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Review

An Overview of the Behavior of Concentrates with Arsenic, Antimony, and Bismuth under Roasting Conditions

by
Alvaro Aracena
1,*,
Miguel Véliz
1,
Oscar Jerez
2,
Eduardo Balladares
3 and
Manuel Pérez-Tello
4
1
Escuela de Ingeniería Química, Pontificia Universidad Católica de Valparaíso, Valparaíso 2362854, Chile
2
Instituto de Geología Económica Aplicada, Universidad de Concepción, Concepción 4070386, Chile
3
Departamento de Ingeniería Metalúrgica, Facultad de Ingeniería, Universidad de Concepción, Concepción 4070386, Chile
4
Departamento de Ingeniería Química y Metalurgia, Universidad de Sonora, Hermosillo 83000, Mexico
*
Author to whom correspondence should be addressed.
Minerals 2023, 13(7), 942; https://doi.org/10.3390/min13070942
Submission received: 1 June 2023 / Revised: 5 July 2023 / Accepted: 11 July 2023 / Published: 14 July 2023
(This article belongs to the Special Issue Thermodynamics, Mechanism and Kinetics of Metallurgical Processes)
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Abstract

:
It is well-known that the mining industry in Chile and the world is searching for eco-friendly, highly efficient mineral treatments. This is because the content of toxic elements such as arsenic, antimony, and bismuth have increased in the copper concentrates in the last years. This trend has affected the market of this metal, as well as increased the potential of producing solid wastes that represent a threat to the environment. In this paper, a review on the fundamentals of the current treatments aimed at removing arsenic, antimony, and bismuth from copper concentrates under roasting conditions is presented. The literature survey included the research conducted from 2000 until now and is focused on the different types of roasting of copper concentrates reported in the literature. A summary of the experimental conditions and major findings of each work is discussed. Depending on the type of roasting, the behavior of arsenic, antimony, and bismuth species during the experiments is analyzed.

1. Introduction

Copper concentrates are currently treated by pyrometallurgy routes to obtain intermediate products with a high content of copper. Typical processes include smelting and converting to produce matte and blister copper in molten state. Although such technologies are widely used worldwide, a number of difficulties typically arise during operation. This includes the production of solid and gaseous wastes, which are potentially harmful to the environment, the high costs of energy associated with the operation of high temperature reactors, and the handling of molten materials, among others. Typical copper concentrates obtained by flotation techniques contain chalcopyrite (CuFeS2), bornite (Cu5FeS4), and chalcocite (Cu2S) as major phases. Such concentrates are generally treated by means of high-temperature technologies [1].
The chemical composition of copper concentrates in Chile varies depending on the region where it is obtained. As an example, Table 1 shows a comparison of typical compositions of concentrates from Chuquicamata [2] and of copper sulfide minerals in Northern Chile [3]. The former represented about 5% of the total Chilean copper production in 2022 [2]. Table 1 shows that the chemical composition is strongly dependent upon the region from which the material was obtained.
Figure 1 shows the typical pyrometallurgical route followed by Chilean copper smelters to produce cathodic copper [4,5]. Here, emphasis is made on the compositions of copper, arsenic, antimony, and bismuth in the several products and effluents obtained during the stages of roasting, smelting, converting, anode casting, and electrowinning. The information shown in Figure 1 is based on plant data collected at the Chuquicamata mine by Barros et al. [3]. It shows that the contents of arsenic, antimony, and bismuth in such streams are significant and, thus, deserve further analysis.
Arsenic is usually present as enargite (Cu3AsS4) and tennantite (Cu12As4S13) [6]; antimony is mostly present as stibnite (Sb2S3) and bismuth may be found as elemental bismuth (Bi) or bismuthine (Bi2S3). These sulfides are difficult to separate by flotation, especially enargite and tennantite. This is because the physicochemical properties of the Cu–As–S sulfides are similar to other copper sulfides present in the concentrate [7]. As a result, such species are carried towards the smelting and converting steps, where they undergo oxidation at high temperatures and distribute in both gas and molten products. The presence of such elements strongly affects the quality of the copper products, causes contamination of the flue dust, and makes further treatment difficult. It also causes operation problems in the acid plant, the collection of wastes, and decreases the efficiency of the electrorefining cells [8,9,10].
The lack of control on the rate of volatilization of arsenic, antimony, and bismuth species during the processing of copper concentrates may cause serious health problems in the human population and represent a threat to living beings in general. An example of the toxicity of these species is the use of diphenylchloroarsine (“adamsite”), a compound composed of arsenic and chloride used as a chemical weapon in World War I [11].
At the present time, few reviews on the pyrometallurgical processing of copper concentrates with high contents of arsenic, antimony, and bismuth are available in the literature. The latest work on the processing of arsenic species was reported by Castro et al. [12], who analyzed the behavior of arsenic sulfides at high temperatures. Regarding the processing of antimony, Moosavi et al. [13] carried out a review on its development through history. The authors focused on the pyrometallurgical route as well as the technologies used to obtain antimony-based products. Compared to arsenic and antimony, the literature on the processing of bismuth is scarce. The present paper is aimed at reviewing the current information on the subject. Such information is provided in a concise, compact form so that the interested reader may find it quickly in the form of tables.

2. Literature Review

Recent studies show that enargite begin oxidation at 375 °C producing tennantite (Cu12As4S13) and sulfur dioxide (SO2) according to Reaction (1):
4 Cu3AsS4 (s) + 3 O2 (g) = Cu12As4S13 (s) + 3 SO2 (g)
Both decomposition and oxidation rates of enargite were observed to be strongly dependent upon temperature and oxygen concentration. Further oxidation of tenantite produced gaseous As4O6 according to Reaction (2) [14]:
Cu12As4S13 (s) + 10 O2 (g) = 6 Cu2S (s) + As4O6 (g) + 7 SO2 (g)
These studies updated reaction mechanisms of tennantite proposed by Secco et al. [15], whose results had similar behavior to the work done by Yoshimura [16]. Padilla et al. [14] showed that under the presence of gaseous oxygen, enargite (Cu3AsS4) first oxidizes at 375 °C producing tennantite (Cu12As4S13) and sulfur dioxide gas (SO2), then tennantite further oxidizes according to Reaction (2).
Under neutral roasting conditions, enargite is assumed to undergo thermal decomposition to produce gaseous As2S3 as the major arsenic gaseous species according to Reaction (3) [15,16].
2 Cu3AsS4 (s) = 3 Cu2S (s) + As2S3 (g) + S2 (g)
In a further study, Padilla et al. [17] used a thermogravimetric analysis technique to conclude that the thermal decomposition of enargite produces As4S4, as shown in Reaction (4).
4 Cu3AsS4 (s) = 6 Cu2S (s) + As4S4 (g) + 3 S2 (g)
Regarding the behavior of antimony, this element is mostly removed in the off-gas streams of smelting and converting processes [18]. This is because antimony and its oxides are volatile at the typical temperatures under which such processes operate. Despite such behavior, during industrial operation, a significant portion of antimony is retained in the condensed phases [18,19,20]. Furthermore, the elucidation of the mechanisms of the decomposition of stibnite (Sb2S3) is relevant for the control of antimony content in both the calcine and condensed phases. It may also help to explain its distribution in subsequent stages of the production process.
Reactions (5) through (7) have been proposed for the decomposition of antimony trisulfide in molten state in a neutral atmosphere.
Sb2S3 (l) = 2 SbS (g) + ½ S2 (g)
Sb2S3 (l) = 2 Sb (l) + 3/2 S2 (g)
Sb2S3 (l) = Sb2S3 (g)
Reactions (5)–(7) were reported by Faure et al. [21], Shendiyapin et al. [22], and Komorova et al. [23], respectively. Reaction (5) indicates that molten Sb2S3 decomposes into antimony sulfide gas and sulfur gas; Reaction (6) states that decomposition occurs with the formation of metallic antimony, whereas Reaction (7) represents the volatilization of molten Sb2S3 as a physical process in which the molecular structure is conserved. The dominant step in the above set of reactions depends on the temperature of operation. Reaction (5) prevails in the range of 670 and 793 K, whereas Reaction (6) prevails between 873 and 1097 K. Finally, Reaction (7) predominates at temperatures higher than 1097 K.
Under the presence of gaseous oxygen, Sb2S3 is rapidly oxidized to produce valentinite (Sb2O3) [24,25]. These authors proposed that stibnite is oxidized to valentinite and, in a consecutive step, it is over-oxidized to antimony dioxide or cervantite (SbO2).
On the other hand, most bismuth sulfides are commonly found in association with lead, copper, and silver. Some bismuth phases found in ore deposits include bismuthine (Bi2S3), bismite (Bi2O3), and bismuth ochre (Bi2O3·3H2O).
Bismuth is found mainly around intrusive rocks, so it is paramagnetic. Bismuthine is the impurity usually found in chalcopyrite-based copper concentrates. Part of the bismuthine present in the concentrates is eliminated in the gas phase during the pyrometallurgical processes [26]. Furthermore, it was reported that 30 to 75% of bismuth in the concentrate is distributed in the matte phase, 5 to 30% in the slag phase, and 15 to 65% in the gas phase during the smelting operation [27].
It is of interest to note that of all three elements of study (As, Sb and Bi), bismuth is the element with the fewest studies reported in the literature since 2000. Furthermore, the information on the processing of bismuth species is scarce.
In this paper, any chemical species containing arsenic, antimony, and bismuth in its structure is considered as a toxic compound. According to the operating conditions under which such compounds are treated, the processes may be classified into three groups: thermal decomposition or inert roasting, oxidative roasting, and reductive roasting. The choice of the type of roasting to be used to treat a specific compound depends on the goal to be achieved; namely, the volatilization of the toxic compound for further cleaning of the carrying gas stream, or the capture of the toxic compound by a solid phase for a nonvolatile post-treatment.

2.1. Thermal Decomposition or Inert Roasting

In general, the concentrates containing As, Sb, and Bi are treated by roasting in a neutral environment (nitrogen, argon, etc.), which causes the volatilization of these elements. Inert roasting can achieve high efficiency removal, but the nature of the products and removal efficiency vary with the temperature of operation. As an example, the roasting of antimony trisulfide (Sb2S3) in the range of 973–1123 K proceeds according to Reaction (7) [28,29]. However, at temperatures higher than 1123 K, Reactions (5) and (6) occur simultaneously. Further, the metallic antimony produced by Reaction (6) slowly volatilizes as a result of its low equilibrium partial pressure:
Sb (l) = Sb (g)
This phenomenon was also observed with antimony (III) oxide (Sb2O3). Under a neutral environment and below 1273 K, such species volatilizes according to reaction (9) [29,30].
2 Sb2O3 (l) = Sb4O6 (g)
At temperatures higher than 1273 K, thermal decomposition produces a variety of both volatile and non-volatile compounds [28,31].
Sb2O3 (l) = SbO2 (l) + SbO (g)
2 SbO2 (l) = 2 SbO (g) + O2 (g)
To test whether a particular species tends to volatilize, the Clausius–Clapeyron equation may be used to calculate its vapor pressure. Table 2 shows the parameters of the Clausius–Clapeyron equation for arsenic [32], antimony [33], antimony trisulfide [34], and bismuth [32]. Figure 2 shows the vapor pressure of elemental arsenic, antimony, and bismuth in the range of 1073–1473 K. As expected, the vapor pressure increases with temperature.
Table 3 shows a summary of the studies on As, Sb, and Bi species of industrial interest. Relevant information regarding the experimental techniques used and the range of temperature under which volatilization was observed are also shown.

2.2. Oxidative Roasting

Unlike inert roasting, under the presence of oxygen, oxidation takes place. Furthermore, oxide species are formed. Oxidation does not necessarily produce volatile species. As an example, the oxidative roasting of antimony trisulfide in the range of 973–1273 K occurs via the following reactions [28].
Sb2S3 (s) + 4.5 O2 (g) = Sb2O3 (s) + 3 SO2 (g)
Sb2O3 (s, l) = Sb2O3 (g)
Sb2O3 (s, l) + 0.5 O2 (g) = 2 SbO2 (s)
When oxidative roasting is carried out under low oxygen partial pressure (1% to 5%), Sb2S3 produces Sb2O3 and the sulfur is volatilized as sulfur dioxide gas. Further, Sb2O3 undergoes volatilization. Reaction (14) requires a high partial pressure of oxygen to produce antimony dioxide (SbO2), also known as cervantite. This species begins to volatilize past 1373 K under the following decomposition reaction.
SbO2 (s) = SbO (g) + 0.5 O2 (g)
Table 4 summarizes the corresponding studies on the oxidative roasting of As, Sb, and Bi species of interest for this work.

2.3. Reductive Roasting

Reductive roasting is an efficient method to produce non-volatile products in which As, Sb, and Bi are captured. An example is the carbothermal reduction of stibine in which the production of sulfur and Sb in the gas phase is avoided [31,51].
The reduction of Sb2S3 using CaO as sulfur carrier between 973–1173 K proceeds according to the following reactions [51]. All the Gibbs free-energy data for the reduction reactions was collected from HSC database [61].
2 Sb2S3 (s) + 6 CaO (s) = Sb (l) + 3 SbO2 (s) + 6 CaS (s)
∆G 973 K = 56.450 kJ/mol
SbO2 (s) + C (s) = Sb (l) + CO2 (g)
∆G 973 K = −122.634 kJ/mol
Once CO2 (g) begins to form according to reaction (17), it reacts with carbon to form CO (g) (carbon monoxide). Further, CO is consumed according to reaction (19).
C (s) + CO2 (g) = 2 CO (g)
SbO2 (s) + 2 CO (g) = Sb (l) + 2 CO2 (g)
∆G 998 K = −122.619 kJ/mol
Reaction (19) is the predominant step, as typically solid–gas reactions, such as Reaction (18), are faster than solid–solid reactions (Reaction (17)). On the other hand, the reduction of stibine using fayalite slag (Fe3O4 and Fe2SiO4) as sulfur carrier, between 998–1173 K proceeds according to the following reactions [31].
Fe3O4 (s) + 2 C (s) = 2 FeO (s) + Fe (s) + CO2 (g)
∆G 998 K = −1.115 kJ/mol
Sb2S3 (s) + 1.5 CO2 (g) = Sb2O3 (s) + 1.5 C (s) + 1.5 S2 (g)
∆G 998 K = 309.573 kJ/mol
In this reaction scheme, magnetite is first reduced with coal according to Reaction (20) to produce wustite (FeO), metallic iron (Fe), and CO2. In the second step, Sb2S3 reacts with CO2 to produce Sb2O3, which is further encapsulated by the remaining magnetite, forming tripuhyite (FeSb2O6).
Sb2O3 (s) + 1.5 Fe3O4 (s) = FeSb2O6 (s) + 5 FeO (s)
The wustite generated in Reactions (20) and (22) also reacts with senarmontite (Sb2O3) to form tripuhyite.
Sb2O3 (s) + 3 FeO (s) = FeSb2O6 (s) + 2 Fe (s)
At temperatures higher than 1373 K, part of the senarmontite produced is decomposed to produce antimony oxide gas (SbO (g)) and cervantite, as shown in Reactions (14) and (15). Table 5 shows a summary of the reductive roasting studies of As, Sb, and Bi species so far reported in the literature.
The overall mechanisms discussed above for neutral, oxidative, and reductive roasting of arsenic, antimony, and bismuth species are schematically summarized in Figure 3. Here, the type of atmosphere, chemical species being processed and produced, the possible outcome regarding the volatilization, and the gaseous products obtained are shown. It is noted that this a general diagram, the details concerning specific data were shown in Table 3, Table 4 and Table 5.

3. Discussion

The treatment of a specific compound by inert, oxidative, or reductive roasting does not guarantee the desired result if the experimental conditions are not established from the beginning of the experiment. This is because a number of factors affect the outcome of such experiments, such as the following.
Particle size: Relatively large particles in the treatment of these concentrates can be beneficial to maintain a control in the roasting and reduce the environmental impact. This is because fine particles may be carried away by the off-gas stream [68].
Temperature: The information shown in Table 3 through Table 5 show the temperature ranges under which volatilization and other chemical reactions of the species of interest may occur. Under such conditions, gas phase species, decomposition products, low partial pressure products, or passivating layers may be observed.
Origin of the compound: This is related to the activation energy of the chemical reactions, the reaction rate, the gas flux, and the experimental technique needed to track the evolution of the chemical processes. Based on the previous information, the following discussion addresses the main features of the processes analyzed.

3.1. Antimony

Because this element has a high vapor pressure, it tends to form volatile compounds. Depending on the experimental conditions, a variety of species can be formed.
Under a neutral atmosphere and in the absence of oxygen, antimony species are highly volatile. As an example, solid Sb2O3 under neutral atmosphere readily evaporates without passing through a liquid state. In contrast, under presence of gaseous oxygen SbO2 or SbO is formed, depending on the oxidizing conditions [51].
Finally, under reductive roasting or carbothermal reduction conditions, the volatilization of antimony species may occur as long as the temperature is high enough to volatilize the compound before it starts reacting with the reducing reactant (CO (g), CO2 (g)). This is especially relevant when a significant amount of antimony is volatilized before the reduction reactions form a stable compound. Other reducing reactants include Fe2O3 and FeO to produce stable species such as FeSb2O6 [31]. This method prevents the compound from escaping the system.

3.2. Arsenic

The behavior of As is similar to that of Sb discussed previously. Under oxidative conditions, arsenic will not volatilize unless the arsenic compound presents a high vapor pressure, which increases with the temperature as shown in Figure 2. Some authors [46,56] used metallic compounds such as Fe2O3 and CaO in addition to oxygen to form FeAsO4 and Ca3(AsO4)2, thus avoiding the volatilization of arsenic. This guaranteed the stabilization of arsenic in a solid phase.
During carbothermal reduction, solid products are formed, as the goal of such treatment is to capture and stabilize the volatile element by adding metallic compounds or salts, such as FeS, Fe2O3, or NaOH. It is noted that both arsenic and antimony behave similarly under identical process conditions. An example is the formation of volatile trioxides. The major difference between both elements is the high toxicity of arsenic. Furthermore, for the handling and processing of arsenic species, the safety regulations must be more stringent than those for antimony species. This reduces the risk of escapes to the environment, thus preventing hazards to the natural flora and fauna.

3.3. Bismuth

In contrast with the behavior of As and Sb species discussed previously, bismuth species typically show a low vapor pressure, and thus are mostly nonvolatile. Furthermore, no volatilization was observed in the studies shown in Table 3 through Table 5 under a variety of experimental conditions. As an example, Bi2S3 under a neutral atmosphere decomposes to form metallic bismuth (Bi) and gaseous sulfur at temperatures lower than 1773 K. Under oxidative roasting conditions, Bi2S3 tends to oxidize to form Bi2O3 and SO2 gas. Finally, under carbothermic reduction conditions with addition of Fe2O3 and Na2O3, the products are metallic bismuth (Bi), the sulfur species FeS and Na2S, and gaseous CO2.

4. Conclusions

A survey of the literature was conducted to summarize the characteristics of inert, oxidative, and reducing roasting to process copper concentrates with significant contents of As, Sb, and Bi.
It was shown that the selection of the type of roasting to be used depends on the goal to be achieved; namely, the separation of the metals of interest in the form of a variety of volatile species, or its capture in a solid phase for further disposal. For the former, inert and oxidative roasting may be used, whereas for the latter, reduction roasting is most appropriate. Of all three elements considered in this review, Bi was observed not to produce gaseous products under typical roasting conditions.
Because the chemistry of all three elements is complex, the selection of the experimental conditions to treat a particular material must be done with caution. This is because the products vary substantially with temperature, type of reactants, and processing time. Finally, both theoretical and experimental research are needed to further elucidate the mechanisms governing the chemistry of As, Sb, and Bi species at high temperatures.

Author Contributions

Conceptualization, A.A., O.J., E.B., M.P.-T. and M.V.; methodology, A.A. and M.V.; software, A.A., M.P.-T. and M.V.; validation, A.A., O.J., E.B., M.P.-T. and M.V.; formal analysis, A.A., O.J., E.B., M.P.-T. and M.V.; investigation, M.V.; resources, A.A.; data curation, A.A., O.J., E.B., M.P.-T. and M.V.; writing—original draft preparation, M.V.; writing—review and editing, A.A., O.J., E.B., M.P.-T. and M.V.; visualization, A.A. and M.V.; supervision, A.A., and M.V. All authors have read and agreed to the published version of the manuscript.

Funding

This research received no external funding.

Data Availability Statement

Not Applicable.

Conflicts of Interest

The authors declare no conflict of interest.

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Minerals 13 00942 g001 550
Figure 1. Flowchart of the copper production from copper concentrate showing the concentration ranges of copper, arsenic, antimony, and bismuth in the main Chilean process and the gaseous products form on roasting and smelting/converting. Data provided by Barros et al. [3].
Figure 1. Flowchart of the copper production from copper concentrate showing the concentration ranges of copper, arsenic, antimony, and bismuth in the main Chilean process and the gaseous products form on roasting and smelting/converting. Data provided by Barros et al. [3].
Minerals 13 00942 g001
Minerals 13 00942 g002 550
Figure 2. Vapor pressure of elemental arsenic, antimony and bismuth between 1073–1473 K. Pressure in Pascals.
Figure 2. Vapor pressure of elemental arsenic, antimony and bismuth between 1073–1473 K. Pressure in Pascals.
Minerals 13 00942 g002
Minerals 13 00942 g003 550
Figure 3. Overall schematic representation of the mechanisms of neutral, oxidative, and reductive roasting of arsenic, antimony, and bismuth species. See Table 3, Table 4 and Table 5 for details.
Figure 3. Overall schematic representation of the mechanisms of neutral, oxidative, and reductive roasting of arsenic, antimony, and bismuth species. See Table 3, Table 4 and Table 5 for details.
Minerals 13 00942 g003
Table
Table 1. Chemical composition of Chuquicamata copper concentrate and copper sulfide minerals in Chile [3], wt%.
Table 1. Chemical composition of Chuquicamata copper concentrate and copper sulfide minerals in Chile [3], wt%.
Mine/RegionChuquicamata ConcentrateNorthern Chile Sulfide Minerals
Element
Cu31.8–33.51.49
As0.48–0.79<0.1
Sb0.012–0.042-
Bi0.0069–0.011-
Table
Table 2. Clausius–Clapeyron equation parameters for arsenic, bismuth, and antimony trisulfides, P in Pascals.
Table 2. Clausius–Clapeyron equation parameters for arsenic, bismuth, and antimony trisulfides, P in Pascals.
Compound/Element *ABReference
As (1)−20,68910.62[32]
Sb (1)−28,53512.336[33]
Sb2S3 (2)−(10,490 ± 200)13.96 ± 0.2[34]
Bi (1)−21,70211.75[32]
* X (1): Log P = exp (A/T + B), X (2): Log P = (A/T + B).
Table
Table 3. Compilation of inert roasting studies of arsenic, antimony, and bismuth species.
Table 3. Compilation of inert roasting studies of arsenic, antimony, and bismuth species.
CompoundMaterial *Experimental Technique *VolatilizationReference
Sb2O3M [32], C [35], S [28,30,31]TG [28,30,31,35], TG/DSC [32]823–1423 K[28,30,31,32,35]
SbO2STG>1423 K[28,31]
Sb2S3STG [28,29,31], TG/DSC [36]973–1423 K[28,29,31,36]
SbSTG1223 K[28,29]
Cu12Sb4S13MTG973–1473 K[36,37]
Bi2S3C [38], S [39]TG/DSC [38], TG/MS [39]No[38,39]
Bi2O3CTG/DSCNo[40]
As2O3C [35,41,42], S [40,43]TG [40,42], TG/DSC [35,41,43]623–1273 K[35,40,41,42,43]
Cu3AsS4M [14,44,45,46], C [17,47,48]TG [14,44,45,46,47], FB [48], TG/DSC [17]848–1773 K[14,17,44,45,46,47,48]
Cu12As4S13M [37,49], C [45,48,50]TG [37,47,49,50], TG/DTG [48]848–1773 K[37,47,48,49,50]
* Material: mineral (M), concentrate (C) or synthetic (S) or not apply (NA). Experimental technique: thermogravimetric (TG), fluidized bed (FB), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC), differential thermal analysis (DTA), inductively coupled plasma atomic emission spectroscopy (ICP-AES) or mass spectroscopy (MS), not apply (NA).
Table
Table 4. Compilation of oxidative roasting studies of arsenic, antimony, and bismuth species.
Table 4. Compilation of oxidative roasting studies of arsenic, antimony, and bismuth species.
CompoundMaterial *ReagentsExperimental Technique *VolatilizationReference
Sb2O3SO2 (g)TGNo[51]
Sb2S3C [52,53], S [28,29]O2 (g)TG/DSCNo[28,29,52,53]
SbSO2 (g)TGNo[29]
Cu12Sb4S13MO2 (g)TG773–1473 K[37]
Bi2S3MMnO2, Mn2O3, O2 (g)TGNo[54]
As2S3CO2 (g)FB873–1173 K[48,55]
As2O3C [56], NA [45]Ca(OH)2, Fe2O3, O2 (g)TG [56], NA [45]No[45,56]
As4O6C [41,57], S [40]CaO, Cu2O, CuO, Fe2O3, O2 (g)TG [40], TG/DSC [41,57]No[40,41,57]
Cu3AsS4MO2 (g)TG648–898 K[14,47,58,59]
Cu12As4S13M [36], C [50]O2 (g)TG723–1323 K[36,50]
FeAsSC [56,59], NA [45]O2 (g)TG [56,59], NA [45]673–1173 K[45,56,59]
Cu3(AsO4)2NAFeS2, O2 (g)NA>873 K[60]
Ca2As2O7SO2 (g)TG>1223 K[40]
* Material: mineral (M), concentrate (C), synthetic (S) or not apply (NA). Experimental technique: thermogravimetric (TG), fluidized bed (FB), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC), differential thermal analysis (DTA), inductively coupled plasma atomic emission spectroscopy (ICP-AES) or mass spectroscopy (MS), not apply (NA).
Table
Table 5. Compilation of reductive roasting studies of arsenic, antimony, and bismuth species.
Table 5. Compilation of reductive roasting studies of arsenic, antimony, and bismuth species.
CompoundMaterial *ReagentsExperimental Technique *VolatilizationReference
Sb2O3C [52], S [31,62]Fe, FeO, Fe2O3, C, Sb2S3TG No[31,52,62]
Sb2S3C [63,64], S [31,36,52,65,66,67]C, CO (g), CaO, Fe2O3, Na2CO3, Fe3O4, ZnOTG [31,51,63,64], TG/DSC [36], TG/DTA [65,66,67]No[31,36,51,63,64,65,66,67]
SbO2SC, CO (g)TGNo[28]
Cu12Sb4S13CCuOTGNo[68]
Bi2S3C [38,68], S [39]C, CO (g), CO2 (g), Fe3O4, Fe2O3, FeOTG/DTG [68], TG/DSC [38], TG/MS [39]No[38,39,68]
Bi2O3C [38], S [39]C, CO (g), CO2 (g), Fe3O4, Fe2O3TG/DSC [38], TG/MS [39]No[38,39]
As2O3C [41,69,70], S [71]C, CuSO4, CuS, NaOH, CaSO4TG [71], TG/DTG [69], TG/DSC [41,70]No[41,69,70,71]
As2O5CC, CO (g), NaOHTG/DTG [69], TG/DSC [41,70]No[41,69,70]
Cu3(AsO4)2CC, H2SO4, FeS2, FeSTG/DTG [69], TG/DSC [41]573–823 K[41,69]
Na6As2O8CCISP/AES [71], TG [72]873–1073 K[71,72]
FeAsO4CNaOHTG/DSCNo[70]
Bi(AsO4)CC, CO (g)NANo[73]
Zn3(AsO4)2CC, CO (g)TGNo[74]
FeAsO4SCaO, Fe2O3, SiO2, Na2CO3TG1273–1523 K[75]
* Material: mineral (M), concentrate (C) or synthetic (S) or not apply (NA). Experimental technique: thermogravimetric (TG), fluidized bed (FB), derivative thermogravimetry (DTG), differential scanning calorimetry (DSC), differential thermal analysis (DTA), inductively coupled plasma atomic emission spectroscopy (ICP-AES) or mass spectroscopy (MS), not apply (NA).
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Aracena, A.; Véliz, M.; Jerez, O.; Balladares, E.; Pérez-Tello, M. An Overview of the Behavior of Concentrates with Arsenic, Antimony, and Bismuth under Roasting Conditions. Minerals 2023, 13, 942. https://doi.org/10.3390/min13070942

AMA Style

Aracena A, Véliz M, Jerez O, Balladares E, Pérez-Tello M. An Overview of the Behavior of Concentrates with Arsenic, Antimony, and Bismuth under Roasting Conditions. Minerals. 2023; 13(7):942. https://doi.org/10.3390/min13070942

Chicago/Turabian Style

Aracena, Alvaro, Miguel Véliz, Oscar Jerez, Eduardo Balladares, and Manuel Pérez-Tello. 2023. "An Overview of the Behavior of Concentrates with Arsenic, Antimony, and Bismuth under Roasting Conditions" Minerals 13, no. 7: 942. https://doi.org/10.3390/min13070942

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