Name: Amierson C.

Tilendo

Subject: ChE 146

Date: March 24, 2014

Safe Design of Cooled Tubular Reactors for Exothermic, Multiple Reactions.
Consecutive Reactions
By K. R. Westerterp and R. R. M. Overtoom
Derivation/Confirmation for the following equations: 8, 9, 10, 15, 21, 22, 23 and 29
We consider a tubular reactor in which two consecutive reactions occurs:
A P X
Where A is the reactant, P is the desired product and X is the undesired product. Both reactions are
irreversible, exothermic and of the first order.

A. For Equation 8:
The following assumptions are:

The reactor is a plug flow reactor

The temperature of cooling medium

The physical and chemical data

T c is constant

g ,

B , C p , H

and U are independent of

temperature.

dCA
=RwA B
dz

[eqn 8.1]

Since,
CA = CAO (1 XA) and RwA = -kPCA
Equation 8.1 will become

d C AO ( 1X A )
dz

=k P C AO ( 1X A ) B

C AO u

d XA
=k P C AO ( 1X A ) B
dz
[eqn 8.2]

d XA
=k P ( 1X A ) B
dz

In order to make both sides of the equation dimensionless, we need to multiply L/uk R

(u ddzX ) uLk =[ k (1X ) ] uLk

[eqn 8.3]

The quantity kR is the reference reaction velocity constant and is defined as the value of k wherein
constants kp and kx are equal and has the equation equal to

k R=k P =k X = A p e

E p
RT R

= AX e

E x
RT R

This will make equation 8.3 to

k L
1 d XA
= P ( 1 X A ) B
kR
z
kRu
d( )
L

( )

Now, we will define K = kp/kR

E p
RT

1( )
k
A e
( ) ; where = E P = T
K= P = p E =e
P
kR
RTR
TR
RT
AP e
p

P
R

By letting Z = z/L, equation 8.4 will become

1 d X A KL
=
( 1X A ) B
k R dZ
u
d X A k R B KL
=
( 1X A )
dZ
u
By letting Da = BkRL/u

dXA
=Da K ( 1X A )
dZ

[eqn 8.4]

B. For Equation 9:

d CX
=RwX B
dz

[eqn 9.1]

The reactor feed does not contain any P and X, so that C PO = 0 and CXO = 0. We then transform the
species concentration according to:

C AOC A C P C X
=
+
C AO
C AO C AO
X A =X P + X X
Equation 9.1 will become

d (C AOC A C P )
=R wX B
dz

[eqn 9.2]

Knowing that
CA = CAO (1 XA)
RwX = kXCP
CP = CPO + CAOXP
Equation 9.2 will be further be transformed to

d (C AOC AO (1 X A )C AO X P )
=k X ( C AO X P ) B
dz
C AO u

d ( X P X A )
=k X ( C AO X P ) B
dz

d ( X P X A )
=k X X P B
dz

In order to make both sides of the equation dimensionless, we need to multiply L/uk R.

d( X P X A )
L
L
u
=
(k X X P B )
u kR
dz
ukR

[ ( ) ( )]

1 d X P d X A k X L B

=
XP
kR
kRu
z
z
d
d
L
L

[eqn 9.3]

Now, we will define KP = kX/kR

EX
RT

p
k
A e
K = X = X E =e
kR
RT
AP e
P

[ ( ( ))]; where =
p 1

EP
E
T
, p= X =
RTR
EP
TR

By letting Z = z/L, eqn 9.3 will become

d X P d X A K P L B k R

=
XP
dZ
dZ
u
According to the article given, Da = kRBL/u, substituting this to our previous equation:

d XP d XA

=Da K P X P
dZ
dZ

Since

dXA
=Da K ( 1X A )
dZ
The above equation will become

d XP
D a K ( 1X A )=Da K P X P
dZ
d XP
=D a K ( 1X A )D a K P X P
dZ
d XP
=Da [ K ( 1 X A ) K P X P ]
dZ

C. For equation 10:

dT
4U
=( H A RWA + H X R WX ) H
(T T c )
dz
g C p d t g C p

dT
4U
=( H A k P C A + H X k X C p ) H
(T T c )
dz
g C p d t g C p

dT
4U
=[ H A k P C AO (1X A )+ H X k X C AO X P ] H
(T T c )
dz
g C p dt g C p

Multiplying L/TRukR to make the equation dimensionless (where TR = reference temperature).

L
dT
L
4U
u
=
H A k P C AO (1 X A )+ H X k X C AO X P ] H
(T T c )
[
T R u k R dz
T Ru kR
g C p d t g C p

( )

L
dT
L
u
=
T R u k R dz
T Ru

( )

{[

H A k P C AO
H X k X C AO
H
4U
(1X A )+
XP

(T T c )
kR
kR
g C p d t g C p k R

By letting T/TR = , z/L = Z, K = K = kp/kR and KP = kp/kR

H X kR B L K P XP
4 UL k R
d H A C AO k R L B K
=
(1X A )+

(T T c )
dZ T R g C p
u
HA
u
T R u dt gC p

ad=

Let

H A C AO
T R g C p ; H = HX/HA and Da = kRBL/u

D k
H Dak X X P
4 UL k R T T c
d
= ad a P (1X A )+

( )
dZ
kR
kR
k R dt g C p T R T R

Letting

U =

4U
k R B g C p d t

and = T/TR

Da k P
H D a k X X P 4 U L k R B
d
= ad
(1X A )+

( c )
dZ
kR
kR
u

By letting Da = kRBL/u

 c
d
= ad Da [ K (1X A )+ H K p X P ]Da U
dZ

D. For equation 15: (Behavior of the - XA functions, the trajectories)

Divide equation 10 (C) by equation 8 (A), we get

H k p 1 X P U ( c )
d
= ad 1+

dXA
1X A
k ( 1X A )

Letting

d
=0
dXA

X
X
1( A) M
( P) M
H k M P1

X
( A)M
1

kM
U ( M c )
1+

ad
X
X
1( A) M
( P) M
H k M P1

X
( A)M
1

kM
U ( M c )
1+=

ad

[eqn 15.1]

X
X
X
1( A) M
( P)M
( A)M + H k M P 1

X
( A )M
1

kM
U ( M c )
1=

ad
X
X
( P)M
( A)M + H k M P 1
U ( M c )
1=
ad k M

X
X
U ( M c )
( P)M
ad k M
( A)M =1+ H k M P1

Substitute

XP

XA

we can get the expression

XX

X
X
X
U ( M c )
( X )M
ad k M
( A) M H k M P1
( A)M =1+ H k M P1

X
X
( X )M
( A)M ( 1H k M

P1

U ( M c )
)= 1 k H k M P1
ad M

X
X
( X )M

U ( M c )
1
H k M P1
ad k M

( A)M =

H kM
( A)M =

X
X
( X ) M

P1

(1H k M P1 )

U ( M c )
1
1

ad k M
( 1H k M P1 )

The second term in the above equation is very small, therefore we can neglect it and so we get the
equation

U ( M c )
1
( A)M =
1
ad k M
( 1H k M P1 )

E. For equation 21:

ma

(XA)ma

The equation of the slope is equal to

d
= 2 1
d X A X A 2 X A 1
The article states that a trajectory starts at its maximum slope at the inlet conditions = o and
XA = 0 and beyond that point the slope decreases (see Figure 1). In order to achieve maximum slope in
the formula, maximizing the numerator is necessary. This can only be done if the maximum allowable is
achieved. Solving for the slope

d
d XA

( )
d
d XA

( )

=
X A =0

=
X A =0

ma o

( X A )ma X Ao

d
d XA

( )

=
X A =0

ma o

( X A )ma 0

ma o
( X A )ma

This is the maximum slope that can be attained, as X A increases the slope will decrease (See Fig
1), therefore the final equation will be

d
d XA

( )

X A =0

ma o
( X A )ma

F. For equation 22:

Given an equation:

d
dX A

( )

X A =0

( dXd )

Now, we are given an equation of

ma o
( X A )ma

which is equal to

U ( c )
XP
d
= ad 1+ H K p1

dX A
1 X A k ( 1 X A )

( )

At inlet conditions, = o and XA = 0, it follows that XP = 0. Substituting these parameters to the

equation

d
dX A

( )

XA

U ( o c )
= ad
ko
=0

Substituting the previous equation to the given equation, we can get

ad

U ( o c ) ma o

ko
( X A )ma

ma o U ( o c )
ad
+
ko
( X A ) ma

(XA)ma can be eliminated by substituting the equation in the article, which is

U ( ma c )
1
1
( X A )ma=
ad K ma
1H K p1
we get an equation of

 ad

U ( o c )
+
ko
U ( ma c )
1
ad K ma

ma o
1
1H K ma p 1

( ma o ) ( 1H K map 1 ) U ( o c )
ad
+
ko
U ( ma c )

ad K ma

G. For equation 23:

When o = c

( ma c ) ( 1H K ma p1 ) U ( c c )
ad
+
ko
U ( ma c )

ad

ad K ma

U ( ma c )
p1
1
( ma o ) ( 1H K ma )
ad K ma

U ( ma c ) ( ma o ) ( 1H K ma p1)
1

ad K ma
ad
U ( ma c )
K ma
ad
( ma o ) ( 1H K ma p1 )

K ma
ad
U ( ma c ) ( ma o ) ( 1H K ma
K ma

ad
ad

p1

) K ma

U ( ma c )
( ma o ) ( 1H K ma p1 ) K ma
K ma +
ad
ad

p1
U ( ma c )
( ma o ) ( 1H K ma )
K ma 1+
ad
ad

H. For equation 29:

From equation 27:
p

km
H k mk m
U
=
+
ad m c
ad

The desire minimum value of U*/ad can be found by equating

U
ad

( )

to zero. However,

m
km is a function of m which is equal to (Westerterp, 1983)

k m =e

( ( ))

p 1

( ( ))

p 1

1
m

H e
U e
=
+
ad
m c

Getting

1
m

( ( 1 ))

p 1

] e

( ( ))

p 1

1
m

ad

U
ad

( )
m

ad

( )=
m

( m c ) e

1
m

( ( ))

p 1

2
m
2

( m c )

( ( ))

p 1

1
m

1
Hp e
ad

( ( ))]

p 1

1
m

p1

( ( ))

p 1

1
m

1
m

( ( ))

p 1

2
m

Knowing that

k m =e

1
m

( ( ))

p 1

U
ad

( )=

( m c ) k m p
2

U
ad

( )=

( m c )

2m

( m c )

( )= k

[
)[

( )
p

U
ad

Letting

2
m

( )= k
m

k
1
Hp k m p1 k m p m2 p
ad
m

2
m

2m
( m c )
p

( m c )

k
1
Hp k m p1 k m p m 2 p
ad
m

1
( Hp k m p 1 1 )
ad

2m +1
2
Hpk m p11 ) ( m c )
( m c ) +
(
p ad
2

( m c )

U
ad

( ) =0

( )

2m +1
2
Hp k m p 1 1 ) ( m c )
( m c ) +
(
p ad
2

( m c )

2m +1
p1
2
( m c ) + ( Hp k m 1 ) ( m c ) =0
p
ad

pk m
2m

( m c ) k m p 2m k m

ad

k m

=0