Amino-modified hollow alumina spheres: effective adsorbent for Cd2+, Pb2+, As(V), and diclofenac removal.

A simple sol-gel method and external gelatinization method of hollow alumina spheres synthesis were developed in this study. The spheres were modified with polyethyleneimine (PEI) producing PEI-Al2O3 via (3-glycidyloxypropyl)trimethoxy-silane, GLYMO, linker. Characterization results, obtained using XRD and SEM microscopy revealed spherical geometry with a hollow core of PEI-Al2O3 adsorbent. Introduction of a large number of the amino group, 6.9 mmol g-1, contributes to achieving high adsorption capacities, qm, of 95.6, 124.9, 61.3, and 125.9 mg g-1 for Cd2+, Pb2+, As(V), and DCF, respectively, which is obtained by using the Langmuir model. Thermodynamic studies indicated feasible adsorption and higher spontaneity with temperature increase. The kinetic study conveniently modeled using pseudo-second-order (PSO) and Weber-Morris kinetic model, as well as single resistance mass transfer model, indicated a change of the contribution of diffusional processes during adsorption with a dominance of intra-particle diffusion. The fixed-bed column adsorption data, fitted using Bohart-Adams, Clark, Yoon-Nelson, and Thomas models, showed lower capacity in comparison to batch study, and thus clear potential applicability of PEI-Al2O3 was deduced even at a high loading of feed water.

Assessment of Leaching Characteristics of Solidified Products Containing Secondary Alkaline Lead Slag.

Reuse of waste is one of the main principles of sustainable development and circular economy. Secondary alkaline lead slag is a hazardous waste generated in the recycling process of lead-acid batteries that may be suitable in construction materials. The environmental impact of the use of lead slag as a partial replacement of fine aggregates in the cement-based stabilization/solidification (S/S) process for the preparation of concrete was studied in this paper. Solidified products containing 10%, 15%, 20%, and 25% slag were laboratory tested by unconfined compressive strength (UCS) analyses and the Toxicity Characteristic Leaching Procedure (TCLP). At the same time, the leachability of toxic elements from solidified products with a high percent of slag was evaluated under environmental conditions for during one year. The results of the UCS and TCLP indicated that utilization of this type of slag in cement-based applications may be justified with its controlled addition. However, the described application of the slag was disputed due to the high release of As under high alkaline environmental conditions. Eh-pH analyses and the geochemical modeling using the software PHREEQC were evaluated, as well as the mechanism of pollutant (Pb, As) immobilization (precipitation, adsorption) as a function of pH conditions.

Solidified structure and leaching properties of metallurgical wastewater treatment sludge after solidification/stabilization process.

The presented study investigates solidification/stabilization process of hazardous heavy metals/arsenic sludge, generated after the treatment of the wastewater from a primary copper smelter. Fly ash and fly ash with addition of hydrated lime and Portland composite cement were studied as potential binders. The effectiveness of the process was evaluated by unconfined compressive strength (UCS) testing, leaching tests (EN 12457-4 and TCLP) and acid neutralization capacity (ANC) test. It was found that introduction of cement into the systems increased the UCS, led to reduced leaching of Cu, Ni and Zn, but had a negative effect on the ANC. Gradual addition of lime resulted in decreased UCS, significant reduction of metals leaching and high ANC, due to the excess of lime that remained unreacted in pozzolanic reaction. Stabilization of more than 99% of heavy metals and 90% of arsenic has been achieved. All the samples had UCS above required value for safe disposal. In addition to standard leaching tests, solidificates were exposed to atmospheric conditions during one year in order to determine the actual leaching level of metals in real environment. It can be concluded that the EN 12457-4 test is more similar to the real environmental conditions, while the TCLP test highly exaggerates the leaching of metals. The paper also presents results of differential acid neutralization (d-AN) analysis compared with mineralogical study done by scanning electron microscopy and X-ray diffraction analysis. The d-AN coupled with Eh-pH (Pourbaix) diagrams were proven to be a new effective method for analysis of amorphous solidified structure.

Kinetics of NiO and NiCl2 hydrogen reduction as precursors and properties of produced Ni/Al2O3 and Ni-Pd/Al2O3 catalysts.

The objects of this investigation were the comparative kinetic analysis of the NiO and NiCl2 reduction by hydrogen during an induction period and elimination of the calcination during the synthesis of Ni/Al2O3 catalysts. The effect of temperature and time on NiO and NiCl2 reduction degrees was studied. Avrami I equation was selected as the most favorable kinetic model and used to determine activation energy of the NiO and NiCl2 reduction for the investigated temperature range (623-923 K) and time intervals (1-5 minutes). The investigation enabled reaching conclusions about the reaction ability and rate of the reduction processes. Afterward, Ni/Al2O3 catalysts were obtained by using oxide and chloride precursor for Ni. The catalysts were supported on alumina-based foam and prepared via aerosol route. Properties of the samples before and after low-temperature hydrogen reduction (633 K) were compared. Obtained results indicated that the synthesis of Ni/Al2O3 catalysts can be more efficient if chloride precursor for Ni is directly reduced by hydrogen during the synthesis process, without the calcination step. In addition, Ni-Pd/Al2O3 catalysts with different metal content were prepared by using chloride precursors. Lower reduction temperature was utilized and the chlorides were almost completely reduced at 533 K.

Characterization of PCBs from computers and mobile phones, and the proposal of newly developed materials for substitution of gold, lead and arsenic.

In this paper, we have analyzed parts of printed circuit board (PCB) and liquid crystal display (LCD) screens of mobile phones and computers, quantitative and qualitative chemical compositions of individual components, and complete PCBs were determined. Differential thermal analysis (DTA) and differential scanning calorimetry (DSC) methods were used to determine the temperatures of phase transformations, whereas qualitative and quantitative compositions of the samples were determined by X-ray fluorescence spectrometry (XRF), inductively coupled plasma optical emission spectrometry (ICP-OES), and scanning electron microscopy (SEM)-energy dispersive X-ray spectrometry (EDS) analyses. The microstructure of samples was studied by optical microscopy. Based on results of the analysis, a procedure for recycling PCBs is proposed. The emphasis was on the effects that can be achieved in the recycling process by extraction of some parts before the melting process. In addition, newly developed materials can be an adequate substitute for some of the dangerous and harmful materials, such as lead and arsenic are proposed, which is in accordance with the European Union (EU) Restriction of the use of certain hazardous substances (RoHS) directive as well as some alternative materials for use in the electronics industry instead of gold and gold alloys.

Selective removal of heavy metals from metal-bearing wastewater in a cascade line reactor.

GOAL, SCOPE AND BACKGROUND: This paper is a part of the research work on 'Integrated treatment of industrial wastes towards prevention of regional water resources contamination - INTREAT' the project. It addresses the environmental pollution problems associated with solid and liquid waste/effluents produced by sulfide ore mining and metallurgical activities in the Copper Mining and Smelting Complex Bor (RTB-BOR), Serbia. However, since the minimum solubility for the different metals usually found in the polluted water occurs at different pH values and the hydroxide precipitates are amphoteric in nature, selective removal of mixed metals could be achieved as the multiple stage precipitation. For this reason, acid mine water had to be treated in multiple stages in a continuous precipitation system-cascade line reactor. MATERIALS AND METHODS: All experiments were performed using synthetic metal-bearing effluent with chemical a composition similar to the effluent from open pit, Copper Mining and Smelting Complex Bor (RTB-BOR). That effluent is characterized by low pH (1.78) due to the content of sulfuric acid and heavy metals, such as Cu, Fe, Ni, Mn, Zn with concentrations of 76.680, 26.130, 0.113, 11.490, 1.020 mg/dm3, respectively. The cascade line reactor is equipped with the following components: for feeding of effluents, for injection of the precipitation agent, for pH measurements and control, and for removal of the process gases. The precipitation agent was 1M NaOH. In each of the three reactors, a changing of pH and temperature was observed. In order to verify. efficiency of heavy metals removal, chemical analyses of samples taken at different pH was done using AES-ICP. RESULTS: Consumption of NaOH in reactors was 370 cm3, 40 cm3 and 80 cm3, respectively. Total time of the experiment was 4 h including feeding of the first reactor. The time necessary to achieve the defined pH value was 25 min for the first reactor and 13 min for both second and third reactors. Taking into account the complete process in the cascade line reactor, the difference between maximum and minimum temperature was as low as 6 degrees C. The quantity of solid residue in reactors respectively was 0.62 g, 2.05 g and 3.91 g. In the case of copper, minimum achieved concentration was 0.62 mg/dm3 at pH = 10.4. At pH = 4.50 content of iron has rapidly decreased to < 0.1 mg/dm3 and maintained constant at all higher pH values. That means that precipitation has already ended at pH=4.5 and maximum efficiency of iron removal was 99.53%. The concentration of manganese was minimum at pH value of 11.0. Minimum obtained concentration of Zn was 2.18 mg/dm3 at a pH value of 11. If pH value is higher than 11, Zn can be re-dissolved. The maximum efficiency of Ni removal reached 76.30% at a pH value of 10.4. DISCUSSION: Obtained results show that efficiency of copper, iron and manganese removal is very satisfactory (higher than 90%). The obtained efficiency of Zn and Ni removal is lower (72.30% and 76.31%, respectively). The treated effluent met discharge water standard according to The Council Directive 76/464/EEC on pollution caused by certain dangerous substances into the aquatic environment of the Community. Maximum changing of temperature during the whole process was 6 degrees C. CONCLUSION: This technology, which was based on inducing chemical precipitation of heavy metals is viable for selective removal of heavy metals from metal-bearing effluents in three reactor systems in a cascade line. RECOMMENDATIONS AND PERSPECTIVES: The worldwide increasing concern for the environment and guidelines regarding effluent discharge make their treatment necessary for safe discharge in water receivers. In the case where the effluents contain valuable metals, there is also an additional economic interest to recover these metals and to recycle them as secondary raw materials in different production routes.