Desulfuracion de Piritas
Desulfuracion de Piritas
Desulfuracion de Piritas
Denis Bois1, Philippe Poirier2, Mostafa Benzaazoua1, Bruno Bussière1, Mukendi Kongolo1
1
Unité de Recherche et Service en Technologie Minérale (URSTM – UQAT)
445, boul. de l’Université
Rouyn-Noranda, Quebec
J9X 5E4
Phone : (819) 762-0971 ext.: 2558
E-mail: [email protected]
2
SNC-Lavalin Environment inc.
455, Rene-Levesque Blvd
Montreal, Quebec
H2Z 1Z3
Phone : (514) 393-8000 ext.: 7783
E-mail: [email protected]
Key Words: Desulphurised tailings, acid mine drainage, dry cover, water covers, paste backfill
ABSTRACT
INTRODUCTION
An important environmental problem of the mining industry is the generation of acid mine
drainage (AMD) resulting from the natural oxidation of sulphides in mine tailings. This
phenomenon involves the generation of acidity which in turn increases the amount of metals in
mine water. To ensure that the contamination does not adversely affect the environment, mining
operations must take actions to be in compliance with environmental regulations. The
environmental impacts of AMD has been described in detail in previous work (e.g. Down and
Stocks, 1977; Ritcey, 1989; Gray, 1997; Ripley et al., 1996; Aubertin et al., 2002).
Different techniques are used to limit the release of AMD into the environment. Essentially,
these techniques try to limit the availability of one or more of the components (water, oxygen, or
sulphides) necessary to the generation of acidity. To limit the influx of water, covers made of
low hydraulic conductivity soils or synthetic materials (such as geomembranes or bentonite
geocomposites) can be used. Some Quebec mine sites are currently using such covers to limit
AMD production (Bienvenu and Dufour, 1996; Lewis and Gallinger, 1999).
There are different techniques available to limit oxygen migration into a mine tailing
impoundment. A water cover can be placed over reactive tailings to reduce oxygen availability
by the use of the low diffusion coefficient of air in water (e.g. Fraser and Robertson, 1994;
Amyot and Vézina, 1997; Simms et al. 2001). An oxygen barrier can also be created by placing
a cover made of oxygen consuming materials, such as wood waste, straw mulch, or other organic
residues (e.g. Tremblay, 1994; Tassé et al., 1997; Cabral et al., 2000). Another alternative is to
build a cover with capillary barrier effects made of either natural materials or non acid
generating mine tailings. This type of barrier relies on the high moisture-retention capacity of
one of its layers to prevent oxygen migration (e.g Nicholson et al., 1989; Aubertin et al., 1995;
Ricard et al., 1997; Bussière et al., 2001).
AP + Security= NP
AP 〉 NP
AP
Desulphurized tailings
non acid generating
NP
Initial Tailings
Acid generating
Sulphide concentrate
Figure 1: Scheme illustrating the environmental desulphurisation principle
This paper is divided into two parts. The first part covers the feasibility of the desulphurisation
technique based 1) on a laboratory study to find the first optimisation elements of the
desulphurisation process and 2) on site continuous pilot tests to verify the laboratory results,
especially those relevant or similar to actual mill conditions (variations in chemical and mineral
composition). The potential use of sulphide concentrate in a paste backfill is also discussed. The
second part focuses on the economic factors associated with mine tailings management by
desulphurisation and compares desulphurisation with other tailings management and
rehabilitation techniques.
TAILINGS DESULPHURISATION
Tailings characteristics
For the laboratory testing, the tailing slurry was sampled at the final discharge of the processing
plant from a base metal mine. The sulphur composition of the tailing samples and the calculated
sulphide composition are presented in Table 1. The main sulphide mineral in the tailings was pyrite.
An important characteristic for desulphurisation is the acid generation potential (or Net
Neutralization Potential NNP) of the tailings. Among the various methods used to evaluate this
parameter, the modified Acid Base Accounting test was chosen because of its consistency from
previous testing. The NNP is calculated as the difference between the Neutralization Potential (NP)
and the Acidity Potential (AP). AP is estimated from the sulphide sulphur content as analyzed by
chemical analysis and NP is determined by volumetric titration (more details on static tests can be
found in Morin and Hutt, 1997). The results are summarized in Table 1 and show that the tailings
studied were acid generating and have a relatively low NP. The tailings grain size was analyzed
because this factor is very important for both the flotation process and sulphide oxidation. Table 1
presents the typical tailing grain size distribution as determined by a Malvern Mastersizer. Table 1
also shows the relative density of grains (Gs) of the tailings determined with a Helium pycnometer.
Gs is largely dependant on the sulphide content of the material tested.
ABA static tests for the tailings studied Main results of the grain size analysis
Ranges Tailings Tailings
S tot. Wt % 9 - 20 D90 (µm) 76.3
S (sulphide) Wt % 16.9 - 37.5 D50 (µm) 17.85
S (sulphate) Wt % 0 - 0.62 D10 (µm) 2.09
AP kg CaCO3/t 281 - 625 Gs 3.11
NP kg CaCO3/t 25 - 60
NNP (total S) -221 - -600
Laboratory testing
Flotation testing was done on the tailing samples under laboratory conditions to optimise the
desulphurisation process. The percentage solid for the sampled pulp was 30%. Conditioning time
was 10 minutes following the addition of collector and frother. All flotation tests were performed
in a Denver D-12 lab flotation machine. The cell volume was 2.5 litres. The speed of the rotor-
stator was adjusted to 1500 rpm and airflow was set at 2.25 l per minute. The froth was removed
with a spatula by the same operator for all flotation tests to obtain consistent results. For each
flotation test, four concentrates and the final desulphurised tailings were recovered separately
and analyzed for sulphur grade to study the kinetics of sulphide recovery.
Different parameters were optimised to obtain the best total sulphide recovery and to avoid the
mechanical trapping of gangue that could cause dilution of the concentrate (increase in volume).
The different optimisation steps for the sampled tailings are listed below; the complete results
can be found in other related publications (Benzaazoua et al. 1998; 1999, 2000, 2002). The main
conclusions for each aspect of the tests are the presented.
100% 10%
80% 8%
S recovery (%)
residual S (%)
60% 6%
40% 4%
20% 2%
0% 0%
0 5 10 15 0 5 10 15
time (min.) time (min.)
10 19 38 57 10 19 38 57
78 98 116 145 78 98 116 145
Figure 2: Flotation kinetic of the studied tailings for eight KAX dosages (in g/t)
a) : Sulphide recovery (%) vs. time b) : Residual sulphide (%) vs. time.
(in Benzaazoua and Bussière, 1999).
The residual sulphide content obtained was approximately 0.4 % with an optimum collector
concentration of 100 g/t (Figure 2). Further increases in the KAX dosage did not improve the
sulphide recovery which stabilized at 97 %. However, a KAX concentration below 40 g/t seemed
to have no effect on sulphide flotation. The concentrate weight percentage was approximately 45
%.
This is a very important factor that should be studied to evaluate if there is selective removing of
carbonates during the desulphurisation process. If not, the carbonate removal is simply due to
entrainment. The results show that there is no difference in selectivity between the two most
significant carbonates, dolomite CaMg(CO3)2 and calcite CaCO3, regardless of their initial grade.
The recovery of Ca and Mg in the concentrates obtained is directly related to the mechanical
entrainment process. Since particle entrapment is an integral part of desulphurisation, Ca and Mg
recovery is dependant on the flotation time.
In general, desulphurisation increases the net neutralization potential (NP-AP) of the treated
tailings. The removal of sulphides essentially increases the proportion of neutralizing elements in
the treated tailings (relative enrichment). Figure 3 shows the difference between the NP of the
treated tailings vs. the NP of the non-treated tailings. This graph accounts for the gangue
entrainment phenomena in the concentrate.
140
100
Final NP (Kg CaCO3/t)
120
80
100
80 60
60
40
40
20 20
0
0 5 10 15 20 25
% Sulphur
The preliminary laboratory testing allowed the optimisation of the desulphurisation process by non-
selective flotation. It was done on a reduced scale with Denver cells. The objective of the pilot tests
was to confirm the feasibility of continuous desulphurisation at a mine site. Figure 4 presents the
installation of the mobile desulphurisation unit at a polymetallic concentrator in Canada.
The performance of the desulphurisation circuit was tested for a month. During this period the
sulphur content of the feed (total tailings) to the mobile unit ranged from 9 to 22 % S. The process
was successful in reducing the sulphide levels in the final residue to levels low enough to be non
acid generating.
The figure 5 shows an operational example when all the process parameters are optimised. 100 g/t of
amyl xanthate was used to lower the sulphur grade of the feed from 20 to 0.5 % in the desulphurised
tailings. One should note that the concentrate has high sulphur grades which shows that there was
very little entrainment of gangue material (approximately 19 %).
a) Exterior view of the small scale pilot plant b) Panoramic view of the small scale pilot plant
c) Flotation cells
Figure 4: URSTM’s small scale pilot plant used for continuous testing
The on site pilot tests using the mobile desulphurisation unit allowed to improve our knowledge of
environmental desulphurisation. The tests were done to verify that desulphurisation results in the
laboratory could be obtained at the pilot scale. The sulphide grade of the desulphurised tailings was
low and the sulphide grades of the concentrates were high. This confirmed that tailings can be
desulphurised using the pilot plant. The mobile desulphurisation unit is a viable tool to process
significant amount of pulp under typical plant discharge conditions.
Flotation bench
Tailings Concentrate
Mass flow 32.2 kg/hr Mass flow 26.7 kg/hr
Weight % 54.7 % Weight % 45.3 %
%S (sulphide) 0.5% %S (sulphide) 43.4%
% dist. S (sulphide) 1.5% % dist. S (sulphide) 98.5%
%Ca 1.48% %Ca 0.196%
%Mg 3.21% %Mg 0.543%
%Mn 0.208% %Mn 0.043%
The potential use of sulphide-rich tailings (flotation concentrates) as paste backfill was studied
by Benzaazoua et al. (2004). The amount of sulphides in the tailings has a direct impact on the
tailings density and consequently, on the quantity of binder to be added per volume unit
(proportions of added binder are always calculated using the dry total mass of tailings). There is
also an indirect effect that corresponds to the amount of sulphates in the initial mixture that is
usually proportional to the amount of sulphides in the tailings. Therefore, to isolate this
parameter, it was necessary to do a series of tests that would both deplete and enrich the
sulphides in the mine tailings sample. The end result was tailing mixtures with five different
compositions: S1, S2, S3, S4 and S5 (concentrate) with sulphur contents of approximately 2 %
(desulphurised tailings), 6 %, 12 %, 18 % and 38.5 % of sulphur respectively. The particle size
distributions for the four different tailings were similar. Two binder types were tested at the same
proportion (4.5 wt % of binder). The first binder was 50 % Portland cement T10 and 50 %
Portland cement T50 and the second was 80 % blast furnace slag and 20 % ordinary Portland
cement T10.
The results from the uniaxial compressive strength (UCS) evolution and its relationship to the
sulphide content are shown in Figure 6. In addition to the clear effect of binder type, the amount
of sulphides had an influence on the strength (UCS) of the pastefill. However, the influence of
the amount of sulphides was dependant on the binder type. Samples with Portland cement (T10-
T50) generally had less mechanical resistance. However, sulphides positive effect was more
noticeable for the binder with slag (T10-Slag) which seemed to generate better resistance after
28 days of curing time. It should be noted that for low sulphide contents (%S lower than 6%), the
strength increase slightly when the sulphide content increased. For higher values of %S
regardless of the binder type, the sulphide proportion in the tailings adversely affects the pastefill
strength up to a sulphide content of 12 %. With higher sulphide contents, there is a beneficial
effect, which could be related to one or the two following factors:
- Higher sulphide content implies higher density and this leads to a higher proportion (of
volume) of the binder
- Higher sulphide content implies higher sulphate available. Consequently, this leads to
precipitation of the sulphates, which enhances the cohesion development.
However, to understand the sulphate production behaviour within pastefill systems, and to
demonstrate the low reactivity of sulphides within the cemented pastefill, oxygen consumption
tests have been performed (Eberling et al., 1994) on the pastefill samples for the two binders.
Furthermore, free binder samples (wet tailings only) were also studied in terms of their sulphide
reactivity and for later comparison with pastefill reactivity. The results of this study are
presented in detail in Benzaazoua et al. (2003) and Ouellet et al. (2003). It has been
demonstrated that sulphide reactivity is limited in pastefill because of the high water saturation
levels (near 100 %) in the backfill. This confirms the assumption that the sulphates affecting
mechanical strength are mainly those that were present in the initial mix (pre-oxidized products).
UCS-14 days UCS-28 days UCS-56 days UCS-120 days UCS-14 days UC S-28 days UCS-56 days UCS-120 days
450 3000
4.5 % ce m e nt (T10-Slag)
400 4.5 ce m e nt (T10-T50)
2500
350
300 2000
UCS (kpa)
UCS (kPa)
250
1500
200
150 1000
100
500
50
0 0
2 6 12 18 39 2 6 12 18 39
% sulphur % sulphur
Figure 6: Effect of sulphur content on the mechanical strength (UCS) of pastefill samples with time
for two different types of binder: Cement Portland (T10-T50) and Slag based cement (T10-Slag).
(in Benzaazoua et al. 2004)
COST EVALUATION OF THE DESULPHURISED TAILINGS TECHNOLOGY
The first part of the paper showed that it is possible to extract sulphide minerals by non-selective
froth flotation and to produce a non acid generating desulphurised fraction. To assess the cost of
implementing desulphurised tailings technology, a comparative cost study was performed by
SNC-Lavalin Environment. The objective of the study was to evaluate and compare the cost of
tailings disposal ($/m3 of tailings) for a new mine with potentially acid generating tailings, using
four different techniques to prevent the onset of acid drainage: 1) a dry cover with capillary
barrier effect (CCBE), 2) underwater disposal, 3) complete desulphurisation of all tailings
generated and 4) partial desulphurisation, i.e. production of desulphurised tailings during the last
years of mine operation to use as a dry cover. Two different site locations were studied; one with
a favourable topography (valley site) and one with a less favourable topography (flat site).
Characteristics of the mine site used for the comparative cost study
In order to compare the tailings disposal cost of the four tailings disposal techniques (CCBE,
underwater disposal, complete and partial desulphurisation), a virtual mine site is used. The base
metal mine is an underground operation, located in a wet (positive water balance) climate. The
new mine site characteristics used for the comparative cost study are presented on Table 2.
A sampling and testing program done by the Ministry of Environment of Québec (Spiegle, 2002)
demonstrated that the majority of non-acid generating tailings tested are leachable under the new
Directive 019 Guidelines for tailings management for the Province of Quebec, using USEPA
1311 or 1312 leaching test method. For this study, it was assumed that the tailings would be
leachable, i.e., that the metal concentrations in the leachate of a tailing sample are higher than the
provincial limits. This hypothesis was also used for desulphurised tailings. Consequently, for all
of the different scenarios studied, the tailings dams were designed with low permeability cores to
reduce tailings pore water seepage. The hypothesis is conservative as some desulphurised
tailings will not be leachable, or because under some of the regulations the tailings dams could
be constructed with tailings or a more permeable material that would significantly reduce dam
construction costs. This would reduce the overall cost for the tailings management and
rehabilitation techniques as such as the use of a CCBE or desulphurisation.
To account for the dam construction costs for the four different tailings management scenarios,
two different tailings locations were studied. The first site was located in a valley (see Figure 7).
This site needed the construction of two dams to close the valley and create a tailings
impoundment. The stratigraphy was variable and was typical of the soil conditions from
Northern Québec, with a resistant silty clay layer at lower elevations and glacial till on the valley
slopes. For this site, it was assumed that a clay layer or a geomembrane would have to be
installed on 20 % of the area to reduce seepage and limit groundwater contamination where more
permeable material is present.
The second site was located in a flat area and needed the construction of four dams to confine the
tailings (see Figure 8). Since the area is flat, it is assumed that the stratigraphy was characterized
by 3 to 10 m of soft clay (20 Kpa of shear strength) and that the low permeability clay would
meet the regulatory requirement for groundwater protection.
For the two sites, a low permeability dam concept with a clay core was developed. The
abutments were made of sand and gravel or till, with a filter chimney and horizontal finger drains
on the downstream side and an erosion protection layer (rip-rap) on the upstream and
downstream slopes. Berms were included in the design where necessary to improve stability.
As mentioned previously, four different tailings management and rehabilitation scenarios were
considered. All of the scenarios are designed to prevent sulphide oxidation and to minimize the
seepage of the leachable tailings. The four different tailings management techniques considered
for this comparative cost study are 1) a dry cover with capillary barrier effect (CCBE), 2)
underwater disposal, 3) complete desulphurisation of all tailings generated and 4) partial tailings
desulphurisation.
CCBE
The capillary barrier concept has been used to rehabilitate two acid generating tailings ponds in
Quebec, Les Terrains Aurifères and Mine Lorraine sites (e.g. McMullen et al., 1997; Ricard et
al., 1997, 1999; Dagenais et al, 2002). The cover acts as a moisture retention structure which
shields the tailings from atmospheric oxygen, allowing construction of thinner layers which
reduces the cost. The moisture retention capability exists because the composite cover system
ensures that the low permeability (fine) material placed between two coarse material layers
remains saturated almost indefinitely. Since the coarse material layer placed underneath does not
easily retain water, its unsaturated hydraulic conductivity is low. Consequently, the fine material
layer in the middle remains saturated because water is attracted to this layer by greater capillary
forces, and because the downward flow is greatly reduced due to the low unsaturated hydraulic
conductivity of the coarse layer. It is assumed that the sulphides will not oxidize during the
deposition of the tailings and will remain saturated. More details on CCBE can be found in the
literature (e.g. Nicholson et al. 1989; Aubertin et al. 1995; Bussière et al. 2003).
For this scenario different cover designs were considered with a total cover thickness ranging
from 1.1 m to 1.5 m. The sand and gravel layers (top and bottom of the cover) ranged from 0.3 to
0.5 m, and the silt layer (middle layer) ranged from 0.3 to 0.6 m. It was assumed that silt could
be found within 1.5 km of the tailings disposal site and that a sand and gravel pit was located
within 1.5 to 7.0 km of the site for the feasibility analysis. The cost of $ 1500 per hectare for
lime addition to the tailings, $ 5000 per hectare for monitoring and $ 7000 for revegetation was
also included.
This concept becomes less feasible when the construction materials are not located nearby. The
construction of the cover is also easier during the winter when machinery can move on the
frozen tailings (Ricard et al. 1997). In warmer climates the construction of a CCBE becomes
more expensive. However, this concept requires dams that are lower than the under water
disposal technique, since the cover can follow the natural deposition slope contours of the
tailings.
Water covers
This tailings management technique refers to depositing the tailings under a water cover.
Research has demonstrated that mine tailings oxidation is reduced to low values (usually
between 1 to 5 moles of O2/m²/year (Li et al. 2000)) by placing them under a water cover
(MEND, 2001). Fresh tailings are disposed of within an engineered tailings management facility,
also referred to as a man-made tailings impoundment, and kept submerged., The depth of the
water cover ranged from 0.8 to 1.2 m for the different scenarios for the cost evaluation study. As
shown by some operators (Talbot and Cayouette, 2003) the cost of tailings placement is
significant and had been considered in the model. The rehabilitation costs of a water cover were
considered to be minimal and an amount of $ 150 per linear meter of dam was used.
It appears from the simulation that water covers represent one of the less expensive methods of
tailings management. However, a water cover can present an increased risk level due to the
possibility of geotechnical containment structure failures.
This technology consists of separating the sulphide fraction of the tailings using froth flotation.
Through this process a high sulphur fraction (acid generating) is produced, which can be
managed more easily due to its reduced volume. The tailings impoundment will be the
depository for all low-sulphur tailings in excess of that used for backfill. Since the desulphurised
tailings are not potentially acid generating there is no requirement to keep them submerged or
saturated. At mine closure the tailings will be revegetated for permanent reclamation. For this
study it was assumed that the entire sulphide fraction was used in the paste backfill. Depending
of the topography of the site and the tailings management technique the sulphide rich material
could also be disposed of in the tailings pond as long as it remains saturated. It has been shown
(Benzaazoua et Bussière 1999; Benzaazoua et al. 2000) that the cost of desulphurisation varies
with the neutralisation potential (NP) of the tailings; the higher the NP the lower the
desulphurisation cost. Different scenarios were studied for NP ranging from 40 kg CaCO3/t to
140 kg CaCO3/t.
As previously shown in this paper the sulphide rich tailings can be successfully used in paste
backfill preparation. The production of low sulphur tailings has been performed in the laboratory
by researchers at the University of Quebec in Abitibi Temiscamingue (UQAT-URSTM)
(Bussière et al. 1998; Benzaazoua et al. 1999, 2000), at INCO’s Clarabelle Mill (McLaughlin,
Robertson, 1994) and also at different Falconbridge sites, including the “New Tailings Area” in
Sudbury.
The main advantage of this technique comes from the fact that non-acid generating tailings pond
does not represent a long term liability. In some locations the use of this technology can help in
obtaining the mine permits.
Under this scenario the tailings are desulphurised only during the last years of mine operation.
The desulphurised tailings are used to cover the potentially acid generating (PAG) tailings as an
inert dry cover. The cover made of depyritized tailings is designed to maintain an elevated water
table, which will keep the PAG tailings deposited during the early years of operation in a
saturated condition to prevent sulphide oxidation. Since the foundation and the tailing dams are
characterized by very low permeability, an elevated water table can be maintained in the PAG
tailings with a layer of 1 to 2 meters of desulphurised tailings. The PAG tailings will act as an
oxygen barrier by limiting oxygen diffusion because of the high degree of saturation in the
tailings. This approach is a variation of the previous scenario and requires the same capital
investment in a flotation circuit at the end of the plant circuit, but has lower operating costs since
only a fraction of the tailings need to be desulphurised.
Table 3 (a-b-c) and Figure 9 show the tailings disposal cost, expressed as $/mt of tailings, for the
four different tailing disposal techniques that were considered.
Table 3 (a-b-c): Results of the cost study analysis (in $/m.t. of tailings)
-A-
- B-
- C-
CCBE
Complete desulphurisation
Partial desulphurisation
Underwater disposal
Considering that the models and design hypotheses used for this study are representative of a
majority of existing sites and can be applied to future mining projects, the results from this study
show that:
• Partial desulphurisation of tailings presents saving opportunities especially when the
tailings pond location is characterized by flat terrain and a soft foundation, a situation
that increases the dam construction cost.
• Under water disposal is the most economical option, when topography of the site and
foundation conditions are favourable. However, the cost difference between this option
and the partial desulphurisation option is very small, especially for tailings with low
neutralisation potentials.
• The construction cost of a CCBE can vary significantly from one site to another,
depending on the proximity of construction materials.
• There is a wide range of field conditions where the four different scenarios are
comparable from an economic point of view.
It should be noted that these results are valid for new operations only. Rehabilitation of existing
tailing impoundments with a water cover may not have the same economic appeal.
This study does not compare the risk levels associated with each scenario. Different mine
operators may not have the same risk tolerance. Some may prefer the CCBE approach to avoid
the risks associated with the management and maintenance of a large water dam. Others may not
be ready to use a new approach such as desulphurisation or may prefer complete
desulphurisation to avoid managing sulphidic tailings on the surface.
Conclusions
This project shows through laboratory tests that the desulphurisation process is technically
feasible. Continuous in-situ testing on a pilot scale demonstrated that good sulphide recoveries
can be obtained without affecting the initial neutralization potential of the tailings. The
concentrate, even if sulphide-rich, can be used to produce high quality paste backfill.
A cost study was performed to compare different tailing management techniques for potentially
acid generating tailings. While underwater disposal is an attractive method when the site
topography is suitable, desulphurisation (total or partial) can also be economically viable under
different conditions. For a new mine the construction of a CCBE at the end of mine-life is more
expensive unless suitable construction materials can be found close to the mine site.
The desulphurisation techniques, particularly when combined with paste backfill, should be
considered as an integrated management technique throughout the mine life, and to facilitate the
rehabilitation at the end of mine life. Desulphurisation may help in the obtention of permits for
new mine projects, particularly in regions with restrictive environmental regulations.
The comparison of tailing management methods presented in this work is based solely on
economic considerations. Risk aspects and long term liabilities were not taken into account. This
study opens the door for further work on Risk analysis, Life cycle analysis and development of
better integration between the upstream metallurgical process for value recovery and the
downstream desulphurisation process for environmental purposes.
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