Application of Ultrasound in Extractive

Metallurgy: Sonochemical Extraction of Nickel

BATRIC PESIC and TAILI Z H O U
The importance of ultrasound in solvent extraction was examined by studying solvent extraction
of nickel with Lix 65N and Lix 70 extractants. The studied parameters were ultrasonic energy
and frequency, pH, temperature, and organic and aqueous solution composition. The stability
of extractants under the influence of ultrasound was also examined. It was found that ultrasound
had a significant importance, because it increased the extraction rates four- to sevenfold. The
effect of ultrasound was physical, i.e., to increase the surface area. Ultrasonic energy consumption was also evaluated. The consumption was high, but it can be significantly reduced
by the appropriate method of application. A novel solvent extraction method, extraction-in-pipe,
was also proposed.

I.

INTRODUCTION

U L T R A S O U N D assists heterogenous processes such

as flotation, r~l leaching, ~zj electrometallurgy, t3~ filtering, I41 drying, ~51 and others. It is believed that cavitation
(bubble formation and implosion), microstreaming, radiation pressure, acoustic pressure, and degassing account for ultrasound's advantages.
Solvent extraction is another typical heterogenous
system that involves two distinct and immiscible phases.
In such a system, ultrasound, because of its compression
and expansion, can tear the liquid droplets, increasing
the contact area between the immiscible organic and
aqueous phases through emulsion and dramatically increasing the rate of extraction. In addition to its emulsifying effect, ultrasonic energy further increases solvent
extraction through (1) enhanced local agitation, (2) induced-circulation currents, (3) prolate-oblate oscillations
inside the liquid drop, and (4) the removal of stagnant
liquid near the interface between the organic and aqueous
phases. [6~
Most of the studies on solvent extraction with ultrasound have been done on nonmetallic liquid-liquid extraction systems, those controlled by mass transfer. Only
a few studies have been done on the solvent extraction
of metals, f6,7,8] However, many systems for solvent extraction of metal are controlled by chemical reaction
mechanisms that may also benefit from ultrasound.
To study the role of ultrasonic energy in solvent extraction, two typical chelating solvent extraction systems
were selected, one acidic and the other strongly basic.
The basic system was used in the extraction of gallium
with Kelex 100, as reported earlier by Pesic and Z h o u . [9]
The present work studies the role of ultrasound on solvent extraction of metals from acidic solutions. The solvent extraction of nickel with hydroxyoxime extractants

BATRIC PESIC, Associate Professor of Metallurgy, and TAILI

ZHOU, Research Associate, are with the College of Mines, University
of Idaho, Moscow, ID 83843-4199.
Manuscript submitted March 11, 1991.
METALLURGICAL TRANSACTIONS B

was selected for study because of nickel's slow rate of

extraction.
The hydroxyoxime-carboxylic acid system for the selective extraction of nickel from cobalt in acidic sulfate
solutions was first recommended by Flett and West. ~t~
They found that when carboxylic acid was added to
c~-hydroxyoxime (Lix 63), a synergistic effect occurred,
increasing the yield of nickel significantly. However, the
rate of extraction was so slow that it took about 3 hours
to reach equilibrium, a phenomenon that may be linked
to the presence of carboxylic acid at the interface, as
indicated by the interracial tension determination.[~ L,~2,13]
However, because of the complicated extraction mechanism, the slow extraction rate of nickel was not fully
explained. Several ways to increase the extraction rate
have been suggested. Nyman and Hummelstedt ~41 reported that the type of diluent and its temperature considerably influenced the extraction rate. They suggested
the addition of a D N N S A (dinonylnaphthalene sulfonic
acid) surfactant into the systems Lix 65N + Versatic 911
or Lix 70 + Versatic 911 to accelerate the rate of nickel
extraction. Hummetstedt et al.,f~5~ who studied the synergistic phenomena between Versatic 911 and Kelex 100,
recommended raising the temperature to increase the extraction rate. Flett et a / . [161 proved that adding Versatic 911
to Kelex 100 can induce an interaction between these
two extractants that prevents the oxidation and extraction
of Co(lI) and increases the separation of nickel from
cobalt.

II.

EXPERIMENTAL

A. Reagents
The following reagents were used: Lix 65N and Lix 70
(Henkel Corporation, lot no. 82B265010 and 8J16029,
respectively), lauric acid (Eastman Kodak Co.), and dinonylnaphthalene sulfonic acid (Pfaltz and Bauer Inc.).
Other chemicals used were Kermac 470B (Triangle
Refineries Co.), Escaid 200 and Aromatic 150 (Exxon
Co.), and N i S O a ' 6 H 2 0 and KNO3 (analytical reagent
grade).
VOLUME 23B, FEBRUARY 1992--13

B. Apparatus and Procedure

A baffled reactor (inner diameter, 71 mm; height,
85 mm) was specially designed to withstand vigorous
stirring by a turbine-type TEFLON* stirrer (diameter,
*TEFLON is a trademark of E.I. Du Pont de Nemours & Co., Inc.,
Wilmington, DE.

25 mm; height, 5.5 mm). Two TEFLON baffles, 13 x

80 mm, were mounted near the wall of the reactor.
The reactor cover was designed to accept an ultrasonic
horn, a mechanical stirrer, and a sampler. Ultrasound
was produced with a Branson Model 184V ultrasonic
generator and a Branson Model 102 convertor. A 1-in.
titanium horn was used to deliver ultrasonic energy at a
frequency of 20 KHz into the solvent extraction system.
The standard ultrasonic energy output was 47 W. Constant temperature conditions were maintained by circulating water cooled by an immersion cooler. The schematic
representation of the experimental apparatus is given in
Figure 1.
The (nickel-free) organic and aqueous phases were
transferred into the reactor, and the ultrasound was turned
on. After the equilibrium temperature was reached, 1 ml
of nickel stock solution was added. Samples of the solution were taken at fixed intervals and immediately centrifuged, and the aqueous phase was analyzed for nickel
by atomic absorption. The rate of nickel solvent extraction was determined from the rate of change of nickel
concentration in the aqueous phase.
The standard experimental conditions were as follows.
The organic phase consisted of 100 ml of 10 pct ( v / v )
Lix 65N (or Lix 70) + 0.1 M lauric acid dissolved in
Kermac 470B. The aqueous phase consisted of 100 ml

of 30 mg Ni2+/1 and 1 M KNO3. The standard temperature was 25 ~ and the stirring speed was 2000 min -1.
III.

RESULTS AND DISCUSSION

A. Effect of Stirring Speed

To simplify the study, it was essential to run experiments in a kinetically limited region. Figure 2 indicates
that when the stirring speed was higher than 2000 rain-1
the extraction rate for both the Lix 65N and the Lix 7lJ
systems was independent of the stirring speed. Therefore, a stirring speed of 2000 min- ~was used in all other
experiments, both with and without ultrasound.
When ultrasound was used, the sonic energy formed
a tremendous number of tiny droplets, whose extreme
turbulence and direction of propagation were visible.
Extraction rates with ultrasound were much greater than
those produced by mechanical stirring. Even though the
contribution of mechanical stirring in sonochemical extraction was small, it was still used to ensure a uniform
distribution of phases in the reactor by bringing the organic and aqueous phases under the ultrasonic horn.

B. Effect of pH
Figures 3 and 4 illustrate the effects of pH on nickel
extraction by the Lix 65N and Lix 70 systems, respectively, both with and without ultrasound. The pH represents initial values, ranging from 4 to 7. The extraction
rate increased with the increase of initial pH until pH =
6.02, above which pH did not have further effect.
The apparent forward reaction rate constant (kf) was
calculated from the slope of the line in the plot [(Co Ce)/Co] In [(Co - C~)/(C, - C~)] vs time, the method

Fig. 1 - - S c h e m a t i c representation of the experimental apparatus for solvent extraction with ultrasound.
14--VOLUME 23B, FEBRUARY 1992

METALLURGICAL TRANSACTIONS B

100 I

100

RPM

I
/

[] 9 1000

o 9 1500

o 9 2000
* * with

& 9 2500

LIX70

ultrasound
(at 2000 rpm)

8 0 -1

I@I 8O
Iii
}- 6O
r

x~ 40

I-- 4 O
X

ILl
9--

U.I

20

"

no ultrasound
with ultrasound
pH
kf
pH
kfund

20

o 4.02
zx 5.05
[] 6.02
o 7.03

solid, I.IxT0 s y s t e m

0
0

20

40

60

80

100

120

140

160

180

20

40

TIME, rain

developed by Flett et al. ,[12] where C = the nickel concentration in the aqueous phase, inferior t = the extraction time, inferior 0 = the initial state, and inferior e =
the equilibrium state. The solvent extraction rate constants, kl, for each extraction system, are presented in
tables in corresponding figures (Figures 3 and 4).
A comparison of the rates of conventional and ultrasound extractions shows that ultrasound increases the extraction rate of nickel by as much as 4 to 7 times. The
extraction rates in the Lix 65N system were faster than
those in the Lix 70 system, which required about 1 hour
to reach equilibrium even with ultrasound. However, the
uptake of nickel was higher with the Lix 70 system than
with the Lix 65 system. The slower kinetic performance
of the Lix 70 system was caused by steric effects. The

100 120 140 160 180 200

C. Effect of Temperature
The effect of temperature on the solvent extraction of
nickel was studied in the range of 25 ~ to 50 ~ Both
extraction systems, Lix 65N (Figure 5) and Lix 70
(Figure 6) were examined. According to the results presented in Figures 5 and 6, temperature had a positive

60 1
LIX65N

LIX65N

40

40

LU
!-- 30
O

0
I--" 20
X
till

with ultrasound

p.

k,

-i/7,/?'

o 402

322

~ff

zx 5.05
[] 6.02
o 7.02

3.46
3.79
4.27

10

7.83
10.1
12.0Z0
13.0

bulky chlorine atom at the ortho position of the phenolic

hydroxyl group in the molecule of Lix 70 diminished the
possibility of a complexation reaction, causing the slower
extraction rates. On the other hand, the inductive effect
of the chlorine atom, because of its electronegativity,
increased the dissociation of the hydrogen ion in the phenolic hydroxyl group and increased the extraction capacity of the extractant.

80

9 4.02
9 5.05
9 6.02
9 7.03

Fig. 4 - - E f f e c t of pH on nickel extraction with Lix 70-1auric

acid-Kermac 470B. Organic phase: 10 pct ( v / v ) Lix 70; 0.1 M lauric
acid; Kermac 470B. Aqueous phase: 30 mg/l Ni2"; 1 M KNO3. Ratio
of O / A : 100 m l / 1 0 0 nal; T = 25 ~ stirring rate = 2000 rpm; ultrasound: 20 KHz, 47 W.

50
t

60

1.43
2.67
2.85
2.79

TIME, rain

Fig. 2 - - S t i r r i n g rate effect on solvent extraction of nickel with

Lix 65N-lauric acid-Kermac 470B and Lix 70-1auric acid-Kermac 470B.
Organic phase: 10 pct (v/v) Lix 65N or Lix 70; 0.1 M lauric acid;
Kermac 470B. Aqueous phase: 30 rag/1 NiZ+; 1 M KNO3; pH~: =
5.05. Ratio of O / A : 100 m l / 1 0 0 ml; T = 25 ~ ultrasound: 20 KHz,
47 W.

~4~

zx

20

40

60

9
9
9
9
80

pH
4.02
5.05
6.02
7.02
100

kf
13.7
16.5
19.8
33.4

20

nd

It//6

I~r
~/
,LF"

o 25
zx 40
m 50

O~

120

TIME, rain
Fig. 3 - - E f f e c t of pH on nickel extraction with Lix 65N-lauric
acid-Kermac 470B. Organic phase: 10 pct (v/v) Lix 65N; 0.1 M lauric
acid; Kermac 470B. Aqueous phase: 30 rng/l Ni-~+; 1 M KNO3. Ratio
of O / A : 100 m l / 1 0 0 ml; T = 25 ~ stirring rate: 2000 rpm; ultrasound: 20 KHz, 47W.
METALLURGICAL TRANSACTIONS B

tU

20

c/

k,
3.46
5.78
13.70

rl~
9 25
9 40
9 50

k,
16.5
27.1
37.1

40

60

80

100

TIME, rnin
Fig. 5 - - T e m p e r a t u r e effect on nickel extraction with Lix 65N-lauric
acid-Kermac 470B. Organic phase: 10 pct (v/v) Lix 65N; 0.1 M lauric
acid; Kermac 470]3. Aqueous phase: 30 m g / l Ni2+; 1 M KNO3; pH~.~,
= 5.05. Ratio of O / A : 100 m l / 1 0 0 ml; stirring rate = 2000 rpm;
ultrasound: 20 KHz, 47 W.
VOLUME 23B, FEBRUARY 1992-- 15

100

1~

trolled b y the rate o f dehydration. Ultrasound can override the contribution o f thermal energy to d e h y d r a t i o n
and the diffusion o f gallate ions. O n the other h a n d , the
rate at which water is r e m o v e d from the shell o f m o l e cules surrounding the nickel ion is several thousand times
faster, but this step is unimportant during the solvent extraction o f nickel. T h e intermediate c o m p l e x o f nickel
and c a r b o x y l i c acid reacts slowly with the m o l e c u l e o f
h y d r o x y o x i m e , and this reaction rate controls the overall
solvent extraction r a t e J 12]
The overall reaction of nickel extraction can be represented b y Eq. [1]:

80

60

40

LII
@/
Ol r
0

o 25
t, 40
t3 50

2.67
7.92
13.30

9 25
9 40
9 50

10.1
23.6
49,3

20

40

60

80

100

120

140

Ni 2~ + 2HOXorg
160

+ 2RHorg

TIME, rain
Fig. 6--Temperature effect on nickel extraction with Lix 70-1auric
acid-Kermac 470B. Organic phase: 10 pct (v/v) Lix 70; 0.1 M lauric
acid; Kermac 470B. Aqueous phase: 30 mg/l Ni2 1 M KNO3; pH~,
= 5.05. Ratio of O/A: 100 ml/100 ml; stirring rate = 2000 rpm;
ultrasound: 20 KHz, 47 W.

effect on the solvent extraction rates o f nickel in both

extraction systems and under both conditions, with and
without ultrasound. This conclusion can also be m a d e
from the calculated extraction rate constants, ks, which
are presented in tables in the c o r r e s p o n d i n g figures
(Figures 5 and 6). These extraction rate constants were
used to calculate the activation energies o f extraction.
F o r extraction with Lix 65N, the activation energy without ultrasound was 42.4 k J / m o l e and the activation energy with ultrasound was 35.8 k J / m o l e . F o r extraction
with Lix 70 without and with ultrasound, the activation
energies were 52.1 k J / m o l e and 50.1 k J / m o l e , respectively. T h e s e values indicated that the solvent extraction
o f nickel by both Lix 65N and Lix 70 was c o n t r o l l e d by
a c h e m i c a l reaction.
The high activation e n e r g y for the s o n o c h e m i c a l extraction o f nickel with the Lix reagents presents a striking contrast to the zero activation e n e r g y o b t a i n e d during
the sonochemical extraction o f gallium with Kelex 100.r91
This p h e n o m e n o n can be explained b y the difference in
the species and the c o m p o s i t i o n o f the two extraction
systems. G a l l i u m , in a strong basic m e d i u m , is present
as a gallate ion, G a ( O H ) 4 - , which is surrounded with a
shell o f water molecules. According to Zhou and Pesic, I~7~
the solvent extraction o f g a l l i u m with K e l e x 100 is con-

K q NiOX2(RH)2org + 2H +

[1]

for which the concentration e q u i l i b r i u m constant, Kex,

can be calculated from the mass action law, Eq. [2]:
K~x = [H+]2[NiOX2(RH)i]org/[Ni 2+] [HOX]2org[HR]2org

[2]
where [NiOX2(RH)2]org is the concentration o f nickel in
the organic phase, [HOX]o~g is the concentration o f hyd r o x y o x i m e , and [RH]o,g is the concentration o f lauric
acid.
The value o f K~., can be calculated from the m e a s u r e d
pH values and concentrations o f nickel in the organic
and aqueous phases. The concentrations o f o x i m e s and
lauric acid were a s s u m e d to be constant, b e c a u s e they
were much higher than the concentration o f nickel. The
equilibrium constants as a function o f t e m p e r a t u r e are
given in T a b l e I.
The Rex values in Table I were used to calculate the
enthalpy c h a n g e o f nickel extraction by the V a n ' t H o f f ' s
equation, In Kex = -AH~
+ C. T a b l e II shows the
calculated A H ~ values o f nickel extraction.
The positive enthalpy changes characterized the nickel
extraction reactions with the h y d r o x y o x i m e extractants
as endothermic.

D. Effect of Diluents
K e r m a c 470B was used as a standard diluent in this
study. Because it contains about 17.3 pct aromatic c o m pounds, the contribution o f such c o m p o u n d s to the solvent extraction o f nickel was e x a m i n e d . The use o f
toluene, a representative aromatic c o m p o u n d , as a diluent during the solvent extraction o f nickel with Lix 70

Table I. Effect of Temperature on the Equilibrium Constant of

Nickel Extraction, K,~, Calculated from Data in Figures 5 and 6

Lix 65N/lauric
acid/Kermac 470B
Temperature
(~

Without
Ultrasound

With
Ultrasound

25
40
50

1.16 10 -5
2.40 x 10 -5
5.53 t0 -5

1.12 x 10 -s
3.03 x 10 -5
5.47 10 -5

16--VOLUME 23B, FEBRUARY 1992

Lix 70/lauric
acid/Kermac 470B
Without
Ultrasound
2.73 10 -5
6.63 x 10 -5
1.05 x 10 -4

With
Ultrasound
3.44 x 10 5
8.47 x 10 -5
1.10 x 10 -4

METALLURGICALTRANSACTIONSB

Table II. Enthalpy Change for Nickel

Extraction With and Without Ultrasound

0.6
. 0.5

&H, KJ/mole
Lix 65N/lauric
acid/Kermac 470B
Without
Ultrasound
48.8

With
Ultrasound
50.8

open: No ultrasound
solid: with ultrasound

Lix 70/lauric
acid/Kennac 470B
Without
With
Ultrasound
Ultrasound
43.4
38.1

Lix70

tit
O3

-1- 0.4

o
z

0.3
0.2

decreased extraction rates (Figure 7). The uptake, however, was significantly higher. For example, with ultrasound, the equilibrium uptake of nickel with toluene was
90 pct, as compared to the equilibrium uptake of 63 pct
with Kermac 470B.
The slower extraction rates are explained by the strong
solvency of the aromatic compound. The aromatic diluent also causes the extractant molecule (Lix 70) to be
predominantly inside the droplets of organic phase instead of at the interface. The increased uptake is explained by the increased solubility of the chelated complex
in the aromatic solvent.

0
._= 0.1

65N

,,,
-

Z
O

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

Ni in AQUEOUS PHASE, g/I

Fig. 8 - - E x t r a c t i o n isotherms of nickel extraction with Lix 65N-lauric
acid-Kermac 470B and Lix 70-1auric acid-Kermac 470B. Organic phase:
10 pct (v/v) Lix 65N or Lix 70; 0.1 M lauric acid; Kermac 470B.
Aqueous phase: Ni2+; 1 M KNO3; pHoq = 3.2 to 3.3 (for Lix 65N);
2.9 to 3.1 (for Lix 70). T = 25 ~ stirring rate = 2000 rpm; ultrasound: 20 KHz, 32.5 W.

E. Effect of Nickel Concentration

The effect of nickel concentration was examined by
comparing the results at two different initial nickel concentrations, 30 and 300 mg N i / L . In the absence of
ultrasound, the extraction rate, with Lix 70, from solution containing 300 m g / L of nickel was about 2.5 times
lower than the rate from 30 mg N i / L . Application of
ultrasound to the system with 300 m g / L of nickel increased the rate of extraction by about 3 times. Ultrasound did not enhance the capacity of the extractant in
the system studied.

F. Effect of Ultrasound on Extraction Isotherms

The equilibrium loading isotherms for solvent extraction of nickel with Lix 65N and Lix 70 are shown in

Figure 8. The open symbols represent the solvent extraction results without ultrasound, and the closed symbols represent the sonochemical extraction results. No
effect of ultrasound on the equilibrium of extraction was
demonstrated.

G. Extraction of Cobalt and Separation of Cobalt

and Nickel
The effect of ultrasound on the solvent extraction of
cobalt was studied in the Lix 70 + lauric acid +
Kermac 470B system, and the results from pH variation
are presented on Figure 9. In this system, the extraction
rate of cobalt, like that of nickel, was slow, failing to

100

L,

pHina

open: no ultrasound
solid: with ultrasound

o 9 404

8O

LIX70

t, 9 5105

8o

Soo
o

[]

,,

~x 4o
,~ 40
Ill

u.I

~
20 ~

open: no ultrasound i ~ 9 Kermac470Btl

solld', wlth ultrasound In 9 Toluene
II

~[
0

60

120

180

240

300

TIME, rain
Fig. 7 - - D i l u e n t effect on solvent extraction of nickel with Lix 70-1auric
acid. Organic phase: 10 pct (v/v) Lix 70; 0.1 M lauric acid. Aqueous
phase: 30 mg/1 Ni 2 1 M KNO3, pHinit = 5.05. Ratio of O / A : 100
m l / 1 0 0 ml; stirring rate = 2000 rpm; ultrasound: 20 KHz, 47 W.
METALLURGICAL TRANSACTIONS B

20

60

120

180

240

TIME, rain
Fig. 9 - - E f f e c t of pH on cobalt extraction with Lix 70-1auric
acid-Kermac 470B. Organic phase: 10 pct (v/v) Lix 70; 0.1 M lauric
acid; Kermac 470B. Aqueous phase: 30 mg/1 Co2+; 1 M KNO3; pHi,,
= 5.05, Ratio of O / A : 100 m l / 1 0 0 ml; T = 25 ~ stirring rate =
2000 rpm; ultrasound: 20KHz, 47 W.
VOLUME 23B, FEBRUARY 1992--17

reach equilibrium even after 3 hours. Ultrasound substantially increased the cobalt extraction rate, so that an
increase in extraction uptake from about 30 pct in the
regular system to about 70 pct with ultrasound was
achieved in 3 hours. However, cobalt stripping from the
organic phase loaded with ultrasound was difficult, especially when loading was performed at a higher initial
pH. Cobalt stripping was possible only with the addition
of a reductant, such as sodium sulfite. In extraction systems without ultrasound, the cobalt(II) extracted with
substituted hydroxyoxime alone can be oxidized to a
Co(Ill) state. The organic phase in which cobalt(II) is
converted to Co(Ill) becomes very difficult to strip. 118)
The addition of a carboxylic acid as a modifier diminishes the oxidation of cobalt in the organic phase. The
interfacial activity of lauric acid slows down the oxidation of cobalt by minimizing the interfacial oxidation
reaction.
During solvent extraction from solutions containing a
mixture of Ni and Co, the presence of nickel suppressed
cobalt extraction. Figure 10 shows that without ultrasound, the equilibrium of cobalt extraction, 12.8 pct, was
quickly achieved (after 10 minutes), while the extraction
of nickel continued throughout the experiment, increasing the separation of nickel from cobalt. With ultrasound, the situation was reversed (Figure 11). Cobalt
extraction continued throughout the experiment, while
nickel extraction reached equilibrium, 61.4 pct, after only
30 minutes. Comparison of the cobalt extraction results
presented in Figures 9 through 11 indicates that without
ultrasound the reaction equilibrium state for cobalt may
not be completely reached and that the obtained plateau
is only the result of an extremely slow reaction. When
ultrasound was added, the extraction of cobalt corresponding to the plateau in Figure 11 continued toward
the true equilibrium position. Unfortunately, the short
duration of the experiment prevented the true equilibrium position of cobalt from being reached. The cobalt
extraction results without ultrasound slowly approach the
corresponding results with ultrasound.

H. Effect of Surfactants
Surfactants play an important role in the kinetics of
solvent extraction of metals. The addition of DNNSA
surfactant, even at a low concentration, increased the extraction rate of nickel in the hydroxyoxime/lauric acid/
Kermac 470B system through enhancement of the interfacial area between the two immiscible phases during
their mixing. Also, the active sulfonic acid molecule has
a preferential position against other extractant molecules
at the interface and can itself take up nickel. [19]
Table III, which compares the effects of DNNSA surfactant and ultrasound in increasing extraction rate by
the formation of microemulsions, shows that ultrasound
had a stronger effect than the addition of DNNSA. In
general, oil and water systems require an appropriate
surfactant and cosurfactant to form an emulsion.
Bauer and Komornicki [2~ used sodium laurylsulfate and
n-pentanol instead of D N N S A to produce a microemulsion in the Lix 70/Versatic 911/kerosene system, obtaining a very fast nickel extraction kinetic. These
surfactants were not compared with the ultrasound in this
study.
18--VOLUME 23B, FEBRUARY 1992

L,X

100

u.I
I0
<
n"
IX
U.I

80

10

r./)
i'n
"lg

z
-irl

60

--I

0
40

20

Z
B.

3
0

o
0

20

40

60

80

100

120

140

160

TIME. rain
Fig. 1 0 - - S o l v e n t extraction of Ni and Co with Lix 70-1auric
acid-Kermac 470B in the absence of ultrasound. Organic phase: 10 pct
(v/v) Lix 70; 0.1 M lauric acid; Kermac 470B. Aqueous phase: 30
m g / l Co 2 and 30 mg/1 Ni2"; 1 M KNO3; pHio~, = 5.05. Ratio of
O / A = 100 m l / 1 0 0 ml, T = 25 ~
stirring rate = 2000 rpm.
SF = {[Ni]0/[Ni]a}/{[Co]o/[Co]a}.

100 1

ux70

,"

d8~

" -

i .z

60

40

0, 0

20

40

. 60 .

.80

100

1;0

120

~176

T I M E , rain
Fig. l l - - S o l v e n t extraction of Ni and Co with Lix70-1auric
acid-Kermac 470B in the presence of ultrasound. Organic phase: 10 pct
(v/v) Lix 70; 0.1 M lauric acid; Kermac 470B. Aqueous phase: 30
m g / l Co 2+ and 30 m g / l Ni2+; 1 M KNO3; pHi., = 5.05. Ratio of
O / A : 100 rnl/100 ml; T = 25 ~ stirring rate = 2000 rprn; ultrasound: 20 KHz, 47 W.

Table III. C o m p a r i s o n o f the Effects o f D N N S A

as a S u r f a c t a n t a n d U l t r a s o u n d on Nickel E x t r a c t i o n

Time to
Equilibrium
(Min)
Ultrasound
(47 W/cm 2)
No
Yes
No
Yes

Surfactant
(mole/l)

Lix 65N
System

Lix 70
System

No
No
0.005M DNNSA
0.005M DNNSA

60
10
30
--

150
60
140
60

Organic: 10 pct (vol.) hydroxyoxime/0.1 M lauric acid/Kermac

470B. Aqueous: 30 mg Ni2"/l; 1 M KNO3; pH~n~ = 5.05. O / A ratio
= 100 m l / 1 0 0 ml; T = 25 ~ stirring = 2000 m i n i .

METALLURGICAL TRANSACTIONS B

I. Stability of the Extractants

Two tests were performed to detemine whether the
powerful cavitation effects produced by ultrasound can
degrade the extractant molecules. In the first test of the
stability of the extractant molecules, a dried and undiluted sample of Lix 65N was continuously irradiated for
6 hours at 60 ~ with ultrasound at a 47 W intensity.
Samples of Lix 65N taken before and after irradiation
were inspected with infrared (IR) and nuclear magnetic
resonance (NMR) spectroscopy. Identical IR and NMR
spectra were obtained, indicating that Lix 65N did not
undergo any change.
In the second test, multiple cycles of loading (under
standard conditions) and stripping (2N H 2 8 0 4 , T = 25 ~
time = 15 minutes) of the organic phase were performed. If ultrasound degraded the stability of the extractant molecule, then the extraction of nickel would
have deteriorated with the number of cycles. The almost
identical results (about 27.8 pct extraction) in each of
five multiple-cycle tests performed with the Lix 65N/lauric
acid/Kermac 470B system indicated that the Lix 65N
molecule did not undergo any change.

J. Effect of Ultrasonic Frequency

The frequency of ultrasound is an important parameter
but is also the most difficult to study because of the lack
of equipment with various frequencies. Most of the
available equipment has a low, 20 to 40 KHz, frequency, because its intended use requires strong cavitation effects.
To study the effect of high-frequency ultrasound on
solvent extraction, a separate reactor was designed. A
2 MHz ultrasonic transducer and the electronic components were obtained by dismantling an ultrasonic humidifier. The 1-in. transducer was mounted on the bottom
of a 200-ml reactor made of an acrylic plastic. Experiments were performed by placing 100 ml of organic phase
and 100 ml of aqueous phase into the reactor and then
turning on the ultrasonic power.
High-frequency ultrasound did not have enough power
to cause any mixing of organic and aqueous phases, resulting in very poor extraction of nickel with both Lix 65N
and Lix 70. The absence of cavitation was responsible
for the poor performance of high-frequency ultrasound,
since cavitation effects can be produced only at low frequencies, most intensely in the 20 to 40 KHz range.

K. Energy Consumption
All of the described experiments took place in the continuous presence of ultrasound. In such batch applications, the total energy consumed was prohibitively high
and could not be offset even by the substantially lower
extraction time. However, it was found that continuous
ultrasound was not required for the extraction of nickel.
When ultrasound was briefly applied, then briefly discontinued, and these cycles repeated, no deterioration of
solvent extraction was found. This phenomenon can be
explained by the microdroplets formed in the presence
of ultrasound, which did not disappear immediately after
the ultrasound was turned off. The interfacial area produced allowed extraction to continue even in the absence
METALLURGICAL TRANSACTIONS B

of ultrasound. When a significant number of droplets coalesced, ultrasound was again required to form a new
batch of droplets and to continue extraction.
These observations prompted an examination of the
effect of intermittent ultrasound on solvent extraction of
nickel. The intermittent study was characterized by the
time when the ultrasound was "on" (T) and "off" (To).
The total on plus off time was fixed at 5 seconds; thus,
the frequency of on and off cycles was fixed to 12 per
minute. The ultrasound generator was turned on and off
by a specially built electronic controller. The total energy consumed by the ultrasonic apparatus during extraction was measured by a watt meter (the watt meter
was placed in line between the wall outlet and ultrasonic
generator). The intensity of introduced ultrasound was
also varied. The results (Table IV) show that energy
consumption was lowest when the on time was
0.25 seconds, the off time was 4.75 seconds, and the
ultrasonic input energy was 61 W. Under these conditions, the total consumed energy was 2.66 W per hour.
It is important to note that the on time can be substantially decreased by increasing the intensity of ultrasound,
with an overall decrease in energy consumption. Even
though a higher intensity ultrasound was used, the shorter
on time reduced energy consumption. The higher intensity ultrasound apparently forms more droplets, and
probably smaller droplets, which take a longer time to
coalesce, lengthening the off time.
When a similar study was performed with Lix 70, it
was found that intermittent ultrasound was not as effective as with Lix 65N. The stability of droplets with Lix 70
was much lower than with Lix 65N, causing them to coalesce faster and reducing their interracial area. Thus, to
achieve the same level of extraction, longer on times were
required with Lix 70.
The encouraging results obtained from the intermittent
application of ultrasound suggested that continuous-flow
solvent extraction might also reduce energy consumption. The objective of using a continuous flow was to
simulate the addition of a variable amount of ultrasonic
energy (of the same intensity) by varying the flow rate.
For this study, a separate reactor was designed (Figure 12),
consisting of two holding containers, one for the organic
phase and the other for the aqueous phase, an ultrasonic

Table IV. Ultrasonic Energy

Consumption during Nickel Extraction
with Lix 65N (ultrasound was used intermittently)

Ultrasonic Equipment Setup

Input
On
Off
(W)
Time
Time
21
21
21
21
41
61

0.25
0.50
1.00
2.00
0.25
0.25

4.75
4.50
4.00
3.00
4.75
4.75

Energy
Consumed
(Wh)

Equilibrium
Achieved
After (Min)

9,56
9.41
7.76
6.71
3.81
2.66

90
60
30
15
30
15

Organic phase: 10 pct (vol.) Lix 65N/0.1 M lauric acid/Kermac

470B. Aqueous phase: 30 nag Ni2+/l; 1 M KNO3, pH~o~ = 5.05.
O / A ratio: 100 ml/100 ml; stirring = 600 min -~. Ultrasonic pulsation cycles (on and off) 12 rain J.

VOLUME 23B, FEBRUARY 1992-- 19

Fig. 12--Schematic representation of the apparatus for continuous solvent extraction in the presence of ultrasound.

c h a m b e r , and a r e c e i v i n g container. The ultrasonic

c h a m b e r , which was w a t e r - j a c k e t e d to control the temperature o f extraction, r e c e i v e d the separate organic and
aqueous phases and mixed them by insonation. The mixed
phases were then p u m p e d into a receiving container. The
residence time in the ultrasonic c h a m b e r was varied b y
the p u m p i n g rate o f the organic and aqueous phases, and
the energy c o n s u m p t i o n was m o n i t o r e d b y a watt-hour
meter.
T h e results (Table V) show that the energy c o n s u m p tion, e x p r e s s e d in k i l o w a t t - h o u r p e r cubic meters o f solution, can be r e d u c e d b y decreasing residence time and
increasing the temperature at which solvent extraction

takes place. U n d e r the conditions studied, the lowest ene r g y c o n s u m p t i o n was a c h i e v e d at 26 ~ and at the highest flow rates, 160 m l / m i n . About 33 pet Ni was extracted
under these conditions. H i g h e r flow rates were not exa m i n e d b e c a u s e o f the limitations o f the e x p e r i m e n t a l
setup. Despite this limitation, w h i c h could affect the accuracy o f the calculated c o n s u m p t i o n o f energy, the experiment still clearly indicated h o w energy c o n s u m p t i o n
could be reduced.
The lowest energy consumption obtained, 11 k w h / m 3,
is still too high to c o m p e t e with solvent extraction perf o r m e d b y c o n v e n t i o n a l m i x i n g , where the upper acceptable energy c o n s u m p t i o n limit is about 1 k w h / m 3.

Table V. Ultrasonic Energy Consumption during Solvent Extraction

of Nickel by Using a Continuous Flow of Organic and Aqueous Phases
Flow rate
Organic
(ml/min)

Flow rate
Aqueous
(ml/min)

10
20
40
40
80
160

10
20
40
40
80
160

T (~
15
15
15
26
26
26

Residence
Time (Min)

Ni Extracted
(Pet)

Energy consumed
( K W h / m 3)

10.0
5.0
2.5
2.5
1.25
0.625

15
15
15
33
33
33

176
88
88
44
22
11

The experimental conditions were as follows. Organic: 10 pet (vol.) Lix 65N/0.1 M lauric acid/Kermac 470B. Aqueous: 30 mg Ni:
KNO3; pHini, = 5.05. Ultrasound: frequency = 20 KHz; intensity = 47 W.
20--VOLUME 23B, FEBRUARY 1992

0.5 M

METALLURGICALTRANSACTIONSB

Fig. 1 3 - - S c h e m a t i c representation of the proposed new method of solvent extraction: solvent extraction-in-pipe, possible because the extraction
rates are significantly enhanced with ultrasound.

However, the results from the continuous-flow and intermittent ultrasound experiments clearly suggest that
optimization studies may show how to further reduce energy consumption. The most promising solvent extraction technique may be the one that utilizes a pipe for
mixing the organic and aqueous phases, with properly
spaced ultrasonic horns inserted through the pipe wall
(Figure 13). In this kind of a plant, in addition to the
composition of aqueous and organic phases, the other
important process parameters would be the flow rate in
the pipe, the size of ultrasonic horns, the spacing of
ultrasonic horns, and the ultrasonic input energy. The
pipe length between a leaching reactor and a settler would
serve as a mixer, thus avoiding the need for a mixer as
in the traditional mixer/settler design.
IV.

CONCLUSIONS

1. Ultrasound dramatically improved solvent extraction

of nickel with Lix 65N and Lix 70, increasing the
extraction rate four- to sevenfold.
2. Ultrasound had no effect on extraction equilibrium.
3. Continuous ultrasound was not needed for solvent extraction of nickel. Intermittent application of ultrasound could produce the same results as continuous
application, thus reducing energy consumption.
4. Because intermittent ultrasound produced the same
results as continuous ultrasound and because ultrasound did not affect the extraction equilibrium, it can
be concluded that ultrasound did not affect chemical
reaction mechanisms. That is, the effect of ultrasound was physical, i . e . , to increase the surface area.
METALLURGICAL TRANSACTIONS B

5. The extraction rate of divalent cobalt and its uptake

by the organic phase were increased by ultrasound.
However, the sonochemical extraction of cobalt entailed more difficult stripping from the loaded organic phase. Because the stripping of trivalent cobalt
is always more difficult than the stripping of divalent
cobalt, it was concluded that ultrasound caused oxidation of cobalt during sonochemical extraction.
6. Further research is needed to develop the application
of ultrasound to the solvent extraction of metals. Special attention should be given to reactor design with
respect to sonochemical extraction under atmospheric
v s pressurized conditions, intermittent application of
ultrasound, application of ultrasound in a pipe, and
other parameters.
7. It should also be noted that because of much faster
solvent extraction rates, ultrasound can also be used
to shorten the equilibrium studies of very slow extraction systems, which are usually enhanced by the
addition of surfactants. Ultrasound provides a better
method of studying the equilibrium reactions, because it does not introduce additional chemical components into the studied systems (a noncontaminating
tool for study).

ACKNOWLEDGMENT
This work was supported by the United States
Department of the Interior, Bureau of Mines, under
Contract No. J0134035 through Department of
Energy Contract No. DE-AC07-76IDO1570.
VOLUME 23B, FEBRUARY 1992--21

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