EQ1021 Chemical Reaction Engineering

Lecture 6. Plug Flow Reactor (PFR)

1 Design Equations
2 Design problems
3 Calculating Reactor Volume or Length
4 Combination of Different Types of Reactors
Lecture 6. Plug Flow Reactor (PFR)

1 Design Equations.
1.1 Mole balance.
1.2 Momentum balance

2 Design Problems.

3 Calculating Reactor Volume or Length.

3.1 Negligible Pressure Drop.
3.1.1 Single Reaction Systems
3.1.2 Multiple Reaction Systems
3.1.3 Mole Balance for PFR in Series
3.2 Significant Pressure Drop. Packed Bed Reactors (PBR).
3.3 Reactors with Distributed Feed: Membrane Reactors.

4 Combination of Different Types of Reactors.

http://encyclopedia.che.engin.umich.edu/Pages/Reactors/Reactors.html
1. Design Equations
Mole Balance in a Plug Flow Reactor

“Plug flow" is an idealized state of flux, such that the reactant mixture moves along its length as if
pushed by a plunger. Mass transfer, in both longitudinal and radial directions, is negligible compared to
the overall flow:

a) The physical properties (P, T and composition) and the velocity of the reactant mixture are
uniform along any cross-section.
b) All macroscopic fluid elements (you can imagine they as if contained within small permeable
envelopes) invest the same time in passing through the reactor (identical residence time) and
undergo the same changes in P, T and composition. The reaction proceeds with the same
extension on each element of fluid and these may therefore be regarded as batch reaction
systems, miniature, traveling along the reactor.
c) According to this, PFR and BR may be considered analogous in that a portion of reactant mixture
undergoes, along the tubular reactor, the same changes expected in the BR over time. If the
reaction time in the BR and the residence time in the PFR were equal, the extent of reaction should
be the same in both cases.
d) The reactor works in the steady-state (no accumulation in any of its cross-sections)
1. Design Equations
Mole Balance in a Plug Flow Reactor

• The velocity, T or concentration profiles in an ideal plug reactor should be shaped as shown to the right
of the figure.
laminar flow: turbulent flow: ideal plug flow
parabolic profile near ideal plug

Possible property profiles in a tubular reactor

• The parabolic profile can be found in highly viscous liquids, as in the case of polymerization reactions.
In these circumstances, fluid elements located at different distances from the walls of the tube (or the
axis thereof) will have different residence times in the reactor: those closest to the walls have much
higher residence time than those closer to the tube axis. This will result in transverse gradients of
temperature and concentration.
• A way to obtain a planar profile is using a packed bed, with a solid filler that can have (or not) catalytic
properties.
1. Design Equations
Mole Balance in a Plug Flow Reactor

• We choose a dV, where all properties (and thus Rj) are homogeneous
• There is no axial mixing of fluids inside the vessel; the reactant mixture moves as if pushed by a plug.
• The reactor works in steady-state, so in each dV accumulation is nil:

Accumulation = In – Out + Generation

 
0  F j  F j  dF j  R j dV

dF j
 Rj Eq. 6-1
dV

For a reactor with a constant section, S:

dF j
dV  S  d  Rj · S
d
where ℓ is reactor length.
1. Design Equations
Mole Balance in a Plug Flow Reactor. Comparison with the Batch Reactor

Batch PFR

dN A dF A
 R A ·V  RA
dt dV

Constant-density system Constant-density system

dc A Identical equations dc A Eq. 6-2

 RA  RA
dt d

Variable-density system Variable-density system

dX dX
N A0   R A [ X ]·V FA 0  RA[ X ]
dt dV
dX Different equations dX
c A0   R A [ X ]·( 1   k X ) c A0  R A [ X ] Eq. 6-3
dt d
1. Design Equations
Mole Balance in a Plug Flow Reactor. Comparison with the Batch Reactor

Batch Vn  Xn dX PFR
Area   
FA0 cA0 X n  RA
Eq. 6-3

Eq. 4-5

-(
(1) For constant-density systems (constant-volume batch and constant-density plug flow) the
performance equations are identical,  for plug flow is equivalent to t for the batch reactor, and
the equations can be used interchangeably.

(2) For variable-density systems there is no direct correspondence between the batch and the plug
flow equations and the correct equation must be used for each particular situation. In this case the
performance equations cannot be used interchangeably.
2. Design problems

What do we know?
• Inlet conditions: Qv0, T0 (not always necessary), cj0, Fj0, etc.
• Reaction rate parameters: A’, A, E, E’.
• Reaction stoichiometry and rate law
• In packed bed reactors, characteristics of the catalyst bed.

Design Problems
1. Finding the reaction rate
2. Calculating the reactor volume (or length) or the spatial time for a given conversion
3. Determining conversion for a given spatial time
4. Maximizing selectivity
5. Maximizing production
6. Maximizing benefit
3. Calculating Reactor Volume or Length

3.1 Negligible Pressure Drop.

3.1.1 Single Reaction Systems. One PFR.
3.1.2 Multiple Reaction Systems. One PFR
3.1.3 PFR in Series

3.2 Significant Pressure Drop. Packed Bed Reactors (PBR).

3.3 Reactors with Distributed Feed: Membrane Reactors.

3. Calculating Reactor Volume or Length
2.1 Negligible Pressure Drop. Holding time and Space Time for Flow Reactors.

QV0

=

Eq. 6-4

QV


3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Holding time and Space Time for Flow Reactors.

• As a simple ilustration of the difference between t or   and , consider a steady-flow popcorn popper,
which takes in 1 liter/min of raw corn and produces 28 liters/min of product popcorn.
• Consider three cases, called X, Y and Z, which are shown in the figure:
 In the first case (case X) all the popping occurs at the back end of the reactor.
 In the second case (case Y) all the popping occurs at the front end of the reactor. 
 In the third case (case Z) the popping occurs somewhere between inlet and exit.

QV0


3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Holding time and Space Time for Flow Reactors.

Calculating Holding Time (Residence Time):

• For a PFR, the holding time is defined for

an infinitely small reactor subvolume: dV
d RFP 
Qv 
dV
d RFP 
Qv 

• Gas at constant P and T:  dV 

X
dV 1  Fk 0 dX
 RFP        r X ,T ( 1    X ) 
Q
 v   Q
 v0 ( 1   k  X ) Qv 0 0 k k
X
 dX
 ck 0  Eq. 6-5
0   k  r X ,T ( 1   k  X )

identical to that deduced for tR

in a Batch Reactor, in which a gas reaction X
develops at constant P and T,  dX
t R  ck 0 
0   k  r X ,T ( 1   k  X )

it can be concluded that the average residence time in a PFR is always

equivalent to reaction time in a Batch Reactor
3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Which is the natural performance measure for a PFR?

• For batch systems the natural variable to measure performance is the time of reaction.

• For plug flow reactors, it should be expected that the holding time was the natural
performance measure, however, holding time does not appear anywhere in the design
equations for plug flow systems.

• Instead, space-time or V/Fk0, does naturally appear in the equations, independently of the
systems being constant-density or variable-density.

• Hence,  or V/Fk0 is the proper performance measure for flow systems.

3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Single-Reaction Systems.

dF j For both single and

We need JUST the molar balance  Rj multiple reaction systems
dV

• In terms of cj (constant density system, QV=QV0):

dF j Q dc dc j dc j
 R j  V 0 j    R j [ c j ,T ]
dV dV dV d
QV 0 Analytically
To solve, we have to integrate Numerically
A single molar balance for a Graphically
species A but RA SHOULD BE a
function of ONLY cA

Example : reaction A+B → C r = k cA cB

We have to get RA as a function of cA, so let’s substitute cB:

dc A
cB= cB0 – (cA0 – cA)   kc A c B 0  c A 0  c A 
d
3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Single-Reaction Systems.

dF j For both single and

 Rj multiple reaction systems
dV

• In terms of X (both constant or variable density systems)

dX dX
Fk 0  ck 0   R k [ X ,T ]
dV d
Substitute ALL concentrations
QV = QV0 appearing in Rk by SOLVE
(constant density) - analytically
j - numerically
c j  c j0  ck 0 X - graphically
k

Substitute ALL concentrations SOLVE

QV ≠ QV0 appearing in Rk by
(variable density) - analytically
j - numerically
c j0  ck 0 X - graphically
k
cj 
P0 T
1   k X 
P T0
3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Single-Reaction Systems.

In terms of X In terms of cj

• For variable-density systems, it is more convenient to use conversion; however, there is no particular
preference for constant density systems. Whatever its form, the performance equations interrelate the
rate of reaction, the extent of reaction, the reactor volume, and the feed rate, and if any one of these
quantities is unknown it can be found from the other three.
3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Single-Reaction Systems.

Constant-Density Systems. Table 1.

Source: Levenspiel
3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Single-Reaction Systems.

Variable-Density Systems: The space-time needed for any given conversion, can always be found by numerical
or graphical integration.
• However, for certain simple kinetic forms, analytical integration is possible -and convenient. To do this, insert
the kinetic expression for r, in the molar balance and integrate.

Variable-Density Systems at constant T. Table 2.

Source: Levenspiel
Source: Levenspiel
1.328
3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Single-Reaction Systems. Summary.

• Where density is constant, put A = 0 to obtain the simplified performance equation.

• By comparing the batch expressions of Lecture 4 with these plug flow expressions, we find:

(1) For constant density systems (constant-volume batch and constant-density plug flow) the
performance equations are identical,  for plug flow is equivalent to t for the batch reactor, and
the equations can be used interchangeably. Use those in Lecture 4 or in this Lecture (Table 1).

(2) For systems where density changes there is no direct correspondence between the batch and the
plug flow equations and the correct equation must be used for each particular situation. In this
case the performance equations cannot be used interchangeably. Use those of Table 2 in this
lecture.
3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Multiple-Reaction Systems.

• Analytical solutions for constant density systems (analogue to the Batch Reactor):

• Parallel Reactions:

A 
k1
B r1  k1c A c1  c10 e  k1  k2   c2  c20 
k1c10
k1  k 2

1  e   k1  k 2   
A 
k2
C r2  k 2 c A
Eqs. 6-7 c3  c30 
k 2 c10
k1  k 2

1  e   k1  k 2   

• Consecutive Reactions:

A1  A2 r1 = k1 c1 (i=1)
A2  A3 r2 = k2 c2 (i=2)

 k2  k1c10  k1   k2 
c1  c10  e  k1  c2  c20 e  (e e )
k 2  k1
Eqs. 6-8
c 3  c 30  c20 ( 1  e
 k2 
)
c10
k 2  k1
k ( 1  e
2
 k1 
)  k1 ( 1  e
 k2 
) 
 3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Multiple-Reaction Systems.

a) Parallel, Irreversible, First-Order Reactions (cont.)

Analogously, we obtain for c3:
c3 t

c3 
 
dc3  k 2 c10 e  k1  k2  t dt 
k 2c10
k1  k 2

1  e   k1  k 2  t  Eq. 4-30
c30  0 0

c 2 k1
The relationship between c2 and c3 is constant during all the operation: 
c3 k 2
k1 c10 k 2 c10
and the limit in concentration for a very long time is: c2   and c3  
k1  k 2 k1  k 2

cj/cj0
1

c1/c10
c3/c10
In this case, k2 > k1

c2/c10

0
tR
 3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Multiple-Reaction Systems.

b) Consecutive, Irreversible, First-Order Reactions: A1  A2  A3

Analogous to the BATCH REACTOR!!!

• The values of k1 and k2 govern the location and

maximum concentration of R.
Eq. 4-10
• This may be found by differentiating
Eq. 4-31 and setting dc2ld = 0. If c20=0:
Eq. 4-32 c3
1 ln k 2 / k1  Eq. 4-33
t max  
k log mean k 2  k1

Eq. 4-33 Eq. 4-31 c2

• The maximum concentration of R is found by
combining Eqs. 4-31 and 4-33 to give
c1
k2
Eq. 4-34 c2 ,max  k1  k 2  k1
Eq. 4-34
Change the reaction time
  
c10  k2 
 (t) for the spatial time (
3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Multiple-Reaction Systems.

Constant density:
 Conversion (X) SHOULD NOT be used save for parallel reactions
 Identify all the species participating and write their reaction rate:
• For each species Aj, remember that:
R
R j    ij ri Rate law in function of
i 1 concentrations, for reaction i

Stoichiometric coefficient of
species Aj in reaction i

 Write as many molar balances as species participate in the different rate laws (can be less than
the total number of species and more than the total number of reactions).

 
R
dc1
   i 1 ri c j
d i 1
Integrate the multiple differential
 
R
dc2
   i 2 ri c j equation system by numerical methods: Eqs. 6-9
d i 1 Runge-Kutta 4th order
…..
3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Multiple-Reaction Systems.

ANY multiple reaction system (constant or variable density, parallel o complex reactions):

 Variable nj (=Fj/Fk0) is recommended:

dn j 1 R

dV

Fk 0

i 1
ij  ri ( j  1,2 ,..., S )

dn j 1 R

dV

Fk 0

i 1
ij  ri [ n1 , n2 ,...nS ] ( j  1,2 ,..., S ) Eqs. 6-10

• This equation can be applied to the S dn 1 1 R 

components of the chemical system dV
  i1 i 1 2
Fk 0 i 1
  r [ n , n ,..., n S ] 

to obtain a set of S differential equations R 
dn 2 1
with V as independent variable and the S
dV
  i2 i 1 2
Fk 0 i 1
  r [ n , n ,..., n S ]  Integrate

nj as dependent variables
 

dn S 1 R

dV
  iS i 1 2
Fk 0 i 1
  r [ n , n ,..., n S ] 

3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Multiple-Reaction Systems.

• This set of ODEs (Ordinary Differential Equations) can be simulaneously integrated by Runge-Kutta 4th
order.
• If the key component is A1, the following table is obtained:

V
t n1 n2 ... ... nS
0 1 2 ... ... S
Vt11 - - -
Vt22 - - -
. . . .

• For a variable-density system, the volume flowrate should be expressed as:

 nt 0    j
nt P0 T  j
Eq. 6-11
QV  QV 0 where  n  n
nt 0 P T0  t  j
 j
Example 6-8. Calculating Concentrations as Functions of Position
for NH3 Oxidation in a PFR

The following gas-phase reactions take place simultaneously on a metal oxide-supported catalyst:

Determine the concentrations as a function of position (t.e., volume) in a PFR.

Data: Feed rate = 10 L/min; volume of reactor = 10 L; and cA0 =cB0= 1 mol/L
Reaction rates (in mol/L·min):
R A   5 c A c 2
B  2 c A c B  ( 10 / 3 )c 2/3
A cC
4 A  5 B  4C  6 D r1  1.25 c AcB 2
Let`s calculate Rj
for every species RB  6.25 c AcB2  1.5 c AcB  10·cBcC2
2 A  1.5 B  E  3 D r2  1·c AcB
RC  5 c Ac B
2
 20 ·c B c C
2
 5 c 2/3
A cC
2C  B  2 F r3  10·cC cB
2

R D  7 . 5 c A c 2
B  3 c A c B  5 c 2/3
A cC
4 A  6C  5 E  6 D r4  5 / 6·cC c A 2/3

RE  c AcB  ( 25 / 6 ) c A2 / 3 cC
dF j RF  20·cBcC2
• And for every species, from A to F,  Rj
the molar balance is: dV
Example 6-8. Calculating Concentrations as Functions of Position
for NH3 Oxidation in a PFR (cont.)

• We have to put all the equations in function of the same variables: nj. For a system with constant
Pressure and Temperature:
Fj n j FA0 Ft 0 1 nj
cj    nj  M0 Eq. 6-12
QV Q Ft QV 0 Ft nt
V0 
Ft 0  M 0  ct 0 FA0
dn A 1  5n A nB2 3 2n A nB 2 10n A2 / 3 nC 5 / 3 
   3
 M0  2
 M0  5/3
 M 0 
dV FA0  nt nt 3 n t 
dnB 1  6.25 n A nB2 3 1.5n A nB 2 10·nB nC2 3 
    M0   M0   M 0 
dV FA0  nt3 nt2 nt3 
dnC 1  5n A nB2 3 20·nB nC2 3 5n A2 / 3 nC 5 / 3 
  3
 M0  3
 M0  5/3
 M 0 
dV FA0  n t nt n t 
dnD 1  7.5n A nB2 3 3n A nB 2 5n A2 / 3 nC 5 / 3 
   M0   M0   M 0 
dV FA0  nt3 nt2 nt5 / 3 
dnE 1  n A nB 2 25 n A2 / 3 nC 5 / 3 
  2  M 0  5/3
 M 0 
dV FA0 n
 t 6 n t 
dnF 1  20·cBcC2 3 
  3
M0 
dV FA0  nt 
dnt 1  1.25 n AnB2 3 0.5 n A nB 2 10·nB nC2 3 5n A2 / 3 nC 5 / 3 
  3
M0  2
M0  3
M 0  5/3
 M 0 
dV FA0  n t n t nt 6 n t 
Example 6-8. Calculating Concentrations as Functions of Position
for NH3 Oxidation in a PFR (cont.)

• Substituting ρM0=2mol/L, FA0=10mol/min

Integrating for the initial conditions: V=0, nA0=A=nB0=B=1. The other j= 0. nt0=2;

1.4
dn A  4 nA nB2 0.8nA nB 1.0583 nA2 / 3 nC 
   3
 2
 
dV  nt nt nt5 / 3 
1.2
dnB  5n A nB2 0.6n A nB 8·nB nC2 
     
nj
3 2 3
dV  n t nt nt 
1.0
dnC  4 nA nB2 16·nB nC2 1.5874 n A2 / 3 nC 
  3
 3
  A
dV  nt nt nt5 / 3 
0.8 B
dnD  6nA nB2 1.2n A nB 1.5874 nA2 / 3 nC 
  3
 2
 5/3

dV  n t nt nt  C
0.6
dnE  0.4 n A nB 1.323 n A2 / 3 nC  D
  2
 5/3

dV  n t 6 nt  E
0.4
dnF  16·nB n  2
F
  C

dV  nt3 
dnt  nA nB2 0.2 nA nB 8nB nC2 0.2646 n A2 / 3 nC  0.2
    
dV  nt3 nt2 nt3 nt5 / 3 
0.0
0 2 4 6 8 10
V(liters)
3. Calculating Reactor Volume or Length

3.1 Negligible Pressure Drop.

3.1.1 Single Reaction Systems. One PFR.
3.1.2 Multiple Reaction Systems. One PFR
3.1.3 PFR in Series

3.2 Significant Pressure Drop. Packed Bed Reactors (PBR).

3.3 Reactors with Distributed Feed: Membrane Reactors.

3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Mole Balance for PFR in Series.

Plug Flow Reactors in Series.

Consider N plug flow reactors connected in series, and let X1, X2, . . . , XN, be the fractional conversion of
component A leaving reactor 1, 2, . . . , N.
Reactor 1 Reactor n Reactor N
FA0
… …
X1  0 X1 Xn Xn XN XN

• Referring the material balance to the feed rate of A

Vn Xn dX
to the first reactor, we find for the nth reactor:
FA 0
  Xn  RA
Eq. 6-6

Substituting for the N reactors in series:

V N
Vn V1  V 2  ...  V n
FA 0
 
n 1 F

F

A0 A0
X1 dX X2 dX Xn dX XN dX XN dX
•
  0  RA
  X 2 X1  RA
 ...   X n  X n 1  RA
 ...  
X N 1  RA
 X0  RA

Hence, N plug flow reactors in series with a total volume V

give the same conversion as a single plug flow reactor of volume V.
3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Mole Balance for PFR in Series.

Plug Flow Reactors in Parallel.

Consider N plug flow reactors connected in parallel, and let FA0,n be the feed rate of key component to
any reactor. The most efficient operation is when all the reactors have the same spatial time  (same
V/Fk0 ) and consequently, the same final conversion:

QV 0 ·V1 V1 X 1 dX
QV 0 ,1  Reactor 1    c A0 
 VN
N
QV 0 ,1 0  RA

Reactor 2
FA0
Same ,
same final
QV0
… conversion X
VN X N dX
Reactor N    c A0 
Q V 0 ,N 0  RA
QV 0 ·V1
QV 0 ,N 
 VN
N
V
 
QV 0
So, N plug flow reactors in parallel give
For equal-size
the same conversion as a single PFR of reactors Total production is
the same total volume, V. N times that of
one of the tubes.
Source: Levenspiel
3. Calculating Reactor Volume or Length
3.1 Negligible Pressure Drop. Mole Balance for PFR in Series.

Plug Flow Reactors in Series-Parallel.

• For the optimum hook up of plug flow reactors connected in parallel or in any parallel-series
combination, we can treat the whole system as a single PFR of volume equal to the total volume of the
individual units if the feed is distributed in such a manner that fluid streams that meet have the same
composition.

Source: Levenspiel
3. Calculating Reactor Volume or Length

3.1 Negligible Pressure Drop.

3.1.1 Single Reaction Systems. One PFR.
3.1.2 Multiple Reaction Systems. One PFR
3.1.3 PFR in Series

3.2 Significant Pressure Drop. Packed Bed Reactors (PBR).

3.3 Reactors with Distributed Feed: Membrane Reactors.

3. Calculating Reactor Volume or Length
3.2 Significant Pressure Drop.

There will be some pressure drop

along the tube!!
Especially in packed bed reactors

• In liquid-phase reactions, the concentration of reactants is insignificantly affected by even relatively

changes in the total pressure. Consequently, we can totally ignore the effect of pressure drop on the
rate of reaction.

• However, in gas-phase reactions, the concentration of the reacting species is proportional to the total
pressure; in many instances, the effects of pressure drop are a key factor in the success or failure of the
reactor operation.

j • If P decreases → cj decreases
• For gas species: c j0  ck 0 X
k • If P decreases → Rj decreases
cj 
P0 T
1   k X 
P T0 • If P decreases → QV increases, so
residence time decreases.

So, pressure drop significantly decreases the reaction

extent in gas reactions
3. Calculating Reactor Volume or Length
3.2 Significant Pressure Drop. Pressure Drop Effects.

QV0 P

ℓ no P
ℓ

Did you expect the volume

flowrate to increase so much
when pressure drops?
ℓ ℓ
3. Calculating Reactor Volume or Length
3.2 Significant Pressure Drop. Momentum Balance for Plug Flow Reactors.

For void PFRs and turbulent flow, the pressure drop is calculated from:

dP v 2
 2 f
d D pipe

where f, the Fanning friction factor, can be approximated as:

0 . 079
f 
Re 1 / 4
More accurate correlations, which take factors like wall roughness into account, are readily available,
but the form used here is adequate for most purposes. It has a simple, analytical form that lends itself to
conceptual thinking and scaleup calculations.

For packed beds in either turbulent or laminar flow, the Ergun equation is often satisfactory:

dP v 2 1    150 1    
   1 . 75 
d d p 3  Re p 
3. Calculating Reactor Volume or Length
3.2 Significant Pressure Drop. Packed Bed Reactors.

Packed-bed reactor —A vessel filled with catalytic pellets and

the reacting fluid passing through the void space between
them.

• For a fluid-solid heterogeneous system, the reaction rate is

based on mass of solid catalyst, W, rather than on reactor
volume, V. The rate of reaction of A is defined as:
mol of A reacted
 R A 
s · gram of catalyst

• The mass of solid is used because the amount of the

catalyst is what is important to the rate of reaction. The
reactor volume that contains the catalyst is of secondary
significance.

• The derivation of the design equation for a packed-bed catalytic reactor will be carried out in a manner
analogous to the development of the tubular design equation. To accomplish this derivation, we simply
replace the volume coordinate in the molar balance with the catalyst weight coordinate W.
3. Calculating Reactor Volume or Length
3.2 Significant Pressure Drop. Packed Bed Reactors.

• We take a differential weight of catalyst, W,

for the molar balance:

Accumulati on  In  Out  Generation

0  FA  FA  dFA   R  A dW
FA  dFA
dFA
 R  A
dW

2 2
dX dX k  c A0  1 X  P 
 FA0  R  A     
dW For example, for a rate law: dW QV 0  1  k X   P0 
 R  A  k  c A2

What are the units of k”?

• For isothermal operation (T = T0) the right-hand side is a function of only conversion and pressure.
• We now need to relate the pressure drop to the catalyst weight in order to determine the conversion
as a function of catalyst weight. Ergun equation.
3. Calculating Reactor Volume or Length
3.2 Significant Pressure Drop. Pressure Drop Effects.

QV0 P

ℓ no P
ℓ

Did you expect the volume

flowrate to increase so much
when pressure drops?
ℓ ℓ
 3. Calculating Reactor Volume or Length
3.2 Significant Pressure Drop. Pressure Drop Calculation: the Ergun Equation.

 150 1      Ft P0 T in SI units (kg, m, s)

dP G 1
Eq. 6-13    1 . 75 G 
d 0Dp 3  D p  Ft 0 P T0

If T is kept constant and equal to T0 (isothermal

systems), then gas viscosity
P = pressure N/m2 is constant. Many terms in the equation
are either constant (G, µ, , Dp)
volume of void or referred to the inlet conditions (0),
 =porosity =
total bed volume so we can define a constant, 0:
1- = volume of solid
total bed volume G 1  150 1     
0    1 . 75 G 
0Dp  3  Dp 
Dp = diameter of particle in the bed, m Eq. 6-14
µ = viscosity of gas passing through the bed, kg/m·s
units: (N/m2)/m
ℓ = length down the packed bed of pipe, m
 = gas density, kg/m3
v= superficial velocity = volumetric flow / cross-sectional area of pipe, (m/s)
G =   v = superficial mass velocity, kg/m2·s)
3. Calculating Reactor Volume or Length
3.2 Significant Pressure Drop. Pressure Drop Calculation: the Ergun Equation.

• And substitute in the Ergun equation:

dP F P0  0 in N / m 3  P in N / m 2
Eq. 6-15   0 t 
d Ft 0 P  0 in atm/m (div. by 101325)  P in atm

• If we are solving for catalyst weight, we have to obtain a relationship between W and ℓ. The catalyst
weight up to a distance of ℓ down the reactor is

W  1    V  C
 volume   density of 
 weight of      solid 
 catalyst    occupied Eq. 6-16
     
by solids   catalyst 
V

W  1     C S ·

dP 0 Ft P0
dW  1     C S d   Eq. 6-17
dW 1   S  C Ft 0 P
3. Calculating Reactor Volume or Length
3.2 Significant Pressure Drop. Packed Bed Reactors (PBR).

Simultaneous solution of Mole Balances and Pressure Drop Equation: R

(Runge-Kutta 4th order) R A   iA· ri
i 1

• In function of reactor length:

dn A S
 RA
dFA d FA0
 S 1    C R  A  S·R A
d   dnB S
 b  bulk in adimensional  RB
S species dFB
catalyst density
variables d FA0
 S 1    C R  B  S·RB ... Eq. 6-19
d
... Fj dnt S R
composition
+ Ft nj 
FA0 d
   i ·ri
FA0 i 1
dP F P0
  0 t P dy  nt
d Ft 0 P y pressure  0
P0 d P0 n t 0 y

and substituted in RA, RB,..

Eq. 6-18
Where the concentrations
for the reaction rate nj
c j  M 0 y
are calculated as: nt
3. Calculating Reactor Volume or Length
3.2 Significant Pressure Drop. Packed Bed Reactors (PBR).

Simultaneous solution of Mole Balances and Pressure Drop Equation:

• In function of catalyst weight: dn A R A


dW FA0
dFA
 R  A in adimensional dnB RB
dW 
S species dFB variables dW FA0
 R  B ... Eq. 6-21
dW Fj R
... dnt 1
nj 
FA0
composition 
dW FA0
  ·r  i i
dP 0 Ft P0 i 1
 P
dW 1   S  C Ft 0 P y dy  nt
P0 pressure 
dW 2 y nt 0

dP / P0 0 Ft P0

dW 1   S  P F P
   C0 t 0  and substituted
 2 1/ y
where  is a in RA, RB,..
constant

20 concentrations for the nj

  ( kg cat )  1 c j  M 0 y
1   S  C P0 reaction rate are calculated nt
again as:
Eq. 6-20
3. Calculating Reactor Volume or Length
3.2 Significant Pressure Drop. Packed Bed Reactors (PBR).

• For a single reaction, the system simplifies. For example, solving in catalyst weight:

dFA dX 1
 R  A  R  A X 
dW dW FA0
Integrate by
Eq. 6-22
Runge-Kutta
dy  nt dy  4th order
  1   k X 
dW 2 y nt 0 dW 2y
3. Calculating Reactor Volume or Length
3.3 Reactors with distributed feed. Membrane Reactors.

• Membrane reactors can be used to increase conversion when the reaction is thermodynamically
limited, as well as to increase selectivity when multiple reactions are occurring.

• Thermodynamically limited reactions are reactions where the equilibrium lies far to the left (i.e.
reactant side) and there is little conversion.
 If the reaction is exothermic, increasing temperature will only drive the reaction further to the left,
and decreasing temperature will result in a reaction rate that is so low that there is very little
conversion.
 If the reaction is endothermic, increasing the temperature will move the reaction to the right to
favor a higher conversion, however, for many reactions these higher temperatures cause the
catalyst to become deactivated.

• The term membrane reactors describes a number of different types of reactor configuration that
contain a membrane. The membrane will provide a barrier to certain components while being
permeable to others.
3. Calculating Reactor Volume or Length
3.3 Reactors with distributed feed. Membrane Reactors.

• Examples:
 Thermodinamically limited reactions: dehydrogenation of hexane to benzene.
H2
Hexane Hexane, benzene, H2

 Increase in selectivity: partial oxidation of hydrocarbons, as well as chlorination, ethoxylation,

hydrogenation, nitration and sulfonation reactions
O2 O2
Isobutane Isobutane, Isobutene O2

Inert Membrane Reactor with Catalyst on the Feed side

CMR: Catalytic Membrane Reactor

 Membrane reactors.
Example 1: Increasing conversion in equilibrium limited reactions.

According to The Department of Energy, an energy saving of 10 trillion Btu per year could result from the use of
catalytic membrane reactors as replacements for conventional reactors for dehydrogenation reactions such as the
dehydrogenation of ethylbenzene to styrene:

and of butane to butene: C 4 H 10   C 4 H 8  H 2

The dehydrogenation of propane C 3 H 8   C 3 H 6  H 2 is another reaction that has proven successful with
a membrane reactor [/. Membrane Scl., 77, 221 (1993)].
All the preceding dehydrogenation reactions above can be represented symbolically as
A  B  C
and will take place on the catalyst side of an IMRCF (Inert Membrane Reactor with Catalyst pellets on the Feed side).
The equilibrium constant for this reaction is quite small at 227°C (i.e., KC= 0.05 mol/L).
The membrane is permeable to B (e.g. H2) but not to A and C. Pure gaseous A enters the reactor at 8.2 atm and
227°C at a rate of 10 mol/min. Plot and analyze the molar flow rates up to a volume of 400 L.
Additional information: Even though this reaction is a gas-solid catalytic reaction, we will write our balances in
terms of reactor volume rather than catalyst weight (recall -RA= -R”Ab= -R”A(1-ε) c). For the bulk catalyst density of
b = 1.5 g/cm3 and a 2-cm inside diameter of the tube containing the catalyst pellets, the rate constant, k, and the
transport coefficient, k’C, are k= 0.7 min-1 and k’C·a = 0.2 min-1, respectively. Suppose that the concentration of B in
the sweep gas is negligible.
•
Membrane reactors.
Example 1: Increasing conversion in equilibrium limited reactions (cont.).

• The molar balance to the species that diffuses through the membrane, in a dV
FB,diff
(FB  dF B )  FB  FB ,diff  R B dV
        
FB FB+dFB Out In Generation

RBdV
• The molar flow of B out of the reactor per unit volume of reactor is taken to be proportional to the
difference in concentration at both sides of the membrane:

FB ,diff   k C c B  c BS  a dV
Area  DL 4
Sweep gas a  
• cBS Volume D 2
L
D
4
where a is the membrane surface area per unit volume of reactor.
Bc
B
So, the molar balance to B is:
dF B dFB
dF B  R B  k C c B  c BS  a  dV  R B  k C c B a
   R B  R B ,diff
dV dV
R B ,diff
Eq. 6-23
Membrane reactors.
Example 1: Increasing conversion in equilibrium limited reactions (cont.).

V nA nB nC nt
0 1 0 0 1 1.6
10 0.8788 0.1188 0.1212 1.1188
20 0.79 0.2021 0.21 1.2021 nA
1.4
30 0.7251 0.2595 0.2749 1.2595 nB
40 0.6773 0.2985 0.3227 1.2985 nj
1.2 nC
50 0.6417 0.3246 0.3583 1.3246
60 0.6149 0.3414 0.3851 1.3414 nt
70 0.5945 0.3515 0.4055 1.3515 1
80 0.5787 0.3568 0.4213 1.3568
90 0.5662 0.3588 0.4338 1.3588
100 0.5561 0.3582 0.4439 1.3582 0.8
125 0.5378 0.3504 0.4622 1.3504
150 0.5247 0.3379 0.4753 1.3379 0.6
175 0.5139 0.3238 0.4861 1.3238
200 0.5042 0.3095 0.4958 1.3095
0.4
225 0.4949 0.2956 0.5051 1.2956
250 0.4858 0.2822 0.5142 1.2822
275 0.4768 0.2696 0.5232 1.2696 0.2
300 0.4679 0.2576 0.5321 1.2576
325 0.4591 0.2464 0.5409 1.2464 0
350 0.4503 0.2357 0.5497 1.2357 0 100 200 300 400 500
375 0.4416 0.2257 0.5584 1.2257
400 0.433 0.2162 0.567 1.2162
V (liters)
Membrane reactors.
Example 2: Membrane Reactor to Improve Selectivity in Multiple Reactions.

The reactions
A  B  D r1  2 c A2 c B in mol/L·s
A  B  U r2  3 c A c B2 in mol/L·s

take place in the gas phase. The overall selectivity, D is to be compared for a membrane reactor (MR) and a
conventional PFR. First, we will use the instantaneous selectivity SD/U to determine which species should be fed
through the membrane (low concentration species).
2 c A2 c B 2 cA
SD / U  
3 c A c B2 3 cB

We see that, to maximize SD/U we need to keep the concentration of A high and the concentration of B low;
therefore we feed B through the membrane.

The reactor volume is 50 L and the entering total concentration is 0.8 mol/L The molar flow rate of A entering
the reactor is 4 mol/s and that of B entering through the membrane is 4 mol/s, uniformly distributed in all the
volume, so that RB,diff=4/50=0.08 mol/L·s. For the PFR, B enters along A.
Plot and analyze the molar flow rates and the overall selectivity D as a function of reactor volume, for both
the MR and PFR.
Membrane reactors.
Example 2: Membrane Reactor to Improve Selectivity in Multiple Reactions.

4.5 FA
dF A
 R A   2 c A2 c B  3 c A c B2 MR FB
dV Fj
4.0
FD

dF B 3.5 FU
 R B  R B ,diff   2 c A2 c B  3 c A c B2  0 .08
dV 3.0

dF D 2.5
 R D  2 c A2 c B
dV 2.0
dFU
 RU  3 c A c B2 1.5
dV 1.0
dFt dF j dF B
   2 c A2 c B  3 c A c B2  0 .08  0.5
dV j dV dV
0.0
0 10 20 30 40 50

V
4.5 FA

Fj 4.0
PFR FB
FD
dF A

0 .512

3  2 F A FB  3 F A FB
2 2
 3.5 FU

dV 4  FB  3.0

dF B

0 .512
 
3  2 F A FB  3 F A FB  0 . 08
2 2 2.5
dV 4  FB  2.0

dF D

0 . 512

3  2 F A FB
2
 1.5
dV 4  FB  1.0

dFU

0 . 512

3 3 F A FB
2
 0.5
dV 4  FB  0.0
0 10 20 30 40 50

V
Calculating Reactor Volume or Length
Increasing the capacity of a tubular reactor

There are three conceptually different ways of increasing the capacity of a tubular reactor:

1. Add identical reactors in parallel. The shell-and-tube design used for heat exchangers is a common and
inexpensive way of increasing capacity.

2. Make the tube longer. Adding tube length is not a common means of increasing capacity, but it is used.
Single-tube reactors exist that are several miles long.

3. Increase the tube diameter, either to maintain a constant pressure drop or to scale with geometric
similarity. Geometric similarity for a tube means keeping the same length-to-diameter ratio L/D upon
scaleup. Scaling with a constant pressure drop will lower the length-to-diameter ratio if the flow is
turbulent.

The first two of these methods are preferred when heat transfer is important.
The third method is cheaper for adiabatic reactors.
4. Combination of Different Types of Reactors

• If reactors of different types are put in series, such as a mixed flow reactor followed by a plug flow
reactor which in turn is followed by another mixed flow reactor, we may write for the three reactors

• These relationships are presented in graphical form in the figure. This allows us to predict the overall
conversion for such systems, or conversion at intermediate points between the individual reactors.
4. Combination of Different Types of Reactors
Best Arrangement of a Set of Ideal Reactors

• For the most effective use of a given set of ideal reactors we have the following general rules:

1. For a reaction whose rate-concentration curve rises monotonically (any nth-order reaction, n > 0) the
reactors should be connected in series. The minimum reaction volume corresponds to a single PFR.

2. If circumstances require mounting a mixed series, reactors should be ordered so as to keep the
concentration of reactant as high as possible if the rate-conversion curve is concave (n > 1), and as
low as possible if the curve is convex (n < 1). As an example, for n > 1 the ordering of units should be
plug, small mixed, large mixed, and the reverse order should be used when n < 1.

-RA -RA

n=2 n = 1/2

X X
4. Combination of Different Types of Reactors
Best Arrangement of a Set of Ideal Reactors (cont).

Continues….
3. Curve 1/(-Rk) =f[X] has a minimum (autocatalytic reaction) This situation is entirely different, since
the curve shows a zone with downward slope.
If the final conversion is close to that of the minimum of the curve (XFXmin), the minimal
reaction volume is obtained with a single CSTR (or several in paralell) .
If XF is much higher than that corresponding to the minimum, one can not know a priori what the
best solution. If you have to use a mixed series of CSTRs and PRFs, place the CSTR in the
minimum or in the zone of steepest downward slope.

XFXmin XF>>Xmin

1/-Rk 1/-Rk

CSTR CSTR PFR

Xmin XF X Xmin XF X
4. Combination of Different Types of Reactors
Best Scheme Changes when Unconverted Reactant can be Separated and Recycled!!!
 Algorithm
1 Number each reaction for Complex Reactions
Reactions 1) A+2B C
2) 3A+C 2D

2 Write a mole balance on each and every species:

Mole balances dFA dFB dFC dFC
 RA ,  RB ,  RC and  RC
dW dW dW dW

Net Rate Laws 3 Write the net rate of reaction for each species:
R A   k1c AcB2  3 k 2 c AcC , RB  2 k1c AcB2
RC  k1c AcB2  k 2 c AcC , RD  2 k 2 c AcC ,

Stoichiometry For isothermal gas-phase reactions, write concentrations in

4 terms of molar flow rates:
FA F
e .g . cA  M0 , cB   M 0 B ,... and Ft   F j
Ft Ft j
For liquid-phase reactions, use them as given: cA, cB,…

Pressure Drop 5 Write the gas phase pressure drop in terms of molar flow:
dy  Ft T P
 with y
dW 2 y Ft 0 T0 P0

Combine 6 Combine all the equations and use an ODE solver to

obtain the profile of molar flow rates, concentrations and
pressure.