2007 HydroCopper Paper
2007 HydroCopper Paper
2007 HydroCopper Paper
ABSTRACT
Sulphide is an effective reagent for precipitation of copper and other base metals for both metal
winning and environmental control. Using its BioSulphide technology, BioteQ Environmental
Technologies Inc. has demonstrated in industrial plants that biogenic sulphide reagent can be
generated at low cost and used profitably to win copper and other metals such zinc and nickel from
low-grade leach solutions, acid mine drainage and wastewater. Commercial plants in which
sulphide reagent is used to produce high quality treated effluents for discharge are also in operation.
A new application of BioteQs sulphide technology utilizing biogenic sulphide in place of chemical
sulphide reagents in the SART process for the recovery of copper and cyanide from cyanide
solutions in the processing of gold-copper ores is also described. In addition, BioteQ has introduced
the ion-exchange technology, Sulf-IXTM, to remove sulphate from wastewaters such as lime plant
effluents, to permit discharge to the environment where concentrations of sulphate must be reduced
to low levels.
This paper was presented at the 2007 HydroCopper Conference in Santiago, Chile.
INTRODUCTION
Efficient and environmentally acceptable technologies for water treatment in the mining industry
have become more important both to improve environmental and process performance, and to
reduce costs, particularly those related to long term liabilities. This is particularly important in the
copper mining industry where the impacts of large scale open pit and underground mining and
processing activities can result in a number of water treatment requirements to ensure the supply of
water suitable for process use and to prevent contamination of rivers and lakes caused by the
discharge of process waters. Water supply and its preservation in an acceptable quality is even
more important in a country like Chile where a large part of the mining activity takes place in areas
with little rainfall and with declining groundwater reserves. In addition, regulations in Chile
demand that the load of sulphate is controlled in discharges to the environment. Up until now, the
mining industry has relied on the treatment of water for discharge using lime plants in either simple
low density sludge (LDS) or high density sludge (HDS) processes where lime is added to
precipitate metals as hydroxides and to neutralize acidity. Although the addition of lime will
remain the lowest cost method of reducing sulphate by the precipitation of gypsum, lime treatment
can only reduce sulphate typically to within the range 1600 to 2000 mg/L due to the solubility of
gypsum. Other processes are therefore required to meet sulphate standards of 500 mg/L or lower.
BioteQ originally developed technology to recover metals from waste water streams such as acid
mine drainage using biogenic sulphide generated from the reduction of sulphate contained in the
water. The company now generates sulphide reagent by the much more cost-effective process of
reducing elemental sulphur, and the use of sulphide reagent lies at the heart of BioteQs technology
and know-how used in its commercial plants to treat water not only for producing clean water for
environmental discharge but also for selective metal recovery from both low grade and higher grade
solutions [1,2,3]. More recently, the generation of sulphide reagent at lower costs by reducing
sulphur has attracted the interest of other sectors within the copper mining industry, notably for the
recovery of copper and cyanide in the processing of gold-copper ores and in the separation by
flotation of copper and molybdenum. In both cases, biogenic sulphide reagent can be used to
replace more expensive chemical reagents such as sodium hydrosulphide. In the same manner that
BioteQ replaced sulphate reduction with sulphur reduction to produce biogenic sulphide, it also
became clear that biological sulphate reduction is an expensive method to reduce sulphate and the
company has developed the Sulf-IXTM process based on ion-exchange.
This paper will discuss sulphide generation and its use in the recovery of copper and other metals,
the treatment of water for environmental discharge, the treatment of copper cyanide solutions for
copper and cyanide recovery, and the use of biogenic sulphide in the separation of copper and
molybdenum in flotation.
BioteQ plants, currently operating or under construction, NaHS is used for selective metal
precipitation and recovery in a process known as ChemSulphideTM.
A typical flowsheet utilizing the biogenic generation of sulphide reagent as hydrogen sulphide to
precipitate selectively metals contained in the feed water is shown in Figure 1.
Bioreactor
H2S
Contactor
Sulphur
Clarifier
Reagents
Treated water
Filter
Feed water
Metal sulphide
to smelter
Hydrogen sulphide is generated by the reduction of elemental sulphur in the presence of an electron
donor such as acetic acid in an anaerobic bioreactor. The gas is passed to an anaerobic agitated
contactor where conditions are controlled to precipitate selectively the metal to be recovered as a
sulphide. The high-grade metal sulphide precipitate is then recovered by conventional clarification
and filtration to produce a filter cake which can be shipped to a smelter. It can be noted that the
feed water does not pass through the bioreactor, which can be operated under ideal conditions at all
times. The operation of the bioreactor is not subject to process upsets due to changes in water
chemistry and flow, unlike other biological processes which act directly on the water to be treated.
The main advantages of using the biological H2S generation include:
Minimal hazards and increased safety mainly due to the low system pressure and low
inventory of H2S. At any point in time the amount of H2S stored in the bioreactor(s) is a
small fraction of the daily H2S production. This allows the avoidance of special
environmental permitting for sulphide reagent storage;
Low capital cost mainly due to the ambient temperature and pressure in bioreactors that
are designed as conventional stirred tanks compared to pressure vessels with expensive
agitator seals; and
Easy to scale-up and down over a wide range of H2S production capacities.
If more than one metal is to be recovered, a single bioreactor can provide sulphide reagent to
separate contactor-dewatering circuits. It is possible, for example, to produce separate and high
grade sulphide concentrates of Cu, Zn, Ni-Co and Mn.
Feed water
BioSulphide Plant
Lime Plant
Treated
water
Metal sulphide
products
Metal-free
sludge
Figure 2. Installation of a BioSulphide plant for metals removal upstream of a lime plant.
Not only can there be a financial benefit due to the reduction of costs from the revenues of metal
sales but lime plant operation can be improved by a reduction in lime consumption and a reduction
in the quantity of sludge produced. The sludge would also have a partial or total reduction in the
quantity of contained heavy metals, thereby increasing disposal options and reducing the long term
liability associated with the storage and maintenance of heavy metal-containing sludge. The sludge,
now containing essentially only iron and aluminum hydroxides, possibly together with gypsum,
could also have a value as a component in concrete construction products.
The Bisbee plant was commissioned in 2004 and was designed to recover up to 3 million pounds
per year of copper from the drainage of a large low-grade stockpile with flows of up to 10,900
m3/day. Figure 2 shows a simplified flowsheet of the operation.
#7 Stockpile
Free acid
BioSulphide Plant
Copper Product
to Smelter (~40% Cu)
Figure 2. Simplified flowsheet showing the use of biogenic sulphide for copper recovery at Bisbee
Precipitation of copper from the drainage is rapid and highly efficient, with copper recoveries
consistently greater than 99.5% from the feed solution containing copper in the range 220 to 360
mg/L at a flow currently in the range of 8000 to 9000 m3/day. The copper sulphide product is
thickened and dewatered using conventional equipment, with the plant effluent containing free
acidity returned to the stockpile. The filtered concentrate, containing typically 40 to 45% copper, is
shipped to the Phelps Dodge-owned smelter in Miami, Arizona for processing to metal.
Some mechanical issues were experienced early in the project and caused some significant
downtime. However, the necessary repairs and replacement of some equipment, together with
improved operational procedures, have resulted in very high plant availability since July 2006, with
monthly copper recoveries of around 150,000 lb per month being achieved at current solution
grades and flow rates. Payback on the US$3.2 million plant is expected to be less than 3 years.
The plant to be constructed upstream of an existing high density sludge (HDS) lime plant in 2007
will initially be a ChemSulphideTM process, although the joint venture plans to increase the plant
capacity in stages, which will likely lead to the installation of a bioreactor to produce lower cost
sulphide reagent at the higher plant capacity. Preliminary estimates completed by BioteQ, using
local consumable and labour pricing provided by Jiangxi Copper, shows a total annual operating
cost of US$ 1.44 million, for the maximum capacity plant, or US$0.32 per pound of copper in direct
operating expenses. The high grade copper product would be refined at the Jiangxi Copper refinery
at commercially competitive rates. Refining charges are not included in the total annual operating
cost estimate. The capital cost has not been finalized, pending detailed engineering, but is expected
to be less than US$ 2 million based on the existing site infrastructure and costs of recent
construction projects at the Dexing site.
The application of BioteQ's technology at the Dexing copper mine has highly favourable project
economics from the production of copper and the plant will provide significant environmental
benefits including:
valuable, high-grade Cu2S by-product which can grade around 70% Cu. The implementation of this
technology allows gold/copper ore bodies to be leached aggressively with cyanide (thereby
maximizing gold recovery), without undue concern for copper cyanide formation. The SART
process also converts zinc cyanide in a leach liquor (which is often the case if the Merrill Crowe
process is used for gold and silver recovery) to free cyanide and the ZnS precipitate.
The SART Process, as originally developed, uses chemical sulphide ions, such as sodium
hydrosulphide (NaHS), to precipitate copper and zinc (if present) and convert cyanide to HCN gas,
under weakly acidic conditions (pH 5). Chemical sulphide can be replaced by lower cost
biogenically-produced hydrogen sulphide, which has the added advantage of lowering the acid
demand by one third for copper cyanide treatment and half for zinc cyanide. The chemistry of
SART using both chemical and biogenic sulphide has been discussed elsewhere [6] .
A simplified process flowsheet in which biogenic sulphide replaces chemical sulphide in the SART
Process is shown in Figure 3.
Barren Cyanide
Solution with Cu
H2S
Sulphur and
Reagents
Bioreactor
Cyanide
Recycle
Scrubber
H2SO4
Lime
Primary
Reactor
Neutralization
Reactor
Thickener
Filter
Cu2S Recycle
Thickener
Gypsum
Cu2S product
Figure 3. Flowsheet showing the use of biogenic sulphide to replace chemical sulphide in the
SART Process for cyanide recycle and copper recovery in gold-copper ore processing
One of the features of the SART process (compared to other cyanide recovery processes such as
AVR and Cyanisorb), is that cyanide is not pre-concentrated prior to recycling. The cyanide
strength of the regenerated cyanide solution is essentially the same or slightly lower than the
cyanide strength of the original solution. The process is therefore ideally suited to heap leach
operations, where barren solution (after gold recovery) is recycled directly to leach. Nonetheless,
the first industrial application for the technology was at the Telfer Mine in Western Australia, where
the process was used to regenerate copper cyanide-rich tailings from a CIP plant. For the SART
process to be applied in this way to pulps in a milling operation, the tailings must be subjected to
solid/liquid separation (filtration or CCD), prior to SART. In order to maximize cyanide recovery,
the wash solution used in CCD or filtration must be free of cyanide, and the combined wash plus
barren solution must be treated by the SART process. This will produce a large volume of lowgrade free cyanide solution, and even if the maximum amount of this water is recycled to the mill
and the leach tanks, excess free cyanide-containing water will be produced in the process. Ideally,
this water should be directed to a heap leach operation so as not to waste the cyanide, provided
there is a heap leach at the same site as the mill.
The strength of the copper price in the current market makes a most compelling economic case for
implementation of the SART process. The sale of a high grade copper sulphide by-product will not
only cover all operating costs associated with the SART process (allowing cyanide to be
regenerated at zero cost) but will add value to the project by generating additional revenues from
any copper that is leached by cyanide in the process. As a result of the very robust copper market
conditions, the metal has gone from being a project-killer in many gold ore bodies around the
world, to an added-value by-product. For example, using NaHS, the operating costs forreagents,
power and labour for treatment of a barren leach solution containing 250 mg/L Cu and 310 mg/L
WAD cyanide in a SART circuit can be estimated to be $0.40 per m3, using H2SO4, NaHS and
Ca(OH)2 costs of $100/t, $1000/t and $250/t, respectively. Using biogenic sulphide, costs would be
reduced. Assuming recoveries of 95% cyanide and 99% copper, unit costs of NaCN and copper of
$0.69/lb and $2.50/lb, respectively, and a net smelter return of 85% for sale of the copper, revenues
of $1.98 per m3 can be estimated. Half of this revenue stems from the sale of copper sulphide,
illustrating the potential added value of the leachable copper in a gold ore. By comparison, the cost
of cyanide detoxification to treat a bleed stream using, for example, the SO2-air process ranges from
$1.50/kg NaCN to $3/kg NaCN, depending on the method used and the presence and concentration
of other species in the leach liquor. Under the most favourable circumstances, the cost of cyanide
detoxification in the above hypothetical example would be about $0.90/m3 of heap leach liquor
treated. Therefore, the true benefit of the SART process with current reagent costs and commodity
pricing is expected to be in excess of $2 per cubic meter of heap leach liquor treated.
The capital cost of a SART plant will be higher than a cyanide detoxification plant, but this will be
more than offset by the revenues generated by copper recovery and the savings realized by cyanide
recycle, allowing for a short pay back time on the incremental capital.
BioteQ is currently working with Columbia Metals Corporation Ltd., Canada, to apply its sulphide
generating and precipitation technology in a SART circuit at both Columbias La Jojoba and Lluvia
de Oro gold projects in northern Mexico. The processing of ores form both mines have challenges
due to the presence of cyanide-soluble copper.
Biogenic Sulphide Reagent in Copper-Molybdenum Separation
As with the SART Process, biogenic sulphide could replace sodium hydrosulphide in mineral
processing for the separation of copper and molybdenum in flotation.
BioteQ is currently
evaluating a number of opportunities to supply reagent in an arrangement in which they would own
and operate the sulphide generating plant at the mine site and supply the reagent to the mine
owner/operator.
Sodium hydrosulphide is used to provide reducing conditions to permit efficient separation of
copper and molybdenum sulphides in many flotation operations around the world. Although NaHS
is very effective for this purpose, it could be replaced by biogenic sulphide reagent as shown in
Figure 4. The existing NaHS storage and delivery systems could remain in place and operable so
that sulphide system availability can remain high in the event of planned or unplanned maintenance
of the biogenic system.
Reagent Storage
Biogenic
Sulphide Generator
Crushed
Ore
Flotation
Comminution
Water recycle
Concentrate
Thickener
Copper sulphides
Molybdenum sulphide
Figure 4. Simplified flowsheet showing the use of biogenic sulphide to replace chemical sulphide
in Cu-Mo separation by flotation
Use of biogenic sulphide in copper-molybdenum flotation would have several advantages
including:
Adding a biogenic sulphide supply system to an existing NaHS system would allow
for very high overall system availability in the event of maintenance or problems
with reagent market shortages.
costs. Initially based on the GYP-CIX technology developed in South Africa, the Sulf-IXTM
technology also uses cation and anion exchange resins to remove Ca2+ and SO42- by exchanging
them for hydrogen and hydroxide ions, respectively, as shown in Figure 5.
Cation Loading
Anion Loading
Water with
high sulphate
Water with
low sulphate
H2SO4
Lime
Cation Resin
Regeneration
Anion Resin
Regeneration
Gypsum
Figure 5: Simple schematic of the Sulf-IXTM ion-exchange process for sulphate reduction
When the cationic and anionic resins are fully loaded, they can be regenerated with an acid and an
alkali respectively. As with GYP-CIX, sulphuric acid and lime are used because of their low cost.
In both stages, gypsum is the product of regeneration. The Sulf-IXTM process, however, overcomes
difficulties associated with limited process flexibility for varying feed chemistry, mechanical
entrainment of gypsum in the regeneration stage, and limitations on sulphate removal when
magnesium is present in significant concentration in the feed water. These and other process
changes have resulted in a reduction in the estimated costs of constructing and operating a
commercial plant. Estimates carried out on a number of potential applications indicate that the
operating cost to reduce sulphate from the concentration of a typical lime plant effluent to less than
500 mg/L will be in the range US$0.60 to $2.00 per m3 depending on several site specific factors,
including flow and the concentration of magnesium in the feed. Magnesium, for example, can build
up in the cation resin regeneration circuit due to the high solubility of magnesium sulphate relative
to calcium sulphate. If this is the case, treatment of a bleed from the cation regeneration circuit is
required to remove magnesium from the circuit.
Since it is likely that the feed to a Sulf-IXTM plant will be the effluent from a lime plant, the
concentration of magnesium will depend on the operating pH in the lime plant. If the final
discharge to the environment is restricted with respect to sulphate, it would be preferable, therefore,
to operate the lime plant with a high pH so that magnesium can be removed with lime as
magnesium hydroxide. This would reduce the costs of the subsequent sulphate reduction stage, not
only due to the need for a magnesium removal stage but also because the feed sulphate
concentration would be higher, due to the presence of higher magnesium in the feed. This would
increase the size and operating costs of the anionic stage.
BioteQ is currently working with a number of companies around the world on sulphate reduction
projects. It is anticipated that a large (>100 m3/h) pilot plant to demonstrate the Sulf-IXTM
Lime Plant
Sulf-IXTM Plant
Clean
water
Metal sulphide
products
Metal-free
sludge
Clean
gypsum
Figure 6. Total Water Treatment Concept the treatment of mining effluents to produce clean
water and value added co-products
CONCLUSIONS
Sulphide reagents are widely used in the mining, mineral processing and hydrometallurgy in a
number of applications including water treatment, metal recovery and flotation. BioteQ utilizes
sulphide reagent in its water treatment and metal recovery plants, either generated biologically in
the BioSulphide Process or as chemical sulphide in the ChemSulphideTM Process. Successful
commercial operations have shown that high quality effluents can be produced for environmental
discharge and that metals can be recovered selectively into saleable high-grade concentrates from
acid mine drainage or leach solutions. The generation of lower-cost biogenic sulphide reagent also
offers additional applications in hydrometallurgy and mineral processing. The replacement of
chemical sulphide reagents by biogenic sulphide in the SART process offers a further cost
advantage to a technology which has great potential to permit the economic processing of many
previously uneconomic gold-copper ores by recovering and recycling cyanide that has been
complexed by cyanide-soluble copper, as well as recovering the copper in a saleable sulphide
concentrate.
Similarly, biogenic sulphide can be used to replace or provide a low-cost
alternative/back up system for chemical sulphide used in the separation of copper and molybdenum
in flotation. BioteQ is also developing the Sulf-IXTM process, an ion exchange technology to reduce
the concentration of sulphate for final effluent discharge, which promises to provide a cost effective
method to meet new sulphate regulations coming into force in a number of countries. Integration of
sulfide precipitation technology, conventional lime plants and Sulf-IXTM offers to provide Total
Water Treatment in which only potentially saleable products, including the clean final water
discharge, are produced.
REFERENCES
[1] Lawrence, R.W., Kratochvil, D., Ramey, D. (2005) A New Commercial Metal Recovery
Technology Utilizing On-Site Biological H2S Production. Proc. HydroCopper 2005 3rd
International Workshop on Copper Hydrometallurgy. Santiago, Chile, November 23-25
[2] Bratty, M., Lawrence, R.W., Kratochvil, D., Marchant, P.B. Applications of Biological H2S
Production from Elemental Sulphur in The Treatment of Heavy Metal Pollution Including
Acid Rock Drainage. Proc. International Symposium on Acid Rock Drainage (ICARD), St.
Louis, March 26-29, 2006.
[3] Jones, L., Bratty, M, Kratochvil, D. Lawrence, R.W. Biological Sulphide Production for
Process and Environmental Applications. Proc. Canadian Mineral Processors Operators
Conference, Ottawa, January, 2006
[4] Barter, J., Lane, G., Mitchell, D., Kelson, R., Dunne, R., Trang, C., Dreisinger, D. Cyanide
Management by SART. In: Cyanide: Social, Industrial and Economic Aspects, ed. C. Young,
TMS (The Minerals, Metals and Materials Society), 549-562, 2001.
[5] MacPhail, P.K., Fleming, C.A., Sarbutt, K.W. Cyanide Recovery by the Sart Process for tThe
Lobo-Marte Project, Chile. Randol Gold and Silver Forum, Denver, April 26-29. 1998.
[6] Lawrence, R.W. and Fleming, C.A. Developments and New Applications for Biogenic
Sulphide Reagent in Hydrometallurgy and Mineral Processing. 39th Annual Canadian
Mineral Processors Conference, Ottawa, Canada, January 23-25, 2007, .