The Industrial Treatment of Copper from Concentrates

With Nitrogen Species Catalyzed Pressure Leaching

and SX/EW.

Corby G. Anderson, Ph.D.

Director

The Center for Advanced Mineral and Metallurgical Processing

Montana Tech
Room 221 ELC Building
Butte, Montana, 59701
Tel/Fax: 406-496-4794
E-mail: CAnderson@mtech.edu
Web: WWW.MTECH.EDU/CAMP

Abstract

Today, with a stringent economic and environmental climate prevailing in the copper business,
there is increased interest in evaluating new processing alternatives for production.
Hydrometallurgical treatment of copper concentrates is one of the more viable approaches. In
recent history, an ammoniacal process and a nitric/sulfuric acid process were built and operated
on an industrial scale (1, 2, 3). In addition, several new technological candidates have emerged. Of all
these, the nitrogen species catalyzed pressure leach process was the first to combine acidic
pressure leaching with SX/EW for copper production successfully on an industrial scale. It offers
several definitive advantages. First of all it is the only proven industrial process over the long term
for pressure leaching of copper sulfides. Second, the rate of reaction is much faster and
subsequent required reactor volume is thus smaller. Third, the process does not require
excessively high temperatures or pressures. Fourth, the ORP is extremely high so it oxidizes
almost any sulfide at low oxygen overpressures. Fifth, the materials of construction are readily
available so there is no need for titanium cladding or brick with lead liners. Thus the capital and
maintenance costs are less. Sixth, there is no need for a dip tube or special design radial agitators
with cowlings and the like. Oxygen transfer is innate with the enhanced nitrogen species
chemistry. So, with no titanium, and no titanium dip tube in particular, there is much less oxygen
fire danger. Seventh, the design of the feed pump system is far less of a challenge as is the flash
system and the choke system.. Eighth, like a smelter, precious metals recovery can be high and
direct. Ninth, there is no complex chemistry to deal with like chlorides. Finally, there is minor
amount of nitrogen species utilized so there are no major economic or environmental issues
Introduction

The industrial nitrogen species catalyzed (i.e. NSC) pressure leaching production plant can be
divided into three primary sections:

. The pressure leach area.

. The silver area.
. The copper area.

A general overview of the plant will serve as a good starting point. Referring to Figure, 1 one can
follow the primary flow of materials through the plant. The analysis of the feed is shown in Table
1.

Table 1. Typical Analysis of Plant Copper Concentrate Feed.

35% Sulfur 1% Antimony 4% Silver 2-20% Lead

24% Copper 18% Iron 2% Zinc 2% Arsenic

The purpose of the leach area is to solubilize the silver and copper values so they are selectively
recovered downstream. In so doing, three major products are produced by the leach area.

1. The pregnant solution which contains the silver and copper values along with other
soluble metals most notably iron.

2. The sulfur pellets which contain the sulfide portion of the sulfide mineral.

3. The "fine" leach residue which is the oxidized and finely divided insoluble metallic
portion of the feed. In this case both the lead and antimony are insoluble in this leach
system and report as lead sulfate and antimony oxide.

This is illustrated in Table 2.

Table 2. Assay and Mass Distribution of NSC Plant Leach Products

Assay Ag Cu Fe Pb Sb As Zn

Pregnant 6 45 25 1 1 2 2
Solution g/l g/l g/l ppm ppm g/l g/l

Leach 2.7% 1% 3% 35% 4% 1% 0.1%

Residue

Sulfur nil 0.5% 1% 0.1% 0.1% 0.1% 0.1%

Pellets

Mass Distribution:

Pregnant 96% 99% 93% nil nil 85% 99%

Solution
Leach 4% 0.5% 7% 100% 100% 15% 1%
Residue

Sulfur nil 0.5% 1% nil nil nil nil

Pellets

The clear emerald green pregnant solution goes on to selective recovery of the silver and copper
values. The first step is to recover the silver from the leach solution as the insoluble precipitate of
silver chloride. The silver chloride is separated and washed by filtration and is reduced to silver
metal with zinc powder. The resulting silver powder (sponge) is cast into a suitable shape for
anodes and then placed in an electrolytic refining circuit. The pure silver crystals produced by the
refining cells are cast into bars and prepared for market.

Meanwhile the silver free copper solution containing the copper along with the other soluble metals
goes on to the copper section. This is the largest part of the plant and consists of neutralization of
the excess acid, followed by liquid-liquid solvent extraction (SX) and copper electrowinning. The
major usage of reagents becomes apparent in this part of the plant, where the acid that is utilized
in the leaching section must be neutralized with lime to make the solution amenable to the solvent
extraction, and eventual tailings treatment. Per the scope of this paper, the following discussion
will elaborate on the NSC leaching area as well as the copper solvent extraction and
electrowinning section.

NSC Leaching

The sequence of events in the leach process is as follows:

1) The copper concentrate is pumped slowly through a regrind mill to a slurry holding tank in the
refinery. The regrind reduces concentrate particle size from P80 = 25 micron to P80 = 10 micron.
With the aid of instrumentation, a given amount of solids are transferred into the reactor feed tank.

2) The reactor feed tank serves multiple purposes. It serves as the vessel to make up the recipe
for each leach batch. Here one third of the leach solution is recycled after silver stripping to
conserve acid and provide soluble copper to prevent the formation of hydrogen sulfide gas. The
solids density and the sulfuric acid concentration are adjusted at this point as required by the
leach. The vessel is also a pre-leach tank where iron carbonates are allowed to react before
entering the leach tank. Finally, the reactor feed tank serves as a heat sink for cooling the
reactors. The reactors are cooled by flashing steam into the reactor feed tank. This heat is not
only required to promote the reaction of the iron siderite, but each leach batch is preheated to
50oC in order to accelerate the start of the leach reaction.

3) The leach reaction is run as a batch system using two reactors under the conditions listed in
Table 4. Initially, the air is purged from the vessel with oxygen. Then 45 kg of sodium nitrite are
added, and the vessel is pressurized with oxygen. The exothermic reaction proceeds and takes
an hour to complete. The ultimate temperature is determined by the amount of sulfide feed
introduced at the reactor feed tank. When the reaction is complete, the reactor vessel is cooled by
flashing the steam pressure into the reactor feed tank which preheats the next batch. The reactor
is discharged with air pressure into the liquid-solid separation equipment.
 Table 3. NSC Plant Pressure Leach Conditions

Batch size = 17,000 liters

Initial Cupric Ion Concentration = 15 g/L
Initial Free Sulfuric Acid Concentration = 200 g/L
Preleach temperature = 50oC
Preleach Time = 1 Hour
Slurry Solids Content = 8 - 20% by weight
Agitator Axial Pumping Rate = 100,000 Lpm
Reactor Working Pressure = 620 kPa maximum (90 psig)
Reactor Working Temperature Range = 50o to 155oC
Nitrogen Species Concentration = 2.0 g/L
Particle size = 80% -10 micron
Reaction Time = 1 Hour

4) The liquid-solid separation segregates the three leach products as sulfur pellets, leach
residue, and pregnant solution. This is done by discharging the reactor slurry across a 20 mesh
screen to collect the sulfur pellets, followed by thickening and filtration to separate the leach
residue and produce a clear pregnant solution.

While the leach operation is straightforward on the flow sheet, there are complexities that should
be appreciated. These include: the leach reaction mechanism and the role of the nitrogen oxide
species, particle size, pressure spikes, agitation, corrosion, heat transfer, oxygen transfer, molten
sulfur handling, and NOx gas handling. Some of these areas will be reviewed here, the others
have been previously discussed.(11,12,14,15,16)

The Leach Reaction Mechanism. The leach reaction mechanism is the heart of the leach process
and has been recently characterized in detail by Anderson.(11,14) This work led to a patented
change in the leach chemistry and significant improvements in silver and copper recovery. The
elegant aspect of the leach chemistry, which was initially patented in 1978, is its use of low levels
of nitrogen oxides which are continuously regenerated within the reaction vessel. The presence of
the nitrogen species allows for a much higher redox potential than could be achieved with mild
oxygen pressures.

The original patent utilized nitric acid as the oxidizer at levels of only 2 grams per liter. The
present chemistry, described by on site research efforts, now uses sodium nitrite at similar
concentrations to bring about improved recoveries. Broadly speaking, the chemistry is similar; but,
a close look at the nitrogen chemistry and the reaction mechanism will reveal the benefits
attributed to the use of the nitrite ion over the nitrate ion.

In addition to this, research indicated that particle size would greatly influence the reaction. It
showed that a reduction of the feed particle size from 80% -25 micron to 80% -10 micron provided
significant improvements in recovery of silver.(15) Coupling the use of the nitrite ion with the fine
particle grinding provided for an improvement in silver recovery from 87% up to 96.5%. The
research efforts in this area resulted in the addition of a 2m x 7m ball mill to the silver refinery for
regrinding the feed to the leach area from the antimony plant.
 Only a small amount of nitrogen species is required to drive the reaction. One needs to
appreciate that without the presence of this type of oxidizer the silver would remain insoluble and
the recovery of copper would diminish.

In order to understand the advantages of nitrogen species catalyzed leaching, it is important to

review the principles behind it. The commonly reported leach reaction of a sulfide mineral with
nitric acid in conjunction with sulfuric acid is shown below.

3 MeS (S)+ 2HNO3 (Aq)+ 3H2SO4 (Aq)  3 MeSO4 + 3So (S) + 2NO (G) + 4H2O (1)

However, it is postulated that the actual reaction species is NO + and not NO3- (18). The
addition of or presence of NO 2- instead of NO3- accelerates the formation of NO +. As shown in
Table 1, the NO+/NO couple is capable of an extremely high redox potential (22). So, NO+ is readily
formed from nitrous rather than nitric acid. For example, a convenient source of nitrous acid can
be sodium nitrite (19) .When it is added to an acidic solution, nitrous acid is readily formed.

NaNO2 (Aq) + H+  HNO2 (Aq) + Na+ (2)

Nitrous acid further reacts to form NO+.

HNO2 (Aq) + H+  NO+ (Aq) + H2O (3)

The NO+ then reacts with the mineral and oxidizes the sulfide to sulfur.

Table 1. Relative Potentials of Hydrometallurgical Oxidizers.

E 0h Oxidant
Redox Equation (pH = 0, H2 ref.)

Fe+3 Fe+3 + e-  Fe+2 0.770 V

HNO3 NO3- + 4H+ +3e-  NO(g) + 2H2O 0.957 V

HNO2 NO2 - + 2H+ + e-  NO(g) + H2O 1.202 V

O2 (g) O2 + 4H+ + 4e- 2H2O 1.230 V

Cl2 (g) Cl2 (g) + 2e -  2 Cl- 1.358 V

NO+ NO+ + e-  NO(g) 1.450 V

2MeS (S) + 4NO+ (Aq)  2Me+2 (Aq) + 2So + 4NO (G) (4)
Of course, at higher temperatures and/or nitrogen species concentrations the sulfide would be fully
oxidized to sulfate.

As can be seen, nitric oxide gas, NO, is produced from the oxidation of sulfides. As this gas has a
limited solubility in aqueous solutions, it tends to transfer out of solution. In the pressure leach
system, a closed vessel with an oxygen overpressure is used. The nitric oxide gas emanating from
the leach slurry accumulates in the head space of the reactor where it reacts with the supplied
oxygen to form nitrogen dioxide gas. The NO is then regenerated to NO +. Overall this can be
viewed as:

2NO (G) + O2 (G) < --> 2NO2 (G) (5)

2NO2 (G) <--> 2NO2 (Aq) (6)

2NO2 (Aq) + 2NO (Aq) + 4H+ <--> 4NO+ (Aq) + 2H2O (7)

Since the nitrogen species is continuously regenerated, its role in the overall reaction as the actual
oxidizer is not obvious. The net overall reaction has the sulfide mineral reacting with the acid
solution and oxygen to solubilize the metal value into the sulfate solution and form some elemental
sulfur. Of course, at higher temperatures and/or nitrous acid concentrations the sulfide would be
fully oxidized to sulfate.

2MeS (G) + 4H+ + O2 (G)  2Me+2 (Aq) + 2So + 2H2O (8)

Overall, the nitrogen intermediates serve as an expedient means to transport oxygen to the
surface of the solid particle and allow the resulting reaction to take place at a heightened redox
potential. This inherent asset of the unique system precludes the use of high temperatures and
high pressures which lead to higher costs in other pressure leach processes. For example,
commonly available stainless steel can be used for the reactor vessel. And, complete oxidation of
sulfide to sulfate can be achieved without the excessive conditions found in other pressure leach
systems. Finally, the rapid kinetics of the system leads to smaller reactor volumes and higher unit
throughputs.

To summarize, from an plant operating perspective, the use of fine grinding and sodium nitrite is
dramatic:

1) The reactions were started at 50o C rather than 90o C, providing a greater operating
temperature range resulting in a 60% increase in feed to each batch.

2) The reactions are more complete, which is evident in the sulfur quality. The silver content of
the sulfur has dropped from an average of 11 kg/tonne to about 0.5 kg/tonne. In addition to this,
the iron content of the sulfur, which is due to unreacted pyrite, has dropped from 10% to 1%. This
is indicated by a distinctly yellow color from the previous black color. This has allowed all of the
sulfur to be recycled as a reagent in the antimony plant. In the past, a complete recycle began to
build a recirculating load of high iron sulfur that would create larger sulfur clinkers which are
difficult to discharge from the pressure vessels.

3) There was an improved recovery of silver from 87% to as much as 96.5%.

 Moreover, one of the more difficult material handling aspects of leaching a sulfide ore can be
the production of elemental sulfur. Other leaching processes also have sulfur as a product of the
reaction. Some systems flash the discharge to atmospheric pressure producing a finely divided
sulfur product that is subsequently separated from the leach residue. Other methods have been
devised where the discharge is held in a surge vessel under pressure and above sulfur's melting
point, which allows the phases to separate. The process utilized in the plant is simple and allows
an immediate separation of the sulfur from the insoluble leach residue. When the reaction is
complete, the vessel is cooled, while under agitation, by flashing steam from the head space. As
the slurry of pregnant solution, leach residue, and molten sulfur cools, the sulfur will form into prills
about 3mm in diameter. The sulfur will wet any residual pyrite, but it does not collect other solids.
Upon discharge, it is a straightforward matter of screening to separate the sulfur.

From an environmental perspective, the leach system requires a gas scrubbing system to remove
the NOX from the flash down. Because the total amount of nitrogen oxides in the system is small,
the scrubber is not a major part of the leach system. The one that has proved effective at is a
chemical solution scrubber that reportedly reduces the NOX to nitrogen and water.

Now that the process has been proven on an industrial scale for over a decade, it has become
clear that this nitrogen species catalyzed sulfuric acid leaching process is an economic, durable,
environmentally compatible, and easily operated alternative to more traditional methods of
extracting values from sulfide concentrates. It offers several definitive advantages. First of all it is
the only proven industrial process over the long term for pressure leaching of copper sulfides.
Second, the rate of reaction is much faster and subsequent required reactor volume is thus
smaller. Third, the process does not require excessively high temperatures or pressures. Fourth,
the ORP is extremely high so it oxidizes almost any sulfide at low oxygen overpressures. Fifth, the
materials of construction are readily available so there is no need for titanium cladding or brick with
lead liners. Thus the capital and maintenance costs are less. Sixth, there is no need for a dip tube
or special design radial agitators with cowlings and the like. Oxygen transfer is innate with the
enhanced nitrogen species chemistry. So, with no titanium, and no titanium dip tube in particular,
there is much less oxygen fire danger. Seventh, the design of the feed pump system is far less of
a challenge as is the flash system and the choke system.. Eighth, like a smelter, precious metals
recovery can be high and direct. Ninth, there is no complex chemistry to deal with like chlorides.
Finally, there is minor amount of nitrogen species utilized so there are no major economic or
environmental issues

The Copper Section

Solvent Extraction. The copper solvent extraction and electrowinning system is conventional in
many respects. It has three stages of extraction and two of strip with the concentrated copper
solution going to the copper electrowinning tank house. But, there are operational differences that
can be pointed out between this system and the more common copper heap leach operation.
Initially, the leach solution is 40 to 60 grams per liter copper with 100 grams per liter free acid. It is
neutralized with a milk of lime slurry to a pH of 2.0 and then filtered. After neutralization, the
aqueous solution is diluted to 8 to 10 grams per liter copper so that subsequent extraction can be
carried out without interstage neutralization.

Through optimization of the SX circuit it was found that the typical parameters regarding the
organic concentration and the organic to aqueous proportions have had to be adjusted to
maximize throughput and minimize copper loss to the raffinate which reports as a loss to tails.
Table 6 indicates the difference between the parameters commonly used and those employed at
the plant.
 The use of lime for neutralization prior to SX is also unusual. Concerns over finely divided
gypsum particulates in the system and scaling from calcium compounds were not entirely
unfounded. After a few years of operation, emulsions began to form in the organic phase. This
phenomenon is promoted by fine solids entering in the aqueous phase, which will occur when the
belt filter is worn. While this routinely happens, the system had become less tolerant of
suspended solids and emulsions would develop upon any minor upset. Along with this, it was
noted, on the bench and with work through the vendor, that the break times between the organic
and aqueous phases were much higher than the expected values. Discussions with reagent
suppliers and with Magma Copper led to the installation of an organic cleaning system that utilizes
montmorillonite clay. (26) The clay is mixed with a portion of the organic phase and then filtered.

Table 6. SX Plant Parameters.

Conventional NSC plant

Feed Cu: 2-8 g/l 8-10 g/l
Raffinate Cu: 0.1-1.0 g/l 0.2-0.3 g/l
Extraction Flow Rate variable 1400 l/min
Extract O/A: 1/1 1.25/1
Strip Flow Rate variable 1800 l/min
Strip O/A : 2/1 0.7/1
Reagent Strength: 5-15 V% 30 V% ACORGA M5640
Strip Electrolyte:
Cu: 30-60 g/l 22-26 g/l
H2SO4: 170 g/l 200 g/l

This process improves the break time and seems to have reduced the tendency for emulsions to
form. The disposal of the clay is feasible and the suppliers of the extractant and diluant are
currently addressing this need. Additionally, some steam has been used to raise the temperatures
of the SX feed solutions. This too has mitigated emulsion formation and enhanced break times. In
reality, this is the only significant process issue to arise in the operation of the SX circuit.

Copper Electrowinning. The copper electrowinning tank house is the smallest commercial one of
its kind, with 17 cells and a capacity of 8 tonnes of cathode copper per day. The operation of the
tank house has been generally uneventful, but there are two points to considered.

As with most plants of this type, a flourocarbon reagent is utilized to control acid mist. From time
to time organic from the solvent extraction settlers has migrated into the cell house causing the
normally white foam on the cells to become brown. The operation now takes additional care to
prevent organic from entering the cell house. In particular, this is facilitated through a novel
recapture system from the electrowinning feed tanks.

Also, after 6 years of operation, the original set of lead anodes were changed out. As a matter of
record, the original anodes were a strontium lead alloy which the fabricator had hoped would prove
more durable than other alloys. They were exchanged with calcium, tin lead alloy anodes.

Tails Treatment. The primary stream to be treated in the silver refinery is the raffinate from the
copper solvent extraction process. Lime neutralization has proven to be an effective approach to
precipitation of metals from this solution. The treatment system consists of a mix tank where the
raffinate, the gypsum from neutralization, and the silver conversion solutions are combined with
milk of lime. The lime addition is controlled by pH instrumentation. A continuously pumped
sample and in-line pH probes provide for a reliable and durable measurement system. Lime
scaling can be a constant problem in these installations and has been reduced, especially on the
pH probes, by the addition of polyacrylate to the suction side of the sample pump. Flexible
discharge hoses are also used which do not allow scale to form and the mix tank is cleaned
several times a year.

This treated effluent is discharged to the tailings impoundment where it combines with the
antimony plant, mill and mine water discharges. The final discharge from the property is
monitored and is held within strict parameters.

Conclusion

The nitrogen species catalyzed pressure leach process was the first to combine acidic pressure
leaching with SX/EW for copper production successfully on an industrial scale. It offers several
definitive advantages. First of all it is the only proven industrial process over the long term for
pressure leaching of copper sulfides. Second, the rate of reaction is much faster and subsequent
required reactor volume is thus smaller. Third, the process does not require excessively high
temperatures or pressures. Fourth, the ORP is extremely high so it oxidizes almost any sulfide at
low oxygen overpressures. Fifth, the materials of construction are readily available so there is no
need for titanium cladding or brick with lead liners. Thus the capital and maintenance costs are
less. Sixth, there is no need for a dip tube or special design radial agitators with cowlings and the
like. Oxygen transfer is innate with the enhanced nitrogen species chemistry. So, with no titanium,
and no titanium dip tube in particular, there is much less oxygen fire danger. Seventh, the design
of the feed pump system is far less of a challenge as is the flash system and the choke system..
Eighth, like a smelter, precious metals recovery can be high and direct. Ninth, there is no complex
chemistry to deal with like chlorides. Finally, there is minor amount of nitrogen species utilized so
there are no major economic or environmental issues

References

1. Bennett, E., Idaho Geological Survey, University of Idaho, Moscow, Idaho, May, 1985.

2. 2. Sunshine Mining Company, Summary of Historical Production, Unpublished data, 1992.

3. Holmes, W.C., "How Electrolytic Antimony is Made at The Sunshine Plant", Engineering and
Mining Journal, 145, March, 1944, pp. 54-58.

4. Gould, W.D., "Sunshine's Tetrahedrite Ores Yield Electrolytic Antimony", Engineering and
Mining Journal, June, 1955, pp. 91-94.

5. Holmes, W.C., "Electrolytic Recovery of Metals", Sunshine Mining Co., U.S. Pat 2,331,395,
October 12, 1943.

6. Scheiner, B.J, and Lindstrom, R.E., "Leaching Complex Sulfide Concentrates Using Aqueous
Chloride Oxidation Systems", 133-138, Mining Year Book, Colorado Mining Association, 1978.
7. Scheiner, B.J, Smyres, G.A., Haskett, P.R., and Lindstrom, R.E., "Copper and Silver Recovery
from a Sulfide Concentrate by Ferrous Chloride-Oxygen Leaching", Bureau of Mines, RI 8290, 11
pages, 1978.

8. Caldon, F., "Treatment of Metal Bearing Mineral Material", Sunshine Mining Co., U.S. Patent
No. 4,084,961, April, 1978.

9. CPM Group, Silver Supply, Demand, and Price to 2005, Feb. 1993.

10. Anderson, C.G., Nordwick, S.M., and Krys, L.E., "Processing of Antimony at the Sunshine
Mine", Residues and Effluents - Processing and Environmental Considerations, Edited by R.G.
Reddy, W.P.Imrie, P.B. Queneau, TMS, San Diego, 1991, pp. 349-366.

11. Ackerman, J.B. and Bucans, C.S., "Plant and Process Startup of the Sunshine Silver
Refinery", Minerals and Metallurgical Processing, AIME-SME, Feb., 1986, pp. 20-32.

12. Anderson, C.G. and Harrison, K.D., "Optimization of Nitric-Sulfuric Acid Pressure Leaching of
Silver From Refractory Sulfide Concentrates", Precious Metals 1990, Proceedings of the 14th IPMI
Conference, D.A. Corrigan ed., IPMI, San Diego, California, 1989, pp. 119-151.

13. Ackerman, J.B. and Anderson, C.G., "Plant-Scale Processing of Silver Chloride", Precious
Metals 1991, L. Manziek, ed. International Precious Metals Institute, Naples, Florida, June, 1991,
pp. 253-274.

14. Ackerman, J.B., "The Sunshine Mining Company's Silver Refinery", Proceedings of the Fourth
Western Regional Conference on Precious Metals and the Environment, AIME, Lead, South
Dakota, 1990, pp. 219-235.

15. Anderson, C.G., Krys, L.E., Harrison, K.D., "Treatment of Metal Bearing Mineral Material",
Sunshine Mining Co., U.S. Patent #5,096,486, March 17, 1992.

16. Anderson, C.G., Harrison, K.D. and L. E. Krys, "Process Integration Of Sodium Nitrite
Oxidation And Fine Grinding In Refractory Precious Metal Concentrate Pressure Leaching",
Precious Metals 1993, Proceedings of the 17th IPMI Conference, R. K. Mishra ed., Newport,
Rhode Island, June 13-16, 1993.

17. Anderson, C.G., Nordwick, S.M., and Krys, L.E., U.S. Patent Application No. 07/962,899, Oct.
1992.

18. Nordwick, S.M. and Anderson, C.G., "Advances In Antimony Electrowinning At The Sunshine
Mine", Proceedings Of The Fourth International Symposium On Hydrometallurgy, AIME, Salt Lake
City Utah, August 1-5, 1993.

19. Anderson, C.G. and Krys, L.E., "Leaching Of Antimony From A Refractory Precious Metals
Concentrate", Proceedings Of The Fourth International Symposium On Hydrometallurgy, AIME,
Salt Lake City Utah, August 1-5, 1993.

20. Chen, C., "Treatment of Waste water from Antimony Hydrometallurgy", Huanjin Wuran Yu
Bangzhi, Vol. 7, 1985, pp. 7-11.
21. Reddy, R. G., Hendrix, J. L., Queneau, P. B., Arsenic Metallurgy, Fundamentals and
Applications, AIME, Phoenix, Arizona, January 25-28, 1988.

22. Bjorling, G., "Leaching of Mineral Sulphides by Selective Oxidation at Normal Pressure",
International Symposium on Hydrometallurgy, Edited by D. J. I. Evans and R. S. Shoemaker,
AIME, N. Y., New York, 1973 pp.701-717.

23. Peters, E., Hydrometallurgical Process Innovation, Hydrometallurgy, 29, 1992, pp. 431-459.

24. Anderson, C. G., Unpublished research.

25. Anderson, C. G., Unpublished research.

26. Jenkins, J. G., Magma San Manuel SX-EW Improvements In Phase Disengagement Time Of
Circuit Organic And Recovery Of Organic From The Raffinate Pond Through Clay Treatment,
Arizona Conference, AIME Annual Meeting, December 1991.

THE SUNSHINE MINING COMPANY'S SILVER REFINERY

by John B. Ackerman

Superintendent, Sunshine Mining Company

Kellogg, Idaho

ABSTRACT

The Sunshine Refinery is a hydrometallurgical plant that recovers silver and

copper from sulfide concentrates. The facility consists of three primary
sections:
1) The leaching section which employs a nitric-sulfuric acid oxidative
pressure leach of the concentrate, dissolving the copper and silver values and
leaving the sulfide portion as an insoluble sulfur product.
2) The silver section where the silver is recovered from the leach
solution as silver chloride, converted to metal and refined to fine silver.
3) The copper section utilizing conventional solvent extraction and
copper electrowinning technology to produce copper cathodes.
With this facility, Sunshine has been able to take silver and copper from the
mine to the market.

INTRODUCTION

The Sunshine mine, located in the Coeur d' Alene Mining District of northern
Idaho, is historically the world's largest producer of silver (Bennet, 1985).
The mine extends over an area of several square miles and extends to a depth of
6000 feet below surface. The primary mineral of concern is argentiferrous
tetrahedrite, which is a copper antimony sulfide containing significant amounts
of silver. Pyrite, arsenopyrite, galena, sphalerite, tennanite, and iron
siderite are also present. From the mine, 1000 stpd (908tpd) per day of ore,
averaging 20 tr oz per ton (682 grams per ton) silver are processed through the
flotation mill to produce 15 to 20 stpd (14-18 tpd) of sulfide concentrate
averaging over 1000 oz per short ton (34,210 grams per ton). The high antimony
content has traditionally made the concentrate difficult to market. During
World War II Sunshine developed and patented a sodium sulfide leach for the
recovery of antimony metal, when antimony had significant economic value (Homes,
1943). Today the antimony plant serves as a method of removing the antimony
making the concentrate more amenable to the subsequent refinery leaching process
and reducing antimony penalties for the refinery by products. The sodium
sulfide leaching process disolves the tetrahedrite producing the simpler
sulfide, calcocite and soluble sodium thio-antimonate (equation 1).

3 CuS.Sb2S3 + 3Na2S(aq) = 3Cu2S(s) + 2Na3SbS3(aq) (1)

The insoluble calcocite, and iron siderite, along with the insoluble sulfides
of silver, lead, zinc, iron, and arsenic report as a leach residue which is the
feed for the silver refinery (Table 1). Until 1985, the antimony free
concentrate was marketed to a smelter. Since then it has been processed by the
Sunshine silver refinery which recovers the silver and copper in a marketable
form (Figure 1). The silver refinery process was also developed by Sunshine and
patented in 1978.

______________________________________________________________________
Table 1 _ Typical Analysis of the Major Constituents
of Silver Reinery Feed
______________________________________________________________________

35% Sulfur 1% Antimony 4% Silver 2-20% Lead

24% Copper 18% Iron 2% Zinc 2% Arsenic
______________________________________________________________________

As a novel technology the silver refinery experienced a number of start-up

difficulties and continues to look at ways of optimizing the process (Ackerman
and Bucans, 1986; Anderson and Harrison, 1990).

THE SILVER REFINERY PLANT AND PROCESS

The refinery can be divided into three primary sections:

. The leach area
. The silver area
. The copper area
Each of these sections will be discussed in detail below, however, a general
overview of the plant will serve as a good starting point. Referring to figure
2 one can follow the primary flow of materials through the plant. The analysis
of the feed is shown in table 1. The purpose of the leach area is to solubilize
the silver and copper values so they can be selectively recovered downstream.
In so doing, three major products are produced by the leach area.
. The pregnant solution which contains the silver and copper values along
with other soluble metals most notably iron.
. The sulfur pellets which contain the sulfide portion of the sulfide
mineral.
. The "fine" leach residue which is the oxidized and finely divided
insoluble metallic portion of the feed. In this case both the lead and antimony
are insoluble in this leach system and report as lead sulfate and antimony
oxide.

Looking at the material balance in table 2 one can see that approximately
half the impurities are left behind in the leaching section as elemental sulfur
and lead and antimony compounds.
______________________________________________________________________
Table 2 - Material Balance of Leach Products
______________________________________________________________________

Weight Ag Cu Fe Pb Sb As Zn

Pregnant 50.0% 87.6% 97.2% 80.0% 0.1% 0.1% 66.0% 99.0%

Solution

Fine Leach 15.0% 9.4% 9.4% 0.9% 99.4% 99.8% 9.0% 0.5%
Residue

Sulfur 35.0% 3.0% 1.9% 14.0% 0.5% 0.1% 25.0% 0.5%

Pellets
______________________________________________________________________

The clear emerald green pregnant solution goes on to selective recovery of the
silver and copper values. The first step is to recover the silver from the leach
solution as the insoluble precipitate of silver chloride. The silver chloride
is separated and washed by filtration and is reduced to silver metal with zinc
powder. The resulting silver powder(sponge) is cast into a suitable shape for
anodes and then placed in an electrolytic refining circuit. The pure silver
crystals produced by the refining cells are cast into bars and prepared for
market.

Meanwhile the silver free copper solution containing the copper along with
the other soluble metals goes on to the copper section. This is the largest
part of the plant and consists of neutralization of the excess acid, followed by
liquid-liquid solvent extraction (SX) and copper electrowinning. The major
usage of reagents becomes apparent in this part of the plant, where the acid
that is utilized in the leaching section must be neutralized with lime to make
the solution amenable to the solvent extraction, and eventual tailings
treatment. The following discussion will elaborate on the details of each area
of the plant. While the concept of the plant is actually quite straight forward
it is the details of the process that make this plant suitable and economic for
Sunshine to recover its silver and copper as marketable products at the mine
site.
The Leach Section
The leaching section is the heart of the process, and is designed to process
30st(33t) of concentrate per day, containing up to 36,000 tr. oz.(1120 kg) of
silver and 8st(8.8t) of copper. A step by step description will help to
illustrate the process. This is a batch system and was designed as such for
process simplicity as discussed below. From figure 2, one can see that this
section of the plant consists primarily of 3 parts, feed preparation and
preleach, leaching, and liquid-solid separation. The leaching process produces
three distinct products: elemental sulfur, an insoluble residue and the
pregnant solution containing the silver and copper to be recovered.
______________________________________________________________________
Table 3 - Presure Leach Conditions
______________________________________________________________________

Initial Cupric Ion Concentration = 15 g/L

Initial Free Sulfuric Ion Concentration = 170 g/L
Preleach temperature range = 90 - 105 oC
Preleach Time = 1 Hour
Slurry Solids Content = 100 g/L
 Agitator Axial Pumping Rate = 12000 gpm
Agitator Horsepower = 60
Reactor Pressure = 90 psig maximum
Oxygen overpressure = 20 psi minimum
Reactor Temperature = 80 to 155 oC
Nitric Acid Concentration = 2.0 g/L
Reacton Time = 1 hour
Reactor Turn around Time = 2 Hours
______________________________________________________________________

1) The antimony free concentrate from the anitmony plant is delivered to

the refinery by truck and dumped into an agitated pit. This affords an
opportunity to account for the material. The feed is mixed with a minumum
amount of water, producing a 50% solids slurry by weight which is then pumped
into a slurry holding tank. It is at this point that the density of the slurry
is accurately measured. With the aid of a nuclear density gage and a flow
measurement a given amount of solids are transferred into the reactor feed tank.
2) The reactor feed tank serves multiple purposes. First of all, it
serves as the vessel to make up the recipe for each leach batch. Here the fee
acid, soluble copper content, and solids density are adjusted as required for
the leach. Second, the vessel is a pre-leach tank where the undesirable iron
carbonates are allowed to react before entering the leach tank. If allowed to
react in the leach, the inert carbon dioxide would build a partial pressure in
the leach vessel that would inhibit the oxidation of the sulfides.
FeCO3 + H2SO4 = FeSO4 + CO2 + H2O (2)

Third, the reactor feed tank serves as a heat sink for cooling the reactors.
The reactors are cooled by flashing steam into the reactor feed tank, and in
turn bringing the reactor up to boiling. This heat is not only required to
promotes the reaction of the iron siderite, but each leach batch must be
preheated to 70 degrees C in order to spontaneously initiate the leach reaction.
The sequence of operation for the reactor feed tank is as follows:
Recycled copper solution is added to recover acid and to prevent the
formation of hydrogen sulfide gas forming when the sulfuric acid is added. The
hydrogen sulfide is readily generated by the sulfuric acid reacting with the
residual sodium sulfide left in the concentrate from the antimony plant process
and to a lesser extent by the action of the acid on the sulfide minerals. The
presence of soluble copper prevents the formation of the hydrogen sulfide by the
formation of copper sulfide, and eleminates, not only, the corrosion of the
stainless steel vessel that would result from this reducing gas, but also the
hazards accosiateed with hydrogen sulfide.
Sulfuric acid is then added to bring the initial free acid up to 170 grams
per liter.
The concentrate slurry is then added.
A this point the reactor feed tank is ready to accept the flash steam from
a reactor that is ready for cooling. Within an hour the flash is completed, the
reactor feed tank is hot and its contents are ready to be transferred into an
empty leach vessel.
3) The leach reaction is run as a batch system and there are three 8000
gal(30,000 l) type 316L stainless steel leach vessels designed for a working
pressure of 90 psig(620kPa) and 160 degrees C. The leach vessel is filled with
4000 gal(15,000 l) of slurry. The air in the vessel is purged with oxygen and
then 10 gal(38 l) of nitric acid are added and the vessel is pressurized with
oxygen. The reaction proceeds in different stages which will be discussed
below, and takes half an hour to an hour to complete. During this time the
oxygen pressure setting is gradually increased to 90 psig, to maintain at least
a 20 psi oxygen overpressure and the temperature rises to a maximum of 155
degrees C. The temperature is determined by the amount of sulfide feed
introduced at the reactor feed tank. If the temperature begins to exceed 155
degrees C then cooling quench water is added. When the reaction is complete the
reactor vessel is cooled by flashing the steam pressure into the reactor feed
tank and thereby preheating the next batch. The reactor is, then, discharged
with air pressure into the liquid solid separation equipment.
4) The liquid-solid separation separates the leach products into three
categories: sulfur pellets, leach residue, and clear pregnant solution. This
is done by discharging the reactor slurry across a screen to separate the sulfur
pellets followed by thickening and filtration to collect the leach residue.
Finally, the pregnant solution is clarified in a pressure leaf filter. From here
the pregnant solution goes on to silver and copper recovery.
While the leach operation is straightforward on the flow sheet there are some
complexities that should be appreciated, which include: the leach reaction
mechanism, pressure spikes, agitation, corrosion, heat transfer, and NOx gas
handling.
The Leach Reaction Mechanism. The leach reaction mechanism is the heart of the
leach process and is characterized by the reactions concerning the nitric acid.
Because the nitric acid is continuously regenerated in the vessel, it dos not
appear in the net reactions. Only a small amount of nitric acid, 2 grams per
liter, is required to drive the reaction. One needs to appreciate that without
the presence of the nitric acid the silver would remain insoluble and the
recovery of copper would also drop off.
The leach reaction mechanism is given below:
3MeS +2HNO3 + H2SO4 = 3MeSO4 + 3So + 2NO + 4H2O (3)
2NO + O2 + H2O = NO2 (4)
3NO2 + H2O = 2HNO3 + NO (5)
In the net overall reaction the role performed by the nitric acid is not
obvious:
MeS + 1/2O2 + H2SO4 = MeSO4 + So + H2O (6)
The reaction proceeds in two distinct phases. The first phase is the steady
gradual increase in the temperature up to 120 degrees C. At this point the
reaction rate will increase, marked by an increase in the oxygen consumption and
the temperature. It is apparent, as discussed by Anderson, that the reaction
rate is diffusion controlled and limited by the insoluble product layer that
accumulates on the concentrate particles. At 120 degrees C the elemental sulfur
product layer melts, exposing fresh surface area to the reagents. Hence the
reaction rate increases. A typical assay of the leach products is shown in
table 4.

______________________________________________________________________
Table 4 - Assay of Leach Products
______________________________________________________________________

Ag Cu Fe Pb Sb As Zn

Preganant 5 g/L 40 g/L 25 g/L 1ppm 1ppm 2 g/L 2 g/L

Solution

Leach 800 oz/T 1% 3% 35% 4% 1% 0.1%

Residue
Sulfur 100 oz/T 0.5% 10% 0.1% 0.1% 5% 0.1%
Pellets
______________________________________________________________________
One of the peculiar aspects of the reaction is a tendency for pressure
spikes. Often in the 100 to 120 degree C range a small pressure spike of 2 to 5
psi(14 to35kPa) will occur, with 10 to 15 psi(70 to 103 kPa) spikes happening on
rare occasions, and laboratory work experienced pressure spikes of 70 psi(482
kPa). These pressure spikes are apparently related to an increased reaction
rate which in turn causes an abundance of NO gas to form in an exothermic
reaction. Subsequent regeneration of the nitric acid is somewhat slower
resulting in a net increase in the mass of the gas phase. At the same time , if
the pressure spike exceeds 90 psig(620kPa), which is the oxygen set point
pressure, then the flow of oxygen is interrupted and the regeneration cycle is
broken. This can then accelerate the pressure spike since the NO gas is not
being oxidized to NO2 and nitric acid. Utilizing a relatively large head space
and a minimal amount of nitric acid helps reduce the problems associated with
the spikes. Oddly enough, leaving the agitator turned off during the nitric acid
addition at the beginning of the leach also minimizes the spikes.

Agitation. The agitator in the reactors consists of a 60 HP (45 kw) drive with
dual impellers. The lower impeller is of a high effeciency design, 54 in (137
cm) diameter and pumps 32,000 gpm (121,000 lpm) axially. The upper impeller is
a standard axial impeller, 44 in (112 cm) in diameter, with flat blades at a 45
degree pitch. There are two aspects to the agitation that have been found to be
critical. The first is that the agitation must be strong enough and have enough
axial pumping action to keep the sulfur product suspended. The sulfur then
forms droplets in the agitated leach slurry which form solid sulfur pellets upon
cooling. These are readily discharged from the reactor. Insufficient agitation
will leave a massive frozen puddle of sulfur on the bottom of the reactor that
obviously prevents discharge of the reactor and also leads to corrosion problems
where ever the sulfur is allowed to settle on the stainless steel and thereby
allow reducing conditions to exist at the metal interface. The handling of
molten sulfur is difficult and one the advantages of this batch system is that
it restricts the molten sulfur to the reactor and avoids the problems associated
with material transfer of sulfur in the molten state. The second aspect with
regard to agitation involves the upper impeller in the reactor. This impeller
is at the slurry-gas interface and it creates a splashing effect that helps
transfer the gas phase reactant, NO2, back into the liquid phase. When the
slurry level is above or below this point the reaction proceeds very slowly, and
the recoveries are not as good.

Corrosion. Conditions in a pressure leach can lead to unexpected corrosion

problems. This has been the case with the refinery reactors. Laboratory
corrosion testing showed good results with 316L SS, however, the plant
experience has shown preferential corrosion of the welds, and corrosion wherever
the molten sulfur is allowed to accumulate and solidify on the stainless steel.
As a part of the routine maintenance program, the reactors are checked regularly
for corrosion and then weld repair is done as required. This repair has been
done quite economically by a certified outside shop, and has been required about
every two years. Coupon testing in the reactors over a period of a year has
indicated that 309SS has a much better resistance to these conditions than
316LSS, and it has been used for the most recent repair with good results. At
this point it is apparent that the vessel walls as well as the welds will
eventually corrode and that vessel replacement will be required, but it is
believed that the expected ten year service life will be realized.

Heat Transfer. The amount of concentrate that can be run in each batch is
limited by the exothermic reaction. At this time, 2 tons of feed will bring the
reactor vessel up to 155 degrees C which is the operating limit of the system.
Laboratory work has shown that the optimal maximum leaching temperature is 125
degrees C and that the feed quantity could be doubled, if the temperature rise
could be controlled. However, convenient methods of effectively cooling the
reactor remain elusive. The most effective method would be the use of internal
cooling coils, however, concern over how this would effect the agitation and the
sulfur in suspension has slowed down the project.

NOx Gas Handling. While the quantity of nitric acid employed is relatively
small, most of it is released as NOx gas when the reactor is flashed down. This
required the installation of a nitrogen oxide scrubber, which has been very
effective.

The Silver Section

The silver section consists of 2 major parts: The silver precipitation area
where the recovery of the silver from the pregnant leach solution and its
subsequent conversion to metallic silver takes place, and the casting and
refining section where the final processing is done to produce fine silver for
market.

In the first section the silver is selectively recovered from the pregnant
solution as silver chloride and then reduced to metallic silver with zinc
powder. The whole process of selective precipitation of the silver chloride and
its conversion to silver metal can be quickly demonstrated on the bench. It is
surprisingly more difficult to run the process on a large scale.

The first step is the stripping of the silver from the pregnant solution with
a sodium chloride brine.

Ag+ + Cl- = AgCl(s) (7)

While the silver chloride presents some unique material handling challenges, its
precipitation is a very effective reaction for the selective recovery of the
silver from the hot pregnant leach solutions. Not only does the process strip
the silver content of the pregnant solution to below 1 ppm but the process is
also selective in that no other insoluble chlorides are present. The reaction
is done on a continuous basis in 2 agitated tanks in series, with a silver
chloride probe that is sensitive to the chloride ion concentration. The probe
adds the salt water when the chloride concentration has been depleted by the
silver ions and cuts off the salt water when there is an excess of 100 to 300
ppm Cl-. The probes are the heart of the silver recovery system and have been a
source of constant maintenance in the past. Over the past 2 years a silver
probe was developed here that is much less expensive to build than the
commercially available probes and can also be repaired. The resulting slurry of
leach solution and silver chloride is fed into a thickener where the silver
chloride is allowed to settle out and separate from the silver free pregnant
leach solution. While floculants are not effective in clarifying the solution,
it has been found that thourogh mixing of the slurry ahead of the thickening
will provide for a clear overflow. This solution then goes through 2 more stages
of filtration to ensure that no silver chloride escapes this area and is lost
downstream in the copper section. Typical assays show 0.5 to 1.0 ppm silver
remaining in the filtered solution. Capturing the final 10 to 20 ppm of silver
chloride solids has been challenging, and was accomplished by switching to a
relatively new and inexpensive pleated polypropylene cartridge filter which can
be washed and used over again. The more common wound cartridge was not as
effective and is not reusable, which has created a disposal problem.

The silver chloride solids collected in the thickener are pumped to a small
vacuum belt filter that provides for washing of the cake. From here the washed
silver chloride cake is repulped with water and pumped to the silver chloride
conversion circuit. Here the silver chloride is reduced to silver metal with
zinc powder.

2AgCl + Zno = Ago + ZnCl2(aq) (8)

This reduction process is controlled very effectively by the use of eH probes in

the slurry tanks. The reaction is fast, and an eh probe indicates a very sharp
cut off where enough zinc has been added. The conversion is carried out in 3
small, 50 gallon tanks with a primary zinc feeder on the first tank and
secondary zinc feeder on the third tank.
The resulting zinc chloride is soluble and is washed from the silver sponge on
another vacuum belt filter. Five to ten percent excess zinc is required to
ensure the conversion of the silver chloride. This excess zinc is dissolved
with a dilute sulfuric acid wash. The slurry is then pumped through a filter
press to dewater and wash the silver sponge. From the filter press the sponge
is dried, fed into a small indirect fired rotary kiln and then stored in a bin
for eventual casting into silver anodes for the refining circuit.

The third part of the process is recycling of one third of the leach solution
back to the leach area reactor feed tank. As mentioned above, this prevents
formation of hydrogen sulfide and recycles about ten percent of sulfuric acid.
It is important, however, that the solution that is returned to the leach is
free of chloride ions in that this would precipitate the silver out of the leach
solutions prematurely and would also promote corrosion of the stainless steel
leach vessels. The recycled stream is stripped of any excess chloride ions by
the addition of pregnant leach solution.

Cl- + Ag+ = AgCl(s) (9)

This too is controled by a silver chloride probe and leaves an excess of several
hundred ppm of silver in the recycled solution. The chloride free solution goes
through two stages of filtration to remove the silver chloride precipitate
before being returned to the leach area.

The major operational difficulties in this area have been materials handling,
filtration, instrumentation, and to some extent the chemistry. The materials
handling problems centered around the difficult nature of the silver chloride to
pack together and plug pipe lines. These problems were eventually resolved by
the use of larger pipe lines and recirculating lines. The forward flow through
the silver chloride circuit is only 1 gpm of silver chloride slurry. The use of
recycle lines allowed higher flow rates that helped prevent plugging, and the
one gallon a minute flow is bled from the recycle lines by means of an open or
closed, on/off timer controlled slurry valve.
The filtration problems were overcome simply by adding more capacity.
Initially, it was felt that relatively small filters would handle the capacity,
because silver chloride is quite easily filtered. On the plant scale, however,
it became evident that the silver chloride remaining in the solution was very
fine and tended to blind the filters. Also, as mentioned above, the final
polishing of the solution leaving the silver area is done with the pleasted
polypropylene filter cartridges. This has reduced silver losses by 50 tr. oz.
per day and has reduced the filter costs by 75%.

Instrumentation demands were initially very high, sometimes requiring 4 hours

per shift by the electricians to keep the meters, probes, and level controls in
operation. As mentioned above the development of a new silver probe gave better
control, and as in any maturing plant, The troublesome equipment was eventually
simplified, changed and modified to operate more reliably for the refinery's
specific requirements.

The chemistry of the process has generally been favorable to the process.
For instance, while silver chloride does have a limited solubility, it is less
than 1 ppm in our hot leach solutions, providing over 99.9% silver recovery from
the pregnant solution. The silver chloride conversion circuit has had some
limitations. The maximum conversion of the silver chloride to silver metal with
zinc is essentially 100% under laboratory conditions, but, in the plant, the
conversion is typically 98% at best. It appears that any residual chlorides in
the solution will redissolve the silver metal reforming the silver chloride.
Since it is not possible to get a fully effective wash on the silver sponge belt
filter, some zinc chloride is left behind in the sponge. Upon dissolving the
excess zinc with dilute sulfuric acid, one is left behind with mildly acidic
solution of chlorides, that in the absence of the zinc reducing agent, begin to
reform the silver chloride. The dissolution of the zinc also naturally forms
hydrogen gas. While this produced only a minor amount of gas, hydrogen has a
very low explosive limit, which resulted in a very loud but fortunately, not
very powerful explosion. Improved ventilation and the use of an explosive gas
meter to warn the operators of any elevated levels of hydrogen has eliminated
the problem.

The second part of the silver section is the area where dried silver sponge
is cast, with an induction furnace, into anodes for the moebius style refining
cells. The moebius cells are electrolytic refining cells, with silver nitrate as
the electrolyte and permanent titanium cathodes. The anodes dissolve in the
cells electrolytically producing pure silver crystals at the cathodes. Any
impurities in the anodes are left behind either dissolved in the solution or as
an insoluble sludge in the filter bags. The crystals are washed in a vacuum
cart and then cast into bars in an induction furnace. It is in this section of
the plant where custom dore metal is accepted for refining. Sunshine also
operates a gold refining section that refines the gold content recovered from
the silver dore and accepts custom gold dore for refining. The spent silver
nitrate electrolyte solutions from the refining section are sent to the silver
precipitation area for recovery of the silver, and the NOx gases produced from
the production of the silver nitrate are vented to the leach area NOx scrubber.

Sunshine produces both 999.5 and 999.9 fine silver and 999.9 fine gold for
the market and also operates a custom minting plant for the production of coins
and small bars in Coeur d' Alene, Idaho.

The Copper Section

The copper section consists of a solvent extraction and copper electrowinning

system followed by tails treatment. This is a small circuit compared to most,
with a production capability of about 8st(8.8 t) of copper per day. The solvent
extraction system is conventional technology that has been somewhat modified for
this particular application. The first step in this process is to neutralize
the strongly acidic silver free leach solution from the silver section. The
solution is 100 grams per liter as it enters the neutralization process and
must be neutralized to a pH of 1.8 to make it amenable to solvent extraction.
The neutralization is done with a milk of lime slurry.

H2SO4 + Ca(OH)2 = CaSO4 + H2O (10)

The resulting gypsum is collected as a filter cake and washed on a vacuum belt
filter and rejected to tails. At this point the copper solution may run 20 gpl
or more and must be diluted down to 8 or 9 gpl for the solvent extraction. Most
solvent extraction systems are processing more dilute and less acidic streams
and do not require this pretreatment.

The diluted silver free leach solution contains primarily copper and ferric
iron sulfates along with the other metals, (except for the silver recovered
upstream), solubilised in the leach (see table 4). The solvent extraction
system consists of three identical stages of extraction mixer settlers and two
stages of strip mixer settlers. This neutralized and diluted solution is
introduced into the extraction side of the SX circuit where the organic phase
selectively collects the copper ions leaving the rest of the aqueous solution
behind as the waste, "raffinate", stream. The "loaded" organic phase is
separated by settling and is mixed with the copper electrolyte from the
electrowinning section. The strong acid in the electrolyte strips the copper
from the organic phase thus concentrating and replenishing the copper in the
electrolyte. The raffinate is closely monitored to keep this stream down to
about 300 ppm in copper since the raffinate must be sent tailings treatment and
any copper in it will be lost. The trade-off here is that of iron buildup in
the tank house. As the solvent extraction becomes more efficient then more
ferric iron is transferred into the copper electrowinning cells potentially
causing cathode drop and lowered current efficiencies. A 1 gpm (4 lpm) bleed
from the tank house back to the leach area is used to keep the iron levels down
to 3 gpl of less. A larger bleed is at times required but it then reduces the
capacity of the plant to handle as much copper because of the higher proportion
of recycled copper solution that has to handled by the solvent extraction
system. The recovery of copper from solution is typically 97%

The tank house is also of a conventional design. Two large surge tanks of
20,000 gallons (76,000 l) each are used, one to feed the cells and the other to
collect the return electrolyte from the cells. The return tank then overflows
into the feed tank, where it continues to recycle. Return from the cells is
usually kept at 25 to 28 gpl, and the feed to the cells is a gram higher. The
return stream is used to strip the organic in SX, and then this fortified copper
stream enters the feed side tank. Acid mist is very successfully controlled by
a foaming reagent. Because of the small scale of the tank house, starter sheets
are purchased from the outside. When the starter sheets reach 200 lbs (90 kg)
they are pulled washed and prepared for shipment.
The refinery has been operational close to 5 years now. It has been found
that as the mmmmanodes have aged and begun to deteriorate that the lead content
of the cathodes has gone up from to . This appears to be an inevitable
consequence of electrowinning due to the entrainment of the oxidized lead scale
coming from the anodes. To control this, the flow rates through the cells was
decreased from about 75 gpm (285 lpm) to 20 gpm (75 lpm) and the copper
concentration was allowed to increase to 35 and 40 gpl. This dropped the
entrained lead in the copper by about 50%. At the same time, however, the
eigher copper concentration of the electrolyte, began to compromise the SX
efficiency, since the organic was not being as effectively stripped. At this
time the cell house continues to run at reduced flows and the electrolyte
concentration has been brought back down to the 25 gpl range, with lead values
in the range of 30 ppm.

Probably one of the most time consuming areas of the plant has been the lime
slaker. The lime consumption is approximately one half ton per hour and for
this a typical paddle type lime slaker was chosen. The lime had a tendency to
gel and then ride on top of the grit screen and be rejected along with the grit.
This is apparently a property of some lime deposits. Laboratory test work
showed that stronger agitation would successfully break up the gel and produce a
cleaner grit. However, it was also learned that a small amount of sulfuric acid
added to the slaker, would break up the gel by changing the surface
characteristics of the slurry (Lewis). To accomplish this a one-quarter gpm(4
lpm) metering pump was set up to pump the pH 1 raffinate directly into the
slaker when it was operating and this has improved the slaking considerably. At
this time, a new slaker is being installed that will provide stronger agitation
and a small ball mill to eliminate the nuisance of grit disposal.

The last part of the plant is the tailings treatment process. The tailings
treatment consists of lime neutralization to a pH of 9 followed by settling and
decantation in the mine tailings impoundment. Sunshine is currently negotiating
for an updated water discharge permit, and it appears that this treatment will
be effective in meeting the permit requirements.

OPTIMIZATION AND COST REDUCTION

At the time of this writing, in June of 1990, silver is at a 12 year low of

$4.77 per tr oz ($0.15 per gram). As a primary producer of silver, Sunshine is
in a difficult position to generate a positive cash flow, much less a profit.
Our emphasis has been to look at means of cost reduction, which at the refinery,
primarily translates into improving efficiencies. During our start-up phase
major operational problems were resolved, and now as the plant matures new ideas
for modifying the process are continually being accessed. The yard stick
against which we measure our costs is the alternative of smelting. Four years
ago the costs of producing an ounce of silver at the refinery was similar to the
smelter charges, except that the cash turnaround was much more attractive. Now
the costs have gradually decreased to the point where the refinery has been able
to improve Sushine's overall mining and milling and refining costs by about 3
million dollars out of approximately 30 million in gross revenues.

As the refinery technology matures, and the market price of silver decreases,
the staff sees further potential savings that can be realized. As with many
hydrometallurgical plants, reagents are the major expense in this process, and
ideas that will conserve reagents and improve recovery seem to offer the most
promise for improved economics. A list of potential projects that will enhance
the profitability of the refinery are given below.

1) Improved recovery of silver in the leach. Each ounce of silver recovered

at the refinery, rather than at a smelter from the leach residue, carries
significant savings. In this area it was found that regrinding of the
concentrate had the most effect on improved recovery. It is expected that fine
grinding of the refinery feed from 40 micron to 10 micron will improve recovery
from 88% up to 95% with payback of the project being one year.

2) Reactor cooling. Processing more material in each batch will conserve

reagents and provide additional capacity in the leach area. This project is not
as straightforward as it might seem and the final approach for controlling
reactor temperature has not yet been finalized.
3) Reduction of silver chloride. The use of zinc has become more expensive
with the high price of zinc. Silver chloride is relatively easy to reduce and
other options are being considered, that will save up to $100,000 per year or 2
cents per ounce of silver produced.

4) Acid recycle. The biggest cost is that of the acid and its subsequent
neutralization. Every dollar of acid saved translates into a similar savings in
lime. Systems have been developed that can recover acid and these are being
investigated.
CONCLUSION

The Sunshine silver refinery is a unique combination of processes that has

enabled Sunshine to mine, refine, and market their products from the mine site
in Kellogg. The reduced production costs realized by the refinery have been one
factor that has droped Sunshine's cost of producing silver from $7.50 per ounce
in 1985 to $4.80 per ounce in 1990. The refinery is a unique combination of
process and includes the only commercially operated nitric-sulfuric acid leach
of a sulfide mineral concentrate. This process may have wider application in
the mineral industry.
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