OXIDATION OF SODIUM SULPHIDE IN A FOAM BED

CONTACTOR

ASHOK BHASKARWAR and R. KUMAR*

Department of chemical Engineering, Indian Institute of Science, Bangalore-560012, India

(Received 4 July 1983; accepted 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- + 4S-2 + 2S,0;2 + 6H,O. (4)

Oxidation of sodium sulphide is an industrially im-
portant 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 solu-
tion to the problem of emission of malodourous
compounds.
The mechanism of oxidation of sodium sulphide to
tbiosulphate is available in literature. At tem-
peratures above 7O”C, the sulphide can be converted
directly to thiosulphate. Sharma et a1.[3,4] have
reported the second order rate constant at 75°C 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 con-
tactors 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 75°C 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-
The polysulphide ions can then yield either sulphur or
thiosulphate.
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 deter-
mine its value for the sulphide solution used in this
work, following the procedure used by Chan-
drasekaran 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 in-
vestigation is shown schematically in Fig. 1. It con-
sists of air supply and foam column sections. Clean
air at constant pressure is metered and then saturated
with water at 75°C through heating and passing
through a heated bubble column. The saturated air at
75°C is then fed into the flow-stabilization chamber
(1) 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.

2S~2+02+2H~0-2S~+40H- (2) Materials used

2 S,* + 9 0, + 12 OH- -8
*Author to whom correspondence
Sodium dodecyl sulphate and octyl phenoxy poly-
SrO,* + 6 H,O (3) ethoxyethanol (Briton X-100) were used as surfac-
tants. Analar grade sodium sulphide in aqueous
solution with excess sodium hydroxide was used as
should be addressed. the reactant solute. Purity of the sulphide is im-

1393
1394 A. B~A~KARW~ and R. KVMAR

Table 1. portant because the oxidation reaction is known to be

sensitive to the presence of metallic impurities[3].
Distribufor plate
Zinc sulphate heptahydrate, iodine, sodium thio-
Material of construction: Stainless steel
Thickness of plate: 1.5875 mm sulphate pentahydrate and starch were used in the
No. of holes: 15, with a triangular pitch chemical analysis of the samples. All the reagents
Diameter of a hole: 0. IS cm used were of analytical grade.
Free area: 0.3375% l”

COlUWWl Experimental procedure

Material of construction: Glass
Diameter of the column (i.d.): 1Ocm At the start of an experimental run, saturated air
Height of the column: 120cm at 75°C was passed through the column and the
system was allowed to reach a steady state. When the

1. Air supply
2. Surge tank
3. CO2 Scrubber
4. Scrubber with glass WOOk
5. Rotameter
6. Preheater
7. Bubble column with heater
8. Flaw &abiL~satibn chamber
9. Reactor section

@l

Fig. 1. Experimental set-up.

l.Air Wet valve temperature of air had been steady at 75°C for about
2. liquid outlet valve half an hour, the solution of sodium sulphide (250 ml)
3. Flow slabilisation at the desired concentration and already heated to
chamber
75°C was poured into the column through the inlet
4. Distributor date
just above the distributor plate. A known quantity of
5. S.S.Sleeuo
6. Inlet port surfactant was present in this solution. The solution
7 Sampling port foamed immediately. In all experiments carried out in
6. Manometer tapping this work, the solution of sulpbide was kept strongly
9. Asbestos insulation alkaline by using excess sodium hydroxide to ensure
T, , T2,13 - Thermometer that no hydrolysis would occur.
sockets
To maintain the height of foam at a desired level,
10. Glass column
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
Fig. 2. Details of foam CO~UIIUI. reaction mixture was withdrawn.
 Oxidation of sodium sulphide in a foam bed contactor 1395

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. Foam section 1 Gas out
The superficial velocity of air was varied from
1.7 cm/set to 5.1 cm/set. Under these conditions sta-
ble foam was obtained and the bed worked in the
semibatch mode. At higher air flowrates, the bed
exhibited recirculation which was not investigated, Draining liquid
012 %l
during the present study. The conversion character-
istics of the foam bed contactor were studied for two Fig. 3. One-stage model of B foam bed.
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. reaction is:
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.
It was decided to verify whether the present reac-
THEORY tion could be expressed as a pseudo-first order one,
A model to predict the conversions in a foam bed during the time r: for which the film is in contact with
contactor has recently been reported by Biswas and the gas. The condition for pseudo-first order
Kumar[S]. Their model divides the contactor in two kinetics[9]
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. is well satisfied for the present case and hence the
The extent of reaction in the foam is calculated by reaction under study has been treated as a pseudo-
assuming a foam IYm to be surrounded by a limited first order one.
quantity of gas. Equation (2) thus becomes:
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 where I = k, * C,.
sub-sections increases, the calculations become in- Assuming the gas phase to be well-mixed, the
creasingly involved. Further, Desai and Kumar[B] boundary conditions for eqn (3) are as follows:
have found that for low viscosity liquids like water At
containing surfactants the liquid holdup decreases
very rapidly near the foam-liquid pool interface t,=o,--aIxIa,C”=O (B.C.])
(within 2-3 cm). and then remains virtually constant.
In view of this, the possibility of visualizing the entire At
foam bed as a single section with a uniform liquid
holdup equal to the average value was explored in
t,>o,x=
v, ac:
f&---=+D,.s.-
ac,
this work. 12 at, ,3X
The idealization of the system is shown in Fig. 3.
The material balance for component B becomes: or

-2 =tQ,+Q>CB-QC,-Q,G,. (1) (B.C.2)

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

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 The solution of (3) with (B.C.l) and (B.C.2) is [lo],
1396

at i, = ry, and

i = 0, 1,2,3, . N.
M=M, (4)
Expansion of e Pl(r,~‘) in the series form and further
simplification gives,
where pn’s are the non-zero roots of

1 - P.
-=k,tank,a and k,f=-‘+. (5)
D.4 1
- P1zP2(ti - I)’ (9)
The concentration of unreacted reactant solute, 3! .
Cs,, at the end of the foam section with a contact time
r*E is Equation (9) gives the concentration of liquid
phase reactant B at any instant t (between the nodes
2Y,M fi and ti +,) in a continuous foam bed contactor. For
c,, =c,----. a semi-batch operation,
v,

From eqns (1) and (6) we have Q = 0, p, = 0, pr = - ?!z$.

1

dC,
-pP,C,=P, Using these in eqn (9), we obtain
where
c,= -qg(t -t,).

1
C&, (10)
PI=: and PI=; 1

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

Equation (7) cannot be solved as it stands, because to t,,,) and M has to be modified after every such
the term P2 depends on M which in turn is a function interval.
of C,, through 1. Unfortunately, M cannot be ex- The calculation of other parameters is based on the
pressed in terms of C, in a straightforward fashion as bubble radius (rb) and the average liquid holdup (Z).
C, appears through eqn (5), the roots of which have to The bubble radius is estimated using the simplified
be used in the solution. However, this problem can be model of bubble formation[ll]. The value of Z is
overcome by dividing the total time of reaction into a determined experimentally. The expressions for the
number (N) of short time intervals and integrating eqn other parameters involved are[5]:
(7) over the successive time intervals. During a short
interval Af, M does not change appreciably, and can C.QC
be treated as a constant and eqn (7) can be integrated
Q,=-1-F (11)
using the value of C, obtained from the previous
interval as the initial value. For the next interval M is V = V.-F
obtained using the value of C, at the end of this 1 6(1--E)
interval. The procedure is repeated for the next short
time interval and so on till C, is found at the desired n .Q
time f. The time interval in the present case was chosen a = 7.537. (1 - c) tan 54” (13)
as one minute which corresponds to approximately P/0
of variation in A. Solving the eqn (7) with constant M Vb
I= (14)
in the ith time interval (between nodes I; and t;,,) with 10.05 . k . rb2tan 54”
the condition that at
I = H - xr,2(1 - E)
t = ti, c, = c,*,,
c (15)
Q,
we obtain The concentration of sodium sulphide in the storage
section (Cs) at any instant and the percentage con-
c, = c,, eP,o,-r) p2 _ _p2 pI( fi -
+ _ 0
version based on the initial concentration of sulphide
e
(8) is computed from eqn (lo), used in the way explanted
PI PI
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 1397

thereby lower interfacial area. However, in the

Experimental 0 A 0 present case the effect is quite significant and cannot
c 0.013 0.033 0.06 be explained on the basis of the above rationale
uc (cmlsec) 1.7 3.4 5.1 alone. The higher effect is really the manifestation of
the effect of the average liquid holdup in the bed. It
H (cm) 34.0 34-o 34.0
has been observed that the average liquid holdup, for
C&(gm/lit) 20.16 20.16 20.16
the same height of the foam bed, is higher for a higher
Thewetical - - -
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 concen-
tration 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
I I I I I I
Fig. 4 that the model takes this factor into account
0 25 50 and predicts this behaviour fairly well. Figure 5
TIME (min.) shows the simulated conversions through the model
Fig. 4. Effect of superS&l velocity of air on the conversion for three superficial air velocities while maintaining a
of sodium sulphide in the storage. 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.

foam bed contactor. The height of the bed was Efecr of initial sulphide concentration
maintained constant at 34cm. It is Seen that the Figure 6 shows the effect of initial concentration on
conversion attained in a given time is higher for a the conversion of sulphide. The points are experi
higher supcriicial air velocity for the same foam mental and the lines represent the theoretical ones
height and the same initial concentration of sulphide. corresponding to eqn (10). The height of foam bed
One should expect a mild increase due to the overall and the superficial air velocity were kept constant. It
higher oxygen concentration in the gas or a mild is evident from Fig. 6 that the rate of conversion is
decrease because of the higher bubble size and lower for the lower initial concentration of sulphide.

w- Theorctyal prediction

uc (cm/set) 1.7 A 5:
H(cm) 31.0 31.0 31.0
Cg,(gmllit) 11.m 11.739 11.739
B 0.023 0.023 0.023
5 oo-

z
LJ

5
Y
E
xl-

I I I
OV 20 40 60
TIME (min 1

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

1398 A. BHASKARWAR
and R. K~XAR

Experimental * * Experimental A 0 0
CD0 (gmllit) 20.16 11.74 H km) 34.0 45.0 62.0
UC lcmL%=cc) 3.4 3 -4 Cg,(gmllit) 11.74 Il.74 11.7‘
H (cm) 34.0 34.0 uc (cmlsrc) 3.4 3.4 3.4
o-033 0.025 P 0.025 0.023 0.019
Theoretical - - TheOretIcal - - -

15 30 45
TIME (min)

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

(surfactant-octyl phenoxy phenethoxyethanol).
0’ I
25 50
I I
?5
TIME (min.)

Fig. 6. Effect of initial concentration of sodium sulphide on This is in agreement with the order of the reaction
conversion. with respect to sodium sulphide. The model also
closely predicts this effect.

E@ct of foam height and nature of the surfactanr

Figures 7 and 8 represent the effect of two surfac-
tants on the conversion of sulphide. Results for two
Experimental 0 A 0 different surfactants, each at three bed heights of
H (cm) 34.0 45.0 62.0 34 cm, 45 cm and 62 cm are shown. The superficial air
Cgo [gmflit) 20.16 20.16 2u.16 velocity was kept the same at 3.4cm/sec.
uc (cmisec) 3.4 3.‘ 3.4 Figure 7, corresponding to the use of sodium
E 0.04 0.016 0.007
dodecyl sulphate as the foaming agent, shows that the
Theoretical --- 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, indi-
cates 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
i height was increased. The conversion decreases actu-
ally 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
TIME (mln) liquid holdup on the conversion, the present system
Fig. 7. Effect of height of foam bed on conversion (k, lower by a factor of more than 2000) is found to be
(surfactant-sodium dodecyl sulphate.). 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 bub-
ble, 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.