Application of dirty-acid wastewater treatment technology in non-ferrous metal smelting industry: Retrospect and prospect.

Dirty-acid wastewater (DW) originating from the non-ferrous metal smelting industry is characterized by a high concentration of H2SO4 and As. During the chemical precipitation treatment, a significant volume of arsenic-containing slag is generated, leading to elevated treatment expenses. The imperative to address DW with methods that are cost-effective, highly efficient, and safe is underscored. This paper conducts a comprehensive analysis of three typical methods to DW treatment, encompassing technical principles, industrial application flow charts, research advancements, arsenic residual treatment, and economic considerations. Notably, the sulfide method emerges as a focal point due to its minimal production of arsenic residue and the associated lowest overall treatment costs. Moreover, in response to increasingly stringent environmental protection policies targeting new pollutants and carbon emissions reduction, the paper explores the evolving trends in DW treatment. These trends encompass rare metal and sulfuric acid recycling, cost-effective H2S production methods, and strategies for reducing, safely disposing of, and harnessing resources from arsenic residue.

Strategy of optimizing anaerobic digestion of cassava distiller wastewater using a novel automatic biological incubation system.

Due to the drawbacks of using fossil fuels and the need to mitigate global warming caused by increasing greenhouse gas emissions, agricultural biomass for bioenergy production is gaining great interest around the world. This work presented a study at a biochemical plant in Lianyungang, Jiangsu Province, China to maximize methane production from cassava distiller wastewater. The plant's annual production of cassava distiller wastewater is more than 3 million tons and currently was treated using a series of 5000 m3 Internal Circulation (IC) reactors. Modification was applied at No.19 IC reactor by connecting it to two 1 m3 automatic biological incubators called Information Bio-Booster (IBB). The effluent of the IC reactor was fed into the IBBs and iron, cobalt and nickel were added directly in the IBBs. The function of the IBBs was to regulate the microbial community. Afterwards, the microorganisms in the IBBs were pumped back into the IC reactor to participate in the methane production reaction. Daily net increase of methane content and COD removal reached 8.02% and 33% respectively in No.19 IC reactor comparing to the unadjusted reactors. Preliminary lab experiments found that improvements of biogas production, enhanced COD removal and VS removal was closely related to the enhancement of anaerobic microbial communities' diversity and the promotion of enzyme activity through the addition of the metal salts. Daily economic value could be estimated to be $218 which indicated the application potential of using the proposed system to enhance anaerobic digestion at industrial plants for bioenergy production.

Changes of MRGs and ARGs in Acinetobacter sp. SL-1 used for treatment of Cr(VI)-contaminated wastewater with waste molasses as carbon source.

Antibiotic resistance genes (ARGs) may be synergistic selected during bio-treatment of chromium-containing wastewater and causing environmental risks through horizontal transfer. This research explored the impact of self-screening bacterium Acinetobacter sp. SL-1 on the treatment of chromium-containing wastewater under varying environmental conditions. The findings indicated that the optimal Cr(VI) removal conditions were an anaerobic environment, 30 °C temperature, 5 g/L waste molasses, 100 mg/L Cr(VI), pH = 7, and a reaction time of 168 h. Under these conditions, the removal of Cr(VI) reached 99.10 %, however, it also developed cross-resistance to tetracycline, gentamicin, clarithromycin, ofloxacin following exposure to Cr(VI). When decrease Cr(VI) concentration to 50 mg/L at pH of 9 with waste molasses as carbon source, the expression of ARGs was down regulated, which decreased the horizontal transfer possibility of ARGs and minimized the potential environmental pollution risk caused by ARGs. The study ultimately emphasized that the treatment of chromium-containing wastewater with waste molasses in conjunction with SL-1 not only effectively eliminates hexavalent chromium but also mitigates the risk of environmental pollution.

Ternary cycle treatment of high saline wastewater from pesticide production using a salt-tolerant microorganism.

The material of this study is provided by biological aerobic treatment of high saline wastewater from pesticide production. The microorganism used for biodegradation has been identified by gene-sequencing as a strain of Bacillus sp. SCUN. The best growth condition for the salt-tolerant microorganism has been studied by varying the pH, immobilized microorganism dosage and temperature conditions. The feasibility of pretreating wastewater in ethyl chloride production containing 4% NaCl has been discussed. It was found that under the pH range of 6.0-8.0, immobilized microorganism dosage of 1.5 g/L, temperature of 30 °C, and NaCl concentration of 0-3%, the microorganism achieves the best growth for biodegradation. After domestication, the strain can grow under 4% NaCl. This salt-tolerant microorganism is effective in the pretreated high saline wastewater. With a newly developed ternary cycle treatment, the chemical oxygen demand removal approaches 58.3%. The theoretical basis and a new method for biological treatments in biodegradation of high saline wastewater in ethyl chloride production are discussed.

Co-recovery of Mn and Fe from pyrolusite and copper slag with hydrometallurgy process: Kinetics and leaching mechanisms.

With the shortage of high-quality raw materials and increasingly strict environmental regulations, the recovery of metals from copper slag and pyrolusite has become a research hotspot. A novel method for simultaneously extracting Mn and Fe from pyrolusite and copper slag has been proposed. Under the optimal conditions (Copper slag / Pyrolusite = 2, H2SO4 = 2 M, liquid-solid ratio = 10, T = 90 ℃, holding time = 60 min), the leaching efficiencies of Mn and Fe can reach 98.28% and 99.04%, respectively. In addition, the treated residue containing 60.04 wt% SiO2 can be used as a raw building material. Through chemical kinetics and mineralogical transformation analyses, Fe2SiO4 in copper slag decomposes to release Fe2+, which can reduce and leach Mn from pyrolusite. The unreacted shrinkage nuclear reaction model under the control of the surface chemical reaction is the most suitable model to describe the process, and when the apparent activation energy is 35.50 kJ/mol, the apparent rate equation is: [Formula: see text].

Highly efficient removal of Cr(VI) from aqueous solution by pinecone biochar supported nanoscale zero-valent iron coupling with Shewanella oneidensis MR-1.

Nanoscale zero-valent iron (nZVI) has been extensively used to remove various pollutants. However, the rapid deactivation due to aggregation and surface passivation severely limits its practical application. In this study, a novel composite with nZVI supported by pinecone biochar (nZVI-PBC) was successfully synthesized and used for the removal of high concentration Cr(VI) from aqueous solution in the presence of Shewanella oneidensis MR-1 (MR-1). The results showed that the nZVI-PBC coupling with MR-1 (nZVI-PBC/MR-1) exhibited an excellent removal performance for high concentration Cr(VI) compared to the nZVI-PBC alone. Under optimal conditions, 100 mg/L Cr(VI) could be removed completely by nZVI-PBC/MR-1 within 48 h, while only 39.50% of Cr(VI) was removed by nZVI-PBC alone. The improvement of Cr(VI) removal is due to the dissolution of the surface passivation layer of nZVI-PBC, formation of sorbed Fe(II) in the presence of MR-1, and an important role of extracellular polymeric substance (EPS) derived from MR-1. X-ray photoelectron spectroscopy (XPS) and Cr K-edge X-ray absorption near-edge structure spectra (XANES) confirmed that most Cr(VI) was reduced to insoluble Cr(III) and formed Cr2O3, CrxFe1-x(OH)3 and FeCr2O4 precipitates, and a small amount of unreduced Cr(VI) was immobilized through adsorption and complexation. The results suggest that nZVI-PBC/MR-1 can effectively overcome the limitations of nZVI and achieve highly efficient removal of high concentration Cr(VI).

Uptake of arsenic(V) using iron and magnesium functionalized highly ordered mesoporous MCM-41 (Fe/Mg-MCM-41) as an effective adsorbent.

Mesoporous silica (MCM-41) is widely used as a supporting material due to its large specific surface area and good stability, but it cannot remove heavy metals due to the lack of adsorption active sites. In this study, the MCM-41 (a mesoporous SiO2 material) decorated with iron and magnesium oxide (Fe/Mg-MCM-41) was found to be an excellent adsorbent to remove arsenic(V) from water. FTIR, BET, TEM-EDS, XRD, XPS, etc. were applied for characterization analysis. Adsorption isotherms were fitted well by the Langmuir model and the experimental maximum adsorption capacity of Fe/Mg4-MCM-41 (magnesium accounts for 4%) was 71.53 mg/g at pH = 3. Thermodynamics analysis suggested exothermic nature of adsorption behavior. Kinetic process was well described by the pseudo-second-order model and adsorption rate was controlled by intraparticle diffusion and film diffusion. Moreover, the adsorption behavior of As(V) onto Fe/Mg4-MCM-41 was investigated under different reaction conditions, such as pH, temperature, Mg-doping and competing ions. The results showed that loading a certain amount of magnesium can significantly improve arsenic removal efficiency. Additionally, Fe/Mg4-MCM-41 exhibits high arsenic(V) removal in the wide pH range of 3-10. The Fe/Mg4-MCM-41 can be regenerated and used after four consecutive cycles. The high arsenic(V) sorption capacity, wide range of pH applications, ability to regenerate, and reusability of Fe/Mg4-MCM-41 confirmed that this adsorbent is promising for treating As-contaminated wastewater.

Mechanochemical activation on selective leaching of arsenic from copper smelting flue dusts.

A novel application, including mechanochemical pre-treating and alkali leaching, for arsenic selective leaching from copper smelter flue dusts (CSFUs) was developed to overcome the disadvantages of hydrometallurgical methods. Compared with raw CSFU powders, the mechanical-activated ones showed higher maximum arsenic leaching efficiency (increased by ~20%), and lower apparent activation energy (decreased by ~7 kJ·mol-1). Furthermore, this novel process only consumed half of alkali and sulfides and needed one-third of the leaching time to compare with the ones used in the traditional alkali leaching process. The promoting effect of mechanical force on arsenic leaching firstly relied on the physical property changes of CSFU powders, including a decrease of particle sizes and an increase of the specific surface. Secondly, mechanochemical force converted As5+ species into reduced phases (e.g. As2O3, NaAsO2), and thio-arsenates (e.g. AsO2S23-, AsO3S3-), which could spur its leaching due to their stronger mobilities in the alkali solution within sulfides. Finally, mechanochemical activation could be facilitated to separate discrete soluble arsenic species or incorporated ones from sulfate minerals in the CSFUs. This work may have important implications for the development of new eco-friendly technologies for purifying arsenic-bearing materials.

A New Method (Ball Milling and Sodium Sulfide) for Mechanochemical Treatment of Soda Ash Chromite Ore Processing Residue.

Hexavalent chromium in soda ash Chromite Ore Processing Residue (COPR) is harmful to the environment, it is imperative to develop a low cost, efficient, and effective treatment. Herein, a new method (ball milling+sodium sulfide) was developed for mechanochemical treatment of water-leached COPR (W-COPR, about 900 mg/kg non-exchangeble Cr(VI) and mostly chromite bounded). Under a stoichiometric ratio of S2- to Cr(VI) of 5, milling speed of 200 rpm, milling time of 30 min, ball-to-powder weight ratios of 8.5, and, a total Cr(VI) of 76.88 mg/kg and a Toxicity Characteristic Leaching Procedure (TCLP) total Cr value of 1.15 mg/L were achieved after treatment. Results of the mineral liberation analyser (MLA) analyses showed 10% increase of chromite grains liberation and grain size reduction were beneficial to the chromite-bound Cr(VI) reduction. Similar effects were also observed on magnesioferrite encapsulated Cr(VI). Particle aggregation and formation of glass phase colloid precipitation could potentially impede Cr(VI) reduction. Results of X-ray absorption near edge structure (XANES) analyses indicated that the treatment method reduced the actual Cr(VI) concentration to 312 mg/kg with Cr(VI) reduction efficiency of 98% being achieved. Overall, the new method is simple and efficient, and provides a guidance for future industrial application.

Bio-leaching of manganese from electrolytic manganese slag by Microbacterium trichothecenolyticum Y1: Mechanism and characteristics of microbial metabolites.

The related microbial metabolomics on biological recovery of manganese (Mn) from Electrolytic Manganese Slag (EMS) has not been studied. This study aimed at open the door to the metabolic characteristics of microorganisms in leaching Mn from EMS by using waste molasses (WM) as carbon source. Results show Microbacterium trichothecenolyticum Y1 (Y1) could effectively leach Mn from EMS in combination with using waste molasses as carbon and energy sources. For the first time, Y1 was identified to be capable of generating and then metabolizing several organic acids or other organic matter (e.g., fumaric acid, succinic acid, malic acid, glyoxylic acid, 3-hydroxybutyric acid, glutaric acid, L(+)-tartaric acid, citric acid, tetrahydrofolic acid, and L-methionine). The production of organic acids by Y1 bacteria was promoted by EMS with the carbon source. This study demonstrated for the first time that metabolic characteristics and carbon source metabolic pathways of Y1 in bioleaching of Mn from EMS.

Electrolytic manganese residue-based cement for manganese ore pit backfilling: Performance and mechanism.

Slag backfilling with electrolytic manganese residue (EMR) is an economical and environmentally-friendly method. However, high ammonium-nitrogen and manganese ions in EMRs limit this practice. In this study, a method of highly efficient simultaneous stabilization/solidification of ultrafine EMR by making EMR-based cementitious material (named EMR-P) was proposed and tested via single-factor and response surface optimization experiments. Results show that the stabilization efficiency of NH4+ and Mn2+ were above 95%, and the unconfined compressive strength of the EMR-P was 18.85 MPa (megapascal = N/mm2). The mechanistic study concluded that the soluble manganese sulfate and ammonium sulfate in EMR were converted into the insoluble precipitates of manganite (MnOOH), gypsum (CaSO4), MnNH4PO4·H2O, and struvite (MgNH4PO4∙6 H2O), leading to the stabilization of NH4+ and Mn2+ in the EMR-P. Leaching tests of EMR-P indicated that NH4+, Mn2+, and others heavy metals in the leachate were within the permitted level of the GB/T8978-1996. The novelty of this study includes the addition of phosphate and magnesium ions to precipitate ammonium-nitrogen and the combination between calcium ions (from CaHPO4∙2 H2O) and sulfate (from the EMR) to form calcium sulfate to improve the stability and unconfined compressive strength of cementitious materials (EMR-P).

Microstructural analyses of Cr(VI) speciation in chromite ore processing residue from the soda ash process.

The microstructure of Chromite Ore Processing Residue (COPR) derived from the soda ash roasting process was investigated prior to and after removal of water exchangeable chromate using a host of microscopy and spectroscopy techniques. Soda ash COPR consists mostly of a magnesioferrite (MgFe2O4) matrix that has substantial substitution of trivalent chromium (Cr) for iron. The chromite particles are generally larger than the overall particle size distribution of COPR, containing most of the Cr mass in areas that are greater than 20 µm in diameter; chromite particles are also associated with most of the non-exchangeable hexavalent Cr (Cr(VI)), even though the binding mechanism is not well understood. The remaining non-exchangeable Cr(VI) was found in association with the surrounding Si- and Al-matrix, with spectroscopic evidence of the presence of Cr(VI)-hydrotalcite.

Microwave-enhanced selective leaching of arsenic from copper smelting flue dusts.

Alkaline sulphide leaching processes have been widely used for the arsenic selective removal from metallurgical wastes. However, high consumption of energy and chemicals as well as long extraction time have forced the industries to find more cost-effective and eco-friendly separation techniques. In this work, a feasible microwave-enhanced leaching process was developed for arsenic selective removal from copper smelter dusts, and arsenic leaching efficiency could reach ∼98 % after leaching for 10 min with 0.5 mol·L-1 alkaline solution, in contrast to 86 % removal for the conventional electrical-heating leaching with even a more intensive alkali content (1.0 mol·L-1) and a longer extract time (1.5 h). Furthermore, energy cost was cut down to one-tenth of the conventional leaching process. Two enhancing mechanisms were proposed: 1) rapid oxidation of As(III) of the dusts occurred under microwave irradiation reduced the energy potential for arsenic dissolving in alkali media; 2) cracks and fissures formed in the dust particles after microwave, coupled with the temporary and localized superheating in the bulk liquid, would dramatically enhance arsenic leaching kinetics and decrease the activation energy value from 42.88 to 35.81 kJ·mol-1 (40-70 ℃). This work may have important implications to the development of new technologies to purify arsenic-bearing materials.

Using Electrolytic Manganese Residue to prepare novel nanocomposite catalysts for efficient degradation of Azo Dyes in Fenton-like processes.

In this study, Electrolytic Manganese Residue (EMR) was treated by EDTA-2Na/NaOH, ultrasonic etching, and hydrothermal reaction to obtain a novel nanocomposite catalyst (called N-EMR), which then was used, together with H2O2, to treat synthetic textile wastewater containing Reactive Red X-3B, Methyl Orange, Methylene blue and Acid Orange 7. Results indicated that the N-EMR had a nano-sheet structure in sizes of 100-200 nm; new iron and manganese oxides with high activity were produced. The mixture of a small amount of N-EMR (40 mg/L) and H2O2 (0.4 × 10-3 M) could removal about 99% of azo dyes (at 100 mg/L in 100 mL) within 6-15 min, much faster than many advanced oxidation processes (AOPs) reported in the literature. The elucidation of the associated mechanism for azo dyes degradation indicates that azo dyes were attacked by superoxide radicals, hydroxyl radicals, and electron holes generated within system. N-EMR was found to be reusable and showed limited inhibition by co-existing anions and cations. Moreover, high removal efficiency of azo dyes could happen in the system with a wide range of pH (1-8.5) and temperatures (25-45 °C), indicating that the process developed in this study may have broad application potential in treatment of azo dyes contaminated wastewater.

Chromium(VI) bioreduction and removal by Enterobacter sp. SL grown with waste molasses as carbon source: Impact of operational conditions.

A technology utilizes bacteria Enterobacter sp. SL grown in an anaerobic reactor with waste molasses as carbon source to bio-reduce hexavalent chromium [Cr(VI)] in wastewater and then remove total chromium has been developed. The performance was elucidated through different initial and operating experiments conditions, and the associated mechanism of Cr(VI) reduction was explained. Results show that Cr(VI) removal is 99.91% at 25 h in the anaerobic reactor initially containing bacteria of 5% (v/v), (NH4)2Fe(SO4)2·6H2O of 0.5 g·L-1, waste molasses of 2.5 g·L-1, Cr(VI) of 100 mg·L-1, pH of 6.0, and with the operational temperature of 45 °C. After 120 h reaction, Cr(total) removal reached 91.10%. The major reduction products [FeS, Cr2O3, Cr(OH)3, S0 granules] together with microbes was removed by sludge separation with Cr(VI) in the supernatant (0.027 mg·L-1) being much lower than that (not excess 0.2 mg·L-1) of Electroplating Pollutant Emission Standard.

Efficient removal of heavy metals by synergistic actions of microorganisms and waste molasses.

In this study, two bacteria strains (Enterobacter sp. SL and Acinetobacter sp. SL-1) and waste molasses (carbon source) were used to remove Zn(II), Cd(II), Cr(VI), and Cr(Total) in the liquid solution (87 mg·L). The results showed the removal efficiencies of Cr(Total) and Cr(VI) could reach over 98.00% after reaction, and the removal efficiencies of Zn(II) and Cd(II) were all about 90.00% by the synergistic actions of microorganisms and waste molasses. In this process, waste molasses provides nutrients for microorganisms and has the characteristics and capability of Cr, Zn, and Cd. Microorganisms mainly use biological adsorption (36.95% and 45.69%) and metabolism (24.37% and 17.05% by producing humic-acid and fulvic-acid like substances) to remove Zn(II) and Cd(II), while waste molasses could to remove Cr(Total) (81.24%) and Cr(VI) (75.90%). This study has potential application value for the treatment of wastewater containing high concentrations of heavy metals.

Removal of cadmium and lead from aqueous solutions by thermal activated electrolytic manganese residues.

Electrolytic manganese residues (EMR) is produced from the electrolysis manganese industry. In this study, the thermal activated EMRs (T-EMR) were used to adsorb cadmium and lead from aqueous solution. X-ray diffractometer (XRD), scanning electron microscope-Energy Dispersive Spectrometer (SEM-EDS), X-ray photoelectron spectroscopy (XPS) were adopted to characterize EMR before and after the modification, and the performance and adsorption mechanisms of T-EMR for cadmium and lead were determined. Results show that the pH has a strong influence on the adsorption of cadmium and lead and the maximum adsorption capacity can be achieved at pH 6. The adsorption of Cd(II) can be better fitted by the Lagergren pseudo-first-order dynamic model, while that of Pb(II) fits the pseudo-second-order kinetic model better. The Freundlich isotherm model fits the adsorption of two metals better than Langmuir model. The thermodynamic results demonstrate that the adsorption of Cd(II) or Pb(II) on T-EMR is endothermic and spontaneous. As the nitric acid with pH 0.5 was used, nearly all of the adsorbed Cd(II) and 75% Pb(II) can be desorbed from the loaded T-EMR. It is concluded that the adsorption of Cd(II) and Pb(II) on T-EMR is in virtue of electrostatic attraction, ion-exchange and surface precipitation. The heavy metals are mainly adsorbed on ferric and manganese oxides and silicate minerals in T-EMR by electrostatic attraction. In addition, cadmium and lead also can be adsorbed via the ion exchange reaction. Moreover, some Pb(II) are adsorbed by forming lead sulfate. Thus, T-EMR may be an environmentally-friendly, effective adsorbent for the removal of heavy metals from aqueous solution.