A COMPARATIVE STUDY OF ION EXCHANGE PROCESS FOR

THE EXTRACTION OF ANTIMONY

MARCO CIFUENTES (1), GERARDO CIFUENTES (2), JAIME SIMPSON (2), CESAR
ZÚÑIGA (3)

(1) CODELCO CHILE, DIVISIÓN CHUQUICAMATA, E-mail: mcifuent@codelco.cl .

(2) Departamento de Ingeniería Metalúrgica, Facultad de Ingeniería, Universidad de
Santiago de Chile, Santiago, Chile.
(3) Departamento de Ingeniería Química, Facultad de Ingeniería, Universidad de
Santiago de Chile, Santiago, Chile.

ABSTRACT
An ion exchange pilot plant, located at the University of Santiago of Chile, was tested
for antimony control in the electrolyte of Chuquicamata Refinery. In the pilot plant
were used three different resins: MX-2, UR-3300S and Duolite C-467. The results
showed that the best behavior for antimony extraction follow the sequence UR3300S
>Duolite C 467 > MX 2. A model with the experimental results was used as
comparative tools to increase the knowledge of this process.

Keywords: Antimony, IX, Modeling, Copper, Electrorefining.

INTRODUCTION

In the last times, Chuquicamata Division has experienced a significant and sustained
increase in the content of impurities, mainly As, Sb and Bi, in the concentrates
produced from the exploitation and processing of the Chuquicamata mine as well as
products recirculation, which has affected the chemical quality of the anodes produced
in concentrates Smelter, additionally with the entry into operation of the new Division
Ministro Hales, whose product, the calcine copper concentrate with high content of
antimony will be processed entirely in the facilities of the Smelter and Refinery
Chuquicamata Division, increasing Sb content in anodes and Refinery electrolytes.
This problem of Sb and Bi in concentrates and calcines, impact the cathode quality
and has been addressed in many studies and engineering: Conceptual Engineering
"Complex Concentrate Treatment and Increase DCN Smelter and Refinery Capacity"
(API N04FP47) and in Basic Engineering "Impurities Treatment Feasibility in anodes
and cathodes DCN" where technological options have been proposed to process
concentrates in Codelco Chuquicamata, recommending a global solution to solve the
problem of chemical quality of the electro-refined cathodes.
Thus for electrolytic refinery was determined installing an ion exchange plant
connected to electro refining circuits, enabling control of Sb in the electrolyte in a
concentration not exceeding 0.3 g/L. In this regard, the Refinery of Chuquicamata
División has performed in the laboratory of Electrometallurgy and Corrosión of the
Metallurgical Enginnering Departament of the University of Santiago of Chile
laboratory pilot tests with different resins to preparing a report with the behaviour of
the resins when was in contact with real electrolyte of Chuquicamata. However,
because it is a new technology is needed gather a lot of information to help you get a
better appreciation of this technology in both aspect, the loading and elution.
In the processes for obtaining de copper by pyrometallurgy a fundamental stage is the
electrorefining of impure copper anodes (98-99.8% de Cu). In this stage by applying
a potential difference the copper present in the anode is dissolved electrochemically
in the electrolytic solution, and is deposited on a stainless steel or pure copper
cathode. At the same time, some of the impurities contained in the anode (As, Sb, Bi,
S, Fe, Zn, Ni, Co) are dissolved in the electrolytic solution and the rest of those
impurities (Ag, Se, Te, Pb) do not go into the solution and precipitate as “anode slime”.
In turn, as a result of matter transfer mechanisms, physical contamination of the pure
copper cathodes occurs (occlusion of solids), affecting the electric properties of the
copper and the quality of the pure copper cathodes(1).
Control of the impurities present in the electrolyte is done mainly by purging the
electrolytic solution. However, the impurities that have the greatest incidence on
cathode contamination and on operational problems are As and Sb compounds. There
is a known ratio between arsenic and antimony (As/Sb ≥2) that prevents the formation
of floating slime that can cause physical contamination of the pure copper cathode,
leading to an As and Sb solubility curve from which it can be concluded that as the
arsenic in solution increases, the solubility of antimony decreases. However, increased
Sb in copper sulfide ores and its concentration in the electrolytic solution in spite of
keeping the (As/Sb ≥2) causes this Sb “equilibrium” difference to form a compound
(Sb2O3) that precipitates throughout the system, clogging ducts and physically
contaminating the cathodes.
This situation has made refineries take short-term measures to remove the excess
antimony. Considering the above and reviewing the literature, there is a large variety
of publications that highlight the benefits of using ion exchange resins to remove the
antimony present in the electrolyte of copper refineries, particularly the work of
Dreissinger and Izatt(2). Industrially, this ion exchange process has been studied on
the pilot scale in the Tamano, Nippon Hitachi, Saganoseki, Noranda, and other
refineries.
In Chile studies have been made(3) and are continuing at both the laboratory and pilot
scales of ion exchange plants aimed at defining parameters for designing ion exchange
plants at the industrial scale for extracting antimony. In view of the economic
perspectives of the ion exchange techniques in mining as such and of their
repercussion on the quality of the copper cathodes, it is of interest for the design and
control of the process (control of flow, height of bed, initial solute concentration, etc.)
to have a model and simulation of the ion exchange process.

Basics of Ion Exchange Resins

Ion exchange operations are mainly substitution chemical reactions of an ion in
solution by another in the insoluble resin. The mechanisms of these reactions and the
techniques used to carry them out are similar to those of adsorption, and in most
practical engineering cases ion exchange is considered as a special case of adsorption.
As in previous studies, the same as in adsorption, it is necessary to determine a
mechanism that will control the ion exchange process for practical design purposes.
Thus, it is found that the rate at which the ion exchange takes place depends (the
same as adsorption) on the following transport phenomena that occur as the ion
exchange progresses(4):
1. Diffusion of ions from the fluid to the outer surface of the resin.
2. Internal diffusion of ions through the solid to the exchange site.
3. Ion exchange.
4. External diffusion of the released ions to the surface of the solid.
When the ion exchange reactions are fast compared to the rate of mass transfer, the
design methods developed for traditional adsorbers can be applied directly to the ion
exchange operations.

Breakthrough Curve
The continuous path of a concentrated solution with an element of interest (Sb)
through a fixed bed (porous) of resin behaves in a way that can be described as
follows, where BV are the Bed Volume Flow of the solution(4):
The solution of concentration C0 comes in contact with the upper part of the resin bed,
extracting practically all the solute, and the remainder is extracted in the lower part
of the bed, ideally getting a solution free of solute, as shown in part a) of Figure 1.
As the solution continues flowing, the extraction zone is displaced downward (part b)
of Figure 1) as a wave. The bed is half saturated and the concentration of the outgoing
solution is still practically zero (Cb).
Part c) of Figure 1 shows that the extraction zone has reached the bottom of the bed
and the solute concentration in the effluent has increased suddenly to a considerable
value Cc. For the first time, it is said that the system has reached the “breaking point”.
Now the outgoing concentration increases rapidly as it goes past the extraction zone
through the bottom of the bed.
In zone d) the outgoing concentration Cd is practically C0, the extraction zone has
touched the bottom of the bed, and the resin is completely saturated.

Figure 1. Breakthrough Curve.

EXPERIMENTAL PART

To obtain the results is necessary to have a proper installation all these considerations
are present in Figure 2.

Figure 2. Pilot Plant

According to Figure 1.2 the follows equipment and conditions was used: glass column
of 14 mm diameter, 1000 mm height (approximately 700 mm resin bed height). The
resin volume was 0,108 L (approximately).
Adsoption (4 h)
Feed to column: 1 L/h electrolyte
Total volume: 4 L electrolyte
Temperature electrolyte: 60 ºC
Washing 1 (80 min)
Feed to column: 300 ml/h bi-destiled water
Total volume: 0,4 L
Elution (1 hr)
Feed to column: 300 mL/h (Solution of HCl 6N)
Total volume: 0,3 L
Washing 2 (80 min)
Feed to column: 300 ml/h bi-destiled water
Total volume: 0,4 L
Total cycle: 13
The electrolytic solution used came from Chuquicamata Refinery. Table 1 show the
characteristic of them.

Table 1.- Initial concentration of the electrolytic solution.

Sb [kg/m3] Cu [kg/m3] Fe [kg/m3] As [kg/m3] H+ [kg/m3]
0.2167 39.4 0.174 9.76 220

RESULTS AND DISCUSSION

Table 2 show the numerical results obtained for each resin in cycle 13, with this
information can graphed the breakthrough curve for all tested resins. The Figures 3,
4 and 5 show the graphic results obtained for adsorption of antimony for the resins
MX-2, Duolite C-467 and UR-3300S respectively.
All the graphics there showed have a typical form of Breakthrough Curve. The control
cycle was the 13th and the 11th and 12th cycles were as control step to confirm the
antimony level and the operational conditions at this level of the test.

Table 2.- Final concentration in cycle 13.

Resin
MX-2 Duolite C467 UR3300-S
Time, [h] BV Cycle 13, [mg Sb/L] Cycle 13, [mg Sb/L] Cycle 13, [mg Sb/L]
1 9.5 29.6 39.8 36.6
2 19.0 102.5 108.5 68.0
3 28.5 113.4 117.0 82.0
4 38.0 109.5 108.5 56.0
5 47.5 119.5 117.5 60.5
6 57.1 113.5 136.5 67.5
7 66.5 152.0 122.4 61.7
8 76.0 152.6 116.0 76.0
 MX-2 Resin
180

160

140

Conc. Sb elec. OUT, mg/L

120

100
Cycle 11, [mg Sb/L]
80 Cycle 12, [mg Sb/L]
Cycle 13, [mg Sb/L]
60

40

20

0
0 10 20 30 40 50 60 70 80
BV

Figure 3. Breakthrough Curve of MX-2 resin.

Duolite C467 Resin

160

140

120
Conc. Sb elec, OUT, mg/L

100

80 Cycle 11, [mg Sb/L]

Cycle 12, [mg Sb/L]
60 Cycle 13, [mg Sb/L]

40

20

0
0 10 20 30 40 50 60 70 80 90
BV

Figure 4. Breakthrough Curve of Duolite C467 resin .

 UR3300-S Resin
90

80

Conc. Sb elec, OUT, mg/L 70

60

50
Cycle 11, [mg Sb/L]
40 Cycle 12, [mg Sb/L]
Cycle 13, [mg Sb/L]
30

20

10

0
0,0 10,0 20,0 30,0 40,0 50,0 60,0 70,0 80,0

BV

Figure 5. Breakthrough Curve of UR3300-S resin.

Like a form to see new scenarios and to anticipate change in the operations conditions,
the use of the model help on this aspect and to do possible to know “a priori” the
process.
The model used in this paper was a result of mass balance in and out the process and
to permit the creations of several operational scenarios and to anticipate some.

 


e
   
 J 0 2 i  
  d

C Li (t )  f correction  C L 0  1  e 0 
 
  (1)
Where:
z  S  k la Li

Uf
(2)
m  t  k la Li
*

1  (3)
   S  CL 0 
t*  t  z    (4)
 U 
 f 
With:
C Li = solute concentration in the fluid phase at time “t”
CL 0 = initial solute concentration in the fluid
z = height of the resin bed
S = cross sectional area of the column
kla Li = volumetric matter transfer coefficient of solute “i” (antimony in this case)
in the Liquid phase
Uf = linear velocity of the fluid phase
m = equilibrium isotherm constant
 = porosity of the resin bed (volume of spaces between resins/volume of bed)
t = time
f correction = mathematical correction factor
The equation (1) was programmed in MATLAB® in order to generate the modeled and
simulated breakthrough curve, so is possible to compare with the experimental curve.

Experimental validation
The experimental data used in this part, Tables 1 and 2, correspond to the same values
determined in pilot experiments made with three different resins: MX-2, UR-3300S,
and Duolite C-467.

Table 2. Outgoing concentration of antimony in the electrolyte for each resin bed
column analyzed.
Resin MX-2 UR-3300S Duolite C-467
t [h] Sb [kg/m3] Sb [kg/m3] Sb [kg/m3]
1 0.0296 0.0366 0.0398
2 0.1025 0.0544 0.1085
3 0.1071 0.0615 0.1170
4 0.1095 0.0616 0.1139
5 0.1195 0.0605 0.1175
6 0.1198 0.0611 0.1186
7 0.1201 0.0617 0.1191
8 0.1201 0.0619 0.1189

Experimental Breakthrough Curve

Figure 6 shows the experimental breakthrough curves obtained for the following
resins:
- Duolite C-467: red line.
-UR-3300S: green line.
- MX-2: blue line.

Figure 6. Experimental breakthrough curves.

Modeled Breakthrough Curve

Figure 7 shows the breakthrough curves (for each resin) modeled from Equation (1).
 Figure 7. Modeled breakthrough curves.

Table 3. Correction factor and percentage error obtained by means of modeling and
simulation.
%
Resin Bed f correction Error
MX-2 0.5531 3.72
UR-3300S 0.2839 2.94
Duolite C-467 0.5455 2.38

Table 3 shows the correction factors and the error delivered by the proposed model,
which are within the acceptability range (less than 10%)(7).
Table 4 shows the volumetric matter transfer coefficients k la  for each resin bed,
which were determined iteratively for each resin. From the kla values it can be inferred
that resin UR-3300S presents less resistance to matter transfer and greater antimony
extraction capacity (at low kla values there is greater resistance to matter transfer),
while resins MX-2 and Duolite C-467 behave quite similarly in the ion exchange
process.

Table 4. Volumetric matter transfer coefficient of Sb adsorption.

Resin k La
[kg/m3 h]
MX-2 0.0238
UR-3300S 0.0431
Duolite C-467 0.0257

Different Operating Scenarios

The behavior of the breakthrough curves modeled for resin UR-3300S under
different operating conditions is shown below.
 Figure 8. Resin UR-3300S breakthrough curve modeled at different kla

Figure 9. Resin UR-3300S breakthrough curve modeled at different resin bed

volumes (Vr).

Figure 10. Resin UR-3300S breakthrough curve modeled at different initial Sb

concentrations, CSb.

Table 5. Values simulated on the model

UR-3300S k la Vr [m3] CSb [kg/m3]
[kg/m3h]
1 0.0431 0.0001078 0.2167
2 0.0517 0.0002 0.3
3 0.0560 0.0003 0.5
CONCLUSIONS

It is possible to conclude that the proposed model that describes the ion exchange
process in a fixed bed column is representative of the process and agrees with the
experimental data given in the available literature. From what has been presented
here, it is inferred that the volumetric matter transfer coefficients are a fitting
approximation of the ion exchange process and they are the ones that have a major
incidence in the process.
It is also possible to generate operating scenarios by means of the proposed model
and its programming in MATLAB®, getting satisfactory results in agreement with what
is predicted by the literature, namely:
As kla increases(Figure 8), leading to less resistance to matter transfer and a greater
capacity for Sb extraction in less time, this is reflected in a decrease of breaking time
and a displacement of the breakthrough curve to the left.
As Vr increases (Figure 9), keeping the column diameter constant, there is an increase
in the height of the resin bed, so the fluid will travel through a longer distance in the
bed, losing a greater amount of Sb and therefore requiring more time for the resin
bed to become completely saturated. Therefore the curve will be displaced to the right,
thereby increasing the breaking time of the breakthrough curve.
Due to the increase of the input concentration of Sb in the electrolyte (Figure 10), the
breakthough curve becomes slightly more pronounced and breakage time decreases
slightly.

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