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Original Title: CRE II L 12

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Catalysis

Prof. K.K.Pant

Department of Chemical Engineering

IIT Delhi.

kkpant@chemical.iitd.ac.in

2

Exercise: Al

2

O

3

n-pentane i-Pentane

Suggested Mechanism:

N + o No

No + o Io + o

Io I + o

Rate laws for each of the steps:

N A V N A

k p k Adsorption of rate Net u u

=

v I S v N S

k k reaction Surface of rate Net u u u u

=

V I D I D

p k k Desorption of rate Net u u

=

3

Case-1

Case-2

N S A N A

eq

I

N S A D

N

p K K p K

K

p

p K K k

r

+ +

=

1

) (

2

) / 1 (

) (

D I N A

eq

I

N A S

N

K p p K

K

p

p K k

r

+ +

=

D

I

D S

I

eq

I

N A

N

K

p

K K

p

K

p

p k

r

+ +

=

1

) (

N A

p k r =

0

2

0

) 1 (

N A

N A S

p K

p K k

r

+

=

Case-3

N S A N A

N S A D

p K K p K

p K K k

r

+ +

=

1

0

n-pentane (N) i-Pentane (I)

4

EXERCISE

5

How to verify whether the rate law confirms

to experimental data or not ??

D

B

C A

eq

B P

C A S

C

K

p

p K

K

p p

p K k

r

+ +

=

1

) (

A S

D

B

C A

C

eq

B P

C

K k

K

p

p K

r

K

p p

p

+ +

=

1

B C

C

eq

B P

C

cp bp a

r

K

p p

p

+ + =

Use regression

How to decide whether the fit is reasonable

??

If the fit is reasonable, evaluate the

constants

6

Design of Fixed Bed Reactor:

7

Design Equation (Reading Assignment Ch.10 (10.4 -10.6 ) Fogler IV

General Mass Balance Equation:

Rate of input = rate of output + accumulation

+ rate of disappearance

F

A

= F

A

+ dF

A

+ 0 + (-r

A

) dW

- dF

A

= (-r

A

) dW

F

A0

dx

A

= (-r

A

) dW

dW

A A

r dW dF = /

8

}

=

A

x

A A A

r dx F W

0

0

/ /

General design equation for a FBR:

dt

dN

W Weight unit time unit

d disappeare A of Moles

r

A

A

1

) )( (

= =

Definition of rate of reaction:

When the rate is expressed in terms of catalyst weight,

mass transfer effects between the catalyst and the bulk

fluid & also within the catalyst are ignored. Such mass

transfer aspects could be important in some cases.

9

Fixed Bed Reactor Integral form

}

=

A

x

A A A

r dx F W

0

0

/ /

1 /-r

A

x

A

W / F

A0

10

Fixed Bed Reactor differential form

A A

r dW dF = /

F

A

W

-r

A x

A

W/F

A0

-r

A

A A A

r dW dx F = /

0

11

How to find the rate data ??

How can we calculate the weight of

the catalyst needed for obtaining the

given conversion ??

D

B

A A

eq

B C

A A S

A

K

p

p K

K

p p

p K k

r

+ +

=

1

) (

}

=

A

x

A A A

r dx F W

0

0

/ /

Express the partial pressures in terms of x

A

A A

A

A

A

x

x

p

p

c +

=

1

1

0 A A

A R

A

R

x

x a r M

p

p

c +

+

=

1

) / (

0

) (

A A

x f r =

Use numerical / graphical integration

12

Finding a Mechanism consistent with the experimental data

Deducing Rate law from experimental data (Example 10.2 , 10.3:

Example : Hydrodemethylation of Toluene

13

Use of Multiple regression technique (Rate or CONVERSION Data from

Differential reactor identical to CSTR)

Y = a

0

+ a

1

X

1J

+ a

2

X

2J

A

0

, a

1

are the parameters of the model.

Use regression methods / Polymath, MATLAB,

etc.

k, K

B

, K

T

are the parameters of the equation

Evaluation of Rate law Parameters

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