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The impact of carbonation on bulk and ITZ porosity in microconcrete materials with fly ash replacement
Scanning electron microscopy was used to evaluate the porosity patterns found in microconcrete materials to better understand the gaseous diffusion pathways and reaction of CO{sub 2} within the bulk cement paste and interfacial transition zone (ITZ) of microconcrete materials containing different fly ash replacement types. Image segmentation was applied to evaluate the porosity as a function of distance from an exposed surface in the bulk cement paste and from aggregate boundaries in the ITZ in both carbonated and non-carbonated microconcrete materials. The ITZ region remained more porous compared to the bulk cement paste for all microconcrete types after carbonation despite a change in the porosity profile across the ITZ region. Results indicate that both the carbonation reaction capacity and porosity before carbonation impact the decrease in porosity observed as a result of carbonation in the ITZ and bulk cement paste regions.
Surface Modified Fly Ash for Value Added Products (SuMo Fly Ash)
The objective of this project is to develop a technology to encapsulate coal fly ash particles in sulfurized vegetable oil, enhancing physical and mechanical properties of the fly ash as a filler material when applied in commercial products. This project significantly advances the knowledge base and technology for synthesizing coated fly ash particles for application in different polymer matrices to increase cross-linking, compatibility, air-entrainment and to decrease the leaching potential of metals of concern. Specifically, the project focuses on (a) collection, and characterization of fly ash material from coal power plants; (b) development of Sulfurized Vegetable Oil (SVO) modified (SuMo) fly ash and their detailed characterization; (c) evaluation of the mechanical properties of the SuMo fly ash incorporated plastic and rubber composites for potential replacement of CaCO 3 or carbon black as filler materials with SuMo fly ash in plastic and rubber composites; (d) leaching potential of SuMo fly ash and SuMo fly ash-incorporated plastic and rubber composites to determine the rate of release of trace metals. The major findings of this project are: i) Sulfurized Vegetable Oil coated fly ash (SuMo fly ash) was successfully prepared with a particle size of ≤ 45 micron which exhibited hydrophobicity of contact angle > 90°; ii) the coating reduces leaching of metals (e.g., B, Cr) from fly ash when exposed to water; iii) incorporation of SuMo fly ash increases thermal stability and yield strength of plastics; iv) SuMo coating helps disperse fly ash particles into cured rubbers, natural rubber; (v) SuMo fly ash-incorporated plastic/cured rubbers compounds protects against leaching of toxic elements.
Distribution of rare earth elements in the pilot-scale processing of fly ashes derived from eastern Kentucky coals: Comparisons of the feed and processed ashes
Beneficiated fly ash from the combustion of Central Appalachian high volatile bituminous coals was extracted with HNO 3 in a pilot-scale processing plant. Several major oxides (notably CaO and SO 3 , but also including Fe 2 O 3 , MgO, K 2 O, and P 2 O 5 ) and minor elements (Mn, As, Sr, Ba, and Pb) are depleted in the post-HNO 3 -extraction spent ash. The total lanthanides, Y, and Sc concentration is reduced by about 20% in the spent ash, with Gd showing the greatest decrease. Along with Gd, Nd and Dy are also well differentiated between the feed and spent ashes, with La and Sm showing minimal partitioning. The Gd decrease is correlated with the depletion of Fe 2 O 3 . The heavy rare earth elements (REE heavier than Eu) and Y are disproportionately concentrated in the HNO 3 -leachate compared to the light REE. For the ashes studied, Sc did not partition between the feed and spent ashes. Pozzolanicity tests show that the compressive strength and strength activity indices of the spent ash + ordinary Portland cement (OPC) mixes are comparable to 100% OPC, indicating that the spent ashes produced in the pilot-scale runs have the potential to be sold as a Class F fly ash. Finally, the beneficiated ash chemistry influences the chemistry of the post-HNO 3 -extraction spent ash and the HNO 3 -leachate. A 500-ppm-REE fly ash will presumably be a more economically favorable feedstock than an ash with a significantly lesser concentration.
Effect of ash in paper sludge on enzymatic hydrolysis
The valorization of paper sludge is a high-potential process to develop renewable fuels and chemicals, which can be integrated with pulp and paper mills. Calcium carbonate is the main ash component in sludge, which plays a role in buffering pH and potentially lowering the conversion during enzymatic hydrolysis. Therefore, it is important to investigate the effect of ash on sugar yields and examine pH change to introduce efficient and economical enzymatic hydrolysis of sludge. Carbohydrate conversion was enhanced when the ash was removed by fractionation. On the other hand, the highest sugar recovery was obtained when the sludge contained 20% ash content. The pH change during enzymatic hydrolysis was influenced by ash and explained why sludge-derived hydrolysate showed lower carbohydrate conversion. Therefore, a high shear process with the increased acid amount is suggested to prohibit the negative effect of ash and enhance the accessibility of cellulase to fibers. Finally, this study highlights the feasibility of using wet waste streams generated by the paper industry.
Effects of chemical composition of fly ash on efficiency of metal separation in ash-melting of municipal solid waste
Highlights: ► Separation of Pb and Zn from Fe and Cu in ash-melting of municipal solid waste. ► Molar ratio of Cl to Na and K in fly ash affected the metal-separation efficiency. ► The low molar ratio and a non-oxidative atmosphere were better for the separation. - Abstract: In the process of metal separation by ash-melting, Fe and Cu in the incineration residue remain in the melting furnace as molten metal, whereas Pb and Zn in the residue are volatilized. This study investigated the effects of the chemical composition of incineration fly ash on the metal-separation efficiency of the ash-melting process. Incineration fly ash with different chemical compositions was melted with bottom ash in a lab-scale reactor, and the efficiency with which Pb and Zn were volatilized preventing the volatilization of Fe and Cu was evaluated. In addition, the behavior of these metals was simulated by thermodynamic equilibrium calculations. Depending on the exhaust gas treatment system used in the incinerator, the relationships among Na, K, and Cl concentrations in the incineration fly ash differed, which affected the efficiency of the metal separation. The amounts of Fe and Cu volatilized decreased by the decrease in the molar ratio of Cl to Na and K in the ash, promoting metal separation. The thermodynamic simulation predicted that the chlorination volatilization of Fe and Cu was prevented by the decrease in the molar ratio, as mentioned before. By melting incineration fly ash with the low molar ratio in a non-oxidative atmosphere, most of the Pb and Zn in the ash were volatilized leaving behind Fe and Cu.
Ranking Coal Ash Materials for Their Potential to Leach Arsenic and Selenium: Relative Importance of Ash Chemistry and Site Biogeochemistry
The chemical composition of coal ash is highly heterogeneous and dependent on the origin of the source coal, combustion parameters, and type and configuration of air pollution control devices. This heterogeneity results in uncertainty in the evaluation of leaching potential of contaminants from coal ash. The goal of this work was to identify whether a single leaching protocol could roughly group high-leaching potential coal ash from low-leaching potential coal ash, with respect to arsenic (As) and selenium (Se). We used four different leaching tests, including the Toxicity Characteristic Leaching Protocol (TCLP), natural pH, aerobic sediment microcosms, and anaerobic sediment microcosms on 10 different coal ash materials, including fly ash, lime-treated ash, and flue gas desulfurization materials. Leaching tests showed promise in categorizing high and low-leaching potential ash materials, indicating that a single point test could act as a first screening measure to identify high-risk ash materials. However, the amount of contaminant leached varied widely across tests, reflecting the importance of ambient conditions (pH, redox state) on leaching. These results demonstrate that on-site geochemical conditions play a critical role in As and Se mobilization from coal ash, underscoring the need to develop a situation-based risk assessment framework for contamination by coal ash pollutants.
Identification of engine oil-derived ash nanoparticles and ash formation process for a gasoline direct-injection engine
Engine oil-derived ash particles emitted from internal combustion (IC) engines are unwanted by-products, after oil is involved in in-cylinder combustion process. Since they typically come out together with particulate emissions, no detail has been reported about their early-stage particles other than agglomerated particles loaded on aftertreatment catalysts and filters. To better understand ash formation process during the combustion process, here differently formulated engine oils were dosed into a fuel system of a gasoline direct injection (GDI) engine that produces low soot mass emissions at normal operating conditions to increase the chances to find stand-alone ash particles separated from soot aggregates in the sub-20-nm size range. In addition to them, ash/soot aggregates in the larger size range were examined using scanning transmission electron microscopy (STEM)-X-ray electron dispersive spectroscopy (XEDS) to present elemental information at different sizes of particles from various oil formulations. The STEM-XEDS results showed that regardless of formulated oil type and particle size, Ca, P and C were always contained, while Zn was occasionally found on relatively large particles, suggesting that these elements get together from an early stage of particle formation. The S, Ca and P K-edge X-ray absorption near edge structure (XANES) analyses were performed for bulk soot containing raw ash. The linear combination approach & cross-checking among XANES results proposed that Ca 5 (OH)(PO 4 ) 2 , Ca 3 (PO 4 ) 2 and Zn 3 (PO 4 ) 2 are potentially major chemical compounds in raw ash particles, when combined with the STEM-XEDS results. Despite many reports that CaSO 4 is a major ash chemical when ash found in DPF/GFP systems was examined, it was observed to be rarely present in raw ashes using the S K-edge XANES analysis, suggesting ash transformation.
Grain Scale Distribution of Rare Earth Elements in Coal Ash by SHRIMP-RG Ion Microprobe
Presented at Geological Society of America Annual Meeting (Denver, CO)
Development of a sintering process for recycling oil shale fly ash and municipal solid waste incineration bottom ash into glass ceramic composite
Highlights: • Glass ceramic composite is prepared from oil shale fly ash and MSWI bottom ash. • A novel method for the production of glass ceramic composite is presented. • It provides simple route and lower energy consumption in terms of recycling waste. • The vitrified slag can promote the sintering densification process of glass ceramic. • The performances of products decrease with the increase of oil shale fly ash content. - Abstract: Oil shale fly ash and municipal solid waste incineration bottom ash are industrial and municipal by-products that require further treatment before disposal to avoid polluting the environment. In the study, they were mixed and vitrified into the slag by the melt-quench process. The obtained vitrified slag was then mixed with various percentages of oil shale fly ash and converted into glass ceramic composites by the subsequent sintering process. Differential thermal analysis was used to study the thermal characteristics and determine the sintering temperatures. X-ray diffraction analysis was used to analyze the crystalline phase compositions. Sintering shrinkage, weight loss on ignition, density and compressive strength were tested to determine the optimum preparation condition and study the co-sintering mechanism of vitrified amorphous slag and oil shale fly ash. The results showed the product performances increased with the increase of sintering temperatures and the proportion of vitrified slag to oil shale fly ash. Glass ceramic composite (vitrified slag content of 80%, oil shale fly ash content of 20%, sintering temperature of 1000 °C and sintering time of 2 h) showed the properties of density of 1.92 ± 0.05 g/cm{sup 3}, weight loss on ignition of 6.14 ± 0.18%, sintering shrinkage of 22.06 ± 0.6% and compressive strength of 67 ± 14 MPa. The results indicated that it was a comparable waste-based material compared to previous researches. In particular, the energy consumption in the production process was reduced compared to conventional vitrification and sintering method. Chemical resistance and heavy metals leaching results of glass ceramic composites further confirmed the possibility of its engineering applications.
New York Ecological Forecasting: Utilizing NASA Earth Observations to Map Ash Distribution and Inform Emerald Ash Borer Control
Since their first sightings in the U.S. in 2002, emerald ash borer beetles (Agrilus planipennis; EAB) have killed millions of native ash (Fraxinus spp.) trees across 35 states. Infected ash stands frequently exhibit complete mortality, with the predicted result being the functional extinction of native ash in U.S. forests. In August of 2020, EAB was discovered in the 6.1-million-acre Adirondack Park. The team’s partners at the Adirondack Park Invasive Plant Program (APIPP) desired ash tree distribution and EAB susceptibility information to help improve EAB bio-control efficiency and apply the methodology to future invasive programs. To assist, the team mapped ash tree distribution using NASA Earth observations from Landsat 7 Enhanced Thematic Mapper Plus (ETM+) and Shuttle Radar Topography Mission (SRTM), along with hyperspectral imagery from the Airborne Visible/Infrared Imaging Spectrometer (AVIRIS). Field data from the Monitoring and Managing Ash (MaMA) project, iMapInvasives and iNaturalist databases, and the New York State Department of Environmental Conservation (NYSDEC) provided ground truthing for mapping and modeling. Results indicate that for ash detection, the team’s Spectral Angle Mapping (SAM) hyperspectral classification is slightly more sensitive but less accurate than multispectral Random Forest (RF) classification, though neither method was above a ~20% detection rate. End products include maps of ash extent derived from both imagery types, a model forecasting future spread scenarios based on current EAB presence, and outreach materials. These products inform APIPP’s management decisions and facilitate public awareness of EAB’s threat to communities within the region.
Effects of calcium in ash on the corrosion performance of Ni-based alloys in simulated oxy-fuel environment
Increasing the efficiency of coal power plants requires raising the operating temperature above 650°C. However, coal ash can severely attack alloy materials at high temperature. For example, the corrosion rates of commercial Fe- and Ni-based alloys are generally greater than 2 mm/year at 750°C in the gas environment of oxy-fuel combustion. Thus, a critical study is needed to determine the effect of the constituents in the ash on corrosion and find an approach to reduce the corrosion rates in an ash-laden environment at high temperature. The role of CaO in the ash (typical of U.S. Western coal ash) has been investigated in laboratory exposure environments with various structural alloys. Detailed results are presented on weight change, scale thickness, internal penetration, microstructural characteristics of corrosion products, and the cracking of scales for the alloys after exposure at 750°C. The thermal stability of K3Al(SO4)3 under the environment of oxy-fuel combustion was determined by thermogravimetric analysis and differential thermal analysis. The reaction of this low melting temperature salt with the CaO-containing ash is discussed. In addition, we performed synchrotron nanobeam X-ray analysis to study the phase and chemical composition of the oxide layers on the alloy surface. Results from these studies are used to address the role of CaO in ash in the long-term corrosion performance of alloys.
Correlation between the critical viscosity and ash fusion temperatures of coal gasifier ashes
Coal gasification yields synthesis gas, an important intermediate in chemical manufacturing. It is also vital to the production of liquid fuels through the Fischer-Tropsch process and electricity in Integrated Gasification Combined Cycle power generation. Minerals naturally present in coal become molten in entrained-flow slagging gasifiers. Molten coal ash slag penetrates and dissolves refractory bricks, leading to costly plant shutdowns. The extent of coal ash slag penetration and refractory brick dissolution depends on the slag viscosity, the gasification temperature, and the composition of slag and bricks. We measured the viscosity of several synthetic coal ash slags with a high-temperature rotary viscometer and their ash fusion temperatures through optical image analysis. All measurements were made in a carbon monoxide-carbon dioxide reducing atmosphere that approximates coal gasification conditions. Empirical correlation models based on ash fusion temperatures were used to calculate critical viscosity temperatures based on the coal ash compositions. These values were then compared with those obtained from thermodynamic phase-transition models. An understanding of slag viscosity as a function of ash composition is important to reducing refractory wear in slagging coal gasifiers, which would help to reduce the cost and environmental impact of coal for chemical and electricity production.
Aggregate material formulated with MSWI bottom ash and APC fly ash for use as secondary building material
Highlights: ► A concrete formulation was optimized using Bottom Ash and APC ash. ► 10% of APC ash achieves good compromise between economic and performance aspects. ► The crushed concrete was evaluated as secondary building granular material. ► The environmental behavior allows its use as secondary material. ► The abrasion resistance is not good enough for its use as a road sub-base material. - Abstract: The main goal of this paper is to obtain a granular material formulated with Municipal Solid Waste Incineration (MSWI) bottom ash (BA) and air pollution control (APC) fly ash to be used as secondary building material. Previously, an optimum concrete mixture using both MSWI residues as aggregates was formulated. A compromise between the environmental behavior whilst maximizing the reuse of APC fly ash was considered and assessed. Unconfined compressive strength and abrasion resistance values were measured in order to evaluate the mechanical properties. From these results, the granular mixture was not suited for certain applications owing to the high BA/APC fly ash content and low cement percentages used to reduce the costs of the final product. Nevertheless, the leaching test performed showed that the concentrations of all heavy metals were below the limits established by the current Catalan legislation for their reutilization. Therefore, the material studied might be mainly used in embankments, where high mechanical properties are not needed and environmental safety is assured.
Study on the Volatility of Cesium in Dry Ashing Pretreatment and Dissolution of Ash by Microwave Digestion System - 13331
Based on the regulation of the activity concentration of Cs-137, Co-58, Co-60, Fe-55, Ni-59, Ni-63, Sr-90, Nb-94, and Tc-99, and the total alpha from the radioactive waste acceptance criteria, the measurement of the activity concentration of these nuclides in low and intermediate levels of radioactive waste such as in paper, cotton, vinyl and plastic samples was investigated. A dry ashing method was applied to obtain a concentration effect of the samples. Owing to the temperature dependence of the volatility for cesium, the temperature of 300 to 650 deg. C was examined. It was found that 450 deg. C is the optimum dry ashing temperature. After dry ashing, the produced ash was dissolved with HNO{sub 3}, HCl, and HF by a high-performance microwave digestion system. The ash sample, for the most part, was completely dissolved with 10 mL of HNO{sub 3}, 4 mL of HCl, and 0.25 mL of HF by a high-performance microwave digestion system using a nova high temperature rotor at 250 deg. C for 90 min until reaching 0.2 g. To confirm the reliability of cesium loss after the performance of the dry ashing procedure, a cesium standard solution for AAS and a Cs-137 standard solution for gamma spectrometry were added to a paper towel or a planchet of stainless steel, respectively. Cesium was measured by AAS, ICP-MS, and gamma spectrometry. The volatility of cesium did not occur until 450 deg. C ashing. (authors)
Toxicity mitigation and solidification of municipal solid waste incinerator fly ash using alkaline activated coal ash
Highlights: Black-Right-Pointing-Pointer Incinerator fly ash (IFA) is added to an alkali activated coal fly ash (CFA) matrix. Black-Right-Pointing-Pointer Means of stabilizing the incinerator ash for use in construction applications. Black-Right-Pointing-Pointer Concrete made from IFA, CFA and IFA-CFA mixes was chemically characterized. Black-Right-Pointing-Pointer Environmentally friendly solution to IFA disposal by reducing its toxicity levels. - Abstract: Municipal solid waste (MSW) incineration is a common and effective practice to reduce the volume of solid waste in urban areas. However, the byproduct of this process is a fly ash (IFA), which contains large quantities of toxic contaminants. The purpose of this research study was to analyze the chemical, physical and mechanical behaviors resulting from the gradual introduction of IFA to an alkaline activated coal fly ash (CFA) matrix, as a mean of stabilizing the incinerator ash for use in industrial construction applications, where human exposure potential is limited. IFA and CFA were analyzed via X-ray fluorescence (XRF), X-ray diffraction (XRD) and Inductive coupled plasma (ICP) to obtain a full chemical analysis of the samples, its crystallographic characteristics and a detailed count of the eight heavy metals contemplated in US Title 40 of the Code of Federal Regulations (40 CFR). The particle size distribution of IFA and CFA was also recorded. EPA's Toxicity Characteristic Leaching Procedure (TCLP) was followed to monitor the leachability of the contaminants before and after the activation. Also images obtained via Scanning Electron Microscopy (SEM), before and after the activation, are presented. Concrete made from IFA, CFA and IFA-CFA mixes was subjected to a full mechanical characterization; tests include compressive strength, flexural strength, elastic modulus, Poisson's ratio and setting time. The leachable heavy metal contents (except for Se) were below the maximum allowable limits and in many cases even below the reporting limit. The leachable Chromium was reduced from 0.153 down to 0.0045 mg/L, Arsenic from 0.256 down to 0.132 mg/L, Selenium from 1.05 down to 0.29 mg/L, Silver from 0.011 down to .001 mg/L, Barium from 2.06 down to 0.314 mg/L and Mercury from 0.007 down to 0.001 mg/L. Although the leachable Cd exhibited an increase from 0.49 up to 0.805 mg/L and Pd from 0.002 up to 0.029 mg/L, these were well below the maximum limits of 1.00 and 5.00 mg/L, respectively.
Effects of Sediment Containing Coal Ash from the Kingston Ash Release on Embryo-Larval Development in the Fathead Minnow, Pimephales promelas (Rafinesque, 1820)
The largest environmental release of coal ash in U.S. history occurred in December 2008 with the failure of a retention structure at the Tennessee Valley Authority (TVA) Kingston Fossil Plant in East Tennessee. A byproduct of coal-burning power plants, coal ash is enriched in metals and metalloids such as selenium and arsenic with known toxicity to fish including embryonic and larval stages. The effects of contact exposure to sediments containing up to 78 % coal ash from the Kingston spill on the early development of fish embryos and larvae were examined in 7-day laboratory tests with the fathead minnow (Pimephales promelas). No significant effects were observed on hatching success, incidences of gross developmental abnormalities, or embryo-larval survival. Results suggest that direct exposures to sediment containing residual coal ash from the Kingston ash release may not present significant risks to fish eggs and larvae in waterways affected by the spill.