Zinc recovery and waste sludge minimization from chromium passivation baths

This work reports the feasibility of applying emulsion pertraction technology (EPT) aiming at zinc recovery and waste minimization in the zinc electroplating processes that include Cr (III) passivation. The assessment consists of firstly the lifetime extension of the passivation baths by selective removal of the tramp ions zinc and iron, and secondly, the recovery of zinc for further reuse. Spent passivation baths from a local industry were tested, being the major metallic content: Cr³⁺ 9000 mg L⁻¹, Zn²⁺ 12,000 mg L⁻¹, Fe³⁺ 100 mg L⁻¹. Working in a Liqui-Cel hollow fiber membrane contactor and using the extractant bis(2,4,4-trimethylpentyl) phosphinic acid, reduction of zinc and iron concentrations below 60 mg L⁻¹ and 2 mg L⁻¹, respectively were obtained, while trivalent chromium, the active metal that generates the passivation layer, was retained in the baths. Zinc was selectively transferred to an acidic stripping phase that in the experimental time reached a concentration of 157,000 mg L⁻¹. Zinc recovery by electrowinning from the acidic stripping phase without any pretreatment of the electrolyte solution provided a purity of 98.5%, matching the lower commercial zinc grade. As a result of the extension of the life time of the passivation bath, significant environmental advantages are derived such as minimization of the volume of hazardous wastes and savings in the consumption of raw materials.     

The biochemical response to different Cr and Cd concentrations in soils amended with organic wastes

The effects of adding municipal solid waste (MSW) or poultry manure (PM) on the biochemical properties of a soil polluted with Cr and Cd were studied. Soil was mixed with Cr(NO₃)₃ and Cd(NO₃)₂ to give three concentrations (0, 100, and 250 mg Cr kg⁻¹ and 0, 100, and 250 mg Cd kg⁻¹) in the soil, which was then treated with MSW at a rate of 10% or PM at a rate of 7.6%. The pH and biochemical parameters were measured at 0 and 120 days. An unamended and no-polluted soil was used as control. Compared with the non-polluted soil, for the 250 mg Cd kg⁻¹ treatment the microbial biomass-C, dehydrogenase, urease, β-glucosidase, phosphatase, and arylsulphatase activities decreases 23%, 26.2%, 36%, 34.8%, 18.4%, and 15.8%, respectively, whereas for 250 mg Cr kg⁻¹ treatment the biochemical parameters were slightly lowest than for 250 mg Cd kg⁻¹ treatment. For 250 mg Cr kg⁻¹ soil + 250 mg Cd kg⁻¹ soil treatment, the inhibition percentages of the biochemical parameters increased. After the application of organic wastes in Cr + Cd polluted soil, the inhibition of biochemical properties was greater with the MSW amendment than with PM, possibly due to its higher humic acid concentration.     

Reduction of trace oxygen by hydrogen leaking during selective vaporization to produce ultra-pure cadmium for electronic applications

A viable method utilizing leaking of high pure hydrogen gas into the distillation retort ambience maintained at 8.0 × 10^− 3 Torr was devised to minimize the incorporation of trace oxygen in cadmium and the possibility of forming cadmium oxides during purification using selective vaporization. Hydrogen leaking at the rate of 5 standard cubic centi-metre per minute (sccm) during distillation at soaking temperature of 450 °C reduced trace oxygen from 230-350 ppm for raw cadmium of 3N8 (99.98%) purity and from 5-10 ppm for distilled cadmium of 6N purity. This can be compared to the presence of 30-38 ppm oxygen in cadmium distilled under simple-vacuum of 2.1 × 10^− 3 Torr achievable in the system. A detailed comparison between distillation under simple-vacuum and hydrogen leaking is presented with reference to purity, distillation rate, soaking temperature, and mean free path of distillate vapors.     

Suppressive effect of magnesium oxide materials on cadmium accumulation in winter wheat grain cultivated in a cadmium-contaminated paddy field under annual rice–wheat rotational cultivation

The effectiveness of two kinds of magnesium oxide (MgO) materials, commercial MgO (2250 kg ha⁻¹) and a material derived from MgO and magnesium silicate minerals named ‘MgO-SH-A’ (2250 and 4500 kg ha⁻¹1), in suppression of uptake and accumulation of cadmium (Cd) into grain of winter wheat (Triticum aestivum L. cv. Ayahikari) was examined in a Cd-contaminated alluvial paddy field under annual rice–wheat rotational system. The MgO materials were mixed into the plough-layer soil only once prior to the preceding rice cultivation. Cadmium concentration in wheat grain produced from the non-amendment control exceeded the maximum limit of Cd in wheat grain adopted by FAO/WHO (0.2 mg kg⁻¹). All of the treatments with the MgO materials significantly lowered plant available Cd fraction in the plough-layer soil. However, only the treatment with the commercial MgO at 2250 kg ha⁻¹ produced wheat grain whose Cd concentration was not only significantly lower than that from the control but also less than 0.2 mg kg⁻¹. It is suggested that the significant suppressive effect of the commercial MgO on Cd accumulation in wheat grain would be mainly attributed to its high soil neutralizing capacity as compared to that of MgO-SH-A.     

The effect of EDDS addition on the phytoextraction efficiency from Pb contaminated soil by Sedum alfredii Hance

Present study reports the results of three pot experiments, conducted to investigate the chelate-assisted phytoextraction of Pb contaminated soils. The optimum phytoextraction was observed when 2.5 mM ethylene diamine disuccinic acid (EDDS) was added in single dosage for 14 days to low Pb soil (treated with 400 mg kg⁻¹ soil). On the contrary, for high Pb soil (treated with 1200 mg kg⁻¹ soil), 5 mM EDDS concentration in single dosage for 10 days produced better results. Post-harvest effects of EDDS on the concentrations of available Pb and dissolved organic carbon (DOC) were significantly higher as compared with check (CK i.e. without EDDS addition), and consequently decreased with the passage of time. Our results suggested that chelate-assisted phytoextraction was more suitable for slightly contaminated soils.     

Study on the distillation rates of LiCl-KCl eutectic salt under different vacuum conditions

A study on the distillation rate of LiCl-KCl eutectic salt under different vacuums from 0.5 to 50 Torr was performed by using thermogravimetric (TG) method. A distillation rate of the order of 10⁻⁴-10⁻⁵ mol cm⁻² s⁻¹ was obtainable at temperatures of 1200-1300 K and vacuums of 5-50 Torr. Based on the non-isothermal TG data, model distillation flux equations could be derived as a function of temperature. Pure gas-phase and gas-liquid interfacial resistances at different vacuum conditions were evaluated from the comparison of experimental vaporization fluxes with the maximum flux obtained from the kinetic theory of gas. The difference between interfacial mass transfer coefficients and gas-phase ones increases with the temperature. Gas-phase resistance is much greater than that of the phase transition between condensed and gas phases at tested vacuum conditions of 0.5-50 Torr.     

Treatment of gaseous alpha-pinene by a combined system containing photo oxidation and aerobic biotrickling filtration

Biofiltration of hydrophobic and/or recalcitrant volatile pollutants is intrinsically limited. In the present study, a combined ultraviolet-biotrickling filter (UV-BTF) was developed to improve the removal of these compounds, and a single BTF as the control was operated under the same conditions. The experimental results showed that the UV-BTF provided higher removal efficiencies than the single BTF at an inlet concentration range of 600-1500 mg m⁻³ under shorter residence times. The maximum elimination capacities (ECs) obtained were 94.2 mg m⁻³ h⁻¹ and 44 mg m⁻³ h⁻¹ in the combined UV-BTF and single BTF, respectively. The mass ratio of carbon dioxide produced to α-pinene removed in the UV-BTF was approximately 2.74, which was much higher than that of the single BTF (1.99). Polymerase chain reaction-denaturing gradient gel electrophoresis (PCR-DGGE) analysis indicated that there was more complicated microbial community in the UV-BTF than that in the single BTF. In addition, we investigated the effect of starvation or stagnation on re-acclimation and removal performance from an engineering standpoint. The results showed that the combined UV-BTF could deal with fluctuating conditions or periods without any flow (air or liquid) supply much better than the single BTF.     

Removal of malachite green by adsorption and precipitation using aminopropyl functionalized magnesium phyllosilicate

We report a method for the removal of malachite green (MG) by adsorption and precipitation using nano-sized aminopropyl functionalized magnesium phyllosilicate (AMP) clay. MG, which is used in aquaculture and fisheries, is a carcinogenic and mutagenic compound. In response to these health risks, many efforts have been focused on adsorption of MG onto various adsorbents, which is a versatile and widely used technique for removing MG from water. Herein, we describe the adsorption and precipitation of MG using AMP clay, as well as the alkaline fading phenomenon of MG. In this study, prepared AMP clay and the precipitate product after the reaction of MG-AMP clay mixture were characterized. In addition, adsorption isotherms and kinetics, as well as thermodynamic studies are presented. Based on the results, we suggest a macro- and microscopic removal mechanism for the adsorption and precipitation of MG using AMP clay. An AMP clay dosage of 0.1 mg mL⁻¹ exhibited a maximum removal capacity of 334.80 mg g⁻¹ and 81.72% MG removal efficiency. With further increases of the AMP clay dosage, removal capacity by AMP clay gradually decreased; at dosage above 0.2 mg mL⁻¹ of AMP clay, the removal efficiency reached 100%.     

Ethylene removal evaluation and bacterial community analysis of vermicompost as biofilter material

Biofiltration of ethylene provides an environmentally friendly and economically beneficial option relative to physical/chemical removal, where selection of appropriate bed material is crucial. Here the vermicompost with indigenous microorganisms as bed material was evaluated for ethylene removal through batch test and biofilter experiment. Temporal and spatial dynamics of bacterial community in the vermicompost-biofilter under different ethylene loads were characterized by culture and denaturing gradient gel electrophoresis (DGGE) methods. The results showed that ethylene was effectively degraded by the vermicompost under conditions of 25-50% moisture content and 25-35 °C temperature. The vermicompost-biofilter achieved nearly 100% ethylene removal up to an inlet load of 11 mg m⁻³ h⁻¹. Local nitrogen lack of the vermicompost in the biofilter was observed over operation time, but the change of pH was slight. DGGE analysis demonstrated that the bacterial abundance and community structure of vermicompost-biofilter varied with the height of biofilter under different ethylene loads. Pseudomonads and Actinobacteria were predominant in the biofilter throughout the whole experiment.     

Removal of acid orange 7 by guava seed carbon: A four parameter optimization study

The preparation of carbon from waste materials is a recent and economic alternative for the removal of dyes. In this study four samples of carbon were obtained by thermal treatment at 1000 °C using as precursor the guava seed with different particle sizes. The Taguchi method was applied as an experimental design to establish the optimum conditions for the removal of acid orange 7 in batch experiments. The chosen experimental factors and their ranges were: pH (2–12), temperature (15–35 °C), specific surface area (50–600 m² g⁻¹) and adsorbent dosage (16–50 mg ml⁻¹). The orthogonal array L₉ and the larger the better response category were selected to determine the optimum removal conditions: pH 2, temperature 15 °C, S_esp 600 m² g⁻¹ and dosage 30 mg ml⁻¹. Under these conditions a total removal of acid orange 7 was achieved. Moreover, the most significant factors were the carbon specific surface area and the pH. The influence of the different factors on the adsorption of acid orange 7 from solution is explained in terms of electrostatic interactions by considering the dye species and the character of the surface.     

Adsorptive separation and photocatalytic degradation of methylene blue dye on titanate nanotube powders prepared by hydrothermal process using metal Ti particles as a precursor

Titanate nanotube powders (TNTPs) with the twofold removal ability, i.e. adsorptive separation and photocatalytic degradation, are synthesized under hydrothermal conditions using metal Ti particles as a precursor in the concentrated alkaline solution, and their morphology, structure, adsorptive and photocatalytic properties are investigated. Under hydrothermal conditions, the titanate nanotubes (TNTs) with pore diameter of 3-4 nm are produced on the surface of metal Ti particles, and stacked together to form three-dimensional (3D) network with porous structure. The TNTPs synthesized in the autoclave at 130 °C for 24 h exhibits a maximum adsorption capability of about 197 mg g⁻¹ in the neutral methylene blue (MB) solution (40 mg L⁻¹) within 90 min, the adsorption process can be described by pseudo second-order kinetics model. Especially, in comparison with the adsorptive and the photocatalytic processes are performed in turn, about 50 min can be saved through synchronously utilizing the double removal ability of TNTPs when the removal ratio of MB approaches 95% in MB solution (40 mg L⁻¹) at a solid-liquid (S/L) ratio of 1:8 under ultraviolet (UV) light irradiation. These 3D TNTPs with the twofold removal properties and easier separation ability for recycling use show promising prospect for the treatment of dye pollutants from wastewaters in future industrial application.     

真空蒸馏法从粗铟中脱除镉锌铊铅的研究

利用纯度为99.7%粗铟为原料,采用真空蒸馏的方法从粗铟中直接脱除镉、锌、铊、铅。分别进行了蒸馏温度、蒸馏时间、投料量等的条件实验。结果表明,控制真空度1~5 Pa,蒸馏温度950℃,蒸馏120 min,可将粗铟中镉、锌、铊、铅可除至6N高纯铟要求。并且以实验结果为依据计算出产物中各种杂质的挥发系数、分离系数、活度系数,对铟的热力学数据的完善有一定的参考意义。     

Purification of cadmium up to 5N+ by vacuum distillation

Cadmium was refined by vacuum distillation, a technique suitable for low boiling and melting point materials, to remove the heavy and low vapour pressure impurities at ppm level. The detailed analysis of the purified Cd as well as raw Cd was done by ICP-OES techniques for 27 impurity elements. Purification was carried out in an efficient high-yield vacuum distillation system designed and fabricated for purifying 3N+ purity indigenous cadmium to 5N+ (99.999%). Analysis confirmed the reduction of total impurity content from 134 ppm (3N7) for raw Cd to 3 ppm (5N7) upon vacuum distilled Cd. The present study shows that the analysis of impurities such as Fe, Mg and Ca are contributed from environmental effect, whereas impurities such as Pb, Bi, Ag, Ni, Cu, Zn and Tl require adaptation of elemental analysing technique to counter dilution effect. The Hg trace analysis can however be carried out by hydride generation techniques.     

Treatment of anaerobic sludge digester effluents by the CANON process in an air pulsing SBR

The CANON (Completely Autotrophic Nitrogen removal Over Nitrite) process was successfully developed in an air pulsing reactor type SBR fed with the supernatant from an anaerobic sludge digester and operated at moderately low temperatures (18–24 °C). The SBR was started up as a nitrifying reactor, lowering progressively the dissolved oxygen concentration until reaching partial nitrification. Afterwards, an inoculation with sludge containing Anammox biomass was carried out. Nitrogen volumetric removal rates of 0.25 g N L⁻¹ d⁻¹ due to Anammox activity were measured 35 d after inoculation even though the inoculum constituted only 8% (w/w) of the biomass present in the reactor and it was poorly enriched in Anammox bacteria. The maximal nitrogen removal rate was of 0.45 g N L⁻¹ d⁻¹. By working at a dissolved oxygen concentration of 0.5 mg L⁻¹ in the bulk liquid, nitrogen removal percentages up to 85% were achieved.     

Evaluation of thin film passivation using inorganic Mg-Zn-F heterointerface for polymer light emitting diode

In this study, we manufactured Mg-Zn-F targets using magnesium fluoride (MgF₂) and zinc (Zn). The passivation films were deposited on a poly-ethylenenaphthalate (PEN) substrate using a radio-frequency magnetron sputter. The thickness of the manufactured passivation film was 120 nm. Among the three targets tested, the 4:6 weight target of MgF₂ to Zn resulted in films with the highest Zn content that would increase the packing density of the thin film. The water vapor transmission rate of a 120 nm Mg-Zn-F film prepared from this target and inserted between two 40 nm MgF₂ interlayers on PEN was 2.9 × 10^− 2 g/(m² day) at a relative humidity of 90% and a temperature 38 °C. Its optical transmittance was approximately 80%.     

Sulfamethoxazole abatement by photo-Fenton: Toxicity,inhibition and biodegradability assessment of intermediates

The objective of this work was to study the abatement of 200 mg L⁻¹ sulfamethoxazole (SMX) solution by means of photo-Fenton process. Biodegradability of the treated solutions was followed by the ratio biochemical oxygen demand at five days/chemical oxygen demand (BOD₅/COD) and toxicity by Microtox^® and inhibition tests. Experiments with different initial concentration of H₂O₂ were carried out. The initial amount of Fe²⁺ and pH of the solution were set at 10 mg L⁻¹ and 2.8 respectively. The temperature of the reactor was kept constant in all the experiments (25 ± 0.8 °C). Photo-Fenton process is thought to be a successful treatment step to improve the biodegradability of wastewater containing SMX. The complete antibiotic removal was achieved for a H₂O₂ dose over 300 mg L⁻¹. Biodegradability (BOD₅/COD) rose from zero (SMX solution) to values higher than 0.3 (treated solutions). Toxicity and inhibition tests pointed out in the same direction: oxidized intermediates for initial H₂O₂ dose over 300 mg L⁻¹ showed no toxicity effects on pure bacteria and no inhibition on activated sludge activity.     

Feasibility of nutrient recovery from industrial sludge by vermicomposting technology

Transformation of industrial sludges into vermicompost is of double interest: on the one hand, a waste is converted into value added product, and, on the other, it controls a pollutant that is a consequence of increasing industrialization. This paper reports the feasibility of utilization of vermicomposting technology for nutrient recovery from industrial sludge in laboratory scale experiment employing Eisenia fetida earthworm. A total of nine vermireactors, having different percentage of wastewater treatment plant sludge of a food industry and cow dung, were established and monitored for fertilizer quality of vermicompost and growth and fecundity of the earthworms for 3 months. The earthworms were unable to survive in 100% FIS. There was a decrease in pH, organic carbon content, organic matter, C:N ratio, and increase in ash content, EC, nitrogen, potassium and phosphorus content in all the vermireactors. Total Kjeldhal nitrogen (TKN) content increased in the range of 12.2–28.7 g kg⁻¹ in different vermireactors after vermicomposting. C:N ratio was 1.59–5.24 folds lesser in final vermicomposts than initial raw substrate. The heavy metals’ content in final vermicomposts was higher than initial feed mixtures. Maximum worm biomass was observed in control, i.e., 100% CD (836 mg earthworm⁻¹) and the lowest in 30% CD + 70% FIS feed mixture (280 mg earthworm⁻¹). Cocoon production was started during 6–7th week in all feed mixture except in feed mixture no. 9. After 12 weeks maximum cocoons (57) were counted in 100% CD and minimum (2) in 30% CD + 70% FIS feed. The results indicated that food industry sludge could be converted into good quality manure by vermicomposting if mixed up to 30% with cow dung.     

High-speed pumping to UHV

Development of a high-speed pumping system for ultra high vacuum (UHV) process dose not reduce only cost and waiting time for experiment and production, but also reduces CO₂ emission that is known as one of the serious causes in the global warming problem. Reduction of vapor water concentration in a purge gas line would be one of the most effective measures to reduce pumping time to UHV. We carried out control of water vapor in a nitrogen gas purge line in addition to surface treatments of chambers using buff polishing and electrolytic polishing, followed by measurement of outgassing rate of the chambers. Under the reasonable control of the water vapor, the pumping time to reach the pressure of 1 × 10⁻⁶ Pa was able to be shortened with two orders of the magnitude. And it was also found that the main residual gas in the chamber was hydrogen after pumping down with the low concentration of water vapor. The quality of residual gas was equivalent to the quality in a baked UHV system. The introduction of well controlled nitrogen gas to the vacuum system which was not baked out during its pumping has proved a pressure of 3 × 10⁻⁸ Pa for 24 h in the chamber without orifice.     

Investigation of a sewage-integrated technology combining an expanded granular sludge bed (EGSB) and an electrochemical reactor in a pilot-scale plant

A sewage-integrated treatment system (SITS) for the treatment of municipal wastewater, consisting of an expanded granular sludge bed (EGSB) reactor to remove soluble organic matter and an electrochemical (EC) reactor to oxidize the NH₃-N, was evaluated. The performance of the EGSB reactor was monitored for 12 months in a pilot-scale plant. Iron shavings were added to the EGSB reactor on the sixtieth day to improve the removal efficiency of the chemical oxygen demand (COD), suspended solids (SS) and total phosphorus (TP). After the iron shavings were added, the effluent COD, SS and TP decreased from 104 to 46 mg L⁻¹, 21 to 8.6 mg L⁻¹ and 3.62 to 1.36 mg L⁻¹, respectively. Moreover, in the EC reactor, which was equipped with IrO₂/Ti anodes, the NH₃-N and total nitrogen (TN) concentrations decreased from 25 to 12 mg L⁻¹ and 29 to 15 mg L⁻¹, respectively. The NH₃-N was directly oxidized to N₂, resulting in no secondary pollution. The results demonstrated the possibility of removing carbon and nutrients in a SITS with high efficiency. The system runs efficiently and with a flexible operation, making it suitable for low-strength wastewater. The results and parameters presented here can provide references for the practical project.     

Thin tristearin deposits as solid hydrogen-rich layers for neutron metrology

Layers of solid material with a relatively high, constant content of hydrogen that is stable over a long period of time are needed for recoil proton telescopes and for precise determination of the cross-section ratio of ²³⁵U(n,f)/H(n,n). Thin layers of tristearin, a material that is relatively rich in hydrogen, have been prepared with an areal density of 0.05 up to 0.5 mg cm⁻² by evaporation in high vacuum. The surface quality was studied by AFM (atomic force microscopy). The thickness of the layers was estimated by several methods and its homogeneity was determined using an optical profilometer. The hydrogen amount in the deposited layer was estimated by combustion analyses.