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With the development of the technical trend, concrete using waste alternate material instead of sand material found economic potential for good structural behaviour. Besides, the susceptible crack, low strength-to-weight ratio, and low compressive strength are the reasons for shrinkage. Due to this reason, the investigation aims to limit the shrinkage under live load and increase the compression and flexural strength by the introduction of coconut waste chopped fiber (wCF), waste fly ash (wFA), and carbon nanotube powder (CNT) blended with conventional Portland paste. The developed concrete consists of 5 wt% wCF, 10 wt% wFA, and 0, 5, 10, and 15 wt% of CNT and is subjected to X-ray diffraction analysis, bulk density, compression and flexural strength, and water absorption studies. The X-ray diffraction pattern revealed the wCF, wFA, CNT, and matrix compositions. The concrete developed with 5 wt% wCF, 10 wt% wFA, and 15 wt% CNT cured within 28 days recorded maximum behaviour of compression strength (47 ± 1.8 MPa), flexural strength (4.9 ± 0.19 MPa), and water absorption of (2.8 ± 0.05 %).
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The use of hybrid fibre-reinforced Self-compacting concrete (HFR-SCC) has escalated recently due to its significant advantages in contrast to normal concrete such as increased ductility, crack resistance, and eliminating the need for compaction etc. The process of determining residual strength properties of HFR-SCC after a fire event requires rigorous experimental work and extensive resources. Thus, this study presents a novel approach to develop equations for reliable prediction of compressive strength (cs) and flexural strength (fs) of HFR-SCC using gene expression programming (GEP) algorithm. The models were developed using data obtained from internationally published literature having eight inputs including water-cement ratio, temperature, fibre content etc. and two output parameters i.e., cs and fs. Also, different statistical error metrices like mean absolute error (MAE), coefficient of determination ( R 2 ) and objective function (OF) etc. were employed to assess the accuracy of developed equations. The error evaluation and external validation both approved the suitability of developed models to predict residual strengths. Also, sensitivity analysis was performed on the equations which revealed that temperature, water-cement ratio, and superplasticizer are some of the main contributors to predict residual compressive and flexural strength.
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Heavy metal ions and antibiotics were simultaneously detected in authentic water systems. This research, for the first time, employed synthesized sophorolipid-modified fly ash(SFA) to eliminate tetracycline(TC) and lead(Pb2+) from wastewater. Various characterization techniques, including SEM-EDS, FTIR, XPS, BET, and Zeta, were employed to investigate the properties of the SFA. The results showed that the sophorolipid modification significantly improved the fly ash's adsorption capacities for the target pollutants. The static adsorption experiments elucidated the adsorption behaviors of SFA towards TC and Pb2+ in single and binary systems, highlighting the effects of different Environmental factors on the adsorption behavior in both types of systems. In single systems, SFA exhibited a maximum adsorption capacity of 128.96â¯mg/g for Pb2+ and 55.57â¯mg/g for TC. The adsorption of Pb2+ and TC followed pseudo-second-order kinetics and Freundlich isotherm models. The adsorption reactions are endothermic and occur spontaneously. SFA demonstrates varying adsorption mechanisms for two different types of pollutants. In the case of Pb2+, the primary mechanisms include ion exchange, electrostatic interaction, cation-π interaction, and complexation, while TC primarily engages in hydrogen bonding, π-π interaction, and complexion. The interaction between Pb2+ and TC has been shown to improve adsorption efficiency at low concentrations. Additionally, adsorption-desorption experiments confirm the reliable cycling performance of modified fly ash, highlighting its potential as a cost-effective and efficient adsorbent for antibiotics and heavy metals.
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A Circular Waste Management alternative is considered in this paper in which a complete ash valorization process is proposed for an Integrated Gasification with Combined Cycle fly ash, trying to extract maximum value from this waste before it is discarded. In the paper, germanium, a scarce resource vital in our modern society, is first extracted from fly ash using water, with an extraction yield of 85%, and subsequently, the leached fly ash is used in the manufacture of fire-resistant boards containing 60% ash, thereby avoiding its disposal in a landfill. The potential environmental impact caused by the two stages of the process was analyzed, and the final effluent was considered to achieve a zero-discharge objective. This paper contributes to the development of a more sustainable management alternative for an industrial waste produced in increased amounts and provides the basis for a symbiotic coupling relationship among various industrial sectors.
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Some areas in Johannesburg abounds with mine wastes namely, acid mine drainage (AMD) as well as fly ash (FA), which are by-products of gold mining and coal burning, respectively. Studies show that a solution formed through mixing these wastes neutralises the acidity of AMD and is an alternative source of irrigation. While studies show improved growth and yield of plants irrigated with fly ash-amended AMD, there are rarely sufficient studies conducted in South Africa showing evidence of altered pH of AMD and that food crops irrigated with fly ash-amended AMD exhibit improved concentration of essential nutrient elements. In this study, AMD was sourced from a gold mine in Johannesburg and fly ash collected from a coal-burning power station in the Mpumalanga Province, mixed at 1:0, 1:1, and 3:1 (w/v) of fly ash to AMD and used to irrigate potatoes. The objective was to assess whether the solutions of FA-amended AMD alter the pH of the AMD and to evaluate if irrigating potatoes with the aforementioned improve the concentration of essential nutrient elements and heavy metals in the tubers. Results show that the pH of AMD was increased in the 1:0 and 1:1 solutions but decreased in the 3:1 solution. The concentrations of Pb and Co were decreased in tubers irrigated with the 50 % AMD and 75 % AMD while that of Ni and Cd were markedly increased in tubers irrigated with solutions of fly ash-amended AMD. In the main, the potato tubers exhibited significantly higher concentrations of Al, Mo, Cu, Ca, Mg, and Zn when irrigated with fly-ash-amended AMD. The pH range levels from FA-AMD treated samples were within the acceptable pH range (5.5-6.5) which is acceptable for water that could be used for irrigation of crops. Also, the decreased Co and Pb and improved concentration of essential nutrient elements indicate that the constituents absorbed large quantities of the heavy metals while releasing the nutrients. In conclusion, the selected fly ash has proven as an alternative low-cost readily-available, affordable, and accessible adsorbent that neutralize the acidity of AMD, decrease the concentration of heavy metals, and increase the concentration of essential nutrient elements. Importantly, the liming potential among other traits of the fly ash improved the quality of the AMD such that the wastes were proven in this study suitable to irrigate potatoes.
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This paper discusses efforts made by past researchers to steady the expansive (problematic) soils using mechanical and chemical techniques - specifically with EPS beads, lime and fly ash. Administering swelling of problematic soils is critical for civil engineers to prevent structural distress. This paper summarizes studies on reduction of swelling potential using EPS, lime and fly ash individually. Chemical stabilization with lime and fly ash are conventional methods for expansive soil stabilization, with known merits and demerits. This paper explores the suitability of different materials under various conditions and stabilization mechanisms, including cation exchange, flocculation, and pozzolanic reactions. The degree of stabilization is influenced by various factors such as the type and amount of additives, soil mineralogy, curing temperature, moisture content during molding, and the presence of nano-silica, organic matter, and sulfates. Additionally, expanded polystyrene (EPS) improves structural integrity by compressing when surrounded clay swells, reducing overall swelling. Thus, EPS addresses limitations of chemicals by mechanical means. Combining EPS, lime and fly ash creates a customized system promoting efficient, long-lasting, cost-effective and eco-friendly soil stabilization. Chemicals address EPS limitations like poor stabilization. This paper benefits civil engineers seeking to control expansive soil swelling and prevent structural distress. It indicates potential of an EPS-lime-fly ash system and concludes by identifying research gaps for further work on such combinatorial stabilizer systems.
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Melting is an efficient method to turn municipal solid waste incineration (MSWI) fly ash (FA) into non-hazardous material. Coal fly ash (CFA) was selected as the silica-alumina source to carry out co-melting research with MSWI FA in this work. The effects of the temperature and the CFA content on mineral transformation and the migration characteristics of heavy metals were analyzed. The results showed that the mixtures of MSWI FA and CFA reacted at high temperatures to mainly generate Ca2Al2SiO7, Ca2SiO4, and CaAl2Si2O8 primarily and then melted and formed the amorphous-phase vitreous body when the CFA content was more than 40% and the temperature was higher than 1300 °C. During the melting process, Cd and Pb were almost volatilized, while Cr, Mn, and Ni were almost retained. Besides, the volatilization rates of Cu and Zn fluctuated with the temperature and the CFA content. Suitable treatment temperature and CFA content were conducive to the transformation of the heavy metals in the FA into stable forms, and the melting products were no longer hazardous wastes because the vitreous body could effectively encapsulate heavy metals. This study aims to help reuse the FA and CFA collaboratively and be more environmentally friendly.
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This article is aimed at discussing the combined effect of mineral admixture and servicing temperature, especially in cold environment, on the properties of magnesium phosphate repair mortar (MPM). The influence mechanism of fly ash content on the microstructure and performance of MPM were firstly investigated, and then the evolution rules in properties of fly ash modified MPM cured at - 20 °C, 0 °C, 20 °C and 40 °C were further revealed. The results show that the incorporation of fly ash has no significant effect on the setting time and fluidity of MPM. When MPM is modified with 10 wt% and 15 wt% fly ash, its mechanical properties, adhesive strength, water resistance, and volume stability are effectively improved. Fly ash reduces the crystallinity and continuity of struvite enriched in hardened MPM, and its particles are embedded among struvite and unreacted MgO. The compressive strength of MPM-10 cured for various ages increases with the elevating of curing temperature, while the flexural strength, interfacial bonding strength, strength retention and linear shrinkage exhibits the opposite laws. When cured at 0 °C and - 20 °C, MPM-10 still has good early strength, water resistance and interfacial bonding properties, which indicates that MPM-10 provides with an ability of emergency repair of cracked components served in cold environments.
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An experiment was conducted in the greenhouse to investigate the feasibility of Vicia faba grown on different fly ash concentrations (0-30%) and dual inoculation with Rhizobium and arbuscular mycorrhizal fungi (AMF). Sampling was done 45 days after sowing to analyse the plant growth parameters, photosynthetic attributes (total chlorophyll and carotenoids content), protein content, nitrogen (N) and phosphorus (P) content, defensive factors (antioxidant activity and proline content) and damage markers (lipid peroxidation, reactive oxygen species and cell viability). The results revealed that the application of fly ash (FA) alone did not result in any significant improvement in growth, biochemical and physiological parameters. However, dual inoculation showed a synergistic impact on legume growth, photosynthetic pigments, protein, proline, and cell viability. Rhizobium, AMF and 10% FA showed maximum enhancement in all attributes mentioned. 20% and 30% fly doses showed a reduction in growth, photosynthesis and antioxidants and caused oxidative stress via lipid peroxidation. The results showed that the synergistic or combined interactions between all three variables of the symbiotic relationship (Rhizobium-legume-AMF) boosted plant productivity.
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Cinza de Carvão , Micorrizas , Rhizobium leguminosarum , Vicia faba , Micorrizas/fisiologia , Solo/química , Fotossíntese , Simbiose , Peroxidação de LipídeosRESUMO
Escalating global surface temperatures are highlighting the urgent need for energy-saving solutions. Phase-change materials (PCMs) have emerged as a promising avenue for enhancing thermal comfort in the construction sector. This study assessed the impact of incorporating PCMs ranging from 1% to 10% by mass into composite Portland cement partially replaced by fly ash (FA) and nanosilica particles (NS). Mechanical and electrochemical techniques were utilized to evaluate composite cements. The results indicate that the presence of PCMs delayed cement hydration, acting as a filler without chemically interacting within the composite. The combination of FA and PCMs reduced compressive strength at early ages, while thermal conductivity decreased after 90 days due to the melting point and the latent heat of PCMs. Samples with FA and NS showed a significant reduction in the CO2 penetration, attributed to their pozzolanic and microfiller effects, as well as reduced water absorption due to the non-absorptive nature of PCMs. Nitrogen physisorption confirmed structural changes in the cement matrix. Additionally, electrical resistivity and thermal behavior assessments revealed that PCM-containing samples could reduce temperatures by an average of 4 °C. This suggested that PCMs could be a viable alternative for materials with thermal insulation capacity, thereby contributing to energy efficiency in the construction sector.
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Selection of a suitable alternative material from a pool of alternatives with many conflicting criteria becomes a Multi-Criteria Decision Making (MCDM) problem. In the present study, ternary blended mortars were prepared using ceramic tile dust waste (CTD), fly ash (FA), and ground granulated blast furnace slag (GGBFS) as binder components. Crusher dust (CD) was used as a fine aggregate component. Binder to aggregate ratios of 1:3 and 1:1 were prepared considering suitable flow. A total of 16 mortar mixes were cast. These mortars were tested for various conflicting criteria compressive strength, flexural strength, porosity, water absorption, bulk density, thermal conductivity, specific heat, thermal diffusivity, and thermal effusivity whose weightages obtained were 29.09%, 20.08%, 12.77%, 10.60%, 8.74%, 6.74%, 5.54%, 4.47%, and 1.97%, respectively, as per AHP analysis. Later, considering these different criteria and alternate mortars, it was observed that a 1:1 mortar with 20% CTD, 30% FA, and 50% GGBFS (RC20F30G50) is found to be the suitable mortar with the highest relative closeness coefficient of 0.861 and the highest net outranking flow of 0.316 with respect to MCDM techniques: technique for order of preference by similarity to ideal solution (TOPSIS) and preference ranking organization method for enrichment of evaluations (PROMETHEE-II), respectively. The ranking of the mortar in both methods complies with the relative weightages of the criteria and the performance of the mortars with respect to the above criteria.
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ABSTRACTThe Ministry of Environment of Korea has proposed a ban on landfill disposal of municipal solid waste (MSW) from 2026. Thus, it is inferred that the amount of incineration ash will increase drastically. Against this backdrop, this study assessed the applicability of a plasma melting process to fly ash. Fly ash was collected from 14 incineration facilities to analyze its basic properties and perform melting experiments. Furthermore, scanning electron microscope (SEM) analysis and economic feasibility assessment were conducted. The molten fly ash slag exhibited a pH value of 9.9, and the ignition loss of fly ash was found to range from 14.5 to 25.7 wt.%. None of seven toxic elements (arsenic (As), cadmium (Cd), cyanide (CN), mercury (Hg), hexavalent chromium (Cr(VI)), copper, and lead (Pb)) was detected from the molten slag. In addition, 99.3 wt.% of chloride ion (Cl-), 97.9 wt.% of fluoride ion (F-), and 98.1 wt.% of sulphate ion (SO42-) were removed. The contents in the molten slag were found to be 0.19, 7.8, 27.8, 33.1, and 38â mg/kg for Cd, Pb, zinc, nickel, and F, respectively, and none of CN, Hg, and As was detected, thereby meeting the criteria for soil pollution. All of the environmental standards were met, and SEM analysis confirmed stable quality with high density and no surface pore. In the economic feasibility assessment, a profit of approximately 152.4 $/ton was also estimated compared to landfill disposal.
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The effect of an alternative source of silica, based on class F fly ash mixed with blast furnace slag and activated by rice husk ash (RHA), to produce concrete exposed to marine environments was evaluated. Four mixtures activated by the combination of 85% NaOH 14M + 15% RHA were manufactured to achieve a liquid/solid ratio of 0.20. Fly ash was incorporated into the steel slag mixture at addition percentages of 20, 40, 60, and 80%, and evaluated at 28, 900, and 1800 days for pore and chloride ion absorption. In general, including rice husk ash in the mixture of fly ash and steel slag significantly affected mechanical performance because it was possible to obtain concrete with high mechanical resistance. Concerning the durability evaluation, the effect of the activator generated by rice husk ash was observed, and the increase in steel slag added to the cementitious samples improved the capacity of the material to resist the penetration and diffusion of chloride ions.
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Fly ash from waste incineration is growing rapidly and has become a global problem. Landfill is the main treatment method, but the release behavior of ultra-alkaline fly ash needs further study. In this study, the release pattern of heavy metals from fly ash, the long-term risk after seepage, and the main control mechanisms were explored by indoor simulation experiments and process simulation modeling. The results show that carbonation is the main control mechanism for the release rate of heavy metals from super-alkaline fly ash, and the release rate is slow at the initial stage, but the release concentration of Zn and Pb may increase tens of times with the continuous reaction between the acidic substances in the leachate and the alkaline substances in the fly ash. The heavy metals released into the leachate can cause the concentration of Zn, Cd and Pb in the groundwater to exceed the standard by 39.50, 6.70 and 5.99 times due to seepage. Furnace type is the key controlling factor for background concentrations of heavy metals in ultra-alkaline fly ash, and the exposure concentrations of Cu, Cd, Zn, and Pb in ultra-alkaline fly ash from grate furnaces as well as the GT1 facility are 4.19, 4.19, 4.14, and 37.5 times greater than those of fluidized beds, respectively, with a higher risk of long-term landfill. Regionally, the regional occupancy rate of heavy metal concentrations indicated that the risk of adequate rainfall was high in the southeastern coastal region, which was five times higher than that in the inland northwest. Therefore, the long-term dynamics and risk evolution of Zn, Cd, and Pb in the groundwater around MSWLs in the coastal area should be paid attention to after the landfilling of ultra-alkaline fly ash in order to ensure the safety of the shallow groundwater environment after landfilling.
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Fly ash, a type of solid waste generated in power plants, can be utilized as a catalyst carrier to enhance its value-added potential. Common methods often involve using a large amount of alkali for preprocessing, resulting in stable quartz and mullite forming silicate dissolution. This leads to an increased specific surface area and pore structure. In this study, we produced a catalyst composed of MnOx/NiOOH supported on fly ash by directly employing nickel hydroxide and potassium permanganate to generate metal active sites over the fly ash surface while simultaneously creating a larger specific surface area and pore structure. The ozone catalytic oxidation performance of this catalyst was evaluated using sodium acetate as the target organic matter. The experimental results demonstrated that an optimal removal efficiency of 57.5% for sodium acetate was achieved, surpassing even that of MnOx/NiOOH supported catalyst by using γ-Al2O3. After loading of MnOx/NiOOH, an oxygen vacancy is formed on the surface of fly ash, which plays an indirect oxidation effect on sodium acetate due to the transformation of ozone to â¢O2- and â¢OH over this oxygen vacancy. The reaction process parameters, including varying concentrations of ozone, sodium acetate, and catalyst dosage, as well as pH value and the quantitative analysis of formed free radicals, were examined in detail. This work demonstrated that fly ash could be used as a viable catalytic material for wastewater treatment and provided a new solution to the added value of fly ash.
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Fly ash was used as raw material to prepare zeolites through silicate gels, assisted by the hydrothermal method. The silicate gels could be effectively formed in a few minutes in a molten alkali environment. The zeolites could be prepared by using these silicate gels through the hydrothermal method, which realizes the transformation from useless materials to highly valuable materials. The obtained zeolites were applied to the removal of ammonium in water, achieving the highvalue utilization of fly ash. The synthesized zeolites were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectrum (EDS), thermogravimetric (TG), and Fourier transform infrared (FTIR) spectroscopy. The study on the adsorption and removal of ammonium in water shows that the adsorption of ammonium is more in line with pseudo first-order kinetics, and the adsorption mainly occurs in the first 20 min. The adsorption can reach equilibrium in 30 min, and the maximum adsorption capacity can reach 49.1 mg/g. The adsorption capacity of ammonium has the best performance at pH = 5. Furthermore, within a certain range, an increase in temperature is beneficial for the removal of ammonium.
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A study was carried out to evaluate phytodiversity along with the metal accumulation potential of native plants growing in the vicinity of a thermal power plant (TPP). We documented 26 tree species, six shrubs, and 35 herbs. Importance value index (IVI), which measures the extent to which a species dominates in an area, was found highest for Senna siamea (95.7) followed by Tectona grandis (56.5), and Pithecellobium dulce (19.6). Soil was acidic (pH 5.4) in nature with higher concentrations of Al and Fe. The pH of ground water was found acidic while pH of nearby river was found slightly alkaline. Values of PM2.5 and PM10 were slightly higher than NAAQS standards for industrial areas. The concentration of metals was found higher in aquatic plants than in terrestrial plants. In general, herbs and shrubs showed more metal accumulation potential than trees. Our results suggest that Senna siamea could be used for revegetation purposes in FA landfills. Further, terrestrial and aquatic plants such as Ageratina adenophora and Stuckenia pectinata could be used for reclamation of Mn, Zn, Al, and Fe from contaminated soils. Hydrilla verticillata (Ni and Mn), Nelumbo nucifera, and Ipomoea aquatica (Cr) can be used for metal removal from contaminated water.
The study focuses on the assessment of phytodiversity, soil and water analysis, ambient air quality, and bioaccumulation of heavy metals in plants growing in and around a thermal power plant. The study assumes significance as more than 65% of India's electricity generation is still by coal-fired power plants, having major implications for air, soil, and water pollution. By selecting native plant species adapted to the region, we can enhance biodiversity, restore habitats, and contribute to the overall ecological health of the area surrounding the power plant.
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This paper investigates the performance of concrete incorporating high-volume fly ash (HVFA) and steel slag aggregates against the detrimental effects of combined cycles of environmental thermal fatigue and exposure to leaked aircraft fluids. A total of 128 cubes and 90 prisms were cast for five mixes and exposed to 60, 120, 180, 240 and 300 combined cycles. The results demonstrate the positive effect of utilization of HVFA which reduces the total amount of portlandite available in the system. The SS aggregates demonstrate a strong interlocking with the surrounding matrix and supply the necessary portlandite for continued pozzolanic reaction. However, their reaction with aircraft fluids causes significant degradation to flexural strength initially, which is redeemed by pozzolanic reaction at a later stage. Hybrid basalt and polypropylene fibres were successful in enhancing the flexural strength and reducing the cracking. The mercury intrusion porosimetry revealed a reduction in pore volume because of HVFA. Scanning electron microscopy and differential scanning calorimetry were also employed to uncover the underlying mechanisms of damage and assess the performance of the cementitious composite.
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Petcoke generated during bitumen upgrading is a potential source of vanadium for the global market. Recovering vanadium from the fly ash originating from the combustion of petcoke appears to be a suitable route for commercial implementation, given its high extraction rate. Although the technical feasibility of the recovery process has been proven, the environmental impact should be addressed. Information on the greenhouse (GHG) emissions from the process is scarce in the public domain. Therefore, a framework was developed for assessment of life cycle GHG emissions for extraction of vanadium from petcoke-based fly ash. This framework was used to perform a life cycle GHG emissions assessment of a water leaching and salt roasting process to extract vanadium from fly ash. For the upstream GHG emissions, we collected direct emissions data and energy consumption from the literature, and, for the process emissions, we developed a model to estimate energy and material balances based on process conditions. The emission factors for electricity production, fuel combustion, production of consumables, and gas treatment were used to obtain the life cycle GHG emissions. The results show that the life cycle GHG emission of vanadium recovery are 26.6-3.9+0.9 kg CO2eq/kg V2O5; 66% of these are direct GHG emissions. The process GHG emissions from fly ash decarbonization contribute the most to the life cycle GHG emissions. The air-to-fuel ratio for roasting and the GHG emission factors for petcoke combustion and the gas treatment operation are the inputs that most effect the model output. Compared with the production of V2O5 from vanadium titano-magnetite ore and bitumen upgrading spent catalyst, the petcoke fly ash pathway generates about twice the life cycle GHG emissions. This study's results can help determine areas of improvement in the upstream operations and the recovery process to reduce the life cycle GHG emissions to levels that can compete with primary and alternative routes to produce vanadium pentoxide. The results of this study can help in decision-making associated with vanadium extract from fly ash produced from combustion of petcoke.
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Cinza de Carvão , Vanádio , Vanádio/análise , Gases de Efeito Estufa/análise , Hidrocarbonetos/análise , Efeito EstufaRESUMO
Developing technologies aimed at ecologically restoring is of great significance in addressing the problem of heavy metal pollution. In this study, NaA zeolites (FAZ) originated from fly ash with outstanding performance were prepared by alkali fusion hydrothermal method and used for the solidification and stabilization of heavy metals in soil. After systematic evaluation, it was found that FAZ may lower the leaching concentration of lead (Pb) in soil to <1 mg/kg and increase the stabilization rate of Pb to 80 % in the single Pb-contaminated soil, lower the leaching concentration of cadmium (Cd) in soil to <3 mg/kg and increase the stabilization rate of Cd to 60 % in the single Cd-contaminated soil, and lower the leaching concentration of Pb to 0.15 mg/kg and the leaching concentration of Cd to 0.74 mg/kg in PbCd complex polluted soil. Additionally, Pb stabilization rates reach 60 % and Cd stabilization rates reach 30 %, respectively. Ion exchange is primarily responsible for the adsorption and solidification of Pb and Cd in soil by FAZ. Generally, FAZ has a wide range of applications in the rehabilitation of contaminated soil and significantly lowers the level of heavy metal pollution in soil.