Reactor sizing and Pressure drop

calculation

Lebanese University
Dr. Reine Ghaleb
Batch Operation
Algorithm for isothermal reactor design 1  dN A 
   rA
1. Mole balance and design equation V  dt 
1 dN A d  N A / V0  dC A
   rA
V0 dt dt dt
2. Rate law
A
 B  rA  kC A2 irreversible, 2nd order in A
3. Stoichiometry
dC A CA=CAo(1-X)
4. Combination   kC A2
dt dX
dC A CAo =kCAo2(1-X)2
dt
5. Analytical Evaluation   dt
kC A2 X dX t

1

kCAo 0 (1-X)2 = dt
0
1 CA dC A t

k C A0 C A2 
 dt
0 t=
1
( X
1-X )
kCAo
1 1 1 
  t
k  C A C A0 

Batch Reaction Times
A
 B
dX r
Mole balance  AV
dt N A0
First - order Second order
Rate law
 rA  kC A  rA  kC A2
NA
Stoichiometry (V=V0) CA   C A0 (1  X )
V0

dX dX
Combine  k (1  X )  kC A0 (1  X ) 2
dt dt
1 1 X
Integration t ln t
k 1 X kC A0 (1  X )
Batch Reaction Times

1st - order (X  0.9, k  10-4 s 1 ) 2nd order (X  0.9, kC A0  10 3 s 1 )

1 1 X
tR  ln tR 
k 1 X kC A0 (1  X )
1 1 0 .9
 ln 
k 1  0.9 kC A0 (1  0.9)
2.3 9
 
k kC A0
2.3
  4 1 
9
10 s 10 3 s 1
 23,000 sec  9,000 sec
 6.4hr  2.5hr
Problem Solving Algorithm
Example Determining k from Batch Data

A. Problem statement. Determine the kA D. Assumptions and approximations:

B. Sketch Assumptions
C. Identify 1. Well mixed
C1. Relevant theories 2. All reactants enter at the same time
Rate law:  rA  k AC A 3. No side reaction
4. Negligible filling and emptying time
dN A
Mole balance:  rAV 5. Isothermal operation
dt Approximations
C2. Variables
Dependent: concentrations 1. Water in excess (CH2O~constant)
Independent: time
C3. Knowns and unknowns E. Specification. The problem is neither
Knowns: CEG = f(t) overspecified nor underspecified.
Unknowns:
1. CEO = f(t) F. Related material. This problem uses the
2. kA mole balances developed in Chap. 1
for a batch reactor and the
3. Reactor volume
stoichiometry and rate laws developed
C4. Inputs and outputs: reactant fed
in Chap. 3.
all at once a batch reactor
G. Use an Algorithm.
C5. Missing information: None
dCA
= -kCA
dt
CA dC t
 
- CAo
A
= k dt ln = kt CA = CAoe-kt
CA0 CA 0 CA

A + B  C

NC=NAoX=NAo-NA

CC=NC/V=NC/Vo= CAo-CA=CAo- CAoe-kt =CAo(1-e-kt)

 ln10 2.3
Rearranging and taking the logarithm k   0.311 min 1
of both side yields t 2  t1 8.95  1.55

C A 0  CC
ln   kt
C A0  rA  (0.311 min 1 )C A
We see that a plot ln[(CA0-CC)/CA0] as a
function of t will be a straight line with a
slope –k.
Design of CSTR
Design Equation for a CSTR
F A0 X
Mole balance V 
( rA ) exit
 C  CA  V C  CA
V  v0  A0    A0 the space time
  rA  v0  rA

For a 1st-order irreversible reaction, the rate law is

Rate law rA  kC A
C A0  C A
Combine 
kC A
Solving for the effluent concentration of A, we obtain

C A0
CA   C A0 (1  X )
1  k Relationship between
space time and
conversion for a 1st-
k order liquid-phase rxn
X 
1  k
Reaction Damköhler number
rA0V Rate of Reaction at Entrance " a reaction rate"
Da   
FA 0 Entering Flow Rate of A " a convection rate"

The Damkohler is a dimensionless number that can give us a quick

estimate of the degree of conversion that can be achieved in continuous-
flow reactor.
rA0V kC A0 0V
For 1st-order irreversible reaction Da    k
FA 0 v 0 C A0

 rA0V kC A2 0V
For 2nd-order irreversible reaction Da    kC A0
FA0 v0 C A0
Da  0.1 will usually give less than 10% conversion.
Da  10.0 will usually give greater than 90% conversion.
k Da
For first order reaction, X = =
1 + k 1 + Da
CSTRs in Series
CA0 CA1, X1
v0
CA2, X2

-rA1, V1 -rA2, V2

For first-order irreversible reaction with no volume change (v=v0) is carried out in
two CSTRs placed in series. The effluent concentration of A from reactor 1 is

C A0
C A1 
1  1k1

From a mole balance on reactor 2,

FA1  FA2 v0  C A1  C A2 
V2  
 rA2 k 2 C A2
CSTRs in Series
Solving for CA2, the concentration exiting the second reactor, we get

C A1 C A0
C A2  
1   2 k 2 1   2 k 2 1  1k1 

If instead of two CSTRs in series we had n equal-sized CSTRs connected in

series (t1 = t2 = … = tn = ti = (Vi/v0)) operating at the same temperature (k1 =
k2 = … = kn = k), the concentration leaving the last reactor would be

C A0 C A0
C An  
1  k  n 1  Da  n
The conversion and the rate of disappearance of A for these n tank reactors
in series would be
X= 1-CA/CAo
1 kC A0
X  1 1  rAn  kC An 
1  k  n =1-
(1+Da)n 1  k  n
Conversion as a Function of Reactors in Series
for different Damkohler numbers for a first-order recation

Da=k=1
Da=k=0.5

Da=k=0.1

Da  1, 90% conversion is achieved in two or three reactors;

thus the cost of adding subsequent reactors might not be justified
Da ~0.1, the conversion continues to increase significantly with each reactor added
CSTRs in Parallel
A balance on any reactor i, gives the individual
reactor volume
FA0 1
 Xi 
Vi  FA0i  

  rAi 
-rA1, V1, X1
FA0 i

X1  X 2    X n  X i

 rA1  rA2    rAn  rA

-rAi, Vi
The volume of each individual reactor, Vi, is
related to the total volume, V, of all the reactors,
n
and similar relationship exists for the total molar
flow rate
V FA 0
Vi  FA 0 i  -rAn, Vn
n n
CSTRs in Parallel
Substituting these values into Eq (4-12) yields FA01
F
FA 0 i  A0
V n
Vi  FA0 1
n  Xi 
Vi  FA0i  
 -r-rA1, V1, X1
  rAi  FA0i A1, V1

V F A0  X i 
  
n n   rAi 
 -rAi-r
, VAii, Vi, Xi
FA0n
FA 0 X i FA 0 X
V  n
 rAi  rA
The conversion achieved in any one of the reactors in
parallel is identical to what would be achieved if the -r,AnV, Vn, Xn
-rAn n

reactant were fed in one stream to one large reactor of

volume V
A Second-Order Reaction in a CSTR

For a 2nd-order liquid-phase reaction We solve the above eq. for X:

being carried out in a CSTR, the
combination of the rate law and the
design equation yields
1  2kC A0   1  2kC A0  2   2kC A0  2
X 
2kC A0

V
FA 0 X FA 0 X
 (4-14) 1  2kC A0   1  4kC A0

 rA kC A2 2kC A0

For const density v=v0, FA0X=v0(CA0-CA)


1  2Da   1  4Da (4-16)
V C A0  C A 2Da
 
v0 kC A2
The minus sign must be chosen in the
Using our definition of conversion, we quadratic equation because X cannot be
have greater than 1.
X
 2 (4-15)
kC A0 (1  X )
A Second-Order Reaction in a CSTR

0.88
0.67

6 60
 Example 4-2: Producing 200 Million Pound/Year in a CSTR

A 1 lb mol/ft3 solution of ethylene oxide (EO) in

water is fed to the reactor together with an equal
olumetric solution of water containing 0.9 wt%
f the catalyst H2SO4. The specific reaction rate
onstant is 0.311 min-1.

a) If 80% conversion is to be achieved, determine

he necessary CSTR volume.

b) If two 800-gal reactors were arranged in parallel,

what is the corresponding conversion?

c) If two 800-gal reactors were arranged in series,

what is the corresponding conversion?
Tubular Reactors
- 2nd-order gas-phase reaction Rate law
X dX

- Turbulent
V  FA0
- No dispersion 0 kC A2
- No radial gradients in T, u, or C
For Liquid-Phase Reaction
PLUG-FLOW REACTOR X dX
X dX
PFR mole balance
V  FA 0 
0 kC A2
= FAo

0 kCAo (1-X)
2 2

dX
FA 0
dV
  rA =
vo
kCAo ( X
1-X )
must be used when there is a DP or heat
exchange between PFR & the surrounds.
1
V/vo=  = kC
Ao
( X
1-X )
In the absence of DP or heat exchange, the kCAo Da2
integral form of the PFR design equation X= =
1+kCAo 1 + Da2
is used.
(Da2=Damköhler number for a 2nd-order RXN)
X dX
V  FA0 0  rA For n-th order RXN, Dan=kCAon-1
For Gas-Phase Reaction
X dX
V  FA 0 
0 kC A2
Conversion as a Function of Distance Down the Reactor

v  (1  0.5 X )v0
v=vo(1+X) the reactant spends more time

v  (1  2 X )v0
the reactant spends less time

ö
V(m3)
The volumetric flow rate decreases with increasing conversion, and the reactant
spends more time in the reactor than reactants that produce no net change in the
total number of moles.
Change in Gas-Phase Volumetric Flow Rate Down the Reactor

v=vo(1+X)
Example 4-3: Determination of a PFR Volume

Determine the PFR volume necessary to produce 300 million pounds of ethylene a year
from cracking a feed stream of pure ethane. The reaction is irreversible and follows an
elementary rate law. We want to achieve 80% conversion of ethane, operating the
reactor isothermally at 1100K at a pressure of 6 atm.

C2H6 (A)  C2H4 (B) + H2 (C)

FB=300x106 lb/year=0.340 lb-mol/sec

FB=FAoX
FAo=FB/X=0.340/0.8=0.425 lb-mol/sec
Pressure Drop in Reactors

 In liquid-phase reaction
- the concentration of reactants is insignificantly affected by even
relatively large change in the total pressure
- ignore the effect of pressure drop on the rate of reaction
when sizing liquid-phase chemical reactors
- that is, pressure drop is ignored for liquid-phase kinetics calculations

 In gas-phase reaction
- 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 FA 0   i  vi X 
Ci  
v v0 (1  X )( P0 / P )(T / T0 )

  i  vi X  P To
C i  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  kC A2
-from stoichiometry for gas-phase reactions

 1 X  P T0
C A  C A0  
 1  X  P0 T
Pressure drop and the rate law
• Then, the rate law
2
  1  X  P T0 
 rA  k C A0   
  1  X P
 0 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)

2 2
dX  C (1  X )   P 
FA0  k  A0   
P 
dW  1  X   0 
• Dividing by FA0

2 2
dX kC A0  1  X   P 
    
dW v0  1  X   P0 
Pressure Drop and Rate Law

• For isothermal operation (T =T0)

-a function of only conversion and pressure

dX
 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 
dz g c D p     Dp 
laminar turbulent

G=ru=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 laminar turbulent
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  
P T F
 0  T0
• Then,

v0 P  T0  FT 0
  0  0  
v P0  T  FT
Pressure Drop in a Packed Bed Reactor
• then, Ergun equation
dP G (1   ) 150(1   )  P0 T  FT
   1.75G   
dz 0 g c D p  3 Dp T F
  P  0  T0

• Simplifying dP P0  T  FT
  0  
dz P  T0  FT 0

G (1   ) 150(1   ) 
0    1.75G 
dP 3
 0 g c D p   Dp 
We need
dW

• The catalyst weight, W  (1   ) Ac z   c

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   
dW 2 T0 P / P0 F 
 T0 

Let y=P/Po dy    T FP0T (1  X )

dP
dW 2y
2 T0 PF/ To
P0

2 0

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 )
dW 2y
2 T0 P / P0

ε < 0, the pressure drop (DP) will be less than ε = 0

ε > 0, the pressure drop (DP) will be greater than ε = 0

• For isothermal operation

dP dX
 f ( X , P) and  f ( X , P)
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 )
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

Pressure ratio P
y=  1  W
only for ε = 0 P0

2 0

Ac (1   ) c P0

W  (1   ) Ac z   c

Pressure as a P 2 z
function of y=  1  0 =f (z)
P0 P0
reactor length, z
Analytical Solution for Reaction with Pressure Drop
Conversion as a function of catalyst weight

2nd-order isothermal reaction Combining

A B
dX kC A2 0
dW

FA0

(1  X ) 2 1  W  1/ 2  2

Mole balance: Separating variable and Integrating

dX FA 0 dX
F A0   rA  1  W  dW
dW kC A2 0 (1  X ) 2
Rate law:
at X  0, W  0 and FA0  C A0 v0
 rA  kC A2
v0  X   W 
   W 1  
Stoichiometry: Gas-phase isothermal with e=0 kC A0  1  X   2 
P
C A  C A0 (1  X )
P0 kC A0W  W 
1  
P v0  2 
y=  1  W X 
P0 kC W  W 
1  A 0 1  
v0  2 
C A  C A0 (1  X )(1  W )1/ 2
Reaction with Pressure Drop
Conversion as a function of catalyst weight

kC A0W  W 
1  
v0  2 
X 
kC W  W 
1  A 0 1  
v0  2 

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

1  1   (2v0 ) / kC A0  X /(1  X ) 1/ 2

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