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Hydrometallurgy, 4 (1979) 147--157 147

© Elsevier Scientific Publishing Company, Amsterdam -- Printed in The Netherlands

SOME ASPECTS OF ION EXCHANGE IN COPPER HYDROMETALLUR--


GY

F.VERNON
Department of Chemistry and Applied Chemistry, University of Salford, Salford, Lancs.
M 5 4 W T (Great Britain)
(Received March 2nd, 1978; in revised form June 28th, 1978)

ABSTRACT

Vernon, F., 1979. Some aspects of ion exchange in copper hydrometallurgy. Hydrometal-
lurgy, 4: 147--157.
Ion exchange systems of chelating ion exchange resins, bead and foam impregnates
have been evaluated for the possible applications to copper winning processes. Whereas
the bulk properties and capacities of the chelating resins are far superior to the impreg-
nates, the latter class of exchanger exhibits far better selectivity and kinetic properties
to the resins. However, only chelating resin systems are likely to find application in cop-
per hydrometallurgy, the copper selective resin XF-4196 finding application in dump
leach processes. Improvements in the uptake rates of XF-4196 are suggested as being
necessary for the incorporation of an ion exchange process into existing copper winning
plant utilising spent acid liquors from electrolysis procedures as the eluting medium.

INTRODUCTION

A system in which continuous ion exchange and solvent extraction pro-


cesses have been used to advantage for copper recovery from oxide ores has
been described by Naden and Willey (1976). However, ion exchange proces-
ses are not, at present, a feature of copper hydrometallurgy but are an at-
tractive alternative to solvent extraction processes which, due to the eco-
nomics of mixing large volumes of liquids and of solvent loss are usually
limited in application to liquors containing more than 1 g/1 of copper. Flett
(1974) has comprehensively reviewed the subject o f solvent extraction in
copper hydrometaUurgy, the extractants being either the LIX range of
reagents --aliphatic ~-hydroxyoximes, ~-hydroxybenzophenone oxime and
its derivatives -- or the Kelex reagents based on substituted 8-hydroxyquino-
line. Ritcey (1973) has described the recovery of copper from concentrated
solutions by solvent extraction with Kelex 100. It would be logical there-
fore to make comparisons between these solvent extraction processes and
ion exchange processes for copper recovery on ion exchangers having the
same functional groups, 8-hydroxyquinoline and ~-hydroxybenzophenone
oxime structure. Vernon and Nyo (1977) have described the optimised
148

procedures for the preparation of 8-hydroxyquinoline chelating ion exchange


resins and Mona (1977) has prepared and examined a resin incorporating
the a-hydroxyoxime functionality. Both of these exchangers are economic
to produce, the former being an 8-hydroxyquinoline-resorcinol-formaldehy-
de polycondensate and the latter a salicylaldehyde -- resorcinol-formalde-
hyde polycondensate treated with hydroxylamine.
As a further comparison the properties of the copper selective chelating
ion exchanger XF 4196 are examined. This exchanger was developed by
Dow Chemicals for application in dump leach copper winning processes and
has been described by Grinstead et al. (1976) and some of its metallurgical
applications have been given by Jones and Grinstead (1977). Warshawsky
(1974) has described the application of solvent-impregnated polystyrene
beads to hydrometaUurgy and both Warshawsky and Patchornik (1976) and
also Vernon and Eccles (1976) have examined the application of such beads
impregnated with the LIX reagents to copper recovery. The latter authors
also studied resin systems impregnated with Kelex 100. Vernon (1978)
has also made a study of ion exchange processes on LIX and Kelex impreg-
nated polyurethane foams. The purpose of the present work is to compare
the copper hydrometaUurgical properties of chelating resins, resin impreg-
nates and foam impregnates. Vernon (1977) has given the following criteria
for ion exchangers:
(1) High capacity for the metal(s) of interest.
(2) High selectivity.
(3) Fast kinetics --rapid equilibration with metal-containing solutions.
(4) High mechanical strength and toughness of exchange particles.
The various ion exchange systems are considered here in view of the first
three of these four criteria and consideration is given to bulk densities of
the systems so that effective column volumes, and also maximum copper
capacities in the eluting acid may be compared.

EXPERIMENTAL

Ion exchange systems studied

The 8-hydroxyquinoline ion exchange resin was the microbead resin


described by Vernon and Nyo (1977), the salicylaldoxime resin was batch
3X described by Mona (1977), and the weakly basic chelating exchange
resin XF 4196 was supplied by Dow Chemical Co. LIX 65N (General Mills
Inc.) and Kelex 100 (Ashland Chemical Co.) were used as received for
solvent extraction studies and for the impregnation of cross-linked poly-
styrene beads (Amberlite XAD-2, The Rohm and Haas Co.) as described by
Vernon and Eccles (1976}. The LIX65N and Kelex 100-impregnated foams
tested were those described by Vernon {1978).
149

Copper capacities

Total capacities of the exchangers were obtained either as copper uptake


at pH 2 from a dilute sulphuric acid medium or at pH 4 from a sodium
acetate/acetic acid buffer.

Selectivity

The selectivity ratios are for Cu/Fe and are the ratios of the weights of
the two metals taken up from solutions which were equimolar in copper (II)
and iron (III). Small quantities of the various ion exchangers were equilibrated
overnight with large volumes of solutions which were 0.05 M in both copper
and iron, the backing electrolyte being sulphuric acid solution or an acetate
buffer. The exchanger/solution ratio was chosen such that the molarities
of copper and iron in the solution fell by a negligible a m o u n t after equila-
bration.

Resin kinetics

Rates of equilibration were determined as tv2values, this being the time


taken by the metal to occupy one-half of the available sites on the exchanger.
The equilibrating metal was copper and its concentration in the equilibrating
solution was 0.05 M for ion exchange resins or 1 g/1 for resin and foam im-
pregnates.

Processing o f a simulated heap leach liquor

XF-4196 was used to process a simulated heap leach of Rio Tinto ore. The
liquor contained: copper, 1 g/l; zinc, 1 g/l; iron (II), 8 g/l; iron(III}, 1 g/l;
traces of arsenic and bismuth; and 10 g/1 of sulphuric acid to give a pH of
1.5. After ion exchange on a column of XF-4196, the column was washed
with several bed volumes of water then eluted with 1 M sulphuric acid which
was the eluting medium used throughout.

RESULTS AND DISCUSSION

Resin capacity and copper elution

In Table 1 are given the copper capacities of the various systems studied,
the values being in g of copper taken up by 1 kg of dry exchanger. Quite
predictably, it is seen t h a t by this criterion the chelating resins are vastly
superior to impregnates, whether bead or foam systems. Flett {1977) has
obtained similar data for LIX 65N impregnated beads, showing t h a t utiliza-
tion of the LIX capacity for copper is only around 50%. Warshawsky and
Patchornik (1976) have described a " w e t " m e t h o d of bead impregnation
150

TABLE 1

Total copper capacities and kinetic properties of the ion exchange systems

System Total capacity W a t e r regain t½ ( m i n )


(g o f C u / k g o f e x c h a n g e r ) (g/g)
pH 2 pH 4

Chelating resins
8~hydroxyquinoline 127 200 4.1 4
salicylaldoxime 82 165 2.5 10
XF-4196 108 124 1.5 10
Impregnated beads
Kelex 1 0 0 ( 3 3 % ) 18 0.3 10
L I X 6 5 N (33%) 7.7 0.7 11
Impregnated foams
Kelex 1 0 0 (33%) 25 0.25
LIX 65N (23.5%) 14 1.25

whereby the degree of copper complexation at equilibrium is 100% b u t this


falls far short of the capacities exhibited by the resins. However, the data in
Table 1 is misleading in that it suggests that the 8-hydroxyquinoline resin
is marginally superior to XF-4196. In-column, the resins will be in their
fully swollen states and, in Table 2, allowances have been made for varia-
tions in water regain and in swollen resin bulk volumes to give the column
volume in litres needed to hold 1 kg of copper when fully loaded. Due to
the relatively low water regain of XF-4196, this resin is much superior to

TABLE 2

Column bulk volumes, water hold-up volumes and theoretical maximal copper concentrations in a 1 M
H2SO 4 eluate

System Column bulk Column volume Water hold-up M a x i m u m Cu content


volume required to retain volume of of eluate if complete
(I/kg of 1 kg of Cu when column (I/l) elutionby one bed volume
exchanger) fullyloaded (I) (g/l)

Chelating resins
8-hydroxyquinoline 1.4 56 0.38 49
Salicylaldoxime 1.9 81 0.5 25
XF-4196 1.4 32 0.3 110
Impregnated beads
Kelex 100 (33%) 1.8 169 0.6 11.2
LIX 65N (33%) 1.8 397 0.6 4.8
Impregnated foams
Kelex I00 (33%) 5 200 (pH 4) O.8 6.1
LIX 65N (23.5%) 5 357 (pH 4) O.8 3.4
151

2(~

Copper
in eluate

(g/l)

10-

water

washing /

hold-um volumes of

M '12SO4 eluted

Fig. 1. Elution histogram of copper from a fully loaded column of XF-4196 by 1 M


I-X2S O 4 .

the other two -- 32 1 of XF-4196 packed column being required per kg of


copper -- approximately one-half the column volume that would be required
for 8-hydroxyquinoline resin and one-third that for salicylaldoxime resin.
Furthermore, it is now seen that bead and foam impregnates are probably
impractical column packings due to the enormous column volumes required
169--397 1 per kg of copper.
An associated problem is t h a t of copper elution from the columns.
In Table 2 are given the water hold-up volumes of each column packing,
so taking the capacity and column volume data and assuming that all the
copper can be eluted in a single hold-up volume of acid gives the theoretical
maximal copper capacities in the acid eluate from each exchange system.
Again it is seen t h a t the chelating resins are vastly superior with theoretical
copper contents of the eluates lying between 25 and 110 g/l of copper. It
should be noted t h a t in the case of XF-4196 the eluate is almost 2 M in
copper so the eluting acid strength required would be considerably in excess
of this value which corresponds to a 196 g/1 sulphuric acid solution. Actually
these values will never be realised in practice and in Fig. 1, where the elution
characteristics of copper by M sulphuric acid from a copper saturated
152

TABLE 3

Separation ratios (Cu/Fe) of the ion exchange systems

System ~ Cu/Fe
pH 2 (H2SO4 ) pH 4 (acetate)

Chelating resins
8-hydroxyquinoline 0.62 6
salicylaldoxime 0.72 14
XF-4196 16 60
Impregnated beads
Kelex 100 (33%) 4.3
LIX 65N (33%) 12.6
Impregnated foams
Kelex 100 (33%) 48
LIX 65N (23.5%) 46
Extractants used in
solvent extraction mode
Kelex 100 32
LIX 65N 80

column of XF-4196 are given, it may be seen that the m a x i m u m attainable


copper concentration is 21 g/1 in the second and third hold-up volumes
eluted. This value is sufficiently high for the solution to be a feed-stock
directly to electrowinning. Again in this c o n t e x t of copper content of eluate,
the impregnate systems show up badly. It would appear unlikely that the
eluate from a bead impregnate could reach a copper concentration of 10 g/1
or t h a t from a foara impregnate could exceed 5 g/1. As solvent extraction of
liquors much leaner than 1 g/1 in copper is impractical, the concentration
factors achieved by use of the impregnates may be too small to be of eco-
nomic importance.

C o p p e r selectivity

As may be seen from Table 3, a completely different picture emerges on


consideration of copper selectivity over iron for the various systems. Com-
pared to selectivities obtained when using Kelex 100 and LIX 65N in solvent
extraction it is apparent t h a t a decrease in Cu/Fe selectivity results in locating
the complexing agent on or in a solid matrix. Impregnated foams exhibit the
highest copper selectivities whilst the chelating resins have the lowest values
being actually iron selective at pH 2 although t h e y become copper selective
at pH 4. This curious variation of selectivity with pH for the two resin
systems studied suggests that the two important factors determining the
separation ratios are metal--resin bond strength and the relative rates of
metal uptake. The former predominates at pH 2 where the greater affinity
153

of iron(III) over copper for the resins results in iron selectivity being ex-
hibited. At pH 4, where b o t h metal--resin complexes are stable entities, the
faster kinetics of copper uptake results in the resins being copper selective.
It has been shown, for instance, that the F e / C u separation ratio for the 8-
hydroxyquinoline resin was 3.0 at pH 1.0 when overnight batch equilibra-
tion of resin and solution was used b u t this value rose to 5.0 for on-column
determination using column retention times of a few minutes.
It appears then, from a consideration of the data in Table 3 and the t~
values in Table 1, that ion exchange is an inherently less selective process
than solvent extraction for a given complex-forming group. Both the hydro-
xyquinoline and the h y d r o x y o x i m e systems reveal that whereas high Cu/Fe
selectivity is obtained in solvent extraction, the constraining influence of
the polyurethane foam matrix on the ligands decreases their selectivities by
some 50--60%. The constraining influence of a rigid polystyrene matrix
in the bead impregnates further reduces the selectivity and the ultimate
constraint -- attachment of the complexing units to a solid p o l y m e r in the
chelating resins -- is a sufficiently large effect to make the resins iron select-
ive over copper. The use of solvent extraction selectivity data in the design
of new chelating resins would n o t therefore appear to be a viable proposi-
tion. Of the resin impregnates LIX 65N demonstrates a significantly higher
copper selectivity than Kelex 100, in comparable solvent extraction studies
extracting equimolar Cu/Fe solutions initially at pH 2.7, separation ratios
of 80 and 32 were obtained for LIX and Kelex 100 respectively. Warshaws-
ky and Patchornik (1976) have suggested that separation ratios of the
order of 500 are possible on LIX 64N bead impregnates but, compared to
values in the range 10--20 obtained by other workers with LIX impreg-
nates and the limiting value of around 80 for solvent extraction data, values
approaching 500 would seem highly unlikely.
In Table 3 it is seen that the copper selectivity of XF-4196 is far better
than the other chelating resins and, in fact, is superior to the LIX 65N
bead impregnate. Total capacity and matrix volume factors having precluded

TABLE 4

Ion exchange o f Rio Tinto heap leach on XF-4196 (a) at an effluent throughout of 0.36 bed
volumes/min and (b) at an effluent throughout of 0.18 bed volumes/rain.

Species present In original leach In column effluent In acid eluate (5 b.v.) Percentage metal
(g/l) (g/l) (g/l) recovery on acid
(a) (b) (a) (b) elution with 5 b.v.)
(a) (b)
Cu 1 0.18 0.07 2.1 4.0 82 93
Zn 1 1 1 10 -2 0.5 × 10 -3 0 0
Fe 9 8 8.8 1 0.8 11 2
154

the impregnates, XF-4196 now becomes the only system of those studied
which m a y be economically viable. It is u n f o r t u n a t e t h a t high values for the
separation ratio require a working medium of pH 4 but the value of 16 at
pH 2 suggests t h a t copper m a y be profitably removed from iron-containing
acid leaches prior to electrowinning, the ion exchange process on XF-4196
being able to ensure a sufficiently high Cu/Fe ratio. A study of ion exchange
on XF-4196 of a simulated Rio Tinto heap leach was carried out, this
system being chosen because of its high iron content, and the results are
shown in Table 4. Obviously, from a heap leach Cu/Fe ratio of 0.11, the
ratio in the acid eluates of 2.1 and 5.0 are highly desirable nineteen and
forty-five fold enhancements in copper over iron, however the latter value
is only obtained at the expense of a reduced column through-put of leach
liquor. As this is a function of the resin kinetics it is convenient to discuss
the phenomena under that heading.

Resin kinetics

In Table 1 are listed the t~ values of the systems studied -- these being
the times to 50 percent exchanger saturation by copper. With the exception
of the 8-hydroxyquinoline chelating resin, which has a fast uptake due to
its high water regain and the foam impregnates which are extremely fast,
the other two chelating resins and the bead impregnates are seen to have t~
values of around 10 min. This is rather slow for practical applications in-
volving possibly several hundred gallons/h of dilute copper leach. For ex-
ample, using the data in Table 2, for a leach through-put of 100 gallons/h
to have a 10 min on-column retention time would require a column volume
of 250 1 which would contain 179 kg of dry XF-4196. Under these con-
ditions the resin capacity would be only 50 per cent utilized when copper
appeared in the effluent. This in turn would mean, from Fig. 1, thatthe
m a x i m u m copper, corttent of a subsequent acid eluate would be only 10.5
g/1.
The effect of slow resin kinetics is shown on a small scale in Table 4 for
the Rio Tinto heap leach. In the first run, the heap leach was put through
the XF-4196 column at a rate corresponding to 0.36 bed volumes/min, or
allowing only a 3 min on-column retention time. The column was loaded
with leach liquor until the green colour of the copper form of the resin just
reached the column end. Water washing and acid elution gave the results
under (a) in Table 4, the column leach effluent still contained 0.18 g/1 of
copper and the acid eluate 2.1 and 1.0 g/1 of copper and iron respectively.
The procedure was repeated with a reduced leach through-put correspond-
ing to 0.18 bed volumes/rain. It was now possible to process almost twice
the volume of leach liquor before completing the column loading as in-
dicated by the column end becoming green. Consequently the leach effluent
from this slower rate of application contained far less copper and the final
acid elution gave a solution containing 4.0 g/1 of copper. It was mentioned
155

previously that, in this instance, the copper selectivity of the column showed
a large increase b u t the enhanced quality of the eluate must be off-set b y
the reduced volume of leach which can be processed in unit time. Obviously
a considerable improvement in XF-4196 kinetics is required, a resin with
the t~ of the 8-hydroxyquinoline resin would be vastly improved b u t this
would m o d i f y the column capacity properties, as given in Table 2, dis-
advantageously. There is, however, an attractive alternative -- using a copper
drop across the tankhouse of 10 g/l, from say 50 g/1 to 40 g/1 and returning
the 40 g/1 solution to ion exchange as eluant. This type of operation is
c o m m o n practice in the solvent extraction recovery of copper and it is
understood that pilot plant work at Butte, Montana, on a counter-current
ion exchange unit, has indicated that the economics are attractive.

Ion exchange in the copper-winning process

Due to the limitations of the ion exchange process which have been dis-
cussed, it seems unlikely that this process will replace solvent extraction in
copper winning. As an, adjunct to solvent extraction plant however, ion ex-
change plant could serve a double purpose: (a) completing the removal of
copper from solvent extraction raffinate; and (b) ensuring complete copper re-
moval from discharged liquors where excess iron must be bled from the sys-
tem. Fig. 2 shows one possible mode of incorporating an ion exchange plant.
Solvent extraction raffinate is passed through the exchanger before going to
waste, the copper being eluted by spent solution from the electrolysis cells
which will be further enriched in copper when used as back-extractant in the
solvent extraction process. Grinstead et al. (1976) have discussed the possibili-
ty of eluting XF-4196 with spent electrolysis liquors and have shown that a
typical liquor containing 20 g/1 of copper in 1 M sulphuric acid is an effi-
cient eluant and that maximal copper concentrations in the eluate can reach
46 g/1. The efficiency of copper removal from raffinate is so great that this
liquor, currently discharged with a copper content less than 1 g/l, would
after ion exchange have a copper content below 10 ppm.

CONCLUSIONS

Of the three types of exchange system studied, only chelating ion ex-
change resins appear to be viable, impregnates being excluded on the grounds
of their low capacities, high bulk volumes and, for bead impregnates, high
cost of the bead matrix. However, impregnates are vastly superior to chelat-
ing resins in terms of selectivity and it could be that impregnated foams will
find hydrometallurgical application for this reason. Such application is un-
likely to be in the winning of c o m m o n metals such as copper b u t rather
for the processing of high cost elements. Vernon and Eccles (1976) have
shown, for example, that Kelex 100 impregnates are a practical medium
for uranium-vanadium separations.
156

Electro ~.'inning
unit

20 g/l Cu ~ 5 0 g/l Cu
J ~

~20 g/1Cu ¢0.5MH2S04~


ion ] --] Solvent
Exchange 1 Extraction
Plant 1 A
Plant
| 1 g/l Cu ~ pH 1.5
~X

3.0 g/l Cu

pH 2

Fe bleed-off
I I0 ppm
Cu; pll 1.5

Fig. 2. Schematic layout of copper winning plant incorporating ion exchange process.

Selectivity, particularly of copper over iron, and rapid rates of equilibra-


tion are the main problems still to be overcome with chelating resins. There
may be a c o m m o n solution to the two problems. The inherently copper
selective exchanger, XF-4196, has an its main draw-back a fairly slow equi-
libration rate, t o o slow for current copper winning processes. Its kinetic
performance can be improved b y varying one or more of three parameters
as this is a macroporous polystyrene<livinylbenzene polymer incorporating
weakly basic functional groups. These performance enhancing variations
are (1) an increase in the macroporosity, (2) a reduction in the degree of
cross-linking, and (3) an increase in the hydrophilicity of the material either
b y the incorporation of polar groups into the polystyrene or possibly b y
using some c o p o l y m e r such as styrene-ethyleneimine-DVB as starting material
for attachment of the weak base functional groups.
157

T h e results in Table 4 o n the Rio T i n t o h e a p leach t r e a t m e n t have d e m o n -


strated t h e n e e d f o r i m p r o v e d kinetic p e r f o r m a n c e . I f resin m o d i f i c a t i o n
c o u l d i m p r o v e t h e c o p p e r t o iron selectivity value o f 16 given here, an
i m p r o v e d X F - 4 1 9 6 c o u l d have an i m p o r t a n t role to p l a y in t h e field o f
copper hydrometallurgy.

REFERENCES

Flett, D.S., 1974. Solvent extraction in copper hydrometallurgy. Inst. Min. Metall.,
Trans., 83 C30.
Flett, D.S., 1977. Resin impregnates: the current position. Chem. Ind., 6: 641.
Grinstead, R.R., Nasutavicus, A.W. and Wheaton, R.M., 1976. New selective ion exchange
resins for copper and nickel. In: Yannopoulos, J.C. and Agarwal, J.C. (Editors), Extractive
Metallurgy of Copper, Vol. 2, AIME, New York, P. 1009.
Jones, K.C. and Grinstead, R.R., 1977. Properties and hydrometallurgical applications
of two new chelating ion exchange resins, Chem. Ind., 6: 637.
Mona, A.T.J., 1977. Ion exchangers incorporating o-hydroxyoxime functionality. M. Sc.
Thesis, Salford.
Naden, D. and Willey, G., 1976. Reduction in copper recovery costs using solid ion ex-
change. In: M. Streat (Editor), The Theory and Practice of Ion Exchange, London
SCI, 44: 1.
Ritcey, G.M., 1973. Recovery of copper from concentrated solution by solvent extrac-
tion using Kelex 100. CIM Trans. 76: 75.
Vernon, F., 1977. The preparation and properties of chelating ion exchange resins. Chem.
Ind., 6: 634.
Vernon, F., 1978. Ion exchange on LIX 65N and Kelex 100 impregnated foams. Se-
paration Science and Technology, in press.
Vernon, F. and Eccles, H., 1976. Some hydrometallurgical applications of hydroxy-
oxime, hydroxyquinoline and hydroxamic acid impregnated resins. In: M. Streat
(Editor), The Theory and Practice of Ion Exchange, London SCI 39.1.
Vernon, F. and Nyo, K.M., 1977. Synthesis optimization and the properties of 8-hydro-
xyquinoline ion exchange resins. Anal. Chim. Acta, 93: 203.
Warshawsky, A., 1974. Solvent impregnated resins in hydrometallurgical applications.
Inst. Min. Metall., Trans., 83: C101.
Warshawsky, A. and Patchornik, A., 1976. Recent developments in metal extraction
by solvent impregnated resins. In: M. Streat (Editor), The Theory and Practice of Ion
Exchange, London SCI, 38.1.

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