Dual mechanochemical immobilization of heavy metals and decomposition of halogenated compounds in automobile shredder residue using a nano-sized metallic calcium reagent

Simultaneous immobilization of heavy metals and decomposition of halogenated organic compounds in different fractions of automobile shredder residue (ASR) were achieved with a nano-sized metallic calcium through a 60-min ball milling treatment. Heavy metal (HM) immobilization and chlorinated/brominated compound (CBC) decomposition efficiencies both reached 90–100 %, after ball milling with nanometallic calcium/calcium oxide (Ca/CaO) dispersion, regardless of ASR particle size (1.0, 0.45–1.0, and 0.250 mm). Concentrations of leachable HMs substantially decreased to a level lower than the regulatory standard limits (Co and Cd 0.3 mg L⁻¹; Cr 1.5 mg L⁻¹; Fe, Pb, and Zn 3.0 mg L⁻¹; Mn and Ni 1 mg L⁻¹) proposed by the Korean hazardous waste elution standard regulatory threshold. Scanning electron microscopy with energy-dispersive X-ray spectroscopy (SEM-EDS) element maps/spectra showed that while the amounts of HMs and CBCs detectable in ASR significantly decreased, the calcium mass percentage increased. X-ray powder diffraction (XRD) patterns indicate that the main fraction of enclosed/bound materials on ASR includes Ca-associated crystalline complexes that remarkably inhibit HM desorption and simultaneously transform dangerous CBCs into harmless compounds. The use of a nanometallic Ca/CaO mixture in a mechanochemical process to treat hazardous ASR (dry conditions) is an innovative approach to remediate cross-contaminated residues with heavy metals and halogenated compounds.

     

Surface ozonation of polyvinyl chloride for its separation from waste plastic mixture by froth floatation

Selective surface modification of polyvinyl chloride (PVC) by ozonation was evaluated to facilitate the separation of PVC from other heavy plastics with almost the same density as PVC, especially polyethylene terephthalate (PET), by the froth flotation process. The optimum froth flotation conditions were investigated, and it was found that at 40°C, 90% of PVC and PET plastics floated. The bubble size became larger and the area covered with bubbles on the plastic surface was reduced with increasing temperature. Optimum PVC separation was achieved with the flotation solution at 40°C and mixing at 180–200 rpm, even for sheet samples 10 mm in size. Combined treatment by ozonation and froth flotation is a simple, effective, and inexpensive method for PVC separation from waste plastics.     

Feasibility study of the separation of chlorinated films from plastic packaging wastes

This study describes the possible separation of chlorinated plastic films (PVC and PVDC) from other heavy plastic packaging waste (PPW) by selective twist formation and gravity separation. Twists formation was mechanically induced in chlorinated plastic films, whereas twist formation did not occur in PS and PET films. After twist formation, all the films had the apparent density of less than 1.0 g/cm³ and floated in water even though the true density was more than 1.0 g/cm³. However, the apparent density of the PS and the PET films increased with agitation to more than 1.0 g/cm³, whereas that of chlorinated plastic films was kept less than 1.0 g/cm³. The main reason would be the air being held inside the chlorinated plastic films which was difficult to be removed by agitation. Simple gravity separation after twist formation was applied for artificial film with 10 wt.% of the chlorinated films and real PPW films with 9 wt.% of the chlorinated films. About 76 wt.% of the artificial PPW films and 75 wt.% of real PPW films after the removal of PP and PE were recovered as settling fraction with 4.7 wt.% and 3.0 wt.% of chlorinated plastic films, respectively. These results indicate that simple gravity separation process after twist formation can be used to reduce the chlorinated plastic concentration from mixed heavy PPW films.     

High immobilization of soil cesium using ball milling with nano-metallic Ca/CaO/NaH2PO4: implications for the remediation of radioactive soils

This report shows that cesium can be immobilized in soils with an efficiency of 96.4% by ball milling with nano-metallic Ca/PO₄. In Japan, the major concern on ¹³⁷Cs deposition and soil contamination due to the emission from the Fukushima Daiichi nuclear power plant showed up after a massive quake on March 11, 2011. The accident rated 7, the highest possible on the international nuclear event scale, released 160 petabecquerels (PBq) of iodine ¹³¹I and 15 PBq of ¹³⁷Cs according to the Japanese Nuclear and Industrial Safety Agency. Both ¹³⁷Cs and ¹³¹I radioactive nuclides are increasing cancer risk. Nonetheless, ¹³⁷Cs, with a half-life of about 30 years compared with 8 days for ¹³¹I, is a major threat for agriculture and stock farming and, in turn, human life for decades. Therefore, in Japan, the ¹³⁷Cs fixation and immobilization in contaminated soil is the most important problem, which should be solved by suitable technologies. Ball milling treatment is a promising treatment for the remediation of cesium-contaminated soil in dry conditions. Here, we studied the effect, factors and mechanisms of soil Cs immobilization by ball milling with the addition of nano-metallic Ca/CaO/NaH₂PO₄, termed “nano-metallic Ca/PO₄.” We used scanning electron microscopy combined with electron dispersive spectroscopy (SEM/EDS) and X-ray diffraction. Results show that immobilization efficiency increases from 56.4% in the absence of treatment to 89.9, 91.5, and 97.7 when the soil is ball-milled for 30, 60 and 120 min, respectively. The addition of nano-metallic Ca/PO₄ increased the immobilization efficiency to about 96.4% and decreased the ball milling time. SEM/EDS analysis allows us to observe that the amount of Cs decreased on soil particle surface. Use of nano-metallic Ca/PO₄ over a short milling time also decreases Cs leaching. Therefore, ball milling with nano-metallic Ca/PO₄ treatment may be potentially applicable for the remediation of radioactive Cs-contaminated soil in dry conditions.     

Total immobilization of soil heavy metals with nano-Fe/Ca/CaO dispersion mixtures

This report shows that soil heavy metals can be totally immobilized by grinding with nano-Fe/Ca/CaO. Remediation of soils contaminated by heavy metals is a critical issue in Japan. Indeed, contaminated soils are notoriously difficult to remediate using available technologies. Major setbacks in typical immobilization techniques for heavy metals are wet conditions, forming secondary effluents and further treatment for effluents. Solidification with nano-Fe/Ca/CaO dispersion mixture is a promising treatment for the total immobilization of soil heavy metals As, Cd, Cr, Pb, and separation in dry conditions. Here, we studied the heavy metal immobilization by simple grinding with the addition of three mixtures: nano-Fe/CaO, nano-Fe/Ca/CaO, and nano-Fe/Ca/CaO/PO₄. Samples were analyzed by inductively coupled plasma optical emission spectrometry (ICP-OES) and scanning electron microscopy combined with electron dispersive spectroscopy (SEM–EDS). Results show that the addition of nano-Fe/Ca/CaO immobilized 95–99 % of heavy metals, versus 65–80 % by simple grinding. After treatment, 36–45 wt% of magnetic and 64–55 wt% of nonmagnetic fractions of soil were separated. Their condensed heavy metal concentration was 85–95 % and 10–20 %, respectively. Nano-Fe/Ca/CaO treatment reduced the concentration of leachates heavy metals to values lower than the Japan soil elution standard regulatory threshold of 0.01 mg/l for As, Cd, and Pb; and 0.05 mg/l for Cr. This technology can therefore immobilize totally soil heavy metals and reduce heavy metal by separation.     

Enhanced heavy metal immobilization in soil by grinding with addition of nanometallic Ca/CaO dispersion mixture

This study investigated the use of a nanometallic Ca and CaO dispersion mixture for the immobilization of heavy metals (As, Cd, Cr and Pb) in contaminated soil. Simple grinding achieved 85-90% heavy metal immobilization, but it can be enhanced further to 98-100% by addition of a nanometallic Ca/CaO dispersion mixture produced by grinding. Observations using SEM-EDS elemental maps and semi-quantitative analysis showed that the amounts of As, Cd, Cr, and Pb measurable on the soil particle surface decrease after nanometallic Ca/CaO treatment. The leachable heavy metal concentrations were reduced after nanometallic Ca/CaO treatment to concentrations lower than the Japan soil elution standard regulatory threshold: <0.01 mg L⁻¹ for As, Cd, and Pb; and 0.05 mg L⁻¹ for Cr. Effects of soil moisture and pH on heavy metal immobilization were not strongly influenced. The most probable mechanisms for the enhancement of heavy metal immobilization capacity with nanometallic Ca/CaO treatment might be due to adsorption and entrapment of heavy metals into newly formed aggregates, thereby prompting aggregation of soil particles and enclosure/binding with Ca/CaO-associated immobile salts. Results suggest that the nanometallic Ca/CaO mixture is suitable for use in immobilization of heavy-metal-contaminated soil under normal moisture conditions.     

Recovery of polypropylene and polyethylene from packaging plastic wastes without contamination of chlorinated plastic films by the combination process of wet gravity separation and ozonation

Wet gravity separation technique has been regularly practiced to separate the polypropylene (PP) and polyethylene (PE) (light plastic films) from chlorinated plastic films (CP films) (heavy plastic films). The CP films including poly vinyl chloride (PVC) and poly vinylidene chloride (PVDC) would float in water even though its density is more than 1.0 g/cm³. This is because films are twisted in which air is sometimes entrapped inside the twisted CP films in real existing recycling plant. The present research improves the current process in separating the PP and PE from plastic packaging waste (PPW), by reducing entrapped air and by increasing the hydrophilicity of the CP films surface with ozonation. The present research also measures the hydrophilicity of the CP films.In ozonation process mixing of artificial films up to 10 min reduces the contact angle from 78° to 62°, and also increases the hydrophilicity of CP films. The previous studies also performed show that the artificial PVDC films easily settle down by the same. The effect of ozonation after the wet gravity separation on light PPW films obtained from an actual PPW recycling plant was also evaluated. Although actual light PPW films contained 1.3% of CP films however in present case all the CP films were removed from the PPW films as a settled fraction in the combination process of ozonation and wet gravity separation. The combination process of ozonation and wet gravity separation is the more beneficial process in recovering of high purity PP and PE films from the PPW films.     

Immobilization and volume reduction of heavy metals in municipal solid waste fly ash using nano-size calcium and iron-dispersed reagent

This study was conducted to examine the synthesis and application of novel nano-size calcium/iron-based composite material as an immobilizing and separation treatment of the heavy metals in fly ash from municipal solid waste incineration. After grinding with nano-Fe/Ca/CaO and with nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash). Heavy metals in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized, respectively. Additionally, scanning electron microscopy combined with energy-dispersive X-ray spectrometry (SEM-EDS) observations indicate that the main fraction of enclosed/bound materials on treated fly ash includes Ca/PO₄-associated crystalline complexes. After nano-Fe/Ca/CaO/[PO₄] treatment, the heavy metal concentrations in the fly ash leachate were much lower than the Japan standard regulatory limit for hazardous waste landfills. These results appear to be extremely promising. The addition of a nano-Fe/Ca/CaO/PO₄ mixture with simple grinding technique is potentially applicable for the remediation and volume reduction of fly ash contaminated by heavy metals.

Implications: After grinding with nano-Fe/Ca/CaO and nano-Fe/Ca/CaO/[PO₄], approximately 30 wt% and 25 wt% of magnetic fraction fly ash were separated. The highest amount of entrapped heavy metals was found in the lowest weight of the magnetically separated fly ash fraction (i.e., 91% in 25% of treated fly ash), whereas heavy metals either in the magnetic or nonmagnetic fly ash fractions were about 98% and 100% immobilized. These results appear to be very promising, and the addition of nano-Fe/Ca/CaO/PO₄ mixture with simple grinding technique may be considered potentially applicable for the remediation and volume reduction of contaminated fly ash by heavy metals.     

Processing plastics from ASR/ESR waste: separation of poly vinyl chloride (PVC) by froth flotation after microwave-assisted surface modification

The feasibility of the selective surface hydrophilization of poly vinyl chloride (PVC) using microwave treatment to facilitate the separation of PVC via froth flotation from automobile shredder residue (ASR) and electronic waste shredder residue (ESR) was evaluated. In the presence of powder-activated carbon (PAC), 60-s microwave treatment selectively enhanced the hydrophilicity of the PVC surface (i.e., the PVC contact angle decreased from 86.8° to 69.9°). The scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS) results are consistent with increased hydrophilic functional groups (i.e., ether, hydroxyl, and carboxyl), amounting to significant changes in the morphology and roughness of the PVC surface after treatment. After only 60 s of microwave treatment, 20 % of the PVC was separated in virgin and ASR/ESR plastics with 33 and 29 % purity, respectively, as settled fractions by froth flotation at a 150 rpm mixing speed. The microwave treatment with the addition of PAC had a synergetic effect with the froth flotation, which brought about 100 and 90 % selective separation of PVC from the other virgin and ASR/ESR plastics, with 91 and 82 % purity. The use of the combined froth flotation and microwave treatments is an effective technology for separating PVC from hazardous waste plastics.