ABSTRACT

Principles of Green Chemistry provide useful guidance for sus-

tainable mineral process development. Laboratory bench scale test-
ing was carried out using pregnant cyanide leach solutions, and a
number of commercially available mercury precipitation reagents
were compared using jar testing to determine the most efficient and
selective reagents for mercury precipitation. The most efficient
reagent identified was sodium polymeric thiocarbonate (NaPTC).
Coagulation experiments with fine diatomaceous earth resulted in a
stable precipitate, with good settling properties. On line monitoring of
the mercury in solution is recommended for process implementation
to conserve reagent removing approximately 90-95% of the mercury
with minimal silver and negligible gold losses.
INTRODUCTION
Newmont Metallurgical Services has been involved in research
and development efforts to control mercury concentrations in metal-
lurgical processing circuits and for meeting discharge requirement for
excess processing water for over a decade. Recent work has
focused on the stepwise removal of mercury from the higher concen-
tration gold bearing (pregnant) cyanide solutions (Bucknam 2001 and
2002), where it will be most beneficial from economic, industrial
hygiene and environmental perspectives.
The American Chemical Society (ACS) supports the use of the
twelve Green Chemistry Principles (Anastas, P. T.; Warner, J. C.,
1998), which are mostly related to chemical syntheses. Several of
the principles, however, provide guidance for sustainable use of
chemicals in metallurgical processing as follows:
1. prevention,
2. atom economy,
3. safer auxiliaries, and
4. real-time analysis for pollution prevention.
This paper explores how these four green chemistry principles
apply to the development of methods for removal of mercury from
pregnant cyanide solutions.
PREVENTION
Use of low concentrations of cyanide for leaching of gold is by
far the best preventative measure to be employed to keep the mer-
cury present in the ore out of solution. Mercury occurs primarily as
cinnabar (HgS) in some gold ores and, as a sulfide, typically requires
higher concentrations of cyanide in solution to dissolve than does the
elemental form of gold present in oxide gold deposits. Heap leach-
ing of oxide deposits for gold may be operated efficiently by monitor-
ing the concentration of cyanide in the pregnant solution by silver
nitrate titration to make sure that there is still a measurable concen-
tration of un-complexed cyanide leaving the heap, which indicates
that the pregnant solution still has the ability to leach additional gold.
Field tests were conducted to determine if addition of sodium
hydrosulfide (NaSH) to leach solutions could be used to prevent mer-
cury from dissolving from the ore. Dark sulfide precipitates were
observed on the surface of the heap which re-dissolved in the leach
solution, demonstrating the instability of inorganic mercury sulfide
precipitates in cyanide leach solutions.
Column tests were conducted at the University of Nevada
Reno (UNR) using potassium dimethyldithiocarbamate (KDMDTC) to
precipitate the mercury in the pregnant solution leaving the column
vs. adding the reagent to the leach solution to prevent the mercury
from leaching (Misra, Lorengo, Nanor and Bucknam, 1998). Results
indicated that precipitation of the mercury leaving the column was
much more efficient for mercury removal than adding the reagent to
the leach solution, which indicates that the reagent was being con-
sumed in the ore by mechanisms other than mercury precipitation.
Mercury precipitation from pregnant cyanide solutions can be
viewed as a preventative measure, however, since it can be used to
control the mercury contamination in the downstream processed if
properly managed.
Research on preventing mercury from dissolving in cyanide
leach solutions needs to focus on development of a reagent to selec-
tively passivate the cinnabar in the ore from dissolving in cyanide.
Work to date using reagents containing sulfide ligands indicate that
they are most effective after the mercury is dissolved and in the
absence of other reagent consuming solids.
ATOM ECONOMY
Conventional technology for the removal of mercury from preg-
nant cyanide solutions relies on sulfide based inorganic and organic
chemicals (Diaz, Cavero and Yataco 1999). From a cost perspective,
inorganic sulfide chemicals are preferred, due to their low cost. From
an atom economy perspective, however, inorganic sulfides do not
perform well overall in cyanide circuits, due to their instability.
A series of screening jar tests (Bucknam, 1997) was carried out
to determine the relative efficiency of sulfide containing reagents for
precipitation mercury from two different cyanide pregnant solutions.
The active ingredient and concentrations of the reagent in the prod-
uct was obtained from the manufacturers so that the reagents could
be directly compared on an equivalent concentration basis. The
active sulfide group in each reagent tested is shown in Table 1.
Reagents tested included:
1. KDMDTC - Potassium Dimethyldithiocarbamate
2. NaCTA Sodium carbonotrithioic Acid
3. NaDBTDC Sodium dibutyldithiocarbamate
4. NaDEDTC - Sodium diethyldithiocarbamate
5. NaDMDTC Sodium dimethyldithiocarbamate
6. NaSH Sodium hydrosulfide
7. NaPDTC Sodium polymeric dithiocarbamate
8. NaPDAET Sodium pyridodiamidoethanethiol
9. NaPTC Sodium polymeric thiocarbonate
10. NaTMT Sodium trimercaptos-triazine
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PREPRINT 04-101
A GREEN CHEMISTRY APPROACH TO MERCURY CONTROL DURING CYANIDE LEACHING OF GOLD
C. H. Bucknam
Newmont Metallurgical Services
Englewood, CO
1 Copyright 2003 by SME
Figure 1. Comparison of Active Sulfide Groups for Mercury
Removal Reagents Tested
The inorganic hydrosulfide is the simplest functional sulfide ion,
followed by the carbonotrithioic, mercaptotriazine, dithiocarbamate,
polythiocarbonate and amidoethanethiol (Matlock, Howerton and
Attwood, 2001) in order of increasing complexity. Some of the organ-
ic sulfide active groups have different functional groups which affect
their activity towards mercury removal from pregnant cyanide solu-
tions.
Jar testing of the reagents on the nominal 3 and 6 g Hg/t preg-
nant cyanide solutions covered the range of 0-25 g reagent/t of preg-
nant solution, starting from 1% stock solutions of the reagents,
except for the NaPDAET, which was provided by the University of
Kentucky as a nominal 15% solution in organic solvent and was
added neat by micropipet. Initial screening eliminated NaTMT,
NaCTA and NaDBTDC in the concentration range tested. Table 1
shows the relative rating of the reagents at 95% mercury removal.
Table 1. Rating of Reagents for 95% Mercury Removal for
Pregnant Cyanide Solutions 0.5-6 g Hg/t
As can be seen from the reagent to mercury mole ratios, the
NaPDAET designed reagent provides near stochiometric results,
resulting in true atomic economy and as such should be designated
as a green reagent for mercury removal.
Many analytical problems were encountered during the screen-
ing testing, which is a common problem for mercury studies. Best
results were obtained after preserving samples with 1% bromide
chloride solution and performing mercury analysis in the preserved
pregnant solutions by inductively coupled plasma (ICP) emission at
Newmont Metallurgical Services. The gold silver and mercury con-
centrations of the pregnant cyanide solutions used in the screening
testing is summarized in Table 2.
Table 2. Summary of Gold, Silver and Mercury Concentrations
in Heap Leach Pregnant Cyanide Solutions Used in Reagent
Screening Testing
SAFER AUXILARIES
Screening studies identified the best candidate precipitation
reagents for mercury removal from pregnant solutions from a chemi-
cal perspective, but it left the question of how to efficiently remove the
fine precipitated solids from the solution without affecting gold recov-
ery. In the excess water treatment process, ferric chloride is used to
co-precipitate arsenic, coagulate the fine solids with the aid of floccu-
lants and lower the pH prior to discharge. A reactor clarifier is
required for solid-liquid separation in this process.
In the case of re-circulating pregnant solutions the simplest
solution is to use the heap leach pad as a filter to remove the fine
mercury precipitates. This concept was tested in the lab using fire
assay to quantify the gold and silver losses in the fine precipitates.
For the NaPDAET reagent, 95% mercury removal indicated
about 9-12% silver losses and gold losses were not significant at
<1%. For NaPTC the indicated silver losses at 95% mercury removal
were 2-62% with gold losses <1%, indicating that a target mercury
removal of 90-95% may be better to limit silver losses. It was recom-
mended to set the mercury removal target where the amount of silver
removed from solution equals the mercury concentration to optimize
reagent use.
Pilot testing for the use of NaPTC for the pregnant solution recir-
culation application was recommended, since NaPDAET reagent is
not available in commercial quantities. The test would simulate the
time that the reagent would have to mix in the surge tank and during
pumping back to the heap and verify that silver losses can be con-
trolled and the gold losses will not be significant in production.
In the case of treated pregnant solutions destined for gold
recovery by Merrill-Crowe, it is desirable to remove the mercury pre-
cipitate from solution prior to or in the clarifier filters. Preliminary
plant trials using NaSH for mercury removal in pregnant solutions
showed that clarifier filters could be easily plugged with fine mercury
and silver precipitates in just a few minutes.
Jar tests were carried out using a fine (-350 mesh) high surface
area diatomaceous earth (DE) product with five minute reaction time
were successful at 77% mercury removal with no gold and silver loss-
es using 2 g NaPDAET/t in a 1.64 g Hg/t pregnant cyanide solution
and 90% mercury removal was obtained in another pregnant cyanide
solution with 6% silver and no significant gold loss. DE is a green
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auxiliary for gold heap leaching processes since it is pure silica, sim-
ilar to the ore that is being leached.
Tests were carried out using NaPTC at twice the NaPDAET
dosage for the lower mercury concentration pregnant cyanide solu-
tion and 1.5 times for the higher mercury concentration mercury preg-
nant cyanide solution and comparable results were achieved. Fine
DE was confirmed to be an effective green auxiliary reagent for use
in solid liquid separation of the fine mercury from pregnant cyanide
solutions. An equal weight of DE to mercury precipitate concentra-
tion is recommended to effectively adsorb the fine precipitate from
solution.
REAL TIME ANALYSIS FOR POLLUTION PREVENTION
At the completion of the preliminary DE testing, the research
was refocused on treatment of pregnant eluant solution at an order of
magnitude higher concentration of gold and mercury and higher tem-
perature. The concentrations of gold, silver and mercury in the preg-
nant eluant and intermediate eluate solutions used in the preliminary
screening tests are shown in Table 3. These solutions were blended
with the heap leach pregnant cyanide solutions at a ratio of about
1:100 parts, prior to Merrill-Crowe gold recovery.
Table 3. Summary of Pregnant Eluate Gold, Silver and Mercury
Concentrations
Screening results eliminated NaPDAET as a suitable reagent
for the pregnant eluate, probably due to hydrolysis of the complex
molecule at the high cyanide concentrations and temperatures. Work
proceeded using NaPTC, which showed excellent atom economy in
development pilot studies carried out on-site by Pocock Industrial.
Bulk sludge produced passed TCLP testing and is scheduled for
long-term stability testing at NMS using water and cyanide solutions.
Since the metals concentrations vary during the cycling of the
carbon stripping process, it will be desirable to monitor the solution in
real time, if the reagents are to be added directly to the holding tank.
A survey was undertaken of analytical instrumentation that could be
used to monitor the mercury concentrations for process control as a
result, four instrumental methods were identified for real-time analy-
sis of mercury concentrations in solution:
1. digestion-cold vapor atomic absorption (CVAAS),
2. digestion-cold vapor atomic fluorescence (CVAFS),
3. inductively coupled plasma emission spectroscopy (ICP), and
4. x-ray fluorescence (XRF).
Do to the relatively high concentrations of mercury in solution
and the relatively low cost of instrumentation, the XRF application
was tested and appeared to give satisfactory results above 50 g Hg/t.
Subsequent plant experience, however, has resulted in lower mercu-
ry concentrations in the 50 g Hg/t range, eliminating that option.
Two on-line CVAAS instruments have been ordered for use in
pollution control in the excess water treatment plant to be installed in
the Fall of 2003. Plant performance of these instruments will be eval-
uated to see if they can be used for real-time control of mercury pre-
cipitation for pollution prevention in the excess water treatment plant.
CONCLUSIONS AND RECOMMENDATIONS
Research and development efforts carried out by NMS on mer-
cury removal from pregnant cyanide solutions have been reviewed
according to four green chemistry principles to see if the implemen-
tation of the technology for mercury removal from pregnant cyanide
solutions can be used as a gauge of the technologys contribution to
sustainable mineral development.
In terms of prevention, use of low concentrations of cyanide in
solution is probably the best option to prevent cinnabar dissolution.
Use of sulfide precipitation chemicals does not prevent mercury dis-
solution, but helps to manage the mercury concentrations in solution
at the heap leach source, preventing mercury contamination in the
processing plant.. Addition of the precipitants are most efficient as
the pregnant cyanide leaves the heap. Addition of NaSH to the leach
solution in ineffective due to dissolution and use of other organic sul-
fide precipitants result in losses if added to the leach solution which
do not contribute to mercury removal from solution. Research is
needed to identify a reagent specific for passivation of cinnabar to
dissolution by cyanide leach solutions.
NaPDAET was shown to have the best atom economy for mer-
cury removal in pregnant heap leach solutions and should be given
preference for use if it can be made commercially available at a rea-
sonable cost. NaPTC showed comparable atom economy in the
pregnant eluate application and the efficiency was proven in pilot
scale testing at site and provides a cost effective option for mercury
control in metallurgical operations using cyanide solutions.
Fine DE was shown to be a green auxiliary to assist in solid-liq-
uid separation during mercury removal from pregnant cyanide solu-
tions at a 1:1 ratio to the mercury precipitate. Sludge produced with
DE and HgPTC during pilot testing was shown to be relatively non
toxic, passing TCLP testing for mercury at relatively high mercury
concentrations in the sludge. Long-term stability testing of this mate-
rial is recommended prior to implementation of the process for mer-
cury removal form pregnant cyanide solutions using NaPTC, fine DE
and filtration.
On-line analysis for pollution prevention is a critical component
of the process for mercury removal from pregnant cyanide solutions.
Mercury analysis and preservation procedures are problematic at
best and real-time control is necessary to achieve sustainable use of
reagents and control of metals losses. Mercury removal is best
achieved by a number of carefully controlled stages to assure the
optimum cost, industrial hygiene, environmental stewardship and
sustainable mineral development goals are reached.
ACKNOWLEDGMENTS
The Author wishes to acknowledge the contributions of Brian
Granger of NMS in carrying out the bench scale testing, Glenn Welch
of Pocock Industrial for making the process work in the plant and
John Huddle of NMS for all of the fire assays necessary to verify the
insignificance of the gold losses during mercury precipitation testing.
REFERENCES
Anastas, P. T.; Warner, J. C. Green Chemistry: Theory and
Practice, Oxford University Press: New York, 1998, p.30
Bucknam, C. H., 1997, Cyanide Solution Detoxification Jar
Tests, Global Exploitation of Heap Leach able Gold Deposits, TMS,
Warrendale, PA, pp.191-204.
Bucknam, C. H., 2001, Bench Scale Screening Test Results for
Mercury Removal from Pregnant Solutions, MYSRL, Cajamarca,
Peru, Newmont Metallurgical Services internal report.
Bucknam, C. H., 2002, Final Bench Scale Testing Results for
Mercury Removal from Pregnant Leach and Pregnant Eluate
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Solutions, MYSRL, Cajamarca, Peru, Newmont Metallurgical inter-
nal report.
Diaz, M., Cavero, A. and Yataco, D., Water Management at
Minera Yanacocha, Presented at the SME Annual Meeting,
February, 1999, Orlando, Florida.
Matlock, M.M., Howerton, B. S., and Attwood, D. A.,
Irreversible Precipitation of Mercury and Lead, Journal of
Hazardous Materials, B84, pp. 73-82, 2001.
Misra, M., Lorengo, J., Nanor, J.B., and Bucknam, C. H.,
Removal of Mercury Cyanide Species form Solutions using Dimethyl
Dithiocarbamates, Minerals & Metallurgical Processing, Vol. 15, No.
4 November 1998, pp. 60-64.
Pocock Industrial, Inc., Mercury Precipitation on Yanacocha
Carbon Stripping Eluate Using Sodium Polythiocarbonate, Report to
Newmont Mining Corporation, September 2002.
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