INSTITUTE OFENGINEERING

DEPARTMENT OF CHEMICAL
ENGINEERING
Bachelor of Engineering (CHEMICAL ENGINEERING)
& CHT 303

DISCOVER . LEARN . EMPOWER

 Experimental rate determination

CO Number Title Level

• Experimental rate
determination
CO1 Basic

To learn about various

experimental rate
determination and
mathematical equation for
Heterogeneous Reaction in
reactor.

CO2 Understandin
To understand various g level

experimental rate determination

and mathematical equation for

Heterogeneous Reaction in

reactor and the different changes.

2
 Experimental rate determination

• Experimental reactors are used on micro scale to

determine the rate and kinetic constants
• These are different from the experiments that are done
to get mechanism (TAP or AES and others) or to test
catalyst activity on micro scale (MAT, Pulsed kinetics)
• We will talk of only of bench scale or pilot scale
continuous units or batch reactor units
• Experimental studies on such units involves measuring
the extent of conversion of fluid passing through a bed
of catalyst in a steady flow with KNOWN FLOW
PATTERN

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 Experimental rate determination
• There are basically four types of reactors with known flow patterns
used for experimentation with hetrogeneous catalysis

- Differential flow reactors

- Integral flow reactors
- Mixed flow reactors and
- Batch reactors for both gas and solid or liquid and solid

A differential reactor is one in which the rate is constant at all points in

the reactor. This means for fast reactions in plug flow we consider
only a small conversion across our reactor. Thus it could be
differential plug flow or small CSTR. For slow reactions this could
be larger in size

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 Differential reactors

• The governing equation for differential reactors is a

plug flow equation with catalyst weight as basis
W/FA0 = ∫dXA/(-rA’)ave = (XAin – XAout)/(-rA’)ave
We find a series of –rA’ ave at average conc.
Then we carry out the differential analysis
When there is a variation in rate in concentration inside
the experimental reactor (usually the case in a pilot
scale reactor), then we call it an integral reactor and
carry out Integral analysis after knowing the flow
pattern(RTD) and sampling data along the length of
reactor
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 Mixed flow and batch reactors

• These are usually micro reactors of fully mixed pattern

Famous examples are CARBERRY and BERTY reactors

as well as RECYCLE reactors (autoclave engineers
catalogue)
In mixed flow reactors the governing equation is
W/FA0 = XAout/(-rA’)out
In recycle reactors, the equation is
W/FA) = (R+1) ∫dXA/(-rA’) limits (R/(R+1))XAf
to Xaf

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 Integral and differential methods of
analysis for rate data
• Example 18.3a gives the procedure for integral analysis for rate data
from a plug flow reactor with varying amounts of catalysts and
concentrations at outlet.
• For reaction A 4R, CA0 = 0.1 mol/L and FA0 = 2 mol/hr
and εA = 3 - rA’ = 95(l/hr.kg cat).CA(mol/l

Same data has been analysed with differential analysis in example

18.3b. From the CA vs. –rA’ graph, we get 93 instead of 95

one can see that the differential method is more involved with three
cross plotting of data after calculations
The difficulty is to decide when to use which method

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 Comparison of experimental reactors
• Integral reactor can have significant temperature variation and heat
loss at the wall. This can make measurements worthless. Berty or
Carberry are better for this.
• Integral reactors are useful for easier scale up and variations in feed
• Differential and mixed flow reactors give rate value more directly
and so these are useful for analysing more complex reaction systems
• Small conversions in differential reactors need more accurate
composition measurement(online GC, UV/VIS, IR..)
• A recycle reactor with large recycle acts as a mixed flow reactor and
we can distribute the catalyst throughout the loop

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 Comparison of experimental reactors
• In exploring heat and mass transfer effects, integral
reactors are more suited to mimic large industrial
reactor conditions. However to find the limits of these
effects, basket, recycle or batch Gas solid reactors are
useful as these operate on transport free zones
• The batch gas solid reactor gives cumulative effect like
integral reactor on a micro scale and thus is useful to
follow the multiple reaction phenomena on micro scale
• Because of the ease of interpreting results from mixed
flow reactors, these are more attractive devices for
studying kinetics of solid catalytic reactions

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 Determining the controlling resistances from
exptl. data
• Interpreting experimental data becomes difficult when
more than one resistance affects the kinetics.
• To avoid this we do preliminary runs to determine the
limits of operation when various resistances become
important.
• This will allow us to select conditions of operations
where in these can be studied separately

• How to study the effect of film resistances

• Heat and mass transfer film resistances

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 Determining the controlling resistances from
exptl. data
• Devise experiments to see if conversion changes at
different gas velocities for the same weight time of
catalysts (adjust the catalyst bed height??) in integral or
differential reactors. One can change the spinning rate
of berty or carberry reactor or by changing recycle rates
in a recycle reactor

• If data can be generated on diffusion and other

parameters, we can arrive at estimates of effect of mass
transfer. Heat transfer effect is more difficult to
experiment with and interpret except perhaps in
monoliths.

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 Determining the controlling resistances from
exptl. data
• Film mass transfer resistance
For fluids moving past a single particle with a relative velocity
u, Froessling(1938) gave a relationship
kg.dp/D = 2 + 0.6(Re^0.5)(Sc^0.33)
This is extended to packed bed by Ranz(1958) as
kg.dp/D = 2 + 1.8(Re^0.5)(Sc^0.33) for Re>80
Thus we roughly have kg ~ 1/dp for small dp and u and
kg ~ (u/dp)^0.5 for large dp and u
To see if film mass transfer resistance is important compare
kobs.Vp with kg.Sext
If these values are both same, then there is possible resistance
If kobs.Vp is far less than kg.S, then we can ignore resistance
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 Determining the controlling resistances from
exptl. data
• Non isothermal effects

if the experimental mass transfer resistances across the film are proved
to be negligible, the chances are that non iso thermal effects are
negligible. We can assume that the catalyst pellet is having the same
temperature as fluid temperature in bulk
If there is a considerable resitance in the film, we have to assume a
temperature profile similar to concentration profile and calculate the
heat transfer resistance.
There will also be indications that the MT vs. E will have a growing
hump when we consider pore resistances. The surface area and pore
size measurements also will give indications of what to expect

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 Determining the controlling resistances from
exptl. data
• Pore resistances

The effectiveness factor accounts for the pore resistances

Based on experimental value of – rA”’ and CA as well as n and k”’, we
can calculate the E which is equal to 1/MT
The existence of pore resistance can be determined by
- Calculation if De is known or experimentally can be found out
- Comparing rates after sieving catalyst particles and using different
particle sizes in experiments
- Noting the drop in Activation energy calculations for the reaction with
rise in temperature, coupled with possible change in reaction order
when graphically plotting the experimental data for finding the order

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 References

1. Levenspiel O., “Chemical Reaction

Engineering”, Third Edition, John Wiley and
Sons, 2003.

2. Smith J. M., “Chemical Engineering Kinetics”,

McGraw-Hill, 1981.

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THANK YOU

For queries
Email: [email protected]