Journal of the UniversityV.

of
Kyoseva, Ek.Technology
Chemical Todorova, Iv.
andDombalov
Metallurgy, 44, 4, 2009, 403-408

COMPARATIVE ASSESSMENT OF THE METHODS FOR DESTRUCTION

OF CYANIDES USED IN GOLD MINING INDUSTRY
V. Kyoseva1, E. Todorova2, I. Dombalov1

1
University of Chemical Technology and Metallurgy Received 05 September 2009
8 Kl. Ohridski, 1756 Sofia, Bulgaria Accepted 12 October 2009
E-mail:: vania225@abv.bg; dombalov@mail.bg;

2
University of Forestry
10 Kl. Ohridski, 1756 Sofia, Bulgaria
E-mail: ek_todorova@mail.bg;

ABSTRACT

A comparative assessment of the methods for destruction of cyanides used for gold containing ores processing in
Chelopech Mining PLC, BMM PLC Krumovgrad, Gorupso - Kurdzhali SA and KCM Plovdiv SA for meeting the
environmental standards is done. Depending on the ratio of cyanide to Caros acid, cyanide to sulfur dioxide or cyanide
to a mixture of polysulphides and hydrogen peroxides, destruction of the cyanides in the wastewaters and pulps to
concentrations that are harmless for the environment is obtained.
Keywords: cyanides, leaching, destruction, concentration.

INTRODUCTION ticles of 45 mm will be dissolved for 10 - 13 h, whereas

Cyanides are used for gold extraction from gold-
containing ores since the 1890s. The first application
of cyanides for gold extraction in Bulgaria is in the ore-
dressing factory Zlata ever since the 30s of the last
century, until the gold ore depletion. Nowadays world-
wide, the cyanide method is the most widely used for
precious metals extraction (including gold). The pro-
cess runs according to the reaction [5,6,8]:
4 Au + 8(NaCN) +O2 + 2H2O = 4NaAu(CN)2 +
4NaOH
Essential technological feature is the concentra-
tion of the cyanide solution, which is low and contains
0.02 to 0.05 %mass NaCN. Another factor in the cyanide
leaching is the extent of uncovering the gold-containing
particles, which reflects on the speed of the process and
the extent of the gold extraction from the raw material.
The more finely grounded the raw material is, the faster
the gold dissolves. For example, gold-containing par-
particles of 150 mm will need 20 - 44 h in the same
solution.
The main threats in the cyanide methods for gold-
leaching are related to the remaining concentration of
cyanides and mostly - the one of the weak acid
dissociable (WAD) cyanides in the after-treatment
refuse. Directive 2006/21/EC of the European Commis-
sion for extraction industries waste management [10]
determines maximum allowable concentration (MAC)
for WAD cyanides up to 50 mg dm-3 for existing pro-
duction installations, but it is predicted that this value
will be lowered to 10 mg dm-3 until 2010. All new in-
stallations which apply for a Complex Permit after 2008
have to abide by the reduced value of 10 mg dm-3.
The aim of the comparative assessment done in
the present publication is to establish wether there is a
compliance of the methods for cyanide destruction, fore-
seen for implementation in four new installations in
Bulgaria, with the environmental standards for remain-

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 Journal of the University of Chemical Technology and Metallurgy, 44, 4, 2009

Table 1. Test results for destruction of cyanides with Caros acid.

-3
Test Molar ratio WAD CN (mg dm )
CN (WAD) : KHSO5 Initial value Final value
1-1 1: 0.98 444 4.8
1-2 1: 1.34 444 6.0
1-3 1: 1.94 444 4.9
2-1 1: 0.98 442 5.7
2-2 1: 1.49 442 4.9
2-3 1: 2.00 442 7.0
3-1 1: 1.00 463 7.9
3-2 1: 1.46 463 7.3
3-3 1: 1.93 463 3.8

ing cyanide quantities in the waste pulp (water and mid- The entire oxidative reaction of the Caros acid
dling slime) according to the Bulgarian (resp. European) with the cyanide is:
legislation. H2SO5 + CN- = OCN-+ SO4-2 + 2H+
The acidic ions H+ generated during the reaction
RESULTS AND DISCUSSION are neutralized by the relatively high pH (>10.5) of the
waste pulp from the leaching and carbon adsorption
The treatment of the cyanides can be realized in cycle. In a case of necessity limestone can be added to
both industrial and natural conditions. In Chelopech support the pH needed.
Mining PLC, the reduction of the cyanides below 10 The quantity of Caros acid which should be added
mg.dm-3 in the waste pulp, before releasing it in the is determined on the base of the quantity of WAD cya-
tailings dam, is done by the method of the nides in the waste pulp. Lime can be also added in the
peroxymonosulfuric acid (so called Caros acid). In the reactor if there is a need the pH level to be regulated.
reactors for leaching and carbon adsorption the cya- The process is absolutely automated.
nides extract the gold from the pulp (WAD cyanides In 2005, Lakefield Research Limited Ontario,
concentration : 300 mg dm-3 ) after the autoclave Canada are carried out tests for treatment of waste pulp
through binding it in gold-cyanide complexes which from Chelopech [1]. The results are summarized in Table 1.
adsorb on activated carbon [1]. In the autoclave run The data in the table show that irrespective of
processes of high-temperature oxidation under pressure the artificial increase of the initial concentrations (made
of the ore, the waste pulp with concentration of free only because of more convincing demonstration of the
cyanides about 150 mg dm-3 are fed in a mixture vessel
where they mix with the Caros acid for destruction of
the cyanides. Caros acid (H2SO5) is received from con-
centrated (70 %mass) solution of hydrogen peroxide and
sulfuric acid (93 %mass) via an exothermic reaction:
H2O2 + H2SO4 = H2SO5 + H2O
The hydrogen peroxide, sulfuric acid and water
are mixed in an external reactor and after that are fed to
the waste pulp, being dozed under permanent automated
control [1, 5]. The reagents are subjected to continuous
mixing for long enough so that an oxidative reaction can
be carried out. For oxidation of the cyanides (free and
weak acid dissociable) to the much less toxic cyanates Fig. 1. Cyanides life cycle according to the investment
and thiocyanates certain technological time is needed. proposal of Chelopech Mining EAD.

404
 V. Kyoseva, Ek. Todorova, Iv. Dombalov
Table 2. Results from the detoxification of cyanides via the INCO process in the processing of gold-containing
ore of Gorupso Kurdzhali.
Cyanides concentration Measure Sample
Before destruction mg dm-3 1-1
1-2
1-3
After destruction mg dm-3 1-1
1-2
1-3

process effectiveness) the final levels of WAD cyanides
obtained, are always lower than the maximum allow-
able concentration. At the same time, the final levels of
WAD cyanides show relatively weak sensibility towards
the Caros acid being fed (varying from 0.98 up to 2
times the quantity of WAD cyanides), which guarantees
a sufficient level of certainty within the normal techno-
logical conditions disturbance. A scheme of the life cycle
of cyanides is shown on Fig. 1.
In this way, after destruction of the cyanides, the
content of WAD cyanides entering the tailings dam will be
between 2 and 5 mg dm-3, which is less than the concentra-
tion of 10 mg dm-3, according Directive 2006/21/EC.
In BMM EAD Krumovgrad and Gorupso
Kurdzhali EAD the expected reagent for cyanides de-
struction is SO2 and cupric sulphate (CuSO4.5H2O) is
used as a catalyst. This is the so called INCO process,
Fig. 2. Life cycle of the cyanides according to the investment
proposal of BMM EAD Krumovgrad (INCO process).
Total WAD cyanides Free cyanides
cyanides
103.0 65.0 36.3
145.0 125.0 83.3
210.0 175.0 146
0.95 0.84 0.5
0.40 0.30 0.6
0.33 0.30 <0.5
which is widely used in the world practice for destruc-
tion of cyanides used for gold leaching [2, 4,10].
To the open reactor reservoirs for cyanide de-
struction in which is the thickened pulp, solution of
sodium pyrosulfite (Na2S2O5), which ensures the quan-
tity of SO2 needed, as well as CuSO4 solution which acts
as a catalysts, with intensive mixing and aeration is fed.
This leads to destruction of the free and WAD cyanide
complexes and their transformation in cyanates, thiocy-
anates and other much less toxic compounds. The life cycle
of the cyanides in the INCO process is shown in Fig. 2.
The maximum concentration of the WAD cya-
nides in the final waste will be much below the standard
of 10 mg dm-3 according to Directive 2006/21/EC. The
semi-industrial tests carried out with ore from Ada Tepe
parcel show that the cyanide in the final pulp at the en-
trance of the tailings dam will be about 1 mg dm-3. Be-
cause of the low concentrations of the entering WAD
cyanides (1 mg dm-3), the possibility for their natural
degradation and the significant area of the tailings dam,
the generation of hydrogen cyanide in quantities over
0.03 mg dm-3 upon the water mirror is not expected. In
the atmospheric air, even close to the installation, be-
cause of the big airflow mass, the content of hydrogen
cyanide is below the maximum allowable standards
0.01 mg dm-3.
The project warranty of Gorupso Kurdzhali
SA assures meeting the normative levels for free cya-
nides before their release in the tailings dam. The cya-
nides destruction is analogical to the one shown on Fig.
2 and the results from the preliminary pre-project stud-
ies are given in Table 2 [4].
Similar results are obtained in the detoxification
of cyanides in gold extraction from other deposits in
different countries, when applying the INCO process
[11-15]. The results are summarized in Table 3.
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 Journal of the University of Chemical Technology and Metallurgy, 44, 4, 2009

Table 3. Summarized results from destruction of WAD cyanides, based on data for INCO process application
Factory Before the technological installation for After the technological
destruction, mg.dm -3 installation for destruction
(at the entrance of the
tailings dam), mg.dm-3
Martha Hill 213 0.5
Golden Cross Mine, New Zealand 150-220 6.8
Summarized data 300 <1.0

Table 4. Summarized results from the destruction of cyanides under natural conditions

Factory At the entrance of the tailings dam,
mg.dm -3
Lupin, NWT, Canada 184
Holt McDermott, Ontario, Canada 74.8
Cannon, Washington, USA 284
Ridgeway, South Carolina, USA 480
Golden Cross, New Zealand 6.8 (WAD)

The treatment of cyanides according to the in-
vestment proposal of KCM SA Plovdiv [3] will be
carried out applying a combined scheme for cyanides
treatment dozing the base reagent CNRid a firm
reagent from the type of the alkaline polysulfides and
additive of hydrogen peroxide or sodium hypo chloride
(hydrogen peroxide is recommended). The reagents are
added under continuous process of mixing. The normal
consumption of CNRid reagent is 3,1 kg kg-1 NaCN.
The controlled feeding of reagents continues until the
level of the cyanides falls below the permissible level of
1.0 mg dm-3, which is determined via manual titration
with silver nitrate.
Processes of additional destruction of cyanides
under atmospheric conditions
European Directive 2006/21/EC regulates the
concentration of cyanides at the entrance of the tailings
dam to be below 10 mg dm-3. In the tailings dam, under
the impact of the solar radiation, the treatment of the
WAD cyanides goes on under natural conditions
[7,8,11-15]. Results from the natural detoxification in
installations in Canada, USA and New Zealand are given
in Table 4. The mechanism of natural degradation of
cyanides in the tailings dam under natural conditions is
shown on Fig. 3. It should be noted that the hydrogen
cyanide has a boiling temperature of 27oC and via the
constant from Henrys law it is found that about 20 %
of the present HCN will be in gaseous phase. The dis-
tribution between CN- and HCN is expressed via the
following equation:
At the exit of the tailings
dam, mg.dm-3
0.17
0.02
<0.05
0.09
0.33 (WAD)
CN- + H+ HCN, pKa = 9.4.
The actual CN-/HCN ratio is shown on Fig. 4.
In the summer relatively small part of the liquid
phase in the waste pulp will evaporate as a result of the
gravity washing, because this part is small compared to
the content of WAD cyanides. Moreover, this part is
even smaller in cold weather conditions.
The clarified water in the tailings dam will have
direct contact with the atmosphere. As a result in this
facility will enter atmospheric rainfalls and processes
of evaporation will run. As a result of carbon dioxide
absorption and iron oxidation, pH will decrease from
8.5 9.5 to 7.6 8.0. As pH decreases the equilibrium
between CN- and HCN changes in advantage to HCN
formation which will pass in the gaseous phase, as it is
shown on the figures above.
It is expected 10 - 30 % of the present WAD
cyanides to evaporate. Simultaneously with the trans-
formation of HCN, the cyanides that are left in the so-
lution can interact with the iron, found in the solution,
and can be destructed as a result of hydrolytic and bio-
logical processes. As a result of all this, it is expected
the content of WAD cyanides in the tailings dam to be
2 to 5 mg dm-3 (if they enter the facility with concentra-
tion of 9 - 10 mg dm-3). The concentration of the cya-
nides and the processes of natural detoxification are in
direct dependence with the meteorological conditions,
the size of the tailings dam (the ratio of the area to the
depth) and the concentration of WAD cyanides in the
incoming pulp.

406
 V. Kyoseva, Ek. Todorova, Iv. Dombalov
Fig. 3. Cyanides life cycle the mechanism of natural degradation under natural conditions (natural detoxification).
Widely popular are the processes of bio-degra-
dation of cyanides [5-9], in which thiocyanate and cy-
ano-metal complexes are formed. It is proved that the
assimilation and the detoxification of the cyanides and
the thiocyanate run under the impact of a large number
of microorganisms, including bacteria like these:
Fig. 4. Behaviour of the cyanide and the hydrogen cyanide
in water solution as a function of pH.
Pseudomonas, different forms of Arthrobacter, rod-like
bacteria (Bacillus), sulfur bacteria (Thiobacillus), Acti-
nomyces and fungi. The bio-degradation of cyanides,
thiocyanate and the cyano-metal complexes is success-
fully applied in Homestake mine in Lead, South Da-
kota (USA) as a full capacity treatment processing of
tailings containing WAD cyanides in concentrations less
than 50 mg dm-3. Cyanides degradation bacteria are iso-
lated from grounds for heap ore leaching. Hence, there
is a huge probability for cyanides degradation in the
tailings dam under bacterial action.
CONCLUSIONS
From the comparative assessment done for the
treatment of cyanides, applied on a world scale and the
ones that are proposed for implementation in the in-
stallations for cyanide gold extraction in Bulgaria for
their compliance with the environmental norms, it is
established that the proposed methods correspond to
the best available techniques (BATs) for control of cya-
nides concentration in the wastes from the mining in-
dustry and comply with the requirements of Directive
2006/21/EC (10 mg/l WAD cyanides), and in this way
they correspond to the Bulgarian legislation as well:
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 Journal of the University of Chemical Technology and Metallurgy, 44, 4, 2009
The final levels of WAD cyanides (2 to 5 mg
dm-3) show relatively low sensitivity towards the quan-
tity of Caros acid fed (varying from 0.98 to 2 times the
quantity of WAD cyanides). In this way the process
guarantees a significant level of certainty in case of dis-
rupting the optimal technological conditions for the
waste pulp from Chelopech Mining AD.
In the INCO process, the cyanide in the final
waste from the installations of BMM AD Kurdzhali
will be about 1-2 mg dm-3.
A mixture of alkaline polysulfides and hydro-
gen peroxide or sodium hypo chlorite (CNRid reagent)
leads to destruction of cyanides to remaining concen-
tration of 1.0 mg dm-3.
There is a possibility for additional degradation
of cyanides under natural conditions in the tailings dam
in the presence of microorganisms, including bacteria
and fungi, as the degree of degradation of the cyanides
depends on the meteorological conditions, the size of the
tailings dam and the WAD cyanides in the incoming pulp.
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