CHE4007 Advanced Chemical Engineering

Supplement to lecture 2 3rd March 2015

Deactivation rate equations:

Case 1: Batch reactor, 1st order reaction, Independent first order deactivation

The reaction rate for a first order reaction (with deactivation) is

[1]

Or for the differential form of the rate expression (in terms of the catalyst weight, W)

1
=

[2]

In terms of CA:

= [3]

The activity is described by the following equation:

[4]

Integrating we obtain:

[5]
[6]

Substituting in the rate expression:

[7]

[8]

=
0
0

[9]

Solving:

0
[1 ] [10]
=

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For , so

[12]

Substituting this above

0
0
[1 ]
=

[13]

0
0
0
=

[14]

[15]

[16]

] = [
]

[17]

This is a linear relation so if we plot [ ] with respect to t we should get a straight line with
slope -kd and

intercept [ ]

[ ]

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Case 2: Mixed flow reactor (batch solits), 1st order reaction, Independent first order
deactivation

The performance equation for a mixed flow reactor is given by:

[18]

And the weight time is defined as

=

0
0

[19]

The rate equation is again

=

[20]

And the deactivation equation is given by Eq. [6]

=

[6]

Substituting Eq. [20] in Eq. [18] expressing in terms of concentration:

= 1

[21]

0
=
0

[22]

0
=
0
0

[23]

0
0
=
0

[24]

And substituting for the weight time of the reactor

=

0 1
1
[25]

1 0
1]
[

[25]

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And rearranging:
0
= 1 +

[26]

We now substitute the deactivation equation in Eq. [26]

0
= 1 +

[27]

If we linearise:
[

0
1] = ln()

[28]

This is a linear expression so if we plot [ 0 1] vs t we get a straight line with a slope of -kd and
an

interecept [ 0

1] = ln()

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Case 3: Mixed flow reactor (batch solids), nth order reaction, dth order deactivation
In this case we want to keep the conversion XA (i.e. the concentration CA) constant throughout the
operation of the reactor to keep product quality constant.
The performance equation for a mixed flow reactor is given by:

[18]

And the weight time is defined as

=

0
0

[19]

The rate equation is now

=

[29]

Because CA is constant we can re-write Eq. 29 as

=

[30]

=
Substituting for the weight time:
=

[31]

We next need to find a generic expression for the deactivation of the catalyst. In this case we have:

[32]

But because CA is constant this can be re-written as:

[33]

For d1 we can integrate and obtain a generic expression for the activity of the catalyst a.

[34]

[35]

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1
[1 ]1 =
1

[36]

1
[1 1] =
1

[37]

1 1 = (1 )

[38]

1 = 1 (1 )

[39]

For d=0
= 1

[40]

And
=

(1 )

[41]

If we linearise:
1

0
0

So Plotting 1/ versus t gives a straight line with slope of

[42]

and intercept of =

For d=2
1 = 1 +

[43]

1
1 +

[44]

0
/(1 + )

[45]

So

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(0 )(1 + )

[46]

(0 )
(0 )
+
[47]

Another linear expression.

For d=1

And
=

[48]

= [

= [

[49]

[50]

0
]

[51]

0
] + [51]