Abstract

As a promising candidate to separate the cathode materials and aluminum foils, the underwater electrical pulse method is an environmentally friendly method that can effectively liberate cathodic active material in a very short time. However, performing the electric pulse separation in aqueous media may cause the release of fluoridated elements, which may come from fluoridated components formed during battery cycles or due to the remaining electrolyte within the cathode particles. Thus, the purpose of this work is to study the solution obtained after pulse discharge in terms of fluoridated entities, to understand their effect on the elution of active cathodic materials. Herein, to investigate the potential source of F and its possible effects on metal extraction, leaching experiments were conducted in the presence of different fluoride concentrations with a solid/liquid ratio of 0.5g/L under circumneutral pH conditions (pH range: 5.7-7.5) using a spent nickel-cobalt-manganese lithium battery sample liberated by N-Methyl pyrrolidone. The results show that the amounts of F ions in solution increased with leaching time, with a maximum value close to 2.34 ppm F obtained after 2 h. It is worth noting that the presence of fluoride-ion can promote the elution of aluminum, as a maximum concentration of 1.85 ppm Al was observed at 2 h in the presence of 40 ppm F, whereas only about 0.32 ppm Al was detected in the case of fluoride-free solutions. Consequently, our results demonstrated that the amounts of transition metals (Ni, Mn, and Co) released towards liquid changed very little irrespective of the concentrations of dissolved fluoride, suggesting that the released F ions do not affect metals elution.

Ferrihydrite is omnipresent in nature, and its adsorption of As(III/V) decides the migration of arsenic. Although As(III) is commonly recognized as the more mobile species of inorganic arsenic, it sometimes exhibits less mobility in ferrihydrite systems, which calls for further insights. In this study, we elucidated the adsorption behavior and mechanisms of As(III/V) on ferrihydrite under different loading levels (molar ratio As/Fe = 0-0.38), solution pH (3-10), and coexisting ions [P(V) and Ca(II)] based on batch adsorption experiments, surface complexation modeling, density functional theory calculations, and X-ray photoelectron spectroscopy. Our results show that As(III) exhibits weaker adsorption affinity but a larger capacity compared with that of As(V). On ferrihydrite, As(III) and As(V) are adsorbed mainly as bidentate mononuclear complexes at type-a sites [≡Fe(OH-0.5)2] and bidentate binuclear complexes at type-b sites (2≡FeOH-0.5), respectively. As the dosage increases, As(III) further forms mononuclear monodentate complexes at both surface sites, resulting in a higher site utilization efficiency, while As(V) does not due to repulsive electrostatic interaction. The difference in surface species of As(III/V) also leads to complex responses when coexisting with high concentrations of P(V) and Ca(II). This study helps us to understand environmental behavior of As(III/V) and develop remediation strategy in As(III/V) contaminated systems.

Abstract

The number of spent photovoltaic (PV) panels is expected to increase significantly in the coming decades. Crystalline silicon photovoltaic cells contain materials, such as silver, copper, aluminum, silicon, glass, and resins. Approximately 600 g/t of silver is used as a current collector, so-called finger wires, in photovoltaic modules; therefore, silver recovery is an important issue. To establish an effective recycling process for spent photovoltaic panels, a wire explosion method using high-voltage pulsed discharge was investigated to expose and separate silver selectively. In this study, acid-leaching experiments were conducted on spent ground photovoltaic panels with and without electric pulse treatment to verify the effect of the pulse treatment on acid-leaching of silver. Electric pulse treatment improved both the maximum silver recovery rate and leaching speed. Leaching experiments were also conducted using photovoltaic samples from three different silver exposure states. It can be concluded that silver recovery was strongly controlled by the exposure state and that the electric pulse treatment could effectively promote silver exposure of spent PV panels, even in the region where the silver wires were not energized.

Ferrous sulfate (FeSO4) combined with acid pretreatment is usually employed to remediate contaminated soils containing Cr(VI). However, the long-term efficiency of this stabilization method is important for its sustainability. In this study, a gradient temperature-elevating exposure test was employed to investigate the stability of Cr in FeSO4-remediated soil when exposed to elevated temperatures (40 °C, 120 °C, and 500 °C), possibly caused by hot weather and/or wildfires. The results of chemical extraction and X-ray absorption near edge structure spectroscopy (XANES) showed that the Cr(VI) in contaminated soil was successfully transformed to Cr(III) after stabilization, resulting in the dramatic decrease of water-leachable Cr(VI). The stabilization efficiency was further improved under 40 °C treatment after 30 days. Subsequently, the 120 °C treatment (7 days) had relatively little effect on the Cr speciation and mobility in soils. However, even one day of 500 °C calcination resulted in the deterioration of stabilization efficiency, and the water-leachable Cr(VI) re-increased and became higher than the Chinese environmental standards (total Cr 15 mg/L, Cr(VI) 5 mg/L) for the classification of hazardous solid wastes. XANES results reflected that heating at 500 °C facilitate the formation of Cr2O3, which was mainly caused by thermal decomposition and dehydration of Cr(OH)3 in the soil. Besides, the transformation of Cr species resulted in the enhanced association of Cr with the most stable residual fraction (88.3%–91.6%) in soil. Based on chemical extraction results, it was suggested that the oxidation of Cr(III) to Cr(VI) contributed to the re-increased mobility of Cr(VI) in soil. However, the XANES results showed that almost no significant re-oxidization of Cr(III) to Cr(VI) happened after heating at 500 °C, which was probably caused by XANES linear combination fits (LCF) uncertainties. Moreover, the changes in soil properties, including a rise in pH to a slightly alkaline range and/or the decomposition of organic matter, possibly contributed to the enhanced mobility of Cr(VI) in soil. This study contributes to clarifying the mobility and transformation of Cr in contaminated soils and provides a support for the sustainable management of remediated soils.

Abstract

Conventional neutralization treatment for manganese (Mn)-bearing mine drainage provides a challenge of cost-efficiency, and new approaches should be explored for efficient removal of Mn. We focused on Mn neutralization sludge, a by-product of the Mn-bearing drainage treatment process, which was assumed to be useful as a water purification material. Mn and zinc (Zn) removal tests in simulated drainage were performed using Mn neutralization sludge, and the reaction mechanism was elucidated using geochemical modeling and X-ray absorption fine structure (XAFS) analysis. The results showed that the addition of sludge enabled to lower the Mn and Zn concentration below Japanese effluent standard (10 mg dm⁻³ for Mn; 2 mg dm⁻³ for Zn) within 1 h. Furthermore, heavy metal immobilization was achieved at neutral pH (7–8) with the sludge addition, while the conventional neutralization process without adding the sludge requires higher pH (>10) to lower Mn concentration. These removal behaviors were not explainable by considering only well-known phenomena: hydroxide precipitation, surface complexation reaction onto δ-MnO₂, and autocatalytic Mn oxidation. Hence, we advanced the geochemical model for simulation, suggesting that a surface complexation reaction onto γ-MnOOH greatly contributed to the removal of Mn. Besides, Zn was calculated to be predominantly precipitated as ZnMn₂O₄. Solid residue analysis by XAFS measurement supported the result of above calculation, validating the reliability of the constructed geochemical model. Overall, we concluded that the advanced geochemical model would be useful in predicting the Mn and Zn behavior during mine drainage treatment with Mn neutralization sludge.

Graphical abstract

A protonated diamide containing tertiary amine (EHBAA) can extract Se(iv) and Se(vi) from HCl via solvation and anion-exchange reactions, respectively.

Ciprofloxacin (CIP), a compound with bioaccumulation toxicity and antibiotic resistance, is frequently detected in water at alarming concentrations, which is becoming an increasing concern. In this study, a low-cost ceramsite was developed from industrial solid wastes through sintering to remove CIP from wastewater. The effects of adsorbent dosage, initial pH, contact time, initial CIP concentration, and temperature were explored. More than 99% of CIP (20–60 mg/L) was removed at around pH 2–4 by the ceramsite. The kinetic data fitted well with the pseudo-second-order model, revealing that chemisorption was the main rate-determining step. The isotherm data was better described by the Freundlich model, suggesting that CIP was removed by the formation of multiple layers on the heterogeneous surface. Moreover, the removal efficiency was practically higher than 95% during five regeneration cycles, when different regeneration methods were used, including calcination, HCl, and NaOH washing, indicating that the ceramsite exhibited outstanding reusability in removing CIP. The primary mechanism of CIP removal by the ceramsite was found to be the synergism of adsorption and flocculation, both of which depended on the release of Ca2+ from the ceramsite. In addition, strong Ca-CIP complexes could be formed through surface complexation and metal cation bridging between Ca2+ and different functional groups in CIP.

Cadmium (Cd), as a type of heavy metal, can increase the incidence of many diseases, even in low concentrations. In this study, tobermorite was hydrothermally synthesized and then applied to adsorb Cd2+ from an aqueous solution. The physicochemical characteristics of the synthesized tobermorite were detected, and the results indicated that the well-crystallized tobermorite had a lot of mesopores and a large specific surface area of 140.92 m2/g. It acquired a pH self-adjustment ability via spontaneously releasing Ca2+ and OH- into the aqueous solution. The effects of different factors on Cd2+ removal were investigated. For Cd2+, the removal efficiency could reach 99.71% and the maximum adsorption capacity was 39.18 mg/g using tobermorite. The adsorption data was best fitted with the pseudo-second-order kinetic and Langmuir isotherm models. In addition, there was no strict limit on the solution pH in Cd2+ adsorption because the tobermorite could adjust the solution pH to an alkaline atmosphere spontaneously. The efficient removal of Cd2+ using tobermorite was a result of surface complexation and ion exchange.

A passive treatment process using sulfate-reducing bacteria (SRB) is known to be effective in removing heavy metals from acid mine drainage (AMD), though there has been little discussion of the mechanism involved to date. In this work, a sulfate-reducing column test was carried out using supplementary ethanol as an electron donor for microorganisms, and the reaction mechanism was examined using geochemical modeling and X-ray absorption fine structure (XAFS) analysis. The results showed that Cu was readily removed from the AMD on the top surface of the column (0–0.2 m), while Zn and Cd depletion was initiated in the middle of the column (0.2–0.4 m), where sulfide formation by SRB became noticeable. Calculations by a developed geochemical model suggested that ethanol decomposition by aerobic microbes contributed to the reduction of Cu, while sulfide produced by SRB was the major cause of Zn and Cd removal. XAFS analysis of column residue detected ZnS, ZnSO4 (ZnS oxidized by atmospheric exposure during the drying process), and CuCO3, thus confirming the validity of the developed geochemical model. Based on these results, the application of the constructed geochemical model to AMD treatment with SRB could be a useful approach in predicting the behavior of heavy metal removal.

With the help of circular strategies, products can be used longer (i.e., reuse, repair, and refurbish). Products that are difficult to use will be recycled efficiently. The present paper provides actionable guidelines for reducing environmental impact at all stages of a product’s life cycle, including the manufacture and assembly of the materials that make up the product, environmental impacts during use, and environmental impacts at final disposal, as well as specific actions and evaluation mechanisms. The circular economy is a concept that encompasses specific actions and their evaluations. To clarify the contribution of this circular economy to carbon neutrality, the present paper highlights how it is important to recognize the role of carbon as both an energy carrier and a material. CO2 is a waste product from burning and powering carbon. CO2 must be disposed of like any other waste product, but carbon itself is also an energy carrier. Thus, when promoting the carbon cycle, it is important to harmonize carbon’s function as a material with its role as an energy carrier. The further introduction of renewable energy and societal shift towards circular economy would contribute to carbon neutrality and more resource efficient use in a mutually complementary manner.

Grinding is a unit of operation of a pure mechanical process. An attritor is a grinder able to be used for fine or selective grinding. However, few studies have reported on the optimum design for the attritor. The attritor’s grinding characteristics and grinding effect depend not only on the operating conditions, but also on the geometry of the agitator. Therefore, we investigated the effect of the agitator shape on the grinding efficiency from the viewpoint of experiments, kinetic analysis, and discrete element method (DEM) simulations. We conducted grinding experiments with two different agitators. One was Agitator A, a traditional design with two pairs of 90° staggered mixing arms at the middle and bottom of the mixing shaft. The other was Agitator B, with a lower mixing arm inclined by 10° along the horizontal direction. We found that the grinding rate constant of Agitator B was approximately 40% greater than that of Agitator A. Although the size distribution of the particles was relatively dispersed after grinding with Agitator B, the distribution was concentrated mainly within two ranges (<0.5 mm and 2–4 mm) with Agitator A. These results and an elemental analysis of each size fraction suggested that the dominating grinding mode in Agitator A was surface grinding, whereas in Agitator B, it was bulk grinding. In terms of the influence of the agitator shape, the DEM simulation results showed that the kinetic energy of the grinding media in Agitator B was 0.0046 J/s, i.e., larger than the 0.0035 J/s obtained for Agitator A. A collision energy analysis showed that the dominating collision was between the media and wall in the tangential direction for both models. The collision energy of the media in Agitator B was larger than that of that in Agitator A. The results from the DEM simulation can help us evaluate the experimental results and infer the reasons why the grinding rate constant in Agitator B is larger than that in Agitator A.

This study presents a novel method to separate positive electrode active materials (PEAMs) and aluminum (Al) foil from positive electrodes (PEs) to enable more effective recycling processes. A pulsed current was applied to a PE sample that was prepared by manual dismantlement of spent lithium-ion batteries (LiBs). Joule heating caused the temperature of the Al foil to increase to be above the melting points of adhesion included in the PEAMs. The influence of the surrounding medium of the PE sample on the delamination phenomenon was investigated. PEAMs were peeled from the Al foil in water and air environments. High-speed visible imaging was employed to discuss separation processes. Differences in the size of the separated PEAMs and the amount of residual PEAM on the surface of the Al foil occurred due to the influence of the medium filled in the voids inside the PEAM layer.

Fine particulate matter (PM2.5) exposure has a risk of inducing several health problems, especially in the respiratory tract. The skin is the largest organ of the human body and is therefore the primary target of PM2.5. In this study, we examined the effects of PM2.5 on the skin using a human 3-dimensional cultured epidermis model. PM2.5 was collected by cyclonic separation in Yokohama, Japan. Global analysis of 34 proteins released from the epidermis revealed that the chemokines, chemokine C-X-C motif ligand 1 (CXCL1) and interleukin 8 (IL-8), were significantly increased in response to PM2.5 exposure. These chemokines stimulated neutrophil chemotaxis in a C-X-C motif chemokine receptor 2-dependent manner. The oxidative stress and signal transducer and activator of transcription 3 pathways may be involved in the increased expression of CXCL1 and IL-8 in the human epidermis model. Interestingly, in the HaCaT human keratinocyte cell line, PM2.5 did not affect chemokine expression but did induce IL-6 expression, suggesting a different effect of PM2.5 between the epidermis model and HaCaT cells. Overall, PM2.5 could induce the epidermis to release chemokines, followed by neutrophil activation, which might cause an unregulated inflammatory reaction in the skin.

The amount of generated waste of lithium-ion batteries (LiBs) that are used in automobiles is expected to increase because of increases in EV usage. Thus, it is required to recover strategic elements, such as lithium, cobalt, nickel, and manganese in the positive electrodes (PEs) found within LiB. In recent years, a direct application of electrical pulsed power to PEs has been reported to separate the active material layer from the aluminum foil in PEs. The electrical pulsed-discharge treatment enables the separation of the active materials from the aluminum foil without changing in a significant manner the chemical composition of the materials. In this study, we investigated the influence of length of rolled PE samples on the separation of active material from the aluminum foil of PE via the electrical pulsed-discharge treatment. Calculated energy and charging voltage for specific sample sizes were applied to PE samples installed in discharging electrodes in water. After the electrical pulsed-discharge treatment, up to 98.8% cobalt and 6.7% aluminum were recovered from liberated particles of 8 mm or less. For a longer length of PE sample, the separation efficiency of cobalt for aluminum was higher, and the aluminum contamination for active material particles was lower. The internal circuit resistance should be reduced as much as possible to reduce the circuit energy consumption. In terms of energy efficiency, a longer, narrower, and thinner aluminum foil had positive effects in the separation of the positive electrode by the electrical pulsed-discharge treatment.

This study evaluated the efficiency of cerium reduction by grinding with microwave irradiation in mechanochemical processing. Grinding experiments with microwave irradiation were conducted using an agitating mixer. Since the structure of the ground samples was amorphous and the cerium concentration was much lower than those of other elements, the valence change and structural change of cerium after grinding with microwave irradiation were investigated using X-ray absorption fine structure (XAFS) analysis in the cerium K-edge. The X-ray absorption near-edge structure (XANES) analysis revealed that a portion of tetravalent cerium was reduced to trivalent cerium by grinding with microwave irradiation. In addition, it was confirmed by extended X-ray absorption fine structure (EXAFS) analysis that oxygen vacancies were produced as a result of the cerium reduction reaction. To evaluate the efficiency of cerium reduction efficiency, the percentage reduction by grinding with microwave irradiation was compared to that by planetary ball milling and microwave irradiation. As a result, it was revealed that the efficiency of cerium reduction via grinding with microwave irradiation was higher than that via microwave irradiation and the same as that via planetary ball milling. Moreover, a larger amount of tetravalent cerium could be reduced to trivalent cerium by grinding with microwave irradiation than when using planetary ball milling and microwave irradiation.

In this study, we investigated the localized and concomitant precipitation of calcium (Ca)/magnesium (Mg)-bearing species and iron oxides/oxyhydroxides, and their depression characteristics to the pyrite floatability in flotation process at pH 9 and pH 10.5 with prolonged pre-oxidation. Contrary to the depression characteristics at pH 9, the incipient (within aeration times of 30 min) depression of pyrite floatability in Ca/Mg-bearing solutions was more obvious at pH 10.5, while the subsequent decline was only slightly when the pre-oxidation time was expanded to 120 min and 360 min. The competitive adsorption among Ca/Mg-bearing species and potassium amyl xanthate (PAX, C6H11OS2K, collector) at specific sites onto the pyrite surface was demonstrated by the regularly decreased zeta potential of the pyrite surface pretreated in Ca/Mg-bearing solutions. Further scanning electron microscopy-energy dispersive spectrometry demonstrated the concomitant secondary Ca/Mg/Fe-bearing precipitates on the pyrite surface. X-Ray photoelectron spectroscopy suggested strong reprecipitation of iron oxides/oxyhydroxides on the pyrite surface via acid–base complexation among Ca/Mg hydroxy species and iron hydroxy species. Incipient occupation efficiency of specific reaction sites by Ca/Mg-bearing species, which were mainly controlled by the metastable distribution of Ca/Mg hydroxy species and their electrostatic affinity with pyrite surface, was the crucial factor that influenced the competitive adsorption of xanthate and pyrite floatability. More obvious incipient depression at pH 10.5 rather than at pH 9 contributed to more effective Ca/Mg-bearing species and their higher affinity to pyrite surface at pH 10.5. The localized and concomitant precipitation of secondary Ca/Mg/Fe-bearing species leads to a slightly increased hydrophilic coverage upon the pyrite surface, thus a slowly decreased pyrite floatability with increasing pre-oxidation time.

Manganese (Mn) is a major element in various aqueous and soil environments that is sometimes highly concentrated in mine water and other mineral processing wastewater. In this study, we investigated Mn removal from alkaline mine water (pH > 9) with an Mn-coated silica sand packed into a pilot-scale column reactor and examined the specific reaction mechanism using X-ray absorption near-edge structure (XANES) analysis and geochemical kinetic modeling. The kinetic effect of dissolved Mn(II) removal by birnessite (δ-Mn(IV)O2) at pH 6 and 8 was evaluated at different Mn(II)/Mn(IV) molar ratios of 0.1–10. Our results confirmed the positive effect of the presence of δ-MnO2 on the short-term removal (60 min) of dissolved Mn. XANES analysis results revealed that δ-MnO2 was more abundant than Mn(III)OOH in the reactor, which may have accumulated during a long-term reaction (4 months) after the reactor was turned on. A gradual decrease in dissolved Mn(II) concentration with depth was observed in the reactor, and comparison with the kinetic modeling result confirmed that δ-MnO2 interaction was the dominant Mn removal mechanism. Our results show that δ-MnO2 contents could play a significant role in controlling Mn removability from mine water in the reactor.

Understanding future changes in the concentrations of elements such as Cd in mine drainages, which can cause severe environmental impacts, is crucial to strategically optimize the treatment and management of such drainages. In this study, on the basis of 17-year data (2003–2019) for 99 untreated drainages from legacy mines in Japan, we developed a Bayesian hierarchical log-linear model that can capture temporal changes in the concentrations of seven elements including six metals (Cd, Pb, As, Cu, Zn, Fe, and Mn) in individual mine drainages. We also projected future changes to understand the prospective trends nationwide. The modeling results showed that, during 2003–2019, although overall decreasing trends were observed for most elements across all the drainages evaluated, decreases in the concentrations of these elements were not evident in many mine drainages (5%–28% of drainages for individual elements); in addition, any rise in the number of mine drainages with element concentrations below nationwide drainage standards over the next 100 years will likely be limited (e.g., approximately 10 drainages for Zn and Fe at median estimates). These results have significant implications for future strategies to manage mine drainages: it is probably too optimistic to assume that the element concentrations of mine drainages will always decrease, or that these drainages will satisfy drainage standards (permits) in the not so distant future.

Recently, the easy disassembly of bonding structures used in lightweight automobile bodies is needed. This is because these bonding structures are difficult to separate efficiently as there are joints using chemicals with a high adhesive strength and are commonly separated manually. In this study, we applied a pulsed discharge for the separation of bonding structures consisting of two adherends bonded by epoxy adhesive. The separation was carried out by controlling the discharge path inside the adhesive with a notch punched on the adherend and peeling the adhesive by the explosive force caused by the discharge. The discharge path in the adhesive was generated by the concentration of electric field at the tip of the notch. The effect of notch geometry on the electric field strength was studied by simulation with the AC/DC module of COMSOL Multiphysics. Simulation results indicated that the notch height affected the electric field concentration, and likewise, that the electric field strength at the notch was higher than the one at the edge of the adhered material. The discharge path of the bonding structure with the notch was visualized using the shadowgraph method. The fracture surfaces of structure without and with the notch after the pulsed discharge were also observed to confirm the discharge crater. The visualized images indicated that the discharge path occurred inside the adhesive from the tip of the notch and that the structure was separated by the expansion of gasified adhesive caused by the discharge when the notch was punched to the structure. A discharge crater was observed in the adhesive surface near the notch. In the case of the structure without a notch, the discharge luminescence appeared not in the adhesive but at the edge of the adherend because of the electric field concentration at the edge, resulting in non-separation due to surface discharge in the structure. These results indicated that the notch was responsible for controlling the discharge path inside the adhesive and caused the separation of the bonding structure.

Abstract

Subsurface limestone beds (SLBs) are used as a passive treatment technique to remove toxic metals from acid mine drainage (AMD). In this study, we investigated the mechanisms and thermodynamics of metal (manganese, copper, zinc, cadmium, and lead) precipitation in the SLB installed at the Motokura Mine. Field surveys in 2017 and 2018 showed that the pH of the SLB influent (initially 5–6) increased to approximately 8 in the drain between 24 and 45 m from the inlet. This increase was caused by limestone dissolution and resulted in the precipitation of hydroxides and/or carbonates of copper, zinc, and lead, as expected from theoretical calculations. Manganese and cadmium were removed within a pH range of approximately 7–8, which was lower than the pH at which they normally precipitate as hydroxides (pH 9–10). X-ray absorption near-edge structure analysis of the sediment indicated that δ-MnO₂, which has a high cation-exchange capacity, was the predominant tetravalent manganese compound in the SLB rather than trivalent compound (MnOOH). Biological analysis indicates that microorganism activity of the manganese-oxidizing bacteria in the SLB provided an opportunity for δ-MnO₂ formation, after which cadmium was removed by surface complexation with MnO₂ (≡ MnOH⁰ + Cd²⁺  ⇄  ≡ MnOCd⁺  +  H⁺). These findings show that biological agents contributed to the precipitation of manganese and cadmium in the SLB, and suggest that their utilization could enhance the removal performance of the SLB.

The wettability and floatability of oxidized chalcocite, bornite, and chalcopyrite with the conditions of sodium hydrosulfide (NaHS) dosages and pHs were studied by contact angle measurements, and single and mixture mineral flotation tests. To evaluate the results of the flotation, the flotation kinetic model for copper sulfide minerals treated by NaHS was derived. In this study, we focused on the activation and depression by NaHS, a well-known activator and depressant of copper minerals. The flotation results showed that there can be a threshold NaHS dosage to activate the mineral surfaces, as evidenced by the depression of the minerals and reduction of recoveries at higher dosages of NaHS. Chalcocite recoveries increased with an increase of NaHS dosage. Bornite recoveries tended to be depressed with a smaller amount of NaHS as pH increased. The recoveries of chalcopyrite increased as pH increased at an optimum NaHS dosage. Moreover, the flotation kinetic model that includes the surface properties and the reaction rate constant between the copper sulfide minerals and NaHS was derived. The trends of the flotation rate constants and mass fractions with NaHS dosages and pHs could quantitatively well-explain the flotation results.

The volume of spent photovoltaic (PV) panels is expected to grow exponentially in future decades. Substantial material resources such as silver (Ag), copper (Cu), aluminum (Al), silicon (Si), and glass can potentially be recovered from silicon-based PV panels. In this paper, we targeted the recovery of Cu and Ag from a cell sheet separated to a glass panel from a spent PV panel. The technical feasibility of a novel electrical dismantling method was experimentally studied. This method employed a pulsed power technology that releases high energy in a short time. It allowed a selective separation of the Cu/Ag wires from the sheet once per discharge in water. The experimental results indicated that 95.6% of the total Cu and 17.2% of the total Ag in the sample were successfully separated from the cell sheet using a 3.5-kJ capacitor bank circuit. Moreover, 3.66% of the total Si in the sample was contaminated by the separated Cu/Ag particles from the cell sheet, mainly by shockwaves generated by plasma expansion, and some of them formed a compound with Cu and Ag by eutectic melting, resulting in low liberation. At the lower energy of 3.5 kJ, eutectic melting of Cu and Ag with Si was more suppressed than 4.6 kJ, and 94.3% of Cu and 77.5% of Ag in the separated particles were liberated, which would be acceptable for further wet gravity and/or shape separation of Cu and Ag.

<p>Since the enactment of the "Feed-in Tariff" scheme in 2012, the solar power generation capacity in Japan has been steadily growing. Therefore, in the near future, the demand for the mass processing of spent photovoltaic (PV) panels is expected to increase. Secondary batteries, especially lithium-ion batteries (LiBs), have become important products for vehicles and mobile devices. The production of LiBs is also expected to significantly increase in the near future. In this study, we address the design of recycling systems for such emerging technologies. From life cycle perspectives, the requirements for the assessment of these technology systems are carefully defined through a bibliometric analysis of technology assessments, critical reviews of current research and developments in the recycling of PV panels and LiBs, and analysis of the intensities of life cycle impacts (such as greenhouse gas emissions and resource use). The necessities for life cycle assessments, material flow analyses, and other assessment methods are clarified, along with the conditions to be examined using these assessment methods.</p>

Mesoporous zerovalent iron-magnetite nanocomposites (ZVI-MNCs) were developed to circumvent the limitations of magnetite, such as its susceptibility to phase transition in air-water interfaces. High-resolution transmission electron microscopy images revealed the presence of Fe0 and Fe3O4 in the as-prepared adsorbent. High-resolution X-ray photoelectron spectroscopy (HR-XPS) Fe 2p deconvoluted spectra showed that electron transfer between Fe0 and Fe3O4 controlled the magnetite transformation. The isotherm equilibrium data for As(III) and As(V) are described by the Sips model, which suggests single- and multilayer formation onto a heterogeneous surface with different binding sites, whereas adsorption is controlled by a pseudo-second-order kinetic model, which indicates chemisorption. The maximum sorption capacities (qm) for As(III) and As(V) are 632.6 and 1000 μmol g-1, respectively, which are larger than the qm of similar adsorbents. The greater qm for As(V) is attributed to a higher multilayer formation and a stronger bonding force compared with As(III). The arsenic uptake capacity showed that the as-prepared adsorbent was effective over a wide pH range, and an optimal uptake capacity was recorded between pH 5.0 and 9.0 for As(III) and 3.0 and 7.0 for As(V). The adsorbent exhibited a remarkable regeneration performance for As(III) and As(V) uptake. Several microscopic analytical tools, including Fourier transform infrared spectroscopy, HR-XPS, and X-ray absorption near-edge structure together with zeta potential, confirmed that the binding mode of As(III) and As(V) on ZVI-MNCs was predominantly inner-sphere coordination. Partial redox transformation occurred for As(III) and As(V) on nearly 10 nm of the adsorbent, which indicates that a surface redox mechanism contributed partially to arsenic uptake on the near surface of the ZVI-MNCs. Extended X-ray absorption fine structure spectral analysis proposed that a corner-sharing monodentate mononuclear (1V) complex occurred for As(III) with a small portion of a corner-sharing bidentate binuclear (2C) complex, whereas As(V) formed a corner-sharing bidentate binuclear (2C) complex with octahedral Fe bonding.

The surface properties of slightly oxidized chalcocite, bornite, and chalcopyrite with sodium hydrosulfide (NaHS) treatment were investigated by solid analyses of X-ray photoelectron spectroscopy, solution analyses, and zeta potential measurements. NaHS is known as a flotation activator for copper-oxide minerals by sulfurizing their surfaces. This study focused on the surface properties before/after sulfurization by the NaHS at several NaHS dosages and alkaline pHs. Iron leaching and precipitates of copper–iron-sulfide minerals have also been investigated. The analysis results showed that NaHS sulfurized the oxidized copper species, CuO and CuSO4, to copper sulfide, but oxidized iron species, Fe2O3 and Fe(OH)3, were not sulfurized by NaHS. These oxidized iron species dissolved into solutions as complex ion, Fe(HS)20, then Fe(HS)20 was decomposed by dissolved oxygen and reprecipitated as Fe2O3. The results of chalcocite showed that Cu2S was generated on the surfaces with NaHS treatment at any pH. The bornite and chalcopyrite results indicated that Fe2O3 was produced on bornite surfaces with an increase in pH, whereas the chalcopyrite surfaces were covered as the pH decreased. A flotation test was conducted using a Chilean copper ore that contained chalcocite, bornite, and chalcopyrite, and the flotation recovery of each mineral was consistent with the surface sulfurization at several NaHS dosages and pHs.

We elucidate the removal mechanism of Cd by birnessite (delta-MnO2) in adsorption and coprecipitation processes in the context of acid mine drainage (AMD) treatments. The removal mechanism was studied through batch removal experiments at different initial Cd/Mn molar ratios (0-2) by zeta potential measurements, X-ray diffraction (XRD), small-angle X-ray scattering (SAXS), and X-ray absorption fine structure (XAFS) analysis. The sorption isotherm and zeta potential measurements suggest that surface complex formation is the dominant mechanism, and that surface precipitation and/or intercalation also occur in the coprecipitation process when the initial Cd/Mn molar ratio is high (1-2). Increasing the initial Cd/Mn molar ratio to above 0.5 decreased the particle size of delta-MnO2 and shifted its (001) XRD peak to lower angles, suggesting that the delta-MnO2 interlayer ((001) and (002) planes) was expanded and the growth of delta-MnO2 crystals was inhibited in the coprecipitation process. The results of XAFS analysis revealed the production of Mn(III) precipitates and surface complex formation with Cd at high Cd/Mn molar ratio condition ( < 1). No significant changes in the crystalline structures of delta-MnO2 over the entire range of initial Cd/Mn molar ratios were observed in the adsorption process, confirming that Cd could be adsorbed by triple-corner-sharing at neutral pH.

The development of efficient and inexpensive boron removal techniques is required to treat wastewater from many industrial processes. We investigated the removal mechanism of boron from wastewater by calcinated ettringite, a concrete sludge, and compared the advantage of this method to coprecipitation with ettringite. The amount of boron remaining in solution decreased slightly from an initial concentration of 2.3 mmol/dm(3) to 1.3-1.4 mmol/dm(3) after reaction for 60 min with ettringites calcinated at 55 and 65 degrees C. The boron removal efficiency increased greatly, with only 0.30 mmol/dm(3) remaining in solution after treatment for 60 min with samples calcinated at 75 degrees C, but samples calcinated at 95 and 175 degrees C removed slightly less boron than those calcinated at 75 degrees C. This enhancement of boron removal performance is due to the amorphization of the ettringite structure by calcination. However, excess heating inhibits ion exchange between the sulfate ions in the ettringite and the borate ions in the solution. The coprecipitation method also achieved efficient boron removal at high Al/B molar ratio (0.44 mmol/dm(3) boron remaining after 60 min). However, uptake by a different amorphous precipitant became the dominant removal mechanism. Large amounts of sludge are generated by this method. Adsorption using calcinated ettringite is therefore the optimal method for the efficient and inexpensive removal of boron from wastewater.

© 2020 by the authors. Licensee MDPI, Basel, Switzerland. There are about 100 sites of acid mine drainage (AMD) from abandoned/closed mines in Japan. For their sustainable treatment, future prediction of AMD quantity is crucial. In this study, AMD quantity was predicted for two closed mines in Japan based on a series tank model in three stages. The tank model parameters were determined from the relationship between the observed AMD quantity and the inflow of rainfall and snowmelt by using the Kalman filter and particle swarm optimization methods. The Automated Meteorological Data Acquisition System (AMeDAS) data of rainfall were corrected for elevation and by the statistical daily fluctuation model. The snowmelt was estimated from the AMeDAS data of rainfall, temperature, and sunshine duration by using mass and heat balance of snow. Fitting with one year of daily data was sufficient to obtain the AMD quantity model. Future AMD quantity was predicted by the constructed model using the forecast data of rainfall and temperature proposed by the Max Planck Institute–Earth System Model (MPI–ESM), based on the Intergovernmental Panel on Climate Change (IPCC) representative concentration pathway (RCP) 2.6 and RCP8.5 scenarios. The results showed that global warming causes an increase in the quantity and fluctuation of AMD, especially for large reservoirs and residence time of AMD. There is a concern that for mines with large AMD quantities, AMD treatment will be unstable due to future global warming.

© 2020 Elsevier Ltd. High contaminated levels of fluoride (F) in groundwater and drinking water are of significant concern for human health in many countries. This study examined adsorption and coprecipitation for effective F- removal from high F-containing water using inexpensive magnesium hydroxide, Mg(OH)2. Fluoride solutions were reacted with Mg2+-or Mg(OH)2-containing solution at different F/Mg molar ratios of 0.05-2, and the F- removal performance and mechanisms were investigated in both processes. As a result, the residual amount of F- in the solution decreased with an increase in Mg2+ concentrations for both processes, and the sorption isotherms followed the Langmuir type. Mg(OH)2 was precipitated only after F- removal, which suggests that adsorption to Mg(OH)2 was the main removal mechanism in both processes. However, the saturated adsorption capacity in the coprecipitation process was two times higher than that in the adsorption process. The chemical equilibrium calculation results implied that the surface complexation of MgF° and MgOH2F° was the dominant mechanism in the adsorption process whereas multiple complexations of Mg-MgF3° and Mg-MgF4- occurred in the coprecipitation process. This complex formation improves F- removal; hence, coprecipitation with Mg(OH)2 exhibited better potential as an efficient process for the treatment of industrial wastewater that contains F-.

This paper aims to examine the effect of cellulose nanocrystals (CNCs) derived from oil palm empty fruit bunch fiber (EFB) incorporating cement mortar on its structural performances. Cellulose nanocrystals (CNCs) were extracted from alpha -cellulose extracted from EFB using an acid hydrolysis process with a concentration of acid used was 64% w/v under the temperature of 45 degrees C for 60minutes. The Cellulose nanocrystals (CNCs) were mixed into the cement mortar ranging from 0 to 0.8% w/w and its mechanical properties were determined. The developed CNCs mortar was characterized for their compressive and flexural properties as well as microstructure. The influence of CNCs concentration, curing method, dispersion of CNCs on mortar's mechanical performance was thoroughly examined to find out the optimum condition. Overall results revealed that an addition of 0.4% cellulose nanocrystals has shown to increase the compressive and flexural strength to 46% and 20%, respectively cured under the wrapping method. The hydration of cementitious composites also improved significantly with the addition of CNCs by the formation of highly crystalline of portlandite observed under the XRD test. This present work demonstrates the importance of palm oil empty fruit bunch waste as a sustainable resource of cellulose nanocrystals admixture to achieve structural strength of cement mortar and promotes green technologies in construction.

The mineral surface characteristic is important for the flotation because it affects the flotation behavior of the mineral. Conventionally, in the flotation process for Cu sulphide ores, the degree of ore floatabilities varies depending on the mineral phase such as chalcopyrite, bornite, or chalcocite. Therefore, mineral surfaces are treated with activators and depressants to control the floatability of target minerals and obtain high recovery performance. There are lots of flotation reagents which have many effects on ores depending on ore characteristics and conditioning methods. For example, sodium hydrosulphide (NaHS) as activator is known to have the effect of re-sulfurizing and activating oxidized surface of chalcocite and bornite. On the other hand, NaHS is reported to depress chalcopyrite floatability. In this study, the evaluation of mineral surfaces was conducted to predict flotation behavior. Activation of Cu minerals (chalcocite, bornite, and chalcopyrite) by NaHS was experimented. The three Cu minerals were treated in two steps. Firstly, they were oxidized in the drying oven. Secondly, they were treated with NaHS solution. After each treatment step, each mineral was measured by contact angle apparatus then analyzed by X-ray photoelectron spectroscopy (XPS). The results of surface characteristics after oxidation and NaHS treatment were utilized to accomplish the study's objective.

To establish an effective recycling process for waste appliances, the process of recovering printed circuit boards (PCBs) containing valuable elements in comminution was investigated and evaluated. The present study performed comminution tests using three different types of waste appliances: smartphones, microwave ovens and electrical rice cookers. Comminution tests showed that a drum-type agitation mill operated at a mid-range rotation speed could achieve a relatively high recovery ratio of PCBs and inhibit excessive breakage of PCBs. Following these experiments, simulations using the discrete element method with a particle-based rigid-body model were conducted to evaluate the comminution performance of the drum-type agitation mill. Experimental and simulation results confirm that the processes of detachment of PCBs from waste appliances and subsequent breakage can be expressed by kinetic equations related to collision energy. It is concluded from these results that the kinetic equations obtained in experiments and simulations can be used to evaluate the recovery process of PCBs from waste appliances.

In this work we investigated the influence of planetary ball milling and vertical stirred ball milling on the leaching of a copper ore containing copper sulfate and covellite. We used a mixed experimental-simulation approach to correlate the kinetic parameters of leaching to the collision energy during grinding. The effect of milling was studied by scanning electron microscopy (FE-SEM), X-ray diffraction (XRD) and X-ray absorption fine structure (XAFS). Results showed that both high-intensity grinding techniques resulted into a dramatic decrease of particle size. Furthermore, under specific grinding conditions, the planetary ball milling determined also the partial amorphization of covellite. The collision energies corresponding to specific grinding conditions in terms of rotational speed and number of grinding media were assessed by DEM simulations and were related to the specific surface area after grinding. The specific surface area of grinded samples was found to be directly proportional to the collision energy in grinding. The leaching of the ore occurred through three subsequent steps: (i) dissolution of copper sulfate, (ii) dissolution of amorphousized covellite and (iii) dissolution of residual crystalline covellite. The results of kinetic fitting highlighted an increase of the rate constants for the leaching of amorphous and crystalline covellite by intensifying the milling conditions. By correlating the collision energies from DEM simulation with the leaching rate constants, we confirmed that the rate constants for the leaching of covellite increased due to an occurred mechanochemical reaction. The mechanochemical reaction that determined the partial amorphization of covellite occurred above 0.25 J/s · g. On the other hand, the rate constants for the leaching of the residual crystalline covellite constantly and progressively increased with the collision energy, thus highlighting an improvement of leaching due to an increase of surface area.

Recently, the discrete element method (DEM) has been widely applied to investigate the influence of operating and design parameters on grinding performances. However, while most studies investigated the effects of such parameters on the fineness of milling products, the relationship between them and the size dispersion of milling products has not been elucidated yet. In this study, we investigated the influence that the direction of the agitator shaft has on grinding performance in a media stirring mill. First, we proved by milling experiments that the media stirring mill with the horizontal direction of the agitator shaft can provide better grinding performances. Then, we further elucidated this experimental evidence by applying DEM simulations to a media stirring milling process in a vertical and a horizontal stirred mill. According to the simulations, in the vertical shaft configuration, the motion of the grinding media in the lower section through the vertical direction was inhibited by a too low velocity. On the other hand, the grinding media in the horizontal stirred mill moved more uniformly but with a lower collision energy. Furthermore, the grinding media in the low sections actively mixed with the grinding media in the upper sections, thereby resulting in a more uniform energy transfer and in a better grinding process. Accordingly, this study demonstrated that not only the collision energy but also the uniformity of the movement of the medium particles should be evaluated in order to investigate the grinding performance in a media stirred mill by DEM simulation.

We investigated the recovery of calcium fluoride (CaF2) from highly concentrated hexafluorosilicic acid wastewater by neutralization- purification. Neutralization was achieved by dosing calcium hydroxide, whereas purification was carried out by alkaline leaching with sodium hydroxide. X-ray diffraction, X-ray absorption fine structure, mineral liberation analyzer, Fourier transform infrared spectroscopy and Inductively-coupled plasma atomic emission spectroscopy were used to quantify the neutralization and leaching performance and to elucidate their mechanisms. The precipitation behavior was strongly dependent on the calcium (Ca)/silicon (Si) molar ratio. For a Ca/Si ratio of 1.12, approximately 25% of the total fluorine was precipitated selectively as CaF2. By increasing the Ca/Si ratio to 3.91, the recovery yield increased to 100% because of the precipitation of CaSiF6 and the hydrolytic decomposition of hexafluorosilicate ion (SiF6 2-) to CaF2. The hydrolytic decomposition of SiF6 2- resulted in the precipitation of silicon dioxide on the surface of the previously formed CaF2. Alkaline leaching by sodium hydroxide at 70°C resulted in an efficient removal of the silicon phase from the neutralized sludge with the formation of a CaF2 product with a grade above 90%. Leaching parameters, such as the kinetic constant and the activation energy, were determined by assuming first-order kinetics. The residual silicon phase in the final product could not be dissolved because of the formation of non-leachable SiO3 2-.

Using N,N,N',N'-tetra-2-ethylhexyl-thiodiglycolamide (TEHTDGA) in n-dodecane as the extractant, we compared the percentages of Pd(II) extracted from HCl and HBr solutions, and analyzed the structures of the Pd(II)-extractant complexes. For comparison, similar experiments were performed with di-n-hexyl sulfide (DHS), a well-known sulfide-type extractant. TEHTDGA extracted Pd(II) from both HCl and HBr solutions much faster than DHS. The Pd(II)/(TEHTDGA or DHS) stoichiometry in the organic phase was 1:2. For TEHTDGA, the extractability of Pd(II) from HBr solution was inferior to that from HCl solution, whereas the opposite was true for DHS. However, FT-IR spectroscopy and EXAFS measurements indicated that the inner-sphere structure of Pd(II) in the TEHTDGA complex was almost the same as that in the DHS system: in both cases, two of the halide ions in the tetrachloro- or tetrabromopalladate(II) ion were replaced by the sulfur atoms of two extractant molecules.

In situ remediation of a bauxite residue by integrating a storage area with CSIRO's soda recovery process was evaluated. The process consisted of the following steps: bauxite residue is neutralized with sulfuric acid; the slurry is separated into a neutralized residue and a leachate. The, residue is sent to a storage area -and washed with rainfall. The leachate and drainage/runoff from the storage area are collected and purified; sodium sulfate in the solution is then split into sodium hydroxide and sulfuric acid using bipolar-membrane electrodialysis. Finally, the sodium hydroxide is used in a Bayer refinery and the sulfuric acid is used for neutralization of bauxite residue. This study investigated the optimum conditions and remediation of the bauxite residue. pH rebounding was observed after sulfuric acid neutralization of bauxite residue. Considering this rebound, the most suitable pH was set at 4.5. Washing remediated the residue to accomplish the goals for bauxite residue rehabilitation. Furthermore, sodium hydroxide and sulfuric acid were recovered by bipolar -membrane electrodialysis. Cost -benefit analysis for an assumed one million tons refinery showed 10% return on investment. Evaluation of the advantages of neutralized residue and technical improvements are expected to make this process feasible for remediation of bauxite residue. (C) 2016 Elsevier B.V. All rights reserved.

Hexavalent chromium (Cr(VI)) attracted researchers' interest for its toxicity, natural availability and removal difficulty. Nevertheless, its sorption mechanism is not clearly understood yet. In this work, we elucidated the sorption mechanism of the co-precipitation of chromates with ferrihydrite through quantitative analysis. The influence of Cr/Fe molar ratio on sorption was investigated by zeta potential measurements, X-ray diffraction (XRD) and X-ray adsorption fine-structure analysis (XAFS). Coprecipitation at pH 5 showed almost twice the sorption density of adsorption at pH 5. In co-precipitation, a shift of the XRD peak due to inner-sphere sorption of chromate was observed at Cr/Fe molar ratio 0.5. For adsorption, the same peak shift was confirmed at Cr/Fe molar ratio of 1. Zeta potential at pH 5 suggested that the sorption mechanism changed at Cr/Fe molar ratio 0.25 for coprecipitation and at Cr/Fe molar ratio of 1 for adsorption. Fitting of Cr and Fe K-edge extended X-ray adsorption fine-structure suggested that ferrihydrite immobilized Cr(VI) via outer sphere surface complexation for lower Cr/Fe ratios and via inner-sphere surface complexation for higher molar ratios. At higher molar ratios, bidentate binuclear Cr Fe bonds were well established, thus resulting in the expansion of the ferrihydrite structure. (C) 2017 Elsevier B.V. All rights reserved.

The separation properties of Pt(IV) over Fe(III) in HCl solutions using N-2-ethylhexyl-bis(N-di-2-ethylhexyl-ethylamide)amine (EHBAA) were investigated and then compared with those using the conventional extractant tri-n-octylamine (TOA). Also, the structural analyses of Pt(IV) in both of the aqueous (HCl solution) and organic (EHBAA in n-dodecane-2-ethylhexanol solution) phases were performed with EXAFS spectroscopy. The extractability of Pt(IV) was much higher with EHBAA than with TOA in the studied HCI concentration range (0.2-8 M HCl); additionally, EHBAA selectively extracted Pt(IV) over Fe(III) under the condition of [EHBAA] &lt;= 0.1 M and [HCI] &lt;= 1 M. The Pt(IV) loading capacity of 0.1 M EHBAA was about 9.2 (about 0.05 M). Most of the Pt(IV) extracted with 0.1 M EHBAA from 1 M HCI was stripped with 0.1 M NaOH; the co-extracted Fe(III) was selectively scrubbed with distilled water. The structural studies indicated that the Pt(IV) extracted with EHBAA from 1 M HCl formed an ion-pair complex, [PtCl6].(EHBAA.H)(2). (C) 2017 Elsevier B.V. All rights reserved.

Bangladesh has emerged as a leading ship breaking nation. We conducted a material flow analysis of steel in Bangladesh with an emphasis on the ship breaking industry (SBI). The total aggregate domestic steel consumption in fiscal year (FY) 2010 was 2,930,000 tonnes (t) in Bangladesh; SBI met approximately 51% of the demand for raw materials and 37% of the demand for finished steel products. Rolling industries output in FY2010 was 1,451,000 t; 23% of the input for this production was from ship breaking sources. Dismantled ships also generate high-quality reusable steel scraps. SBI was found to be the sole source of scraps for small rerolling industries in Bangladesh, and their output in 2008 more than doubled as compared to 2005. Larger rolling industries fulfilled their input needs for steel scraps by using both SBI and imported materials. We found a sharp increase in input imports during the global ship breaking recession in 2003-2007 and when Bangladesh's SBI faced a temporary ban in 2010. Induction furnaces in Bangladesh in FY2010 produced a total of 787,000 t of billets; more than 40% was from ship-sourced scraps. In 2008, the country's steel consumption was 3,220,000 t, that is, 22 kilograms per person, and the intensity of steel use was 40 grams per U.S. dollar, which was much higher than that of other developing countries with a similar per capita gross domestic product (GDP). The country exhibited a high level of steel consumption relative to its GDP, which is indicative of the contribution of SBI.

<p>Smaller grinding media beads in bead mills are well known for determining high grinding performances. However, the post-grinding separation between beads and slurry might be a difficult task, especially in bead mills with centrifugal bead separation, where the separating performances are strongly affected by the shape of the rotors in the mill. Aiming to study and design grinding operations, the discrete element method (DEM) is a powerful tool which allows for predicting the grinding and separating performances in the mill. In this study, by using DEM simulations, we examined the slurry-beads separation in a bead mill and we investigated the influence of the rotor shape on the separating performances. We compared the performances of two kinds of rotors, one with conventional shape and one with outside projections for the activation of the media beads. Results of DEM simulation were in good agreement with experimental results.</p>

The handling of wet particles in chemical engineering is often difficult because cohesive forces acting on wet particles cause particulate aggregation and the adherence of devices, unlike what occurs under a dry condition. The liquid-bridge force is introduced to the discrete element method in the investigation of the behavior of wet particles. However, existing numerical modeling has problems from the viewpoint of the effect of cohesion in contact states. Specifically, the cohesive force is treated as a constant value for contact states. This means the effect of the cohesive force is not only dependent on the spring constant in the discrete element simulation but is also frequently overestimated. To solve this problem, the present study developed a numerical contact model considering quantitatively the effect of the cohesive force in contact states and validated the model for a pan pelletizer. The behaviors and cascading angles of wet particles in simulation and experiments were in good agreement and the validity of the contact model was thus demonstrated. The present numerical contact model is thus a promising model for the numerical simulation of wet particles. (C) 2016 The Society of Powder Technology Japan. Published by Elsevier B.V. and The Society of Powder Technology Japan. All rights reserved.

For the establishment of appropriate recycling process, the delamination of electric components from printed circuit boards (PCBs), which are major components of c-waste, is expected, because some of useful critical metals are concentrated in specific components. However, the knowledge about the mechanism of the delamination process in a drum typed agitation mill is still limited and uncertain. To better comprehend the mechanism, in this study, the particle-based simulation and comminution tests using handmade PCBs were conducted. The behavior of PCBs and the air flow in the mill having flexible chains was simulated by the discrete element method (DEM) coupled with computational fluid dynamics (CFD). To model the shape of PCBs, the particle based rigid body model was introduced into the DEM. Since this model could not directly simulate the breakage phenomena, collision energy was calculated to qualitatively evaluate the comminution performance. In addition, the simulation results were compared with the experimental comminution tests, This study demonstrated the behavior of PCBs and the air flow in the mill, and the effect of the air to comminution process in the mill. It was also shown that the collision energy related to parts collision was better correlated with the experimental results and this correlation can be assumed using first order rate equation, which suggested part detachment was mainly brought by direct collision to parts in the mill.

Die filling is an important aspect of powder molding in chemical engineering. The discrete element method (DEM) has been applied to simulations of die filling systems in the literature. In these simulations, the die has been modeled by simple shapes such as cylinders and cuboids. However, industries require modeling of complex die shapes in the computations. In addition, the existing DEM is problematic from the viewpoint of industrial applications, since complexly shaped dies might not be modeled by existing technologies. To solve this problem, the signed distance function (SDF) model is applied to the DEM simulation (DEM/SDF) and the DEM/SDF approach is validated for arbitrarily shaped dies. Focusing on macroscopic powder flow, simulation results are compared with experimental results, and good agreement is confirmed for the spatial distribution of velocity, the projection areas of the shoe, and the final mass of filling particles. Therefore, the adequacy of the DEM/SDF model is newly demonstrated in the die filling system; i.e., the DEM/SDF method is shown to be an effective method for the numerical simulation of particle flow into arbitrarily shaped dies. (C) 2015 Elsevier Ltd. All rights reserved.

The sorption mechanism of dilute Zn [initial Zn(II) concentration up to 40 mg dm(-3)] on aluminum hydroxide was investigated. Adsorption and coprecipitation at pH 7 were compared. The adsorption process gave a Langmuir-type isotherm and the zeta potential of Zn(II)-adsorbed aluminum hydroxide decreased linearly with increasing sorption density of Zn on aluminum hydroxide. The adsorption mechanism is therefore mainly surface complexation. In contrast, in the coprecipitation process, a Brunauer-Emmett-Teller like isotherm was obtained; the slope of the zeta potential versus Zn(II) sorption density decreased when the initial Zn/Al molar ratio was greater than 0.5. The X-ray diffraction pattern of Zn(II)-coprecipitated aluminum hydroxide changed from that of poorly crystalline gibbsite to a Zn-Al layered double-hydroxide (LDH) when the initial Zn/Al molar ratio was greater than 0.5, showing that surface complexation was the main sorption mechanism, but surface precipitation of Zn-Al LDH was also involved when the initial Zn/Al molar ratio in the coprecipitation process was greater than 0.5. A quantitative diffuse-layer model was constructed. The aluminum hydroxide exchange capacity was set at 0.61 mol mol-Al-1, based on the experimentally determined surface area, 340 m(2) g(-1). Surface complexation coefficients for H+, OH-, and Zn(II) adsorption on aluminum hydroxide were determined by fitting to the experimental adsorption results. The obtained parameters were in excellent agreement with those previously reported for a database of gibbsite adsorption equilibrium constants. The pH edge for Zn(II) removal by aluminum hydroxide was successfully reproduced by the constructed model. (C) 2015 Elsevier B.V. All rights reserved.

Acid mine drainage from approximately 80 abandoned or closed Japanese mines has been treated by neutralization over the last forty years. A more efficient and cost-effective treatment process is required, as the national government spends billions of yen each year to protect the environment from acid mine drainage discharge. Surface complexation at the interface between hydroxides such as ferrihydrite or aluminum hydroxide and wastewater is the most important mechanism for the removal of dilute toxic ions. We have categorized the immobilization mechanism of inorganic toxic elements at the hydroxide solid/liquid interface into surface complexation and surface precipitation. We have introduced this concept using experimental methods to understand their mechanism, for example arsenate co-precipitation with ferrihydrite, fluorine co-precipitation with aluminum hydroxide, and boron co-precipitation with magnesium hydroxide. From detailed investigations using isotherm formation, X-ray diffractometry, and Fourier-transform infrared spectroscopy analysis, we found that co-precipitation achieved a more efficient removal of toxic anions than simple adsorption, because of surface precipitation or surface complexation of multiple complexes.

Dismantling (or "breaking") of ships invigorates global shipping by replacing older ships and recycling or reusing as much as 95 % of their materials. Recently, Bangladesh is dominating global ship breaking. Here, we aimed basically at expounding the inflows of the ship breaking industry (SBI) in Bangladesh from the perspectives of origin, types, and lifespan of dismantled ships in order to develop a better understanding of this industry. The inflows in SBI have been increasing and the tonnage dismantled rose to a record high of 2,308,525 LDT (light displacement tonnage) in 2009. Interestingly, ships dismantled in Bangladesh were relatively younger having the mean age of 27 years. Of the outflows from ships dismantled, reusable/recyclable steel comprised 85 % of the total weight of ships; the rest were machinery, hardware, fittings, and consumable items. The major hurdle we faced was the unwillingness of stakeholders in disclosing available but relevant information due to widespread suspicion. We suggest that keeping organized records and their disclosure is critical to developing a comprehensive understanding of this industry. We are hopeful that this research will pave the path for continued objective scientific investigations into the contributions, both positive and negative, as well as the evolution of SBI in Bangladesh.

The removal mechanisms of silicate using an aluminum hydroxide co-precipitation process was investigated and compared with an adsorption process, in order to establish an effective and validated method for silicate removal from wastewater. Adsorption isotherms, XRD and FT-IR analyses showed that silicate uptake occurred by adsorption to boehmite for initial Si/Al molar ratios smaller than two, but by precipitation of poorly crystalline kaolinite for the ratios larger than two, in both co-precipitation and adsorption processes. Silicate was removed by two steps: (i) an initial rapid uptake in a few seconds; and (ii) a slow uptake over several hours in both processes. The uptake rate in the first step was higher in the co-precipitation process than in adsorption process, presumably due to increased silicate adsorption to boehmite and rapid precipitation of kaolinite. These results suggest that silicate removal using aluminum salts could be effectively achieved if the pH adjustment and aluminum concentration are strictly controlled.

The discrete element method (DEM) coupled with fluid analysis was applied to describe the basic characteristics of media beads in a wet-type media agitation grinding mill, which is expected for ultrafine particles grinding or dispersion. Three types of agitator were compared by both of simulation and experimental investigation to know which one is suitable for ultrafine particles grinding and how the shape of agitator affects grinding performance. In the simulation, the collision energy and collision number between beads or bead and wall were calculated from kinetic energy at the instant of impact, separately in normal and tangential direction. On the other hand, the grinding rate and minimum ground size were obtained from experimental grinding results using calcium carbonate particles. The grinding rate had positive correlation to the average value of the collision energy between bead and wall, and the minimum ground size was correlated to the ratio of the collision energy in tangential direction to total collision energy between beads. This means that these two values obtained from DEM simulation are useful for a optimization design of a wet-type agitation mill. We also investigated the correlation between the collision energy for bead and wall calculated from DEM simulation results and the degree of abrasion in the wall observed in experimental grinding tests. At the part in which remarkable abrasion of wall was observed inside the mill, larger value of the collision energy between bead and wall was obtained from DEM simulation.

We investigated co-precipitation using magnesium (Mg) salt as a cost efficient method of removing B from wastewater. To clarify the mechanism of co-precipitation and the effect of precipitation rate against B sorption mechanism, we conducted co-precipitation experiments changing reaction time at different temperatures. For these experiments, we carried out sorption isotherm formation and XRD analysis to clarify how co-precipitation of B with magnesium hydroxide (Mg (OH) ₂) occurred. The sorption isotherm of co-precipitation was a BET type, while the XRD peak shift occurred as the initial B/Mg molar ratio increased. These results suggested that the mechanism of B uptake was a combination of surface precipitation and surface complexation, and the later mechanism became more apparent as the initial B/Mg molar ratio increased. XRD spectrum of co-precipitated residues was relatively similar to that of hydromagnesite, which indicated that structure of surface precipitation is similar to that of hydromagnesite. Co-precipitation experiments for 6 hours revealed that Mg precipitation rate was faster at the higher temperature, while sorption density became worse as the temperature increased. At 40<tt>℃</tt> and 60<tt>℃</tt>, XRD peak shift did not occur when the initial B/Mg molar ratio was0.063, which suggests that fast precipitation rate disturbed production of surface precipitation. In addition, the initial B/Mg molar ratio in which B sorption mechanism changed from formation of surface compexation to production of surface precipitation became larger as Mg precipitation rate increased.

Fenton reaction has been focused as an option of CO₂ reduction to organic compounds such as alcohol. We investigated the effect of morphology of precipitates during Fenton reaction to CO₂ reduction in order to establish effective and validated process. Precipitates during/after reactions were analyzed by X-ray diffraction (XRD) and Fourier-transform infrared spectroscopy (FT-IR). Morphology of precipitates was gradually changed from ferrihydrite to schwertmannite when the reaction time and pH were increased. The chemical thermodynamics equilibrium calculation suggested that schwertmannite was the main precipitate in Fenton reaction. In the actual experiments, ferrihydrite was also formed because schwertmannite is hardly precipitated under pH sharp fluctuation associated with Fenton reaction. Reactivity between hydrogen peroxide and artificial sludge (ferrihydrite or schwertmannite) was measured by Absorptiometer using the Mutarotase-GOD method. Ferrihydrite consumed more hydrogen peroxide than schwertmannite, which suggested that hydroxyl radical was produced by the reaction between hydrogen peroxide and the surface of ferrihydrite. All experimental results showed that more CO₂ was reduced to organic compounds when more ferrihydrite was formed in precipitates. These results suggested that ferrihydrite was more largely contributed to Fenton reaction than schwertmannite.

Acid Mine Drainage (AMD), high acid water containing heavy metals discharged from mines, not only from the operating ones but also from the already abandoned ones, has been recognized as major cause of mine pollution. In Japan, the government spends billions of yen every year to prevent pollution caused by AMD in about 80 abandoned mines. It is widely believed that the treatment will continue for decades or an even century,but it is difficult to predict how long it will be and how much it will cost.Therefore, a predictive model is quite helpful. In our previous work, a two-steps predictive model for solution composition and neutralization chemical requirements of AMD in future was constructed based on the regression analysis and geochemical modeling. The model requires the past historical water quality data from AMD monitoring, such as metal concentration and pH in the solution, instead of the sample rocks as other conventional prediction methods. In this paper, two more case studies were carried out for Japanese abandoned mines. In each case study, future solution composition, neutralizer dosage and sludge generation were estimated. Then, the time when the water quality satisfies Japanese effluent standard was estimated. The results of this study demonstrate the effectiveness of our model for the prediction of AMD quality and chemical requirements of neutralization treatment after mine closing. These results were analyzed in the context of TMR (Total Material Requirement) and the environmental burden of this neutralization process is relatively small comparing to the burden of operations and the long time span of neutralization seems more serious concern. Comparing the result of this paper with that of our previous works, it is revealed that we have to carry out more case studies in order to obtain the general idea of future AMD treatment.

The effects of NO3- and SO42- ions on chloride ion removal from neutralized sludge were investigated to determine if removal of chloride ions enabled the use of sludge for cement production. An artificial sludge prepared from iron, calcium and chloride that primarily consisted of two-line ferrihydrite was prepared. Chloride ions in the sludge were easily washed out by distilled water, NO3- water or SO42- water to levels below those specified in the standard for Eco-cement production (1,000 mg/kg), but the washed sludges did not meet the standard for ordinary Portland cement (350 mg/kg). Conversely, artificial sludge prepared from aluminum, calcium and chloride mainly consisted of low crystalline boehmite with other minor components. Chloride ions in this sludge were only reduced to below those specified in the standard for the ordinary cement production if SO42 water was used to wash the sludge. The filtration rate during washing using SO42 water was faster than when distilled water or NO3- water was used because SO42 ions were adsorbed onto the sludge particles and the absolute value of the zeta potential of the sludge particles decreased. Overall, sludge washing using SO42-water was the best process for chloride ion removal and efficient filtration.

This study investigates the removal mechanism of arsenate, i.e., As(V), by coprecipitation with aluminum hydroxide in solution at pH 5. Both the filtrates and precipitates were analyzed. The removal mechanisms of As(V) were investigated by constructing sorption isotherms and by analyses of X-ray diffraction (XRD) patterns, zeta potentials, and Fourier-transform infrared (FT-IR) spectra. The sorption isotherms showed Brunauer-Emmett-Teller (BET) behavior. The sorption densities showed a rapid uniform increase when the initial As/Al solution molar ratio was more than 1.5. This suggests two sorption mechanisms of As(V), namely surface complexation and three-dimensional uptake, which were dependent on the initial As/Al molar ratio. It is important to note that the As(V) and Al(III) concentrations were unable to reach the thermodynamic solubility product of aluminum arsenate in the bulk solution. The three-dimensional uptake was therefore estimated to be not bulk precipitation but surface precipitation of aluminum arsenate. Surface precipitation, generation of a new surface phase, is known to be derived from surface complexes. XRD, zeta potential, and FT-IR analyses of the precipitates for each As/Al molar ratio confirmed that As(V) was predominantly removed by the adsorption of the As(V) oxyanions to the aluminum hydroxide surface when the initial As/Al molar ratio was less than 1.5. At an initial As/Al molar ratio greater than 1.5 at pH 5, As(V) was removed mostly by surface precipitation, evidently by poorly crystalline aluminum arsenate on the surface. This sorption as surface precipitation is a phenomenon specific to the coprecipitation process.

Conversion of carbon dioxide to useful chemicals or fuels has become an active area of research. However, most methods used in these studies need expensive or precious reagents, such as hydrogen or rare metals. The objective of this study is the reduction of carbon dioxide to organic compounds using a cyclic Fenton reaction that uses only inexpensive reagents. We achieved carbon dioxide reduction to methanol and ethanol using this reaction at ambient temperatures and pressures. The Fenton reaction was promoted by the repetitive addition of H2O2 and Fe(II) salts, resulting in the synthesis of methanol/ethanol and formic/acetic acids from carbon dioxide saturated water. In addition, it was found that H2O2 and Fe(II) in a molar ratio of 1 or 2 is optimal for the reaction as this increase the generation of OH. The catalytic effects of magnetite, pyrite, sodium hypophosphite and copper sulfate were also investigated in the reduction of carbon dioxide to acetic acid. All reagents acted as a catalyst, and the concentration of TOC and acetic acid was increased. The highest concentration of acetic acid was achieved with the addition of copper sulfate. This enhanced the generation of H or H− as Cu(II) forms more stable complexes with oxalic acid than Fe(II)/Fe(III), meaning more free Fe(II)/Fe(III) ions were present in the solution. © 2013, The Resources Processing Society of Japan. All rights reserved.

Removal of fluorine in effluent with low concentration is difficult technique and an effective method has not been established. This paper describes a novel fluorine-removal process that composed the following processes, addition of Al(III) source to feed water, conditioning of the slurry with magnesium oxide (MgO), neutralizing reaction, returning the settled slurry, and gravitational settling of the solids. This process allows the formation of a mixed Mg(II)-Al(III) hydroxide precipitate, which gradually develops into Layered Double Hydroxides (LDH) compound. MgO, which serves as both the neutralizer and the Mg(II) source, contributes to both the excellent settling and dewatering characteristics of the resulting solids. The sludge returning technique, well-known as High Density Sludge (HDS) method, is employed to prolong the sludge retention time to dissolve as much MgO as possible. Repeated batch-wise fluorine-removal tests showed that the residual fluorine concentration gradually decreased according as the number of batch test increased. Optimum fluorine removal ratio reached 96 %, where initial fluorine concentration 20 mg/L decreased below the national environmental standard, 0.8 mg/L. Powder X-ray diffraction analysis indicated the presence of both LDH phase and Periclase phase in the formed solids. Considering the good settling and dewatering characteristics of solids, the proposed process served as alternative treatment technique for low concentrated fluorine-containing effluents.

Construction and calculation using surface precipitation model were attempted for As(V) coprecipitaiton treatment with ferrihydride. Surface precipitation model was defined as extended surface complexation model. Original surface complexation model with parameter values reported by Dzombak and Morel was validated to adsorption experimental results for As(V) removal using ferrihydrite. The surface complexation model could represent experimental As(V) removal and isotherm quantitatively. In surface precipitation model, precipitation was described by the formation of solid compound between ferric hydroxide and ferric arsenate. Activity of these precipitates was determined by surface precipitation ratio of FeAsO₄(s) obtained experimentally from XANES analyses. Solubility products of surface precipitation of FeAsO₄(s) (K_spAsO4(_suf. ) were determined by fitting to sorption densities and surface precipitation ratio in each condition. The values of K_spAsO4(_suf.) were determined 10<tt>⁻</tt>^7.7 at pH5 and 10<tt>⁻</tt>^10.2 at pH7, respectively. These values were reasonably relative to the literatures and previous studies. Based on the obtained K_spAsO4(_suf.) value, As(V) removal and isotherm were calculated for As(V) coprecipitation treatment using surface precipitation model. Good agreement between experimental and calculated values was observed. For both of observed and calculated data, the sorption isotherms in coprecipitation treatment indicated saturated shapes because the species of surface precipitation was FeAsO₄(s) and surface precipitation rate largely increased when As/Fe molar ratio is relatively low. These results were suggested that the quantitative prediction of As(V) coprecipitation treatment was possible if K_spAsO4(_suf.) value was estimated experimentally.

The reaction mechanism of H3BO3/B(OH)(4)(-) with MgO in aqueous phase was investigated using sorption isotherm, XRD, B-11-NMR and FTIR. Release of Mg2+ was observed soon after contact of MgO with H3BO3 and maximum released Mg2+ was proportional to the initial boron concentration, suggesting ligand-promoted dissolution of MgO by H3BO3. The molecular form of H3BO3 was more reactive with MgO in releasing Mg2+ ions than B(OH)(4)(-). B-11-NMR results indicated that trigonal B (B-[3]) was predominant over tetrahedral B (B-[4]) in solid residues after sorption of H3BO3. The molar ratio of B-[4]/B-[3] increased with H3BO3 sorption density. XRD patterns for the solid residues were assigned to Mg(OH)(2) and peaks broadened with increasing H3BO3 sorption density, except for (hk0) planes due to c-axis lattice strain induced by incorporation of H3BO3 between layers. These results indicated that H3BO3 interfered in the c-axis stacking of in Mg(OH)(2). Molecular H3BO3 acted as a trigger when reacting with the MgO surface, releasing Mg2+ to produce an unstable complex leading to the precipitation formation of Mg(OH)(2), which is a sink for the immobilization of H3BO3/B(OH)(4)(-).

Acid mine drainage (AMD) from about 80 abandoned or closed mines in Japan are actively treated by neutralization; the government spends billions of yen every year to protect the environment from these discharges, and treatment will have to continue for many years. However, it is difficult to predict the future AMD chemistry, neutralizer requirements, and volume of sludge to establish future costs, chemical inputs, and wastes. The water monitoring data or source rock samples for conventional predictive methods are not available. In this study, a predictive model for AMD composition and the neutralization process was constructed based on geochemical modeling, assuming first order kinetics for the dissolution of several minerals. The solution composition, neutralizer requirements, and sludge generation were estimated for case studies at two abandoned mines in Japan: a sulfur mine, and a copper and iron mine. The model effectively predicted AMD composition after termination of mining and was also useful for estimating future neutralizer requirements and sludge volumes. This research will increase understanding of the lifecycle environmental costs in the mining industry.

The effects of attrition on sandy and silty Pb-contaminated soil from shooting ranges were quantitatively investigated. The abrasion rate could be quantitatively evaluated using a population balance model from the size distribution of soil particles before and after attrition in an intensive mixer. The maximum abrasion rate was 0.047 mu m/s in the first stage of attrition (1 mm of grinding), and then declined between 2 and 4 min of grinding. The two samples had similar maximum abrasion rates, but the decline in the abrasion rate was larger in the silty soil, which would have a thinner soft layer on the surface of the soil particles, than the sandy soil. The incremental change in the mass fraction of Pb in the &lt;20 mu m particle size fraction increased proportionally with the abrasion thickness from the surface of the soil particles. Although the Japanese regulatory standard for the Pb concentration in soil (150 mg/kg) was not met for either sample, the Japanese regulatory standard for the concentration of leached Pb (0.01 mg/L) was met for silty soil after attrition. Sequential extraction using Tessier's procedure for the &gt;20 mu m size fraction before and after attrition showed the attrition was more effective for the oxides or organic-bound species and carbonate species of Pb chemical forms. [doi:10.2320/matertrans. M2012240]

Recycling of printed circuit boards (PCBs) is an important subject not only from the treatment of waste but also from the recovery of valuable materials including rare metals. We have tried a special and selective grinding such as parts detachment from the board using drum typed agitation mill to concentrate a part of “rare metals”. The objective of this study is revealing the mechanism of parts detachment process from PCBs. A simulant PCBs on which nine capacitors were solder-mounted were used for the communition test using the agitation mill. Effects of rotation speed and the number of boards for parts detachment or board breakage were investigated. Both of parts detachment rate and board breakage rate were increased as rotation speed increased. On the other hand, as the number of boards increased, parts detachment rate was increased while board breakage rate was slightly increased. DEM simulation with and without particle breakage model was conducted. DEM simulation with spherical particle model (without particle breakage model) showed that board breakage was strongly affected by collision of PCBs to the wall in the normal direction while parts detachment was affected by both of collision of PCBs to the wall in the tangential direction and interaction between PCBs. To investigate the mechanism of parts detachment process more directly, DEM simulation with particle breakage model was also conducted. Simulation results obtained from DEM with particle breakage model corresponded to these experimental trends successfully. © 2012, The Resources Processing Society of Japan. All rights reserved.

This paper describes the possibility of concentrating minor rare metals contained in cellular phones by applying a novel comminution and the combination of physical separation technologies, which were followed by metallurgical processes to extract them. We compared two kinds of comminution processes, conventional and novel, from the viewpoint of compositional separation and combined two kinds of physical separation categories, &amp;ldquo;Device Separation&amp;rdquo; and &amp;ldquo;Powder Separation&amp;rdquo; to achieve an effective concentration of rare metals. It was demonstrated that the novel comminution process could separate printed circuit board (PCB) from the body in the first stage and detach the installed electronic devices from the board in the second stage and that several kinds of rare metals could be concentrated by combining the novel comminution and &amp;ldquo;Device/Powder Separation&amp;rdquo;. The &amp;ldquo;Device&amp;rdquo; and &amp;ldquo;Powder&amp;rdquo; products concentrated are expected to be further treated by hydrometallurgical processes to extract rare metals and/or stocked as &amp;ldquo;Artificial Deposits&amp;rdquo; in accordance with the concept of &amp;ldquo;RtoS (Reserve to Stock)&amp;rdquo;.

Gallium metal under the freezing point was observed to maintain its liquid state by dispersing silica nanoparticles of a given particle size and concentration. Though the freezing point of pure gallium is 302.9 K, the liquid gallium maintained its supercooling state at 276-277 K for more than 400 days by dispersing 1.0 wt. % of silica nanoparticles (10 nm in size). Extended x-ray absorption fine structure analysis shows that the supercooled gallium liquid has a beta-Ga-like feature, and the nearest neighboring atom distance is 0.1 angstrom larger than that of pure liquid gallium. This method opens the way to use liquid gallium as a promising fluid carrier in energy conversion devices. (C) 2011 American Institute of Physics. [doi:10.1063/1.3645596]

The mechanism for removal of dilute As (V) by coprecipitation with aluminum hydroxide was investigated using sorption isotherms, X-ray diffraction (XRD) patterns, and zeta potential analysis. The results from the coprecipitation experiments were compared with those from simple adsorption experiments. &lt;BR&gt;During simple adsorption of As (V) on aluminum hydroxide, the sorption density obeyed a Langmuir-type isotherm. XRD patterns of the adsorbed As (V) were independent of the mass adsorbed. The relationship between zeta potential and sorption density was linear. These results suggest that As (V) was removed mainly by surface complexation.&lt;BR&gt;In comparison, during As (V) co-precipitation with aluminum hydroxide, the sorption density followed a BET-type isotherm at pH 5 and 7, and there was a steep increase in sorption density at a transition point. XRD patterns and zeta potential analysis also supported the existence of a transition point during As (V) co-precipitation. The transition was from surface complexation to precipitation, and occurred when the initial molar ratio was As/Al=1.5. These results suggest that during coprecipitation As (V) is removed by surface complexation at molar ratios of As/Al &amp;le; 1.5, and by the formation of amorphous aluminum arsenate at As/Al &amp;ge; 1.5.

Comparison of removal characteristics between coprecipitation and adsorption method of aluminum hydroxide for wastewater containing F (-I) was attempted by sorption isotherms, X-ray diffraction (XRD) patterns, and zeta potential analysis. &lt;BR&gt;When F (-I) was coprecipitated with aluminum hydroxide, the sorption density was higher at pH 7 than at pH 5. The sorption density at both pH values followed a BET-type isotherm. High sorption density was obtained when the initial F/Al molar ratio was high, and some of the aluminum hydroxide dissolved. The sorption density in adsorption treatment was slightly lower than that in coprecipitation treatment. These results suggest that the mechanism of F&lt;SUP&gt;&amp;mdash;&lt;/SUP&gt; coprecipitation was not simply surface complexation of F&lt;SUP&gt;&amp;mdash;&lt;/SUP&gt;.&lt;BR&gt;At pH 7, the XRD patterns for F (-I) coprecipitates and aluminum hydroxide were identical. The slope between zeta potential and sorption density changed when the initial molar ratio was F/Al=3 in both coprecipitation and adsorption experiments. This F/Al=3 transition point corresponded to the point where the sorption density increased abruptly in the sorption isotherm. These results reveal that F (-I) was primarily adsorbed as a surface complex to aluminum hydroxide when the initial molar ratio was F/Al&amp;lsaquo;3. In contrast, when the initial molar ratio was F/Al&amp;rsaquo;3, amorphous compounds of F&lt;SUP&gt;&amp;mdash;&lt;/SUP&gt; and Al (III) formed or F-Al complexes such as AlF&lt;SUP&gt;2-&lt;/SUP&gt;, AlF&lt;SUB&gt;2&lt;/SUB&gt;&lt;SUP&gt;+&lt;/SUP&gt;, AlF&lt;SUB&gt;3&lt;/SUB&gt;&lt;SUP&gt;0&lt;/SUP&gt; and AlF&lt;SUB&gt;4&lt;/SUB&gt;&lt;SUP&gt;-&lt;/SUP&gt; were adsorbed.

Deep-sea minerals extraction has been attracted as domestic resources of Japan from the viewpoint of resources security. This study investigates feasibility evaluation with uncertainties for deep-sea mineral resources development project using real option analysis. Resources development has a lot of unique uncertainties. We propose multi-investments (compound option) model considering volatility of metal prices and ore deposit scale. Results from this model imply high option value at a case study of Sunrise ore deposit in Japanese EEZ, and show marginal investment prices and marginal cost to abandon the project by comparative statics. Furthermore, considering historical trend of metal prices, different types of stochastic process i.e. mean reverting process and geometric brownian motion are compared.

水酸化第二鉄による希薄As(V)の共沈機構について、収着等温線の作成、ゼータ電位測定、XRD測定およびXAFS測定によって多面的に考察を行った。初期As/Fe>0.4の範囲において、ヒ酸鉄の飽和度には達していないものの、非晶質ヒ酸鉄を主成分とする表面沈殿が生成することがわかった。EXAFSによる考察により、初期As/Feモル比が増加するにつれて、単核二座錯体が増加し、逆に二核二座錯体が減少して、徐々に表面錯体構造から沈殿構造へと推移することがわかった。

XRD/XAFS analysis were conducted to investigate the As(V) co-precipitation mechanism with ferrihydrite (γ-FeOOH). In As(V) co-precipitation with ferrihydrite, XRD results showed that As(V) complexation to the surface of ferrihydrite was dominant when the initial molar ratio of As/Fe was less than 0.25, whereas surface precipitation of amorphous ferric arsenate was formed when the initial molar ratio of As/Fe was more than 0.5.<BR>Both of XANES and EXAFS analysis on K-edge of As showed As(V) co-precipitates with ferrihydrite was the mixture of As(V) adsorbed ferrihydrite and amorphous ferric arsenate. Molar ratio of amorphous ferric arsenate in As(V) co-precipitates was estimated to be more than 0.5 when the initial molar ratio of As/Fe was more than 0.5. These results are in good agreement with the XRD results. EXAFS analysis assuming one surface complex for As-Fe bond showed the coordination number of As to Fe in As(V) co-precipitates increased with increasing the initial molar ratio of As/Fe. Moreover, EXAFS analysis assuming three kinds of surface complexes for As-Fe bond showed the coordination number for 2.85 Å of the atomic distance of As-Fe increased and it for 3.24 Å of the atomic distance of As-Fe decreased with increasing the initial As/Fe molar ratio. All experimental data obtained in this study showed As(V) co-precipitation mechanism shifted gradually from As(V) complexation to the surface of ferrihydrite toward amorphous ferric arsenate with increase in the initial molar ratio of As/Fe.

Dilute arsenate (As(V)) coprecipitation by ferrihydrite was investigated to determine if treatment of acid mine drainage containing dilute As(V) using coprecipitation is feasible. The sorption density obtained at pH 5 and 7 was nearly identical when As(V) was coprecipitated with ferrihydrite, while it was higher at pH 5 when As(V) was adsorbed on the ferrihydrite. The high sorption density of As(V) to ferrihydrite in coprecipitation with 1-h reaction time suggested that coprecipitation Occurs via both adsorption and precipitation. Furthermore, the relationship between residual As(V) and sorption density revealed a BET-type isotherm, with a transition point from a low residual As(V) concentration to a high residual As(V) concentration being observed for all initial As(V) concentrations between 0.15 and 0.44 mmol/dm(3) when the initial molar ratio was 0.56 at pH 5 and 7 X-ray diffraction and the xi potential revealed that the transition point from surface complexation to precipitation was obtained when the initial As/Fe ratio was 0.4 or 0.5. When dilute As(V) was coprecipitated with ferrihydrite at pH 5 and 7, it was primarily adsorbed as a surface complex when the initial molar ratio was As/Fe &lt; 0.4, while a ferric arsenate and surface complex was formed when this ratio was &gt;= 0.4.

The discrete element method (DEM) was applied to describe the basic characteristics of particles in an intensive mixer that is expected to grind only the surfaces of particles with a particular agitator and is applied in many industries. Surface grinding experiments using a sample of bauxite particles were also conducted to compare with the simulation. The roles of the pan and agitator were estimated from the DEM simulations and it was revealed that employing only agitator rotation increases the particle mobility in the vertical direction, while employing both pan and agitator rotation increases the mobility in the horizontal direction and stably maintains large mobility in the vertical direction.<br> We also investigated the correlation between the rates of energy dissipation during interparticle contact calculated from DEM simulation results and the abrasion rate estimated from experimental results. The abrasion rate was estimated from the particle size distribution obtained from the surface grinding experiments using an intensive mixer charged with bauxite particles and a population balance model in which two mechanisms of attrition—abrasion and fracture—are considered. The results show that the abrasion rate decreased with an increase in energy dissipation due to friction, which suggests that the energy dissipation of the friction obtained from the DEM simulation results could be used to estimate the abrasion rate in the surface grinding process. <br>

Although numerous qualitative studies have been published on removal characteristics from wastewater of dilute anions by co-precipitation treatment with Fe(III) or Al salts, detailed mechanisms or quantitative characteristics are not well understood. In this study, a quantitative modeling of co-precipitation phenomena in wastewater containing dilute As(V), Se(VI), Cr(VI) or F with ferrihydrite was tried using a diffuse layer model (DLM), which is one of the most popular and simplest of surface complexation models. Co-precipitation experimental results from wastewater containing 2 mg/dm³ of Se(VI), 2 mg/dm³ of Cr(VI), or 15 mg/dm³ of F with ferrihydrite could be predicted quantitatively by the DLM with a existing set of parameters. However, results from wastewater containing 10 mg/dm³ of As(V) with ferrihydrite could not be predicted quantitatively but only qualitatively by the model. It was confirmed from the comparison of co-precipitation experimental results and simple adsorption ones that this quantitative difference between experimental and calculation data resulted from the procedure difference between co-precipitation and simple adsorption; in short, the precipitation of ferrihydrite and adsorption of As(V) develop simultaneously in the former system, and only As(V) adsorbs onto prepared ferrihydrite in the latter system.<br>

In this work, the size classification of a mixture of submicron and micron size Ni particles dispersed in aqueous solution was investigated. The suspension of Ni particles was allowed to flow, under laminar condition, through a burette filled with an adhesion medium (i.e. substrate). The difference between zeta potentials of larger particles and adhesion medium created a base for the heterocoagulation. Thus, the larger particles move towards the medium assisted by the Saffman lift force and are attracted to its surface. The finer particles, on the other hand, flow off the burette and were collected as a separate fraction. This phenomenon was then explained by numerical simulating the particle's motion and showing that a stronger Saffman lift force will act in the direction of the substrate only for large particles, leaving the smaller ones unaffected as they sediment out. (c) 2006 Elsevier B.V All rights reserved.

The feasibility of making ferrite at ambient temperature from aqueous solutions of simulated acid mine drainage was investigated following our previous report. In this paper, qualitative and quantitative effects of coexisting ions such as Mn(II), Zn(II), Al(III) and Si(IV), on ferrite formation were investigated.&lt;BR&gt;As the first step, influences of several coexisting ions on the settling volume of the precipitates were investigated. In the case of Mn(II) or Zn(II) coexisting system, which are well known to have the capacity to substitute to the part of the lattice of ferrite, the settling volume increased a little, but in the case of Al(III) or Si(IV) coexisting system, which are known to impede ferrite formation, the settling volume considerably increased. However, the interference of Al(III) or Si(IV) to ferrite formation was weakened in the sludge recycling system.&lt;BR&gt;Secondly, their influences on the yield of magnetite or ferrite, which are calculated by the total oxygen consumption in the aerial oxidation reaction test, were investigated. The yield of magnetite decreases with an increase of Al(III) or Si(IV), but their interferences on ferrite formation were weakened in the presence of restored magnetite seed.&lt;BR&gt;Thirdly, their influences on the reaction rate in the aging process were also examined by solid-solid reaction test in which Fe(OH)&lt;SUB&gt;2&lt;/SUB&gt;, FeOOH and coexisting ions reacted directly in reduction atmosphere and at a fixed pH. The reaction coefficient considerably decreased not only by Al(III) or Si(IV), but also by Mn(II) or Zn(II), which are estimated not to impede ferrite formation.

The removal of iron and various heavy-metal ions in waste water into stable ferrite-type precipitates at ambient temperature is a promising alternative to clean up large volumes of polluted effluents. In this study, quantitative evaluation of ferrite formation method from aqueous solutions containing iron and sulfate at ambient temperature was considered, toward future application of this method to the treatment of acid mine drainage containing iron. In order to evaluate suitable conditions of Fe&lt;SUB&gt;3&lt;/SUB&gt;O&lt;SUB&gt;4&lt;/SUB&gt; formation quantitatively, these formation process was considered to be divided into two processes, i.e. oxidation process and aging process.&lt;BR&gt;The reaction rate in the oxidation process was examined by aerial oxidation reaction test. The results showed that the oxidation rate of ferrous iron was determined by the mass transfer of oxygen from atmosphere to solution, so the yield of Fe&lt;SUB&gt;3&lt;/SUB&gt;O&lt;SUB&gt;4&lt;/SUB&gt; in precipitation could be evaluated quantitatively by the total oxygen consumption which could be estimated from the oxygen transfer coefficient and the oxidation time.&lt;BR&gt;The reaction rate in the aging process was also examined by solid-solid reaction test in which Fe(OH)&lt;SUB&gt;2&lt;/SUB&gt; and FeOOH reacted directly in reduction atmosphere and at a fixed pH. At the initial stage of the reaction, the concentration change of FeOOH followed the first-order reaction concerning with FeOOH concentration. Surface complexation model which Fe(II) adsorbed to Fe(III) oxide could describe this phenomenon qualitatively.&lt;BR&gt;Relation between quantitative indexes which investigated in this study and several reaction conditions such as pH, Fe concentration and stirring intensity agrees with the results of Fe&lt;SUB&gt;3&lt;/SUB&gt;O&lt;SUB&gt;4&lt;/SUB&gt; forming reaction from aqueous solutions at 25 &amp;deg;c which have been investigated by us or other researchers. These quantitative indexes are useful to understand suitable conditions or mechanisms of ferrite formation.

酸性坑廃水の最適中和処理法の確立を目指し，旧幌別硫黄鉱山からの酸性坑廃水処理への水酸化カルシウム (Ca(OH)&lt;SUB&gt;2&lt;/SUB&gt;)，現状の2段中和 (CaCO&lt;SUB&gt;3&lt;/SUB&gt;およびCa(OH)&lt;SUB&gt;2&lt;/SUB&gt;)，および酸化マグネシウム (MgO) の利用を比較検討した。中和処理により，溶液中のヒ素はAs(III) あるいはAs(V) のどちらの形態で存在している場合でも，Fe(III) との共沈あるいは吸着によって，pH7で排水基準値以下に処理されることが確認された。Ca(OH)&lt;SUB&gt;2&lt;/SUB&gt;および2段中和を用いて殿物繰り返し法を行なった場合には，殿物の大半は水酸化第二鉄および石膏 (CaSO&lt;SUB&gt;4&lt;/SUB&gt;･2H&lt;SUB&gt;2&lt;/SUB&gt;O) であり，中和剤の未溶解成分はわずかであることがわかった。一方，MgOを用いて殿物繰り返しを行なった場合には，殿物は塩基性硫酸鉄とわずかなMgOの未溶解成分から成ることがわかった。殿物の沈降速度は，繰り返し回数が増加するにしたがってやや減少したが，MgOを用いた場合の殿物の沈降速度は，Ca(OH)&lt;SUB&gt;2&lt;/SUB&gt;や2段中和を用いた場合に比べて速くなる傾向が見られた。MgOを用いた場合には，他の中和剤を用いた場合に比べて高密度の殿物が得られ，繰り返し回数が増加するにしたがってその密度は更に増大し，最適な中和法であることが示唆された。

The diffuse layer model (DLM) of surface complexation modeling (SCM) was applied to discuss in the removal of dilute arsenic in wastewater. The equilibrium constants for complexation reactions of arsenic to ferric/aluminum hydroxide were based on several reference values and the total site capacity of ferric/aluminum hydroxide was determined by fitting to experimental results, since it is difficult to obtain surface area of amorphous hydroxide in wastewater system directly by experiment. The fitting results turns out that the total site capacity ratio becomes smaller as the concentration of ferric or aluminum hydroxide precipitates in wastewater increases. The experimental approximation formula between the total site capacity and the concentration of ferric or aluminum hydroxide precipitates was obtained. The model gave a quantitative correct description of experimental results for As(V) removal by ferric or aluminum hydroxide.&lt;BR&gt;The above-mentioned examination was also applied to As(V) removal in waste water with SO&lt;SUB&gt;4&lt;/SUB&gt;. In Fe(III) salts, the total site capacities in wastewater with SO&lt;SUB&gt;4&lt;/SUB&gt; became a little smaller than them in wastewater without SO&lt;SUB&gt;4&lt;/SUB&gt;, but in Al(III) salts, they are almost same value regardless of coexistence of SO&lt;SUB&gt;4&lt;/SUB&gt;. The removal of As(V) by ferric hydroxide at pH6 were predicted quantitatively by the model, also when SO&lt;SUB&gt;4&lt;/SUB&gt; is contained.

The removal of As(V) from wastewater containing low concentration of As(V) was investigated by addition of Fe(III), Al or Pb salts. Results show wastewater that contains 5 mg/dm³ As(V) is reduced below the regulated concentration of Japanese effluent standard (0.1 mg/dm³) when treated at pH 4.5&sim;7.5 with the addition of 50 mg/dm³ Fe(III) salts and at pH 6&sim;8 with the addition of 20 mg/dm³ Al salts. Successful removal of 3.75 mg/dm³ As(V) in wastewater is also possible when treated at pH 7&sim;11 with the addition of 20.7 mg/dm³ Pb salts, subsequently reducing Pb concentration below the regulated concentration of Japanese effluent standard (0.1 mg/dm³).<BR>Chemical equilibrium calculation which considering the formation of arsenic salts with Fe(III), Al or Pb hardly explains the experimental results. Furthermore, as the concentration of As(V) increases, the isoelectric point (IEP) of precipitations after the removal of As(V) by Fe(III), Al or Pb shifted to acidic pH. It is surmised that As(V) is removed by adsorption on the surface of ferric, aluminum or lead hydroxide.<BR>Solid/liquid separation from these As(V) removal experiments using a column bed method packed with fibrous ferro-nickel slag was also investigated. Ferric, aluminum or lead hydroxide particles adsorbing dilute As(V) that have several hundred nm in sizes, are thinly dispersed and can perform rapid solid/liquid separation (2.5mm/sec).

Dry gravity concentration method using a fluidized bed is being investigated. We employ polystyrene (PS) balls and glass beads (GB) as a fluidizing medium. Pieces of corrugated cardboard, paulownia wood, polypropylene (PP), polyvinyl chloride (PVC) and Al are employed as test materials. The separation efficiency is experimented and vertical position of separated materials in the fluidization bed is simulated, by changing the superficial velocity. It is found by experiment that high recovery (&gt;90%) of sink products and float products is achieved, even if the density difference between them is slight. These high recoveries are achievable when the superficial velocity is slightly higher than the minimum fluidization velocity.&lt;BR&gt;The recovery of float products is found to be sensitive to the superficial velocity: i.e., the recovery is low when the superficial velocity is either too high or too low. In order to examine the influence of the superficial velocity on the recovery of float products in detail, we employ two-dimensional simulation based on the discrete element method (DEM). The grater the superficial velocity is, the wider the vertical positioning of float materials becomes. It is found by DEM simulation that the recovery of float products tends to be low when the superficial velocity is too high, because the lowest vertical position during separation test is lower than that when the superficial velocity is optimal.&lt;BR&gt;It is found from these series of experiments and simulation in this study that high efficient separation by dry gravity concentration using a fluidized bed is possible.

Distinct element method (DEM) requires enormous computation time because it needs small time increments that are sufficient to follow high frequency fluctuations in contact dynamic model. In general, the equations of motion of particles are solved by the second order Adams-Bashforth method, which estimates the contact force for the next time step by linear extrapolation, or by multistep methods such as predictor-corrector method. In order to overcome the deficit of conventional methods, we propose a Contact Force Prediction Method that allows us to use larger time increments. The method incorporates the contact force at every contact point obtained as the exact solutions or numerical solutions of differential equations that describe two particle contacts. It is confirmed that the proposed method gives the simulation results for packing and discharge of particles which are consistent with the experimental data, while accelerating DEM computation by 3 to 8 times.

The boundary conditions for an axial diffusion model were overviewed and then modified concerning the pulp layer boundaries in a flotation column. It has been confirmed through the transfer function representation that the four general boundary conditions for an axial diffusion model correspond to the particular cases of Wehner and Wilhelm's, which considers not only the reaction section itself but also those of its top and bottom sides.
Various mathematical models have been proposed for the pulp layer in a flotation column and the most popular one may be an axial diffusion with first order reaction model of one stage. They are, however, unable to estimate the behaviors of free particles which have not attached to bubbles at the pulp-froth interface.
In this study, therefore, the authors, represented the transportation of free particles in the pulp layer of a flotation column by the two-stage axial diffusion with first order reaction model. The Wehner and Wilhelm's, as well as Danckwerts' boundary conditions have been partly modified and then applied to the feed point, the pulp-froth interface and the tailing discharge point of the flotation column. The proposed models and their boundary conditions made it possible to estimate the behaviors of free particles at the pulp-froth interface. (C) 2000 Elsevier Science Ltd. All rights reserved.

The experimental collision frequency factors of monodispersed polystyrene latex (PSL) particles in KCl solutions were measured by the use of the dynamic light scattering method. This method determines the cluster-size distribution by counting the number of different clusters during the coagulation process and therefore permits the determination of the rough collision frequency factors by the fitting curves for the data. The fitting curves were calculated on the assumption that the coagulation between two same-fold particles is dominant. <br> Numerous studies have revealed significant discrepancies between the theoretical collision frequency factors that can be calculated from Smoluchowski and Fuchs formulation and the experimental results, especially in the slow coagulation region. In this paper's results, good qualitative agreement was found for the theoretical collision factors in the rapid coagulation, but in the slow coagulation, significant discrepancies were confirmed both qualitatively and quantitatively, especially for high-fold particles.<br>

The boundary conditions for an axial diffusion model are overviewed and modified concerning the pulp layer in a column flotation cell. It is confirmed by the transfer function representation that the four general boundary conditions for an axial diffusion model correspond to the particular cases of Wehner and Wilhelm&#039;s, which considers not only the reaction section itself but also its fore and after ones. &lt;br&gt; Various mathematical models for the pulp layer in a column flotation cell have been proposed and the most popular one of them is an axial diffusion with first order reaction model of one stage. However, they can&#039;t estimate the behaviors of non-adhesive particles at the pulp level. &lt;br&gt; In this paper, the authors, therefore, represented the transportation of non-adhesive particles in the pulp layer of a column flotation cell by the two-stage axial diffusion with first order reaction model. The Wehner and Wilhelm&#039;s as well as Danckwerts&#039; boundary conditions have been partly modified and then applied to the feed point, the pulp level and the tailing point of the column flotation. The proposed models with their appropriate boundary conditions make it possible to estimate the behaviors of non-adhesive particles at the pulp level.&lt;br&gt;

The authors proposed the mathematical model for the pulp layer in a flotation column by the two-stage axial diffusion with first order reaction model in the former paper. The &lt;i&gt;Wehner&lt;/i&gt; and &lt;i&gt;Wilhelm&lt;/i&gt;&#039;s as well as &lt;i&gt;Danckwerts&lt;/i&gt;&#039; boundary conditions have been partly modified and then applied to the feed point, the pulp level and the tailing point of the column. This model makes it possible to estimate the behaviors of particles that haven&#039;t yet attached (free particles) at the pulp level. &lt;br&gt; The proposed model has three unknown parameters, that is, the Peclet &amp;middot; Bodenstein number, the collection rate constant and the concentration of drainage particles from the froth layer. From the sensitivity analysis, it was found that the proposed model has little sensitivity to the Peclet &amp;middot; Bodenstein number, but some sensitivity to other parameters, especially to the concentration of drainage particles. In this study, the Peclet &amp;middot; Bodenstein number was assumed from the empirical expression derived by &lt;i&gt;Mankosa&lt;/i&gt; et al.(1992), and the collection rate constant and the concentration of drainage particles were estimated by a least squares regression fit to the data sampled from an industrial operation, concerning the superficial concentration of attached particles as well as free particles. It is estimated by investigation of those parameters that the cleaning effect prevails exclusively not in the pulp layer but in the froth layer.&lt;br&gt;