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L 25: Fluid- Fluid Reactions (Non

catalytic)

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in

-r =
A
'

CAg

H
H
H
A +
A
+ A +
k a k a k ac k ' C f
Ag i
Al i
Ac
A B s
1

First order rate constant for A

-r ' =k vgC
A
Ag

HYDROGENATION OF ACETONE IN A PACKED BUBBLE COLUMN

Aqueous acetone (CB0, = 1000 mol/m3 1, vl = 10-4 m3 l /s) and


hydrogen (1 atm, vg = 0.04 m3 g /s, HA = 36845 Pa.m3 l /
mol) are fed to the bottom of a long, slender column (5-m
high, 0.1-m2 cross section) packed with porous Raney nickel
catalyst (dp, = 5 x 10-3m cat, ps = 4500 kg/m3 cat, fs = 0.6, De
= 8 X 10-10 m2 / s based on vol of l /m of cat) and kept at 140C.
At these conditions acetone is hydrogenated to propanol
according to the reaction

What will be the conversion of acetone in this unit?


Additional Data:
The mass transfer rate constants are estimated to be the

CBo = 1000, mol/m3

CA is given by Henry's law as

CB >> CA
Since pure hydrogen; p A is constant throughout the packed column. And since
the rate is only dependent on CA and not on CB, this means that the rate of
reaction is constant throughout the column.
Thiele Modulus MT or

= 1/ = ~0.01
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Substituting all values in the equation.

Fluid Fluid Reactions ( Non catalytic /Gas -Liquid


Reactions)

For notation consider a unit volume of contactor Vr with its


gas, liquid, and solid

Tower and Tank for Gas Liquid reaction

Setting up the rate equation for straight mass transfer based


on the two film theory.

The Rate Equation for Straight Mass Transfer (Absorption) of A

Here two resistances in series, of the gas film and of the liquid
film. The rate of transfer of A from gas to liquid is given by the rate
expressions, for the gas film

In the liquid film

Combining the two eqns and using Henrys law


PAi= H CAi

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All sorts of special forms of the rate equation can result depending
on the relative values of the rate constants k, kg, and k,, the
concentration ratio of reactants pA /CB, and Henry's law constant HA.
There are eight cases to consider, going from the extreme of
infinitely fast reaction rate (mass transfer control) to the other
extreme of very slow reaction rate (no mass transfer resistance
need be considered)
Case A: Instantaneous reaction with low CB,
Case B: Instantaneous reaction with high CB
Case C: Fast reaction in liquid film, with low CB
Case D: Fast reaction in liquid film, with high C,
Case E and F: Intermediate rate with reaction in the film and in the
main body of the liquid
Case G: Slow reaction in main body but with film resistance
Case W: Slow reaction, no mass transfer resistance

Figure : Concentration of reactants as visualized by the twofilm theory for an infinitely fast irreversible reactions of any
order, A + bB products. Case A-low CB, Case B high CB,

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General rate expression

The absorption of A from gas is larger when reaction occurs within the
liquid film than for straight mass transfer.
Thus for the same concentrations at the two boundaries of the liquid film
we have
E >1

Instantaneous Reaction with Respect to Mass Transfer. : Since an


element of liquid can contain either A or B, but not both, reaction will occur
at a plane between A-containing and B-containing liquid.
Also, since reactants must diffuse to this reaction plane the rate of diffusion of
A and B will determine the rate, so that a change in p, or C, will move the
plane one way or the other

kAg, and kAl ,: mass transfer coefficients in gas and liquid


phases. The liquid side coefficients are for straight mass transfer
without chemical reaction and are therefore based on flow
through the whole film of thickness x0.
In addition, since the movement of material within the film is
visualized to occur by diffusion alone, the transfer coefficients
for A and B are related by

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General rate expression

The absorption of A from gas is larger when reaction occurs within the
liquid film than for straight mass transfer.
Thus for the same concentrations at the two boundaries of the liquid film
we have

E >1

Can be correlated with HATTA MODULUS/ NUMBER (MH)

M H, stands for the Hatta modulus,


M2H=

(k CAi CB x0 )/ kAl CAi

MH >1 ALL REACTION IN FILM and surface area is controlling factor. MH >2 ,
REAXN IN FILM, INSTANTANEOUS Reaction (BUBBLE COLUMN)
MH < 1, No Reaction in Film, and bulk liquid volume is controlling
MH < 0.02 INFINITELY SLOW REACTION ( BUBBLE COLUMN )

The enhancement factor for fluid-fluid reactions as a function of MH and Ei


modified from the numerical solution of van Krevelens and Hoftijzer