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Michael M. Botz
Elbow Creek Engineering, Inc.
mike@botz.com
1
Overview of Cyanide Treatment Methods
Figure 1
Classifications of Cyanides
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The theoretical usage of SO2 in the process is The primary application of the hydrogen
2.46 grams SO2 per gram of CN- oxidized, but in peroxide process is with solutions rather than
practice the actual usage ranges from about 3.5 slurries due to the high consumption of hydrogen
to 4.5 grams SO2 per gram of CN- oxidized. The peroxide in slurry applications. The process is
SO2 required in the reaction can be supplied typically applied to treat relatively low levels of
either as liquid sulfur dioxide or as sodium cyanide to achieve cyanide levels that may be
metabisulfite (Na2S2O5). suitable for discharge. The hydrogen peroxide
process is effective for the treatment of solutions
Oxygen (O2) is also required in the reaction and for the oxidation of free and WAD cyanides, and
this is generally supplied by sparging iron cyanides are removed through precipitation
atmospheric air into the reaction vessels. The of insoluble copper-iron-cyanide complexes. As
reaction is typically carried out at a pH of about indicated in the above reaction, hydrogen
8.0 to 9.0 in one ore more agitated tanks, and peroxide reacts to form cyanate and water, a
lime is added to neutralize the acid (H+) formed process which limits the build-up of dissolved
in the reaction to maintain the pH in this range. solids in the solution being treated.
Lime usage is generally on the order of about 3.0
to 5.0 grams per gram of CN- oxidized. As The theoretical usage of H2O2 in the process is
indicated, copper (Cu+2) is required as a catalyst, 1.31 grams H2O2 per gram of CN- oxidized, but
which is usually added as a solution of copper in practice the actual usage ranges from about
sulfate (CuSO4-5H20) to provide a copper 2.0 to 8.0 grams H2O2 per gram of CN- oxidized.
concentration in the range of about 10 to 50 The H2O2 used in the process is typically
mg/L. Upon completion of the indicated provided as a liquid in 50% strength.
reaction, metals previously complexed with
cyanide, such as copper, nickel and zinc, are The reaction is typically carried out at a pH of
precipitated as metal-hydroxide compounds. about 9.0 to 9.5 for optimal removal of cyanide
and metals such as copper, nickel and zinc.
This process is capable of achieving low levels However, if iron cyanide must also be removed
of both cyanide and metals. Generally, the best to low levels, then the pH is lowered somewhat
application of this process is with slurries to increase the precipitation of copper-iron-
containing low to moderately high initial levels cyanides at the expense of lowering the removal
of cyanide when treated cyanide levels of less efficiencies of copper, nickel and zinc. As
than about 1 to 5 mg/L are required. In some indicated, copper (Cu+2) is required as a soluble
cases, solutions treated with this process may be catalyst, which is usually added as a solution of
of suitable quality to permit their discharge. copper sulfate (CuSO4-5H20) to provide a copper
concentration in the range of about 10% to 20%
Hydrogen Peroxide of the initial WAD cyanide concentration. Upon
The hydrogen peroxide treatment process completion of the indicated reaction, metals
chemistry is similar to that described for the previously complexed with cyanide, such as
INCO process, but hydrogen peroxide is utilized copper, nickel and zinc, are precipitated as
rather than sulfur dioxide and air. With this metal-hydroxide compounds.
process, soluble copper is also required as a
catalyst and the end product of the reaction is
cyanate.
2
H2O2 + CN- Cu
Catalyst
-
OCN + H2O
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Overview of Cyanide Treatment Methods
This process is capable of achieving low levels cyanide is converted to cyanogen chloride
of both cyanide and metals. Generally, the best (CNCl) and the second step in which cyanogen
application of this process is with solutions chloride hydrolyzes to yield cyanate.
containing relatively low initial levels of cyanide
when treated cyanide levels of less than about 1 Cl2 + CN- CNCl + Cl-
mg/L are required. Oftentimes, solutions treated
with this process may be of suitable quality to CNCl + H2O OCN- + Cl- + 2H+
permit their discharge.
In the presence of a slight excess of chlorine,
Caro’s Acid cyanate is further hydrolyzed to yield ammonia
Peroxymonosulfuric acid (H2SO5), also known in a catalytic type of reaction.
as Caro’s acid, is a reagent used in a recently
developed cyanide treatment process that has OCN- + 3H2O Cl2 Catalyst
found application at a few sites. NH4+ + HCO3- + OH-
H2SO5 + CN- OCN- + SO4-2 + 2H+ If sufficient excess chlorine is available, the
reaction continues through ‘breakpoint
Caro’s acid used in the process must be produced chlorination’ in which ammonia is fully oxidized
on-site using sulfuric acid and hydrogen to nitrogen gas (N2).
peroxide since Caro’s acid decomposes rather
quickly (Norcross, 1996). Caro’s acid is used in 3Cl2 + 2NH4+ N2 + 6Cl- + 8H+
slurry treatment applications where the addition
of a copper catalyst is not desirable, which is In addition to reacting with cyanide, cyanate and
typically only in situations where the sulfur ammonia, the alkaline chlorination process will
dioxide and air process is not suited. In solution oxidize thiocyanate, which in some cases can
applications, other destruction processes, such as lead to excessively high consumptions of
the hydrogen peroxide process, are preferred to chlorine.
the Caro’s acid process.
4Cl2 + SCN- + 5H2O
The theoretical usage of H2SO5 in the process is SO4-2 + OCN- + 8Cl- + 10H+
4.39 grams H2SO5 per gram of cyanide oxidized,
but in practice 5.0 to 15.0 grams H2SO5 per gram The primary application of the alkaline
of cyanide oxidized is required. Acid produced chlorination process is with solutions rather than
in the reaction (H+) is typically neutralized with slurries due to the high consumption of chlorine
lime. in slurry applications. The process is typically
applied to treat low solutions flows initially
Alkaline Chlorination containing low to high levels of cyanide to
Alkaline chlorination at one time was the most achieve cyanide levels that may be suitable for
widely applied of the cyanide treatment discharge. The process is effective for the
processes, but it has gradually been replaced by treatment of solutions for the oxidation of free
other processes and is now only used and WAD cyanides, but a lesser amount of iron
occasionally. Alkaline chlorination is effective cyanides are removed depending on the levels of
at treating cyanide to low levels, but the process other base metals in the solution being treated.
can be relatively expensive to operate due to As can be seen in the above reactions, a
high reagent usages. The cyanide destruction significant increase in the treated water dissolved
reaction is two-step, the first step in which
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Overview of Cyanide Treatment Methods
solids concentration may result, particularly with cyanide (MXFeY(CN)6) compounds such as those
chloride. with copper or zinc (Adams, 1992).
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and/or leaching circuits. This approach to are accurate under a wide variety of weather,
recovering cyanide should be evaluated for all pond/impoundment geometry and chemistry
operations utilizing cyanide, and its performance conditions.
can be determined by a simple mass balance
calculation. An example of the use of natural attenuation
would be with a cyanide recovery facility where
solution or slurry with a cyanide concentration of
NATURAL CYANIDE ATTENUATION about 20 mg/L is placed into a lined pond or
impoundment. The lined pond or impoundment
It is well known that cyanide solutions placed in could then be designed to maximize natural
ponds or tailings impoundments undergo natural attenuation such that the resultant cyanide
attenuation reactions which result in the lowering concentration would be less than about 1 mg/L.
of the cyanide concentration. These attenuation
reactions are dominated by natural volatilization
of hydrogen cyanide, but other reactions such as SUMMARY
oxidation, hydrolysis, photolysis and
precipitation also occur. Natural cyanide As indicated in the previous discussion, there are
attenuation occurs with all cyanide solutions over ten cyanide treatment processes that have
exposed to the atmosphere, whether intended or been successfully used worldwide for cyanide
not. At several sites, ponds or tailings removal at mining operations. The key to
impoundments are intentionally designed to successful implementation of these processes is
maximize the rate of cyanide attenuation, and in by considering the following:
some cases resultant solutions are suitable for
discharge. Site water and cyanide balances under both
average and extreme climatic conditions
Two approaches have been developed to predict
the rate of cyanide attenuation in ponds and The range of cyanide treatment processes
tailings impoundments. The first method is available and their ability to be used
empirical in nature and uses experimentally individually or in combination to achieve
derived rate coefficients to estimate the rate of treatment objectives
attenuation using a first order decay equation
(Simovic et al., 1985). This approach is Proper testing, design, construction,
relatively simple to apply, but its applicability at maintenance and monitoring of both water
a given site must be verified by conducting field management and cyanide management
testwork and the results may not be accurate facilities
under changing weather, pond/impoundment
geometry or chemistry conditions. By carefully considering these aspects of water
and cyanide management before, during and
The second approach to modeling natural after mine operation, operators can reduce the
cyanide attenuation was developed by Botz and potential for environmental impacts associated
Mudder (2000). This approach utilizes detailed with the use of cyanide.
solution chemical equilibria and kinetic
calculations to predict the rate of cyanide losses Another aspect of cyanide treatment to be
from ponds and impoundments through a variety considered is the potential environmental impact
of reactions. This approach can be time- of the cyanide related compounds cyanate,
intensive to apply at a given site, but the results thiocyanate, ammonia and nitrate. These
compounds may be present in mining solutions
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to varying extents and may require treatment if Table 1 provides a simplified summary of the
water is to be discharged. Each of these cyanide general applications of various treatment
related compounds is affected differently in the technologies for the removal of cyanide and its
treatment processes discussed and this should be related compounds cyanate, thiocyanate,
considered when evaluating cyanide treatment ammonia and nitrate. This table represents a
alternatives for a given site. very simplified summary, but can be used as a
conceptual screening tool when evaluation
cyanide treatment processes.
Table 1
Preliminary Selection Guide for Cyanide Treatment Processes
Iron WAD
Slurry Solution
Treatment Process Cyanide Cyanide
Application Application
Removal Removal
SO2/Air
Hydrogen Peroxide
Caro’s Acid
Alkaline Chlorination
Iron Precipitation
Activated Carbon
Biological
Cyanide Recovery
Natural Attenuation
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Botz, M.M., “Overview of Cyanide Treatment Methods’, Mining Environmental Management, Mining
Journal Ltd., London, UK, pp. 28-30, May 2001.
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database or retrieval system, without the express prior written permission of the publisher.
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