Ozone Treatment for Cyanide

Effluents in Mining Industries

Introduction
This fact sheet presents a brief introduction outlining the
advantages of ozone treatment applied to mining industries,
especially to the gold mining industry.
Ozone can be used for successfully transforming toxic cyanide
wastes into harmless substances. Hereby, ozone mitigates the
adverse environmental effects associated with cyanide gold
extraction processes.
The cyanide treatment with ozone is resulting in clean offsite
effluents, permissible for indirect or even direct discharge from
the gold-ore processing.
WEDECOs ozone treatment solutions provide state of the art
oxidation processes for the mining industry. The ozone treatment
processes can be designed suiting site specific treatment targets.
These include: cyanide removal of wastewater/process water by
oxidation, cyanide regeneration processes and pre-ozonization for
process optimization and reduction of cyanide consumption.
Gold Mining
Gold mining, depending on the exploitation methodology, can be
a tedious, labor and cost intensive process. This is especially true
for mines with low-grade deposits. Some ores contain as little as
0.001% gold. In such scenarios the chemical extraction processes
(i.e. cyanide leaching) are one of the most efficient and economical
extraction options. In general cyanide leaching (hydrometallurgical
extraction) is now the dominant method used in the gold mining
industry. Annually ~2500 tons of gold are extracted from mines
worldwide; 90% of which are extracted by cyanide leaching
techniques.

The dominance of the cyanide leaching process is due to its

efficiency compared to alternative processes that utilize complexing
agents such as: chloride, bromide, thiourea and thiosulfate. All
these alternatives form less stable complexes and thus require more
aggressive conditions and oxidants to dissolve the gold. In contrast
the cyanide leaching exhibits much more efficient extraction rates
(85% - 95%). In comparison the conventional complexing agents
exhibit only extraction efficiencies between 40% - 50%. The cyanide
process uses varying cyanide concentrations depending on the local
mineralogy. Typically concentrations range from 300 to 500 mg/l.
Today there are commonly two predominant leaching techniques
employed for gold extraction:
VAT leaching
Flooded heap leaching
Leaching Techniques
VAT leaching utilizes reaction tanks. The excavated and ground up
ore is collected and the cyanidation reaction is performed inside
the vats. Further on the gold is separated from the ore resulting
gold/cyanide mixture.

Flooded heap leaching process utilizes stockpiles of ground up

ore. This method is more commonly in use than VAT leaching. The
excavated ore is heaped onto, so called, leach pads (see Figure 1).

Figure 1: Cyanide Leaching Pad

These pads are constructed with an impervious base (usually

asphalt or plastic sheeting). The leaching pads can cover an
enormous area (several football fields large and up to 30 meters
in height). The actual cyanide extraction process is rather simple.
A diluted cyanide solution is sprayed and distributed on the top
of the leach pad by a sprinkler system. Subsequently the cyanide
solution permeates through the heap in a period of several weeks
leaching out the gold from the ore. Cyanide has a natural affinity
for gold that is similar to dissolving sugar or salt in water. This gold
enriched cyanide solution (so called pregnant solution) is then
collected in a pond below the leaching pad. In a separate process
the gold is recovered from the pregnant solution.

Both cyanide extraction processes outlined above permit the recycling of a fraction of the cyanide extraction
solution that is fed back into the extraction process again. However, due to the bulk material handling and the low
gold concentration in the ores an immense amount of cyanide containing waste water is produced.
Cyanide Toxicity
Please note, despite its affinity binding to metals (i.e. gold, silver, etc.) cyanide is a highly toxic compound. Cyanide
is normally stored and transported in solid form and is stable when dry (i.e. sodium cyanide). Many cyanide solids
readily dissolve in water with a risk of even releasing actual toxic cyanide gas (HCN) when reacting with other
compounds in the water matrix and depending on various parameters of the water body (i.e. pH, temperature,
etc.). Dissolved cyanide solids are relatively stable in the environment until they are oxidized. Due to its toxicity
the uncontrolled release to the environment must be prevented. This is very important as small amounts of
cyanide can already harm or even kill a person (one teaspoon full of a 2% cyanide solution is already deadly). In
the human body cyanide blocks the absorption of oxygen by cells. In result this is causing the victim to effectively
suffocate. Any cyanide that enters the environment and river systems can cause immediately immense damage.
Aquatic species are particularly sensitive to cyanide exposure. Environmental research has reported that low
concentrations as five parts per billion in surface waters can already inhibit fish reproduction.
The World Health Organization (WHO) has set threshold values for hydrogen cyanide (0.07 mg/l). However on
worldwide perspective there is a large variety of national threshold limits for cyanide. These range from 0.1 mg/l in
Argentina, South Africa and Germany, 1.5 mg/l in Mexico to limit up to 50 mg/l in Australia.
Ozone Treatment of Gold Mining Discharges
As highlighted above, in order to protect wildlife, nature and people it is absolutely essential to treat cyanide
containing effluents prior to discharge.
The oxidation and detoxification of cyanide containing waste waters can be achieved by introducing a variety of
different treatment agents including chlorine gas, sodium hypochlorite and hydrogen peroxide, where the most
commonly used chemicals are chlorine gas and sodium hypochlorite. The main disadvantages of the detoxification
agents listed above are high operating costs, the associated bulk handling, and storage of highly toxic and dangerous
chemicals on-site. This in itself poses an additional environmental risk alone that needs to be managed at high costs.
An alternative and also environmental safe oxidation agent is ozone, being one of natures most powerful oxidants.
Ozone is easy to produce on-site and on-demand. Ozone can be easily applied to any industrial waters, waste
waters and air treatment processes. During the treatment process ozone itself disintegrates and does not generate
harmful byproducts. It just turns back to oxygen. Therefore ozone provides not only an environmentally friendly,
but also a cost effective alternative to halogenated oxidants (i.e. chlorine, sodium hypochlorite), absorption
techniques (i.e. activated carbon) or separation processes (i.e. reverse osmosis).
Chemistry of the Ozone Oxidation Process of Cyanide containing Waste Waters
The cyanide oxidation process can be described by two main chemical reaction pathways as highlighted below:
The first step is the oxidation of cyanide to cyanate (see reaction 1).
(1)
CN + O3 CNO + O2
The second reaction (2) shows the reaction, where cyanate is hydrolyzed and oxidized in the presence of excess
ozone to bicarbonate, nitrogen and oxygen:
(2)
2CNO + 3O3 + H2O 2HCO3 + N2 +3O2
The total reaction time for the entire oxidation process of cyanide ranges typically between 10 to 30 minutes. Most

of the time is required for the second reaction (2).

Ozone Applications in Gold Extraction Process Optimization
Additionally, ozone can be used to enhance and improve the gold extraction yields by improving the exploiting
refractory ores and cyanide regeneration.
Ore Pre-ozonization
The so-called refractory ores are naturally resistant to the cyanidation process due to strong cyanide consumers
within the ore. Therefore the yield of the gold extraction process can be impacted being less than 50% in some
cases. In order to overcome this problem a preoxidation step is used to eliminate these cyanide consumers in
the refractory ores. At present, technical processes such as roasting, chemical oxidation, high- or low pressure
oxidation or bacterial oxidation are used. However, these techniques are disadvantageous due to very high capital
costs, environmental problems and the need of highly trained personnel. Ozone pretreatment of the ores can
overcome these problems highlighted above by eliminating these cyanide consuming compounds.
Pilot trials have demonstrated that the pre-oxidation of refractory ores is able to increase the gold extraction
efficiency to over 85% from initially 53%.
Furthermore, research in this field has shown that the ozone pre-oxidation processes can increase gold recovery
rates by more than 85%. Another advantage of ozone pre-treatment is the oxidation of sulphuric components
within the ore. This in result prevents the formation of unwanted thiocyanates (SCN) during the gold extraction
procedure. In consequence the cyanide consumption is greatly reduced in the cyanidation process.
Ozone Oxidation for the Regeneration of Cyanide
During the cyanidation process the cyanide can react with several other scavenging constituents of the ore. This
leads to increased cyanide consumption due to a fraction of the cyanide that is lost reacting with these scavenging
compounds instead of reacting with the gold in the ore. This is resulting in a less efficient extraction process with
negative economical impact. One of these scavenging compounds is sulphur, being a strong cyanide consumer.
The sulfur content of the ores can be very high in certain regions. The reaction of sulfur and cyanide forms
thiocyanate, following reaction (3).
S0 + CN SCN (3)
Furthermore thiocyanate is also posing an environmental threat. Thiocyanates are also toxic and can harm aquatic
species when released. Common waste water treatment systems in the mining industry might not be able to
reduce thiocyanates sufficiently. Additional detoxification steps would be required for its removal. Ozone can
overcome these negative impacts by oxidation of thiocyanate and the regeneration of cyanide. Research has
shown that cyanide regeneration can reach up to 75% after short reaction time of approximately 20 minutes, see
reaction (4).
SCN +O3(g) + H2O SO42 + HCN + H+ (4)

Case Studies: Ozone Treatment

Total Cyanide Reduction of Waste Water Effluents from a Malaysian Gold Mine
WEDECO has successfully demonstrated the reduction of total cyanide levels of contaminated waste water
effluents from a Malaysian gold mine. The aim of this trial was to reduce the total cyanide levels in the waste
water to the national permissible level of 0.1 mg/L. The total cyanide concentration (CNtotal) is a combination of all
occurring cyanide complexes, such as free cyanide (CN, HCN), WAD cyanides (weak acid dissociable) as well
as strong metal cyanide complexes as highlighted in figure 2 below.

Strong metal cyanide complexes of Fe

Weak and moderately strong metal cyanide

complexes of Ag, Cd, Cu, Hg, Ni and Zn

Total
Cyanide

WAD
Cyanide

Free
Cyanide

CN
HCN

Figure 2: Overview of different cyanide species

Mine Waste Water Treatment Trial

The cyanide concentration of the Malaysian gold mine waste water sample was initially 13.8 g/m3. The treatment
target was to achieve a final cyanide concentration in the effluent of less than 0.1g per cubic meter (CNtotal 0.1 ppm).
The results of the ozone treatment trials are shown in figure 3 below.

Figure 3: Reduction of cyanide with ozone

Results
It has been demonstrated that the treatment goal cyanide reduction can be achieved by applying an average
ozone dose of 170 gO3/m3. The cyanide concentration was reduced by more than 99% down to 0.083 mg/l. The
treatment target of <0.1g CNtotal/m3 was successfully met.
As part of this comprehensive study the treatment performance of the reduction of all cyanide species were
measured. This is allowing designing treatment solutions for scenarios that require only treatment for cyanide subparameters such as free cyanide.
WAD Cyanide Removal of Effluents from a South African Gold Mine
This pilot study was conducted to demonstrate the removal of WAD cyanides (Figure 2) from the effluent of a
South African gold mine with a design capacity of more than two million tones per year. The motivation for the
implementation of this treatment process is to protect the people and the environment. Ozone has been chosen,
being a powerful oxidant and highly destructive toward WAD cyanides. The process waste streams from the
cyanide leaching procedure were treated with ozone, thereby reducing the WAD cyanide levels discharged from
the plant to slimes dam and underground. The picture below resembles the key components of the treatment
system (Figure 4).

Figure 4: Ozone treatment system

The overall treatment target for the study was to comply with the maximum WAD cyanides level of less than 50
ppm as specified by the International Cyanide Management Code for the Manufacture, Transport and Use of
Cyanide in the Production of Gold (Cyanide Code). The treatment trial has successfully demonstrated to reduce
the WAD cyanide concentrations by 99%. Throughout the trial WAD cyanide levels in the effluent leaving the
treatment were always below 50 ppm and therefore compliant with the Cyanide Code. Particularly advantageous
of this treatment process are the rapid WAD cyanide destruction and that no harmful off-gases are formed.

Conclusion
The ozone treatment and process optimization methods for the gold mining industry discussed here clearly
demonstrate the advantages and effectiveness of ozone. Ozone is a very effective solution achieving detoxification
of cyanide containing waste water and furthermore resulting in a significant reduction (up to 99%) of the general
cyanide consumption in the gold mining/extraction process. Additionally ozone treatment offers further process
benefits as highlighted below:
Key advantages of cyanide oxidation using ozone
1. Ozone is produced on-site from oxygen feedgas or even ambient air. Many gold mines already have oxygen
supply.
2. Ozone is very reactive, so the reaction in the treatment process is very fast and does not require special
conditions such as high temperatures or pressures.
3. Extremely effective against most cyanides species (free and WAD complexed forms).
4. Ozone does not form any undesirable by-products such as chlorinated organics or ammonia, which are
generated by chlorine oxidation.
5. Ozone is always generated on-site on a demand basis (on & off).
6. The ozone treatment process does not require frequent purchases and delivery of large amounts of
chemicals. Additionally there is no requirement for storage and handling of dangerous chemicals on-site
(i.e. site safety protocols).
7. Ozone can be used for increasing the gold extraction yields, when dealing with refractory ores and sulfur
impurities.

Xylem Water Solutions Herford GmbH

Boschstrae 4
32051 Herford, Germany
Tel +49 (0)5221 930 0
Fax +49(0) 5221 930 222
www.wedeco.com
WEDECO is a trademark of Xylem Inc. or one of its subsidiaries.
2013 Xylem, Inc.
July 2013