Recovery of Manganese from Spent Batteries ... - ACS Publications

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Recovery of Manganese from Spent Batteries Using Guar Meal as a Reducing Agent in a Sulfuric Acid Medium Sait Kursunoglu* and Muammer Kaya Department of Mining Engineering, Division of Mineral Processing, Eskisehir Osmangazi University, 26480 Eskisehir, Turkey ABSTRACT: The reductive leaching of manganese from mixed zinc−carbon and alkaline battery powder using guar meal as a new reducing agent in a sulfuric acid medium was investigated. The effects of the sulfuric acid concentration, amount of guar meal, leaching temperature, leaching time, and stirring speed were tested. The optimal leaching conditions for −88 μm particles were determined to be a sulfuric acid concentration of 2 mol L−1, a guar meal concentration of 100 g L−1, a stirring speed of 400 rpm, a leaching time of 180 min, and a leaching temperature of 70 °C. Under these conditions, 99.7% of the manganese was leached. The zinc was almost completely dissolved without a reducing agent because zinc oxide dissolved directly in the sulfuric acid medium. The SEM−EDX, FT-IR, and XRD results showed that no manganese-containing phases were detected in the remaining leach residue.

1. INTRODUCTION Manganese plays an important role in the development of various industrial fields, such as the production of zinc−carbon and alkaline batteries, steel production, and the preparation of dietary additives, fertilizers, fine chemicals, nonferrous alloys, and some medicines.1−4 The consumption of rich manganese ores has focused attention on the possible exploitation of lowgrade manganese ores and wastes. In addition, low-grade manganese ores and wastes have generated much interest as a potential source of associated valuable metals, such as zinc, nickel, copper, vanadium, chromium, and molybdenum.3 Therefore, several hydrometallurgical processes have been developed for these ores and wastes involving the dissolution of manganese as a soluble sulfite or nitrate and the purification of the obtained liquor by techniques such as precipitation (as sodium or potassium hydroxide), solvent extraction, and electrowinning. A zinc−carbon battery consists of a zinc case that serves as both a container and negative terminal. The positive terminal is a carbon rod surrounded by a mixture of manganese dioxide and carbon powder. The electrolyte is a paste of zinc chloride and ammonium chloride dissolved in water. A carbon rod serves as the current collector for the positive electrode. The battery is inserted into a steel case with a plastic separator. As the battery is discharged, zinc is oxidized, and manganese dioxide is reduced. A simplified overall battery reaction can be written as Zn + 2MnO2 → ZnO + Mn2O3 (1)

and wastes by using a reducing agent in an acidic medium, such as roasting followed by reductive acid leaching,5 pyrite reductive leaching,6 iron(II) sulfate reductive leaching,7 aqueous sulfur dioxide reductive leaching,8,9 mixed methanol−sulfuric acid solution reductive leaching,10 phenol reductive leaching,11 lactose reductive leaching,12,13 sucrose reductive leaching,14,15 glucose reductive leaching,16−19 sawdust reductive leaching,13,20 corncob reductive leaching,21 oxalic acid reductive leaching,1,22 citric acid and ascorbic acid reductive leaching,23,24 waste newspaper reductive leaching,25 hydrogen peroxide reductive leaching,2,26 cane molasses reductive leaching,27 biogas residual reductive leaching,28 and activated carbon powder reductive leaching.4 The following reactions describe the dissolution of zinc oxide and manganese oxides (Mn3O4, Mn2O3, MnO2, and MnO) from mixed zinc−carbon and alkaline battery powders. ZnO and MnO are fully dissolved by sulfuric acid according to eqs 3 and 4:

MnO + H 2SO4 → MnSO4 + H 2O

(4)

Mn2O3 + H 2SO4 → MnO2 + MnSO4 + H 2O

(5)

Mn3O4 + 2H 2SO4 → MnO2 + 2MnSO4 + 2H 2O

(6)

As shown in eqs 5 and 6, manganese dioxide cannot be leached by sulfuric acid directly. However, manganese dioxide’s oxidizing ability improves in the acidic medium.27 To obtain a high manganese leaching efficiency, a reducing agent must be added to the acidic solution. Guar gum is a polysaccharide composed of α-D-galactose (C6H12O6) and β-mannose (C6H12O6) in varying proportions depending on the source.29,30 Guar meal, Received: Revised: Accepted: Published:

(2)

Recently, much effort has been made to develop a commercial hydrometallurgical process to recover low-grade manganese ores © 2013 American Chemical Society

(3)

According to eqs 5 and 6, the dissolution of Mn2O3 and Mn3O4 is partial in a sulfuric acid medium because of the formation of MnO2:

In an alkaline battery, the negative terminal is made of zinc powder, which provides more surface area for increased current, and the positive terminal is composed of manganese dioxide. The active materials in these batteries are manganese dioxide, an aqueous alkaline electrolyte, and powdered zinc metal. The electrolyte is a concentrated solution of KOH. A simplified overall battery reaction can be written as 2Zn + 3MnO2 → 2ZnO + Mn3O4

ZnO + H 2SO4 → ZnSO4 + H 2O

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May 27, 2013 November 27, 2013 December 3, 2013 December 3, 2013 dx.doi.org/10.1021/ie401682f | Ind. Eng. Chem. Res. 2013, 52, 18076−18084

Industrial & Engineering Chemistry Research

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which is used in the reductive leaching process, is essentially composed of the same polysaccharide. In this system, guar meal was hydrolyzed to release galactose and mannose in the acidic conditions, where they act as reducing agents. The chemical reaction that takes place during the dissolution of manganese dioxide by guar meal is similar to the dissolution of glucose (C6H12O6), as shown in eq 7:14,31 12MnO2 + C6H12O6 + 12H 2SO4 = 12MnSO4 + 6CO2 ↑ +18H 2O

The aim of this study was to investigate a new reductant for manganese recovery from mixed zinc−carbon and alkaline battery powder using sulfuric acid leaching in the presence of guar meal (fodder) as a reducing agent. The effects of the sulfuric acid concentration, amount of guar meal, leaching temperature, leaching time, and stirring speed were investigated. The zinc leaching efficiency from the mixed battery powder was also studied in the absence of a reducing agent.

Figure 1. Experimental setup: 1, reactor; 2, mechanical stirrer; 3, glass condenser; 4, circulating water bath; 5, temperature controller; 6, hot water circulation.

Table 1. Composition of the Crushed Battery Cells component

battery powder

steel cases

papers

plastics

moisture

wt %

55.3

28.94

6.12

2.25

7.40

(7)

2. EXPERIMENTAL SECTION 2.1. Materials and Methods. Spent AA- and AAA-sized zinc−carbon and alkaline batteries were collected from the

Table 2. Chemical Compositions of the Unwashed and Washed Battery Powders element wt % unwashed washed

Mn

Zn

Cl

K

Mg

Si

Fe

Ni

S

Al

31.16 32.80

28.21 32.92

5.42 1.29

2.59 0.24

0.81 0.27

0.79 0.62

0.77 0.84

0.46 0.54

0.41 0.28

0.35 0.30

Figure 2. XRD pattern of the washed battery powder. 18077

dx.doi.org/10.1021/ie401682f | Ind. Eng. Chem. Res. 2013, 52, 18076−18084


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powder was determined. The dried battery powder was mixed carefully to ensure its homogeneity and then ground to the required particle size (−88 μm) for 30 min in a laboratory bond ball mill. All of the leaching tests were performed with this battery powder fraction. The reductive leaching tests were performed using varying amounts of guar meal (with a particle size of −1.18 mm), 5 g of battery powder, and 100 mL of sulfuric acid in a 250 mL waterjacketed reactor equipped with a reflux condenser. The battery powder slurry was stirred at the required temperature in a temperature-controlled circulating water bath with a mechanical stirrer for a specified leaching time. At the end of each leaching test, the battery powder in the reactor was filtered, and the residue was washed with distilled water. The filtrate was then diluted with 5% nitric acid for analysis. The manganese concentration during the leaching process was measured using atomic absorption spectroscopy. The leaching efficiency was calculated by comparing the amount of leached metal in the liquor to the amount in the input. The experimental setup used in the tests is shown in Figure 1. In the reductive leaching tests, Merck-grade, concentrated sulfuric acid, 97% by weight (d = 1.84 g cm−3), was used.

Table 3. Technical Composition of the Guar Meal component

%

test method

moisture cured protein cured oil fiber ash

10 ± 3 50 ± 5 4±1 12 ± 2 5±1

GAFTA 130-IS:7874-1975 GAFTA 130-IS:7874-1975 GAFTA 130-IS:7874-1975 GAFTA 130- IS:7874-1975 GAFTA 130-IS:7874-1975

Table 4. Composition of the Mineralogical Fraction of the Guar Meal

a

component

mass, %

component

mass, %

Na2O MgO SiO2 P2O5 SO3 Cl K2O CaO

0.047 1.250 0.976 1.225 0.283 0.021 1.279 0.408

MnO Fe2O3 Co2O3 NiO ZnO ZrO2 LOIa

0.013 0.057 0.009 0.010 0.005 0.010 94.407

Loss on ignition.

battery collection bins at Eskisehir Osmangazi University in Eskisehir, Turkey. The batteries were first dismantled by a laboratory hummer crusher and then dry-screened with a 2 mm sieve to manually remove the steel cases, plastics, and papers. The obtained battery powder was incubated in an oven at 105 ± 5 °C for 24 h. The moisture content of the battery

3. RESULTS AND DISCUSSION 3.1. Composition of the Battery Cells. Table 1 shows the composition of the crushed battery cells. The chemical composition of the battery powder was analyzed using a Philips PW-2404 X-ray fluorescence spectrometer. Before

Figure 3. FT-IR spectra of the guar meal. 18078



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Figure 6. Effect of the leaching time and temperature on the manganese leachability at a guar meal concentration of 100 g L−1, a sulfuric acid concentration of 2 mol L−1, and a stirring speed of 400 rpm.

Figure 4. Effect of the sulfuric acid concentration on manganese and zinc leachability without a reducing agent at a leaching temperature of 70 °C, a leaching time of 180 min, a liquid-to-solid ratio of 20:1, and a stirring speed of 400 rpm.

product, has no additional chemicals or preservatives, and is a non-GMO product. Guar meal contains amino acids such as isoleucine, proline, arginine, and tyrosine. The technical composition of the guar meal is given in Table 3. The mineralogical fraction of the guar meal was analyzed by X-ray fluorescence spectrometry, as presented in Table 4. The Fourier transform infrared (FT-IR) spectroscopy results of the guar meal are shown in Figure 3. The IR bands in the region between 3000 and 2800 cm−1 show C−H stretching modes. The peak in the spectra near 3300 cm−1 is due to the O−H stretching vibration of the polymer and water involved in hydrogen bonding. The peaks in the spectra between 800 and 1200 cm−1 represent the highly coupled C−C−O, C−O−H, and C−O−C stretching modes of the polymer backbone. The associated water molecules cause the band near 1650 cm−1 in the spectra. The absorption band near 1655 cm−1 shows the polymer’s increased association with water molecules.41 3.3. Effect of the Sulfuric Acid Concentration. The leaching tests were performed at initial sulfuric acid concentrations ranging from 0.15 to 2 mol L−1 without a reducing agent. In all of the tests, the leaching time, leaching temperature, stirring speed, and liquid-to-solid ratio were kept constant at 180 min, 70 °C, 400 rpm, and 20:1 mLg−1, respectively. The results shown in Figure 4 illustrate that the leaching efficiencies of manganese and zinc increased as the sulfuric acid concentration increased. The leaching efficiency of zinc increased slightly as the sulfuric acid concentration increased to 1 mol L−1 and then remained constant as the sulfuric acid concentration increased further. Increasing the sulfuric acid concentration from 0.15 to 2 mol L−1 significantly increased the leaching efficiency of manganese from 39.25% to 60.85%. A mineralogical study of the mixed zinc−carbon and alkaline battery powder identified hausmannite as the primary manganese mineral in the powder. In addition, waste battery powder contains other manganese oxides, such as Mn3O4, Mn2O3, and MnO.4,22−24 The dissolution of manganese dioxides requires a highly acidic medium to completely recover manganese, which results in consumption of the H+ ions. Therefore, an initial sulfuric acid concentration of 2 mol L−1 was chosen for the subsequent reductive leaching experiments.

Figure 5. Effect of the guar meal and temperature on the manganese leachability at a leaching time of 180 min, a stirring speed of 400 rpm, and a sulfuric acid concentration of 2 mol L−1.

reductive leaching, the battery powder was washed with distilled water to remove salts, including potassium and chloride, from the battery powder. The chemical compositions of the unwashed and washed battery powders are given in Table 2. The washed battery powder contained approximately 66% valuable metals (zinc and manganese) by weight. The mineralogical composition of the washed battery powder was determined by a Rigaku Rint 2000 X-ray diffractometer using Cu Kα at 1.54 Å, calibrated with a silicon standard for alignment of the θ/2θ radiation generated at 30 mA and 40 kV. On the basis of the X-ray diffraction (XRD) analysis shown in Figure 2, the major phases in the washed battery powder were hausmannite (Mn3O4), simonkolleite (Zn5(OH)8Cl2·H2O), graphite (C), and zincite (ZnO). 3.2. Content of the Guar Meal. Processed guar meal is a high-protein animal and poultry feed stuff. Guar meal is the byproduct that is obtained after the guar gum is extracted from the guar seed (Cyamopsis tetragonoloba) of the leguminous plant. The meal is processed by toasting at a high temperature to remove the natural trypsin inhibitor and to enhance the meal’s nutritive value and digestibility. Guar meal is rich in proteins and carbohydrates, is a 100% natural agricultural 18079



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temperatures and guar meal amounts (Figure 5). When the temperature was increased from 30 to 70 °C, the leaching efficiencies of manganese increased from 67.23% to 99.7% at a guar meal concentration of 100 g L−1. The efficiency of manganese strongly depends on the leaching temperature and amount of guar meal. To achieve maximal manganese leaching efficiency, the leaching temperature and amount of guar meal were determined to be 70 °C and 100 g L−1, respectively. 3.5. Effects of the Leaching Time and Temperature on Reductive Leaching. Figure 6 illustrates the effect of the leaching time on the leaching efficiency of manganese at different temperatures. The other leaching conditions remained constant in the tests. As shown in this figure, the efficiency of manganese increased slightly with increasing leaching time up to 180 min. A manganese dissolution of 90.93% was obtained after 60 min, and a dissolution of 99.7% was obtained after 180 min in a 2 mol L−1 sulfuric acid concentration at 70 °C. Therefore, a longer leaching time and a higher temperature increased the dissolution of manganese. The optimal leaching time was determined to be 180 min at 70 °C because most of the manganese in the system dissolved under these conditions. 3.6. Effect of the Stirring Speed on Reductive Leaching. To determine the optimal stirring speed, the experiments were conducted at a sulfuric acid concentration of 2 mol L−1, guar meal concentrations of 40 and 60 g L−1,

Figure 7. Effect of the stirring speed on the manganese leachability at a leaching time of 180 min, a leaching temperature of 70 °C, and a sulfuric acid concentration of 2 mol L−1.

3.4. Effects of the Guar Meal and Temperature on Reductive Leaching. To evaluate the effect of the guar meal, a series of leaching tests were performed in which the amount of guar meal was varied from 40 to 100 g L−1, while the sulfuric acid concentration was maintained at 2 mol L−1. The manganese leaching efficiencies increased with increasing

Figure 8. XRD pattern of the reductive leaching residue. 18080



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Figure 9. FT-IR analyses of the washed battery powder and reductive leaching residue.

a leaching time of 180 min, a leaching temperature of 70 °C, and stirring speeds of 200, 400, and 600 rpm. The results in Figure 7 show that the manganese leachability increased slightly with increasing stirring speed up to 400 rpm, after which further increases in the stirring speed showed a negligible effect on the manganese recovery. The dependence of the leaching process on the stirring speed is indicative of a diffusion-controlled leaching process. The effect of diffusion on manganese leaching can be minimized by increasing the stirring speed. To ensure complete dispersion and stirring, all of the subsequent experiments were conducted at a stirring speed of 400 rpm. 3.7. Analyses of the Washed Battery Powder and Leaching Residue by XRD and FT-IR. The mineralogical forms of the battery powder sample after the reductive leaching treatment were investigated by XRD, and the result is shown in Figure 8. One solid leach residue, obtained with a sulfuric acid concentration of 2 mol L−1, a guar meal concentration of 100 g L−1, a temperature of 70 °C, a stirring speed of 400 rpm, and a time of 180 min, was chosen for XRD analysis. After 180 min of reductive leaching, no manganese-containing materials were detected in the residue. FT-IR analysis of the washed battery powder, as shown in Figure 9, is in agreement with the patterns produced by manganese oxides, commercial zinc oxide, and simonkolleite that have been reported in the literature.32−39 Julien and

Figure 10. SEM image of the reductive leaching residue.

Massot indicated that IR spectroscopy provides more reliable information about the manganese oxide phases and yields than XRD.40 The absorption at 527 cm−1 is characteristic of simonkolleite, and the IR spectrum of a commercial zinc oxide powder shows a broad band below 550 cm−1, which is the 18081



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Figure 11. EDX analysis of the reductive leaching residue.

characteristic adsorption of zinc oxide. The IR bands in the region 1000−400 cm−1 reveal information about the MnO6 octahedron. The high-frequency bands of the IR absorption spectrum located at 629 cm−1 are assigned to MnO2. The zincand manganese-containing peaks disappeared, as demonstrated by FT-IR analysis after reductive leaching. This result suggests that most of the manganese content was leached from the sample by using guar meal in a sulfuric acid medium. 3.8. Morphological Study and Characterization of the Reductive Leaching Residue. A surface morphology study was performed after reductive leaching by scanning electron microscopy (SEM) coupled with energy-dispersive X-ray (EDX; Jeol JSM-5600 LV). The resulting SEM image is presented in Figure 10. The SEM image of the leaching residue shows that the waste particles are heterogeneous in size and have a rough surface structure. EDX analysis of the leaching residue and the EDX results are shown in Figure 11 and Table 5. EDX analysis verified that the manganese-containing phases disappeared, as indicated by the XRD and FT-IR results. Therefore, the results of the XRD, FT-IR, and SEM−EDX studies indicated that 99.7% of the manganese was dissolved from the mixed zinc−carbon and alkaline battery powder under the optimal reductive leaching conditions. 3.9. Comparison of Previous Reductive Leaching Studies with the Present Study. Many studies have been performed to reduce tetravalent manganese from raw ores and secondary sources using organic reductants, including sawdust,

Table 5. EDX Analysis of the Spectrum element

intensity (cs−1)

error 2σ

atom %

concentration

C O Na Al Si Cl Fe total

633.14 91.81 1.82 23.43 50.43 14.62 58.67

11.253 4.285 0.603 2.165 3.176 1.710 3.426

74.154 23.279 0.069 0.434 0.801 0.187 1.076 100.000

65.221 27.274 0.116 0.857 1.647 0.485 4.400 100.000

units wt wt wt wt wt wt wt wt

% % % % % % % %

corncob, molasses, lactose, glucose, sucrose, oxalic acid, citric acid, and ascorbic acid. The reduction of tetravalent manganese to the bivalent state is necessary because manganese(II) is readily leached. In the battery powder, manganese is present in both the bivalent and tetravalent states. Total dissolution of zinc and manganese oxides can be achieved by acidic reductive leaching using different acids and reductants.12,16 A manganese sulfate and zinc sulfate solution is obtained, together with other dissolved metals. The aqueous solution is sent to a precipitation step where manganese is precipitated by sodium or potassium hydroxide at pH 10 as a form of manganese hydroxide.24 Table 6 compares the previous and present study results. Under the tested experimental conditions, the highest manganese recovery was achieved using guar meal. The current market value of the guar meal is approximately 15−20 cents kg−1.44 Compared to 18082



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Table 6. Comparison of Previous Studies with the Present Study ore/battery type

reagents

leaching time (min)

stirring speed (rpm)

120

200

manganese ore

1.9 M H2SO4 with 60 g L−1 cane molasses 5% (v/v) H2SO4 with 5 g of sawdust 1.9 M H2SO4 with 3 g of corncob 0.543 M H2SO4 with 30.6 g L−1 oxalic acid 1.5 M H2SO4 with 20 g L−1glucose

manganese ore

2 M HCl with 0.4 M H2O2

zinc−carbon and alkaline batteries zinc−carbon batteries

stochiometric H2SO4 and ascorbic acid 2 M H2SO4 with 10 mL of H2O2

180

zinc alkaline batteries

2 M H2SO4 with 9 g L−1 lactose

zinc−carbon and alkaline batteries

manganese ore manganese ore manganese ore manganese ore

temperature (°C)

recovery (%)

ref(s)

90

1:5

Mn: 97

27

240

90

1:10

Mn: 74.4

20

60 105

85 85

1:10 1:20

Mn: 92.8 Mn: 98.4

21 1

240

70

1:10

16

60−95

1:12

Zn: 100 Mn: 94.8 Zn: 98 Mn: >97 Mn: 97

60 200

90

200

25

180

200

90

0.5 M H2SO4 with 13 g L−1 ascorbic acid

180

200

70

zinc−carbon and alkaline batteries

1 M H2SO4 with 3 g of activated carbon

180

400

80

mixed zinc−carbon and alkaline batteries

2 M H2SO4 with 60 g L−1 guar meal

180

400

70

1:20

2 23

1:20

Zn: 93.3 Mn: 82.2 Zn: 100 Mn: 98 Zn: 100

24

1:20

Mn: 99.2 Zn: 84.08

4

Mn: 86.39 Mn: 99.7

42 43

present study

in Eskisehir, Turkey. The authors are grateful to Agricultural Engineer Iskender Kip from the Bandirma, Turkey, branch of Agro Fodder for supplying the guar meal.

the other reductants, guar meal is considered to be a new, costeffective, and nonhazardous waste reductant material.

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4. CONCLUSIONS A reductive leaching process for manganese recovery from mixed zinc−carbon and alkaline battery powder has been successfully demonstrated using guar meal as a new reducing agent in a sulfuric acid medium. The results indicate that the manganese leaching efficiency increased as the amount of guar meal and the leaching time increased. The manganese leaching efficiency from mixed zinc−carbon and alkaline battery powder strongly depended on the leaching temperature. The optimal leaching conditions for the tested samples were determined to be a sulfuric acid concentration of 2 mol L−1, a guar meal concentration of 100 g L−1, a stirring speed of 400 rpm, a leaching time of 180 min, and a leaching temperature of 70 °C with particles smaller than 88 μm. Under these conditions, the leaching efficiency of manganese was 99.7%. The SEM-EDX, FT-IR, and XRD results verified that no manganese-containing phases were detected in the remaining leach residue. These results illustrate that guar meal may be used as a new reducing agent for manganese recovery from spent zinc−carbon and alkaline battery powder in a sulfuric acid medium.

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solid-to-liquid ratio

REFERENCES

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AUTHOR INFORMATION

Corresponding Author

*Tel.: +90-5446266735. Fax: +90-2222290535. E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work was supported by the Research Projects Funding Unit of Eskisehir Osmangazi University (Project BAP 2009/15018) 18083



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