Handouts for L24-28

Prof. K.K.Pant
Department of Chemical Engineering
IIT Delhi.
kkpant@chemical.iitd.ac.in
SLURRY BUBBLE COLUMN REACTORS : DESIGN APPROACH

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Steps in Slurry Reactors
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Reactions Steps in slurry reactors

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 2. Rate of gas absorptions ( Hydrogenation Reaction)

3. Transport to the Catalyst Pellet

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4. Diffusion and Reaction in the Catalyst Pellet

m = mass of cata/vol of solution

Determination of RDS

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 Trickle Bed Reactors
Trickle-bed reactors are the most widely used
type of three-phase reactors. The gas and liquid
co-currently flow downward over a fixed bed of
catalyst particles.
Concurrent down-flow of gas and liquid over a
fixed-bed of catalyst. Liquid trickles down, while
gas phase is continuous
In a trickle-bed, various flow regimes are
distinguished, depending on gas and liquid flow
rates, fluid properties and packing
characteristics.
 Approximate dimensions of commercial trickle-bed reactors
are a height of 10 m and a diameter of 2 m.
 Comparison of Three Phase
Trickle- Bed and Bubble Fixed Bed
Reactors
Overall or Apparent reaction rate (gas limiting)
Kinetic Factors
 Theory of Catalytic Gas- Liquid
Reactions
A(G) + B(L) C
Gaseous reactant A reacts with non-volatile liquid
reactant B on solid catalyst sites.
Mechanism Of Three- Phase Reactions:-
Mass Transfer of component A from bulk gas to
gas-liquid interface
Mass transfer of component A from gas-liquid
interface to bulk liquid
Mass transfer of A& B from bulk liquid to catalyst
surface
Intraparticle diffusion of species A& B
through the catalyst pores to active sites.

Adsorption of both or one of the reactant

species on catalyst active sites.

Surface reaction involving at least one or

both of the adsorbed species.

Desorption of products, reverse of forward

steps .
Three-Phase Gas-Liquid Catalytic Reactor- Design
Model

(Trickle-Bed, Fixed-upflow Bubble-Bed, Bubble Slurry

Bed, 3-Phase Fluidized Bed)

Non-Volatile Liquid-phase mass balance:

 rA= kg ai (CA(g-C Ai(g)/(1-) c = kl ai (CAi(g - C Ab )/(1-) c

= kc ac (CAb CAs ) = k CAs CBs Moles/gcat.s

ai= interfacial area/ vol. of bed., = bed void fraction

Eliminate intermediate concentrations

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 CAg
-r =
'

A 1 H H H
+ A + A + A
k a k a k ac k ' C f
Ag i Al i Ac A B s
First order rate constant for A

-r ' =k vgC
A Ag
Mole balance for A dF
A =r' =-k C g
dW A vg A
1 mol
-r ' = C
B 1 1 B gcat.s
+
k c ap nKC
AS
-r =k C
B vl B

Mole balance for B

dF dC
B =v B =-r' =k C
dW 1 dW B vg B
 REACTOR MODEL
In kinetic models for trickle beds, the reaction is often
assumed to be first order to both reactants
For the ideal case of plug flow and completely wetted
catalyst, the conversion for a first-order reaction is
given by:
Conversion may be given as a function of the liquid
hourly space velocity (LHSV), and the apparent rate
constant, kapp, includes the effect of partial wetting as
well as the effect of internal concentration gradients.

where
The Rate:
Select the contactor which favors the weakest step in the
rate. (RDS)
For example,
if the main resistance lies in the G/L film, use a contactor
with large interfacial surface area.(bubble column/spray)
if the resistance lies at the L/S boundary, use a large
exterior surface of solid, thus large fs, or small particles.
if the resistance to pore diffusion intrudes, use tiny
particles.
Boosting the weakest step in the rate by a proper choice of
particle size, solid loading and reactor type can strongly affect
the overall economics of the process. 23
Example : 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

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What will be the conversion of acetone in this unit?

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

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 CAg
-r =
'

A 1 H H H
+ A + A + A
k a k a k ac k ' C f
Ag i Al i Ac A B s
First order rate constant for A

-r ' =k vgC
A Ag
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 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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Fluid- Fluid Reactions (Non catalytic)
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 two-
film 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
 Role of the Hatta Number, MH
To identify whether reaction is fast or slow, we focus on unit
surface of gas-liquid interface, assume that gas-phase
resistance is negligible, and we define a film conversion
parameter

If MH >>1, all reaction occurs in the film, and surface area is the controlling rate
factor.
On the other hand, if MH <<1 no reaction occurs in the film, and bulk volume
becomes the controlling rate factor. More precisely, it has been found
that:

From Fig. 23.4, for MH >1000 42

 To find the rate from the general expression, we need to first evaluate
Ei and MH. :
1. If MH > 2, reaction occurs in the film and we have Cases A, B, C, D.
2. If 0.02 < MH < 2, we then have the intermediate Cases E, F, G.
3. If MH < 0.02, we have the infinitely slow reaction of Case H.

(a) locate the resistance to reaction (what % is in the gas film, in the liquid
film, in the main body of liquid)
(b) locate the reaction zone
(c) determine the behavior in the liquid film (whether pseudo first-order
reaction,
instantaneous, physical transport, etc.)
(d) calculate the rate of reaction (mol/m3 hr)

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 Eliminating the unmeasured intermediates x, x0, pAi, CAi,

For the special case of negligible gas-phase resistance, for example, if you used
pure reactant A in the gas phase, then

= KAl CAi E , E = x0/x

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Case C: Fast Reaction; Low CW The plane of reaction for
case A now spreads
into a zone of reaction in which A and B are both present.
However, reaction is fast enough so that this reaction zone
remains totally within the liquid film.
Thus, no A enters the main body of liquid to react there.
Since the last resistance term in the general rate equation, Eq.
5, (I/kfl )is negligible (large k), the rate form for this case is
Case G: Slow Reaction with Respect to Mass Transfer. all
reaction occurs
in the main body of the liquid; however, the film still provides a
resistance to the transfer of A into the main body of liquid. Thus,
three resistances enter into the rate expression, Thus

Case H: Infinitely Slow Reaction.

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Slow reactions Case G still shows film resistance. Case H shows no film
resistance.

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Factors to Consider in Selecting a Contactor
(a) Contacting pattern.

Towers approximate plug G plug L.

Bubble tanks approximate plug G / mixed L.
Agitated tanks approximate mixed G / mixed L.
Towers have the largest mass transfer driving force and in this respect have an
advantage over tanks.
Agitated tanks have the smallest driving force.
(b) kg and kL. For liquid droplets in gas kg is high, kL, is low.
For gas bubbles rising in liquid, kg is low, kL is high.
(c) If the resistance is in the gas and or liquid films : Use a large interfacial
area "a," thus most agitated contactors and most columns. If the L film
dominates, stay away from spray contactors. If the G film dominates stay
away from bubble contactors.
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d) If the resistance is in the main body of the L you want
large fl = Vl/Vr. Stay away from towers. Use tank contactors.
(e) Solubility. For very soluble gases, those with a small
value of Henry's law constant H (ammonia, for example), gas
film controls, thus avoid bubble contactors.
For gases of low solubility in the liquid, thus high H value (O2,
N2, as examples) liquid film controls, so avoid spray towers.
(f) Reaction lowers the resistance of the liquid film, so
For absorption of highly soluble gases, chemical reaction is not
helpful. For absorption of slightly soluble gases, chemical
reaction is helpful and does speed up the rate.
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Fluid Solid non catalytic
Reactions
Substituting all values in the equation.

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