FIXATION OF ARSENIC AND ANTIMONY FROM COPPER

SMELTER FLUE DUST AND ELECTROREFINERY BLEED-OFF AS

CRYSTALLINE SCORODITE

Felipe Lagno, Iván García, & Claudio Ledesma

EcoMetales Limited (ECL), Chile

Andrés Reghezza
North Division, CODELCO Chile

George Demopoulos, Levente Becze, Mario Gómez, & Lydia Katsarou

Department of Mining and Materials Engineering, McGill University, Canada

ABSTRACT
A feasibility study, aimed at removing arsenic and antimony in the form of crystalline scorodite
from a copper smelter flue dust and Cu electrorefinery bleed-off solution, has been undertaken by
EcoMetales Limited (a CODELCO Chile Subsidiary). The process has been demonstrated in a pilot
plant for one month of continuous operation, based on metallurgical criteria defined by
EcoMetales, the most important issues considered for the proven of the technology are: arsenic
removal efficiency; copper co-precipitation; and the chemical stability of the final solids. In
addition, one representative solid sample produced at EcoMetales' Pilot Plant was sent to McGill
University’s Hydrometallurgy Laboratory, in order to subject it to through characterization and to
evaluate its medium-term stability. The major findings of this study are:
- The process has an arsenic and antimony removal efficiency of 98% and 99% respectively,
whereas copper co-precipitation is lower than 2%. It constitutes best option for the fixation of
arsenic from arsenic-rich dusts and electrorefinery bleed-off solutions, generated for CODELCO
Norte.
- The material produced by step-wise precipitation at EcoMetales’s pilot plant consists on
approximately 65 % gypsum and 35 % crystalline scorodite with a molar ratio Fe to As of 1.2.
such residue can be declared as no-dangerous material as it meet the TCLP and SPLP
leachability criteria for As, Hg, Ba, Se, Ag, Pb, Cd, and Cr.
- The residue has neither chronic nor acute toxicity and approves inflammability, corrosivity and
reactivity tests. EcoMetales fulfill the standards and norms of the stricter environmental
regulations. EcoMetales has an Environmental Impact Declaration approved (DIA, Declaración
de Impacto Ambiental) for disposing this residue in an authorized landfill (RCA 086 009).

HYDROCOPPER 2009, Antofagasta, Chile 290

- Based on medium term stability studies, it is concluded that the EcoMetales scorodite has similar
stability than the scorodite produced from nitrate solutions, in an autoclave.

INTRODUCTION
Currently Codelco North Division applies two methods for the disposal of the arsenic generated
through the processing of copper concentrates at CODELCO Norte Smelter and Refinery. Most of
the arsenic is captured in the acid plant effluents (~60%) and treated by precipitation with lime,
which leads to the formation of several calcium arsenite compounds [1].The latter compounds are
considered unstable over the long term because of the gradual formation of calcium carbonate and
concomitant release of arsenic, these calcium arsenites are deposited at the Monte Cristo hazardous
substances landfill-type site.
The rest of the arsenic reports to the smelter flue dust and the electrorefinery bleed-off. The flue
dusts are currently leached with sulfuric acid at EcoMetales facilities, for the recovery of copper.
The solutions produced for leaching of the smelter flue dust along with the ER bleed-off are sent to
a heap leaching plant (HidroSur, División CODELCO Norte) for the recovery of copper (SX-EW).
These arsenic bearing solutions irrigate a dump of ripios (coarse old vat leach tailings) where the
impurities are removed by adsorption onto subjacent gravels. However, the treatment of ENMS
(Extensión Norte Mina Sur) has reduced the amount of subjacent gravel, where arsenic and
antimony are stabilized, making this industrial practice no longer be possible beyond 2012.
EcoMetales Limited has carried out a feasibility study aimed at removing arsenic and antimony
in the form of crystalline scorodite from a copper smelter flue dust and Cu electrorefinery bleed-off,
this novel process resolves this environmental problem fixing the impurities in a stable chemical
compound form such as crystalline scorodite (FeAsO4·2H2O) contributing to the sustainable
development of the CODELCO Norte Smelter and Refinery.
The novel industrial process for the precipitation of arsenic and antimony correspond is an
ongoing research program carried out for EcoMetales, during the last three years; this research has
been based on studies conducted for CODELCO Chile and Alliance Copper Limited (for the
BioCop Project). Moreover, EcoMetales Process has incorporated the major findings of the research
conducted at McGill University for the precipitation of scorodite [2,3].

Description of Scorodite Precipitation

One of the most important issues regarding EcoMetales Process is the fixation of arsenic in the form
of scorodite (a crystalline ferric arsenate, FeAsO4·2H2O), that shows several operational advantages.
Among those are its low solubility (typically <1 mg/L of As at pH = 5 [4]) compliance with
environmental most stricter regulations [5]. Scorodite has a high arsenic content (25-30%), good
thickening and filtration properties, compact volume, and low water retention.
There are basically two routes available for the production of scorodite; the hydrothermal route
that involves autoclave processing at elevated temperature (150-180°C) and pressure [6] and the
atmospheric pressure precipitation route at around 85-95°C by a supersaturation-controlled
approach.
The concept behind the development of this process can be understood by referring to the
Figure 1. This figure shows the experimentally determined values of critical arsenic concentration
Ccr and the equilibrium concentration Ceq in sulfate solutions of molar ratio Fe(III) to As(V) equal

HYDROCOPPER 2009, Antofagasta, Chile 291

to 1.0 at 95°C. The critical concentration indicates the threshold where the formation of amorphous
ferric arsenate is favored.
The region between the two lines defines the operating window for the precipitation of
crystalline scorodite in the presence of seed. Step-wise increase of pH as shown on the figure
ensures operation within the crystallization zone. Each step represents a reactor tank in a
continuous circuit.
It is important to observe in Figure 1 that the value of Ccr is two orders of magnitude higher than
that of Ceq at the same pH, i.e., the critical supersaturation is at the level of 100. Such high value
allows easy supersaturation control with no strict pH control and high arsenic precipitation
efficiency using only a few steps.

1000

100
Amorphous
Concentration of As(V) [g/L]

C cr
10 Zone

1
C eq
0.1
Crystalization
0.01 Zone

0.001

0.0001
0.0 0.5 1.0 1.5 2.0 2.5
pH

Figure 1: Supersaturation control area for atmospheric precipitation of scorodite

at 95°C from Fe(III)-As(V)-SO4 solution (reproduced from reference [2])

Process Flowsheet
The process developed at EcoMetales for the removal and fixation of arsenic and antimony is
shown in Figure 2. The process can be separated in three main stages: (i) the oxidation of trivalent
arsenic; (ii) the precipitation of arsenic and antimony; and (iii) a solid-liquid separation unit.
For scorodite precipitation, arsenic has to be in its pentavalent state, for the oxidation of As(III),
a number of oxidants can be used, and one of the environmentally preferred agent is hydrogen
peroxide (H2O2). It is easily handled and the decomposition products, water and oxygen, are
harmless. The oxidation of trivalent arsenic to pentavalent arsenic can be represented by the
following reaction:

H3AsO3 + H2O2 → H3ASO4 + H2O (1)

The pregnant leach solution generated during the leach of smelter flue dust and the Cu
electrorefinery bleed off are iron deficient solutions, Fe(III) has to be added to the process prior
precipitation, in order to control the Fe(III) to As(V) molar ration in solution around 1.0 to 1.2. For
precipitation of arsenic in the form of scorodite, a two-stage precipitation circuit is used with each
stage operating at different pH determined by the procedure of Figure 1.

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Scorodite precipitation, reaction (2), is almost completed when pH = 1.5 is reached. At this pH any
soluble metal, for example copper, remains in solution while arsenic concentration has been down
to less than 100 mg/L. The pH is controlled using limestone as neutralizing agent giving the
formation of gypsum as is shown in reaction (3).

Fe2(SO4)3(aq) + 2H3AsO4(aq) + 4H2O → 2FeAsO4·2H2O(s) + 3H2SO4 (2)

CaCO3(s) + H2SO4(aq) + H2O → 2CaSO4·2H2O(s) + CO2(g) (2)

As is shown in Figure 3, recycling part of the product (scorodite-gypsum) to act as seed may be
used to speed up the precipitation process. Seeding is mandatory when scorodite precipitation takes
places in a batch reactor, however in continuous reactors there are always solids present for
crystallization of scorodite to take place.

CaCO3 (18% w/w)

Ferric Sulfate
H2O2 (50% w/w)

PLS (As(III)-As(V)) Solid-Liquid Separation

Solución Filtrada

As(III) Oxidation Precipitación de As

Water (washing)

PLS
(<300 mg/L of As)

Seed
Scorodite-Gypsum to disposal

Figure 2: Process flowsheet for arsenic and antimony precipitation

The last stage is the solid: liquid separation unit. In this stage of the process, high solid-liquid
separation efficiency is sought due to the needs of removing most of the impregnate solution. In the
case of incomplete washing, some As2O5(s) might precipitate during evaporation of water and
subsequently dissolves readily in water during the stability analysis which can lead inaccurate
values in terms of TCLP or SPLP test.

Process Demonstration at Pilot Plant Scale

Since 2006, EcoMetales has conducted a number of projects and metallurgical tests designed to
optimize and to improve a process for the fixation of arsenic and antimony. These studies are the
technical support for the pre-feasibility and feasibility studies carried out for ECL. Pilot Plant
facilities are shown in Figure 3, the demonstration campaign for proving the process runs over three
weeks of continuous operation. The latter constitutes more than 60 mean residence times.

HYDROCOPPER 2009, Antofagasta, Chile 293

 Figure 3: EcoMetales' pilot plan

Impurity Removal
The process solution, produced in EcoMetales' Pilot Plant contained about 15 g/L As(V), 20-30 g/L
Cu(II) and 50 g/L H2SO4. The pH of the solution was approximately 0.5. Small amount of arsenic
being in trivalent state in the solution was oxidized with hydrogen peroxide. Since the solution was
iron deficient, ferric sulfate was added to adjust the Fe/As molar ratio to 1.2. Subsequently,
scorodite was produced by atmospheric step-wise precipitation in two stages at 85oC. The retention
time was 8 hours per reactor and the pH was adjusted with limestone. The resulted precipitate, a
mixture of scorodite and gypsum, was separated from the solution by pressure filtration.
Solution compositions during pilot plant demonstration are shown in Figure 4. The variation of
As, Sb, and Bi during the pilot campaign are shown in Figures 5 and 6, it can be seen a very high
efficiency on the removal of As, Sb and Bi. Based on the results shown on Figures 4, 5, and 6 and a
mass balance carried out during the pilot campaign, the impurity removal efficiencies are 98% for
Arsenic, 99% for Antimony, and 98% for Bismuth. A copper loss due to co-precipitation is
estimated in 1.7%.

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 70 70
Cu
Concentration [g/L] 60 60

Concentration [g/L]
50 50 H2SO4
40 40
Fe
30 30

20 20
As
10 10

0 0
0 3 6 9 12 15 18 21 0 3 6 9 12 15 18 21
Day Day

Figure 4: Solution composition during pilot plant validation campaign. Feed solution to precipitation
(left); free-arsenic solution after scorodite precipitation (right)

100
Concentration of As, [g/L]

16.6

15.6

13.2

week 1 week 2
10
week 3
1.3
1.1

0.9

0.3
0.2

0.1
0.1
Feed pH = 0.5 TK1 pH = 1.0 TK2 pH = 1.5

Figure 5: Average concentration of as in each reactor tank

1000 1000
Concentration of Sb, [mg/L]

Concentration of Bi, [mg/L

week 1 week 2 week 1 week 2

100 100
week 3 week 3
10 10

1 1

0.1 0.1
Feed pH = 0.5 TK1 pH = 1.0 TK2 pH = 1.5 Feed pH = 0.5 TK1 pH = 1.0 TK2 pH = 1.5

Figure 6: Average concentration of Sb and Bi in each Reactor Tank.

Antimony concentration (left) and bismuth concentration (right)

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Solids Characterization
The solids were characterized via a series of techniques. XRF, XRD, Raman, ATR-IR, TGA. In
Table 1, the X-Ray fluorescence analysis of the solids produced during the pilot campaign is shown.
It can be seen the important amount of As, Fe, Ca, and S (due to the formation of gypsum). Minor
amounts Sb and Bi are also found confirming the removal of such impurities. On the basis of
chemical analysis the solids consists of approximately 65% gypsum (CaSO4·2H2O), 34% scorodite
(FeAsO4·2H2O) and 0.6% SiO2.

Table 1: X-Ray fluorescence analysis of the solids

S Fe Cu As Sb Si Zn Bi K Ca Ti O Na Mo
9.3 11.3 0.3 12.6 0.3 0.25 0.02 0.15 0.5 16.2 0.05 37.1 0.12 0.33

For XRD analysis the scorodite was isolated from the sample, the gypsum is removed by contacting
8 g of as-produced material with 4 L of D.I H2O for 24 h under agitation; subsequently, the solution
was filtered and the filter cake was washed three times with 1 L of D.I. H2O. The XRD study of the
sample after gypsum removal confirms the formation of crystalline scorodite; the obtained
diffractogramm is shown in Figure 7.

Counts
Chile prec bef wash; Chile prec bef wash

1000

500

0
10 20 30 40 50 60 70
Position [°2Theta]

Figure 7: X-ray diffraction pattern of the isolated scorodite

[Reference peaks of scorodite (00-037-0468) are shown with gray lines]

From the Raman and IR spectra shown in Figure 8, the presence of gypsum in the as-received
material is evidenced from the sulfate and hydroxyl vibrations at ~ 1000 -1200 cm-1 and 3000 -
4000 cm-1 respectively. In the case of the isolated scorodite, it is observed from the Raman in Figure
8 that the sulfate vibrations corresponding to gypsum are gone. However, the IR spectra of the
residue after gypsum removal there is a sulfate vibration occurring not like that of gypsum in terms
of symmetry (peak shape) and position; for that reason, the additional sulfate vibrations observed in
the isolated scorodite may be sulfate groups replacing arsenate molecular groups in scorodite.

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 SO4 OH-H2O
SO4 SO4
SO4 Pure gypsum (Aldrich)
SO4 SO4 H2O
SO4 SO4

SO4 Pure gypsum (Aldrich) H2O

SO4 AsO4 SO4 As-recieved sample
SO4
SO4 AsO4
AsO4
OH-H2O
SO4
As-received sample isolated scorodite
AsO4 AsO4
AsO4 AsO4 H2O OH-H2O
AsO4 SO4 OH-H2O
Isolated scorodite
AsO4
SO4 H2O OH-H2O
OH-H2O
Scorodite synthesized at McGill
AsO4 AsO4
AsO4 AsO4
AsO4
Scorodite synthesized at McGill
AsO4

200 400 600 800 1000 1200 1400 1000 1500 2000 2500 3000 3500 4000

Wave numbers (cm-1)

-1
Wave numbers (cm )

Figure 8: Raman spectra (left) and ATR-FTIR spectra (right) of the as-received sample, the isolated scorodite, scorodite
synthesized at McGill and pure gypsum (CaSO4·2H2O) provided by Aldrich.

Stability Investigation of the Scorodite

Results of TCLP and SPLP tests for As, Cd, Pb, Hg, Cr, Ba, Se and Ag are presented in Table 2. It
can be seen that all metals concentrations are below the limits.

Table 2: TCLP y SPLP test results mg/L (ppm)(a)

Element As Cd Pb Hg Cr Ba Se Ag
Limit 5.0 1.0 5.0 0.2 5.0 100 1.0 5.0
TCLP 2.8 0.5 < 0.2 < 0.01 < 0.1 < 5.0 < 0.05 < 0.2
SPLP 1.3 0.4 < 0.2 < 0.01 < 0.1 < 5.0 < 0.05 < 0.2
(a)
TCLP: Toxicity characteristic leaching procedure; SPLP: Synthetic precipitation leaching procedure

The above results tell us that the residue meet the TCLP and SPLP limits; however, these tests
are not accurate for predicting or understanding the behavior of the solids over the long term;
hence, two analyses were conducted on the solids: (1) a medium term stability, and (2) further
TCLP-like test.
A medium term stability tests were conducted on as-produced scorodite (without gypsum
removal). Before the study, the residue was washed with gypsum-saturated water. The purpose of
this treatment was to remove the water soluble arsenic containing phases without dissolving
gypsum. The water soluble compounds could form either during the step-wise precipitation as trace
fraction and/or in-situ drying, (due to the incomplete washing).
In the later case, As2O5(s) can precipitate during evaporation of water and subsequently
dissolves readily in water, during the stability investigation which can lead inaccurate evaluation, in
terms TCLP test results. The experimental conditions for the medium term stability investigation
were the following:

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• Temperature: environment
• pH range (in case of medium term stability): 7-8 (nominal pH 7.5). When the pH was out of the
targeted range, it was adjusted with Mg(OH)2 (suspension) or HNO3
• Solid/liquid ratio (S/L) = 1/40 (5 g scorodite/200 cm3 D.I. H2O). Thus, based on the
mineralogical composition, 14.28 g of sample was used
• Shaker in orbital mode.

Medium term stability test results on the as-produced scorodite previously washed with gypsum
saturated water are shown in Figure 10(a). It can be seen that arsenic release was stabilized after
approximately one month equilibration attaining practical equilibrium with a concentration of 4.05
mg/L of As (at pH 7.12). This value can be compared with those reported by Bluteau and
Demopoulos [4] where the equilibrium arsenic concentration with scorodite produced
hydrothermally in nitrate solution is 0.35, 0.96 and 5.87 mg/L at pH 5, 6, and 7.
Further TCLP-like test on the as-received sample was also conducted in 5 consecutive stages, in
this test; 14.28 g of as-received sample containing 5 g of scorodite was taken into 200 cm3 of D.I.
H2O for 24 h, the same way such as in the aforementioned tests. However, after each 24 hours, the
leachate solution was removed and replaced with fresh D.I. H2O.
The change of As concentration was plotted (see Figure 9(b)). It can be seen that upon multiple
contacting with fresh water the concentration of arsenic in the leachate decreased from 2 mg/L to
0.5 mg/L, reflecting the partial removal of water soluble arsenic containing compounds. This is so
because of the occasional trace amount of amorphous material, co-precipitated with scorodite that
dissolves during the leachability test, giving erroneous results. Thus, after such thorough washing a
TCLP leachability value < 1 mg/L of As may reflect the true As concentration.

10 2.5
(a) (b)
Concentration of As [mg/L]

Concentration of As [mg/L]

8 2.0

6 1.5

4 1.0

2 0.5

0 0.0
0 20 40 60 1 2 3 4 5 6
Time [d] Number

Figure 9: Stability investigations. (a) Change of As concentration versus time for the residue, final pH 7.2
(note: pH was regularly adjusted but not kept constant); (b) TCLP-like test on the as-received sample
conducted in 6 consecutive stages.

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CONCLUSIONS
The major findings of this study are.
• The process has an arsenic and antimony removal efficiency of 98% and 99% respectively,
whereas copper co-precipitation is lower than 2%. It constitutes best option for the fixation of
arsenic from arsenic-rich dusts and electrorefinery bleed-off solutions, generated for CODELCO
Norte.
• The material produced by step-wise precipitation at EcoMetales’s pilot plant consists of
approximately 65% gypsum and 35% crystalline scorodite with a molar ratio Fe to As of 1.2.
such residue can be declared as no-dangerous material as it meet the TCLP and SPLP
leachability criteria for As, Hg, Ba, Se, Ag, Pb, Cd, and Cr.
• The residue has neither chronic nor acute toxicity and approves inflammability, corrosivity and
reactivity tests. EcoMetales fulfill the standards and norms of the stricter environmental
regulations. EcoMetales has an Environmental Impact Declaration approved (DIA, Declaración
de Impacto Ambiental) for disposing this residue in an authorized landfill (RCA 086 009).
• Based on medium term stability studies it is concluded that the EcoMetales scorodite has similar
stability than the scorodite produced from nitrate solutions in an autoclave.

ACKNOWLEDGMENT
The authors wish to thank EcoMetales Limited and Codelco Chile for permission to publish this
paper.

REFERENCES

Bothe, J. V.; Brown, P. W. Mechanism of arsenic immobilization by calcium arsenate formation,

Environmental Science and Technology, 1999, 33, 3806-3811. [1]

Demopoulos, G. P.; Lagno, F.; Wang, Q.; Singhania, S. The atmospheric scorodite process. In
Copper 2003-Cobre 2003, Hydrometallurgy of Copper; Riveros, P.A.; Dixon, D.; Dreisinger
D.B.; Menacho J., Eds.; The Canadian Institute of Mining, Metallurgy and Petroleum (CIM):
Montreal, QC, 2003, Book 2, p.p. 597-616. [2]

Demopoulos, G. P. On the preparation and stability of scorodite. In Arsenic Metallurgy; Reddy,

R.G.; Ramachandran, V.; Eds.; The Minerals, Metals & Materials Society Warrendale, PA,
2005, p.p. 25-50. [3]

Bluteau, M-C.; Demopoulos, G. P. The incongruent dissolution of scorodite — Solubility, kinetics

and mechanism. Hydrometallurgy, 2007, 87(3-4), 163-177. [4]

Langmuir, D.; Mahoney, J.; Rowson, J. Solubility products of amorphous ferric arsenate and
crystalline scorodite (FeAsO4·2H2O) and their application to arsenic behavior in buried mine
tailings. Geochimica et Cosmochimica Acta, 2006, 70(12), 2942-2956. [5]

Dutrizac, J. E.; Jambor, J. L. Characterization of the iron arsenate-sulphate compounds

precipitated at elevated temperatures. Hydrometallurgy, 2007, 86, 147-163. [6]

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