PARTIAL ROASTING OF COPPER CONCENTRATE

WITH STABILISATION OF ARSENIC AND MERCURY

. Holmstrm1, *L. Hedstrm1 , K. Lundholm1 and M. Andersson1, and L. Nevatalo2

1
Outotec (Sweden) AB
Gymnasievgen 14, P.O. Box 745
SE-93127 Skellefte, Sweden
(*Corresponding author: lars.hedstrom@outotec.com)
2
Outotec Research Center Pori
Kuparitie 10, P.O. Box 69
FI-28101 Pori, Finland

ABSTRACT

Several copper deposits have the arsenic bearing minerals enargite (Cu3AsS4) and tennantite
(Cu12As4S12). Since this mineral contain both arsenic and copper, it is not possible to remove the arsenic
by selective flotation. Partial roasting is a method to clean the concentrate from arsenic and thereby
produce a suitable raw material for the copper smelter. Also mercury is commonly found in copper
bearing minerals. In partial roasting process the both the arsenic and mercury are volatilized, while a part
of the sulphur is used as energy during the roasting. This gives a calcine suitable as feed to a smelter much
like an ordinary copper concentrate. A typical analysis of calcine would be: S content 1822%, As content
below 0.3%, Cu content not affected, grain size not affected. The mercury content in sulphuric acid
will be very high unless the SO2-rich process gas is treated by the Boliden/Norzink process that recovers
mercury as calomel, Hg2Cl2.

The volatilized arsenic in the gas phase can be recovered either by dry or wet methods. However,
one problem is that arsenic also contaminates the fine grained calcine dust that is captured downstream in
the gas cleaning system. The calcine dust contains valuable metals such as copper, gold and silver that
needs to be separated from the arsenic. The ultimate aim is to stabilize the recovered arsenic as a
compound with minimum impact on the environment and recover the valuable metals. By using wet
recovery methods it is possible to selectively precipitate copper, gold and silver as sulphides while arsenic
is dissolved is the liquid, which is sent to effluent treatment. The precipitated metal sulphides can be
mixed with the calcine and sent to the copper smelter. The dissolved arsenic in the effluent is further
treated in Outotec ferric arsenate precipitation process, where arsenic is precipitated as the stable
compound basic ferric arsenate, formula FeAsO4xFe(OH)3.

All concentrates containing arsenic are unique and the process design of a roaster plant must be
based on relevant process data. The process data is collected during tests in lab scale and pilot scale. Here
is studied influence of critical process parameters on the quality of the calcine. The ability to run tests both
in lab scale and pilot scale is crucial to the development of the correct roasting process. Outotec is well
equipped for this.

KEYWORDS

Copper concentrate, Enargite, Tennantite, Arsenic, Mercury, Partial roasting, Gas cleaning, Effluent
treatment, Outotec ferric arsenate process, Boliden/Norzink process, Laboratory test, Pilot plant test
 INTRODUCTION

Roasting is used as a pretreatment process of copper concentrates with the main focus on
removing arsenic and in some cases also antimony and mercury. The product from roasting is called
calcine and this material can be further processed just like any clean copper concentrate by conventional
copper making processes without the negative of effects of arsenic.

Arsenic can normally not be removed from the copper concentrate in the flotation plant since
arsenic and copper are present in the same mineral. Alternative methods to separate copper from arsenic is
pressurized oxidizing leach, POX, or by sodium sulphide leach. These technologies have in common that
they on a fundamental basis break down the original structure of the solid minerals. Arsenic is either
volatized as by roasting or dissolved as by leaching. Copper will remain in the calcine during roasting but
could either be dissolved as during POX treatment or remain as solid sulphide mineral during leaching.

The roasting process is well integrated into the conventional copper plant flow sheet, since the
calcine will contain sulphur in an amount that makes it possible to further process by conventional matte
smelting processes, e.g. flash smelting or bath smelting. The roaster plant itself can either be located at the
mine site or at the smelter site since the calcine can be handled like conventional copper concentrate.

This presentation will describe how a modern Outotec partial roasting process operates and how
minor elements that normally are present in the concentrate are handled in the roasting process itself and
the following gas treatment process and effluent treatment.

THE PRESENCE OF ARSENIC RICH MINERALS IN A COPPER CONCENTRATE

There exists a wide range of arsenic containing minerals in nature. However, the presence of
arsenic in a sulphide copper concentrate is normally closely associated with the presence of minerals like
enargite, Cu3AsS4 and tennantite Cu12As4S12. The mineralogical beneficiation of an ore containing
enargite and tennantite typically includes flotation. This process still does not remove arsenic, but rather
concentrate it to the copper concentrate, since the copper mineral itself has arsenic as a main component.
In some cases the copper concentrate may contain up to 10 15% As after flotation.

The case is different if arsenic is present as arsenopyrite, FeAsS in the ore. The presence of
arsenopyrite in a copper concentrate can be avoided by selective flotation of copper mineral and not of the
arsenopyrite. Gold is frequently found in association with arsenopyrite and roasting is also an efficient
process to pre-treat the gold concentrate before cyanide leaching since arsenopyrite will make the
concentrate refractory during the cyanide leach process. Arsenopyrite containing concentrates are only
treated at copper smelters in special cases, e.g. in the gold content is very high. The gold recovery
throughout a copper smelter is normally very high but also more costly than the conventional cyanide leach
route.

Tennantite and enargite normally also contain some small amount of antimony but in much
smaller amount than arsenic. Antimony is partly removed to the gas phase during roasting, but the focus is
normally on the degree of arsenic removal. If present, mercury will be removed to the gas phase during
roasting and the degree of removal is often close to 100%.

REASONS FOR REMOVING ARSENIC BEFORE SMELTING THE COPPER CONCENTRATE

Straight forward smelting of high arsenic copper concentrates to matte has some significant
drawbacks. The reason is that the matte will become contaminated with high levels of arsenic and in order
to obtain blister copper and subsequently anode copper with acceptable contents of arsenic, extra refining
steps have to be performed during the converting process. The allowed Ascontent in anode copper is
generally 0.25 %; otherwise there will be a negative effect on cathodes in the electrolytic refining process.
As a result of smelting high arsenic copper concentrates, the arsenic will be distributed between all the
outgoing material streams from matte smelting and converting, particularly the dusts. Consequently,
uncontrolled Ascontaminated materials are created as well as working condition issues and environmental
problems.

ROASTING REACTIONS AND CALCINE QUALITY

Description of partial roasting process

The solution to the problem is to roast the highAs copper concentrate in order to remove the
arsenic before it is smelted in the matte smelting furnace. The advantage with roasting is that the arsenic
can be concentrated into one gas stream that can be specially designed to handle and stabilize the arsenic.

Roasting is a pyrometallurgical process, where the material is chemically transformed in order to

suit the subsequent process steps; roasting does not involve melting or agglomeration of the material.
Partial roasting of sulphide concentrates is generally an exothermal process (generating heat), where air or
oxygen-enriched air reacts with the sulphide at temperatures below the melting temperature. The heat is
created from the oxidation of sulphur to SO2 and iron to Fe3O4. Most modern roasting processes of copper
concentrates are done in fluidised beds. Figure 1 shows the basic units of the Outotec partial roasting
process for arsenic-containing feed.

Figure 1 Basic units of the Outotec partial roasting process

When highAs copper concentrates are roasted for subsequent matte smelting it is important to
preserve as much sulphur as possible in the roasted product so that there will be enough fuel left for the
required heat generation in the subsequent matte smelting process. Therefore, the roasting is partial, which
means that the access of oxygen in (air) to the roasting furnace is well controlled, i.e. the O2 content is kept
low relative the concentrate feed rate. Thus, only a predetermined amount of sulphur is removed by
transforming the enargite (and tennantite) to solid copper sulphides and mainly gaseous arsenic sulphide,
where the principal roasting reaction for enargite is:

2 Cu3As4(s) + Heat Cu2S(s) + CuS(s) + As2S3(g) (1)

The necessary heat in the roasting furnace is generated from the simultaneous oxidation of pyrite
(FeS2) and chalcopyrite (CuFeS2) to Fe3O4 and SO2:
 3FeS2 (s) + 8O2 (g) Fe3O4 (s) + 6SO2 (g) + Heat (2)

4CuFeS2 (s) + 7O2 (g) 2Cu2S (s) + FeS (s) + Fe3O4 (s) + 5SO2 (g) + Heat (3)

Oxygen enrichment or preheating of fluidizing air can be used to minimize sulphur oxidation.

By this roasting process the arsenic in the concentrate is transferred to the gas phase. The gas
phase is further treated to extract the arsenic either by wet or dry methods. A well designed and operated
roasting process can decrease the Ascontent in the calcine to about 0.30 %As or even less.

Examples of other impurity elements that are also removed during partial roasting are antimony
and mercury.

PROCESSES USED TO RECOVER ARSENIC AND MERCURY INCLUDING GAS CLEANING

AND EFFLUENT TREATMENT

The elements arsenic and mercury need special attention and these two elements must be
transformed into compounds with highest possible stability and the minimum of solubility. Special
processes have been developed to both enable an efficient recovery from the process gas and a
transformation of the elements that produce stable compounds with minimum impact on the environment.
The processes used for recovery and stabilization must be closed due to the hazardous nature of the
elements if they are transferred into the working environment.

Dry recovery of fine grained calcine and stabilization of arsenic

The typical flow sheet of a roaster with dry arsenic recovery is illustrated by Figure 2. In this case
the roaster is operating on arsenic contaminated copper and gold concentrates and the calcine is further
processed by smelting in a copper plant.

Figure 2 The Outotec partial roasting process in combination with a conditioning tower and bag house to
recover dry crude arsenic trioxide

The process gas leaving the roaster cyclones is first oxidized by a post combustion process to
oxidize arsenic compounds being as sulphides or in metallic state as well as oxidizing hydrogen sulphide in
the gas. The fine grained calcine that passes through the cyclones is normally recovered in a hot ESP while
arsenic mainly stays in the gas phase as gaseous arsenic trioxide. Arsenic trioxide can either be recovered
as a solid (dry) As2O3 or by a wet method.

The dry method uses a combination of controlled gas cooling in a specially designed conditioning
tower and a bag filter. The method was mainly used in the past to produce crude arsenic that was further
processed into refined arsenic trioxide. This market does not exist anymore due to obvious reasons and
arsenic trioxide is nowadays normally stabilized and eventually stored at special sites for toxic waste. The
operating temperature of conditioning tower and bag filter is 120 ~130 C. Also stable mercury
compounds like HgS and HgSe tend to precipitate in the bag filter dust at this low temperature. Recently
designed partial roasting plants do not use the dry process any more.

Wet recovery of fine grained calcine and stabilization of arsenic

An efficient way of combining the recovery of fined grained calcine containing valuable metals
like copper, gold and silver with removal of arsenic trioxide from the process gas has been developed. The
number of hot operating unit processes is reduced since the adiabatic cooling tower, hot ESP, conditioning
tower and bag filter are taken out of the flow sheet. The process for wet recovery of fine grained calcine
and arsenic trioxide is shown in Figure 3.

Figure 3 The Outotec partial roasting process in combination with a wet recovery of fine grained calcine
and arsenic trioxide

The recovery of fine grained calcine and arsenic trioxide take place in the first part of the wet gas
cleaning system. Hot roaster gas coming from the post combustion unit is quenched and cleaned from
remaining calcine, arsenic trioxide and acid mist. The modified gas cleaning method consists of the
following unit processes that also include the mercury removal process:
 Quenching of hot process gas in a venturi scrubber system, consisting of a quencher and a venturi
scrubber. The gas becomes saturated with water while fine grained calcine and arsenic trioxide in the
process gas are almost completely transferred to the scrubber solution.
A droplet separator is used to recover remaining droplets in the process gas.
A packed cooling tower is used to cool the process gas. This is necessary to obtain a high efficiency in
the mercury removal process downstream.
Wet electrostatic precipitators are used to remove final small amounts of very fine calcine and
sulphuric acid mist.
A packed tower for mercury removal from process gas by the BolidenNorzink process.
The cleaned process gas is further processed for production of sulphuric acid.

The wet recovery of fine grained calcine and arsenic trioxide has a great advantage since it avoids
production of dusty material from the hot ESP while also maximizing the arsenic removal from the calcine
product. The main reactions that take place during quenching and treatment of scrubber solution can be
summarized as:

Oxidized copper and arsenic trioxide will dissolve in the scrubber solution that has a low pH.
The dissolved copper is selectively precipitated at low pH while dissolved arsenic trioxide is
maintained in the scrubber solution.
Dissolution of arsenic trioxide and oxidized copper as well as copper precipitation takes place in one
or two stirred reaction tanks.
The liquid phase of the slurry will after finalized reaction contain dissolved arsenic but a very low
content of dissolved copper.
A liquid/solid separation is made by settling the solids to transfer the valuable metals like copper, gold
and silver into thickened slurry that easily can be dewatered in e.g. a filter press.
Dissolved arsenic remains in the liquid phase that is transferred to the effluent treatment plant where
arsenic trioxide is oxidized and converted into stable compounds like basic ferric arsenate.
The filter cake consisting of fine grained calcine has a low content of arsenic and can be mixed into
the dry calcine to become the final product send to a smelter.

Effluent treatment alternatives of arsenic precipitation

The liquid stream from arsenic dissolution and copper precipitation is treated in the effluent
treatment plant to precipitate and stabilize arsenic. Arsenic is initially present in trivalent (As3+) form but it
can be oxidized to pentavalent form (As5+) as part of the effluent treatment process. The most common
forms of arsenic precipitation are:

Calcium arsenate precipitation (Ca3(AsO4)2) based on pentavalent form (As5+)

Calcium arsenite precipitation (Ca3(AsO3)2) trivalent form (As3+).
Basic ferric arsenate precipitation (FeAsO4xFe(OH)3) pentavalent form (As5+).
Scorodite precipitation (FeAsO42H2O) pentavalent form (As5+).

For process OPEX and CAPEX, the calcium arsenate process is the cheapest and the scorodite
process is the most expensive process solution. When these processes are evaluated from an environmental
perspective, ferric arsenate and scorodite are better options than calcium-based precipitation. Although the
theoretical crystalline scorodite precipitate has the lowest solubility, according to many recent studies the
stability does not vary much from the empirical stabilities obtained with basic ferric arsenate precipitates
when the ferric arsenate process is properly designed and operated. For this reason the ferric arsenate
process is a feasible and environmentally sound arsenic treatment process where arsenic is removed from
water phase to a stable solid form.
 The Ferric arsenate precipitation process is proposed as a best available technique for arsenic
removal from acid plant effluents in the draft reference document on best available techniques for the non-
ferrous metal industries (IPCC 2011). A well designed effluent treatment plant that use ferric arsenate
precipitation processes, can reach low arsenic levels (< 1 mg/l) and stable solid products (leaching of
arsenic < 25 mg/kg in the CEN test and < 5 mg/l in the TCLP test).

The principles of arsenic removal as ferric arsenate compounds

The incoming arsenic rich stream has a low pH and milk of lime is used to gradually neutralize
the liquid. Ferrous sulphate solution is fed to the first reactor in order to precipitate arsenic as ferric
arsenate in the first two reactors. The pH in these first two reactors is kept at approximately 4 4.5 which
is favourable for the formation of ferric arsenate. For the design of ferric arsenate precipitation, it is
necessary to enable the use of at least four times the stoichiometric amount of ferrous iron. In the third
reactor the pH is further raised to 8 or higher in order to precipitate the other metal impurities out of
solution as metal hydroxides and to stabilize the ferric arsenate. The neutralization is carried out by using
an automatically controlled lime milk feed from a lime milk circulation line. The Outotec ferric arsenate
precipitation process is shown in Figure 4.

The precipitation reactors are also provided with compressed air injection. Air is needed to
oxidize Fe2+ to Fe3+ and As3+ to As5+ form. Air is fed to the first two reactors, but if either one of these is
by-passed, air can also be fed to the third reactor.

Figure 4 The Outotec ferric arsenate precipitation process of effluent water from wet gas cleaning of
arsenic containing process gas

Arsenic precipitation reaction taking place during the effluent treatment process is:

4HAsO2 + 4FeSO4 + 2H2O + 3O2(g) 4FeAsO4 + 4H2SO4 (4)

Acid is neutralized according to:

H2SO4 + Ca(OH)2 CaSO42H2O (5)

Metal impurities (Me2+ and Me3+) present at the effluent solution will precipitate according to:
 Ca(OH)2 + Me2+ Me(OH)2 + Ca2+ (6)
3
/2Ca(OH)2 + Me3+ Me(OH)3 + 3/2Ca2+ (7)

From the third reactor the neutralized slurry flows by gravity to the gypsum slurry pump tank.
From this pump tank part of the slurry is recycled back to the first reactor for seeding purposes. Seeding of
the process with recycled slurry decreases the scaling and improves the settling properties of the solids.
The main control philosophy of the precipitation process includes feeding lime milk and ferrous sulphate to
the reactors based on effluent feed volume, acid concentration and arsenic concentration.

Recovery and stabilization of mercury

Mercury is frequently present in both zinc and copper concentrates. A sulphuric acid with
elevated mercury content will be produced unless the process gas is cleaned from mercury before the SO 2
is converted into sulphuric acid.

Mercury is almost completely vaporized during roasting and various mercury compounds might
be formed when the gas is cooled in the wet gas cleaning system. A few mercury compounds like mercury
sulphide (HgS) and mercury selenide (HgSe) are very stable and form solid particles when the process gas
is cooled down. These compounds will be found in the wet gas cleaning sludge formed in gas quench, gas
cooler and wet ESP. Mercury in elemental form will stay as vapour in the gas unless the mercury content
exceeds the saturation level. Figure 5 illustrates a typical distribution of mercury in the wet gas cleaning of
a roaster plant.

Figure 5 The typical mercury distribution throughout the gas cleaning system at a roster treating mercury
rich gold ores or concentrates

The mercury content in sulphuric acid will be very high unless the process gas is treated by the
Boliden/Norzink process that recovers mercury as calomel, Hg 2Cl2. The principle of the B/N process is
illustrated by Figure 6. Acid with below 0.1 g/t Hg can be produced by operating the B/N process in
combination with well working wet ESPs and an efficient gas cooling. The process is based on the
reaction between liquid mercuric chloride and mercury vapour in the process gas that forms solid calomel
and reduces the mercury content in the process gas by about 99%. The reaction is written:

Hg(g) + HgCl2(l) Hg2Cl2 (s) (8)

The process gas temperature should be as low as possible since the remaining mercury content is
strongly depending on the temperature. This is illustrated by Figure 7. The gas temperature must be below
30 C to produce acid with a mercury content of < 0.1 g/t.

Mercury in effluent water from the B/N process must be precipitated and stabilized before the
residue can be send to a final storage. This is made by a specially designed process that shown in Figure 8.
The combination of mercury removal from process gas by the B/N process and the stabilization process of
mercury contaminated effluent water is a complete process package that ensures a very efficient and safe
elimination of mercury from the SO2 rich process gas and also a safe future storage of the separated
mercury residue.
 Figure 6 Mercury removal by the BolidenNorzink process that converts mercury vapour into calomel

Figure 7 The temperature dependency of process gas temperature on the Hg content in acid

PARTIAL ROASTING TEST WORK AN EFFICIENT WAY OF GETTING DESIGN DATA

The principle in the process design work at Outotec is to develop a process solution customized
for the client. The process solution is always designed according to site conditions and technological
process relevant criteria such as throughput, particle size, arsenic and sulphur contents.

Each ore and concentrate is unique with respect to mineralogical and chemical composition and a
very useful way of checking the expected future product quality is to test the material with laboratory tests.
These tests are preferably made already in the early stage of the mineralogical test work since important
information is obtained also from small scale roasting test. There are several different test methods from
small laboratory scale to pilot scale, available at the Outotec research centre:
 Figure 8 The effluent treatment process of mercury contaminated process water

Figure 9 Staircase of different test methods used for partial roasting; amount of test material needed,
results from test and usage of the test results. A time axis illustrates the phase of a project that the test
method is most suitable

Analysis with STA (simultaneous measurements of thermogravitmetry and differential scanning

calorimetry) demands for minimal amount of material but still clearly show the reaction temperatures,
and hence a suitable operating temperature.
A small, but significantly reliable partial roasting test is the rotary tube furnace roasting test, where the
suitability for roasting is examined.
 The suitability for roasting is also obtained in the batch operated fluid bed laboratory roasting test.
However, more material is needed for the test, but results also shows more reliable agglomeration and
sintering tendencies and also fluidization properties.
For a design basis of a full scale partial roasting plant, pilot plant roasting tests will be needed. The
test methods are summarized in Figure 9.

The Outotec partial roasting reference list for arsenic containing concentrates is long and gives an
indication that this technology has been developed during years. Due to a generally more complex nature
of new ores, with increased content of disturbing elements, this technology is advancing

THE CODELCO ROASTING PLANT AT MMH IN CHILE

The roasting plant supplied by Outotec to Codelco at the MMH site close to Calama is presented
in the following photos, Figures 10 to 12, showing some general views of roaster plant, gas cleaning
system and acid plant. The pictures were taken in July 2013.

Figure 10 Roasting plant at MMH, looking south

Figure 11 Gas cleaning and effluent treatment Figure 12 Drying towers and sulphuric acid plant
plants at MMH at MMH
 SUMMARY

Outotec partial roasting processes is an efficient method to pre-treat arsenic containing copper
concentrates before the calcine is used as feed to a conventional copper plant.
Elements like arsenic, sulphur and mercury are vaporized and oxidized and calcine with low content of
impurities is produced. This is essential to avoid contamination of the copper plant with arsenic and
minimizing the mercury content in the sulphuric acid. .
The hazardous elements arsenic and mercury are recovered from the process gas and transformed into
concentrated and stable compounds.
Roasting avoids hazardous elements to be distributed in the large tonnage of matte, slag and dust at the
copper plant, which could be the case if no roasting is used.
Roasting is normally a process that can operate autogenously since the heat balance of the roaster can
be oxygen enriched or pre-heated if necessary.
The sulphur is converted into sulphuric acid.
Arsenic (from Ascontaining copper concentrates) can be stabilized to solid precipitate waste by the
Outotec roasting process in combination the Outotec ferric arsenate process.
The ferric arsenate precipitation process is proposed as a best available technique for arsenic removal
from acid plant effluents in the draft reference document on best available techniques for the non-
ferrous metal industries (IPCC 2011).

REFERENCES

Hedstrm, L., Holmstrm, ., & Hammerschmidt, J. (2012, May). Roasting of Refractory Gold
Concentrates and Handling of Minor Elements. Paper presented at ALTA 2012 Gold Conference,
Perth , Australia.

Salokannel, A., Nevatalo, L. M., Martikainen, M., van der Meer, T., & McCulloch, J. (2013, July).
Technology Selection for Removal of Contaminants from an Industrial Wastewater. Paper
presented at MetPlant 2013, AusIMM, Perth, Australia.

Dyvik, F. (1985, September). Mercury removal and control application of the Boliden-Norzink
process in sulphuric acid manufacture. Paper presented at Extraction Metallurgy 85 Symposium,
IMM, London, England.

Holmstrm, ., Hedstrm, L., & Mlsnes, A. (2012, November). Gas Cleaning Technologies in Metal
Smelters with Focus on Mercury. Paper presented at Sino Swedish Cooperation on Capacity
Building for Mercury Control and Management in China (2012 2013), Bejing, China.

Lundholm, K., Holmstrm, ., Wrobel, M., & Hammerschmidt, J., (2013, June). Partial Roasting of
Copper and Gold Concentrates for Removal of Arsenic and other Elements. Paper presented at
European Metallurgical Conference 2013, Weimar, Germany.

Holmstrm, ., Berg, G., Andersson, M., Carrasco, S., & Deutsch, D. (2013, December).
Development of Partial Roasting Technology for Arsenic Containing Copper Concentrates. Paper
presented at 8th International Copper Conference 2013, IIMCh, Santiago, Chile.