TMn | Mn4+ | TFe | SiO2 | Al2O3 | P | Ba | CaO |
53.7 | 51.4 | 0.92 | 0.95 | 1.01 | 0.29 | 7.87 | 0.32 |
Cite this article as: | Hao Liao, Shengen Zhang, Bo Liu, Xuefeng He, Jixin Deng, and Yunji Ding, Valuable metals recovery from spent ternary lithium-ion battery: A review, Int. J. Miner. Metall. Mater., 31(2024), No. 12, pp.2556-2581. https://dx.doi.org/10.1007/s12613-024-2895-7 |
As a fundamental raw material of the steel industry, manganese helps sustain the normal operation of the national economy, promote and expand the new energy industry, and support essential sources to advance high-tech and new industries involving power batteries, magnetic materials, etc. [1–3]. Manganese occurs in various substantial deposits. For industrial manufacturing, manganese ores are mainly manganese oxide, manganese carbonate, and manganese sulfide, of which pyrolusite ore is the foremost manganese oxide, containing 60wt%–63wt% TMn (total Mn) with the chemical formula of MnO2, which frequently coexists with hollandite [4]. The global reserves of manganese ore are abundant and widely distributed across various regions, whereas as exploitation proceeds annually, treasury of manganese-rich ores (TMn > 35wt%) decreases drastically [5]; hence, the realization of the resources of poor-manganese ores is imminent [6–7]. Most of the minerals with fine particle sizes are embedded in manganese ores with uneven distribution; there are multiple co-occurring and associated valuable metal minerals in the ores and a partially high content of harmful impurity components in the ores. In summary, manganese ores will inevitably be used to satisfy the requirements of manganese in metallurgy and chemical industry, so the comprehensive utilization of valuable components of manganese ores must be maximized.
The distribution of minerals in manganese ores in complex geochemical environments is characterized by dense relationships and fine-grained embeddedness. In geological records of different environments and origins, iron and manganese are always present in deposits because of their similar chemical and physical properties [8]. The existence of silicon, nickel, cobalt, copper, and other elements in the ore creates tremendous difficulty for the beneficiation and enrichment of manganese. The technical means of beneficiation for pyrolusite ore are broadly grouped into three categories: traditional beneficiation, chemical beneficiation, and pyrometallurgy. Traditional beneficiation methods, including gravity separation, strong magnetic separation, flotation, etc., focus on the simple mineral components and structure of pyrolusite ore [9–10]. Chemical beneficiation adds various reducing agents to extract metals in acidic solutions, so chemical beneficiation is suitable for low-grade and complex ores. The advantages of chemical beneficiation are a high recovery rate and comprehensive recovery of valuable components, but it has a sophisticated reaction process, restrictive conditions, and a relatively high production cost [11–12]. Advances in biotechnology in recent years have led researchers to investigate the effective recovery of manganese through the enhancement of bioleaching [13–14]. This beneficiation approach is promising because it has low energy consumption without the depletion of pharmaceuticals, but no industrial-scale production remains to be achieved at this point in time [12,15]. The fundamental principle of pyrometallurgy lies in controlling the temperature in accordance with various reduction temperatures associated with other elements, such as manganese, iron, and phosphorus, to accomplish selective reduction; carbon-based reductants are generally involved, including carbon monoxide [16–17], which are currently reported as petroleum coke [18], stone coal [19], and biomass charcoal [20–21]. Nonetheless, the consumption of such reductants is inconsistent with the current carbon-reducing development paradigm, since it consumes conventional fossil fuels and produces large amounts of environmentally polluting emissions [18,22–23]. The current roasting of manganese ore mainly relies on rotary kilns, shaft furnaces, and fluidized beds, among which fluidized beds exhibit higher production efficiency and superior heat transfer rates [24–25]. Fluidized roasting involves a gas–solid phase reaction. Previous reports focused on the reduction of manganese ores in combination with CO, H2, and CH4 gases [26–28], although most of the literature has been devoted to the reduction by CO [29]. Research on the application of methane (CH4) as a reducing agent revealed that methane cracking and the associated carbon deposition decreased the rate of the reduction reaction; hence, a new process remains under investigation for improvement [30–31]. H2 reduction is similar to CO reduction and is cleaner and more environmentally friendly [32–33]; however, there are fewer studies on H2 reduction [26]. Thus, this paper proposes a hydrogen-based mineral phase transformation technology based on fluidized roasting, i.e., hydrogen is used as a reducing agent to destabilize the existing structure of high-valence manganese oxides in the suspension state to reduce pyrolusite (MnO2) to manganosite (MnO) [34] for the subsequent wet leaching treatment or magnetic separation to improve the Mn/Fe ratio of the ore.
In this study, a regulatory mechanism study of reduction roasting in a hydrogen atmosphere system was systematically performed for high-purity pyrolusite ore to analyze the kinetics and mechanism of pyrolusite ore and elucidate the reduction characteristics and reaction process through mineral phase transformation technology. Furthermore, X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area determination, and scanning electron microscopy (SEM) were used to investigate the phase transformation regulation and microstructure evolution of pyrolusite during this process. The results establish a foundation and provide theoretical guidance for the efficient utilization of complex and refractory manganese ore resources.
High-quality massive natural pyrolusite ore was collected from Sichuan, China and underwent the crushing–grinding–shaking table treatment to yield enriched concentrates of qualified grades, which were used as the raw ore for the experiments. In accordance with the roasting experimental requirements, raw ore was ball milled until the selected particle size was less than 0.074 mm, and the mass fraction was 50% ± 1%. A multi-element chemical analysis was conducted, and Table 1 shows the results. Then, XRD was performed to mineralogically characterize the raw ore, as shown in Fig. 1.
TMn | Mn4+ | TFe | SiO2 | Al2O3 | P | Ba | CaO |
53.7 | 51.4 | 0.92 | 0.95 | 1.01 | 0.29 | 7.87 | 0.32 |
Fig. 1 and Table 1 show that the raw ore was dominated by tetravalent manganese (Mn4+), a large amount of pyrolusite ore, and small amounts of iron, barium, and other impurities, which are attributed to hollandite.
As demonstrated in Fig. 2, hydrogen-based mineral phase transformation experiments were performed with multifactor controlled variable tests in a laboratory-type roaster (OTF-1200S-S-FB, Hefei Kejing Material Technology Co. Ltd., Hefei, China). This roaster can withstand temperatures of up to 1100°C, which perfectly satisfies the experimental requirements. Before the experiment began, raw ore in the quartz tube was ventilated with nitrogen to complete the air replacement and fluidization of the ore particles. After the furnace temperature reached a predetermined value, the reducing gas was introduced, and timing was started. Upon completion of the experiments, the roasted products were cooled to room temperature in a nitrogen atmosphere, sealed, and prepared for subsequent elemental assays.
The determination of the indicator of the roasted product depends on the calculated distribution rate (∂) of Mn2+ in the roasted product (Eq. (1)) from the quantitative analysis results of chemical elements (mass fractions of Mn2+ and TMn), which helps assess the effectiveness of the pyrolusite reduction.
∂=ω(Mn2+)ω(TMn)×100% | (1) |
where ω(Mn2+) is the Mn2+ mass fraction and ω(TMn) is the total manganese mass fraction of the roasted products.
The kinetics of the pyrolusite in the H2 reduction experiments were determined in the same laboratory-type mineral phase transformation furnace at temperatures of 823 K (550°C), 873 K (600°C), 923 K (650°C), and 973 K (700°C). The process of pyrolusite ore gas–solid reduction adheres to the rule of step-by-step transformation; in accordance with Gais’ law, the complete transformation of MnO2 to MnO is defined as follows:
MnO2(s)+H2(g)=MnO(s)+H2O(g) | (2) |
For the raw ore with a total mass of 15.00 g (assuming that all manganese minerals exist in the form of pyrolusite), the purity of the pyrolusite was 84.94wt% according to the chemical analysis, the weight was 12.74 g, and the gangue mineral mass was 2.26 g. The reaction equilibrium is as follows:
mMnO=10.40α | (3) |
where α is the degree of conversion of pyrolusite ore to manganosite ore, wt%; mMnO is the mass of newborn manganosite (MnO) in the roasted product, g.
At this point, the remaining pyrolusite ore in the roasted product is mMnO2=12.74(1−α), and the mass of gangue is 2.26 g. Therefore, the mass fraction of nascent manganosite (ωMnO) in the roasted product is:
ωMnO=mMnOmMnO+mMnO2+2.26=10.40α15−2.34α | (4) |
ωMn2+=mMn2+mMnO=5571 | (5) |
where ωMn2+ is the mass fraction of Mn2+ ions in the roasted product.
The association of Eq. (4) with Eq. (5), which tabulates α, is as follows:
α=15ωMn2+8.06+2.34ωMn2+ | (6) |
Reaction rate v is obtained by differentiating the conversion degree α with respect to time t, and its unit is expressed as s−1. The kinetic equation of the reduction reaction of pyrolusite can be acquired via the degree of conversion, reaction rate, and reaction time. The most likely mechanism function was confirmed based on an analysis of the linear coefficients between data and fitting lines. The equations are as follows [35]:
v=dαdt=k(T)f(α) | (7) |
G(α)=∫α0dαf(α)=∫t0k(T)dt=k(T)t | (8) |
k(T)=Aexp(−EaRT) | (9) |
lnk=lnA−EaRT | (10) |
where f(α) is the kinetic function in differential form, G(α) is kinetic function in integral form, k is the temperature-dependent reaction rate constant (s−1), A is the pre-exponential factor (s−1), Ea is the apparent activation energy (J·mol−1), T is the temperature, and R is the gas constant with a value of 8.314 J·(mol·K)−1. Reaction rate constant k of the mechanism function at different reaction temperatures was substituted into Eq. (10). Regression calculations and linear fitting were performed on lnk and 1/T to obtain A and Ea.
The oxygen potential (ΔGoxidation)–temperature diagrams (commonly known as Ellingham diagrams) for various common oxidation reactions are thermodynamic tools that enable comparisons of the relative stability between oxides. When an oxide is at a lower position in the Ellingham diagram, it is more stable at the same temperature. Among the manganese oxides in Fig. 3(a), the stability of the oxides increases with decreasing valency, and manganosite (MnO) is the most stable. As demonstrated in Fig. 3(b), the manganese mineral reduction reaction depends less on the H2 atmosphere, and all of the reductions of MnO2 → Mn2O3 → Mn3O4 → MnO spontaneously progress [16].
Hydrogen functions as a reducing agent, and the reduction product consists of water vapor, which offers clean and environmentally friendly characteristics. Single-factor experimental investigations of the roasting time, roasting temperature, and H2 concentration were conducted. To ensure the effectiveness of the experiment, the raw ore was preheated for 3 min before the experiments started. The roasted product was cooled in a circulating N2 atmosphere, which prevented the re-oxidation of the roasted product by air.
The roasting time determines the adequacy of the reduction reaction, which is one of the significant factors that affect the distribution rate. Roasting time experiments with the experimental conditions labeled in the pictures were performed, and XRD analysis of the roasted products under different time conditions was performed; Fig. 4 shows the results.
Fig. 4(a) shows that the Mn2+ distribution rate reached 28.9% at 5 min of roasting time, increased to 92.4% at 20 min of roasting time, and was 98.44% at 30 min of reaction time. Thus, the roasting time is one of the key factors that affect the experimental results, the inadequate transformation of pyrolusite to manganosite is a consequence of insufficient roasting time, and the Mn2+ distribution rate increases with increasing roasting time [36]. When the distribution rate exceeded 90%, the reduction reaction of pyrolusite approached completion; hence, the increase in distribution rate slowed. According to Fig. 4(b), the diffraction peaks of MnO2, Mn2O3, Mn3O4, and MnO appeared in the roasted products when the roasting time was 5 min, which indicates that the reduction reaction of pyrolusite ore has initiated at this time. At 20 min, the diffraction peak of MnO2 disappeared, the intensity of the diffraction peaks of Mn2O3 and Mn3O4 gradually decreased, and the intensity of the diffraction peak of MnO continued to increase. Only the diffraction peaks of MnO were present when the roasting time was 25 min, which demonstrates that the transformation of the mineral phase essentially completed. Thus, the optimal roasting time is 25 min, and the Mn2+ distribution rate is 96.44%.
The roasting temperature affects the distribution rate of manganese mainly by influencing the chemical reaction rate; therefore, it is necessary to examine the effect of the roasting temperature on the reduction effect. Fig. 5 shows the distribution rates and XRD patterns of the roasted products.
Fig. 5(a) shows the trend of the distribution rate under different temperature conditions, and the Mn2+ distribution rate reached 76.7% at a roasting temperature of 450°C. When the roasting temperature continued to increase from 600°C, the distribution rate increased from 94% to 98% at 700°C. This increase occurred because the increase in roasting temperature increased the mineral reduction reaction rate, decreased the activation energy of the reaction, and favored the reaction [37]. However, after the roasting temperature had reached 600°C, further increases in temperature had a diminished effect on the pyrolusite reduction reaction, since the reaction was in a saturated state. According to Fig. 5(b), when the roasting temperature was 450°C, the diffraction peaks of MnO2, Mn2O3, and Mn3O4 were weak, and the diffraction peak of MnO had high intensity. The diffraction peaks of MnO2 and Mn2O3 disappeared with increasing roasting temperature to 550°C. At 600°C, the diffraction peak of Mn3O4 disappeared. Elevating the temperature clearly contributes to the occurrence of phase transformation. Hence, the optimal roasting temperature for the H2 reduction of pyrolusite ore is 650°C at a roasting time of 25 min.
The relationship between H2 concentration and reduction effect was investigated via various experiments with different H2 concentrations. The distribution rates and XRD results of the roasted products are summarized in Fig. 6.
Fig. 6(a) shows that the Mn2+ distribution rate improved from 31.2% to 96.4% when the concentration increased from 5vol% to 20vol%. This improvement is due to the increase in H2 concentration, which provided more opportunity for the effective contact between H2 molecules and minerals per unit time/space. Thus, the increase in distribution rate is positively promoted by increasing the H2 concentration. Fig. 6(b) indicates that the reduction reaction and intermediate product transformation reaction can occur at a 5vol% H2 concentration, which is consistent with the thermodynamic analysis results. When the H2 concentration increased to 20vol%, the diffraction peaks of Mn2O3 and Mn3O4 disappeared, and only the diffraction peak of MnO was present, which indicates that the transformation of MnO2 was nearly complete.
In summary, the optimal conditions for the experiment were a roasting time of 25 min, a roasting temperature of 650°C, and an optimal H2 concentration of 20vol%, to yield an Mn2+ distribution rate of 96.44% and MnO in the roasted product.
SEM and energy spectroscopy (EDS) analyses were performed on the raw ore and roasted product under optimal conditions to investigate the microstructural effects of reduction roasting on pyrolusite ore and the internal and surface structural evolution of the mineral particles.
In Fig. 7(a)–(c), the surface of the pyrolusite particles was intact and dense without cracks, and the particle section shows that the pyrolusite particles were seamless. Fig. 7(d)–(f) shows that microcracks of various widths appeared on the surface of the mineral particles after reduction roasting, and some of the particles presented an encapsulated structure according to the particle sections. According to the EDS spectra, the internal manganese content of the particles was low, and the external manganese content was high, which implies that the reduction process proceeded from the outside to the inside, and the cracks on the surface and interior of the ore particles increased the specific surface area of the particles.
The pore structure variation pattern of pyrolusite ore was explored via a specific surface area analyzer during the phase transformation. Fig. 8(a) reveals that according to the types of adsorption isotherm determined by the International Union of Pure and Applied Chemistry (IUPAC), the adsorption curve of the raw ore and roasted product is a type-III adsorption isotherm, which indicates that there was an interstitial structure in the mineral particles. Moreover, the roasted product decreased the retention ring area compared with that of the raw ore, which demonstrates that the roasting process resulted in a wider interstitial width and increased porosity of the mineral particles. The evolution of the pore structure attributed to roasting was also noted, and as shown in Fig. 8(b)–(c), the BET specific surface area of the raw ore was 8.1536 m2/g; however, the specific surface area of the roasted product was only 5.8870 m2/g. The H2 reduction clearly increased the pore size of mineral particles. Thus, the pore structure of approximately 4 nm in the raw ore was destroyed and replaced by larger cracks or pores, which decreased the specific surface area of the roasted product. Moreover, other pores may simultaneously merge or increase in size in response to the sintering of the particles, which increased the average pore size [38].
XPS is extremely sensitive to the material surface, and variations in the chemical state of the mineral surface significantly affect the shape of the photoelectron peak, which describes the surface chemical composition and manganese elemental valence of the raw ore and roasted products [39–40]. As Fig. 9(a) shows, XPS survey scans of the samples demonstrated the presence of Fe, O, and Mn.
The magnitude of the Mn 3s peak splitting can be used to distinguish the oxidation state of manganese, as shown in Fig. 9(b). The doublet separation energy difference (ΔEs) values were 4.78 and 6.14 eV for the spin-orbit peaks in the Mn 3s spectra of the raw ore and roasted product, respectively. With reference to previous literature [40–41], these peaks correspond to MnO2 and MnO, respective1y, which is consistent with the XRD results. Depending on the binding energy, the O 1s spectra were fitted by the lattice oxygen, oxygen vacancy, and physically adsorbed water on the surface of the composite with peaks at 529.11, 530.86, and 532.40 eV, respectively. The changes in number of oxygen vacancies and the change in content of different oxygen species are displayed in Fig. 9(c)–(d). Lattice oxygen is the bulk-phase oxygen in metal oxides. Oxygen vacancies are vacancies formed when oxygen atoms in the oxidized lattice of a metal are detached, which causes a lack of oxygen, and are simply defects when oxygen escapes from its lattice [42–44]. As shown in Fig. 9(c)–(d), the proportion of oxygen vacancies is much larger in the roasted product than in the raw ore, which can be corroborated from the transformation of mineral MnO2 to MnO.
During the transformation process from pyrolusite to manganosite, the SEM analysis (Fig. 7) shows that there were microcracks on the inside and surface of the particles of the roasted products, which later promotes the penetration of H2 into the particles and further reactions with the internal pyrolusite [45]. The cross section of the particles shows clear phase boundaries, and the reduction effect was greater on the outside than on the inside of the particles. In addition, the thermodynamic results in Section 3.1 demonstrate that the roasted products of pyrolusite are not homogenous. For a clearer and more intuitive representation of the reduction process of pyrolusite, the mineral phases of the products roasted at various roasting times were analyzed via XRD. Angular intervals (25°–45°) of the diffraction peaks were scanned. The relative contents of the phases were analyzed to characterize the relative tendency of the phase transformation, as shown in Fig. 10. When the roasting time was extended to 25 min, the relative contents of hausmannite and bixbyite fluctuated, whereas the relative content of manganosite gradually increased.
Consequently, our proposed mechanism of the hydrogen-based mineral phase transformation of pyrolusite can be summarized as follows:
(1) The phase transformation of pyrolusite ore proceeds step by step in the sequence of MnO2 → Mn2O3 → Mn3O4 → MnO, whereas the reduction of manganese oxides in each valence state is simultaneous.
(2) Through the reduction process, the reducing gas (H2) is adsorbed and pyrolusite is reduced from the surface layer to the core layer; eventually, all pyrolusite ore particles are reduced to manganosite.
Fig. 11 shows the variation curves of the degree of conversion α and reaction rate ν with increasing roasting time at different roasting temperatures. As shown in Fig. 11(a), at the same roasting temperature, with increasing roasting time, the degree of conversion rapidly increased and subsequently tended to be stable. In Fig. 11(b), increasing the roasting temperature appropriately accelerated the reaction rates and reduced the time required for the roasting reaction.
In the study of the hydrogen reduction kinetics of hematite, data processing occasionally adopts a model-fitting approach. To date, many scholars have established mechanism functions to describe the chemical reactions, which can be summarized into five categories: diffusion models, reaction-order models, power laws, geometrical contraction models, and nucleation models [46–49]. In this section, the degree of conversion α was substituted into 30 common kinetic mechanism functions (Table 2), and the linear fitting results, i.e., the correlation coefficients (R2), were calculated and are shown in Fig. 12.
No. | Differential function, f(α) | Integral function, G(α) | Reaction model |
1–8 | n(1−α)[−ln(1−α)]−(1/n−1) (n = 1, 2, 3, 4, 3/2, 1/4, 1/3, 1/2) | [−ln(1−α)]1/n (n = 1, 2, 3, 4, 3/2, 1/4, 1/3, 1/2) | A1/A2/A3/A4/A3/2/A1/4/A1/3/A1/2 |
9–14 | n(1−α)−(1/n−1) (n = 1/2, 1/3, 1/4, 2, 3, 4) | 1−(1−α)1/n (n = 1/2, 1/3, 1/4, 2, 3, 4) | R1/2/R1/3/R1/4/R2/R3/R4 |
15 | 1/2α−1 | α2 | D1 |
16 | [−ln(1−α)]−1 | α+(1−α)ln(1−α) | D2 |
17 | 3/2(1−α)2/3[1−(1−α)1/3]−1 | [1−(1−α)1/3]2 | D3 |
18 | 3/2(1−α)−1/3−1]−1 | 1−2/3α−(1−α)2/3 | D4 |
19 | 3/2(1+α)2/3[(1+α)−1/3−1]−1 | [(1+α)1/3−1]2 | D5 |
20–21 | (3/n)(1−α)2/3[1−(1−α)1/3]−(n−1) (n = 2, 1/2) | [1−(1−α)1/3]n (n = 2, 1/2) | D6/D7 |
22 | 3/2[(1−α)−1/3−1]−1 | 1−2/3α−(1−α)2/3 | D8 |
23–27 | (1/n)α−(n−1) (n = 4, 3, 2, 1, 2/3) | αn (n = 4, 3, 2, 1, 2/3) | P4/P3/P2/P1/P3/2 |
28 | 2(1−α)3/2 | (1−α)−1/2 | F1 |
29 | (1−α)2 | (1−α)−1 | F2 |
30 | (1/2)(1−α)3 | (1−α)−2 | F3 |
Fig. 12 shows that the correlation coefficients of different mechanism functions significantly differed, and the mechanism function with an average R2 value closest to 1 was likely the mechanism during the reduction reaction. The average correlation coefficients of the A3/2: f(α) = 3/2(1−α)[−ln(1−α)]1/3 and R2: f(α) = 2(1−α)1/2 mechanism functions (0.99800 and 0.99362, respectively) slightly varied but were optimal compared with those of the other equations. A3/2 refers to the random nucleation and growth model, with reaction order n = 3/2. Similarly, R2 represents the geometrical contraction model, also known as the two-dimensional contracting area model. The experimental data were subjected to a G(α)–t fitted equation (Eq. (8)), and the slope of the line, i.e., the reaction rate constant (k), is listed in Table 3 and Fig. 13.
Mechanism functions | Temperature / °C | Reaction rate constant, k / s−1 | R2 | Average R2 |
A3/2: G(α) = [−ln(1−α)]2/3 | 550 | 0.000957 | 0.99751 | 0.99800 |
600 | 0.001130 | 0.99772 | ||
650 | 0.001450 | 0.99865 | ||
700 | 0.001610 | 0.99812 | ||
R2: G(α) = 1−(1−α)1/2 | 550 | 0.000372 | 0.99248 | 0.99362 |
600 | 0.000432 | 0.99675 | ||
650 | 0.000524 | 0.99453 | ||
700 | 0.000564 | 0.99071 |
The two mechanism functions had similar apparent activation energies (Ea). To further determine the reduction reaction kinetic model mechanism function, it is necessary to deduce the theoretical reduction rate α and compare it with the actual reduction rate, which is consistent with a high degree of the best reaction mechanism model. Fig. 14 reveals that the theoretical values from the A3/2 model more proximally approach the experimental values with a consistent trend. By eliminating operational errors during the experimental process, one can determine that the isothermal kinetic model for the transformation of pyrolusite ore into hydrogen-based mineral phases is the random nucleation and growth model (n = 3/2). The apparent activation energy Ea is 24.119 kJ·mol−1, and the pre-exponential factor A is 0.03229 s−1.
In this study, a clean and efficient reduction of pyrolusite ore was realized through advanced mineral phase transformation technology, where hydrogen was adopted as a reducing agent, and a 96.44% distribution rate of divalent manganese (Mn2+) was achieved under optimal experimental conditions. A systematic roasting experimental approach was investigated based on the kinetics of the reduction reaction, phase transformation, and structural evolution of pyrolusite ore. The kinetic mechanism model of the pyrolusite reduction isotherm is the random nucleation and growth model (n = 3/2), the apparent activation energy Ea is 24.119 kJ·mol−1. Thermodynamic, XRD, and XPS analyses were performed to clarify the phase transformation law. As the reaction proceeded, the pyrolusite was gradually reduced in the following order: MnO2 → Mn2O3 → Mn3O4 → MnO, whereas manganese oxides in each valence state were simultaneously reduced. The BET and SEM analyses revealed that microcracks were generated on the surface of the particles in response to high-temperature and phase transformation, and the reduction of pyrolusite was accomplished from the surface layer to the core layer. The investigation results lay the foundation for key scientific aspects of efficiently utilizing complex and refractory manganese ore resources.
This work was sponsored by the National Natural Science Foundation of China (Nos. 52204412 and U2002212), the National Key R&D Program of China (No. 2021YFC1910504), the Fundamental Research Funds for the Central Universities (No. FRF-TP-20-031A1).
The authors declare no conflict of interest.
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TMn | Mn4+ | TFe | SiO2 | Al2O3 | P | Ba | CaO |
53.7 | 51.4 | 0.92 | 0.95 | 1.01 | 0.29 | 7.87 | 0.32 |
No. | Differential function, f(α) | Integral function, G(α) | Reaction model |
1–8 | n(1−α)[−ln(1−α)]−(1/n−1) (n = 1, 2, 3, 4, 3/2, 1/4, 1/3, 1/2) | [−ln(1−α)]1/n (n = 1, 2, 3, 4, 3/2, 1/4, 1/3, 1/2) | A1/A2/A3/A4/A3/2/A1/4/A1/3/A1/2 |
9–14 | n(1−α)−(1/n−1) (n = 1/2, 1/3, 1/4, 2, 3, 4) | 1−(1−α)1/n (n = 1/2, 1/3, 1/4, 2, 3, 4) | R1/2/R1/3/R1/4/R2/R3/R4 |
15 | 1/2α−1 | α2 | D1 |
16 | [−ln(1−α)]−1 | α+(1−α)ln(1−α) | D2 |
17 | 3/2(1−α)2/3[1−(1−α)1/3]−1 | [1−(1−α)1/3]2 | D3 |
18 | 3/2(1−α)−1/3−1]−1 | 1−2/3α−(1−α)2/3 | D4 |
19 | 3/2(1+α)2/3[(1+α)−1/3−1]−1 | [(1+α)1/3−1]2 | D5 |
20–21 | (3/n)(1−α)2/3[1−(1−α)1/3]−(n−1) (n = 2, 1/2) | [1−(1−α)1/3]n (n = 2, 1/2) | D6/D7 |
22 | 3/2[(1−α)−1/3−1]−1 | 1−2/3α−(1−α)2/3 | D8 |
23–27 | (1/n)α−(n−1) (n = 4, 3, 2, 1, 2/3) | αn (n = 4, 3, 2, 1, 2/3) | P4/P3/P2/P1/P3/2 |
28 | 2(1−α)3/2 | (1−α)−1/2 | F1 |
29 | (1−α)2 | (1−α)−1 | F2 |
30 | (1/2)(1−α)3 | (1−α)−2 | F3 |
Mechanism functions | Temperature / °C | Reaction rate constant, k / s−1 | R2 | Average R2 |
A3/2: G(α) = [−ln(1−α)]2/3 | 550 | 0.000957 | 0.99751 | 0.99800 |
600 | 0.001130 | 0.99772 | ||
650 | 0.001450 | 0.99865 | ||
700 | 0.001610 | 0.99812 | ||
R2: G(α) = 1−(1−α)1/2 | 550 | 0.000372 | 0.99248 | 0.99362 |
600 | 0.000432 | 0.99675 | ||
650 | 0.000524 | 0.99453 | ||
700 | 0.000564 | 0.99071 |