Process and mechanism of recovering layered double hydroxides (LDHs) from acid mine drainage (AMD) and synergetic

removal of manganese... https://www.sciencedirect.com/science/article/abs/pii/S221334372301583X

Journal of Environmental Chemical Engineering

Volume ��, Issue �, October ����, ������

Process and mechanism of recovering layered double hydroxides (LDHs) from acid mine
drainage (AMD) and synergetic removal of manganese
Qingsheng Xu a, Zhengbo Yue a b c , Rui Deng a b, Xinquan Wang a, Xin Chuai d, Kai Zhang d, Jin Wang a b c

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Abstract

The neutralization-precipitation method is widely used for treating acid mine drainage (AMD). However, the accumulation of sludge and the requirement for a high pH for the precipitation
of Mn2+ limit the widespread application of this technology. In this work, layer double hydroxides (LDHs) were obtained by chemical neutralization of AMD, and the mechanism of LDHs for
synergistic removal of Mn2+ was investigated by studying the morphological of metal elements during the neutralization process. The results showed that pH=8.5 was the critical condition
for the formation of LDHs, and the sludge mainly consisted of Mg-Al-LDHs and manganese oxides. With increasing pH, Mn2+ was synergistically removed by LDHs through ion exchange (at
the site 6) and complexation (with Mg-O). At pH=9.0, the concentration of Mn2+ was reduced to 1.5 mg/L, but it should be noted that high pH could destroy the structure of LDHs. Moreover,
LDHs recovered from actual AMD were also found to have the ability to remove environmental pollutants. These findings not only enhance our understanding of the morphological change
of metal elements during the neutralization process and the mechanism of Mn2+ removal, but also provide new insights for the recycling and utilization of neutralized sludge.

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Introduction

Acid mine drainage (AMD) refers to the acidic wastewater formed by pyrite (FeS2) or other sulfide ore exposed to oxygen, water and microorganisms during mining operations [31]. The
water quality of AMD has the following characteristics. First, the pH is neutral or below, typically between 1.8 and 7.3, and most are extremely acidic (pH < 4) [28]. Secondly, AMD carries
large number of anions and cations. Currently, the main cations in AMD which caused the most toxic to ecosystem are Al3+, Ca2+ and Mg2+ [3], not least of Fe3+, Zn2+, Mn2+, Cu2+, Pb2+ and
other highly toxic heavy metal elements (Table S1) [24], while the anions are mainly sulfate [28], [3]. With the development of the mining industry, the long-term accumulation of AMD
will seriously pollute the water and soil and destroy the diversity of microorganisms in the surrounding environment. It has become a severe challenge for the control of environmental
pollution to China and the world [18], [6]. Therefore, it is urgent to find an inexpensive and efficient method to treat AMD.

AMD treatment is mainly divided into physical, chemical and biological methods [26]. Among them, the physical method consumes a lot of human and material resources, usually
generating high cost [3]. Bioremediation effect is easily affected by biological growth environment and toxic ions [26]. Relatively speaking, chemical treatment has the advantages of strong
adaptability and high efficiency, which is more widely used [18]. Neutralization as the main chemical method to treat AMD at present has attracted wide attention. However, there are still
some bottlenecks in neutralization treatment. It is known that the neutralization method changes the pH in AMD and purifies the water through the precipitation and co-precipitation of
metal ions, so this method will produce a large amount of metal sludge [23], which is considered as hazardous waste that needs further safe disposal [13], [28]. However, the treatment of
AMD containing manganese is more difficult, because the pH required in the process is higher than other metals. A comparison of Table S2 shows that Mn2+ begins to precipitate at pH= 8.0
and completely precipitates at pH= 10.0. Currently, most countries have clear requirements for wastewater discharge standards. Take China as an example, the effluent pH should be
between 6 and 9, and the concentration of heavy metals is also limited (Mn2+ ≤ 2.0 mg/L). Therefore, conventional methods are not only expensive, but also can not meet the requirements
of effluent, which puts forward higher demands for enterprises and sewage treatment plants to meet the discharge standards. It can be seen that the landfill of sludge and the effective
treatment of Mn2+ are the biggest difficulties in the promotion of neutralization method at present. There is an urgent need for relevant research to address the above-mentioned issues in
order to break the restrictions faced in the promotion of the neutralization method.

At present, there are some studies on the recovery of valuable by-product schwertmannite from AMD by adjusting pH, but this method has some limitations [17], [39]. However, its
synthesis conditions are not only limited by the concentration of iron ions, but also need to be carried out under acidic conditions [30], so this is obviously not suitable for the treatment of
AMD containing manganese.

Layered double hydroxides (LDHs) is lamellar compounds with general formula [M2+1−xM3+x (OH)2](An−)x/n·mH2O, where M2+ are divalent metals (e.g., Mg2+, Zn2+, Fe2+, Cu2+, Mn2+, etc.),
M3+ are trivalent metals (e.g., Al3+, Fe3+, etc.), An- are anions (e.g., SO42-, CO32-, Cl-, etc.), and x is the M3+/(M3+ + M2+) molar ration [2]. Currently, LDHs synthesis methods include
hydrothermal approach, anion exchange method and co-precipitation method. Hydrothermal method, also known as the one-pot method, was for LDHs preparation. The salt solutions
containing M2+ and M3+ are mixed and the reaction process is under high temperature and high pressure conditions in a closed pressure vessel, followed by centrifugation, washing, and
drying to obtain the final product [16]. Anion exchange is used to adjust the structure of LDHs, enlarge the channels for ion diffusion and storge, and increase the number of available active
sites [40]. The rule of preparation is that high valence anions are easier to enter between the layers to replace low valence anions [46]. The co-precipitation method involves mixing two or
more metal salt solutions and adjusting the pH of the solution by adding NaOH and Na2CO3. Under the action of the precipitant NaOH, different metals in the solution crystallize and
precipitate simultaneously, resulting in the desired LDHs [40]. By comparison, the process of recovering LDHs from AMD by pH regulation is most similar to the co-precipitation method
[10]. Therefore, some scholars have focused on the recovery of LDHs from wastewater by co-precipitation. For example, Peligro et al. obtained Mg-Al-CO32--LDHs by co-precipitation in
simulated wastewater, and the material was applied to the adsorption of Cu2+, Pb2+ and Zn2+ pollutants with good results [1]. Frau et al. synthesized LDHs in AMD rich in divalent metal
ions and poor in trivalent metal ions by adding aluminum salt, which enhanced the removal of Zn, Ni, Pb and Mn [7]. Huang et al. added Mg-Al-flocculant to swine wastewater and kept n
(Mg:Fe)= 2:1. The removal efficiency of total phosphorus (TP) and chemical oxygen demand (COD) by the coagulated Mg-Fe-LDHs were 82.55 % and 98.51 %, respectively. In addition, Mg-
Fe-LDHs coagulated sludge can also be applied to the catalytic degradation of organic matters after pyrolysis [14]. These show that LDHs itself has the function of ion exchange and

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Process and mechanism of recovering layered double hydroxides (LDHs) from acid mine drainage (AMD) and synergetic removal of manganese... https://www.sciencedirect.com/science/article/abs/pii/S221334372301583X

complexing pollutants, especially suitable for the remediation of heavy metal wastewater. However, the above studies only used LDHs as a material and focused on the recovery application
and removal results of LDHs, lacking research on the mechanism of LDHs formation. In fact, the essence of the LDHs formation during the neutralization process lies in the morphology
change of the metal elements. In-depth research not only provides theoretical guidance for the performance regulation of LDHs but also, provides insights into the removal mechanism of
heavy metals (such as Mn2+) in AMD.

Since AMD usually possesses a low pH and the optimal pH regulation implies an acidic to alkaline process. Under weakly acidic conditions (pH≤5), trivalent metal ions such as iron and
aluminum precipitate completely, and these hydroxides provide precursors for the formation of LDHs. At this time, most of SO42- exists as the form of M-SO42-. However, with the further
increase of pH, SO42--M (M represents for metal) dissociates [35], and these independent SO42- is extremely easy to be adsorbed by metal precipitation. Since SO42- is the only main
intercalation anion of LDHs, this process will strongly influence the spatial structure of LDHs sludge [2], [29]. It should be noted that in the current research, the metal elements that form
LDHs are mostly in a single valence state (such as Mg2+, Al3+, etc.) [19], and the reaction conditions are often more stringent (such as high-temperature hydrothermal treatment, overnight
reaction, etc.). Even if there are variable valence metal elements (such as Mn, Cu, Co, etc.) in the solution [9], [20], they also participate in the formation of LDHs. The reaction conditions for
neutralizing AMD are a rapid and mild process, so there may be multiple phases of Mn2+ precipitates, which is crucial for understanding the removal mechanism of Mn2+. In addition,
whether too high pH will also break the metal bonds of the laminates of LDHs is also a question to be considered. These processes are important for understanding the state migration of
metal elements in AMD.

Therefore, it is of great significance to deeply explore the mechanisms of LDHs formation regulated by AMD, which not only can reveal the change of element occurrence state in AMD, but
also has important value for the recovery and application of LDHs. This paper intends to change pH to simulate neutralization reaction and induces LDHs recovered from AMD at different
pH, analyzing the in-situ formation mechanism of LDHs and the removal path ways of Mn2+ under the influence of pH. This work has not only effectively dealt with the pollution problem
of AMD, but also deepened the understanding of elemental morphological changes and pollutant removal pathways during the neutralization process, and has implications for future
sludge recycling and recovery work.

Section snippets

In situ induction of LDHs and adsorption experiment

The water quality indicators of an actual AMD in Maanshan, Anhui Province was determined. To study the formation process of sludge, it was necessary to eliminate the interference of
impurities. Therefore, the four highest concentrations of heavy metal ions were selected and sulfate was used to prepare simulated wastewater (Table S3). The concentration of simulated
acid mine drainage with initial pH=3.0 was shown in Table S3 which was prepared by MgSO4, MnSO4, Al2(SO4)3·18H2O and Fe2(SO4)3. 10 % …

Changes in physicochemical properties of sludge

Results showed that the average particle size of chemical sludge varied between 20 and 25 µm when the solution pH was adjusted from 7.0 to 8.0. However, when pH is 8.5, the particle size
rapidly decreased and thus the surface area increased (Fig. 1a). It was mainly because AMD contained a large amount of Al3+. When the pH was adjusted to 5.0, Al3+ can be fully
precipitated in the process of LDHs synthesis, which effectively improved the density and stability of sludge [38], [5]. The zeta…

Conclusion

In this paper, LDHs was recovered from simulated AMD, the mechanism and formation of neutralization sludge was revealed by studying the changes in the occurrence of metal elements
during the neutralization process, which can synergistically remove manganese. SEM, XRD, and FTIR results showed that at pH=8.5, the neutralization sludge consisted of Mg-Al-LDHs and
manganese oxides, and the crystal structure of LDHs was optimal at pH=9.0 because excessively high pH could destroy its lattice chain…

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CRediT authorship contribution statement

Qingsheng Xu: Conceptualization, Methodology, Investigation, Validation, Data curation, Formal analysis, Writing – original draft, Writing – review & editing. Zhengbo Yue: Resources,
Writing – review & editing, Supervision, Data curation, Supervision, Project administration. Rui Deng: review & editing, Investigation. Xinquan Wang: Validation, Investigation. Xin Chuai:
Data analysis and discussion. Shaoping Wang: Data analysis and discussion. Jin Wang: Conceptualization, Writing – review &…

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.…

Acknowledgments
This research was funded by the National Natural Science Foundation of China (Grant U20A20325 and U19A20108) and Key Research and Development Plan of Anhui (2022107020015).…

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