Recovery of Nd and Dy from rare earth magnetic waste sludge by hydrometallurgical process

This paper describes a hydrometallurgical process for recovering neodymium (Nd) and dysprosium (Dy) from a magnetic waste sludge generated from the Nd–Fe–B(–Dy) manufacturing process. Phase analysis by XRD study revealed Nd(OH)₃ and Fe₂O₃ as main mineral phases, and chemical analysis by ICP showed the contents of 35.1 wt% Nd, 29.5 wt% Fe, 1.1 wt% Dy and 0.5 wt% B. A solution of 1 M HNO₃ + 0.3 M H₂O₂ was used to dissolve up to 98 % Nd and 81 % Dy, while keeping Fe dissolution below 15 % within 10 min. Fe dissolved in solution was completely removed as Fe(OH)₃ at pH 3 followed by precipitation of Nd and Dy with oxalic acid (H₂C₂O₄) and recovered 91.5 % of Nd and 81.8 % of Dy from solution. The precipitate containing Nd and Dy was calcined at 800 °C to obtain Nd₂O₃ as final product with 68 % purity, and final recovery of 69.7 % Nd and 51 % of Dy was reported in this process.     

Photochemical Kinetic Modeling of Degradation of Aqueous Polyvinyl Alcohol in a UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> Photoreactor

This study presents a photochemical kinetics model to describe the degradation of water-soluble PVA (Polyvinyl Alcohol) polymer in a UV/H₂O₂ batch reactor. Under the effect of UV light, the photolysis of hydrogen peroxide into hydroxyl radicals can generate a series of polymer scission reactions. For a better understanding and analysis of the UV/H₂O₂ process in the cracking of the PVA macromolecules, a chemical reaction mechanism of the degradation process and a relevant photochemical kinetics model are developed to describe the disintegration of the polymer chains. Taking into account the probabilistic fragmentation of the polymer, the statistical moment approach is used to model the molar population balance of live and dead polymer chains. The model predicts the PVA molecular weight reduction, the acidity of the solution, and hydrogen peroxide residual. In addition to previously published data collected in this laboratory, a new set of experiments were conducted using a 500 mg/L PVA aqueous for different hydrogen peroxide/PVA ratios for model validation. Measurements of average molecular weights of the polymer, hydrogen peroxide concentrations and pH of the PVA solution were determinant factors in constructing a reliable photochemical model of the UV/H₂O₂ process. Experimental data showed a decrease in the PVA molecular weight and a buildup of the solution acidity. The experimental data also served to determine the kinetics rate constants of the PVA photochemical degradation and validate the model whose predictions are in good agreement with data. The model can provide a comprehensive understanding of the impact of the design and operational variables.     

Photochemical Degradation of Aqueous Polyvinyl Alcohol in a Continuous UV/H<Subscript>2</Subscript>O<Subscript>2</Subscript> Process: Experimental and Statistical Analysis

Polyvinyl alcohol (PVA), being a dominant contributor of total organic carbon (TOC) in textile wastewater, is not easily degradable by conventional methods of wastewater treatment. This study investigates the degradation of aqueous PVA in a continuous UV/H₂O₂ photoreactor since the feeding strategy of hydrogen peroxide proves to have considerable effects on the process performance. Response surface methodology involving the Box–Behnken method is adopted for the experimental design to study the effects of operating parameters on the process performance. Experimental analysis shows that the TOC removal varies from 16.11 to 42.70 % along with a reduction of the PVA molecular weights from 56.7 to 95.3 %. The TOC removal is significantly lower than the molecular weight reduction due to the generation of the intermediate products during oxidation. Operating the UV/H₂O₂ process in a continuous mode facilitates the degradation of highly concentrated polymeric solutions using a relatively small hydrogen peroxide concentration in the feed with a small residence time ranges from 6.13 to 18.4 min.     

Citric Acid and Vitamin C as Coupling Agents for the Surface Coating of ZrO<Subscript>2</Subscript> Nanoparticles and Their Behavior on the Optical,Mechanical, and Thermal Properties of Poly(vinyl alcohol) Nanocomposite Films

A series of bio-nanocomposites (BNC)s were fabricated through solution casting method. At first, the surfaces of ZrO₂ NPs were functionalized with citric acid and Vitamin C as green modifier agents. Then, PVA as polymer matrix was embedded with different contents (4, 8 and 12 wt%) of modified ZrO₂ (m-ZrO₂) NPs with the aim of ultrasonic irradiation process. The resulting BNCs were studied by various techniques. Thermal stability of obtained BNCs was enhanced after NPs’ addition to the PVA matrix. Optical activity of these new BNCs makes them potential candidate for UV shielding material. Lastly, the tensile strengths of the BNCs were increased in comparison to the pure PVA.     

Green Synthesis of Fe<Subscript>3</Subscript>O<Subscript>4</Subscript>/Cellulose/Polyvinyl Alcohol Hybride Aerogel and Its Application for Dye Removal

A novel Fe₃O₄/cellulose–polyvinyl alcohol (PVA) aerogel was successfully synthesized by an eco-friendly and facile method in this work. Cellulose/PVA matrix was prepared through an environmental friendly physical cross-linking process and further in-situ decorated with Fe₃O₄. Series of Fe₃O₄ decorated aerogels were prepared and the effects of Fe₃O₄ nanoparticles (NPs) on the aerogels were systematic investigated. As-prepared aerogels exhibited desirable properties including nanostructure, relatively high porosity, improved mechanical and superparamagnetism. The TEM results showed that Fe₃O₄ NPs were integrated in the three-dimensional matrix of cellulose/PVA with a diameter of 9–12 nm. Furthermore, the mechanical strength of the aerogels was significantly enhanced after the introduction of Fe₃O₄ NPs. Meanwhile, the obtained Fe₃O₄/cellulose/PVA aerogel exhibited excellent adsorption performance toward methyl blue dye, and can be reused through fenton-like catalysts oxidative degradation of organic dye in H₂O₂ solution. Therefore, they will have a great potential application as eco-friendly and economical adsorbents.     

Enhanced decomposition of (4-chloro-2-methylphenoxy) acetic acid by combined ultrasonic and oxidative treatment

Combined ultrasonic (US) irradiation and sodium peroxodisulfate (Na₂S₂O₈) treatment has been investigated for promotion of both decomposition of (4-chloro-2-methylphenoxy) acetic acid (MCPA) and mineralization of organic residues. This treatment is expected to accelerate both reactions, because the US cavitation effect promotes the production of radicals, such as SO ₄ ^? · and OH·, by the decomposition of Na₂S₂O₈ and water. In this study, decomposition experiments were performed on 100?ppm MCPA aqueous solutions in a sonoreactor at reaction temperatures of 298?C333?K with US irradiation alone, Na₂S₂O₈ treatment alone, and the combination of US and Na₂S₂O₈ treatment. It was found that the combined treatment achieved a higher MCPA decomposition rate and total organic carbon (TOC) removal ratio than either treatment alone. The decomposition ratios of both MCPA and TOC increased with reaction temperature, and especially steep increases were observed at 333?K due to a significant promotion of thermal decomposition of Na₂S₂O₈. The production of radical species was also promoted by the combined treatment. These results suggest that the higher MCPA decomposition rate and TOC removal ratio are due to the increased formation of sulfate and hydroxyl radicals via thermal and US decomposition of Na₂S₂O₈.     

Preparation of MgCr<Subscript>2</Subscript>O<Subscript>4</Subscript> from waste tannery solution and effect of sulfate,chloride, and calcium on leachability of chromium

This paper presents a study regarding the preparation of MgCr₂O₄ from waste tannery solution, and chromium leaching behavior is also investigated with varying amounts of sulfate, chloride and calcium. The phase transformation, crystallinity index and crystallite diameter were characterized using XRD, FT-IR and thermal analysis. A well-crystallized MgCr₂O₄ was successfully prepared at 1400 °C. The sintering temperature had a major impact on the formation of MgCr₂O₄ compared with sintering time. The MgCr₂O₄ phase was observed initially at 400 °C and its crystallite diameter increased with increasing temperature. The concentration of total chromium leached and Cr(VI) decreased gradually with increasing temperature. The considerable amount of Cr(VI) was found in the leachate at 300–500 °C caused by Cr(VI) intermediary products. Sulfate and chlorine could impact the transformation efficiency of chromium adversely, and chlorine has a more significant effect than sulfate. The presence of calcium disturbed the formation of MgCr₂O₄ and new chromium species (CaCrO₄) appeared, which resulted in a sharp increase in the concentration of leached Cr(VI). Incorporating Cr(III) into the MgCr₂O₄ spinel for reusable products reduced its mobility significantly. This was demonstrated to be a promising strategy for the disposal of chromium containing waste resource.     

Dynamic studies on lead volatilization from CaO–SiO2–Al2O3 molten slag under N2–CO–CO2, N2–HCl and N2–H2S gas atmospheres

Dynamic studies on the volatilization of lead from CaO–SiO₂–Al₂O₃ molten slags were conducted in a lab-scale melting furnace from 1623 to 1773 K under different mixed gas atmospheres of CO 0.05–0.3 atm to CO₂ 0–0.3 atm to N₂ (balance), HCl 1.7 × 10^?3–6.7 × 10^?3 atm to N₂ (balance), and H₂S 3.0 × 10^?4 to 1.7 × 10^?3 atm to N₂ (balance). The slag samples consisted of the mixed powders of 20–50 wt% CaO, 30–60 wt% SiO₂, and 10–40 wt% Al₂O₃, containing 2000 ppm PbO.Results showed that the rates of volatilization of lead from the CaO–SiO₂–Al₂O₃ molten slags under the N₂–CO–CO₂, N₂–HCl, and N₂–H₂S gas atmospheres were higher than those under the simulated air (N₂–O₂), which increased with CO, HCl, and H₂S partial pressures. At \(p_{{HCl}}\)  =  \(p_{H_{2}S}\)  = 1.7 × 10^?3 atm, the apparent rate constants for the volatilization of lead under the N₂–H₂S and N₂–HCl gas atmospheres were nearly equal, which increased with a rise in temperature. Results also showed that the rate of volatilization of lead from the molten slag decreased drastically with the increasing viscosity of the molten slag, in the viscosity range lower than 3 Pa s. Consequently, the volatilization of lead from the CaO–SiO₂–Al₂O₃ molten slag was significantly influenced by CO, HCl, and H₂S partial pressures and by the viscosity of the molten slag.     

Photocatalytic Degradation of Poly(Vinyl Alcohol) on Pt/TiO<Subscript>2</Subscript> with Fenton Reagent

In this research Fenton reagent (Fe²⁺/H₂O₂) was investigated as oxidants to degrade poly (vinyl alcohol) (PVA). The role of nano-TiO₂ photocatalyst was discussed as an additive in Fenton reagent (Fe²⁺/H₂O₂). Pt/TiO₂ composites were also synthesized by photo-reaction to be used as additive in Fenton reagent. The rapid degradation of PVA was obtained when Pt/TiO₂ composites served as photocatalyst. The different photocatalytic efficiency of Pt/TiO₂- Fenton reagent (Fe²⁺/H₂O₂) was studied compared with TiO₂- Fenton reagent (Fe²⁺/H₂O₂) during the degradation of PVA.     

Extracellular Biopolymer Production by Aureobasidium pullulans MTCC 2195 Using Jackfruit Seed Powder

In this present paper, statistical screening and optimization of jackfruit seed powder based medium components were investigated for pullulan production from Aureobasidium pullulans. Seven medium variables jackfruit seed powder, K₂HPO₄, yeast extract, (NH₄)₂SO₄, NaCl, MgSO₄·7H₂O and ZnSO₄·7H₂O were screened by employing Plackett–Burman (PB) method. PB method showed jackfruit seed powder, ZnSO₄·7H₂O, K₂HPO₄ and yeast extract were significant. Central composite design of response surface method applied to optimize the significant variables identified from the PB experiment. Statistical analysis of the experimental results showed optimal values were found to be jackfruit seed powder 2 % (w/v), K₂HPO₄ 0.55 % (w/v), yeast extract 0.30 % (w/v) and ZnSO₄·7H₂O 0.006 % (w/v) with maximum pullulan concentration of 18.76 (g/L). Maximum pullulan concentration of 17.95 (g/L) was observed in the validation experiment. This experimental result explained the model was fitted 96 % as compare with the result predicted by response surface method.     

Effects of Modified Starch and Different Molecular Weight Polyvinyl Alcohols on Biodegradable Characteristics of Polyvinyl Alcohol/Starch Blends

The common biodegradable properties of polymer make them an excellent pair for blending, and the water solubility of polyvinyl alcohol (PVA) makes it easy to mix evenly with the starch. In this study, PVAs with different molecular weights were blended with various compositions of cross-linked starch (CLS) to explore the effects of molecular weight of PVA on the biodegradable characteristics of the PVA/starch blends. Comparing the biodegradability of all the various PVA/starch blends, a PVA was singled out from the PVA/starch blends of higher biodegradability. Further, the chosen PVA was then blended with the acid-modified starch (AMS) to systematically investigate the effects of the modified processing of starch on the biodegradable characteristics of the PVA/starch blends. Differential scanning calorimetry (DSC) analysis of PVA and PVA/starch specimens reveal that the T_m values of PVA/starch specimens reduce gradually as their CLS or AMS contents increase. After the CLS is blended in PVAs of different molecular weights, the tensile strength (??_f) and elongation at break (??_f) values of (P₁₀₀S₀)G₂₀M₁ specimen increase and simultaneously reduce, respectively, as their molecular weights of PVA increase from about 80,000 (PVA_BF-17) to 120,000 (PVA_BF-26). The ??_f and ??_f values of the PVA/modified-starch blends decrease with an increase in the modified starch contents. The ??_f values of the PVA/AMS specimens decrease with an increase in the concentrations of hydrochloric acid. Comparing the ??_f values of the PVA/CLS specimens with those of the PVA/AMS specimens, the ??_f values of the PVA/CLS specimens are better than those of the PVA/AMS specimens. On the contrary, the ??_f values of the PVA/AMS specimens are better than those of the PVA/CLS specimens. According to the biodegradability of all the PVA/starch blends, PVA with higher molecular weights displays higher biodegradability. The biodegradability of the PVA/modified-starch blends increase as the modified starch contents of the PVA/modified-starch blends increase. As evidenced by the results of the biodegradability test, the biodegradability of the PVA/modified-starch blends, therein PVA is blended with 1N AMS, shows better biodegradability. The result of bio-reaction kinetics experiment can evaluate the decomposition tendency of the PVA/starch blends up to any biodegradable rate under ambient environment. Using the kinetic model of the first order reaction, it is estimated that 16.20?years and 12.47?years will be needed for the PVA_BF-17/starch blends, containing 20 and 40% of CLS respectively, to be degraded up to 70% under ambient environment. In addition, it is 1.68?years for the PVA_BF-26 blends with the 40% 2N AMS under decomposition environment while it is 1.94?years for the 40% 1N AMS. Overall, the decomposition potential of PVA/AMS specimens is better than PVA/CLS specimens. Furthermore, the 1N(26P₆₀AS₄₀)₁₀₀G₂₀M₁ specimen is coincidence the biodegradable material criteria of Environmental Protection Administration (EPA) of Taiwan.     

Degradation of petroleum hydrocarbons from bottom sludge of crude oil storage tanks using in-vessel composting followed by oxidation with hydrogen peroxide and Fenton

In this research the feasibility of aerated in-vessel composting process followed by chemical oxidation with H₂O₂ and Fenton for removal of petroleum hydrocarbons from oily sludge of crude oil storage tanks was investigated. The ratios of the sludge to immature compost were 1:0 (as abiotic control), 1:2, 1:4, 1:6, 1:8 and 1:10 (as dry basis) at a C:N:P ratio of 100:5:1 and 55 % moisture content for a period of 10 weeks. Six concentrations of H₂O₂ and Fenton were added to the compost mixture for a period of 24- and 48-h reaction times. Results showed that petroleum hydrocarbons removal in ratios of 1:2, 1:4, 1:6, 1:8 and 1:10 were 66.6, 73.2, 74.8, 80.2 and 79.9 %, respectively. The results of the abiotic experiments indicated that the main mechanism of hydrocarbon removal in the composting reactors was biological. The application of combined composting and chemical oxidation demonstrated a remarkable (about 88 %) overall removal. The study showed that in-vessel composting combined with chemical oxidation is a viable choice for the remediation of the sludge.     

Green Synthesis and Physical Properties of poly(Vinyl Alcohol) Maleated in an Aqueous Solutions

The objective of this work was to synthesize maleated poly(vinyl alcohol) (PVAM) in aqueous solution through esterification, and to seek near optimal degree of grafting and crosslinking. The effects of maleic anhydride (MA) content on the properties of PVAM were investigated. The experimental observations included characterizations by ATR–FTIR and thermo gravimetric analyses (TGA), and determinations of grafting ratio, dynamic viscosity, and swelling ratio. The percentage degree of grafting, dynamic viscosity, and particle size increased with MA content, while the swelling ratio decreased due to copolymerization of poly(vinyl alcohol) (PVA) and MA. The peaks at 945 and 918 cm^?1 in the spectrum of PVA indicated the presence of carboxylic groups, while in the spectrum of PVAM only one peak at 920 cm^?1 indicated presence of carboxylic groups, due to copolymerization of PVA and MA. Moreover, the thermal stability of PVA-g-MA was enhanced as observed from TGA. The results suggest 7:3 PVA/MA mass ratio as near optimal for PVA-g-MA.     

Utilization of the used tire rubber particle in hydrogen sulfide control

The adsorption capacity of fine rubber particle media (FRPM) derived from discarded vehicle tires and the consumer wasted rubber sources was evaluated for hydrogen sulfide treatment. H₂S breakthrough tests were performed at various zinc contents, temperatures, and packing quantities. High zinc concentrations increased the adsorption capacity of FRPM significantly. H₂S removal by FRPM was optimized at a packing quantity of 75 % of the column volume, and the adsorption capacity increased with reactor temperature within the range of 20–85 °C. The regeneration of ZnCl₂ solution was reliable for increasing regeneration capacity of the FRPM-adsorbed H₂S. FRPM seems to be an attractive alternative of H₂S adsorbents in terms of cost effectiveness compared to traditional materials.     

Bio-oil production by fast pyrolysis of cellulose/polyethylene mixtures in the presence of metal chloride

Cellulose/polyethylene mixture (3:1 w/w) and Tetra Pak wastes with and without metal chloride (ZnCl₂, AlCl₃, CuCl₂, FeCl₃) addition were subjected to a fast pyrolysis process at 350–500 °C and heating rate 100 °C/s to evaluate the possibility of liquid product formation with a high yield. The addition of zinc, aluminum, iron and copper chlorides has influenced the range of samples decomposition as well as the chemical composition of resulting pyrolytic oils. It was found that formation of levoglucosan, the main product of cellulose thermal decomposition, and phenol and its derivatives decreased in a presence of metal chlorides. Non-catalytic fast pyrolysis of polyethylene leads to the formation of solid long chain hydrocarbons, whereas the addition of metal chlorides promotes the formation of more liquid hydrocarbons.     

Laboratory studies on the remediation of mercury contaminated soils

Mercury, in contrast to other toxic metals, cycles between the atmosphere, land, and water. During this cycle, it undergoes a series of complex chemical and physical transformations. Because of these transformations, it is found in the environment not only as simple inorganic and organic compounds, but also as complex compounds. As a result, it is difficult to remediate mercury contaminated materials. Laboratory studies were conducted with a mercury contaminated complex waste from an industrial site to evaluate the ability of extractants such as H₂O₂, H₂SO₄ and Na₂S₂O₃ to decontaminate the waste. Up to 87 percent of the total mercury present in the waste was extracted. Mercury was recovered as insoluble mercury sulfide by adding Na₂S solution to the combined filtrates from the H₂O₂ + H₂SO₄ and Na₂S₂O₃ treatment steps. The technique described in this article is capable of recovering mercury in a usable form and can be used as a pretreatment to remediate mercury contaminated waste before laud disposal.     

Biosorptive removal of Pb(II) and Cu(II) from wastewater using activated carbon from cassava peels

The ability of activated carbon from cassava peels to remove heavy metals like Cu(II) and Pb(II) from hospital wastewater was investigated. The study showed that a pH of 8 was the best for the sorption of both metal ions onto the biosorbent. The time-dependent experiments for the metal ions showed that the binding of the metal ions to the biomass was rapid and occurred within 20–120 min. Sorption efficiency increased with a rise in adsorbent dosage. It increased from 12 to 73 % for Pb(II) and 26 to 79 % for Cu(II) when the adsorbent dose increased from 2 to 12 g. An increase in temperature led to an increase in sorption for both metal ions. The Langmuir model showed that the biomass has a higher sorption capacity for Cu(II) than Pb(II), with q _m = 5.80 mg g^?1 for Pb(II) and 8.00 mg g^?1 for Cu(II). The Freundlich isotherm K _f was 1.4 for Pb(II) and 1.8 for Cu(II), indicating a preferential sorption of Cu(II) onto the biosorbent. Adsorption capacity was found to decrease with an increase in particle sizes. Sorption occurred by physical mechanisms and was mainly controlled by intraparticle diffusion.     

Sonophotocatalytic Degradation of Chitosan in the Presence of Fe(III)/H2O2 System

The degradation of chitosan by means of ultrasound irradiation and its combination with homogeneous photocatalysis (photo-Fenton) was investigated. Emphasis was given on the effect of additive on degradation rate constants. 24 kHz of ultrasound irradiation was provided by a sonicator, while an ultraviolet source of 16 W was used for UV irradiation. To increase the efficiency of degradation process, degradation system was combined with Fe(III) (2.5 × 10⁻⁴mol/L) and H₂O₂ (0.020–0.118 mol/L) in the presence of UV irradiation and the rate of degradation process change from 1.873 × 10⁻⁹−6.083 × 10⁻⁹ mol^1.7 L s⁻¹. Photo-Fenton process led to complete chitosan degradation in 60 min with the rate increasing with increasing catalyst loading. Sonophotocatalysis in the presence of Fe(III)/H₂O₂ was always faster than the respective individual processes. A synergistic effect between ultrasound and ultraviolet irradiation in the presence of Fenton reagent was calculated. The degraded chitosans were characterized by X-ray diffraction (XRD), gel permeation chromatography (GPC) and Fourier transform infrared (FT-IR) spectroscopy and average molecular weight of ultrasonicated chitosan was determined by measurements of intrinsic viscosity of samples. The results show that the total degree of deacetylation (DD) of chitosan change, partially after degradation and the decrease of molecular weight led to transformation of crystal structure. A negative order for the dependence of the reaction rate on total molar concentration of chitosan solution within the degradation process was suggested. Results of this study indicate that the presence of catalyst in the reaction medium can be utilized to reduce molecular weight of chitosan while maintaining the power of irradiated ultrasound and degree of deacetylation.     

Sources and Variability of Indoor and Outdoor Gaseous Aerosol Precursors (O3, NOx and VOCs)

Measurements of indoor and outdoor aerosol concentrations and their gaseous precursors (O₃, NO and NO₂) as well as volatile organic compounds (VOCs) concentrations were performed at two houses in the Oslo metropolitan area. The variability of the concentration of gaseous compounds was studied in respect to their sources in the indoor and outdoor environments. Domestic heating during the winter and photochemical production during the summer were the main sources for outdoor NOx and O₃. In the indoor environment infiltration of outdoor air, candle burning, smoking and indoor chemical reactions were the main sources affecting their concentrations. The concentrations of VOCs outdoors were enhanced during the summer due to biogenic emissions whereas in the indoor environment their values were affected mostly by emissions from materials used during the recent refurbishing of the houses (>0.4 mg/m³).     

Gasification applicability study of polyurethane solid refuse fuel fabricated from electric waste by measuring syngas and nitrogenous pollutant gases

To recycle polyurethane foam waste generated from electric appliance recycling centers for use as fuel in a gasification process, polyurethane solid refuse fuel fabricated as pellets was analyzed for the characteristics of elemental composition, proximate analysis, heating value, and thermo-gravimetric testing. It has a high heating value of 29.06 MJ/kg with a high content of combustibles, which could be feasibly used in any thermal process. However, the nitrogen content, of up to 7 %, was comparably higher than for other fuels such as coal, biomass, and refuse-derived fuel, and may result in the emission of nitrogenous pollutant gases of HCN and NH₃. By conducting gasification experiments on polyurethane solid refuse fuel in a fixed-bed reactor, a syngas with a heating value of 9.76 kJ/m³ and high content of both H₂ and CO were produced with good gasification efficiency; carbon conversion 54 %, and cold gas efficiency 60 %. The nitrogenous pollutant gases in syngas were measured at the concentrations of 160 ppm hydrogen cyanide and 40 ppm ammonia, which may have to be reduced using proper cleaning technologies prior to the commercialization of gasification technology for polyurethane waste.