Industrial Insight Ion Exchange

Developments in Ion Exchange:

The Mintek Perspective
B.R. Green, M.H. Kotze, and J.P. Wyethe

Mintek has been involved in the
development of ion-exchange technolo-
gies for the gold industry for more than
25 years. These technologies include the
development of gold-selective anion-
exchange resins, design and engineering
aspects of resin-in-pulp and resin-in-
solution for the recovery of gold, and
the use of ion exchange for the recovery
and recycling of cyanide. More recently,
an automated ion-exchange process
was developed to recover gold powder
from carbon eluate in an attempt to
limit gold theft during the final stages
of processing.
INTRODUCTION
After the development of cyanide
processing of gold ores over a century
ago, no significant advance in technol-
ogy took place until the introduction of
large-scale carbon-in-pulp (CIP) in the
late 1970s. Work started soon thereafter
on the related process of resin-in-pulp
(RIP) because of the belief that resin
could be tailor-made to be a superior
adsorbent to carbon. This became a
major effort at Mintek, culminating in
the development of specialty resins,
Minix and Aurix, and the MINRIP
process. After favorable results were
obtained in RIP with Minix, attention
was focused on using the resin to
recover gold from clear solutions such
as heap-leach liquors.
It became evident during the early
1990s that cyanide in gold processing
would become an increasingly important
environmental issue. In this area, Mintek
investigated ion exchange to recycle
cyanide. After initially considering the
possibility of specialty resins, a process
route was proposed that would use a
commercial resin and that drew on the
It became evident
during the early
1990s that cyanide
in gold processing
would become an
increasingly important
environmental issue.
more favorable approaches reported in
the literature.
Theft of gold at mine sites is an
age-old problem. Recent reports have
suggested that as much as 8% of South
Africas annual production is stolen.1
A large proportion of this gold is
believed to be lost at the stage of
processing where it is handled in its most
concentrated form: during recovery
of the electrowinning sludge for smelt-
ing. Minteks WINIX process, an
automated ion-exchange-based process
to recover gold powder from carbon
eluate, was developed to improve
security.
This article discusses Minteks ion-
exchange developments for the gold
industry during the years following
implementation of CIP.
RESIN-IN-PULP
Carbon-in-pulp (CIP) is the preferred
method in the Western World for the
recovery of gold from cyanided pulp.
However, significant developments
around gold-selective anion exchange
resins and the commercialization of a
number of these products have made
RIP available as an alternative to CIP
for the upgrading of gold from cyanided
pulps.2
Gold-selective resins have some
distinct advantages over activated
carbon for the recovery of gold from
cyanide leach liquors. Resins have
potentially higher loading capacities,
higher loading rates, are less likely to
be poisoned by organics, and do not
require thermal regeneration. The main
disadvantage of gold-selective resins
is that they are more expensive than
activated carbon. However, despite their
higher costs they can be significantly
more cost-effective than activated

Table I. Metallurgical Performance of Various Adsorbents*

Au Ag Zn Ni Co Cu Fe Au/M**
Feed (mg/L) 5 0.5 2 5 1 10 10
Adsorbent: Metal Loading (mg/kg)
Minix 36,300 300 10,000 7,300 <330 1,200 330 0.65
Activated Carbon 25,200 <200 <200 460 <200 <200 1,500 0.93
A161L 13,300 <250 9,000 17,800 4,600 15,800 21,300 0.16

* Metallurgical performance of adsorbents was determined by a column-loading test, which is one of the adsorbent screening tests used at Mintek. This involves passing a synthetic leach
solution through an adsorbent bed at a relatively high flow rate for 72 h.
** Ratio of gold concentration (mg/kg) to total metal concentration (mg/kg) on loaded resin, which is a measure of selectivity of adsorbent for gold.

2002 October JOM 37

 Table II. Metals Loaded at Steady State onto the First Adsorption Stage
dynamically describes the ore grade,
During Countercurrent Mini-plant Campaigns with Various Solutions solution concentration, and adsorbent
Solution Type Metal in Solution (mg/L) and on Adsorbent (mg/kg)
gold loading with time and takes into
account the tank active volume and pulp
Adsorbent Au Ag Zn Ni Co Cu Fe
High-grade Solution 10 Absent 4 9 0.5 10 Absent
bypass. Thus, the thermodynamic and
Minix 37,700 10,500 9,800 <140 900 kinetic dimensions are combined and
Carbon 19,000 <70 350 <70 70 converted into a gold-loading value on
Standard Solution 5 0.5 2 5 1 10 10
Minix 25,800 1,300 6,500 10,100 200 1,700 400
the adsorbent in a counter-current plant.
Carbon 17,900 800 <100 500 <100 <100 400 This determines the overall adsorbent
Dump Solution 0.5 0.05 1 10 1 10 2 inventory, the inventory per stage, and
Minix 4,200 630 4,400 18,200 200 1,300 100
Carbon 3,260 200 <100 1,000 <100 <100 300
the flow of adsorbent. The elution plant
can be sized accordingly.
carbon, as illustrated in this article. Ca(CN)2 is returned to the leach plant. The optimum adsorbent for a specific
Mintek developed the Minix and Selection of the optimum process application should then be selected on
Aurix gold-selective resins for the option for a specific application should be an economic basis. In order to do a
recovery of gold from cyanide leach done on an economic basis. Mintek has techno-economic comparison between
liquors. Minix (manufactured commer- developed a process simulation package CIP and RIP (employing the MINRIP
cially by the Dow Chemical Company) to predict the process parameters for contactor), countercurrent mini-plant
is a strong-base resin, while Aurix is both activated carbon and ion-exchange campaigns were conducted on three
a medium-base resin (developed for resin for the recovery of gold from a types of solution, namely high-grade,
and being commercialized by Cognis). cyanided pulp. In order to model the standard, and dump. As these were clear
Adsorption and stripping reactions leaching and adsorption circuits, it is solutions, tests were done in fixed-bed
(Equations 1 and 2) for Minix, which necessary to know the rate of gold columns. Results obtained from these
contains tributylamine as the functional dissolution from the ore, the equilibrium campaigns for the Minix resin and
group, are as follows: conditions between the adsorbent and activated carbon are given in Table II.
the solution, and the rate of gold The metal loadings onto the adsorbent
Adsorption:
adsorption by the adsorbent. This are given for the loaded stage coming
R-N(Bu)3+(SO42)12 + Au(CN)2
information is obtained from batch off-line when the resin is transferred.
R-N(Bu)3+Au(CN)2
laboratory tests. The metallurgical results were used as
+ 12(SO42) (1)
The process-design model can be part of a preliminary techno-economic
used to simulate adsorption-in-pulp or comparison between CIP and RIP.4
Stripping:
adsorption-in-leach configurations.2 The costing of the adsorption facilities
R-N(Bu)3+Au(CN)2 + 2TU
The active volume of the adsorption encompassed the tank farm, adsorbent
+ H2SO4
tanks is governed by the pulp throughput inventory, interstage screens and pumps,
R-N(Bu)3+(SO42)12
and residence time required. In this compressor, and samplers. The adsorbent
+ Au(TU)2+(SO42)12 + 2HCN (2)
simulation, the gold dissolution and inventory was assumed to be nine
where TU is thiourea and R is the gold adsorption rate expressions are stage inventories. The CIP tanks (flat-
polymer backbone. used in conjunction with a continuous bottomed, mechanically agitated) were
The metallurgical performance of stirred tank reactor mass balance to sized for 30 min. pulp residence time
Minix in relation to that of some other describe the operation mathematically. per stage, while the RIP tanks (conical
adsorbents is illustrated in Table I.3 These The dissolution-adsorption model bottomed, air agitated) were sized for
results illustrate that although Minix
is less selective for gold than activated
2,000 140
carbon, it can have a significantly
120
higher gold-loading capacity. It is
1,500 100
also clear that Minix has a much-
Relative Costs

Relative Costs

improved selectivity for gold and gold- 80

loading capacity when compared to 1,000
60
a conventional water-treatment-type 40
strong-base resin such as Rohm and 500
20
Haas A161L.
0 0
Stripping of Minix is done in two CIP MINRIP
stages. In the first stage, the base metals CIP MINRIP
Adsorbent
are stripped with sulfuric acid followed Inventory
by stripping of gold and silver with an Elution/Reagents Reagents
acidic thiourea solution. The HCN that Adsorption Power
a b
is evolved during stripping of the resin
Figure 1. The relative (a) CAPEX and (b) OPEX for CIP and MINRIP plants.
is scrubbed in a caustic soda or lime
solution and the resultant NaCN or

38 JOM October 2002

 Table III. Predicted Cost Savings for MINRIP over CIP (%)
10 kt/month 25 kt/month
Dump Solution
CAPEX 17 31
OPEX 46 44
Standard Solution
CAPEX 20 33
OPEX 52 50
High-grade Solution
CAPEX 23 38
OPEX 55 51
15 min. pulp residence time per stage.
Seven adsorption stages were assumed
for both plants. The CIP interstage
screens were NKM submerged screens
and carbon transfer was carried out
by vertical-spindle recessed-impeller
pumps. The RIP interstage screens were
external sieve bends onto which the pulp
and resin were lifted by airlifts.
The costing of the elution facilities
encompassed all elution, thermal
regeneration, and acid-washing equip-
ment, and the reagent dosing and storage
facilities. It was assumed that carbon
would be stripped at 130C in a 316
stainless-steel column, gold would be
recovered by electrowinning, regenera-
tion would be done in rotary kilns,
and acid washing of the carbon after
regeneration would be done in mild-
steel, rubber-lined columns. For Minix,
an acid wash (to strip most of the base
metals) and the elution of gold and silver
with acidic thiourea would be done
in a mild-steel, rubber-lined column
at 60C. Gold would be recovered
by means of direct electrowinning
from the eluate. One elution per day
was assumed. Leach and smelt-house
facilities were excluded from the costs,
but purchasing, erection, and installa-
tion were included. The costs were
normalized by assuming that the cost
of the adsorption section of a 25
kt/month CIP plant would be equivalent
to 1,000.
In the case of a plant treating 25
kt/month of ore and producing standard
leach liquor (Table II), the relative costs
for CIP and MINRIP plants for the
different cost elements are given in
Figure 1a and b. Because actual costs
are time- and country-sensitive, a
relative cost comparison is more useful.
The potential cost savings in capital
(CAPEX) and operating expenditures
(OPEX) for a MINRIP plant relative to
2002 October JOM
150 kt/month
15
33
22
39
23
42
a CIP plant for all three types of solution
(Table II) and for different production
rates are given in Table III. The cost
study indicated that the MINRIP process
compared favorably with CIP for all
three solution types.
RESIN-IN-LEACH
In the case of carbonaceous ores in
which the bulk of the contained gold is
available for direct cyanidation, carbon-
in-leach (CIL) is generally applied
for the recovery of gold with varying
degrees of success, depending on the
aggressiveness of the preg-robber. In
cases where the activity of carbon is
insufficient to compete effectively with
the preg-robber, it is common practice to
use CIL in conjunction with a blanking
agent. However, the blanking agent,
generally an organic reagent, does not
only foul the carbonaceous preg-robber,
but the activated carbon as well. Resins
are less prone to organic fouling,5 and
can be successfully used in the presence
of some organic blanking agents.6
Minix was evaluated for its capability
to recover gold from preg-robbing
ores. Batch gold-dissolution tests
100
Auhead = 5.2 g/t
80 Corg = 0.59%
Au Recovery (%)
60
40
20
0 batch tests.
ROM-A
CN
were performed on three ore samples
originating from the same ore source
300 kt/month
using conventional leaching conditions
(pH~10.5, 50% solids). These included
10
28
two run-of-mine (ROM A and B) ore
samples and one flotation concentrate
13 (FC) sample. The organic carbon content
37
of these samples varied between 0.42%
14 and 2.34%. Tests were done on direct
40 cyanidation (CN), cyanidation in the
presence of the adsorbent (RIL, CIL),
and cyanidation in the presence of
the adsorbent and a blanking agent
(RIL+BA, CIL+BA).
Results indicated that gold recovery
can be very different for different ore
sources, and that the gold recovery is
not related to the carbon content of
the ore but rather to the aggressiveness
of the preg-robber (Figure 2). Results
illustrated that RIL, in combination
with a blanking agent (RIL + BA), was
beneficial in all three cases and enhanced
gold recovery significantly.
The optimum adsorbent for a par-
ticular gold-recovery application is not
necessarily the adsorbent that yields
the highest gold loading, but rather
the adsorbent that results in the most
profitable operation. A preliminary
economic evaluation comparing RIL
and CIL was carried out for an operation
located in West Africa, which treats
40 kt of preg-robbing ore per month.
Process simulation and cost models
were used to estimate the CAPEX and
OPEX for conceptual RIL and CIL
plants, and the results are shown in
Figure 3. Since pulp flowrate and gold
dissolution determine the size of the
leach/adsorption circuit, the CAPEX for
Auhead = 4 g/t Auhead = 32 g/t
Corg = 0.42% Corg = 2.34%
Figure 2. Gold
recovery during
ROM-B ROM-C
Ore Type
CIL CIL+BA
RIL RIL+BA
39
 Table IV. WINIX Ion Exchange Feed
Flowrate and Composition
Flowrate Au Ag Ni
8.75 m3/h 270 mg/L 17 mg/L 37 mg/L
this section of the circuit was assumed
to be the same for both adsorbents. The
flowrate of the adsorbent is dependent on
its metallurgical response in the specific
pulp and determines the adsorbent
inventory, size of the elution facility,
reagent consumption for stripping,
and adsorbent losses. The adsorbent
flowrate was estimated using a process-
simulation model with the equilibrium
and kinetic response of the adsorbent in
this specific pulp as input parameters.
The batch dissolution tests indicated
gold recoveries of 80% and 87% for the
CIL and RIL operations, respectively.
Apart from the lower CAPEX and
OPEX predicted for the RIL operation,
higher revenues should also be realized
as a result of the higher gold recovery.
The difference in gold recovery can
be significantly higher for other preg-
robbing applications.
It is therefore clear that RIL can
be a more cost-effective technology
than CIL for the recovery of gold from
preg-robbing ores. The cost savings and
additional revenue that can be realized
by using RIL instead of CIL has to be
quantified for each ore. A niche market
exists for the use of the Minix resin
for the recovery of gold from preg-
robbing ores where the superiority of
this resin over activated carbon has been
demonstrated on an operating plant in
Malaysia since September 1999.6 The
use of this adsorbent in a RIL circuit has
resulted in significant improvements in
gold recovery when compared to the
CIL and RIL (with a non-selective resin)
technologies previously employed.
RESIN-IN-SOLUTION
As a result of a relatively depressed
gold price, there is a worldwide trend
toward low-cost heap-leaching opera-
tions. Heap leaching provides relatively
low-grade, clear solutions from which
gold has to be upgraded. Carbon-in-
solution (CIS) is generally used for this
purpose. After Mintek had completed
developments of its RIP process and
Minix resin, attention was given to the
recovery of gold from clarified solutions
40
Table V. WINIX Precipitation Design Criteria
Feed
Au 20 g/L
Ag 1.1 g/L
with this resin.8
During 1999, Mintek and LTA Process
Engineering (currently Grinaker LTA)
completed a techno-economic evalua-
tion to compare RIS, using Minix, and
CIS for the recovery of gold from a
typical heap leach liquor. A lead-lag-lag
(three columns in series) fixed-bed
adsorption circuit was proposed for
the recovery of gold from heap leach
liquors at a typical gold concentration of
1.5 mg/L. An 8 min. residence time was
allowed for both adsorbents to decrease
the gold of the feed to below 0.01 mg/L
in the barren.
In order to minimize resin handling
and associated resin losses, it was
proposed that the resin elution be done
in the same column as adsorption.
A resin loss of 5% per annum was
assumed. After adsorption, carbon has
to be transferred to a separate elution
column that can tolerate the relatively
high temperature and pressure during
elution. Although transport of carbon
exacerbates its physical degradation,
the low cost of replacing carbon makes
this more economical than to construct
all the columns to comply with elution
5.0
4.0
Relative Costs
3.0
2.0
1.0
0.0
CIL RIL
Adsorbent Inventory
Elution Circuit
Adsorption Circuit
a b
Figure 3. A comparison of (a) CAPEX and (b) OPEX for CIL and RIL circuits.
Barren Vessel and Conditions
Au <50 mg/L Product ~90% Au
column specifications, so that loaded
carbon could be eluted in-situ. Carbon
loss was assumed at 0.02 g/t of ore
treated.
For sizing of a full-scale plant that
needs to treat 150 m3/h of clarified
pregnant liquor, it was assumed that the
resin and carbon loadings and kinetics
would be similar in a typical heap
leach solution. Mintek sized adsorption
circuits for both Minix and carbon,
which were similar based on the above
assumptions. LTA Process Engineering
used this information to prepare a
preliminary comparative costing for
RIS and CIS plants. Summaries of
the preliminary comparative CAPEX
and OPEX for CIS and RIS plants are
presented in Figure 4. Maintenance
of each plant was assumed at 5% of
CAPEX per annum. Labor and water
requirements were assumed to be the
same for both plants.
For this application, it was estimated
that the CAPEX for the RIS plant would
be about 30% lower than that of a
CIS plant. The main difference in the
CAPEX for these two plants was the
regeneration kiln required to regenerate
12.0
9.0
Relative Costs
6.0
3.0
0.0
CIL RIL
Adsorbent Replacement
Reagent Consumption
Power Requirements
JOM October 2002
 Minataur process. A carbon eluate would contain silver-
Table VI. Countercurrent Extraction of The use of ion exchange to recover cyanide and some base metal-cyanides,
Metal-cyanide Species from Synthetic
Effluent with Duolite A374*
gold from leach liquors, as an alternative predominantly nickel and copper. Silver
adsorbent to carbon, was described in is less strongly adsorbed onto resin than
Stage
the previous section on RIP. However, gold and the base metals. Therefore,
Metal Feed 1 2 3 prior to the development of WINIX, it would be necessary to take account
Metal in Solution Leaving Stage (mg/L) use of ion exchange to recover gold at of this during design of a process if
Zn 97 43 17 5 relatively high feed and resin-eluate silver is not to be lost. Special measures
Ni 10 10 9 7
Co 10 8 7 6
concentrations, such as those that would would also need to be adopted in the
Cu 9 9 9 8 be encountered in the envisaged process, presence of nickel and copper.
pH 11.4 had not been attempted. The intended Various methods of elution were
Metal on Resin (g/kg)
Zn 35 14 4
process would employ similar chemistry considered. However, acidic thiourea
Ni 2.0 2.2 1.6 and would be adapted to accommodate appeared to be the most suitable reagent
Co 1.4 1.0 0.5 the specific problems that would result with peak eluate concentrations of
Cu 0.9 0.7 0.6
because of the high concentrations.9 about 40 g/L being achieved. Gold
* Volume of resin per stage: 6 ml; resin transfer rate: Gold is adsorbed onto a commercial can be precipitated from the eluate by
1 stage every 8 h; flow-rate of solution: 132 ml/h.
anion-exchange resin from a carbon various methods. The method that was
eluate in which the gold is present as preferred, and is convenient, involves
activated carbon, while no thermal the aurocyanide species, as shown in contacting of the eluate with a small
regeneration of the resin is required. It Equation 3: stoichiometric excess of copper powder
was estimated that the OPEX for RIS until the solution is depleted of gold
R+(SO42-)12 + Au(CN)2-
would be 40% lower than that of the (Equation 4). The product contained
R+Au(CN)2- + 12(SO42-) (3)
equivalent CIS plant. gold, silver, copper, and a small amount
The preliminary techno-economic The high concentration of gold in the of unidentified impurity.
comparison between RIS, employing carbon eluate tested (about 300 mg/L
Au [SC(NH2)2]2
the Minix resin, and CIS indicated that compared with about 5 mg/L in a leach
+ SC(NH2)2(excess) + Cu
major savings could be realized when liquor) would result in higher loadings
(small excess)
RIS is employed for the recovery of than are obtained from leach liquors. In
Cu[SC(NH2)2]n + Cu
gold from low-grade gold solutions practice, maximum loading of about 150
+ impurity + SC(NH2)2 (4)
such as heap leach liquors. g/L gold was achievable with a typical
commercial resin. It was considered Two potential problems that were elimi-
WINIX
that this would be more than adequate nated by correct design of the process
Currently, the preferred method for to produce a sufficiently concentrated were the formation of supersaturated
the production of gold from ores is the resin eluate from which the gold could solutions and unacceptable impurity
CIP process, which involves adsorption be recovered conveniently. levels in the gold product.
of leached gold onto activated carbon,
elution, and recovery of the gold
from the eluate by electrowinning.
WINIXTM presents an alternative to 1.0
the electrowinning and smelting steps of 0.9 1
the process. Because WINIX lends 0.8
0.8
itself to automation, it is more secure 0.7
Relative Costs

than electrowinning and smelting, where

Relative Costs

0.6 0.6
most gold theft is believed to occur. 0.5
WINIX includes the steps of: 0.4 0.4
Adsorbing gold-cyanide from 0.3
0.2
carbon eluate using an anion- 0.2
exchange resin. 0.1 0
Eluting the gold using a suitable 0.0 CIS RIS
eluant to produce a high-concen- CIS RIS
Maintenance
tration gold solution. Stripping Labor
Precipitating the gold in a relatively Regeneration Power/Diesel
small vessel so that the precipitate Electrowinning and Smelting Reagents
is contained and can be processed a
Adsorption
b
Adsorbent Replacement
further without having to be
handled. Figure 4. The relative (a) CAPEX and (b) OPEX estimates for CIS and RIS.
Subsequent treatment of the precipitate
might involve smelting or re-dissolution
in HCl/oxidant for refining by Minteks

2002 October JOM 41

 The choice of resin and ion-exchange
design was based on results of mini- and
large-scale column breakthrough tests
at typical linear velocities envisaged
for the full-scale plant. A lead-lag-lag
configuration of columns was chosen.
Transfer of the lead column to elution
takes place when the desired degree
of breakthrough has occurred. Feed is
then transferred to the first lag column.
The loaded column, containing ~70 g/L
gold and now out of the loading circuit,
is stripped and returned to become
the second lag column. Effluent from
the adsorption circuit contains less
than 2 mg/L gold. Feed flowrate and
composition for a particular application
are given in Table IV.
Eluate is collected in the precipitation
vessel and then treated with copper
powder for half an hour to precipitate
gold. Details of precipitation are sum-
marized in Table V.
The barren precipitation solution
is neutralized, combined with the ion-
exchange barren, and returned to the
leaching section of the plant to ensure
that no gold in the solution is lost. It has
been established that the constituents in
this solution have no measurable effect
on leaching of gold. An alternative is
to maintain a low level of copper in this
solution by precipitation, so that thiourea
can be recycled to the elution section to
minimize its consumption.
The plant design includes safety
features such as venting of sealed vessels
and pipes to a scrubber wherever there is
the possibility of HCN generation.
Features and financial aspects of the
process are as follows:
The plant is fully automated
and therefore offers increased
security.
An improvement in gold recovery
would ensure a rapid payback
of capital outlay (CAPEX is typi-
cally less than 0.3 percent of
annual production). Operating
expenditures are expected to be
less than 0.05 percent of the gold
produced if thiourea is recycled.
Gold residence time is less than
24 h, resulting in significantly
reduced lock-up compared to
the conventional electrowinning
process.
The process can be designed to
be very efficient, with less than
42
3 mg/L of gold being recycled to
the CIP plant.
The process is simple and based
on well-established technology
adapted for the high concentrations
encountered.
It produces gold powder of about
90% purity, suitable for melting,
compacting, or as a direct feed to
the Minataur refining process.
The process has wide application in
terms of gold and silver concentra-
tions.
The high-security sections of the
plant are small and should fit into
most existing high-security areas
of gold mines.
The process is simple to operate,
has a low manpower requirement,
and requires low maintenance.
CYANIDE RECOVERY
Gold-recovery processes produce
effluents that contain free and complexed
cyanide. During the past few years, a
number of incidents involving cyanide
have resulted in a strict stance being
adopted in the United States regarding
the use of cyanide. This attitude is now
spreading to other countries. Mining
companies are feeling pressured to
remove these species from their effluents
although, by being contained in slimes
dams, aqueous-phase cyanides are not
strictly released into the environment.
Ion exchange is one of the few methods
that is non-destructive and that provides
the possibility of recovering cyanide for
re-use. Mintek reviewed past work and
carried out further work in an attempt to
develop a practical process for cyanide
recovery that is economically viable.
The potential for recovery of cya-
nide from gold-mine effluents by
ion exchange has been an interest of
researchers for four decades, 10 but
despite a few industrial trials, ion-
exchange technology has not been
fully implemented. A reason for this
is probably that process configurations
tend to be complex (depending on the
composition of the liquor). Furthermore,
unpublished preliminary assessments
at Mintek of various routes suggest that
economics are unfavorable. However,
with pressure being applied to attend
to the cyanide problem, and with the
possible need to offset the cost of a
process by recycling cyanide to the
leach, this type of approach to the
problem could become attractive.
A typical cyanide effluent consists of
free cyanide (CN) and complexed metal
cyanides (M(CN)xy) [e.g., Cu(CN)32,
Zn(CN)42, etc.]. In the presence of
sufficient cyanide, to ensure that the
metals in solution are present as these
anionic species, an anion-exchange
resin will be effective in recovering
them.
Some methods for the recovery of
cyanides, reported in the literature,
were summarized by Mintek.11 From
this prior work it is apparent that free
cyanide is poorly loaded by anion
exchangers and, in order to recover
cyanide efficiently, complexation with
metals such as iron, zinc, or copper to
form anions that have a greater affinity
for the resin is necessary. Preliminary
work at Mintek with strong- and weak-
base resins led to a preference for
the least technically complex route.
This involved a weak-base resin where
elution is accomplished with alkali that
causes the resin to lose its positive charge
through removal of a proton.
The favored resin had a higher pKa
value than the conventional weak-base
resin so that a sufficiently high pH could
be used to avoid formation of HCN and
concomitant volatilization.
Mechanisms of weak-base loading
and elution are given in Equations 5
and 6:
Loading:
Resin-NR2 + H2O Resin-
NR2H+OH
yResin-NR2H+OH + M(CN)xy
[Resin-NR2H+]yM(CN)xy
+ yOH (5)
Elution:
[Resin-NR2H+]yM(CN)xy
+ yOH yResin-NR2 + M(CN)xy
+ yH2O (6)
After elution, metal-cyanides would be
decomposed with acid to obtain HCN
(Equation 7), which will be scrubbed
and recycled:
M(CN)xy + xH+ M(x-y)+
+ xHCN (7)
Some species might not dissociate
completely [e.g., Cu(CN)32 to CuCN +
2(HCN)], and these and other metal salts
formed might require further treatment.
JOM October 2002
 This route was originally investigated
for treatment of effluent from a process
in which gold was recovered by cementa-
tion with zinc and, therefore, the
predominant complexing metal of
cyanide was zinc. The effluent was free
of solids and could be treated in a
fixed-bed column.
The more important application in the
future would be treatment of tailings
arising from a CIP process.12 Clarifica-
tion would be impractical and RIP
for removal of cyanides would be
appropriate.
In the development of MINRIPTM, a
laboratory countercurrent column
procedure was useful in determining the
feasibility and the operating parameters
of the in-pulp process. 13 A similar
experimental set-up was used in this
work to evaluate the removal of metal-
cyanide species with Duolite A374
medium-base resin. Free cyanide, which
is likely to be present in this effluent,
will have to be complexed to facilitate
recovery. Thus, a synthetic effluent,
containing added zinc to complex free
cyanide, was treated in a three-stage
counter-current configuration. Table VI
gives the solution and resin profiles
obtained at steady state. It is apparent
that zinc-cyanide was removed fairly
well and selectivity was in the order
Zn>Ni~Co>Cu.
Optimization of this configuration, in
order to remove the other base metal-
cyanides more effectively, should include
the use of an additional stage and
variation of the relative resin-to-solution
flow rates. Changing the pH and the use
of different metal salts to complex all
free cyanide could alter the affinity of
the resin for a particular metal because
of changes in species distribution that
might take place.
Characterization of cyanide species
in this work proved to be uncertain and
is the reason for reporting results in
terms of the metals rather than specific
metal-cyanides. This problem had been
recognized in other areas of work
involving metal-cyanides and has since
received attention at Mintek and else-
2002 October JOM
where, so that today reliable results could
be obtained if further developmental
work were to be undertaken.
Various methods of elution, including the
use of alkali and acid, were attempted, but
the preferred eluant had the composition
of 0.05 M Ca(OH)2, 0.05 M Ca(CN)2.
By use of 23 bed-volumes of this eluant,
92% Zn, 98% Ni, 93% Cu, and 23%
Co were stripped. It was necessary to
include cyanide in the eluant to obtain
an efficient elution of zinc. In the
absence of cyanide, it is thought that
a poorly soluble basic zinc-cyanide
species might have formed and possibly
precipitated in the pores. The reason for
the poor elution of cobalt is not clear.
However, there is evidence from other
work that cobalt will build up to an
insignificant level on the resin and then
remain constant without measurably
affecting loading.
The eluate, with alkali almost
depleted, would be treated with acid to
generate hydrogen cyanide that can be
flushed from the solution and recycled
to the leaching section of the plant,
either directly or after neutralization
with lime. The effluent that will contain
metal salts and stable metal-cyanide
precipitates might have to be treated
further.
A preliminary economic assessment
involved only the RIP units and not
peripheral processes such as scrubbing
of hydrogen cyanide. These peripheral
processes involve costs that will have
an impact on the economics. The
process was not promising from an
economic viewpoint. Although the input
parameters used gave a positive cash
flow, a negative cash flow resulted
when costs of peripheral processes
were included. A sensitivity analysis
suggested that capacity of the resin
should be improved.
It seems unlikely that this process
could be made economical; the value of
cyanide recovered would, at best, only
partially offset the cost of processing.
An environmentally driven motivation
for applying the process would be
necessary.
ACKNOWLEDGEMENTS
This paper is published by permission
of Mintek.
References
1. Theft Hits Gold Mine Profits Hard, Business Day (8
February 2001).
2. C.A. Fleming, The Potential of Anion Exchange
Resins in the Gold Industry, EPD Congress 1998, ed.
B. Mishra (Warrendale, PA: TMS, 1998), pp. 95117.
3. M.H. Kotze, B.R. Green, and G. Steinbach, Progress
in the Development of the Minix Gold-selective
Strong-base Resin, Hydrometallurgy Fundamentals,
Technology and Innovation, ed. J.B. Hiskey and J.W.
Warren (Littleton, CO: Society for Mining, Metallurgy
and Exploration, 1993), pp. 395406.
4. M.W. Johns and D. Marsh, A Technical and Economic
Comparison Between the Carbon-in-Pulp Process and
the MINRIP Resin-in-Pulp Process, Randol Gold Forum
(Golden, CO: Randol International Ltd., 1993), pp.
293299.
5. C.A. Fleming, Recovery of Gold by Resin-in-Pulp at
the Golden Jubilee Mine (Paper presented at the
Precious Metals 89 Symposium, Las Vegas, March
1989).
6. G.O. Lewis and W. Bouwer, Resin-in-Leach: An
Effective Option for Gold Recovery from Carbonaceous
Ores (Randol Gold Forum, Vancouver, Canada, 2528
April 2000).
7. G.V. Lewis, The Penjom Process, An Innovative
Approach to Extracting Gold from Carbonaceous Ore
(Paper presented at the Gold Processing in the 21st
Century: An International Forum, AJ Parker Cooperative
Research Centre for Hydrometallurgy, 2223 November
2000).
8. J. Van Deventer et al., Comparison of Resin-in-Sand
Carbon-in-Solution for the Recovery of Gold from
Clarified Solutions, Extractive Metallurgy 1999
(Johannesburg, South Africa: South African Institute of
Mining and Metallurgy, 1999), pp. 5561.
9. R.L. Paul and B.R. Green, Recovery of Gold from
Carbon Eluate, PCT Patent Application PCT/
ZA02/00045 (2002).
10. E. Goldblatt, Recovery of Cyanide from Mine Waste
Solutions by Ion Exchange, Ind. Eng. Chem., 48 (12)
(1956), p. 2107.
11. T.E. Chantson and B.R. Green, The Removal of
Cyanide from Mine Effluents by Ion Exchange (Paper
presented at the South African Chemical Institute
Symposium: Cyanide in Gold Processing: The Next 100
Years, Johannesburg, South Africa, 56 November
1990).
12. B.R. Green, M.H. Kotze, and J.P. Engelbrecht,
Resin-in-PulpAfter Gold, Where Next? EPD
Congress 1998, ed. B. Mishra (Warrendale, PA: TMS,
1998), pp. 119136.
13. M.W. Johns, B.R. Green, and D. Marsh, Resin-in-
Pulp (South African Institute of Mining and Metallurgy,
School: Hydrometallurgy, Randburg, South Africa, 2729
July 1994).
B.R. Green, M.H. Kotze, and J.P. Wyethe are with
MINTEK, Hydrometallurgy Division.
For more information, contact Brian R. Green,
MINTEK, Hydrometallurgy Division, 200 Hans
Strijdom Avenue, Randburg, Gauteng 2125, South
Africa; 011-709-4547; fax 011-709-4160; e-mail
briang@mintek.co.za.
43