CATALYSTS

CONTENTS
Intoduction to Catalyst

Reaction kinetics and catalysis

Catalyst performance
measurement and
Quantification
CATALYST
“A catalyst is any substance that alters the rate of a
chemical reaction without being consumed
during the process.”
Catalyst affects only the rate of the reaction ,i.e. Kinetics.
It changes neither the thermodynamics of the reaction
nor the equilibrium composition.
INTRODUCTION TO CATALYST
KINETICS VS THERMODYNAMICS
 Thermodynamics says NOTHING about the rate of a reaction.
 Thermodynamics : Will a reaction occur ?
 Kinetics : If so, how fast ?

 A reaction may have a large, negative Grxn, but the rate

may be so slow that there is no evidence of it occurring.
 Conversion of graphite to diamonds is a
thermodynamic favorable process ( G -ve ).
 C (graphite) C (diamond)

 Kinetics makes this reaction nearly impossible (Requires a very

high pressure and temperature over long time)
GENERAL DEFINITIONS
 Positive Catalysts
 Negative Catalysts (Inhibitors)
 Promotors
 Inhibitors
 Activation energy
 Rate of chemical reaction
 Equilibrium
 Reaction Kinetics
 Homogeneous and Heterogeneous catalysis
 ESSENTIAL CATALYST PROPERTIES

• Ability to convert • Catalyst ability to • Catalyst ability to

reactants into give the desired keep sufficient
product per unit product out of all level of activity &
cat. per unit time possible products selectivity

Activity Selectivity Stability

CATALYST COMPONENTS
• Constituent that catalyze the
ACTIVE reaction. Usually are transition
PHASE elements.

• Enhance activity, selectivity and

PROMOTERS stability of the active phase

INHIBITORS • Retards undesirable reactions

• Provide support to active phase.

CARRIER (Highly porous, chemically and
thermally stable)
 COMMON PROBLEMS WITH
CATALYSTS
Common Problems With
Catalyst

Fall in apparent activity Increase in pressure drop

Breakage of
Poisoning/Sintering
catalyst

Poor Gas Carryover on

Distribution catalyst

Poor mixing of Collapse of bed

reactants support
REACTION KINETICS AND
CATALYSIS
RATE EQUATION
-rA = KCA n
Where,
-rA = rate of reaction
K = equilibrium constant
CA = Concentration
n = order of reaction

ARRHENIUS EQUATION
K = Koe-Ea/RT
Where,
Ko= Frequency factor
Ea = Activation Energy
R = General Gas Constant
T = Temperature
LETS SEE WHAT IS HAPPENING
ENERGY CHANGES DURING
CHEMICAL REACTIONS
HOW CATALYST WORKS?
MECHANISM OF SURFACE CATALYSIS
CATALYSIS OF AMMONIA SYNTHESIS

With Without
Catalyst Catalyst
Temperature, °C 400 3150

Production, 1300 6
Tones / day
 CATALYSTS AT OUR PLANT
Service Reaction Active Trade Name
Phase

Desulphurization ZnO+H2S = ZnS+H2O ZnO HTZ-5

Steam Reforming CH4+H2O = CO+3H2 Ni R-67R-7H

(Primary) R-67-7H

Steam Reforming CH4+H2O = CO+3H2 Ni RKS-2

(Secondary) RKS-2-7H

High Temp. Shift CO+H2O = CO2+H2 Fe2O3 SK-201-2

Conversion

Low Temp. Shift CO+H2O = CO2+H2 Cu LSK-821-2

Conversion LSK

Methanation CO+3H2 = CH4+H2O Ni PK-7R

CO2+4H2 = CH4+2H2O
Ammonia Synthesis 3H2+N2 = 2NH3 Fe KM
CATALYST PERFORMANCE
MEASUREMENT AND
QUANTIFICATION
 CATALYST PERFORMANCE
MEASUREMENT TECHNIQUES
Analysis

Mass Balance

Catalyst Bad Temperature Rise

Catalyst Bed Temperature Profile

Radioactive Tracing

Pressure Drop
ANALYSIS
 Primary source of information for conversion
 Can be done online or by analyzing in
laboratory.
MATERIAL BALANCE

 Can be done by using analysis

 Used to calculate yield.
CATALYST BED TEMPERATURE RISE

 Can be measured by measuring temperatures

at inlet and outlet of catalyst bed.
 Can be used to measure an accurate amount
of conversion.
6
CO concentration, mole % dry

0
100 200 300 400 500 600
Temperature, °C
CATALYST BED TEMPERATURE PROFILE
 Can be measured by passing a travelling
thermocouple through a sheath in the bed.
 Can be used directly to measure catalyst
activity or active volume of catalyst.
215
210
Bed temper-

205
atures

200
195
190
0 0.5 1 1.5 2 2.5 3
Distance from inlet (m)
RADIOACTIVE TRACING
 Used to check poor distribution and
bypassing in reactors.
PRESSURE DROP
 If measured regularly then any change in it is
a good measure of catalyst performance.
 It should be measured from reactor inlet and
outlet or by using dP cell across reactor.
QUANTIFYING CATALYST PERFORMANCE

Catalyst Performance
Quantification

Measurement Activity or
Approach to
of Composition active volume
Equilibrium
at exit of catalyst
COMPOSITION AT REACTOR EXIT
 Applicable when
i) Reactor operating temperature are
held constant
ii) When reaction over the catalyst is
not equilibrium limited.
 APPROACH TO EQUILIBRIUM
“ It is the difference between the gas temperature
at the exit of the catalyst bed and the
equilibrium temperature corresponding to gas
composition.”
 Applicable when

i) Reactor operating temperature held

constant
ii) Reaction is equilibrium limited.
iii) Gas composition does not change
during sampling
CALCULATION OF APPROACH TO EQUILIBRIUM

Temperature approach to
Carbon Monoxide

equilibrium = Te-T
Equilibrium
Curve

T
Te

Temperature

It is true for exothermic reaction. For endothermic

reaction, temperature approach to equilibrium = T- Te
ACTIVITY OR ACTIVE VOLUME
 Used when
i) Reaction is equilibrium limited
ii) Operating temperature vary with
time
iii) Large variation in gas composition
at reactor inlet
iv) Catalyst activity loss is nearly even
throughout the reactor bed
 CALCULATION OF CATALYST
ACTIVITY OR ACTIVE VOLUME
ACTIVITY:-
Ka = (Q/VKr) ln{(Ai-Ae)/(Ao-Ae)}
Ka = (QCe/VKr) ln{(Ce-Ci)/(Ce-Co)}
ACTIVE VOLUME:-
Va = (Q/Kr) ln{(Ai-Ae)/(Ao-Ae)}
Va = (QCe/Kr) ln{(Ce-Ci)/(Ce-Co)}

Where,
Ka = Catalyst activity relative to design activity
Va = Active volume of catalyst
Kr = Rate constant at operating conditions
Q= Volumetric flow rate
V= Volume of Catalyst
Ai/Ao/Ae = Concentration of reactant of interest at
inlet/outlet/equilibrium
Ci/Co/Ce = Concentration of product of interest at inlet/outlet/equilibrium
 APPLICATION AT OUR PLANT
Measurement CATALYST
technique R-201 F-201 R-203 R-204 R-205 R-311 R-501

Exit Analysis Yes Yes Yes Yes Yes Yes Yes

Mass Balance Yes Yes
Temp. Rise Yes Yes Yes Yes
Temp. Profile Yes Yes Yes Yes
Press. Drop Yes Yes Yes Yes Yes Yes Yes
Quantifying CATALYST
technique R-201 F-201 R-203 R-204 R-205 R-311 R-501

Exit Analysis Yes

Approach to Yes Yes
equilibrium
Catalyst activity Yes Yes
Active Volume Yes Yes
QUESTIONS