Article pubs.acs.org/IECR
New Source of Unavoidable Ions in Bornite Flotation Aqueous Solution: Fluid Inclusions Jiushuai Deng, Shuming Wen,* Jian Liu, Yongjun Xian, Danan Wu, and Shaojun Bai Faculty of Land Resource Engineering, Kunming University of Science and Technology, 68 Wenchang Road, Kunming, Yunnan, 650093, PR China S Supporting Information *
ABSTRACT: This study aims to determine the presence and release of fluid inclusions in natural pure bornite while investigating the types, structures, and compositions of such inclusions. This work also measures the total concentrations of Cu (CCuT), Fe (CFeT), and Cl−, SO42−, which are released to the bornite aqueous solution from fluid inclusions. The results indicate that numerous fluid inclusions are distributed in isolation or along the crevices in the bornite. The fluid inclusions take on such shapes as long strips and irregular strips, with the body sizes ranging from 3 to 40 μm. Through the crushing and grinding process, the inclusions that are captured from the diagenetic and metallogenic process of bornite would be released to the flotation pulp along with Cu, Fe, Cl−, SO42−, etc. Results indicate that the CCuT and CFeT values in the solution are significantly higher than those from the experimental dissolution. Therefore, results confirm that the release of inclusions is a new source of Cu and Fe ions in the aqueous solution. Moreover, the findings exhibit a new discovery of an unavoidable ion source in the flotation pulp, and the residual position domain after the release of the inclusions causes the difference in bornite surface composition and roughness. The new discovery expands the research objectives and scope in flotation solution chemistry and is significant in the study of flotation theory.
1. INTRODUCTION Flotation is a primary method of mineral processing that has been widely used for the recovery of sulfide minerals.1,2 The composition and physicochemical properties of flotation pulp determine the flotation effect. A large number of studies have been conducted on the physicochemical properties of various kinds of mineral flotation pulps and their effect on flotation.3−11 Hence, an important research direction called “Flotation solution chemistry” has been developed.12−14 In the practical process of mineral flotation, the flotation pulp is a complicated system in which ion composition can have an important influence on flotation results, particularly on the surface properties of the mineral and on the electrochemical properties of the solution. These properties can either promote or inhibit the adsorption of mineral and collector. The existence of inevitable ions can promote or hinder the electrochemical effects of the flotation solution.11,15 During metal sulfide flotation separation, the existence of Cu2+, Fe2+, and Pb2+ will result in nonselective activation or inhibition,2 thus making separation difficult. Various ion species are present in the practical mineral flotation pulp, including Ca2+, Mg2+, Na+, K+, Cr2+, Fe2+, Cl−, SO42−, CO32−, etc., which are all unavoidable. The ions in the pulp solution are defined as “unavoidable ions”. To date, no special study has been conducted to introduce the sources of unavoidable ions. Generally, large quantities of unavoidable ions can originate from water sources. As an example, seawater is periodically employed with increasing usage in such areas as northern Chile, bore waters in Western Australia have higher salt content than seawater, and water derived from tailings areas can be high in thiosalts.5,8,16−18 All of these sources outweigh the quantities obtained from the ore itself. © 2013 American Chemical Society
In addition several researchers have recently investigated sources of the metal ions such as surface dissolution, surface dissociation, and surface oxidation.15,19,20 Evidence exists on superficial oxidation dissolution, especially when galvanic effects are included. Several authors have concluded that bornite dissolution depends on the redox potential of the solution, with the best results being achieved under moderately oxidizing conditions.21 The increase in metal ion release from base metal sulfides in the presence of pyrite is well documented.22 Flotation plants have acted on this principle, judiciously introducing reducing agents to suppress metal ion release.23 On the other hand, a process (GalvanoxTM) that exploits galvanic accelerated oxidation to increase dissolution kinetics of bornite by introducing pyrite has also been presented.24,25 Petruk26 emphasizes that Cu ions are readily generated from more reactive secondary Cu minerals such as chalcocite, which are often present in bornite ores.27 In other words, unavoidable ions can have sources other than such secondary minerals are present in extremely small amounts. The results of these investigations are usually inconsistent with theoretical calculations for the dissolution equilibrium of minerals, and almost all the reported results of experimental calculations are significantly higher than those from theory.28−31 Theories on the sources of unavoidable ions, such as surface dissolution, surface dissociation, and surface oxidation, remain incapable of providing a comprehensive Received: Revised: Accepted: Published: 4895
October 6, 2012 February 27, 2013 March 8, 2013 March 8, 2013 dx.doi.org/10.1021/ie302721c | Ind. Eng. Chem. Res. 2013, 52, 4895−4901
Industrial & Engineering Chemistry Research
Article
explanation for the occurrence of such ions in the flotation process of metallic sulfide ores. Fluid inclusions are small relicts of fluid that are trapped in natural minerals during their growth from hydrothermal solutions (primary inclusions) or during later deformation (secondary inclusions). These inclusions are the most direct record of the chemical and physical properties of ancient fluids that are trapped deep in the Earth’s crust, thus providing essential information on the geological formation of hydrothermal ore deposits.32 Generally, ore-forming fluid was always captured into mineral fluid inclusions, and the composition and properties of original fluids would be maintained. With mineral grinding, fluid inclusions would be broken, and the ore-forming fluid would overflow into the pulp solution. This process affects the chemical composition and properties of the pulp solution, the changes of which would influence mineral flotation. A large number of works on geochemistry have been conducted to study the compositions and properties of ore-forming fluid in inclusions.33,34 However, the effects of the compositions of fluid inclusions on flotation have rarely been reported. Therefore, research on the release of fluid inclusions to the pulp solution serves as an important guide to the flotation theory. The measures that are used to determine the compositions of inclusions are X-ray diffraction (XRD) analysis, laser Raman spectroscopy, infrared optical imaging analysis, scanning electron microscopy-energy dispersive spectroscopy (SEMEDS), etc.35−41 By using near-infrared light as a light source, studies on the internal structures of opaque minerals as well as the infrared optical imaging and determination of the thermodynamic characteristics of fluid inclusions have been achieved.36 A series of determinations on opaque and translucent mineral fluid inclusions has subsequently emerged, including wolframite,37,42 enargite,43 stibnite,44 hematite and hausmannite,45 etc. Pyrite has been the most studied among these inclusions. 43,46−48 These previous works provide references for the study of opaque mineral inclusions. A good opportunity to analyze the composition of single inclusion has been created by SEM-EDS. The morphology analysis of SEM enabled us to identify open inclusions, thus laying a foundation for the analysis of the composition of single inclusions. Second, broken inclusions can be analyzed by directly using the energy. Thus, the composition of single inclusions could be determined. The chalcopyrite daughter mineral from the fluid inclusion in a porphyry copper deposit has been discovered by Roedder by using SEM.49 Inductively coupled plasma-mass spectrometry (ICP-MS) served as one of the most sensitive methods for the analysis of trace elements with the advantages of high sensitivity, low detection limit, and simple mass spectrum features. ICP-MS that uses a quadrupole mass filter (hereinafter ICP-MS, unless further specified) has become the main instrumentation for multielement applications from major- to trace-element levels.50−53 In our experiments, the aforementioned infrared optical imaging, SEM-EDS analysis, and ICP-MS analysis technology have been applied to determine the characteristics of bornite fluid inclusions. In addition to mineral surface oxidation solvation and water sources, no report has been made on other sources and on the primary source of the unavoidable metal ions in pulp. Pure bornite mineral is used as the research object in this study. Cu, Fe, Cl−, SO42−, etc. are considered to be the ions in the bornite inclusion that are released to the solution at the time of grinding. The concentration of copper and iron ions in the
solution and mineral dissolution has been comparatively studied. Infrared optical imaging and SEM-EDS have been applied to study the structure of the inclusions to explain the existence of fluid inclusions in the bornite mineral. The results prove that the release of ore-forming components in inclusions is a new source of Cu and Fe ions in pulp, thus providing a new object in the study of bornite flotation solution chemistry.
2. EXPERIMENTAL SECTION 2.1. Materials. This study used material from YunTong Company, midland Yunnan Province, China. High-purity bornite crystal was obtained from the material after the manual removal of gangue minerals such as calcite and quartz. The XRD experiments were performed by using a Japan Science D/ max-R diffraction apparatus with Cu Kα radiation (λ = 1.5406 Å), operating voltage of 40 kV and a current of 40 mA. The diffraction angle (2θ) used for scanning ranged from 10° to 90°. The XRD pattern and the chemical composition of the bornite crystal are shown in Figure 1 and Table 1, respectively.
Figure 1. XRD pattern of the original bornite.
Table 1. Chemical Composition of the Pure Bornite That Was Used in the Experiments element
Cu
Fe
S
SiO2
Al2O3
CaO
MgO
content (%)
63.01
12.34
27.32
2.06
1.25
1.03
0.43
As shown in Figure 1, the three strongest peaks appeared at 55.10°, 32.91°, and 38.18°. These peaks are consistent with crystal faces (220), (111), and (200) respectively, which are consistent with the values of the Joint Committee on Powder Diffraction Standards card (No. 73-1667). From these values, a bornite lattice parameter of 5.47 Å × 5.47 Å × 5.47 Å, α = β = γ = 90° can be obtained. This finding confirms that bornite has a tetragonal structure, the space group of which is FM-3M. Although impurity elements were found to be present in the bornite, as shown in Table 1, the intensity of XRD is insufficient because of the low content of these elements. On the basis of the combined results of Figure 1 and Table 1, the bornite is found to have high purity with only minor SiO2 and CaO impuritie. 2.2. Infrared Optical Observation of the Bornite Inclusions. The sample was sliced thinly and then placed on a double-sided polished inclusion film with a thickness of 60 to 200 μm to increase light transmission. The inclusion film was observed though inclusion petrography by using an Olympus infrared microscope (Olympus Company, Japan). The object lenses equipped were 10×, 20×, 40×, and 50×. The image was 4896
dx.doi.org/10.1021/ie302721c | Ind. Eng. Chem. Res. 2013, 52, 4895−4901
Industrial & Engineering Chemistry Research
Article
Figure 2. Infrared microscopic images of the shallow and surface fluid inclusions in bornite: L represents the liquid phase and V represents the gas phase.
Fe2+. The negative ions are mainly Cl−, SO42−, and F−.54 In the field of geochemistry, numerous studies have focused on the compositions and concentrations of these ions and have then established a direct measurement method. Thus, desirable effects have been achieved. However, few geochemical researches have been conducted on the heavy metal ions. Indirect measuring methods are thus recommended. The indirect measurement method was used to measure heavy metal Cu2+ in the fluid inclusions of bornite. First, 2 g pure bornite with a particle size of approximately 1 mm was weighed and then cleaned five times with deionized water before being air-dried. A small ball mill (MM400, Retsch, Germany) was used for grinding, whose grinding device was a stainless steel milling pot with a volume of 50 mL, and there was only a stainless steel ball with a diameter of 25 mm placed in it. Then set the frequency as 900 min−1 in the devices tab and grind through vibration. The washed pure mineral was ground to different degrees of fineness with the ball mill and
transformed into a data signal by using infrared electronic induction, and the output picture was then processed by using computer software. For this study, infrared optical imaging experimental work on bornite inclusions was performed in the State Key Laboratory for Mineral Deposits Research of Nanjing University. 2.3. SEM-EDS Analysis of the Residual Position Domain of Bornite Fluid Inclusions. The morphology of the residual position domain of bornite fluid inclusions was determined by using SEM on a Philip XL30 scanning electron microscope. The sample was first fixed on the SEM at low magnification for scanning until inclusions appeared. Photography and spectrum analysis were then performed on the position domain of inclusions. 2.4. Measurement of Cu, Fe, Cl−, and SO42− Released from Bornite Fluid Inclusions. The positive ions in the bornite fluid inclusion are usually alkali metal ions such as Ca2+, Mg2+, Na+, and K+ as well as intrinsic ions such as Cu2+ and 4897
dx.doi.org/10.1021/ie302721c | Ind. Eng. Chem. Res. 2013, 52, 4895−4901
Industrial & Engineering Chemistry Research
Article
the product was then placed into a glass centrifugal sedimentated pipe, and 40 mL deionized water was added. Ultrasonic (SY2200, SCI, China) cleaning was performed for 1 min. A centrifuge (TL-4.7W, SCI, China) was used for solid− liquid separation. The supernatant liquor was removed, and the concentrations of Cu and Fe ions was detected by using ICPMS (ElAN-DRCII, PE, USA), whereas concentrations of Cl− and SO42− were determined by using an ion chromatograph (IC; 820-413, Waters, USA). The above processes were conducted in a glovebox under an inert environment (i.e., argon-saturated atmosphere) to avoid contamination by the atmosphere. The experiments were performed at room temperature of 25 °C. Pure deionized water with a resistivity of 18 MΩ (Mill-Q5O, USA) was used throughout the experiments. 2.5. Bornite Dissolution in Pure Deionized Water. Before dissolution, the material and deionized water with the longest grinding time (14 min) was placed in a centrifuge tube, and ultrasonic cleaning was performed for 1 min. Next, a centrifuge was used for solid−liquid separation, and the solid was cleaned for dissolution. This process was used to remove the Cu and Fe released from the fluid inclusions of the bornite. The dissolution experiment was performed by using a digital magnetic stirrer (DF-101S, Gongyi, China). The air-dried 2 g solid with 40 mL of pure deionized water was added to a 50 mL glass reactor, followed by rapid magnetic stirring (1000 rpm) for 7 h. When the dissolution experiment was finished, a centrifuge was used for solid−liquid separation. The separated liquid was stored in closed vials and then detected by using ICP-MS. This experimental process was also conducted in a glovebox in an inert environment at room temperature of 25 °C.
Figure 3. SEM morphology of fluid inclusions residual position domain of bornite.
Some inclusions have isolated shapes, whereas others are fractured. Inclusions take on strip shapes and irregular shapes. The results on inclusion structure and state that were obtained by using SEM morphology analysis are consistent with the results obtained from infrared optical microscopic imaging on the surface and shallow fluid inclusions of bornite. To prove that the hollow region present on the fracture surface is the inclusion residual position domain, rather than scratches caused by slicing the surface, as well as to compare the differences of composition from hollow region and flat area, EDS analysis was performed on hollow regions of the hollow. For comparison, region point analysis was performed on the following locations: the flat area (A) around the hollow regions as shown by the crisscrosses and the hollow location (B, C, and D) in Figure 3. The EDS diagrams are shown in Figure 4, and the resulting elemental contents based on semiquantitative analysis are shown in Table A in the Supporting Information. Only the peaks of Cu, Fe, and S are shown on the electron spectrum in Figure 3A. From the semiquantitative analysis, the Cu, Fe, and S atomic concentration ratio is 50.72:9.96:39.32, which is close to the theoretical value of 5:1:4. No impurity elements are found in the mineral around the hollow domain, which indicates purity. Aside from the S, Fe, and Cu elements, the peaks of C, O, Mg, Al, Si, S, Ag, K, and Ca also appeared on the hollow domain energy spectrum (Figure 3B). On the basis of the semiquantitative analysis, the weight ratios of these elements are close to 15% with an atomic concentration ratio of 35.51%. The atomic number ratio of S, Fe, and Cu is far from the stoichiometric number. Apparently, the composition of the hollow domain differs from that of the flat area. The other element types and their namesake cations (i.e., Cu and Fe) in the hollow domain can be found. These components are believed to have originated from the release of fluid inclusions, which is also proven by the characteristics derived from the EDS and semiquantitative analysis results of the A and C hollow domains in Figure 3. The EDS and semiquantitative analysis results show that the hollow regions are not caused by the slicing of the surface but rather exist naturally. The phase interface components Cu, Fe, Al, Si, Ca, Mn, and Cr that are detected by using EDS exist inherently. These components came from the release of the fluid inclusions. The hollow region was preserved after the breaking of the inclusions. Fluid inclusions contain gas as well as liquids; some ions are released into the solution while others are adsorbed on the inclusion interface after volatilization. 3.3. Quantitative Analysis of the Release of Bornite Fluid Inclusions. ICP-MS and IC were used to measure the concentrations of Cu, Fe, Cl−, and SO42− that were released from the fluid inclusions of the bornite after the grinding process. The results are shown in Table 2.
3. RESULTS AND DISCUSSION 3.1. Infrared Optical Microscopy Imaging of Bornite Surface and Shallow Fluid Inclusions. The structure and morphology of the bornite surface and shallow fluid inclusions are shown as the dark areas in Figure 2. A number of microscopic minerals were generated by the reaction of the captured fluid and the host mineral. These microscopic minerals easily absorbed infrared radiation, thus causing the fluid inclusions to darken.47 Infrared microscopy imaging results show that the fluid inclusions within the bornite distribute isolated (Figure 2A and C) or along the fissures (Figure 2B, E, and F), which could be distinguished under room temperature as gas−liquid two-phase fluid inclusions (Figure 2A and C). The inclusion body sizes are between 3 and 40 μm, with most being less than 10 μm. Moreover, the phenomenon of fluid inclusion fracturing could be observed at this slice, as shown in the position of triangular symbol in Figure 2A and D. The fracturing of fluid inclusions may be attributed to the grinding process of the bornite. The infrared optical microscopic imaging results show the existence of a large number of fluid inclusions in bornite. 3.2. SEM-EDS Analysis of Inclusion Residual Position Domain. The surface morphology after the breaking of bornite inclusions is shown in Figure 3A to F. Numerous hollow regions caused by the breaking the inclusions were present on the bornite fracture surface. These regions can be called the inclusion residual position domain. From the structure and morphology of the inclusion residual position domain that were directly observed by using SEM, the inclusions clearly have different sizes and shapes. The sizes range from 1 to 20 μm. 4898
dx.doi.org/10.1021/ie302721c | Ind. Eng. Chem. Res. 2013, 52, 4895−4901
Industrial & Engineering Chemistry Research
Article
Figure 4. EDS of the inclusions domain.
Table 2. Concentration of Cu, Fe, Cl−, and SO42− Released from the Bornite Fluid Inclusions
interaction. A number of studies have shown that NaCl, H2S, CO2, sulfate, and other compositions exist largely in fluid inclusions.55,56 Therefore, the anion concentrations of Cl− and SO42−, which were released with the bursting of bornite inclusions, were tested simultaneously. Results show that Cl− and SO42− concentrations in the solution increase gradually with the gradual increase of the grinding degree. During the grinding time from 6 to 14 min, the Cl− concentration increases from 1.41 × 10−6 to 9.31 × 10−6 mol/L, and the SO42− concentration increases from 17.81 × 10−6 to 29.48 × 10−6 mol/L, which are relatively large values. The concentration order of magnitude of the cations and anions in Table 2 is consistent with the test data of fluid inclusions.57 The test values of Cl− and SO42− concentrations in blank sample are 7.6 × 10−10 and 20.4 × 10−10 mol/L, respectively, which differ from those of Cl− and SO42− in solution by approximately 3 orders of magnitude. The experiment and analysis system clearly had a minimal effect on the experimental results. To eliminate the possibility that the abundance of Cu and Fe in the solution came from mineral dissolution, the mineral particles that were fractured for 14 min were repeatedly washed until the solubility of Cu and Fe in the solution were at 12.6 × 10−9 and 34.1 × 10−9 mol/L, respectively. The particles were then dissolved for 7 h in a
concentration × 10−6 mol/L grinding time, min
Cu
Fe
Cl−
SO42−
6 8 10 12 14
0.28 0.36 0.70 1.43 1.65
0.06 0.07 0.21 0.33 0.34
1.41 2.54 4.51 7.05 9.31
17.81 24.38 27.81 29.28 29.48
Table 2 reveals that after ultrasonic cleaning for 1 min, the total concentrations of Cu and Fe (CCuT and CFeT) in the solution increase significantly with increasing grinding time. Increased grinding time from 6 to 14 min remarkably increases CCuT from 0.28 × 10−6 to 1.65 × 10−6 mol/L. Similarly, the CFeT increases from 0.06 × 10−6 to 0.34 × 10−6 mol/L. The value increases significantly. Meanwhile, blank run experiments were also performed. The concentrations of Cu and Fe contributed by grinding medium and deionized water are respectively 0.99 × 10−10 and 9.15 × 10−10 mol/L, which reveals that the grinding medium and deionized water have weak impact on the concentration of metal ions. Most sulfide ores including bornite result from the process of hydrothermal mineralization, along with the brine contact and 4899
dx.doi.org/10.1021/ie302721c | Ind. Eng. Chem. Res. 2013, 52, 4895−4901
Industrial & Engineering Chemistry Research
■
glovebox with argon gas protection. The test results for the Cu and Fe concentrations in the solution are shown in Table 3.
dissolution time, h
pH
experimental CCuT, mol/L
experimental CFeT, mol/L
14
7
7.59
0.02 × 10−6
0.04 × 10−6
The results in Table 3 show that after the pure bornite mineral was dissolved for 7 h, the Cu and Fe concentrations in the solution are 0.02 × 10−6 and 0.04 × 10−6 mol/L, respectively. These results differ from the results in Table 2 by approximately 2 orders of magnitude. Thus, the abundance of Cu, Fe, Cl−, and SO42− can most likely be attributed to the release of mineral fluid inclusions rather than from bornite dissolution.
4. CONCLUSIONS The foregoing results and discussions yield the following conclusions: (1) The results of the infrared optical microscopy imaging of the bornite surface and shallow fluid inclusions as well as the SEM-EDS analysis of the residual inclusion position domain of bornite show that fluid inclusions exist in large amounts in bornite. The inclusions exhibit a directed distribution along the bornite crystal growth zone and are either isolated or concentrated. The inclusions take the following shapes: long strip and irregular shape. Inclusion body sizes fall between 3 and 40 μm. (2) From the quantitative analysis results of the release of fluid inclusions in bornite, a large amount of Cu and Fe, Cl−, and SO42− clearly existed in solution. The primary source of these elements is not the dissolution of the bornite, but rather the release of fluid inclusions in the minerals. (3) The ions released from the fluid inclusions in bornite are a new source of unavoidable ions in flotation pulp. The conclusion extends the research object and scope of flotation solution chemistry.
■
ASSOCIATED CONTENT
S Supporting Information *
Table A as described in the text. This material is available free of charge via the Internet at http://pubs.acs.org.
■
REFERENCES
(1) May, F.; Gock, E.; Vogt, V.; Bruser, V. Plasma-modification of sulfides for optimizing froth-flotation properties. Miner. Eng. 2012, 35, 67−74. (2) Chandra, A. P.; Gerson, A. R. A review of the fundamental studies of the copper activation mechanisms for selective flotation of the sulfide minerals, sphalerite and pyrite. Adv. Colloid Intefaces 2009, 145 (1−2), 97−110. (3) Subrahmanyam, T. V.; Forssberg, K. S. E. Mineralsolutioninterfacechemistry in minerals engineering. Miner. Eng. 1993, 6 (5), 493−454. (4) Subrahmanyam, T. V.; Forssberg, K. S. E. Grinding and flotation pulp chemistry of alowgradecopperore. Miner. Eng. 1995, 8 (8), 913− 921. (5) Chen, J. M.; Liu, R. Q.; Sun, W.; Qiu, G. Z. Effect of mineral processing wastewater on flotation of sulfide minerals. T. Nonferr. Metal. Soc. 2009, 19 (2), 454−457. (6) Pugh, R.; Stenius, P. Solutionchemistry studies and flotation behaviour of apatite, calcite and fluorite minerals with sodium oleate collector. Int. J. Miner. Process. 1985, 15 (3), 193−218. (7) Bicak, O.; Ekmekci, Z.; Can, M.; Ozturk, Y. The effect of water chemistry on froth stability and surface chemistry of the flotation of a Cu-Zn sulfide ore. Int. J. Miner. Process. 2012, 102, 32−37. (8) Coetzer, G.; du Preez, H. S.; Bredenhann, R. Influence of water resources and metal ions on galena flotation of Rosh Pinah ore. J. S. Afr. I. Min. Metall. 2003, 103 (3), 193−207. (9) Chen, G. L.; Tao, D. Effect of solution chemistry on flotability of magnesite and dolomite. Int. J. Miner. Process. 2004, 74 (1−4), 343− 357. (10) Hu, Y. H.; Chi, R.; Xu, Z. H. Solution chemistry study of salttype mineral flotation systems: Role of inorganic dispersants. Ind. Eng. Chem. Res. 2003, 42 (8), 1641−1647. (11) Zhang, Q.; Xu, Z.; Bozkurt, V.; Finch, J. A. Pyrite flotation in the presence of metal ions and sphalerite. Int. J. Miner. Process. 1997, 52 (2−3), 187−201. (12) Somasundaran, P.; Ananthapadmanabhan, K. P. Solution Chemistry of Flotation. Advances in Mineral Processing: a Half-Century of Progress in Application of Theory to Practice; New Orleans, Louisiana, Mar 3−5, 1986; pp 137−153. (13) Somasundaran, P.; Wang, D. Z. Solution Chemistry, Minerals and Reagents; Elsevier Science: Netherlands, 2006. (14) Wang, D. Z.; Hu, H. Solution chemistry of flotation; Science & Technology Press: China, 1988. (15) Finkelstein, N. P. The activation of sulphide minerals for flotation: a review (vol (52, pg 81, 1997). Int. J. Miner. Process. 1999, 55 (4), 283−286. (16) Hidalgo, J. L.; Gomez, M. A.; Caballero, M.; Cela, R.; PerezBustamante, J. A. Determination of Mo(VI) in tap-water and sea-water by differential-pulse polarography and co-flotation. Talanta 1988, 35 (4), 301−5. (17) Corin, K. C.; Reddy, A.; Miyen, L.; Wiese, J. G.; Harris, P. J. The effect of ionic strength of plant water on valuable mineral and gangue recovery in a platinum bearing ore from the Merensky reef. Miner. Eng. 2011, 24 (2), 131−137. (18) Cabezon, L. M.; Caballero, M.; Cela, R.; Perez-Bustamante, J. A. Simultaneous separation of copper, cadmium and cobalt from seawater by co-flotation with octadecylamine and ferric hydroxide as collectors. Talanta 1984, 31 (8), 597−602. (19) Lin, H. B.; Yin, W. Z.; Sun, C. Y. XPS analysis on adsorption law of metal ion on surface of silicate minerals. Non-Ferr. Min. Metallurgy 2003, 29, 21−24. (20) Zeng, Q. H.; Zhao, H.; Wang, D. Z. Influence of metal cations on cassiterite flotation. T. Nonferr. Metal. Soc. 2000, 10 (1), 98−101. (21) Bevilaqua, D.; Garcia, O.; Tuovinen, O. H. Oxidative dissolution of bornite by Acidithiobacillus ferrooxidans. Process. Biochem. 2010, 45 (1), 101−106. (22) Leja, J. Surface chemistry of froth flotation; Plenum Publishing Corp.: New York, 1982.
Table 3. Cu and Fe Concentrations of Natural Bornite Dissolution grinding time, min
Article
AUTHOR INFORMATION
Corresponding Author
*Tel./Fax: +86-13095315156. E-mail:
[email protected]. Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS This research project was supported by the Key Program of the N a t i o na l N a t u r a l Sc i e n c e F o u nd a t i o n o f C h i n a (KKGE201121001&51204078), Natural Science Foundation of Yunnan Province Education Department (2012J085), and Excellent Doctoral Dissertation Foundation of Kunming University of Science and Technology (41118011). 4900
dx.doi.org/10.1021/ie302721c | Ind. Eng. Chem. Res. 2013, 52, 4895−4901
Industrial & Engineering Chemistry Research
Article
High-Sulfidation Cu-Au Deposit. Geochim. Cosmochim. Acta 1995, 59 (19), 3909−3916. (44) Bailly, L.; Bouchot, V.; Beny, C.; Milesi, J. P. Fluid inclusion study of stibnite using infrared microscopy: An example from the Brouzils antimony deposit (Vendee, Armorican massif, France). Econ. Geol. Bull. Soc. 2000, 95 (1), 221−226. (45) Luders, V.; Gutzmer, J.; Beukes, N. J. Fluid inclusion studies in cogenetic hematite, hausmannite, and gangue minerals from highgrade manganese ores in the Kalahari manganese field, South Africa. Econ. Geol. Bull. Soc. 1999, 94 (4), 589−595. (46) Richards, J. P.; Kerrich, R. Observations of zoning and fluid inclusions in pyrite using a transmitted infrared light microscope (Lambda< or= 1.9 mu m). Econ. Geol. 1993, 88, 716−723. (47) Luders, V.; Ziemann, M. Possibilities and limits of infrared light microthermometry applied to studies of pyrite-hosted fluid inclusions. Chem. Geol. 1999, 154 (1−4), 169−178. (48) Kouzmanov, K.; Bailly, L.; Ramboz, C.; Rouer, O.; Beny, J. M. Morphology, origin and infrared microthermometry of fluid inclusions in pyrite from the Radka epithermal copper deposit, Srednogorie zone, Bulgaria. Miner. Deposita 2002, 37 (6−7), 599−613. (49) Roedder, E. Fluid inclusions. Reviews in Mineralogy. Miner. Soc. Am. 1984, 12, 444−445. (50) Eggins, S. M.; Kinsley, L. P. J.; Shelley, J. M. G. Deposition and element fractionation processes during atmospheric pressure laser sampling for analysis by ICP-MS. Appl. Surf. Sci. 1998, 127, 278−286. (51) Durrant, S. F. Laser ablation inductively coupled plasma mass spectrometry: achievements, problems, prospects (vol 14, pg 1385, 1999). J. Anal. Atom. Spectrom. 2000, 15 (2), 237−237. (52) Gunther, D.; Heinrich, C. A. Comparison of the ablation behaviour of 266 nm Nd: YAG and 193 nm ArF excimer lasers for LAICP-MS analysis. J. Anal. Atom. Spectrom. 1999, 14 (9), 1369−1374. (53) Gunther, D.; Horn, I.; Hattendorf, B. Recent trends and developments in laser ablation-ICP-mass spectrometry. Fresen J. Anal. Chem. 2000, 368 (1), 4−14. (54) Kesler, S. E.; Reich, M.; Jean, M. Geochemistry of fluid inclusion brines from Earth’s oldest Mississippi Valley-type (MVT) deposits, Transvaal Supergroup, South Africa. Chem. Geol. 2007, 237 (3−4), 274−288. (55) Crawford, M. L. Phase equilibria in aqueous fluid inclusions. In fluid inclusions: Applications to petrology. Miner. Assoc. Can. 1981, 6, 75−100. (56) Ding, J. Y.; Ni, P.; Rao, B. Synthetic fluid inclusion of CaCl2H2O system. Acta Pet. Sin. 2005, 21 (5), 1425−1428. (57) Czamanske, G. K.; Roedder, E.; Burns, F. C. Neutron Activation Analysis of Fluid Inclusions for Copper, Manganese, and Zinc. Science 1963, 26 (3565), 401−403.
(23) Finch, J. A.; Rao, S. R.; Nesset, J. E. Iron control in mineral processing. In 39th annual meeting of the Canadian mineral processors of CIM, Ottawa, Canada, Jan 23−25; Folinsbee, J., Ed.; CIM: Ottawa, 2007. (24) Dixon, D. G.; Mayne, D. D.; Baxter, K. G. Galvanox (TM) - A novel galvanically-assisted atmospheric leaching technology for copper concentrates. Can. Metall. Q. 2008, 47 (3), 327−336. (25) Cordoba, E. M.; Munoz, J. A.; Blazquez, M. L.; Gonzalez, F.; Ballester, A. Leaching of chalcopyrite with ferric ion. Part II: Effect of redox potential. Hydrometallurgy 2008, 93 (3−4), 88−96. (26) Petruk, W. Applied Mineralogy in the Mining Industry; Elsevier: New York, 2000. (27) Lundstrom, M.; Liipo, J.; Aromaa, J. Dissolution of copper and iron from sulfide concentrates in cupric chloride solution. Int. J. Miner. Process. 2012, 102, 13−18. (28) Acero, P.; Cama, J.; Ayora, C. Sphalerite dissolution kinetics in acidic environment. Appl. Geochem. 2007, 22 (9), 1872−1883. (29) Deng, J. S.; Wen, S. M.; Xian, Y. J.; Liu, J.; Liu, D. Spectroscopic Characterization of Dissolubility and Surface Properties of Chalcopyrite in Aqueous Solution. Spectrosc. Spect. Anal. 2012, 32 (2), 519−524. (30) Jianye, J.; Binming, L.; Xiande, X.; Daqing, W.; Yanjie, T.; Yan, W.; Jiancheng, W. Relationship between solubility of sulfides and solution pH value. J. Changchun Univ. Sci. Technol. 2001, 31, 241−246. (31) Liu, J.; Wen, S. M.; Xian, Y. J.; Deng, J. S.; Huang, Y. L. Dissolubility and surface properties of a natural sphalerite in aqueous solution. Miner. Metall. Proc. 2012, 29 (2), 113−120. (32) Hollister, L. S.; Crawford, M. L. Fluid inclusions: applications to petrology. A short course sponsored by the Mineralogical Association of Canada and held immediately prior to the Annual Meeting, Calgary, Alberta, May 7−10; Mineralogical Association of Canada, 1981; Vol. 6 p 304. (33) Philippot, P.; Menez, B.; Drakopoulos, M.; Simionovici, A.; Snigirev, A.; Snigireva, I. Mapping trace-metal (Cu, Zn, As) distribution in a single fluid inclusion using a third generation synchrotron light source. Chem. Geol. 2001, 173 (1−3), 151−158. (34) Canet, C.; Franco, S. I.; Prol-Ledesma, R. M.; Gonzalez-Partida, E.; Villanueva-Estrada, R. E. A model of boiling for fluid inclusion studies: Application to the Bolanos Ag-Au-Pb-Zn epithermal deposit, Western Mexico. J. Geochem. Explor. 2011, 110 (2), 118−125. (35) Anthony, E. Y.; Reynolds, T. J.; Beane, R. E. Identification of daughter minerals in fluid inclusions using scanning electron microscopy and energy dispersive analysis. Am. Mineral. 1984, 69, 1053−1057. (36) Campbell, A. R.; Robinson-Cook, S. Infrared fluid inclusion microthermometry on coexisting wolframite and quartz. Econ. Geol. 1987, 82, 1640−1645. (37) Campbell, A.; Robinson-Cook, S.; Amindyas, C. Observation of fluid inclusions in wolframite from Panasqueira, Portugal. Bull. Minér. 1988, 111, 251−256. (38) Farrow, C. E. G.; Watkinson, D. H.; Jones, P. C. Fluid inclusions in sulfides from north and south range Cu-Ni-PGE deposits, Sudbury structure, Ontario. Econ. Geol. 1994, 89, 647−655. (39) Molnar, F.; Watkinson, D. H.; Everest, J. O. Fluid-inclusion characteristics of hydrothermal Cu-Ni-PGE veins in granitic and metavolcanic rocks at the contact of the Little Stobie deposit, Sudbury, Canada. Chem. Geol. 1999, 154 (1−4), 279−301. (40) Shan, Q.; Niu, H. C. Studying of the composition of the single fluid inclusion using scanning electron microscopy and energy dispersive analysis. Acta Petrol. Sin. 2000, 16 (4), 711−714. (41) Campbell, A. R.; Hackbarth, C. J.; Plumlee, G. S.; Petersen, U. Internal features of ore minerals seen with the infrared microscope. Econ. Geol. 1984, 79, 1387−1392. (42) Campbell, A. R.; Panter, K. S. Comparison of Fluid Inclusions in Coexisting (Cogenetic) Wolframite, Cassiterite, and Quartz from StMichaels Mount and Cligga Head, Cornwall, England. Geochim. Cosmochim. Acta 1990, 54 (3), 673−681. (43) Mancano, D. P.; Campbell, A. R. Microthermometry of Enargite-Hosted Fluid Inclusions from the Lepanto, Philippines, 4901
dx.doi.org/10.1021/ie302721c | Ind. Eng. Chem. Res. 2013, 52, 4895−4901
