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
EXPERIMENTAL
Copper capacities
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
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.
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
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
TABLE 2
Column bulk volumes, water hold-up volumes and theoretical maximal copper concentrations in a 1 M
H2SO 4 eluate
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
TABLE 3
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
C o p p e r selectivity
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.
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 ~
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.
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.