Mechanisms contributing to the thermal analysis of waste incineration bottom ash and quantification of different carbon species

The focus of this study was to identify the main compounds affecting the weight changes of bottom ash (BA) in conventional loss on ignition (LOI) tests and to obtain a better understanding of the individual processes in heterogeneous (waste) materials such as BA. Evaluations were performed on BA samples from a refuse derived fuel incineration (RDF-I) plant and a hospital waste incineration (HW-I) plant using thermogravimetric analysis and subsequent mass spectrometry (TG–MS) analysis of the gaseous thermal decomposition products. Results of TG–MS analysis on RDF-I BA indicated that the LOI measured at 550 °C was due to moisture evaporation and dehydration of Ca(OH)₂ and hydrocalumite. Results for the HW-I BA showed that LOI at 550 °C was predominantly related to the elemental carbon (EC) content of the sample. Decomposition of CaCO₃ around 700 °C was identified in both materials. In addition, we have identified reaction mechanisms that underestimate the EC and overestimate the CaCO₃ contents of the HW-I BA during TG–MS analyses. These types of artefacts are expected to occur also when conventional LOI methods are adopted, in particular for materials that contain CaO/Ca(OH)₂ in combination with EC and/or organic carbon, such as e.g. municipal solid waste incineration (MSWI) bottom and fly ashes. We suggest that the same mechanisms that we have found (i.e. in situ carbonation) can also occur during combustion of the waste in the incinerator (between 450 and 650 °C) demonstrating that the presence of carbonate in bottom ash is not necessarily indicative for weathering. These results may also give direction to further optimization of waste incineration technologies with regard to stimulating in situ carbonation during incineration and subsequent potential improvement of the leaching behavior of bottom ash.     

Feasible conversion of solid waste bauxite tailings into highly crystalline 4A zeolite with valuable application

Bauxite tailings are a major type of solid wastes generated in the flotation process. The waste by-products caused significant environmental impact. To lessen this hazardous effect from poisonous mine tailings, a feasible and cost-effective solution was conceived and implemented. Our approach focused on reutilization of the bauxite tailings by converting it to 4A zeolite for reuse in diverse applications. Three steps were involved in the bauxite conversion: wet-chemistry, alkali fusion, and crystallization to remove impurities and to prepare porous 4A zeolite. It was found that the cubic 4A zeolite was single phase, in high purity, with high crystallinity and well-defined structure. Importantly, the 4A zeolite displayed maximum calcium ion exchange capacity averaged at 296 mg CaCO₃/g, comparable to commercially-available zeolite (310 mg CaCO₃/g) exchange capacity. Base on the optimal synthesis condition, the reaction yield of zeolite 4A from bauxite tailings achieved to about 38.43%, hence, this study will provide a new paradigm for remediation of bauxite tailings, further mitigating the environmental and health care concerns, particularly in the mainland of PR China.     

The behaviour of selected rare-earth elements during the conversion of phosphogypsum to calcium sulphide and residue

Phosphogypsum (PG) is a large hazardous waste from fertiliser and phosphoric acid industries from which useful products including rare-earth elements (REEs) can be recovered depending on the treatment process. Its conversion to calcium sulphide (CaS) which was achieved at 95% followed by the formation of S, CaCO₃ and residue is one of the plausible treatment processes leading to economic and environmental benefits. This study aimed at monitoring selected REEs behaviour during the conversion of (PG) to (CaS). The concentrations of REEs in the raw PG, the produced CaS and the obtained residue were determined after digestion (microwave and traditional acid leaching) using ICP-OES. The effect of CO₂ and H₂S used in the process of forming CaCO₃ and S from PG on the concentrations of REEs was also investigated. Microwave digestion proved to be more effective than traditional acid leaching in the recovery of REEs. Microwave digestion using 3 mL HNO₃ + 1 mL HCl was more effective than 1 mL HNO₃ + 3 mL in REEs recovery. CaS contained the highest amount of Ce, Pr, Nd, Sm, Eu, Gd, Dy, Ho, Er, La and Y with values of 2646, 476, 2255, 320, 60.5, 376, 79.8, 1.24, 476, 1185 and 318 µg/g respectively. Based on these findings, the residue could be further processed to recover REEs despite less than 40% decrease in concentration for the majority of REEs observed due to the use of H₂S and CO₂. CO₂ was found to be more suitable as fewer REEs were leached as compared to H₂S. All things considered, the obtained residue could be a good secondary source of REEs as it is easier to leach, retained good amount of REEs and lesser impurities.

     

Chemical characterization of emissions from a municipal solid waste treatment plant

Gaseous emissions are an important problem in municipal solid waste (MSW) treatment plants. The sources points of emissions considered in the present work are: fresh compost, mature compost, landfill leaks and leachate ponds. Hydrogen sulphide, ammonia and volatile organic compounds (VOCs) were analysed in the emissions from these sources. Hydrogen sulphide and ammonia were important contributors to the total emission volume. Landfill leaks are significant source points of emissions of H₂S; the average concentration of H₂S in biogas from the landfill leaks is around 1700 ppmv. The fresh composting site was also an important contributor of H₂S to the total emission volume; its concentration varied between 3.2 and 1.7 ppmv and a decrease with time was observed. The mature composting site showed a reduction of H₂S concentration (<0.1 ppmv). Leachate pond showed a low concentration of H₂S (in order of ppbv). Regarding NH₃, composting sites and landfill leaks are notable source points of emissions (composting sites varied around 30–600 ppmv; biogas from landfill leaks varied from 160 to 640 ppmv).Regarding VOCs, the main compounds were: limonene, p-cymene, pinene, cyclohexane, reaching concentrations around 0.2–4.3 ppmv.H₂S/NH₃, limonene/p-cymene, limonene/cyclohexane ratios can be useful for analysing and identifying the emission sources.     

Treating landfill gas hydrogen sulphide with mineral wool waste (MWW) and rod mill waste (RMW)

Hydrogen sulphide (H₂S) gas is a major odorant at municipal landfills. The gas can be generated from different waste fractions, for example demolition waste containing gypsum based plaster board. The removal of H₂S from landfill gas was investigated by filtering it through mineral wool waste products. The flow of gas varied from 0.3 l/min to 3.0 l/min. The gas was typical for landfill gas with a mean H₂S concentration of ca. 4500 ppm. The results show that the sulphide gas can effectively be removed by mineral wool waste products. The ratios of the estimated potential for sulphide precipitation were 19:1 for rod mill waste (RMW) and mineral wool waste (MWW). A filter consisting of a mixture of MWW and RMW, with a vertical perforated gas tube through the center of filter material and with a downward gas flow, removed 98% of the sulfide gas over a period of 80 days. A downward gas flow was more efficient in contacting the filter materials. Mineral wool waste products are effective in removing hydrogen sulphide from landfill gas given an adequate contact time and water content in the filter material. Based on the estimated sulphide removal potential of mineral wool and rod mill waste of 14 g/kg and 261 g/kg, and assuming an average sulphide gas concentration of 4500 ppm, the removal capacity in the filter materials has been estimated to last between 11 and 308 days. At the studied location the experimental gas flow was 100 times less than the actual gas flow. We believe that the system described here can be upscaled in order to treat this gas flow.     

Pathogen reduction in minimally managed composting of bovine manure

Spread of manure pathogens is of considerable concern due to use of manure for land application. In this study, the effects of four static pile treatment options for bovine manure on die-off of a generic Escherichia coli, E. coli O157:H7 surrogate, Salmonella Senftenberg, Salm. Typhimurium, and Listeria monocytogenes were evaluated. Bovine manure spiked with these bacteria were placed in cassettes at the top, middle, and bottom sections of four static pile treatments that reflect minimal changes in pile construction with and without straw. Temperatures were monitored continuously during the 28 day self-heating period. E. coli and salmonellae were reduced from 8 to 9 log₁₀ CFU g^?1 to undetectable levels (<1.77 log₁₀ MPN g^?1) at 25–30 cm depths within 7 days in all pile sections except for the manure-only pile in which 3–4 logs of reduction were obtained. No L. monocytogenes initially present at 6.62 log₁₀ CFU g^?1 were recovered from straw-amended piles after 14 days, in contrast with manure-only treatment in which this pathogen was recovered even at 28 days. Decline of target bacterial populations corresponded to exposure to temperatures above 45 °C for more than 3 days and amendments of manure with straw to increase thermophilic zones. Use of straw to increase aeration, self-heating capacity, and heat retention in manure piles provides producers a minimal management option for composting that enhances pathogen die-off and thereby reduces risk of environmental spread when manure is applied to land.     

The potential of algae blooms to produce renewable gaseous fuel

Ulva lactuca (commonly known as sea letuce) is a green sea weed which dominates Green Tides or algae blooms. Green Tides are caused by excess nitrogen from agriculture and sewage outfalls resulting in eutrophication in shallow estuaries. Samples of U. lactuca were taken from the Argideen estuary in West Cork on two consecutive years. In year 1 a combination of three different processes/pretreatments were carried out on the Ulva. These include washing, wilting and drying. Biomethane potential (BMP) assays were carried out on the samples. Fresh Ulva has a biomethane yield of 183 L CH₄/kg VS. For dried, washed and macerated Ulva a BMP of 250 L CH₄/kg VS was achieved. The resource from the estuary in West Cork was shown to be sufficient to provide fuel to 264 cars on a year round basis. Mono-digestion of Ulva may be problematic; the C:N ratio is low and the sulphur content is high. In year 2 co-digestion trials with dairy slurry were carried out. These indicate a potential increase in biomethane output by 17% as compared to mono-digestion of Ulva and slurry.     

Anaerobic digestion of autoclaved and untreated food waste

Anaerobic digestion of autoclaved (160 °C, 6.2 bar) and untreated source segregated food waste (FW) was compared over 473 days in semi-continuously fed mesophilic reactors with trace elements supplementation, at organic loading rates (OLRs) of 2, 3, 4 and 6 kg volatile solids (VS)/m³ d. Methane yields at all OLR were 5–10% higher for untreated FW (maximum 0.483 ± 0.013 m³ CH₄/kg VS at 3 kg VS/m³ d) than autoclaved FW (maximum 0.439 ± 0.020 m³ CH₄/kg VS at 4 kg VS/m³ d). The residual methane potential of both digestates at all OLRs was less than 0.110 m³ CH₄/kg VS, indicating efficient methanation in all cases. Use of acclimated inoculum allowed very rapid increases in OLR. Reactors fed on autoclaved FW showed lower ammonium and hydrogen sulphide concentrations, probably due to reduced protein hydrolysis as a result of formation of Maillard compounds. In the current study this reduced biodegradability appears to outweigh any benefit due to thermal hydrolysis of ligno-cellulosic components.     

Comparison of different liquid anaerobic digestion effluents as inocula and nitrogen sources for solid-state batch anaerobic digestion of corn stover

Effluents from three liquid anaerobic digesters, fed with municipal sewage sludge, food waste, or dairy waste, were evaluated as inocula and nitrogen sources for solid-state batch anaerobic digestion of corn stover in mesophilic reactors. Three feedstock-to-effluent (F/E) ratios (i.e., 2, 4, and 6) were tested for each effluent. At an F/E ratio of 2, the reactor inoculated by dairy waste effluent achieved the highest methane yield of 238.5 L/kgVS_feed, while at an F/E ratio of 4, the reactor inoculated by food waste effluent achieved the highest methane yield of 199.6 L/kgVS_feed. The microbial population and chemical composition of the three effluents were substantially different. Food waste effluent had the largest population of acetoclastic methanogens, while dairy waste effluent had the largest populations of cellulolytic and xylanolytic bacteria. Dairy waste also had the highest C/N ratio of 8.5 and the highest alkalinity of 19.3 g CaCO₃/kg. The performance of solid-state batch anaerobic digestion reactors was closely related to the microbial status in the liquid anaerobic digestion effluents.     

Recovery of lithium and cobalt from waste lithium ion batteries of mobile phone

In view of the stringent environmental regulations, availability of limited natural resources and ever increasing need of alternative energy critical elements, an environmental eco-friendly leaching process is reported for the recovery of lithium and cobalt from the cathode active materials of spent lithium-ion batteries of mobile phones. The experiments were carried out to optimize the process parameters for the recovery of lithium and cobalt by varying the concentration of leachant, pulp density, reductant volume and temperature. Leaching with 2 M sulfuric acid with the addition of 5% H₂O₂ (v/v) at a pulp density of 100 g/L and 75 °C resulted in the recovery of 99.1% lithium and 70.0% cobalt in 60 min. H₂O₂ in sulfuric acid solution acts as an effective reducing agent, which enhance the percentage leaching of metals. Leaching kinetics of lithium in sulfuric acid fitted well to the chemical controlled reaction model i.e. 1 ? (1 ? X)^1/3 = k_ct. Leaching kinetics of cobalt fitted well to the model ‘ash diffusion control dense constant sizes spherical particles’ i.e. 1 ? 3(1 ? X)^2/3 + 2(1 ? X) = k_ct. Metals could subsequently be separated selectively from the leach liquor by solvent extraction process to produce their salts by crystallization process from the purified solution.     

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.     

A novel process for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps intended for lithium-ion batteries

To solve the recycling challenge for aqueous binder based lithium-ion batteries (LIBs), a novel process for recycling and resynthesizing LiNi_1/3Co_1/3Mn_1/3O₂ from the cathode scraps generated during manufacturing process is proposed in this study. Trifluoroacetic acid (TFA) is employed to separate the cathode material from the aluminum foil. The effects of TFA concentration, liquid/solid (L/S) ratio, reaction temperature and time on the separation efficiencies of the cathode material and aluminum foil are investigated systematically. The cathode material can be separated completely under the optimal experimental condition of 15 vol.% TFA solution, L/S ratio of 8.0 mL g^?1, reacting at 40 °C for 180 min along with appropriate agitation. LiNi_1/3Co_1/3Mn_1/3O₂ is successfully resynthesized from the separated cathode material by solid state reaction method. Several kinds of characterizations are performed to verify the typical properties of the resynthesized LiNi_1/3Co_1/3Mn_1/3O₂ powder. Electrochemical tests show that the initial charge and discharge capacities of the resynthesized LiNi_1/3Co_1/3Mn_1/3O₂ are 201 mAh g^?1 and 155.4 mAh g^?1 (2.8–4.5 V, 0.1 C), respectively. The discharge capacity remains at 129 mAh g^?1 even after 30 cycles with a capacity retention ratio of 83.01%.     

Evaluation of landfill leachate treatment by advanced oxidative process by Fenton’s reagent combined with membrane separation system

A high content of refractory organic matter, ammonia and toxic compounds is characteristic of landfill leachate. Advanced oxidative processes (AOPs) are an attractive alternative for landfill leachate treatment. However, when applied as a unique process treatment, they do not provide a complete solution for the effluent treatment. Combining AOP with a membrane separation process (MSP) presents a number of benefits and provides an adequate solution for this problem. With this in mind, the present work aims to evaluate, using a bench scale, leachate treatability through AOP by Fenton’s reagent (AOP/Fenton) combined with microfiltration (MF) and nanofiltration (NF). A high efficient removal of COD (63%), true color (76%) and humic substances (50%) was observed during AOP/Fenton under optimized conditions (1.7 g H₂O₂/g COD_{raw leachate}; FeSO₄·7H₂O:H₂O₂ = 1:5.3; pH = 3.8; reaction conditions = 115 rpm/28 min). According to the evaluated parameters, MSP presented an efficient complementary treatment, in which the integrity of the stages was sufficient for reaching regulatory levels in the effluent (Deliberação Normativa Conjunta COPAM/CERH-MG N^o. 1, May 5, 2008).     

An investigation on pollutant emissions from co-firing of RDF and coal

Pollutant emissions from co-firing of refuse derived fuel (RDF) and coal were investigated in a vortexing fluidized bed combustor (VFBC). RDF-5 was made of common municipal solid waste (MSW). CaCO₃ was injected in the combustor to absorb HCl at 850 °C. The results show that NO_x and HCl emissions increase with RDF-5 co-firing ratio. The NO_x concentration in flue gas at the bottom of the combustor is higher than that at the top. However, the trend of HCl released is reverse compared with NO_x emissions. It was found that the HCl concentration decreases with increasing the molar ratio of Ca/Cl. However, the effect of CaCO₃ addition on HCl retention is not significant when the molar ratio of Ca/Cl is higher than 5. The chlorine content in fly ash increases obviously with the molar ratio of Ca/Cl. PCDD/Fs emissions decrease slightly with an addition of CaCO₃. In this study incomplete combustion is regarded as the main cause for polychlorinated dibenzo-p-dioxins and dibenzofurans (PCDD/Fs) formation.     

Treatment of mature landfill leachate by biofilters and Fenton oxidation

A series of processes by biofilter and Fenton oxidation to treat mature landfill leachate has been devised. At a hydraulic loading rate of 20 l m^?3 d^?1, a biofilter packed with aged refuse is found to remove 80% of chemical oxygen demand (COD), 89% of ammonia nitrogen and 96% of total phosphorus (TP). Particularly, TP levels dropped below 1 mg l^?1. The optimal condition for Fenton oxidation was selected to be an initial pH of 5, a dosage of 0.01 and 0.02 mol l^?1 of FeSO₄ and H₂O₂, respectively, and a duration of 3 h, where COD removal efficiency reaches 58.6%, and BOD₅/COD ratio is raised from 0.05 to 0.20. Subsequent treatment by a biofilter packed with slag reduces COD, ammonia nitrogen levels to less than 100, 25 mg l^?1, respectively. A pilot scale experiment conducted in situ demonstrates that this series of processes exhibits a high efficiency in removing pollutants from mature landfill leachate and it is viable for application.     

What is the acceptable margin of error for the oxygen uptake method in evaluating the reactivity of organic waste?

The acceptable margin of error for the organic waste reactivity measured by the oxygen uptake method was assessed. Oxygen uptake was determined by the Dynamic Respiration Index (DRI) (mgO₂/kgVS h). The composed uncertainty (uC) of the experimental set up used for the DRI test was evaluated and the uncertainty (u) of all the components of the apparatus was evaluated. A procedure for calculating the uC of the apparatus is proposed. The components affecting the uC of the DRI to a more significant extent were the one of the oxygen mass rate and the u of the amount of VS in the sample analyzed. For a confidence level of 99.73%, the extended uC (UC) interval for a DRI = 1024 mgO₂/kgVS h was ±440 mgO₂/kgVS h, whereas for a DRI = 3489 mgO₂/kgVS h, the UC interval was ±1288 mgO₂/kgVS h. When oxygen consumption and VS content become lower than 600 mgO₂/h and 0.9 kg, respectively, the UC interval is similar to the measured DRI.     

Thermogravimetric analysis and kinetic study on large particles of printed circuit board wastes

Pyrolysis of large printed circuit board (PCB) waste particle was conducted on a specially designed laboratory-scale thermobalance (Macro-TG) with sample loading of 30 g under dynamic nitrogen atmosphere. The effects of heating rate (10, 15, 20 and 25 °C min^?1) and particle size (1 mm × 1 mm, 5 mm × 5 mm, 10 mm × 10 mm and 10 mm × 20 mm) were examined. To compare the different decomposition behavior of fine and large one, the thermal decomposition of PCB waste powder (approximately 5 mg) was also performed on a thermogravimetric analyzer (common TG) under various heating rates (10, 15, 20 and 40 °C min^?1) and particle size ranges (0.198–0.165 mm, 0.165–0.074 mm, 0.074–0.055 mm and 0.055–0.047 mm). Experimental results show that large particle has a pyrolysis reaction retardancy compared to fine one. The distributed activation energy model was used to study the pyrolysis kinetics. It was found that during pyrolysis process, values of frequency factor (k₀) changed with different activation energy (E) values. On common TG, the E values range from 156.95 to 319.37 kJ mol^?1 and k₀ values range from 2.67 × 10¹³ to 2.24 × 10²⁷ s^?1. While, on Macro-TG, the range of E was 31.48–41.26 kJ mol^?1 and of the frequency factor was 19.80–202.67 s^?1.     

The usability of the IR,RAC and MRI indices of heavy metal distribution to assess the environmental quality of sewage sludge composts

To assess the environmental quality of compost, it is insufficient to use only total metal concentration. Therefore in this study, the stability of metals in compost and the environmental risk they pose were assessed by three indices that have been proposed for soils or sediments: the I_R, the RAC and the MRI. In mature composts, the highest bonding intensity was for Ni (0.79 < I_R < 0.93), then for Cu (0.56 < I_R < 0.65) and Pb (0.55 < I_R < 0.73), and the lowest for Zn (0.19 < I_R < 0.25). Although, both the I_R and the RAC are useful indices for evaluating the mobility of metals, they do not take into account their toxicity. Therefore, the overall classification of compost should also include the MRI, at which metal toxicity from the most available fractions is considered. Based on the MRI ranged between 10.0 and 11.6, all composts evaluated posed a low risk.     

Evaluation of a classification method for biodegradable solid wastes using anaerobic degradation parameters

We studied the biochemical and anaerobic degradation characteristics of 29 types of materials to evaluate the effects of a physical composition classification method for degradable solid waste on the computation of anaerobic degradation parameters, including the methane yield potential (L₀), anaerobic decay rate (k), and carbon sequestration factor (CSF). Biochemical methane potential tests were conducted to determine the anaerobic degradation parameters of each material. The results indicated that the anaerobic degradation parameters of nut waste were quite different from those of other food waste and nut waste was classified separately. Paper was subdivided into two categories according to its lignin content: degradable paper with lignin content of <0.05 g g VS^?1, and refractory paper with lignin content >0.15 g g VS^?1. The L₀, k, and CSF parameters of leaves, a type of garden waste, were similar to those of grass. This classification method for degradable solid waste may provide a theoretical basis that facilitates the more accurate calculation of anaerobic degradation parameters.     

Changes in cadmium mobility during composting and after soil application

The effect of twelve weeks of composting on the mobility and bioavailability of cadmium in six composts containing sewage sludge, wood chips and grass was studied, along with the cadmium immobilization capacity of compost. Two different soils were used and Cd accumulation measured in above-ground oat biomass (Avena sativa L.). Increasing pH appears to be an important cause of the observed decreases in available cadmium through the composting process. A pot experiment was performed with two different amounts of compost (9.6 and 28.8 g per kg of soil) added into Fluvisol with total Cd 0.255 mg kg^?1, and contaminated Cambisol with total Cd 6.16 mg kg^?1. Decrease of extractable Cd (0.01 mol l^?1 CaCl₂) was found in both soils after compost application. The higher amount of compost immobilized an exchangeable portion of Cd (0.11 mol l^?1 CH₃COOH extractable) in contaminated Cambisol unlike in light Fluvisol. The addition of a low amount of compost decreased the content of Cd in associated above-ground oat biomass grown in both soils, while a high amount of compost decreased the Cd content in oats only in the Cambisol.