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Overview

Arsenic Immobilization by Controlled


Scorodite Precipitation
Dimitrios Filippou and George P. Demopoulos

In the past four years, a new process has flue dusts is of even greater concern due at McGill University involves supersatu-
been developed at McGill University for the to the extremely high solubility and tox- ration control by a neutralization tech-
immobilization of arsenic from metallurgi- icity of the compound. nique so as to avoid the precipitation of
cal effluents and flue dusts by the controlled Crystalline ferric arsenate , known also any amorphous arsenic compounds. In
precipitation of scorodite under atmospheric- as a natural mineral named scorodite this case, precipitation of crystalline
pressure conditions. So far, the process has (FeAsO 42H2O), is the alternative carrier scorodite is induced by the addition of
been successfully tested in the laboratory that has been proposed as a suitable scorodite seed material into the arsenic-
with chloride and sulfate solutions contain- compound for arsenic disposal due to its rich solution. The concept of the new
ing arsenic and with As2O3 smelter flue low solubility (typically less than 1 ppm process is presented schematically in
dusts. It has been also tested with equal arsenic at pH 5) and its high arsenic Figure 1. The experimental work involves
success at a copper smelter with industrial content (2530 wt.%). 1,3 One way to pro- first the determination of the solubility
arsenic-containing sulfate effluents. duce scorodite is hydrothermally in an line of scorodite (i.e., the determination
autoclave at temperatures of 150C or of the equilibrium line C* of [As] versus
INTRODUCTION
higher. 2 However, the use of autoclaves pH) in solutions of similar composition
In the nonferrous extractive metal- is capital intensive, and, therefore, the to the ones used in precipitation tests at
lurgy industry, arsenic is a major con- process may become economically at- the temperature of interest. Then, con-
taminant that either reports in aqueous tractive only if arsenic stabilization can trolled precipitation of scorodite is car-
effluents or is captured from smelter be operated concurrently with the pro- ried out by neutralization along a
gases as arsenic trioxide flue dust (As2O3) cessing of a valuable concentrate (e.g., stepwise path in the presence of sus-
and stockpiled. The fixation of arsenic gold-carrying pyrite or copper concen- pended scorodite seed particles. The size
from aqueous effluents is currently trate). of each step is chosen so that a critical
achieved by the precipitation of amor- An alternative way for producing supersaturation line Cc (or equivalently,
phous arsenic-bearing iron hydroxides scorodite has been developed at McGill a critical supersaturation ratio Sc = Cc/
with a high Fe:As molar ratio (higher University in Canada and involves the C*) is not exceeded.7 The equilibrium
than four)1 or if autoclaves are used (as ambient-pressure crystallization of line C* and the critical supersaturation
in the case of refractory gold pressure scorodite out of arsenic-rich solutions line Cc, which is also determined experi-
oxidation), by the formation of scorodite- by stepwise neutralization. This process, mentally, delimit a working region of
like compounds (FeAsO42H2 O).2 In the operated at about 90C, requires a con- [As] versus pH.
case of As2O 3 flue dusts, stockpiling in siderably lower capital investment and By controlling the solution pH (and
protected areas is practiced. offers versatility as it does not require [As]) within the limits of the working
The problems associated with the the simultaneous treatment of concen- region, scorodite crystal growth on the
present practice of arsenic disposal are trate and is less dependent on a process seed particles is ensured. On the other
the generation of large volumes of ferric scale (i.e., it can be used for either small hand, if the pH is raised too quickly
hydroxide and gypsum sludges upon or large amounts of arsenic waste). beyond the critical supersaturation line,
neutralization of arsenic-rich acidic so- instantaneous homogeneous nucleation
ARSENIC IMMOBILIZATION
lutions and the long-term stability of
THROUGH SUPERSATURATION
those sludges. Concern has been ex-
CONTROL
pressed that over the long term the fer-
ric-hydroxide phases will eventually Four years ago, research was initiated
transform to alpha-goethite (-FeOOH), at McGill University on the ambient-
hence, releasing arsenic to the environ- pressure precipitation and fixation of
ment.3 Long-term stockpiling of As2 O3 arsenic in the form of scorodite by a
novel supersaturation-control approach.
In almost all previous investigations con-
ducted under ambient-pressure condi-
tions, precipitation of arsenate com-
pounds was effected by direct neutral-
ization to a terminal pH above four.46
This relatively fast neutralization, how-
ever, results in a sharp increase in ar-
senic and iron supersaturation in the
solution and a high birth rate of small
solid-phase nuclei. The end result is the
production of amorphous iron-arsenic
compounds that are apparently not stable Figure 2. A neutralization test of chloride-
Figure 1. The concept of supersaturation con- enough for safe disposal if the molar based As(V) solution for three hours at 95C.
trol by stepwise neutralization. C*equilib- ratio of iron to arsenic in the mother Conditions: 3.0 mol/l Cl; 2.0 g/l scorodite
rium concentration; Cccritical supersatura- solution is less than four. 1 seed; 2:1 Fe:As molar ratio; and NaOH used
tion; and Sccritical supersaturation ratio. In contrast, the approach developed as a base (adapted from Reference 8).

52 JOM December 1997


media, the difficult sulfate system was 20 minutes). Furthermore, it was ob-
tackled. As a result of this work, it was served that the rate of oxidation of As(III)
demonstrated for the first time that was controlled by the rate of the H2O2
scorodite production can be achieved addition, while stoichiometric amounts
from strongly acidic sulfate solutions of H2O2 were sufficient to oxidize all of
under ambient-pressure conditions the As(III). In subsequent precipitation
(95C) as long as proper pH control is experiments, stable scorodite precipi-
exercised and seed is used.12 It was also tates were successfully produced out of
determined that a seed concentration of seeded arsenate solutions containing up
50 g/l or more is necessary for accelerat- to 100 g/l of dissolved As(V) by stepwise
ing the crystallization kinetics, because neutralization with Mg(OH)2. Of course,
the supersaturated sulfate solutions are prior to precipitation the arsenate solu-
much more stable than the chloride ones. tion had to be spiked with Fe2(SO4)3 at an
More than 90% arsenic was removed in Fe:As molar ratio 1.11.2. In this work, it
three hours in the form of crystalline was also demonstrated that -FeOOH
scorodite when magnesium hydroxide can be used as an iron source instead of
[Mg(OH)2] was used as a neutralizing Fe2(SO4 )3.
agent (Figure 3). The use of slaked lime This process was tested in a prelimi-
Figure 3. Neutralization of sulfate-based As(V) [Ca(OH)2 ] instead of Mg(OH)2 did not nary fashion at a laboratory scale with
solution to a terminal pH 0.9. Conditions: seem to alter the process kinetics, but industrial As2O3 baghouse dust supplied
95C, 0.4 mol/l SO4 2; 50 g/l scorodite seed; resulted in the precipitation of gypsum by a gold/copper smelting company.
1:1 Fe:As molar ratio; and Mg(OH)2 used as a along with crystalline scorodite The results were very encouraging, with
base (adapted from Reference 12). (CaSO42H2O). However, in terms of about 90% of arsenic removed in the
product stability, the pure scorodite pre- form of crystalline scorodite in four
and precipitation of amorphous com- cipitate produced with Mg(OH)2 proved hours precipitation time.16
pounds occurs. The pH at which homo- slightly more stable than the mixtures of
geneous nucleation and precipitation of scorodite and gypsum produced with ON-SITE TESTS WITH
amorphous compounds occur is termed Ca(OH)2 [TCLP solubility of 0.7 ppm INDUSTRIAL EFFLUENTS
induction pH and depends on the initial arsenic for scorodite produced with After the successful laboratory tests,
concentration of arsenic in the solution. Mg(OH)2 versus 1.5 ppm arsenic for the ambient-pressure arsenic immobili-
The first experiments of scorodite pre- scorodite-gypsum mixtures produced zation process was tested at a copper
cipitation under ambient-pressure con- with Ca(OH)2].13 smelter for the treatment of an acid-
ditions were carried out with chloride After discovering that it was possible plant effluent that contained about
solutions.8 For such solutions, there were to produce scorodite from Fe(III)-As(V)- 10 g/l As(III), 25 g/l H2SO4 , and small
already some indications that the pro- H2SO4 solutions, the conversion of ar- amounts of copper (0.3 g/l), iron
cess could be successful; while working senic trioxide smelter flue dusts into (0.1 g/l), and zinc (0.1 g/l). The test
on jarosite precipitation Dutrizac and stable scorodite was investigated.14 This method involved oxidation of As(III)
Jambor 9 observed that crystalline work led to the elaboration of a process with 30% weight per volume H2O2:
scorodite was produced from chloride scheme involving the dissolution of ar-
mediabut not from sulfate mediaat senic trioxide (As2 O3) in a weak acid H3 AsO3 (aq) + H2O2(aq)
97C and pH below 1.5. Indeed, in the H3AsO4(aq) + H2O (1)
(H2SO4 ) solution, oxidation of As(III) by
first tests, crystalline scorodite was pro- hydrogen peroxide (H2 O2), and precipi- followed by the addition of Fe2 (SO4)3 at
duced at 8095C (Figure 2). The pre- tation of scorodite by
cipitate proved very stable with a solu- stepwise neutralization
bility less than 0.1 ppm arsenic when after ferric sulfate
subjected to 24 hour toxicity characteris- [Fe 2(SO 4 ) 3 xH 2 O] and
tics leaching procedure (TCLP) leach- scorodite seed have
ability tests at ambient temperature and been added. (Figure 4).
pH about 5.0.10 It was found that high
In these preliminary experiments, temperatures in the
2 g/l of scorodite seed material was range of 90100C are
added to arsenate solutions. In the first essential for fast dissolu-
experiments, the seed material was pro- tion of As2O3, since the
duced from nitrate solutions in an auto- solubility of As2 O3 in-
clave at about 150C following a method creases dramatically
developed by Van Weert and Droppert;11 from 12 g/l at 25C to
later, scorodite produced under ambi- 114.5 g/l at 100C.15 With
ent-pressure conditions was also tested regard to the effect of dis-
as seed material with equal success. In solution media acidity, a
all experiments with chloride solutions, neutral-to-moderate
the initial concentration of As(V) before acidic solution seemed to
any precipitation was 2 g/l, but the ini- be the optimum medium
tial molar ratio of Fe(III) to As(V) varied for As2 O 3 dissolution.
from experiment to experiment from 1:1 The arsenious acid
to 4:1. Nonetheless, it was found that a (H3AsO3), which forms
stoichiometric amount of iron was suffi- upon dissolution of
cient for precipitating about 90% of ar- As2O 3, was found to be
senic at a final pH about 1.1. Above that easily oxidized to arsenic
pH, precipitation of beta-goethite (- acid (H3AsO 4 ) by the Figure 4. A conceptual flowsheet for the conversion of arsenic
FeOOH) predominantly took place. slow addition of H2O2 (to- trioxide to crystalline scorodite. Conditions: 95C and 1.2:1
Subsequent to the tests with chloride tal reaction time of about Fe:As molar ratio (adapted from Reference 14).

1997 December JOM 53


precipitation was determined to be about tralization occurs to a pH of about 9 with
50 g/l or higher. Nevertheless, recycled slaked lime.
mixtures of scorodite and gypsum were
ECONOMICS AND OUTLOOK
found to be equally effective as seed
material (Figure 5). A preliminary feasibility study that
In terms of product stability, precipi- followed the on-site testing showed that
tates produced either with Mg(OH)2 or the process is very competitive in terms
Ca(OH)2 were found to be very stable, of capital cost. In terms of operating
releasing, on average, 1.5 ppm arsenic costs, the major costs are associated with
when subjected to TCLP leachability tests the use of Fe2 (SO4)3 (60% of the operating
(those values actually ranged from 0.5 cost) and H2O2 (20% of the operating
2.2 ppm arsenic). These concentration cost) (Figure 7). The fact that the cost of
levels are well below the current 5 ppm ferric sulfate and hydrogen peroxide
toxicity limit.10 In addition to good sta- constitute the major part of the operat-
bility, the produced solids exhibited very ing cost of the ambient-pressure process
good settling and filtration properties. for arsenic immobilization has led to
Figure 5. Neutralization of industrial acid efflu- A flowsheet was designed from the ideas of replacing these reagents with
ent containing 10 g/l As(III) and 25 g/l H2 SO4 results obtained from the on-site testing other less costly ones.
to a terminal pH about 1.5. Conditions: 85C,
(Figure 6). According to the flowsheet, One particularly attractive alternative
1.2:1 Fe:As molar ratio, and Ca(OH)2 used as
base. the effluent is first subjected to aeration is the use of iron residues from other
to remove any dissolved SO2 gas to re- metallurgical industries (e.g., goethite
an Fe:As molar ratio 1.11.2 and neutral- duce the consumption of H 2O2 in the from zinc plants that use the Goethite
ization to precipitate scorodite next oxidation step. Oxidation is done at process18) as a substitute for Fe 2(SO4)3.
90C with 50% weight by volume H2O2 Goethite has already been tested14 and
2H3AsO4(aq) + Fe2(SO4)3(aq)
for a total retention time of 30 minutes. not only provides an excellent iron
2FeAsO4 2H2O(s) + 3H2SO4(aq) (2)
The fully oxidized solution is then source, but also reduces the base re-
pumped to a two-stage scorodite pre- quirements needed for neutralization of
H2 SO4(aq) + Mg(OH)2 (s)
cipitation circuit. In this circuit, ferric the acid generated upon scorodite pre-
MgSO4 (aq) + 2H2O (3)
sulfate is added at a stoichiometric ratio cipitation and, hence, the amounts of
As indicated in Reaction 3, one neutral- to arsenic together with recycled gypsum produced. The cost of iron resi-
izing agent tested was Mg(OH)2 . How- scorodite/gypsum seed. A retention time dues (mainly due to transportation and
ever, most of the tests were carried out of four to six hours is deemed necessary handling) can be one-tenth that of ferric
with Ca(OH)2, which produces gypsum for the removal of 95% of arsenic in the sulfate or less.
form of crystalline scorodite by stepwise Another cost-reducing alternative is
H2SO4(aq) + Ca(OH)2(s)
neutralization with slaked lime at 90C. using gas mixtures of SO2/O2 as an oxi-
CaSO42H2O(s) (4)
Limestone can also be used as a base in dant of As(III). Such gas mixtures have
Lime or limestone are preferable to in- the scorodite precipitation circuit, thus been widely used for 15 years now for
dustry because of their low cost. The reducing the operating cost of the pro- the oxidative destruction of cyanide ions
tests were carried out at 8589C. Once cess. The resulting slurry may be either in gold mills (Inco process19), but re-
again, the test with Ca(OH)2 was suc- thickened to 50 wt.% solids or preferably cently Nishimura and coworkers20 also
cessful, and crystalline scorodite was filtered to 80 wt.% solids prior to its observed that such mixtures are quite
produced in all tests. discharge. effective in oxidizing As(III) at a pH
On-site oxidation of As(III) by H2 O2 Part of the filter cake is recycled to the above 1.5. Preliminary work at McGill
was somewhat slower than with syn- first scorodite precipitation tank, where University shows that such a gas mix-
thetic solutions in the laboratory (i.e., the scorodite-seed concentration must ture works in acidic metallurgical efflu-
reaction time of about 30 minutes in- be maintained at a minimum of 50 g/l. ents with a pH below 1.5 as well.
stead of 20 minutes). Also, a peroxide The filtrate is pumped to
excess of at least 30% more than the the polishing stage,
stoichiometrically required amount was where the rest of the ar-
found to be necessary for effective oxi- senic is precipitated at
dation of all As(III). Those adverse ef- pH 3 or higher as amor-
fects were attributed to the presence of phous arsenate-hydrox-
SO2 gas dissolved in the effluent, which ide compounds that, af-
reacts with H2O 2 to form H2SO4 , and the ter thickening to about
presence of fine solids in the effluent, 10 wt.% solids, are re-
which apparently can catalyze the de- cycled back to the
composition of peroxide to water and scorodite precipitation
oxygen gas.17 circuit. In this manner,
Scorodite precipitation also appeared all arsenic entering the
to be somewhat slower with the indus- effluent treatment plant
trial effluent than with laboratory solu- is effectively immobi-
tions. In general, a four hour precipita- lized and removed as
tion time was necessary in order to re- crystalline scorodite. The
move more than 90% of the arsenic in the neutralized arsenic-free
form of scorodite. The slower kinetics liquor can be treated for
were attributed to the lower tempera- the recovery of its metal
ture employed (85C against 95C) and content (e.g., copper),
the lack of reliable pH controla critical recycled to the plant for
feature for the obtainment of optimum other uses, or even dis- Figure 6. A conceptual flowsheet for the immobilization of
results with this process. The seed con- charged to the environ- arsenic from an acid-plant effluent containing 10 g/l As(III) and
centration required for efficient scorodite ment after further neu- 25 g/l H2SO4 .

54 JOM December 1997


ate and Sulphate, Hydrometallurgy 94 (London: Chapman McGill University, Montreal (1996).
and Hall, 1994), pp. 177190. 17. A. Griffins and G. Vickell, Treatment of Gold Mill
Ferric 3. R.G. Robins, The Stability and Solubility of Ferric Arsen- Effluents with Hydrogen Peroxide: Operating Experience
Sulfate 60% ates: an Update, EPD Congress 90, ed. D.R. Gaskell and Costs (paper presented at the 21st Canadian Mineral
(Warrendale, PA: TMS, 1990), pp. 93104. Processors Conference, Ottawa, 1719 June 1989).
4. E. Krausse and V.E. Ettel, Solubilities and Stabilities of 18. K.J. Torfs and J. Vliegen, The Union Minire Goethite
Ferric Arsenate Compounds, Hydrometallurgy, 22 (1988), Process: Plant Practice and Future Aspects, Iron Control and
pp. 311337. Disposal, eds. J.E. Dutrizac and G.B. Harris (Montreal, Canada:
5. G.B. Harris and S. Monette, The Disposal of Arsenic CIM, 1996), pp. 135146.
Bearing Residues, Productivity and Technology in the Metal- 19. G.H. Robbins, Historical Development of the INCO
Other lurgical Industries, eds. M. Kock and J.C. Taylor (Warrendale, SO2 /Air Cyanide Destruction Process, CIM Bulletin, 89
PA: TMS, 1989), pp. 545561. (1003) (1996) pp. 6369.
2% 6. N. Papassiopi, M. Stefanakis, and A. Kontopoulos, Re- 20. T. Nishimura, Q. Wang, and Y. Umetsu, Removal of
Labor moval of Arsenic from Solutions by Precipitation as Ferric Arsenic from Process Liquors by Oxidation of Iron(II),
3% Arsenate, Arsenic Metallurgy Fundamentals and Applications, Arsenic(III) and Sulfur(IV) by Oxygen, Iron Control and
eds. R.G. Reddy, J.L. Hendrix, and P.B. Queneau (Warrendale, Disposal, eds. J.E. Dutrizac and G.B. Harris (Montreal, Canada:
Transportation PA: TMS, 1988), pp. 321336. CIM, 1996), pp. 535548.
7. G.P. Demopoulos, Precipitation in Aqueous Processing
& Maintenance
of Inorganic Materials: A Unified Colloid-Crystallization ABOUT THE AUTHORS
8% Approach to the Production of Powders with Controlled
Hydrogen Peroxide Water, Steam,
Electric 7% Properties, Processing Materials for Properties, eds. H. Henein Dimitrios Filippou earned his Ph.D. in met-
20% and T. Oki (Warrendale, PA: TMS, 1993), pp. 537540.
8. G.P. Demopoulos, D.J. Droppert, and G. Van Weert, Pre- allurgical engineering at McGill University in
Figure 7. The operating-cost distribution for cipitation of Crystalline Scorodite (FeAsO4 2H2 O) from Chlo- 1994. He is currently a hydrometallurgist at
ride Solutions, Hydrometallurgy, 38 (1995), pp. 245261. Noranda Technology Center.
the arsenic immobilization process depicted 9. J.E. Dutrizac and J.L. Jambor, The Behaviour of Arsenic
in Figure 6. during Jarosite Precipitation: Reactions at 150C and the
George P. Demopoulos earned his Ph.D. in
Mechanism of Arsenic Precipitation, Canadian Metallurgical
These two processing alternatives con- Quarterly, 26 (1987), pp. 91101. metallurgical engineering at McGill Univer-
10. Environmental Protection Agency, TCLP-1311: Test sity in 1982. He is currently professor and
stitute part of a current on-going envi- Methods for Evaluating Solid Wastes, document SW-846
(1990). chair of the Department of Mining and Metal-
ronmental research project on arsenic 11. G. Van Weert and D.J. Droppert, Aqueous Processing of lurgical Engineering at McGill University. Dr.
immobilization. Preliminary operating- Arsenic Trioxide to Crystalline Scorodite, JOM, 46 (6) (1994), Demopoulos is also a member of TMS.
pp. 3638.
cost estimates of an arsenic immobiliza- 12. D.J. Droppert, G.P. Demopoulos, and G.B. Harris, Am-
For more information contact G.P. Demopoulos,
tion process incorporating the SO2/O2 bient Pressure Production of Crystalline Scorodite from
Department of Mining and Metallurgical Engi-
Arsenic-rich Metallurgical Effluent Solutions, EPD Con-
oxidation of As(III) and the precipita- gress 1996, ed. G.W. Warren (Warrendale, PA: TMS, 1996) pp. neering, McGill University, 3610 University Street,
tion of scorodite with goethite residues 227239. Motreal, Quebec, H3A 2B2; (514) 398-4755; fax
13. D.J. Droppert, The Ambient Pressure Precipitation of
Crystalline Scorodite (FeAsO4 2H2 O) from Sulphate Solu-
look very favorable. (514) 398-4492.
tions, M.Eng. thesis, McGill University, Montreal (1996).
References 14. R. Dabekaussen, D. Droppert, and G.P. Demopoulos,
An Ambient Pressure Hydrometallurgical Process for the Visit JOM
1. G.B. Harris and E. Krausse, The Disposal of Arsenic from Conversion of Arsenic Trioxide to Crystalline Scorodite,
Metallurgical Processes: Its Status Regarding Ferric Arsen- Paper submitted for publication to CIM Bulletin (1997). on the World Wide Web at
ate, Extractive Metallurgy of Copper, Nickel and Cobalt, vol. 1, 15. D.R. Lide, ed., CRC Handbook of Chemistry and Physics, 72
eds. R.G. Reddy and R.N. Weizenbach (Warrendale, PA: ed. (Boca Raton, FL: CRC Press, 1992), p. 4:41. http://www.tms.org/pubs/
TMS, 1993), pp. 12211237. 16. R. Dabekaussen, Hydrometallurgical Conversion of
2. P.M. Swash and A.J. Monhemius, Hydrothermal Precipi- Arsenic Trioxide to Crystalline Scorodite, M.Eng. thesis, journals/JOM/JOM.html
tation from Aqueous Solutions Containing Iron(III), Arsen- Delft University of Technology, Delft, Netherlands, and

THIRD INTERNATIONAL
CONFERENCE ON GRAIN GROWTH ICGG-3
1418 June 1998 Pittsburgh, Pennsylvania, U.S.A.
Carnegie Mellon University in Pittsburgh, Pennsylvania, will host the Third Inter-
national Conference on Grain Growth (ICGG-3). The conference is being spon-

T S
sored by The Minerals, Metals & Materials Society (TMS), Materials Research
Society (MRS), and ASM International.
Following in the tradition of the two previous International Conferences on Grain
Growth, which were held in Rome, Italy, in 1991 and Kitakyushu, Japan, in 1995,
ICGG-3 will examine the phenomena of grain growth and their impact on the
evolution of microstructure in crystalline materials under a wide variety of pro-
Minerals Metals Materials
cessing conditions.

Presentation topics include: For More Information,


Theory, Modeling and Simulation of Normal and Abnormal Grain Growth Please Contact:
Texture, Microtexture and Orientation Correlations TMS Customer Service
Particle and Other Drag Effects 420 Commonwealth Drive
Thermodynamic and Kinetic Properties of Interfaces Warrendale, PA 15086-7514
Grain Boundary and Interface Structure Telephone: (412) 776-9000, ext. 270
Topological Characteristics of the Interfacial Network Fax: (412) 776-3770
E-mail: csc@tms.org
Grain Growth in Thin Films and Fine Grain Materials
New Experimental Techniques
Applications of Grain Growth Phenomena to the Manipulation Information on ICGG-3
and Control of Properties and Performance and all TMS-sponsored and
Process Modeling/Annealing cosponsored conferences is available
via TMS OnLine on the World Wide Web
The presentations will be published in a at http://www.tms.org/Meetings/
peer-reviewed proceedings volume. Meetings.html.

1997 December JOM 55