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Catalysis Communications 67 (2015) 8789

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Catalysis Communications

journal homepage: www.elsevier.com/locate/catcom

Short communication

Cyanide leaching of gold catalysts


M.C. Raphulu a, M.S. Scurrell b,
a
Molecular Sciences Institute, School of Chemistry, University of the Witwatersrand, University of the Witwatersrand, Johannesburg, South Africa
b
Department of Civil and Chemical Engineering, University of South Africa, Florida, Johannesburg, South Africa

a r t i c l e i n f o a b s t r a c t

Article history: Gold catalysts remain of great interest, but a high gold price presents a concern. Gold can be leached from gold
Received 15 February 2015 titania catalysts using alkaline cyanide solutions. The specic activity of gold for CO oxidation can thereby be in-
Received in revised form 4 April 2015 creased substantially, though the precise nature of the gold before and after treatment remains unclear. It seems
Accepted 6 April 2015
unlikely that leaching proceeds in a simple manner by selective dissolution of metallic gold particles. Rather it is
Available online 8 April 2015
likely that cyanide ions interact with gold centers in several ways and, in addition, alkali metal ions may also
Keywords:
modify activity.
Gold 2015 Published by Elsevier B.V.
Titania
Cyanide
Leaching
CO oxidation
Thrifting

1. Introduction to selective leaching of ionic gold, or might also result in deactivation of


ionic gold by poisoning if the cyanide remains in a coordinated state. We
The interest in high activity gold catalysts continues but several as- do accept that a variety of gold oxidation states is likely to exist on gold/
pects remain controversial. The confusion in the literature as to whether metal oxide catalysts as evidenced by Mossbauer [6] or EXAFS [7] stud-
ionic or metallic gold is responsible for the catalytic activity of gold cat- ies, even without the use of any special oxidative or reductive treat-
alysts has aroused our interest in investigating the effect of gold cata- ments. In both types of work Au(I) is implicated in CO oxidation
lysts freed of metallic gold species. In addition, we are intrigued by the catalysis. But, using cyanide leaching, an intrinsically oxidative process,
possibility that the thrifting of gold might be possible if unreactive or to probe gold's oxidation state [2] is clearly unsound. Nevertheless we
less active metal can be removed in a selective manner by cyanide treat- do agree that the use of cyanide treatment is an interesting research
ment. The price of gold was in the range US$200250 oz1 in the early topic and one which may lead to a better understanding of the action
part of the century but now reaches US$13001500 oz1 so that gold of gold catalysts, including opportunities for thrifting of the precious
has become a much more expensive commodity. In the work of Moreau metal.
et al. [1] it has been suggested that the activity of titania-supported gold
for CO oxidation is directly proportional to the gold loading, so that 2. Experimental
thrifting would seem difcult if not impossible. In contrast, with gold
on ceria catalysts for the water gas shift reaction, cyanide leaching TiO2 (Degussa P25) (5.06 g) was mixed with distilled water (1 l) and
removes a lot of the gold but activity remains unchanged [2]. Clearly, stirred for 10 min. A solution of HAuCl4xH2O with distilled water was
in this system, a large fraction of the gold is inert or of low activity. added dropwise after which the ammonium solution was added drop
The interpretation that cyanide selectively removes metallic gold is, in wise to precipitate the catalyst until a certain pH was reached (note:
our view largely unsubstantiated and, in fact, probably incorrect. Metal- we are aware that there are inherent dangers in using ammonium
lic gold reacts readily with cyanide but this is an oxidative process, and salts in this way because of the potential for formation of the explosive
furthermore requires alkaline conditions to proceed [35]. Cyanide can gold fulminate). We wanted to prepare gold/titania free of alkali metals
almost certainly bind to ionic gold (e.g., Au+) and this reaction is prob- and, in our experience, careful handling of the materials and operating
ably faster because no oxidation of the gold is required. This could lead on a small scale minimize any risks. The catalyst was aged, ltered
and washed with distilled water (~ 3 l), dried at 120 C for 16 h and
then calcined at 400 C for 5 h. Various pH (in the range 5 to 11) and
Corresponding author. aging times (in the range 0 to 12 h) were investigated as shown
E-mail address: scurrms@unisa.ac.za (M.S. Scurrell). below. The nominal gold content was 2%. Selected catalysts were

http://dx.doi.org/10.1016/j.catcom.2015.04.011
1566-7367/ 2015 Published by Elsevier B.V.
88 M.C. Raphulu, M.S. Scurrell / Catalysis Communications 67 (2015) 8789

leached with potassium cyanide (KCN) at different concentrations. The


simplied equation for gold leaching is:

Au 2CN AuCN2 :

Thus 2 mol of CN are needed to leach 1 mol of Au. We investigated


the use of cyanide in excess or deciency, employing 1, 2 or 6 mol CN :
1 mol Au with no addition of base, or with the addition of NaOH, in
which case a pH = 9 was employed. In blank runs we also leached
with neutral water alone. The leaching period was kept short at 5 min
in all cases. The leached catalysts were dried in the oven for 16 h and
sieved (150250 m). After leaching all catalysts were dried at 120 C
and resieved (150250 m).
The CO oxidation reactions were carried out in tubular quartz reac-
tor. About 200 mg of the catalyst was loaded and treated in 20% oxygen
in helium at 100 C. The reaction mixture consisted of 10% CO and 5% O2
balanced by helium at a total ow rate of 40 ml/min. This ow rate
corresponded to a space velocity of 2500 h1. A GC equipped with a
Porapak column and a thermal conductivity detector (TCD) was used
Fig. 1. Catalytic activity for CO oxidation of 2%Au/TiO2 catalysts after various leaching
to analyze the reaction products. treatments.
Gold contents of various catalysts, fresh and leached, were deter-
mined by complete dissolution followed by analysis using Inductively
Coupled Plasma-Optical Emission Spectrometry. 100 mg solid sample We propose that cyanide has several likely roles: (1) The oxidative
was rst digested with 3 ml hydrogen uoride (HF) and 5 ml nitric dissolution of metallic gold takes place with a removal of gold to solu-
acid (HNO3) for 60 min in a MultiWave 3000 (Anton Paar Co.) micro- tion. This action proceeds in a corrosive manner such that small Au par-
wave solvent extraction oven. ticles are eaten away from the outer surface, so that it is quite possible
that some smaller metallic particles may result. Whether these smaller
3. Results and discussion particles are more reactive towards further cyanide attack or whether
they are increasingly stabilized by stronger interaction with the support
The method of silver and gold extraction from their ores by dissolv- is not known. (2) Cyanide anions can complex with metallic gold or gold
ing them in a dilute solution of sodium cyanide or potassium cyanide ions and be retained on the surface. They can however be removed by
was patented in 1888 [3] and has been extensively used since. In washing or can effectively desorb at higher temperatures during subse-
cyanidation, metallic gold is oxidized and dissolved in an alkaline solu- quent catalysis. (3) The sodium and potassium ions can exert a positive
tion (more gold is recovered by cyanidation than by any other process). or negative effect on catalysis, depending on their residual concentra-
The oxidant employed is atmospheric oxygen which, in the presence of tions, in turn affected by the extent of post-leach washing that is ap-
an aqueous solution of potassium cyanide, causes the dissolution of gold plied. Such ions were reported to increase the rate of CO oxidation [8,
and the formation of cyanoaurite, as part of the overall process [4] The 9], but the optimum amount of these ions on the surface of the catalyst
cyanidation process of materials is a heterogeneous reaction (i.e., a reac- has not been thoroughly investigated. (4) Cyanide ions may exert a fur-
tion driven by unlike components) and is a corrosion process. The over- ther affect on catalytic activity in the same way as observed for other an-
all leaching of gold depends on the following reaction [3,5]: ions [1012] and, again, the observed effects are likely to be anion
concentration dependent. Leaching removes the bulk Au from the sur-

4Au 8CN O2 2H2 O 4AuCN2 4OH : 4 face of the catalyst, leaving small, well dispersed Au particles strongly
interacting with the support [2,13,14]. Minato et al. [14] observed a
The cyanide treatment thus involves the attack of small metallic gold
particles, rendering them smaller, the complete dissolution of gold
metal, the oxidation of gold and the complexation of cyanide ligands
with gold either in the solid or in solution. The resulting catalytic activity
of the solid will depend on the balance between several activating and
deactivating steps and on the subsequent treatment of the solid before
catalysis is attempted.
The reactivities of metallic and ionic gold on a support may well be
sufciently different to allow for a selective attack of cyanide on gold
though this remains speculative at this stage of our knowledge. What
is almost certainly true is that while some gold contributes to high cat-
alytic activity much gold plays a spectator role.
Fig. 1 shows clearly that cyanide-treated samples of Au/TiO2 retain
activity, particularly for high temperature operation. Water leaching
had little or no effect on activity. Leaching with sodium hydroxide was
very deleterious, presumably because excess sodium ions are retained
on the catalysts. Indeed cyanide treatment also leads to a severe de-
crease in catalytic activity but this can be overcome by washing the
leached solids before using them in the catalytic reaction.
The Au contents of the cyanide leached solids were substantially re-
duced (Figs. 2, 3), but, overall, the specic activity of Au for CO oxidation
at 50 C was increased (by a factor of almost 3) as the Au content fell. The Fig. 2. Gold content of catalysts after leaching with: a) original sample, b) water alone,
specic turnover frequency is increased from 1.3 to 3.3 102 s1. c) NaOH alone, d) KCN + NaOH, e) KCN alone.
M.C. Raphulu, M.S. Scurrell / Catalysis Communications 67 (2015) 8789 89

by Moreau et al. [1]. It seems likely that a substantial part of the gold in
Au/TiO2 is of low or zero activity but that the partition of gold between
the active and less active states is an essentially constant so that a linear
relationship between Au content and activity is obtained. The water gas
shift system involving Au/CeO2 may well operate differently.
In conclusion, cyanide leaching can be used to thrift gold, at least in
the Autitania system for CO oxidation. Whether the approach can be
applied more generally requires more work. The interaction between
cyanide and gold catalysts shows promise for elucidating further the
structure and action of gold catalysts, including the much researched
question of gold speciation and the detailed nature of the active sites.
It seems likely that this quest will be fruitful if due recognition is given
to the chemistry of cyanide interaction with gold species and if very
careful characterization, probably using advanced spectroscopic
methods of fresh and leached samples is carried out in conjunction
with leaching work.

Fig. 3. Removal of gold from catalysts as a function of the KCN concentration used. Acknowledgments

Financial support by the Johnson Matthey Technology Centre, UK, the


decreased particle size with decreasing coverage of Au on the surface of
National Research Foundation and the University of the Witwatersrand
TiO2 using Scanning Tunneling Microscopy (STM).
is gratefully acknowledged.
It has been reported that the CO oxidation reaction occurs on the
steps, edges, and corner atoms, and these were found to increase in
number with decreasing particle size [15,16]. When leaching the cata- References
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