Recycling of high purity selenium from CIGS solar cell waste materials

Copper indium gallium diselenide (CIGS) is a promising material in thin film solar cell production. To make CIGS solar cells more competitive, both economically and environmentally, in comparison to other energy sources, methods for recycling are needed. In addition to the generally high price of the material, significant amounts of the metals are lost in the manufacturing process. The feasibility of recycling selenium from CIGS through oxidation at elevated temperatures was therefore examined. During oxidation gaseous selenium dioxide was formed and could be separated from the other elements, which remained in solid state. Upon cooling, the selenium dioxide sublimes and can be collected as crystals. After oxidation for 1 h at 800 °C all of the selenium was separated from the CIGS material. Two different reduction methods for reduction of the selenium dioxide to selenium were tested. In the first reduction method an organic molecule was used as the reducing agent in a Riley reaction. In the second reduction method sulphur dioxide gas was used. Both methods resulted in high purity selenium. This proves that the studied selenium separation method could be the first step in a recycling process aimed at the complete separation and recovery of high purity elements from CIGS.     

Valorisation of used cooking oil sludge by codigestion with swine manure

The addition of lipid wastes to the digestion of swine manure was studied as a means of increasing biogas production. Lipid waste was obtained from a biodiesel plant where used cooking oil is the feedstock. Digestion of this co-substrate was proposed as a way of valorising residual streams from the process of biodiesel production and to integrate the digestion process into the biorefinery concept.Batch digestion tests were performed at different co-digesting proportions obtaining as a result an increase in biogas production with the increase in the amount of co-substrate added to the mixture. Semi-continuous digestion was studied at a 7% (w/w) mass fraction of total solids. Co-digestion was successful at a hydraulic retention time (HRT) of 50 d but a decrease to 30 d resulted in a decrease in specific gas production and accumulation of volatile and long chain fatty acids. The CH₄ yield obtained was 326 ± 46 l/kg VS_feed at an HRT of 50 d, while this value was reduced to 274 ± 43 l/kg VS_feed when evaluated at an HRT of 30 d. However these values were higher than the one obtained under batch conditions (266 ± 40 l/kg VS_feed), thus indicating the need of acclimation to the co-substrate. Despite of operating at low organic loading rate (OLR), measurements from respirometry assays of digestate samples (at an HRT of 50 d) suggested that the effluent could not be directly applied to the soil as fertiliser and might have a negative effect over soil or crops.     

Metal concentrations in used engine oils: Relevance to site assessments of soils

Used engine oils contain metals, which upon entering soils may pose risks to human health or the environment. In this study, previously published concentrations of 23 metals in 213 used engine oil samples from the early 1970s to the mid-1990s are statistically evaluated. Neat (100%) used engine oils were found to contain relatively high concentrations of lead, calcium, and zinc, attributable to piston blow-by of leaded gasoline, calcium salt detergent additives, and zinc-bearing anti-corrosion/anti-oxidation additives, respectively. Wear metal concentrations were lower. The lead concentration in used engine oils in the U.S. declined between the 1970s and early 1990s, potentially providing a basis to constrain the “age” of used engine oil(s) in soils. The concentrations of 23 metals in used engine oils were compared to soil risk benchmarks in 15 representative jurisdictions in the U.S., Canada, Australia, and Europe. The maximum concentrations in neat (100%) used engine oil of eight metals – Be, Co, Fe, Mn, Ni, Se, Ag, and Ti – were lower than their collective minimum benchmarks in soils for the jurisdictions surveyed, indicating their concentrations in soils could not be reasonably expected to exceed any soil benchmarks. Nine metals (As, Ba, Cd, Cr, Cu, Pb, Sn, V and Zn), but particularly arsenic, cadmium, lead, tin, and zinc, were identified as potential contaminants of concern (PCOC) for soils from locations impacted with used engine oils, owing to their higher median concentrations (i.e., 2.5, 1.4, 1038, 5.0, and 922 mg/kg in oil, respectively) relative to most soil benchmarks. Site-specific benchmarks and metal concentrations at reasonable oil in soil concentrations require consideration when developing the suite of PCOC metal analytes for conducting site assessments of soils impacted by used engine oil.     

二噁英类物质CALUX报告基因法在造纸行业的应用探究

选择典型造纸厂,采用化学激活报告基因法(CALUX)测定造纸过程中废水和纸浆中的二噁英类物质,并将部分样品测定结果与高分辨气相色谱-高分辨质谱(HRGC-HRMS)法测定结果作线性回归,换算系数为0.21,表明CALUX可用于造纸行业废水中二噁英类物质的快速筛查。将CALUX用于测定造纸厂废水中二噁英类物质,结果表明用含元素氯的漂白工艺会产生大量二噁英类物质,其中漂白废水中的目标物毒性当量浓度最高,经处理后可达到国家排放标准;而用无元素氯的漂白工艺,二噁英类物质的产生量会大幅降低。     

Review of LCA studies of solid waste management systems – Part I: Lessons learned and perspectives

The continuously increasing solid waste generation worldwide calls for management strategies that integrate concerns for environmental sustainability. By quantifying environmental impacts of systems, life cycle assessment (LCA) is a tool, which can contribute to answer that call. But how, where and to which extent has it been applied to solid waste management systems (SWMSs) until now, and which lessons can be learnt from the findings of these LCA applications? To address these questions, we performed a critical review of 222 published LCA studies of SWMS. We first analysed the geographic distribution and found that the published studies have primarily been concentrated in Europe with little application in developing countries. In terms of technological coverage, they have largely overlooked application of LCA to waste prevention activities and to relevant waste types apart from household waste, e.g. construction and demolition waste. Waste management practitioners are thus encouraged to abridge these gaps in future applications of LCA. In addition to this contextual analysis, we also evaluated the findings of selected studies of good quality and found that there is little agreement in the conclusions among them. The strong dependence of each SWMS on local conditions, such as waste composition or energy system, prevents a meaningful generalisation of the LCA results as we find it in the waste hierarchy. We therefore recommend stakeholders in solid waste management to regard LCA as a tool, which, by its ability of capturing the local specific conditions in the modelling of environmental impacts and benefits of a SWMS, allows identifying critical problems and proposing improvement options adapted to the local specificities.     

Co-treatment of fruit and vegetable waste in sludge digesters. An analysis of the relationship among bio-methane generation,process stability and digestate phytotoxicity

The co-digestion of a variable amount of fruit and vegetable waste in a waste mixed sludge digester was investigated using a pilot scale apparatus. The organic loading rate (OLR) was increased from 1.46 kg VS/m³ day to 2.8 kg VS/m³ day. The hydraulic retention time was reduced from 14 days to about 10 days. Specific bio-methane production increased from about 90 NL/kg VS to the maximum value of about 430 NL/kg VS when OLR was increased from 1.46 kg VS/m³ day to 2.1 kg VS/m³ day. A higher OLR caused an excessive reduction in the hydraulic retention time, enhancing microorganism wash out. Process stability evaluated by the total volatile fatty acids concentration (mg/l) to the alkalinity buffer capacity (eq. mg/l CaCO₃) ratio (i.e. FOS/TAC) criterion was <0.1 indicating high stability for OLR <2.46 kg VS/m³ day. For higher OLR, FOS/TAC increased rapidly. Residual phytotoxicty of the digestate evaluated by the germination index (GI) (%) was quite constant for OLR < 2.46 kg VS/m³ day, which is lower than the 60% limit, indicating an acceptable toxicity level for crops. For OLR > 2.46 kg VS/m³ day, GI decreased rapidly. This corresponding trend between FOS/TAC and GI was further investigated by the definition of the GI ratio (GIR) parameter. Comparison between GIR and FOS/TAC suggests that GI could be a suitable criterion for evaluating process stability.     

Hazard property classification of waste according to the recent propositions of the EC using different methods

Hazard classification of waste is a necessity, but the hazard properties (named “H” and soon “HP”) are still not all defined in a practical and operational manner at EU level. Following discussion of subsequent draft proposals from the Commission there is still no final decision. Methods to implement the proposals have recently been proposed: tests methods for physical risks, test batteries for aquatic and terrestrial ecotoxicity, an analytical package for exhaustive determination of organic substances and mineral elements, surrogate methods for the speciation of mineral elements in mineral substances in waste, and calculation methods for human toxicity and ecotoxicity with M factors.In this paper the different proposed methods have been applied to a large assortment of solid and liquid wastes (>1 0 0).Data for 45 wastes – documented with extensive chemical analysis and flammability test – were assessed in terms of the different HP criteria and results were compared to LoW for lack of an independent classification. For most waste streams the classification matches with the designation provided in the LoW. This indicates that the criteria used by LoW are similar to the HP limit values.This data set showed HP 14 ‘Ecotoxic chronic’ is the most discriminating HP. All wastes classified as acute ecotoxic are also chronic ecotoxic and the assessment of acute ecotoxicity separately is therefore not needed. The high number of HP 14 classified wastes is due to the very low limit values when stringent M factors are applied to total concentrations (worst case method). With M factor set to 1 the classification method is not sufficiently discriminating between hazardous and non-hazardous materials. The second most frequent hazard is HP 7 ‘Carcinogenic’. The third most frequent hazard is HP 10 ‘Toxic for reproduction’ and the fourth most frequent hazard is HP 4 “Irritant – skin irritation and eye damage”. In a stepwise approach, it seems relevant to assess HP 14 first, then, if the waste is not classified as hazardous, to assess subsequently HP 7, HP 10 and HP 4, and then if still not classified as hazardous, to assess the remaining properties.The elements triggering the HP 14 classification in order of importance are Zn, Cu, Pb, Cr, Cd and Hg. Progress in the speciation of Zn and Cu is essential for HP 14. Organics were quantified by the proposed method (AFNOR XP X30-489) and need no speciation. Organics can contribute significantly to intrinsic toxicity in many waste materials, but they are only of minor importance for the assessment of HP 14 as the metal concentrations are the main HP 14 classifiers. Organic compounds are however responsible for other toxicological characteristics (hormone disturbance, genotoxicity, reprotoxicity…) and shall be taken into account when the waste is not HP 14 classified.     

典型钢铁企业汞排放水平及排放特征研究

以某典型钢铁企业为研究对象,测定企业废气、废水、固废汞排放水平,并分析汞排放特征。研究表明,球团、烧结、高炉工艺废气排口烟尘中汞排放浓度和排放速率明显低于烟气;汞主要以气态形式排放,烧结工艺排口废气汞最高浓度分别是其他2个排口的7倍和3倍。球团、烧结、高炉、电炉四工艺环节中,烧结汞排放速率占四工艺汞排放速率总和的87%。半干法脱硫、氨法脱硫、石灰石石膏脱硫对废气中汞的去除效率分别为90.0%、78.7%和29.9%。企业废水排放未检出汞,脱硫产生固废汞含量明显高于除尘产生固废汞含量,脱硫灰汞含量是脱硫石膏的15倍。     

Recycling-oriented characterization of plastic frames and printed circuit boards from mobile phones by electronic and chemical imaging

This study characterizes the composition of plastic frames and printed circuit boards from end-of-life mobile phones. This knowledge may help define an optimal processing strategy for using these items as potential raw materials. Correct handling of such a waste is essential for its further “sustainable” recovery, especially to maximize the extraction of base, rare and precious metals, minimizing the environmental impact of the entire process chain. A combination of electronic and chemical imaging techniques was thus examined, applied and critically evaluated in order to optimize the processing, through the identification and the topological assessment of the materials of interest and their quantitative distribution. To reach this goal, end-of-life mobile phone derived wastes have been systematically characterized adopting both “traditional” (e.g. scanning electronic microscopy combined with microanalysis and Raman spectroscopy) and innovative (e.g. hyperspectral imaging in short wave infrared field) techniques, with reference to frames and printed circuit boards. Results showed as the combination of both the approaches (i.e. traditional and classical) could dramatically improve recycling strategies set up, as well as final products recovery.     

Mechanical and toxicological evaluation of concrete artifacts containing waste foundry sand

The creation of metal parts via casting uses molds that are generally made from sand and phenolic resin. The waste generated after the casting process is called waste foundry sand (WFS). Depending on the mold composition and the casting process, WFS can contain substances that prevent its direct emission to the environment. In Brazil, this waste is classified according to the Standard ABNT NBR 10004:2004 as a waste Class II (Non-Inert). The recycling of this waste is limited because its characteristics change significantly after use. Although the use (or reuse) of this byproduct in civil construction is a technically feasible alternative, its effects must be evaluated, especially from mechanical and environmental points of view. Thus, the objective of this study is to investigate the effect of the use of WFS in the manufacture of cement artifacts, such as masonry blocks for walls, structural masonry blocks, and paving blocks. Blocks containing different concentrations of WFS (up to 75% by weight) were produced and evaluated using compressive strength tests (35 MPa at 28 days) and toxicity tests on Daphnia magna, Allium cepa (onion root), and Eisenia foetida (earthworm). The results showed that there was not a considerable reduction in the compressive strength, with values of 35 ± 2 MPa at 28 days. The toxicity study with the material obtained from leaching did not significantly interfere with the development of D. magna and E. foetida, but the growth of the A. cepa species was reduced. The study showed that the use of this waste in the production of concrete blocks is feasible from both mechanical and environmental points of view.