Recovery of zinc and lead from fly ash from ash-melting and gasification-melting processes of MSW--comparison and applicability of chemical leaching methods

Fly ash generated from MSW ash-melting and gasification-melting plants, known as Melting Furnace Fly Ash (MFA), contains considerable amounts of heavy metals such as Pb and Zn. These metals can be recovered using a smelting furnace after "pre-treatment" for removal of unnecessary elements such as Cl, Sn and Si. Chemical methods have been studied for pretreatment in the past. However, they have been discussed only with regard to treatment cost and the concentration of Pb and Zn recovered, but neither applicability to various types of MFA nor the environmental impact have been considered. In this study, acid, alkaline and ammonia/chloride leaching methods were compared from the standpoints of: (1) applicability to MFA, (2) concentration of Pb and Zn recovered, (3) treatment cost, and (4) environmental impact. Twenty-three samples of MFAs were collected and classified into 4 types based on element contents. A Pb and Zn recovery experiment was conducted for the representative MFA of those types. The results showed: (1) MFA from gasification-melting plants cannot be treated by chemical methods; (2) the other MFA can be treated to an acceptable quality by existing smelting furnaces; (3) only MFA from electric resistance ash-melting plants can be treated easily by the water washing method; and (4) alkaline and ammonia/chloride leaching methods were more effective than acid leaching.     

Effect of Poly(Vinyl Alcohol) and Polyethylene on the Growth of Red Pepper and Tomato

Poly(vinyl alcohol) (PVA) and polyethylene (PE) were blended with a soil for cultivation, and their effects were investigated on the growth behavior of red pepper and tomato by examining the stems, the leaves, and the roots. PVA retarded the growth of red pepper significantly even at a concentration as low as 0.05%. The roots were depauperated more than the stems and the leaves. Tomato was also affected by PVA but to a lesser extent than red pepper. In contrast, the presence of both round pieces (10 mm diameter) of PE film and powdery PE influenced negligibly the growth of red pepper as well as that of tomato up to 35 wt% in soil.     

Effect of the Recycling and Annealing on the Mechanical and Fracture Properties of Poly(Lactic Acid)

The aim of this work is to evaluate the use of Poly(lactic acid) (PLA) industrial waste as a source of raw material for certain applications, as well as to understand the effects of the annealing on the fracture behavior of PLA. PLA waste has been simulated by an initial step of extrusion in a single screw extruder and pelletizing. Specimens of virgin and reprocessed PLA were obtained by injection molding. An annealing treatment capable of increasing the percentage of crystallinity (determined by differential scanning calorimetry) was also analyzed in reprocessed and non reprocessed specimens. The fracture behavior was studied at slow and high testing speed, applying the linear elastic fracture mechanics (LEFM) on single edge notched bend (SENB) specimens. This study revealed that the fracture toughness of the reprocessed PLA was basically the same that the virgin PLA and also that the increase in the crystalline fraction produced an improvement on the fracture toughness, at slow loading rate.     

Study on Properties of Poly(urethane-ester) Synthesized from Prepolymers of ε-Caprolactone and 2,2-Dimethyl-1,3-Propanediol Monomers and Their Biodegradability

Poly(urethane-ester) was prepared by polymerization of 4,4′-methylenebis(phenyl isocyanate) (MDI) and prepolymers of ε-caprolactone and 2,2-dimethyl-1,3-propanediol monomers P(CL-DP) with various chain lengths as polyol sources. Characterizations of poly(urethane-ester) were carried out by analysis of functional groups (FTIR), thermal properties (DTA/TGA), mechanical properties (Tensile tester), crystallinity (XRD), and biodegradability. The chain length of prepolymers used in polymerization has a significant effect in properties of poly(urethane-ester) as well as their biodegradability. The formation of poly(urethane-ester) was indicated by the presence of new absorption peaks at wave number of 3,348.2 and 1,596.9 cm^?1 for urethane (–NH–) and aromatic groups in chain of polymers, respectively. The increase chain length of prepolymer used in polymerization with 4,4′-methylenebis(phenyl isocyanate) was observed the increase thermal property and crystallinity of poly(urethane-ester). However, the maximum mechanical property and also biodegradability in activated sludge were observed in poly(urethane-ester) prepared by polymerization of 4,4′-methylenebis(phenyl isocyanate) (MDI) and P(CL-DP) prepolymers with DP/CL ratio of 1/20. Apparently, the amorphous parts of polymers are rapidly decomposed by enzymes of microorganisms, so the crystallinity on the whole of poly(urethane-ester) increases after incubation time of 30 days.     

Biodegradation of Pro-oxidant Filled Polypropylene Films and Evaluation of the Ecotoxicological Impact

The biodegradability of calcium stearate (CaSt) and cobalt stearate (CoSt) filled polypropylene (PP) films were investigated in this work. The PP films were prepared using melt blending technique followed by hot press moulding. On the basis of their tensile properties, the optimum amount of pro-oxidants was taken as 0.2 phr. Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were used for the characterization of optimized films. Presence of pro-oxidant in the PP was confirmed by the FTIR studies. Addition of pro-oxidants in the films decreased the thermal stability as revealed by TGA analysis. Crystallinity of the pro-oxidant filled PP decreased with addition of pro-oxidants as showen by DSC. The maximum biodegradation of CaSt and CoSt containing PP films was showen 7.65 and 8.34%, respectively with 0.2 phr. Both the microbial test and plant growth test (on corn and tomato) indicated that biodegradation intermediates were non toxic.     

Fabrication and Characterization of PLA/PHBV-Chitin Nanocomposites and Their Foams

This paper examines the effect of biobased chitin nanowhisker fillers on the thermal, rheological, physical, mechanical and morphological properties of biobased polylactic acid (PLA) and PLA/polyhydroxybutyrate-co-valerate (PHBV) blended nanocomposites as well as the physical, mechanical and morphological properties of porous PLA and PLA/PHBV nanocomposite foams. Solid nanocomposites of PLA, PLA/PHBV and chitin nanowhiskers were manufactured through melt blending while porous nanocomposites foams were fabricated through a batch foaming process with the aid of CO₂ as blowing agent. It was found that by incorporating small quantities of chitin nanowhiskers (<2 wt%) the mechanical properties of solid specimens are improved while strength and expandability of the foam can be significantly improved, yielding a homogenously distributed cell morphology with average cell size of 1.5 μm.     

Effects of cement on redistribution of trace metals and dissolution of organics in sewage sludge and its inorganic waste-amended products

The suitability of using cement-stabilized sludge products as artificial soils in earth works was evaluated. The sludge products investigated were cemented sludge, cement-treated clay-amended sludge (SS+MC), and cement-treated copper slag-amended sludge (SS+CS). The leachability of lead (Pb), zinc (Zn), copper (Cu), and chromium (Cr) were assessed using the sequential extraction technique, toxicity characteristic leaching procedure (TCLP), NEN 7341 availability test, and column leaching test. The results indicated that Zn leachability was reduced in all the cement-stabilized sludge products. In contrast, Cu was transferred from the organic fraction to the readily leachable phases in the cement-stabilized sludge products and therefore exhibited increased leachability. The increased Cu leachability could be attributed to dissolution of humic substances in the sludge as a result of elevated pH. Good correlation between dissolved organic carbon (DOC) and heavy metal leaching from the cement-stabilized sludge products was observed in the column leaching experiment. Even with a cement percentage as small as 12.5%, calcium silicate hydrate (C-S-H) was formed in the SS+MC and SS+CS products. Inclusion of the marine clay in the SS+MC products could reduce the leaching potentials of Zn, and this was the great advantage of the marine clay over the copper slag for sludge amendment.     

Release of nitrogen and trace metal species from field stacked biosolids

Concerns over elevated nitrate (NO3-) levels found in groundwater near former biosolid stockpiling locations resulted in the Maine Department of Environmental Protection (MDEP) imposing stricter regulations governing the stockpiling of biosolids in October 2002. The goals of this study were to measure the amount and speciation of nitrogen (N) and trace metals leaving stockpiled biosolids and travelling through the soil column. The biosolids were placed on plastic-lined cells to collect all leachate. Ammonium (NH4+), ranging from 2000 to 4900 mg L(-1), was the dominant N species (90% of total N) in the leachate from the Class B lime-stabilized biosolids in the lined cell experiment. Nitrate (NO3-) and nitrite (NO2-) concentrations were negligible, remaining below 0.25 and 0.1 mg L(-1), respectively. Dissolved organic carbon (DOC) concentrations as high as 8900 mg L(-1) and chemical oxygen demand (COD) as high as 37 000 mg L(-1) were measured in the leachate leaving the lined cell. Fifteen zero-tension pan lysimeters (ZTP-lysimeter) were installed in a 90 m2 plot at depth intervals of 30, 60, and 100 cm. Leachate passing through the soil column underlying the biosolids stockpile was collected in the ZTP-lysimeters. The average ZTP-lysimeter NH4+ concentrations ranged from 1400 mg L(-1) at 60 cm depth to 145 mg L(-1) at 90 cm depth. The average ZTP-lysimeter DOC concentrations ranged from 2000 mg L(-1) at 60 cm to 525 mg L(-1) at 90 cm. Trace metal determinations of the leachate collected from the lined cell and ZTP-lysimeters showed arsenic loading rates exceeded the state limits of 0.5 kg ha(-1) year(-1) by an order of magnitude. Arsenic concentrations were in excess of several thousand milligrams per litre in the lined-cell leachate and several hundred milligrams per litre in the ZTP-lysimeters as deep as 90 cm under the biosolid stockpile. Phosphorus, iron and manganese in excess of several thousand milligrams per litre were observed in both the lined-cell leachate and ZTP-lysimeters. Significant concentrations of other trace metals were found at depth in the zero-tension ZTP-lysimeter plot. Trace metals were largely mobilized by the DOC from the biosolids and due to the presence of anaerobic environment, especially in the underlying soil.     

Determination of MBT-waste reactivity – An infrared spectroscopic and multivariate statistical approach to identify and avoid failures of biological tests

The Austrian Landfill Ordinance provides limit values regarding the reactivity for the disposal of mechanically biologically treated (MBT) waste before landfilling. The potential reactivity determined by biological tests according to the Austrian Standards (OENORM S 2027 1-2) can be underestimated if the microbial community is affected by environmental conditions. New analytical tools have been developed as an alternative to error-prone and time-consuming biological tests. Fourier Transform Infrared (FT-IR) spectroscopy in association with Partial Least Squares Regression (PLS-R) was used to predict the reactivity parameters respiration activity (RA₄) and gas generation sum (GS₂₁) as well as to detect errors resulting from inhibiting effects on biological tests. For this purpose 250 MBT-waste samples from different Austrian MBT-plants were investigated using FT-IR spectroscopy in the mid (MIR) and near infrared (NIR) area and biological tests. Spectroscopic results were compared with those from biological tests. Arising problems caused by interferences of RA₄ and GS₂₁ are discussed. It is shown that FT-IR spectroscopy predicts RA₄ and GS₂₁ reliably to assess stability of MBT-waste materials and to detect errors.     

Methanolysis and Hydrolysis of Polycarbonate Under Moderate Conditions

Alkali-catalyzed methanolysis and hydrolysis of polycarbonate (PC) in a solvent in which PC can substantially dissolve such as N-methyl-2-pyrrolidone, 1,4-dioxane, tetrahydrofuran and so on were studied. Reaction conditions were optimized for the purpose of recycling PC in the form of bisphenol A and carbon carbonate. The results showed that both the methanolysis and hydrolysis of PC could take place under moderate conditions. Under the conditions of reaction temperature 40 °C, m(PC):m(MeOH) = 1:1, m(PC):m(NaOH) = 50:1, reaction time 35 min and using tetrahydrofuran as solvent, the methanolysis conversion of PC was almost 100% and the yield of bisphenol A was over 95%. Moreover, under the conditions of reaction temperature 100 °C, m(PC):m(H₂O) = 1:0.7, m(PC):m(NaOH) = 10:1, reaction time 8 h and using 1,4-dioxane as solvent, the hydrolysis conversion of PC was almost 100% and the yield of bisphenol A was over 94%.     

Time-series product and substance flow analyses of end-of-life electrical and electronic equipment in China

Given the amounts of end-of-life electrical and electronic equipment (EoL-EEE) being generated and their contents of both harmful and valuable materials, the EoL-EEE issue should be regarded not only as an emerging environmental problem but also as a resource management strategy in China. At present, in order to provide the basis for managing EoL-EEE at both product and substance levels in China, it is necessary to carry out a quantitative analysis on EoL-EEE and to determine how much of it will be generated and how much materials and substances it contains. In this study, the possession and obsolescence amounts of five types of household appliance (HA) including television (TV) sets and the amounts of substances contained in EoL TV sets were estimated using time-series product flow analysis (PFA) and substance flow analysis (SFA). The results of PFA indicated that the total possession amounts of those five types of HAs will exceed 3.1 billion units in 2030, which will be two times higher than those in 2010. In addition, it was estimated that cumulatively over 4.8–5.1 billion units of these five types of EoL HA would be obsoleted between 2010–2030. The results of SFA on TV sets indicated that the generated amounts of most of the less common metals and a part of common metals such as copper (Cu) would tend to decrease, whereas those of other common metals such as iron (Fe) as well as precious metals would tend to increase in EoL TV sets in 2015–2030. The results of this study provide a quantitative basis for helping decision makers develop strategic policies for the management of EoL-EEE considering both environmental and resource aspects. Moreover, a calculation scheme of obsolete HAs presented in this study can be applied to estimate other types of EoL durable good. Meanwhile, the frameworks of this study will help not only the policy decision makers in the Chinese government but also those in developing countries that are facing similar problems.     

Kinetics assessment and modeling of biogas production by anaerobic digestion of food wastes and acclimated sewage sludge

Journal of Material Cycles and Waste Management - In this work, food wastes (FWs) and domestic sewage sludge (DSS) were used as raw materials for energy recovery by anaerobic digestion (AD). AD was...     

Physico-chemical analysis and calorific values of poultry manure

Spain is one of the major producers of broilers and laying hens in the European Union, with an overall market share of around 12%. The poultry manure that is produced is usually employed as fertilizer on cropland, either directly or after a composting process. In some cases, however, this waste is transported over 120 km to be used as fertilizer, with the resulting high transport costs. In other countries, poultry manure is used as an alternative natural fuel source for power generation. In this study, poultry manure from all the laying hen farms in Asturias was characterized with a view to its possible use as an energy source. The Higher Heating Values on a dry basis (experimental) varies between 12,052 and 13,882 kJ/kg. Lower Heating Values (LHVs) on a wet basis range are much lower (mean values of 2664 kJ/kg) due to the high moisture content of poultry manure. Accordingly, the co-combustion of this waste with other types of waste such as forest and wood waste (LHV on a wet basis of 8044 and 15,830 kJ/kg, respectively) or municipal solid waste (LHV on a wet basis of 10,725 kJ/kg) should be considered as an alternative energy source. Chlorine and sulphur contents in dry matter vary around mean values of 0.64% and 0.11%, respectively. The waste also presents high amounts of Ca (4.84%) and K (2.38%).     

Synthesis and Properties of Poly(d,l-lactide-co-p-dioxanone) Random and Segmented Copolymers

Two different polymerization routes, one-step and two-step bulk ring-opening polymerizations of d,l-lactide (LA) and p-dioxanone (PDO) monermers using stannous octoate [Sn(Oct)₂]/n-dodecanol as the initiating system, were employed to synthesize poly(d,l-lactide-co-p-dioxanone) P(LA-co-PDO) random and segmented copolymers with different compositions and chain microstructure. For the two-step copolymers, the average sequence lengths of the lactidyl (L_LA) and dioxanyl (L_PDO) units calculated from the ¹H-NMR spectra were much longer than those values for the one-step copolymers with the same LA/PDO feed ratio. Corresponding to this difference in microstructure, the two-step copolymers were semi-crystalline even when the PDO content was as low as 14.5 mol%, while the one-step copolymers were completely amorphous with PDO content below 60.6 mol%. However, irrespective of polymerization route, both types of copolymers displayed a single glass transition temperature that was in a linear relation with composition. The decrease of maximum decomposition temperature of the copolymers was in accordance with the decrease of L_PDO value. The mechanical and degradation properties of the copolymers were significantly affected by both the polymerization route and the chemical composition as well. In conclusion, the properties of P(LA-co-PDO) copolymers could be adjusted conveniently to meet specific applications by changing the composition and microstructure of the copolymers via different polymerization routes.     

Organic oxalate as leachant and precipitant for the recovery of valuable metals from spent lithium-ion batteries

Spent lithium-ion batteries containing lots of strategic resources such as cobalt and lithium are considered as an attractive secondary resource. In this work, an environmentally compatible process based on vacuum pyrolysis, oxalate leaching and precipitation is applied to recover cobalt and lithium from spent lithium-ion batteries. Oxalate is introduced as leaching reagent meanwhile as precipitant which leaches and precipitates cobalt from LiCoO(2) and CoO directly as CoC(2)O(4)·2H(2)O with 1.0 M oxalate solution at 80°C and solid/liquid ratio of 50 g L(-1) for 120 min. The reaction efficiency of more than 98% of LiCoO(2) can be achieved and cobalt and lithium can also be separated efficiently during the hydrometallurgical process. The combined process is simple and adequate for the recovery of valuable metals from spent lithium-ion batteries.     

Pyrolysis of waste animal fats in a fixed-bed reactor: Production and characterization of bio-oil and bio-char

Several animal (lamb, poultry and swine) fatty wastes were pyrolyzed under nitrogen, in a laboratory scale fixed-bed reactor and the main products (liquid bio-oil, solid bio-char and syngas) were obtained. The purpose of this study is to produce and characterize bio-oil and bio-char obtained from pyrolysis of animal fatty wastes. The maximum production of bio-oil was achieved at a pyrolysis temperature of 500 °C and a heating rate of 5 °C/min. The chemical (GC–MS analyses) and spectroscopic analyses (FTIR analyses) of bio-oil showed that it is a complex mixture consisting of different classes of organic compounds, i.e., hydrocarbons (alkanes, alkenes, cyclic compounds…etc.), carboxylic acids, aldehydes, ketones, esters,…etc. According to fuel properties, produced bio-oils showed good properties, suitable for its use as an engine fuel or as a potential source for synthetic fuels and chemical feedstock. Obtained bio-chars had low carbon content and high ash content which make them unattractive for as renewable source energy.     

Wet extraction of heavy metals and chloride from MSWI and straw combustion fly ashes

Fly ash residues from combustion often do not meet the criteria neither for reuse as construction materials nor landfilling as non-hazardous waste, mainly because of the high concentration of heavy metals and chlorides. This work aimed to technically evaluate an innovative wet treatment process for the extraction of chloride (Cl^?), cadmium (Cd), copper (Cu), lead (Pb) and zinc (Zn) from fly ashes from a municipal solid waste incineration (MSWI) plant and from a straw combustion (SC) facility. Factors investigated were liquid/solid (L/S) ratio, full carbonation (CO₂ treatment), influence of pH and leaching time, using a two-level full factorial design. The most significant factor for all responses was low pH, followed by L/S ratio. Multiple linear regression models describing the variation in extraction data had R² values ranging from 58% to 98%. An optimization of the element extraction models was performed and a set of treatment conditions is suggested.     

Sustainable construction: composite use of tyres and ash in concrete

An investigation was carried out to establish the physical, mechanical and chemical characteristics of a non-standard (unprocessed) pulverised fuel ash (PFA) and waste tyres from a former landfill site at the Power Station Hill near Church Village, South Wales, United Kingdom. Investigations are on-going to establish the suitability of the fly ash and/or tyres in road construction (embankment and pavement) and also in concrete to be used in the construction of the proposed highway. This paper reports on concrete-based construction where concrete blends (using various levels of PFA as partial replacement for Portland cement (PC), and shredded waste tyres (chips 15-20mm) as aggregate replacement) were subjected to unconfined compressive strength tests to establish performance, hence, optimising mix designs. Strength development up to 180 days for the concrete made with PC-PFA blends as binders (PC-PFA concrete), with and without aggregate replacement with tyre chips, is reported. The binary PC-PFA concrete does not have good early strength but tends to improve at longer curing periods. The low early strength observed means that PC-PFA concrete cannot be used for structures, hence, only as low to medium strength applications such as blinding, low-strength foundations, crash barriers, noise reduction barriers, cycle paths, footpaths and material for pipe bedding.     

Recycling of waste biomass and mineral powder for preparation of potassium-enriched compost

An attempt was made to recycle waste biomass and mineral powder (waste mica) as an alternative source of potassium (K) through composting technology. Two different waste biomass, isabgol straw and palmarosa distillation waste along with two levels of waste mica (2 and 4% as K) were used for preparation of enriched composts. A notable decrease of C:N ratio was observed at the end of the composting (150 days) as an indicator of compost maturity. The mature composts were evaluated for K-supplying capacity through laboratory leaching and soil incubation study. Significantly higher water-soluble K released initially followed by a sharp decrease up to 21 days of leaching thereafter gradually decreased up to 35 days of leaching. Water-soluble K was released from K-enriched (mica charged) compost significantly higher than the ordinary compost throughout the leaching period. Soil incubation study also revealed that application of K-enriched compost greatly improved the available K (water soluble and exchangeable) pools in K-deficient soil which indicated that a considerable amount of K releases during composting. Therefore, K-enriched compost could be an effective alternative of costly commercial K fertilizer and eco-friendly approach to utilize low-cost waste mineral powder and plant residue.     

Mercury Capture on Fly Ash and Sorbents: The Effects of Coal Properties and Combustion Conditions

The US fleet of coal-fired power plants, with generating capacity of just over 300 GW, is known to be a major source of domestic mercury (Hg) emissions. To address this, in March 2005, the Environmental Protection Agency (EPA) promulgated the Clean Air Mercury Rule (CAMR) to reduce emissions of mercury from these plants. It is generally believed that most of the initial (Phase I) mercury reductions will come as a co-benefit of existing controls used to remove particulate matter (PM), SO₂, and NO _X . Deeper reductions in emissions (as required in Phase II of CAMR) may require the installation of mercury-specific control technology. Duct injection of activated carbon sorbents is the mercury-specific control technology that has been most widely studied and has been demonstrated over a wide range of coal types and combustion conditions. The effectiveness of the mercury control options (both “co-benefit control” and “mercury-specific control”) is significantly impacted by site-specific characteristics such as the combustion conditions, the configuration of existing air pollution controls, and the type of coal burned. This paper identifies the role of coal properties and combustion conditions in the capture of mercury by fly ash and injected sorbents.