OXIDATION OF ACETALDEHYDE TO ACETIC

ACID IN1 A SPARGER REACTOR

BALAKRISHNAN VENUGOPAL, RAJIINDER K U M A R , AND N. R . K U L O O R
Defiartment of Chemical Engineering, Indian Institute of Science, Bangalore, India

The kinetics of oxidation of acetaldehyde to acetic acid was studied in a sparger reactor using manganese
acetate as the catalyst. Data obtained in a stirred tank reactor are used for analyzing the sparger reactor
data. The rate of chemical reaction i s extremely fast and can be neglected for the rate equation of the
sparger reactor. A kinetic model applicable at any temperature and concentration within the range of the
variables studied i s developed which predicts the performance of the sparger reactor satisfactorily.

CETALDEHYDE is readily oxidized to acetic acid by air or
A oxygen in the liquid phase in the presence of a catalyst.
A survey of the literature indicates that whereas manganese
salts are effective catalysts for conversion of acetaldehyde to
acetic acid, cobalt salts or mixtures of cobalt and copper salts
give high yields of acetic anhydride. The salts of iron, chro-
mium, and nickel are less effective catalysts.
The catalyst most commonly employed is manganese ace-
tate. The reaction when conducted with pure components is
extremely fast and the reaction mixture is generally diluted with
acetic acid to have reasonable rates of oxidation in continuous
reactors. The object of this investigation is to study this
reaction with a sparger-type reactor and put forth proper rate
equations.
I n the analysis of data on sparger reactor it is necessary to
assess the relative importance of diffusion and chemical reac-
tion, where the reaction rate constant has to be used. As the
rate constant must be evaluated independently, experiments
are conducted in a stirred tank reactor under conditions of high
turbulence where chemical reaction is rate-controlling. I n
addition to their use in the analysis of a sparger reactor, these
results have a value of their own as studies in the kinetics of the
summary reaction of oxidation of acetaldehyde to acetic acid.
Experimental
Sparger Reactor. The setup is shown in Figure 1. The
apparatus consists mainly of four sections.

To gas sampler
2 . Aspirator Bottle IO Mercury
3. Ca!cium Chloride II Reaction Mixture
4.Animal Charcoal 12 Funnel
5 Mercury Manometer 13 Outer Jacket
6 Rotameter 14 Water From Thermostat
7 Needle Valve 15 Water To Thermostat
8 Capillary Tube

Figure 1. Experimental setup for studies of oxidation of acetaldehyde to acetic acid

VOL. 6 NO. 1 JANUARY 1967 139

 FORMATION OF AIR STREAM, DRYING,AND METERINGOF
AIR. T h e air in a 20-liter aspirator bottle is compressed to a
constant pressure by running water into it from a constant
level tank. The outlet to the bottle being initially closed, the
pressure of the air increases until it attains the head of the
constant level tank. T o maintain constant pressure, water
E+- Tachometer

0-
must flow continuously through the overflow pipe.
The air thus obtained is dried by passing through a series
of bubblers containing anhydrous calcium chloride and animal Fractional Horse Power Motor
charcoal. The dry air at a constant pressure is passed through
a rotameter and then through a needle valve before it enters
the capillary for the formation of air bubbles.
FORMATION OF BUBBLES.Bubbles are formed through a
glass capillary housed at the bottom of the reactor.
REACTOR.The reactor essentially consists of a vertically
mounted borosilicate glass column, 20 mm. in diameter. At
the bottom of the reactor column is fitted a B,a joint and the Out let Tu be
bubble-forming capillary tube is introduced through this joint
as indicated in Figure 1. During an experimental run the
space inside the reactor column enclosed between the bottom
joint and the capillary is filled with glass wool, over which
mercury is poured, The mercury level is maintained up to the
tip of the capillary at which the bubbles are formed. This
arrangement ensures contact of the entire liquid phase used
with the dispersed phase.
Above the mercury, liquid phase reactant-Le., the solution
of acetaldehyde in acetic acid of known proportions and con-
taining manganese acetate dissolved in it-is poured to occupy
a known height above the tip of the capillary. The height of
the liquid column is altered for every run in order to get
different values for the time of contact between the two phases.
The entire length of the reactor column is enclosed in a glass
jacket through which water is circulated; its temperature is
controlled by an ultrathermostat. The precision of the
thermostat being of the order of z i ~ 0 . 0 1C.,
~ the temperature Figure 2. Stirred tank reactor
of the reactant can be maintained at any desired value with
sufficient accuracy.
Product Collection Unit. After the reaction, the outlet
gas is collected through an inverted funnel, which in turn is Acetaldehyde concentration in liquid feed
attached to a gas sampler of the type devised by Kumar and Oxygen concentration in gas
Catalyst concentration
Kuloor (2). The funnel is kept immersed in the liquid u p to Temperature of reaction
the stem to ensure that air after reaction enters the gas sampler
free from contamination with atmospheric air. The levels of the various hydraulic parameters studied are:
The gas thus collected is analyzed for its oxygen
,- content by
absorpgon in alkaline pyrogalloi solution. Solution height, cm. 3.3, 3.9, 5.6, 5.9, 7.5, 7.9,
Experimental Technique. Air bubbles, released at a 9.8, 11.8, 12.1, 14.7,
known frequency through a capillary of known diameter, are 15.8, 21.4, 22.4, 32.8,
allowed to react with the reaction mixture of specified com- 44.0
position. The height of the liquid column, catalyst concen- Average bubble size, cc. 0.00471, 0.01090, 0.0354
tration, and the temperature of the reaction are also fixed for a Bubble frequency, bubbles per min. 1080
particular run. Bubble rise velocity, cm./sec. 42.0, 31.6, 29.6
The time during which a uarticular bubble staw inside the Reactor gas cm./sec. 0.027, 0.068, 0.204
solution of acetaldihyde in a'cetic acid of a definitk bed height
is found by photographic methods. The bubbles are photo- The influence of each of these variables is described sepa-
graphed during their formation and ascent by a cine camera, rately and then combined to develop the rate equation.
run at a known speed. From the knowledge of the speed of
the camera and the number of frames taken by a bubble to THE EFFECT OF ACETALDEHYDE CONCENTRATION on the
travel from the tip of the capillary to the top level of the rates of reaction is studied for different oxygen concentrations
reactant solution, the contact time is calculated. and temperatures. The final results are shown graphically
Stirred Tank Reactor. The experimental setup is the same in Figure 3, from which the direct proportionality between the
as for sparger reactor except that, instead of a vertical sparger rate and the acetaldehyde concentration is evident.
reactor, a three-necked flask with a stirrer arrangement is
employed (Figure 2). The stirrer is 27 mm. in length and THEEFFECTOF INITIAL OXYGEN CONCENTRATION is studied
5 mm. in diameter. in a manner similar to that for acetaldehyde concentration.
The results obtained are presented in Figure 4, which shows a
linear relationship between the two variables.
Results and Discussion CATALYST CONCENTRATIOS is varied from 0.2 to 1.6% by
The experiments in this reactor were conducted under weight. No effect on the rate is observed.
conditions where the chemical reaction was controlling, by These results indicate that for a particular temperature the
increasing the stirrer speed and the air flow rate until both reaction rate can be expressed by the equation of the form
parameters cease to influence the rate of oxygen absorption.
r = k GAG',, (11
The final values of these parameters fixed on the basis of the
above study were: The plot of r us. GAG',, is presented in Figure 5, using tempera-
ture as parameter. The slopes of these lines yield the values of
Stirrer speed 2000 r.p.m. k given in Table I.
Gas flow 5.1 cc. per minute
The effect of temperature on the reaction rate has been
The different variables then studied are: expressed in terms of the Arrhenius equation :

140 I&EC PROCESS DESIGN A N D DEVELOPMENT

 (OXYgen concentrotion a Acefoldehyde c o n c e n t r a l i o n )

Figure 5. Plot of rate vs. acetaldehyde and oxygen

Figure 3. Plot of rate vs. acetaldehyde concentration concentrations

I
41 Legend i Ac,elo;lo~; -
Concentration
Acetic acid

0-40:60
2.10 -
f 0.4
A -
.-a0

-10
',70
20 : BO
:go 208 -
._ 0 0 I 0.2 0 3 0 4 0.5 0.6 0.7 0.8 0.9

Temperature 50.C d Temperature 65'C

5
*
N 2.02-

200-
1.98-

1.96 -
1.94-

1.92-

1.90 -
1.88-
0 0.1 0.2 0.3 0.4 0.5 0.6 0.70.8 0.9 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 C
1b86-
Oxygen concentration

Figure 4. Plot of rate vs. oxygen concentration

f x 104,'u

k = Ae-AE/RT Figure 6. Plot of In k vs. 1 / T

(2)
A plot of In k us. I / T is presented in Figure 6, which gives a
straight line with a negative slope, as expected from Equation 2. Table I. Values of k at Various Temperatures
By substituting Equation 2 in 1 and putting the values of A k X 2.69 X 706,
and E in the resulting equation, we obtain Temp., C. Gram iMoleslCc. Min.
49 6.37
r = 3.02 X lo3 e--39aIRT
CACac (3) 56 7.64
65 8.80
which is the rate equation for the summary reaction of the
oxidation of acetaldehyde to acetic acid.
The value of k can be calculated a t any temperature by Height of liquid column in the eductor tube. This pa-
rameter decides the time of contact of the bubble with the liquid
using the following equation : reactants.
k = 3.02 X lo3 e--39@JIRT Concentration of acetaldehyde in the mixture.
(4) Concentration of oxygen in the gas mixture fed to the sparger
This equation has been used to evaluate k, which is employed reactor.
Bubble size. This influences the area of contact which can
in the analysis of the performance of the sparger reactor. be expected to be available for the reaction.
Sparger Reactor. The important variables which can Catalyst concentration.
influence the final conversion are : Temperature.

VOL. 6 NO. 1 J A N U A R Y 1 9 6 7 141

 HEIGHTOF LIQUIDCOLUMN.This was varied in order to
change the contact time of the bubble with the liquid reactant.
The bubbles were collected in the stem of a small funnel to
reduce the free area a t the surface of the liquid and ensure
negligible interaction of the reaction taking place at the surface
on the total conversion. The influence of the time of contact
on the conversion is presented in Figures 7 to 9. The conver-
sion increases with the contact time, as expected.
As rates of reaction have to be obtained from these curves, it
was decided to express each curve by a polynomial. Two
polynomials-viz., those of second and third degrees-were
tried. The variance obtained by applying a third degree
polynomial was greater than that obtained by a second degree
one. Therefore all the curves were expressed through second
degree polynomials of the type x = ut bt2, where x is the +
conversion and t is the time of contact. The initial constant
term of the polynomial was taken to be zero, so that it can
satisfy the boundary condition of zero conversion at zero time

z
e
24t I
24
22

20 -
'g
>
e
V

/ Acetaldehyde I
-Acetic Acid
Concentration
wt.)
( % by wt
0 - 40:60
-30 : 70
A -2 0 : 8 0 Tempe'rature - : 56' C
0 0.1 0 . 2 0 3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 .O 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Contact l i m e , Sec. Contact t i m e , uec. Contaci t i m e , a e c .

Figure 7. Effect of contact time on conversion

24 F
-
.-
"1
20

18-
1
Temperature -: 4 4 * c z
Temperature -: 49.C
/

Concentral Ion
IO h by Wt.
0- 40:60

A
-
- 30 : 70
20 80

0 0.1. 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4 I.
Contact t i m e , a c e .
contact time, sec.

-
24
Temperature - : 56OC

Figure 8. Effect of contact time on con-

version

Contact time , sec.

142 l & E C PROCESS D E S I G N A N D DEVELOPMENT

 -4
2 24
1
3
.-5c 20
Temperature - ; 49' c
22t
20

> I ,1 Temperature -: 56' C

I
0
0

C o n c e n t r a t i o n 1 % by wt.
0- 4 0 : 60
a- 30 ; 70
A- 2 0 : BO
.0- 10 : 90
0
0 0.1 0 . 2 0.3 0.4 0.5 0.6 0.7 .0.8 0.9 1.0 1.1 1.2 1.3 1.4 1.5 I , &
C o n t a c t t i m e , see. C o n t a c t time I see.

Temperature - : 65'C

16 / /

Figure 9. Effect of contact time on con-

version

2L
00- 0.1 0.2 0.3 0 4 0.5 0.6 0.7 0.8 0.9 1.0 1.1 1.2 1.3 1.4

C o n t a c t t i m e , see.

0.9
of contact. The constants were evaluated by the method of Capillary diameter :O ~ l l l c m
least squares. 0.8 Tcmpraturc
INFLUENCE OF ACETALDEHYDE CONCENTRATION, studied
a t zero contact time. The rate gives a combined effect of the
variation of both the acetaldehyde and oxygen concentrations.
T h e initial rates are determined by differentiating the poly-
nomial and evaluating the rate at zero time. Thus, if,
x = at + bt2
then E
Capillary diameter :O ~ J l O c m .
ro = (dx/dt),,o = a
e-44.C //*4c
The plot (Figure 10) of initial rates, thus obtained, against .-49.C
acetaldehyde concentration, for various temperatures for the 0.35 A-56.C ,, ,

'"4 f l
0.301
bubble size of 0.00471 cc. shows that r is directly proportional
to Cat. A similar result is also obtained for other bubble sizes. 0.25-

This behavior is expected both from chemical reaction and 0.2 A

diffusion mechanisms.
OXYGEN CONCENTRATION. The rates for different oxygen
concentrations are evaluated from the differentiated poly-
nomials because the oxygen concentration of the bubble
0 10 20 30 40 0 10 20 30 40
varies with the contact time.
Acetaldehyde concentration I%b y wt.1
The rates of oxygen utilization are plotted against concentra-
tion in Figure I 1 for one capillary diameter. The figure Figure 10. Initial rate vs. acetaldehyde concentration
indicates a linear relationship. Similar relationship is in-
dicated for other capillary diameters. Here again, the rate
may be explained as thLat of diffusion of oxygen or that of first- T h e areas of the bubbles are evaluated and the initial rates
order reaction with respect to it. compared for different areas. Rate change can be quantita-
BUBBLESIZE. The bubble size can influence the rates by tively expressed for all the bubble sizes studied by taking their
changing the velocity of the bubble and the interfacial area. interfacial area into consideration.

VOL. 6 NO. 1 JANUARY 1967 143

 considered to be proportional to its local concentration.
By making further assumptions of low solubility of the gas and
Capillary diameler : O.II3cm.
Acetaldehyde -Acetic acid immediate attainment of steady state in the liquid film, the
Concentrationl% by wl.) equation governing the diffusion rate is
0-40'60
- 30 : 70
1-20! 80
e--10 : 90

the boundary conditions being :

At Z = 0, CA = CAo
- 0.10-

At Z = 6, CA = CAa
Temperature 56. C
The solution of the above equation, given by Bird, Stewart,
and Lightfoot ( I ) , is

CA/CAO=
r sinh bl< + sinh bl (1 - <)
sinh 61

in which = Z/6, r = CAa/CAo, and 61 = d k m

Further, the mass flux is given by
I C
0.18 0.19 0.20 0.21 0.18 0.19 0.20 0.21
v ~ x mypen
, ~ concpnlrotion,~A,~ram
mole /cm3

Figure 1 1. Rate of oxygen absorption vs. oxygen concen-

tration

CATALYST CONCENTRATION. The catalyst concentration is

varied from 0.2 to 1.6% by weight. The influence obtained
is insignificant.
TEMPERATURE. The initial rates vary linearly with tem-
perature as is evident from Figure 12. This departure from
the Arrhenius equation, where the relationship should be Equation 6 is used generally for evaluating apparent film
exponential, can be explained if diffusional rates are important thickness by putting r = 0 and this film thickness can then be
because the diffusivity is proportional to the temperature used in Equation 5 to predict the influence of the chemical
raised to the 0.93 power (3). reaction (7).
Development of Rate Equation. Results obtained for the The same procedure was adopted in the present investiga-
effect of temperature show that the diffusion mechanism is the tion. As no correlation exists for evaluating DAB for multi-
rate-controlling step. The extent to which diffusional resis- component diffusion in concentrated solutions, the equation
tances play a part is determined by taking a large amount of proposed by Sitaraman, Ibrahim, and Kuloor (3) for evaluat-
liquid for a small number of bubbles so that the acetaldehyde ing the approximate value was used. The value of CA is
concentration essentially remains constant with chemical known a t the entry point and the (NAZ) value at CAo is the slope
reaction. Thus the rate of disappearance of oxygen can be of the curve of conversion us. time at t = 0, modified to bring the
results to unit area. Thus, DAB = 4.43 X 10-6 sq. cm. per
--
o,,l Capillary diomiter :0~113cm.
second.

0.6

0.5

0.4
-
-
-
spz I Acatoldnhyde -Acetic
Concenfralion I% by wt.)
0 -40:60
acid
NAZ (experimental) = 0.0715 X 10-5 gram mole/sq. cm. sec.

The evaluated 6 = 580 X l o p 6cm.

0.3-
-30 : 70 The values thus obtained and the value of kl' obtained from
A -2O:EO
e -IO :go the stirred tank reactor are substituted in Equation 5 . The
0.2r
term ( b l cosh bl/sinh b l ) in Equation 5 becomes almost equal
-
Do0
01
to unity, from which it can be deduced that the rate of chemical

,/:::::
' ' I I ' C I ' L

- 0 7 14 21 28 35 42 49 56 63 reaction is extremely fast and can be completely neglected for

go 45-
- the rate equation of the sparger reactor. Under these condi-
0 40-Copillary diameter : 0 , i 8 4 c m Capillary diameter : 0 , 3 1 0
tions,
0.35-
0.30 -
025-

0.20-

0.15- If the above conclusion is correct, the rate of absorption

0.10- 0.10-
without chemical reaction found by independent means must
0.05 - 0.05 - agree with the experimental values.
0.0 ' ' ~ ~ * o ~. o ', , ., , ', , , , For this purpose, use was made of the available equations
(7) for the mass transfer rate from a bubble to a quiescent
liquid. The development assumes toroidal circulation inside
the bubble. The final equation is

144 I&EC PROCESS DESIGN A N D DEVELOPMENT

 where CAo= concentration of oxygen in air = 0.21.
(7) The value of integral [(I - C A O X ) / ~ / -
~ x]dx works out to

Equation 7 was applied for the evaluation of mass flux, the 1 (1 + mI2 1
- -4
5
actual figures being: (1 - m + mz) tan- ___

DAB = 4.43 X 10-6 sq. cm./sec. where

V t = 42 cm./sec. (by photographic means)
D = 0.200 cm.
SA,, = 4.46 X 10-6
O n substituting the above values in Equation 7, the rate of The final equation becomes
mass transfer is found to be 0.0487 X 10-6gram mole/sq. cm.
sec. 6 x 22,400 #J (T,P)
t =
Thus the rate predicted by this equation is about 3070 DAB Ao No CAo
less than the experimentally observed one. This is considered
+ m)
to be a good approximation because the evaluation of both
D A B and SA, is approximate. The equation for D A B is recom-
mended only for dilute solutions, whereas it has been used here
1 (1 1
--
d3tan- v5 2m-11
~

(11)
for concentrated solutions and for multicomponent diffusion. For easy calculations the values of the integral
Further, the values of SA, for oxygen in mixtures of acetic acid
and acetaldehyde are not available in the literature and the (1 - CAo X ) l 3 dx
value of SAo employed is for nitrogen in acetic acid. (1 - 4
The above discussion indicates that the rate of reaction with are given in Table I1 for various values of x .
diffusion in a sparger reactor can be expressed by an equation
Equation 11 contains the ratio DABIS. As no reliable corre-
of the following form:
lation could be found in the literature giving the value of D A B
as a function of composition and temperature of the mixture,
D A B / 6 was empirically expressed in terms of acetaldehyde
concentration, C,, as
where DAB/6is a function of both acetaldehyde concentration
DAB
and temperature. - = KC,,
The NA of Equation 8 can be expressed as 6

The K at various temperatures could be expressed as

_1 dx
_
A dt K = (a + bT)
where A = A I N , , A I being the area of one bubble and No, the values of constants a and 6 being graphically obtained.
the number of bubbles. Further, C , can be expressed in The equation therefore is :
terms of conversion as
Oxygen moles 1 _ - [--11.4 X 10-4
DAB
6
+ 0.625 X T ] C,, (12)
total moles 22,400 6 ( T , P )
Substituting the above expression in Equation 11 we obtain
where + ( T , P ) is the volume correction for the existing tempera- the final equation,
ture and pressure.
Equation 8 with the above substitution becomes 22,400 $I (T,P)
t =
(-11.4 X + 0.625 X T ) CaJoNoCAo X
CAo - CAo
AikO dds DY[
- 0.79 + CAo - CAOX 1 1
22,400 6 (T,P)
Equation 9 cannot be integrated as it stands because A I
(9) 1 (1 + m) - -1
ditan -l

changes as the conversion proceeds. Thus it is necessary to The above equation is applicable a t any temperature and
express the area in terms of conversion. concentration within the range of these variables studied.
For a definite contact time, t , the conversion of oxygen, x ,
Total area per mole a t any conversion = can be evaluated by the trial and error method. However,
A,N0(0.79 + CA0)/(0.79+ CAO - C A O X ) - ~ ~ its applicability in the present case has been checked by evalua-
ting t for various values of x, and comparing it with the experi-
As the number of bubbles remain the same irrespective of mental t .
the extent to which the conversion has proceeded, the value of
No remains constant. Thus Equation 9 becomes
1 Table 11. Values of the Integral ( 1
at Various Values of x
CAox)/(l - - x)dx
A,N, [0.79 f CA, - CA,X
x Integral Values
0.00 0.568
0.05 0.036
0.10 0.099
Rearranging Equation 10 we obtain 0.15 0.163
0.20 0.226
0.25 0.290
0.30 0.354

VOL. 6 NO. 1 JANUARY 1967 145

 The calculated and experimental t for various values of x, 4 0 area of a bubble before reaction, sq. cm.
=
plotted in Figure 13, results in a straight line of slope 1. The Ai area of a bubble after reaction, sq. cm.
=
present equation predicts the performance of a sparger reactor CA concentration of oxygen
=
CA, initial concentration of oxygen
=
satisfactorily.
CAa concentration of oxygen a t 6
=
C,, concentration of acetaldehyde
=
D bubble diameter, cm.
=
binary diffusivitiy for system A-B, sq. cm./sec.
=
la7 - DAB
AE = molal activation energy, cal./gram mole
1.6 - k = chemical reaction rate constant, gram mole/cc. min.
1.5-
kl I = chemical reaction rate constant, sec.-1
K = proportionality constant
14 - (NA),,= average rate of mass transfer of A , gram mole/sq.
1.3 - cm. sec.
NAz = molar flux, gram mole/sq. cm. sec.
No = number of bubbles in one mole of gas
T = rate of reaction, gram mole/cc. min.
= initial rate of reaction, set.-'
2 = universal gas constant, cal./gram mole O C.
SAo = solubility of nitrogen in acetic acid
t = time of contact, sec.
T = temperature, K.
Vt = terminal velocity of rising bubble, cm./sec.
X = conversion, moles of oxygen absorbed/mole of
oxygen at the inlet
Z = rectangular coordinate, cm.
6 = film thickness, cm.
CAS
7 = dimensionless concentration variable defined by -
CAO
1: = dimensionless position variable defined by Z/g

literature Cited

Figure 13. Comparison between calculated and experi- (1) Bird, R. B., Stewart, W. E., Lightfoot, E. N., Transport
mentally found ts Phenomena, pp. 535, 541, Wiley, New York, 1960.
( 2 ) Kumar, R., Kuloor, N. R., Brit. Chem. Eng. 9,400 (1964).
( 3 ) Sitaraman, R., Ibrahim, S. H., Kuloor, N. R., J . Chem. Eng.
Nomenclature Data 8, 198 (1963).
A = frequency factor RECEIVED
for review May 3, 1966
A = area of a bubble, sq. cm. ACCEPTED September 27, 1966

FORMATION OF SPHERES FROM FINELY

DIVIDED SOLIDS IN LIQUID SUSPENSION
C. E. CAPES AND J . P. SUTHERLAND
National Research Council, Ottawa 7, Canada

Finely divided solids suspended in a liquid are caused to agglomerate by agitating the suspension with a
small amount of a second (bridging) liquid which preferentially wets the solid. Spherical agglomerates can
be produced in a specially designed vessel shaken in a reciprocating fashion. The agglomeration of sands
of various size distributions suspended in organic liquids and collected with aqueous solutions has been in-
vestigated as a model system. Spherical agglomerates were generally formed when the bridging liquid
filled between 44 and 81 yo
of the voids between the highly compacted sand particles. The ways in which
the sphere size attained in the process may be controlled have also been investigated. The results are
consistent with the postulate that the sphere size represents a balance between the destructive and cohesive
forces acting on the agglomerates.
investigation concerns the process known as spherical
HIS liquid and to agglomerate, being held together by the second
Tagglomeration developed by Puddington et al. (6, 72) (or bridging) liquid.
Research into this agglomeration process has been directed
at the National Research Council of Canada. By this process,
finely divided solids in liquid suspension are agglomerated and along two main lines, selective agglomeration and spherical
separated from the suspending liquid by the addition of a agglomeration. In selective agglomeration, one suspended
small amount of a second liquid which preferentially wets the solid can be separated from other suspended solids as well as
solid and is immiscible with the first liquid. Subsequent from the suspending liquid by judicious zhoice of surface
agitation causes the solids to become coated with the second conditioning agents (as is done in the flotation of minerals)
and of bridging liquids. The shape of the agglomerates
produced in this case is not usually important. Examples of
Present address, Chemcell (1963), Ltd., Edmonton, Alberta,
Canada. this separation technique have been given by Farnand, Smith,

146 l&EC PROCESS DESIGN AND DEVELOPMENT