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Article

Selective Recovery of Copper from Acid Leaching Solution through Slow Release Sulfide Precipitant

by
Xianping Luo
1,
Zhizhao Yang
1,
Hepeng Zhou
1,*,
Yongbing Zhang
1,
Wei Sun
2 and
Haisheng Han
2
1
Jiangxi Province Key Laboratory of Mining and Metallurgy Environmental Pollution Control, Jiangxi University of Science and Technology, Ganzhou 341000, China
2
School of Minerals Processing and Bioengineering, Central South University, Changsha 410083, China
*
Author to whom correspondence should be addressed.
Minerals 2022, 12(12), 1571; https://doi.org/10.3390/min12121571
Submission received: 7 November 2022 / Revised: 25 November 2022 / Accepted: 30 November 2022 / Published: 7 December 2022
(This article belongs to the Section Mineral Processing and Extractive Metallurgy)
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Abstract

:
A new kind of sulfide precipitant, namely, slow release sulfide precipitant (SRSP), was developed and prepared first to realize the selective recovery of copper from an acid leaching solution. The experimental results indicated that SRSP as a precipitant could selectively and efficiently recover copper and the high purity of copper sulfide slag with a Cu grade of 48.16%, and a Cu recovery rate of 97.84% could be obtained. Moreover, copper in leaching solution could be recovered more efficiently and selectively by SRSP compared with Na2S. The results of H2S gas release, chemical reaction energy calculation, and SEM image analyses illustrated that realizing the selective recovery of copper mainly depended on the ions of S2− and HS− produced by the dissolution of SRSP. Moreover, the concentrations of S2− and HS− should always be kept at a low level in the process of selective recovery of copper; this is the biggest difference from the traditional precipitant and the key to preventing the escape of H2S gas in the copper recovery process. More pivotally, SRSP provides an alternative sulfide precipitant for the selective recovery of copper from the acid leaching solution of copper smelting dust.

1. Introduction

A large amount of copper smelting dust is produced in the process of copper smelting, which has the characteristics of large displacement, high content of valuable metal copper, difficult recovery, and high toxicity [1,2]. It can cause serious environmental harm and waste of resources [3]. First of all, copper is a strategic mineral resource in great shortage in China [4]. It is the core metal in the field of electric power, infrastructure construction, and new energy vehicles [5,6]. As the largest demand country for copper concentrate in the world, the copper concentrate consumption in China is about 35% of the total global output [7]. However, the copper resource reserves in China account for only 3.0% of the total global reserves; thus, it is difficult to be self-sufficient [8]. Therefore, China’s demand for copper concentrate is highly dependent on foreign countries, resulting in the serious restriction of industrial development [9,10]. Secondly, copper smelting dust is a typical representative of copper solid wastes [11]. Although it has a high content of valuable metal copper, large output, and great recycling value, it contains high concentrations of toxic arsenic substances [12,13]. Long term storage not only wastes land, but also a large amount of heavy metal ions enter the underground by the leaching of rainwater [14,15]. If copper smelting dust is directly returned to the smelting system, the balance of the copper smelting system will be destroyed due to the cycle and accumulation of copper smelting dust [16]. It will not only reduce the smelting efficiency, but also affect the normal operation of the smelting process [17]. Hence, the comprehensive treatment and recovery of copper smelting dust has great significance in relieving the external dependence of copper resources, promoting national economic development, and protecting the ecological environment [18].
Many scholars have studied the recovery of valuable copper components based on the physical and chemical characteristics of copper smelting dust [19,20]. Sulfuric acid is often used as a leaching agent in leaching processes to obtain acid copper leaching solution [21]. Moreover, the method of extraction, adsorption, ion exchange, and chemical precipitation are the most commonly used to recover or remove the copper component from the solution [22,23,24]. For example, monoclinic pyrrhotite was used to selective sulfide precipitation of copper ions from arsenic wastewater, and more than 96% of copper ions were removed [25]. In addition, a gas–liquid sulfidation reaction was proposed and applied to the separation of copper and arsenic from acidic wastewater; CuS with a high Cu grade could be obtained [26]. After comparing these common methods, we know that the method of sulfide precipitation in chemical precipitation has many advantages. For example, Cu2+ in acid solution can be precipitated in the form of CuS in a wide range of pH value, the Cu grade of copper sulfide slag is high, and solid–liquid separation efficiency is high, and the process is simple [27]. Thus, the method of sulfide precipitation recovery is the most economical and effective to recover the valuable copper component in the acid leaching solution. Moreover, Na2S is often used as a precipitant to selectively recover copper, which will quickly hydrolyze a large amount of S2− and HS− in the acid leaching solution. A part of S2− and HS− is combined with Cu2+ to recover copper components in the form of CuS, and another part of S2− and HS− is combined with H+ to release a large amount of H2S gas [28,29], resulting in the efficiency of selective recovery copper being low and the H2S resulting in serious harm. Therefore, it is necessary to develop an excellent performance sulfide precipitant to realize efficient copper recovery that is clean and highly selective [30].
This paper is based on the principle of slow release sulfide, and a slow release sulfide precipitant (hereinafter referred to as SRSP) with excellent performance was prepared by using metal ions, a sulfur source, and a surfactant as the main components. It can consume a large amount of H+ in acidic solution to gradually ionize S2− and HS− and combine with Cu2+. Therefore, the purpose of this study is to provide a new method for selectively and efficiently recovering copper. Firstly, the effects of SRSP dosage, pH value, and reaction time on copper selective recovery were investigated. Then, the contrastive experiment of copper selective recovery by SRSP and Na2S was studied to explain the excellent performance of SRSP. In addition, H2S gas release; chemical reaction energy calculation; and SEM images analysis were used to reveal the mechanism of efficient, clean, and selective copper recovery by using SRSP as a sulfide precipitant.

2. Experimental

2.1. Materials and Reagents

The acid leaching solution of copper smelting dust was taken from Western Mining Co., Ltd. (Qinghai Copper Co., Ltd., Xining, China) in Qinghai Province, China. The color of the leaching solution was blue because it contained a large amount of Cu2+. Moreover, ICP analysis showed that the contents of copper and arsenic in the acid leaching solution were 29,700 mg/L and 10,400 mg/L, respectively, and the original pH value of the leaching solution was 1.04. Its strong acidity and the high content of copper were suitable for the selective recovery study of copper.
FeCl2 required for the preparation of SRSP was purchased from Xilong Science Co., Ltd. (Shantou, China). MnSO4, ZnSO4, Na2S, and C12H25NaO3S were purchased from Shanghai McLean Biochemical Technology Co., Ltd. (Shanghai, China). Analytical grade H2SO4 was used as the leaching agent, and the pH value of the leaching solution was adjusted, which was produced by Xilong Science Co., Ltd. In order to reduce the influence of water ions on copper-selective recovery, ultrapure water produced by a UPH ultrapure water machine was used in the whole process of the test.

2.2. Preparation of SRSP

Using FeCl2, MnSO4, and ZnSO4 as metal ion sources, Na2S as a sulfur source, and C12H25NaO3S as surfactant, the SRSP could be obtained by reacting for 30 min according to the molar ratio of FeCl2:MnSO4:ZnSO4:Na2S:C12H25NaO3S of 5:1:1:7:0.015. According to the principle of chemical reaction, SRSP is a mixed nano–micron metal sulfide of FeS, MnS, and ZnS, or a nano–micron metal compound composed of Fe, Mn, Zn, and S elements. Figure 1 shows the SEM images of SRSP. It can be clearly seen that some particles of SRSP had good crystallinity, but a part of the particles had incomplete crystallization.

2.3. Copper Selective Recovery Experiments

According to the designed experiment process, 100 mL of the acid leaching solution of copper smelting dust was taken into a clean beaker for each test. Next, the pH value of the leaching solution was adjusted by sulfuric acid and transferred to a three-mouth flask and placed in a thermostatic water bath for heating and stirring. Then, the prepared SRSP was added to the flask for the selective recovery of copper, and the reaction temperature was controlled to 50 °C. After the reaction of copper, selective recovery ended, and solid–liquid separation was achieved through the circulating water multipurpose vacuum pump. A schematic diagram of the experimental setup is presented in Figure 2. The filtrate and the copper sulfide slag after vacuum drying were detected by ICP and XRF, respectively. The recovery rate of Cu and precipitation rate of As were calculated according to the weight of copper sulfide slag, volume of filtrate, and ICP and XRF analysis results.

2.4. H2S Gas Release Analysis

A SKY2000 portable hydrogen sulfide gas detector was used to detect and analyze the H2S release in the selective recovery process of copper. The unit storage time of H2S gas concentration was set to 5 s, and the stored concentration value was the average value within 5 s, and the unit was ppm. We inserted the gas guide pipe of the gas detector into the three-port flask when the copper selective recovery experiment was carried out. If H2S gas would escape during the chemical reaction, it would reach the H2S gas sensor through the air inlet of the detector under the action of the sampling pump, and the gas would be discharged from the exhaust hole of the detector after the H2S concentration value was stored. The stored data of the H2S concentration value could be driven and exported by Multi2019CN and plotted.

2.5. Chemical Reaction Energy Calculation

In this paper, the Gaussian software was used to calculate the chemical reaction energy in the recovery process of the copper slow-release sulfide precipitation. First, the software Gaussian View 6.0 was used to establish the structural model of the compound or ion to be calculated. Next, the established model was structurally optimized under the B3LYP/6-311G basis set of density functional theory (DFT). Then, the final energy was obtained after calculating the frequency of the compound or ion with the optimal structure under the condition of the same base group. It was necessary to pay close attention to ensure that the ∆G of the chemical reaction was equal to the sum of the product energies minus the sum of the reactant energies. The ease and sequence of each chemical reaction were judged by comparing the ∆G combined with the result of H2S gas release analysis to reveal the mechanism of a an efficient and clean process selective for copper precipitation recovery.

2.6. SEM Images Analysis

For SEM measurements, a model MLA650F field emission scanning electron microscope was used to analyze the SRSP and the recovered copper sulfide slag. The conductive adhesive had to be cut into squares of appropriate size and placed on the copper plate before SEM measurement, and a round cell climbing sheet with a diameter of 6 mm was placed in the middle of the conductive adhesive. Then, a small amount of analytical sample was taken to be tested into a clean beaker, and an appropriate amount of absolute ethanol was added as a dispersant. Next, a rubber pipette was used to absorb a small amount of sample on a round cell climbing sheet after the sample was evenly dispersed. The SEM measurement samples had to be dried by natural air or low temperature drying, and the samples had to be sprayed with gold to increase the conductivity before SEM analysis.

3. Results and Discussion

3.1. Copper Selective Recovery Results

3.1.1. Effect of SRSP Dosage

As presented in Figure 3, the Cu grade and As precipitation rate of copper sulfide slag were significantly affected by the molar ratios of SRSP to copper. However, the recovery rate of Cu always maintained a high index with an increased dosage of SRSP. On the one hand, when the molar ratios of SRSP to copper increased from 1:1 to 1.2:1, the Cu grade decreased from 47.16% to 40.88%, and the As precipitation rate increased from 8.47% to 18.55%. On the other hand, the recovery rate of Cu could be as high as 98.12% when the molar ratio of SRSP to copper was set to 1:1. Therefore, the results indicated the selective recovery of copper from the acid leaching solution of copper smelting dust by using SRSP as a sulfide precipitant. In addition, the optimum molar ratio of SRSP to copper should be 1:1.

3.1.2. Effect of pH

The relationship between the pH value and the effect of copper selective recovery is shown in Figure 4. Obviously, the pH value of the acid leaching solution had significant influence on Cu grade and As precipitation rate. The Cu grade of copper sulfide slag first increased from 43.16% to 47.42 and then decreased to 45.58% with the pH value being gradually reduced. Moreover, the precipitation rate of As decreased from 15.87% to 7.65% when the original pH value was adjusted to 0.70. The results illustrated that reducing the pH value properly could improve the efficiency of selective recovery of copper from the acid leaching solution. Hence, the leaching solution pH value should be adjusted to 0.70 for the better effect of copper selective recovery.

3.1.3. Effect of Reaction Time

SRSP as a sulfide precipitant can gradually dissolve and ionize S2− and HS− to react with Cu2+ in the acidic leaching solution. Therefore, sufficient chemical reaction time should be guaranteed to improve the effect of copper recovery due to the strong acid resistance of SRSP. As seen in Figure 5, it was obvious that the grade and recovery rate of Cu gradually improved as the chemical reaction time increased. It should be noted that the copper sulfide slag with the Cu grade and recovery rate of 47.39% and 97.42%, respectively, could be obtained when the reaction time was 40 min; moreover, the grade and precipitation rate of As were only 1.33% and 7.75%, respectively. Thus, in order to efficiently achieve selective recovery of copper, the optimum reaction time should be 40 min.

3.2. Contrastive Results of Copper Selective Recovery by SRSP and Na2S

3.2.1. Contrastive Experiment

Based on the study of copper selective recovery by SRSP, Na2S was used as a precipitant to form a contrast with SRSP. The results of copper precipitation recovery differences between SRSP and Na2S is presented in Table 1. From the results of Na2S as a precipitant, the copper sulfide slag with a Cu grade of 48.16% and a Cu recovery rate of 86.74% could be obtained. It indicated that the Cu grade difference of copper sulfide slag was very small when using SRSP and Na2S to recover copper. However, the precipitation rate of As was about 10% higher than that of SRSP, and the recovery rate of Cu was about 12% lower than that of SRSP when Na2S was used as a precipitant. Therefore, the results illustrated that copper could be recovered more efficient and selective by SRSP compared with Na2S.

3.2.2. H2S Gas Release Analysis

In the experiment of copper selective recovery by SRSP and Na2S, special attention should be paid to the fact that obvious H2S gas could be smelled in the process of copper recovery by Na2S. During the entire process of selectively recovering copper, no H2S gas escaped using SRSP as a sulfide precipitant. Thus, the H2S gas release behavior using SRSP and Na2S as precipitants was studied to explain and highlight the environmental performance of SRSP. The result is shown in Figure 6.
It can be clearly seen from Figure 6 that the H2S gas concentration always stayed at 0 ppm when using SRSP to realize the recovery of copper from the acid leaching solution. However, the Na2S used to recover copper could release a large amount of H2S gas, and the concentration of H2S gas rose rapidly and remained at about 430 ppm for 9 min. The result proved that SRSP as sulfide precipitant avoided the serious harm of H2S gas when recovering copper from acid leaching solution. From the physical and chemical characteristics of SRSP and the chemical reaction perspective, on the one hand, SRSP had strong stability and acid resistance to prevent its structure from being completely destroyed on short notice in the acidic solution. On the other hand, SRSP was composed of a large number of metal sulfides; it should have consumed H+ to produce some H2S gas in the acid leaching solution. H2S gas can be rapidly dissolved into solution and converted into hydrogen sulfuric acid. Then S2− and HS− were produced to react with Cu2+ by the ionization of hydrogen sulfuric acid. Moreover, the key to preventing H2S gas escapes in the copper precipitation recovery process was to keep the concentrations of S2− and HS− in the solution at low levels. In this way, it could not only realize the precipitation recovery of copper, but also avoid the production and escape of excessive H2S gas.

3.3. Chemical Reaction Energy Calculation Analysis

The results of the copper selective recovery experiment and H2S gas release behavior showed that no H2S gas escaped from the reaction system using SRSP to realize the recovery of copper. Hence, the energy of the chemical reaction was calculated to reveal the mechanism of copper selective recovery without H2S gas escapes combined with the possible components of SRSP. The possible chemical reaction equations and the corresponding calculation results of ∆G are shown in Table 2.
It can be seen from Table 2 that SRSP as a sulfide precipitant needed roughly two processes to realize the selective recovery of copper from acid leaching solution. First, FeS, MnS, and ZnS contained in SRSP could consume a large amount of H+ in the acid leaching solution to produce H2S gas. However, H2S gas produced by SRSP dissolution could be absorbed by the leaching solution and ionized to produce the ions of S2− and HS−. Secondly, the ions of S2− and HS− reacted with Cu2+ contained in the acid leaching solution to form the precipitation of CuS. From the results of the chemical reaction energy calculation, the ∆G values of S2− and HS− that reacted with Cu2+ to form CuS were −2720.36 kJ/mol and −2105.98 kJ/mol. This indicated that the binding capacity of S2− and Cu2+ was greater than that of HS− and Cu2+, and the sulfide precipitation reaction of copper could easily [31]. In addition, the ∆G value of ZnS that reacted with Cu2+ to form CuS was −283.18 kJ/mol, which illustrated that the displacement reaction could occur between Cu2+ and ZnS. On the whole, achieving the selective recovery of copper mainly depended on the chemical reaction of S2− and HS− with Cu2+. It is noteworthy that H2S gas also could be produced in the process of copper precipitation when SRSP was used as a sulfide precipitant, but all the H2S gas may dissolve into the solution due to the small amount and slow generation rate.
In summary, the concentrations of S2− and HS− should always be kept at a low level in the process of selective recovery of copper due to the strong acid resistance of SRSP. This is the key to preventing the escape of H2S gas from the reaction system of copper selective recovery. Moreover, low ion concentrations of S2− and HS− in the acid leaching solution also had great significance in reducing the side reaction of As2S3 formation and improving the separation efficiency of copper and arsenic. Therefore, the selective recovery of copper from the acid leaching solution of copper smelting dust could be efficiently realized by SRSP.

3.4. SEM Images Analysis

As seen in Figure 7, the SEM images of copper sulfide slag were mainly honeycomb, semi honeycomb, and flocculent. A large number of irregular flocci were easy to gather, which improved the particle size of precipitated slag and provided an ability to increase solid–liquid separation efficiency. As seen in Figure 1 and Figure 7, it was obvious that there were large differences of the SEM image characteristics between SRSP and copper sulfide slag, which indicated that SRSP had a violent chemical reaction, generating a large number of new sediment in the acid leaching solution [32], and the component content of copper sulfide slag was completely different from that of SRSP. Therefore, realizing the recovery of copper from acid leaching solution mainly relied on the S2− and HS− produced by the dissolution of SRSP reacted with Cu2+ to form CuS.

4. Conclusions

In this paper, an SRSP with excellent performance was developed and prepared for the first time to realize the selective recovery of copper without H2S gas harm. From the experimental results of copper selective recovery, the purity of copper sulfide slag with high Cu grade was about 48%, and a Cu precipitation rate of about 98% could be obtained when the molar ratio of SRSP to copper, the leaching solution pH, and the reaction time were 1:1, 0.70, and 40 min, respectively. Moreover, copper could be recovered more efficiently and selectively by SRSP compared to Na2S. The results of H2S gas release, chemical reaction energy calculation, and SEM image analyses illustrated that realizing the selective recovery of copper mainly depended on the S2− and HS− produced by the dissolution of SRSP. Moreover, the concentrations of S2− and HS− should always be kept at a low level in the process of selective recovery of copper; this is the key to preventing the escape of H2S gas in the process of copper recovery. On the whole, the selective recovery of copper from the leaching solution of copper smelting dust can be efficiently achieved using SRSP as a sulfide precipitant.

Author Contributions

Conceptualization, X.L., H.Z. and H.H.; methodology, X.L., Z.Y., H.Z., Y.Z., W.S. and H.H.; validation, Z.Y.; formal analysis, X.L., Z.Y., H.Z. and Y.Z.; investigation, X.L. and Z.Y.; resources, H.Z.; writing-original draft preparation, Z.Y.; writing-review and editing, H.Z.; visualization, X.L., Y.Z. and W.S.; data curation, X.L., Z.Y., Y.Z., W.S. and H.H.; project administration, H.Z.; funding acquisition, H.Z. All authors have read and agreed to the published version of the manuscript.

Funding

This research was funded by the National Key Research and Development Program (grant no. 2018YFC19016); the Program of Qingjiang Excellent Young Talents, Jiangxi University of Science and Technology (grant no. JXUSTQJBJ2020002); and the Youth Jinggang Scholars Program in Jiangxi Province (grant no. QNJG2020048).

Data Availability Statement

Not applicable.

Conflicts of Interest

The authors declare no conflict of interest.

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Figure 1. SEM images of slow release sulfide precipitant. (a) 10,000×; (b) 50,000×.
Figure 1. SEM images of slow release sulfide precipitant. (a) 10,000×; (b) 50,000×.
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Figure 2. Schematic diagram of copper precipitation recovery experiment setup: 1—water bath thermostat; 2—SRSP; 3—thermometer; 4—magnetic rotor; 5—three mouth flask.
Figure 2. Schematic diagram of copper precipitation recovery experiment setup: 1—water bath thermostat; 2—SRSP; 3—thermometer; 4—magnetic rotor; 5—three mouth flask.
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Figure 3. Effect of different molar ratios of SRSP to copper on copper selective recovery (pH value: 0.70, reaction time: 40 min).
Figure 3. Effect of different molar ratios of SRSP to copper on copper selective recovery (pH value: 0.70, reaction time: 40 min).
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Figure 4. Effect of different pH values on copper selective recovery (molar ratio of SRSP to copper: 1:1, reaction time: 40 min).
Figure 4. Effect of different pH values on copper selective recovery (molar ratio of SRSP to copper: 1:1, reaction time: 40 min).
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Figure 5. Effect of different reaction times on copper selective recovery (molar ratio of SRSP to copper: 1:1, pH value: 0.70).
Figure 5. Effect of different reaction times on copper selective recovery (molar ratio of SRSP to copper: 1:1, pH value: 0.70).
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Figure 6. The H2S gas concentration at different times in the copper recovery process (experimental conditions: molar ratio of SRSP/Na2S to copper: 1:1, pH value: 0.70).
Figure 6. The H2S gas concentration at different times in the copper recovery process (experimental conditions: molar ratio of SRSP/Na2S to copper: 1:1, pH value: 0.70).
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Figure 7. SEM images of copper sulfide slag: (a) 50,000×; (b) 100,000×; (c) 100,000×; (d) 200,000×.
Figure 7. SEM images of copper sulfide slag: (a) 50,000×; (b) 100,000×; (c) 100,000×; (d) 200,000×.
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Table
Table 1. The results of the contrastive experiment of copper selective recovery by SRSP and Na2S (experimental conditions: molar ratio of SRSP/Na2S to copper: 1:1, pH value: 0.70, reaction time: 40 min).
Table 1. The results of the contrastive experiment of copper selective recovery by SRSP and Na2S (experimental conditions: molar ratio of SRSP/Na2S to copper: 1:1, pH value: 0.70, reaction time: 40 min).
Type of Sulfide PrecipitantCu Grade (%)As Grade (%)Cu Recovery Rate (%)As Precipitation Rate (%)
Na2S48.163.0186.0417.19
SRSP47.221.2598.067.31
Table
Table 2. The possible chemical reaction equations and corresponding calculation results of ∆G in the copper precipitation process.
Table 2. The possible chemical reaction equations and corresponding calculation results of ∆G in the copper precipitation process.
NumberChemical Reaction Equations∆G (kJ/mol)
1FeS + 2H+ = H2S + Fe2+−598.22
2MnS + 2H+ = H2S + Mn2+−753.38
3ZnS + 2H+ = H2S + Zn2+−1054.26
4S2− + Cu2+ = CuS−2720.36
52HS− + Cu2+ = CuS + H2S−2105.98
6ZnS + Cu2+ = CuS + Zn2+−283.13
7S2− + 2H+ = H2S−3491.49
8HS− + H+ = H2S−1438.55
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Luo, X.; Yang, Z.; Zhou, H.; Zhang, Y.; Sun, W.; Han, H. Selective Recovery of Copper from Acid Leaching Solution through Slow Release Sulfide Precipitant. Minerals 2022, 12, 1571. https://doi.org/10.3390/min12121571

AMA Style

Luo X, Yang Z, Zhou H, Zhang Y, Sun W, Han H. Selective Recovery of Copper from Acid Leaching Solution through Slow Release Sulfide Precipitant. Minerals. 2022; 12(12):1571. https://doi.org/10.3390/min12121571

Chicago/Turabian Style

Luo, Xianping, Zhizhao Yang, Hepeng Zhou, Yongbing Zhang, Wei Sun, and Haisheng Han. 2022. "Selective Recovery of Copper from Acid Leaching Solution through Slow Release Sulfide Precipitant" Minerals 12, no. 12: 1571. https://doi.org/10.3390/min12121571

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