total molar flow rate

n
FT  F
j 1
j = FA + FB + FC + FD + FI
 Algorithm for Gas Phase Reaction
aA  bB 
 cC  dD

 Mole balances:
Batch CSTR PFR

dN A F  FA dFA
 rAV V  A0  rA
dt  rA dV
dN B F  FB dFB
 rBV V  B0  rB
dt  rB dV
dN C
 rCV F  FC dFC
V  C0  rC
dt  rC dV
dN D
 rDV F  FD dFD
 rD
V  D0
dt  rD dV
 Algorithm for Gas Phase Reaction
 Rate law:  
 rA  k AC A CB

 Stoichiometry:
rA r r r
Relative rate of reaction:  B  C  D
a b c d
b c d
rB  rA rC   rA rD   rA
a y a a
FA P T0 FB P T0
Concentration: C A  CT 0 C B  CT 0
FT P0 T FT P0 T
FC P T0 FD P T0
CC  CT 0 C D  CT 0
FT P0 T FT P0 T
Total molar flow rate: FT  FA  FB  FC  FD
 Algorithm for Gas Phase Reaction
 Combine:
   
dFA     FA   FB  dFB b     FA   FB 
 k ACT 0       k ACT 0    
dV  FT   FT  dV a  FT   FT 
   
dFC c     FA   FB  dFB d     FA   FB 
 k ACT 0      k ACT 0    
dV a  FT   FT  dV a  FT   FT 

- Specify the parameter values: kA, CT0, , , T0, a, b, c, d

- Specify the entering number: FA0, FB0, FC0, FD0, and final value: Vfinal

 Use an ODE solver