OXIDATION

OF SODIUM SULPHIDE
CONTACTOR

IN A FOAM

BED

ASHOK BHASKARWAR
and R. KUMAR*
Department of chemical Engineering, Indian Institute of Science, Bangalore-560012,
(Received 4 July 1983; accepted

India

14 December 1983)

Abstract-Oxidation
of sodium sulphide to sodium thiosulphate has been experimentally investigated in
a foam bed contactor using air as oxidizing medium. The variables studied are supertick air velocity,
initial aulphide. wnwntration, height of the foam bed and the nature of the surfactant. The results indicate
that the conversion increases with the increase in the superficial air velocity and initial sulphide
concentration.
Thenatureof the surfactant has considerable influence on the conversion, even when their
surface resistance is negligible. When sodium dodecyl sulphate is used as a surfactant, the conversion
decreases as the foam height increases. Opposite trend has heen observed when octyl phenoxy
polyethoxyethanol is used. The apparently contradictory results are satisfactorily explained on the basis

of a simplifiedsingle stage model of a foam bed cootactor.

INTRODUCTION

S8 + 12 OH- +

Oxidation of sodium sulphide is an industrially important reaction. It is encountered in the manufacture

of sodium thiosulphate from sulphide and in coal gas
chemical recovery process[l]. It is also used in Kraft
pulp mills[2] where it is employed as a partial solution to the problem of emission of malodourous
compounds.
The mechanism of oxidation of sodium sulphide to
tbiosulphate is available in literature. At temperatures above 7OC, the sulphide can be converted
directly to thiosulphate. Sharma et a1.[3,4] have
reported the second order rate constant at 75C for
tbis reaction.
Recent work on foam bed contactors shows them
to offer high gas-liquid interfacial area per unit
volume of the liquid and large contact times apart
from having moderate pressure drops[5]. Such contactors could be usefully employed for contacting
relatively large quantities of gases with liquids.
The present investigation concerns itself with the
oxidation of sodium sulphide with air at 75C using
a foam bed contactor and predicting the performance
of the contacting device.
MECHANISMAND KINETICS
The mechanism of oxidation of sodium sulphide
involves the following reaction steps [3,6].
16S2+70;+

14H,O+ZS,*+28OH-

(1)

The polysulphide ions can then yield either sulphur or

thiosulphate.
2S~2+02+2H~0-2S~+40H2 S,* + 9 0, + 12 OH- -8

*Author to whom correspondence

(2)
SrO,* + 6 H,O

(3)

4S-2 + 2S,0;2

+ 6H,O.

(4)

The reversion reaction (4) results in an incomplete

oxidation of sodium sulphide. However, it is possible
to avoid the formation of elemental sulphur almost
completely

by operating

at temperatures

above

70%

f31.
The oxidation of sodium sulphide is a second order
reaction. It is first order each with respect to sodium
sulphidc and oxygen. As the rate constant of this
reaction is reported to depend upon the presence of
metallic impurities, experiments were done to determine its value for the sulphide solution used in this
work, following the procedure
used by Chandrasekaran and Sharma[3]. The rate constant was
found to be 4340 cm/gmole . set and was used while
making calculations through the model. This value,
as can be seen, is close to the reported value of
4460 cm/gmole . sec[4].
EXPERIMENTAL
Experimental
set-up
The experimental set-up used in the present investigation
is shown schematically in Fig. 1. It consists of air supply and foam column sections. Clean
air at constant pressure is metered and then saturated
with water at 75C through heating and passing
through a heated bubble column. The saturated air at
75C is then fed into the flow-stabilization chamber
from where it is sparged in the foam column section.
The details of tbe column and the distributor plate
are given in Table 1 and those of the foam column
in Fig. 2.
Materials

used

Sodium dodecyl sulphate and octyl phenoxy polyethoxyethanol

(Briton
X-100)
were used as surfac-

tants. Analar grade sodium sulphide in aqueous

solution with excess sodium hydroxide was used as
the reactant solute. Purity of the sulphide is im-

should be addressed.
1393

A. B~A~KARW~ and R. KVMAR

1394

portant because the oxidation reaction is known to be

sensitive to the presence of metallic impurities[3].
Zinc sulphate heptahydrate, iodine, sodium thiosulphate pentahydrate and starch were used in the
chemical analysis of the samples. All the reagents
used were of analytical grade.

Table 1.
Distribufor

plate

Material of construction: Stainless steel

Thickness of plate: 1.5875 mm
No. of holes: 15, with a triangular pitch
Diameter of a hole: 0. IS cm
Free area: 0.3375%

COlUWWl

Experimental procedure
At the start of an experimental run, saturated air
at 75C was passed through the column and the
system was allowed to reach a steady state. When the

Material of construction: Glass

Diameter of the column (i.d.): 1Ocm

Height of the column: 120cm

1. Air

supply

2. Surge

tank

3. CO2 Scrubber
4. Scrubber

with

glass

WOOk

5. Rotameter
6. Preheater
7. Bubble
8. Flaw

column

with

&abiL~satibn

9. Reactor

heater
chamber

section
@l

Fig.

l.Air

Wet

2. liquid

1. Experimental set-up.

valve

outlet

valve

3. Flow slabilisation
chamber
4. Distributor

date

5. S.S.Sleeuo
6. Inlet

port

7 Sampling
6. Manometer
9. Asbestos

port
tapping
insulation

T, , T2,13 - Thermometer
sockets
10. Glass

column

Fig. 2. Details of foam CO~UIIUI.

temperature of air had been steady at 75C for about

half an hour, the solution of sodium sulphide (250 ml)
at the desired concentration
and already heated to
75C was poured into the column through the inlet
just above the distributor plate. A known quantity of
surfactant was present in this solution. The solution
foamed immediately. In all experiments carried out in
this work, the solution of sulpbide was kept strongly
alkaline by using excess sodium hydroxide to ensure
that no hydrolysis would occur.
To maintain the height of foam at a desired level,
a sieve-plate was suspended from the top of the
column at the required height. As the foam attained
this height, it collapsed and the released gas escaped
through the holes in the plate, whereas the liquid
drained down to the storage through the Plateu
borders. The progress of the reaction was determined
by withdrawing samples of the reaction mixture in the
storage pool at suitable time intervals. At the end of
the experimental run, the entire quantity of the
reaction mixture was withdrawn.

Oxidation of sodium sulphide in a foam bed contactor

The samples were analysed for thiosulphate using
the standard iodimetric method of chemical analysis
given by Vogel[n.
Liquid holdup was measured experimentally using
a manometer connected at a height of 10 cm from the
distributor plate.
The superficial velocity of air was varied from
1.7 cm/set to 5.1 cm/set. Under these conditions stable foam was obtained and the bed worked in the
semibatch mode. At higher air flowrates, the bed
exhibited recirculation which was not investigated,
during the present study. The conversion characteristics of the foam bed contactor were studied for two
initial concentrations of the sulphide solution, viz.
20.16 g/l and 11.74 g/l. These fall within the range of
concentrations of interest in the oxidation of black
liquor from pulp mills.
The effect of nature of surfactant and its influence
on the conversion characteristics of foam bed was
studied using two surfactants, viz. sodium dodecyl
sulphate and octyl phonoxy polyethoxyethanol.
THEORY

A model to predict the conversions in a foam bed

contactor has recently been reported by Biswas and
Kumar[S]. Their model divides the contactor in two
sections, viz. the storage section and the foam section.
Liquid from the storage section is carried into the
foam section, where it reacts with the gas and the
partially converted solution continuously drains back
to the storage through a network of Plateau borders.
The extent of reaction in the foam is calculated by
assuming a foam IYm to be surrounded by a limited
quantity of gas.
To account for the variation of liquid holdup with
height, the foam section is further divided into a
number of sub-sections, each having a different but
constant holdup. The number of sub-sections are to
be decided by judgement; and as the number of
sub-sections increases, the calculations become increasingly involved. Further, Desai and Kumar[B]
have found that for low viscosity liquids like water
containing surfactants the liquid holdup decreases
very rapidly near the foam-liquid pool interface
(within 2-3 cm). and then remains virtually constant.
In view of this, the possibility of visualizing the entire
foam bed as a single section with a uniform liquid
holdup equal to the average value was explored in
this work.
The idealization of the system is shown in Fig. 3.
The material balance for component B becomes:

-2

=tQ,+Q>CB-QC,-Q,G,.

1395

:__-___-_____-_
Foam

1 Gas

out

Draining
liquid
012 %l

Fig. 3. One-stage model of B foam bed.

reaction is:

It was decided to verify whether the present reaction could be expressed as a pseudo-first order one,
during the time r: for which the film is in contact with
the gas. The condition for pseudo-first order
kinetics[9]

is well satisfied for the present case and hence the

reaction under study has been treated as a pseudofirst order one.
Equation (2) thus becomes:

where I = k, * C,.
Assuming the gas phase to be well-mixed, the
boundary conditions for eqn (3) are as follows:
At
t,=o,--aIxIa,C=O

(B.C.])

At

t,>o,x=

v, ac:

f&---=+D,.s.-

12

at,

ac,
,3X

or
(B.C.2)

(1)

To solve eqn (l), C,, has to be expressed in terms of

C,. This is done by considering the reaction to occur
in a f&n surrounded by limited amount of gas. The
gaseous reactant A diffuses into the liquid film and
reacts with the solute B. The pertinent differential
equation for the present second order, irreversible

section

where

The solution of (3) with (B.C.l)

and (B.C.2) is [lo],

1396
at i, = ry,

and

i = 0, 1,2,3,

M=M,

N.

(4)
Expansion
of e Pl(r,~) in the series
simplification
gives,

where

pns are the non-zero

1 - P.
-=k,tank,a

roots

(5)

D.4

- P1zP2(ti - I)

The concentration
of unreacted
reactant
solute,
Cs,, at the end of the foam section with a contact time
r*E is
c,,

2Y,M

=c,----.

v,
From

eqns

and further

of

k,f=-+.

and

form

(9)

3!

Equation
(9) gives the concentration
of liquid
phase reactant B at any instant t (between the nodes
fi and ti +,) in a continuous foam bed contactor. For
a semi-batch operation,

(1) and (6) we have

= 0, p,

= 0,

pr = -

?!z$.
1

dC,
-pP,C,=P,

Using

these in eqn (9), we obtain

where
PI=:

and

PI=;

Equation (7) cannot be solved as it stands, because

the term P2 depends on M which in turn is a function
of C,, through
1. Unfortunately,
M cannot be expressed in terms of C, in a straightforward
fashion as
C, appears through eqn (5), the roots of which have to
be used in the solution. However, this problem can be
overcome by dividing the total time of reaction into a
number (N) of short time intervals and integrating eqn
(7) over the successive time intervals. During a short
and can
interval Af, M does not change appreciably,
be treated as a constant and eqn (7) can be integrated
using the value of C, obtained
from the previous
interval as the initial value. For the next interval M is
obtained
using the value of C, at the end of this
interval. The procedure is repeated for the next short
time interval and so on till C, is found at the desired
time f. The time interval in the present case was chosen
as one minute which corresponds to approximately
P/0
of variation in A. Solving the eqn (7) with constant M
in the ith time interval (between nodes I; and t;,,) with
the condition that at
t = ti, c, = c,*,,

= c,,

eP,o,-r)

p2 _ _p2 pI( fi PI PI

+ _

C&,

-qg(t

-t,).

(8)

(10)

Equation (10) is applicable for short time intervals (r,

to t,,,) and M has to be modified after every such
interval.
The calculation of other parameters is based on the
bubble radius (rb) and the average liquid holdup (Z).
The bubble radius is estimated using the simplified
model of bubble formation[ll].
The value of Z is
determined experimentally. The expressions for the
other parameters involved are[5]:

C.QC

Q,=-1-F
V =

(11)

V.-F

1 6(1--E)
n .Q

a = 7.537. (1 - c) tan 54
I=

Vb
10.05 . k . rb2tan 54
I = H - xr,2(1 - E)
c

Q,

we obtain
c,

c,=

(13)

(14)

(15)

The concentration
of sodium sulphide in the storage
section (Cs) at any instant and the percentage
conversion based on the initial concentration
of sulphide
is computed from eqn (lo), used in the way explanted
in the text.

where
RESULTS AND

DISCUSSION

Efict of air powrate on conversion

Figure 4 shows the effect of the superficial air
velocity on the conversion of sodium sulphide in the

Oxidation of sodium sulpbide in a foam bed contactor

Experimental

0.013

0.033

0.06

1.7

3.4

5.1

H (cm)

34.0

34-o

34.0

C&(gm/lit)

20.16

20.16

20.16

Thewetical

c
uc (cmlsec)

thereby lower interfacial area. However, in the

present case the effect is quite significant and cannot
be explained on the basis of the above rationale
alone. The higher effect is really the manifestation of
the effect of the average liquid holdup in the bed. It
has been observed that the average liquid holdup, for
the same height of the foam bed, is higher for a higher
superficial air velocity. This is also reported and
explained earIier[l]. The diffusion and reaction of
oxygen in the libn of a limited thickness gives rise to
the development of a concentration profile of the
unreacted dissolved oxygen in the film of a foam
bubble. The concentration of the unreacted oxygen
which is initially zero at the centre of the tilm builds
up with time as oxygen goes on accumulating in the
tilm while the foam bubble rises through the bed. This
results in the lower concentration gradients on both
sides of the film. For a higher superficial air velocity,
the liquid lilm is thicker and the effective concentration gradient on each side of the film is higher.
This results in high mass fluxes into the film, which
in turn implies higher conversion. It is evident from
Fig. 4 that the model takes this factor into account
and predicts this behaviour fairly well. Figure 5
shows the simulated conversions through the model
for three superficial air velocities while maintaining a
constant E. It is clear that the effect is very small,
which further reinforces the tinding that the real
change in behaviour is due to the variation of Z only.

50

25
TIME (min.)

Fig. 4. Effect of superS&l velocity of air on the conversion

of sodium sulphide in the storage.

foam bed contactor.

The height of the bed was
maintained constant at 34cm. It is Seen that the
conversion attained in a given time is higher for a
higher supcriicial air velocity for the same foam
height and the same initial concentration of sulphide.
One should expect a mild increase due to the overall
higher oxygen concentration in the gas or a mild
decrease because of the higher bubble size and

w-

1.7

5:

H(cm)

31.0

31.0

31.0

Cg,(gmllit)

11.m

11.739

11.739

0.023

0.023

0.023

B
5

Efecr of initial sulphide concentration

Figure 6 shows the effect of initial concentration on
the conversion of sulphide. The points are experi
mental and the lines represent the theoretical ones
corresponding to eqn (10). The height of foam bed
and the superficial air velocity were kept constant. It
is evident from Fig. 6 that the rate of conversion is
lower for the lower initial concentration of sulphide.

prediction

Theorctyal

uc (cm/set)

oo-

z
LJ
5
Y
E
xl-

OV

20

1397

40
TIME (min 1

60

Fig. 5. Simulated effect of superlicial air velocity on conversion at constant L

A. BHASKARWAR
and R. K~XAR

1398

Experimental

CD0 (gmllit)

20.16

11.74

UC lcmL%=cc)

3.4

H (cm)

34.0

3 -4
34.0

o-033
Theoretical

Experimental

H km)

34.0

45.0

62.0

Cg,(gmllit)

11.74

Il.74

3.4

3.4

3.4

0.025

0.023

0.019

uc (cmlsrc)

0.025

P
TheOretIcal

11.7

30

15

45

TIME (min)

Fig.

0
Fig.

25

?5

50
TIME (min.)

6. Effect of initial concentration

conversion.

This is in agreement with the order of the reaction

with respect to sodium sulphide. The model also
closely predicts this effect.

of sodium sulphide on

E@ct

Experimental

H (cm)

34.0

45.0

62.0

Cgo [gmflit)

20.16

20.16

2u.16

uc (cmisec)

3.4

3.

3.4

0.04

0.016

0.007

E
Theoretical

---

TIME

8. Effect of height of foam bed on com%?r~ion

(surfactant-octyl
phenoxy phenethoxyethanol).

(mln)

Fig. 7. Effect of height of foam bed on conversion

(surfactant-sodium dodecyl sulphate.).

of foam height and nature of the surfactanr

Figures 7 and 8 represent the effect of two surfactants on the conversion of sulphide. Results for two
different surfactants, each at three bed heights of
34 cm, 45 cm and 62 cm are shown. The superficial air
velocity was kept the same at 3.4cm/sec.
Figure 7, corresponding to the use of sodium
dodecyl sulphate as the foaming agent, shows that the
conversion attained in a given time decreases as the
height of the bed is increased. Figure 8, for octyl
phenoxy polyethoxyethanol, on the other hand, indicates just the opposite trend. The conversion here
increases as the height is increased.
These trends are also explained in terms of the
average liquid holdup in the bed. For sodium dodecyl
sulphate, the average holdup decreased sharply as the
height was increased. The conversion decreases actually because of the considerably lower E for a higher
height, in spite of the larger contact time. In the other
case, the increase in height of bed resulted in only a
slight decrease in the average liquid holdup. Here the
slight effect of Z on conversion is suppressed by the
larger contact time corresponding to a higher height.
Thus, the conversion increases as the height of foam
bed is increased. The model also predicts these trends.
It is interesting to observe that though Biswas and
Kumar[S] did not find any effect of the variation in
liquid holdup on the conversion, the present system
(k, lower by a factor of more than 2000) is found to be
significantly sensitive to variation of Z.

Oxidation of sodium sulphide in a foam bed contactor

The surfactants used do not seem to o&r any
surface resistance but influence the conversion by
changing the surface viscosity and thereby the liquid
holdup.
In all the cases discussed above the one-step model
for a foam bed contactor predicts the conversions
fairly well and the average deviation in prediction of
the experimental values is found to be of the order of
10%.
It would appear from the present investigation that
a single step model can be used with advantage for
systems involving liquids of low viscosity.
NOTATION

thickness of a liquid film, cm

concentration
of reactant A in liquid film,
g mole/cm
concentration
of reactant A at the liquid
film-gas interface, g mole/cm3
concentration of reactant A in the gas bubble, g mole/cm
concentration
of liquid phase reactant B in
the storage section at time r, gmole/cm3
inlet concentration
of liquid phase reactant
B, g mole/cm3
concentration
of liquid phase reactant E in
the liquid draining into the storage section
from the foam section, gmole/cm
diffusion coefficient of reactant A in liquid
phase, cm/sec
height of foam section, cm
equilibrium distribution factor
second
order
reaction
rate
constant,
cm3/(g mole . set)
defined in eqn (5)
equals V,/12ks, cm
total amount of reactant A, both free to
diffuse and immobilized. in half the liquid
film of surface area s at contact time rz g
mole.
total amount of reactant A, both free to
diffuse and immobilized, in half the liquid
film of surface area s after infinite time, g
mole.
number of intervals in the total time of
reaction
integer number 1,2, 3, _.
equals Q/v
defined in text
defined in eqn (5)

1399

flow rate of liquid entering the foam bed

reactor, cm/sec
flow rate of the liquid draining into storage
section from the foam section, cn?/sec
average radius of a bubble, cm
average radius of the contactor column, cm
surface area of a liquid tilm, cm2
time of operation of the foam bed contactor,
set
time-nodes corresponding to the ith interval,
SeC

contact time between the liquid film and the

gas bubble in the foam section, sec.
total contact time between the liquid film and
the gas bubble in the foam section, set
ith time interval after which I from (i - 1)th
interval is corrected, set
storage section liquid volume, cm
volume of a liquid film in foam section, cm3
volume of the bubble, cm3
distance from the centre of a liquid film
towards the gas-liquid interface, cm
stoichiometric
factor, i.e. moles of liquid
phase reactant B consumed per mole of
gaseous reactant A
average value of the liquid holdup in the
foam bed
pseudo-first order kinetic rate constant for
the reaction, set-
REFERENCES

[l] Kirk-Othmer, Encyclopedia of Chemical Technology,

2nd Edn, Vol. 20, p. 236. Interscience, New York 1969.

[2] Kirk-Othmer, Encyclopedia of Chemical Technology,
3rd Fdn, Vol. 16, p. 770. Wiley-Interscience, New York
1981.
[3] Chandrasekaran K. and Sharma M. M., C/u-m.Engng
Sci. 1974 29 2130.
[4] Chandrasekaran K. and Sharma M. M., Chem. Engng
Sci. 1976 31 861.
[5] Biswas J. and Kumar R., Chem. Engng Sci. 1981 36
1547.
[6] Murray F. E., Pulp Paper Mug. Can. 1968 69 3.
[7] Vogel A, I., A Texr Book of Quantitative Inorganic
Analvsis. 3rd Edn, D. 352. ELBS and Longman,

.
Loncion 1962.
[S] Desai D. and Kumar R., Chem. Engng Sci. (In Press).
[9] Danckwerts P. V., Gas-Liquid Reactions, p. 89.
McGraw-Hill, New York 1970.
[IO] Crank J., The Mathematics of Difliiom Clsrendon
Press, Oxford 1956.
[ll] Kumar R. and Kuloor N. R., Advances in Chemical
Engineering, Vol. 8, p. 286. Academic Press, New York
1970.