BITS, PILANI K. K.

BIRLA GOA CAMPUS CATALYSIS AND CATALYTIC REACTORS Chapter 10

PROF. SRINIVAS KRISHNASWAMY ASSOCIATE PROF. & HEAD OF DEPARTMENT DEPARTMENT OF CHEMICAL ENGINEERING BITS PILANI, K. K. BIRLA GOA CAMPUS

Introduction
After this chapter you will be able to
Define a catalyst and its properties

Describe steps in a catalytic reaction

Apply concept of rate limiting step to derive a rate law Size isothermal reactors for reactions with Langmuir-Hinshelwood kinetics
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Catalyst types
Homogeneous catalyst Propylene + CO + H2 Isobutylaldehyde (Cobalt catalyst) Heterogeneous catalyst Dehydrogenation of cyclohexane to Benzene using Platinum on alumina catalyst Gas liquid (mass transfer limited) Gas liquid solid
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U. S. Football field
10 gms. of catalyst possess more surface area than this football field

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Catalyst Terminology
Porous catalyst Molecular sieves Monolith catalyst

Supported / Unsupported catalyst

Promoters

Deactivation
Active Sites
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The para-Xylene example

p-xylene

m-xylene

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Turnover frequency (TOF) / Dispersion

Parameter which quantifies the activity of catalyst Number of molecules reacting per active site per second at the conditions of the experiment Fraction of metal atoms deposited that are on the surface (D)

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Turnover frequency (TOF) / Dispersion

CO + 3H2 CH4 + H2O Fischer Tropsch synthesis (0.5% Ru on alumina), D = 49%, P = 988 kPa, T = 574 K, f = 0.1607 s-1 for methane. What is the rate of formation of methane in mol/s?
Rate in mol/s.g of catalyst NCH4 D (1/MWRu)%Ru/100
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Review : Catalytic Reactors Brief Introduction Major Steps

Bulk Fluid

CAb

1. External Diffusion Rate = kC(CAb CAS)

External Surface of Catalyst Pellet

7 . Diffusion of products from pore mouth to bulk

CAs

2. Defined by an Effectiveness Factor Internal Surface of Catalyst Pellet

3. Surface Adsorption A + S <-> A.S Catalyst Surface A B 4. Surface Reaction

6 . Diffusion of products from interior to pore mouth

5. Surface Desorption B. S <-> B + S

Where are we heading?

Develop a rate law for a catalytic reaction Postulate mechanisms towards rate law development Rate law use to design reactors **

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Diffusion from bulk to external surface of catalyst

Rate = kc (CAo Cas)
Where kc = DAB /

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Internal Diffusion
Rate = kr Cas Large particles. More time to diffuse into pellet Reactant consumes at surface and hence catalyst wastage (a t centre of pellet)

As pellet size decreases kr increases

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Adsorption
A S A + S A.S

Ct = Total molar concentration of active sites per unit mass of catalyst = number of active sites per unit mass / Avogadros number Cv = Total molar concentration of vacant sites per unit mass of catalyst = number of vacant sites per unit mass / Avogadros number Pi = partial pressure of species i in the gas phase

Ci.S = surface concentration of sites occupied by species i (mol/g/ cat)

SITE BALANCE Ct = Cv + CA.S + CB.S
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Adsorption
Postulate models, develop isotherm & then see which fits data
Two models possible

Molecular or non-dissociated adsorption

CO + S CO.S Dissociative adsorption

CO + S C.S + O.S

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Adsorption
Rate of attachment to active sites is proportional to number of collisions that molecules make with active sites per second The collision rate is proportional to the partial pressure Pi and also to the concentration of vacant sites rad = kAPiCv (rate of adsorption) :For 1 vacant site Rate of detachment = k-ACi.S
Net rate of adsorption = rad = kA[PiCv (Ci.S / KA)]
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Adsorption

At equilibrium

Equation for adsorption Isotherm

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Dissociative Adsorption

What happens if you have a reaction AB + 2S = A.S + B.S?

At equilibrium

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Surface Reaction
Single Site

Dual Site
A.S + B.S C.S + D.S

LangmiurHinshelwood Eley-Rideal
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A.S + B.S C.S + D.S

A.S + B (g) C.S + D(g)
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Improvement in Octane number

Catalytic Reaction to Improve the Octane Number of Gasoline from 62 to 90

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Improvement in Octane number

A

SR D

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Improvement in Octane number

Assume surface reaction is rate limiting

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Improvement in Octane number

Site Balance

Substituting for CN-S, CI-S, and CV into CT = CV (1 + KN PN + KI PI)

where KP is the thermodynamic equilibrium constant for the reactor

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Improvement in Octane number

Linearizing the Initial Rate

What happens if adsorption is the rate limiting step? See Section 10.3 of text.

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Understanding it better!!!

For steady state operation we have

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Understanding it better!!!
For steady state operation we have

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Understanding it better!!!
NOTE: Strictly speaking, We really cannot compare the magnitudes of kA, kS, and kD directly, because kA has different units than kS and kD. Consequently, we must compare the product (kAPC) with kS and kD to determine which reaction step may be limiting. If the surface reaction is limiting, we say kAPC and kD are very large with respect to kS

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Understanding it better!!!
A site balance yields

Grouping the equilibrium constants together into one constant, KP

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Objective Assessment
Define a catalyst

Understand steps involved in a catalyst reaction Understand catalyst mechanisms Develop rate expressions and determine rate limiting steps
I do the very best I know how - the very best I can; and I mean to keep on doing so until the end Abraham Lincoln
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