Search Results (31)

Coal fly ash and acid mine drainage are significant environmental issues in South Africa, causing storage constraints and impacting water quality. This study explores the use of coal fly ash and acid mine drainage in preparing zeolite HBEA-supported Fe catalysts. The Na-BEA parent catalysts were synthesised hydrothermally using coal fly ash as a feedstock. The Fe was loaded upon the H-BEA form zeolite using liquid-phase ion exchange or wet impregnation, using Fe-rich acid mine drainage as the metal precursor. The ion-exchanged Fe-BEA catalysts exhibited excellent activity, with the highest selectivity achieved over the 25 AHW after 0.5 h on stream. The study also found that when impregnation was used to load Fe onto the zeolite support, other metals present in the AMD affected the overall activity, with Mn, Ca, Mg, and Na decreasing conversion and selectivity, while Ni had a promoting effect. This study demonstrates that green solid acid catalysts with high catalytic activity can be prepared using two waste materials, coal fly ash and acid mine drainage. To the best of our knowledge, we are reporting for the first time the use of acid mine drainage as a metal precursor in Fe-BEA catalyst preparation. Full article

Coal fly ash zeolites with Sodalite structure were synthesized by ultrasound-assisted double stage fusion-hydrothermal synthesis. Monometallic Ni and bimetallic Ni–Cu supported catalysts with 5 wt.% Ni and different copper contents of 1.5, 2.5 and 5.0 wt.% Cu were prepared by post-synthesis incipient wetness impregnation. The catalysts were characterized by X-ray powder diffraction, N₂ physisorption, transmission electron microscopy (TEM), Mössbauer spectroscopy and H₂ temperature programmed reduction analysis. It was found that crystalline Cu⁰ and Ni_xCu_y intermetallic nanoparticles were formed in the reduced powder and 3D printed catalysts and that they affected the reducibility of the catalytically active nickel phase. Three-dimensionally printed 5Ni2.5Cu/Sodalite catalysts were prepared via modification with metals before and after 3D printing for comparative studies. The powder and 3D printed catalysts were studied in the lignocellulosic biomass-derived levulinic acid (LA) to γ-valerolactone (GVL). The formation of NiCu alloy, which is found on the powder and 3D printed catalysts, favors their catalytic performance in the studied reaction. In contrast with powder catalysts, the preservation of the Sodalite structure was detected for all 3D printed samples and was found to have a positive influence on the metal dispersion registered in the 3D spent catalysts. The powder 5Ni2.5Cu/Sodalite catalyst showed the highest LA conversion and high GVL yield at 150 °C reaction temperature. Three-dimensionally printed catalysts show more stable catalytic activity than powder catalysts due to the preservation of the zeolite structure and metal dispersion. Full article

Zeolites with different structures (P1, sodalite, and X) were synthesized from coal fly ash by applying ultrasonically assisted hydrothermal and fusion–hydrothermal synthesis. Bimetallic catalysts, containing 5 wt.% Ni and 2.5 wt.% Cu, supported on the zeolites, were prepared by a post-synthesis incipient wetness impregnation method. The catalysts were characterized by X-ray powder diffraction (XRPD), N₂ physisorption, transmission electron microscopy (TEM), Mössbauer and X-ray photoelectron spectroscopies (XPS), and H₂–temperature-programmed reduction (H₂-TPR) analyses. The XRPD results showed that crystalline Cu⁰ and Ni_xCu_y intermetallic nanoparticles were formed in the reduced catalysts. The presence of the intermetallic phase affected the reducibility of the nickel by shifting it to a lower temperature, as confirmed by the H₂-TPR curves. Based on the Mössbauer spectroscopic results, it was established that the iron contamination of the coal fly ash zeolites (CFAZs) was distributed in ionic positions of the zeolite lattice and as a finely dispersed iron oxide phase on the external surface of the supports. The formation of the NiFe alloy, not detectable by XRPD, was also evidenced on the impregnated samples. The catalysts were studied in the upgrading of levulinic acid (LA), derived from lignocellulosic biomass, to γ-valerolactone (GVL), in a batch reactor under 30 bar H₂ pressure at 150 and 200 °C, applying water as a solvent. The NiCu/SOD and NiCu/X catalysts showed total LA conversion and a high GVL yield (>75%) at a reaction temperature of 200 °C. It was found that the textural parameters of the catalysts have less influence on the catalytic activity, but rather the stable dispersion of metals during the reaction. The characterization of the spent catalyst found the rearrangement of the support structure. The high LA conversion and GVL yield can be attributed to the weak acidic character of the support and the moderate hydrogenation activity of the Ni-Cu sites with high dispersion. Full article

Zeolites have been increasingly applied in various fields such as energy conversion, environmental remediation, chemical production, and so on, being used as membranes, catalysts, and supports due to their large specific areas and strong gas adsorption. And, developing low-cost strategies for the preparation of zeolites has attracted the extensive attention of researchers. Coal fly ash, waste glass, discard zeolites, and slags are typical industrial wastes and rich in Si and Al, indicating that these industrial wastes can be utilized as alternative raw materials of zeolite synthesis. Firstly, the chemical composition and properties of these industrial wastes are summarized. Then, the strategies involved in synthesizing different zeolites from various industrial wastes are discussed. In addition, the applications of these zeolites are comprehensively reviewed. Full article

The compound p-Nitrophenol (p-NP) is widely recognized as a highly toxic nitro-aromatic substance that urgently requires emission control. Reducing p-NP to p-aminophenol (p-AP) not only decreases its toxicity and mineralization properties in nature but also provides a key raw material for the chemical and pharmaceutical industries. The study used coal fly ash (CFA) as a catalyst carrier for synthesizing the p-NP reduction catalyst. Using CFA as an alternative option not only reduces costs but also achieves the objective of treating waste with waste compared to utilizing commercial solid materials for synthesizing catalysts. By employing hydrochloric acid and sodium hydroxide pretreatment methods, the physicochemical properties of CFA are significantly improved, enhancing the dispersion of palladium (Pd) nanoparticles. The structural features of the prepared samples were characterized using various surface analysis techniques, and both intermittent and continuous modes were experimentally tested for the model catalytic reaction involving the sodium borohydride (NaBH₄)-mediated reduction of p-NP. The results demonstrate that CFA has potential in wastewater treatment. Full article

Combining biomass co-firing with oxy-fuel combustion is a promising Bioenergy with Carbon Capture and Storage (BECCS) technology. It has the potential to achieve a large-scale reduction in carbon emissions from traditional power plants, making it a powerful tool for addressing global climate change. However, mercury in the fuel can be released into the flue gas during combustion, posing a significant threat to the environment and human health. More importantly, mercury can also cause the fracture of metal equipment via amalgamation, which is a major risk for the system. Therefore, compared to conventional coal-fired power plants, the requirements for the mercury concentration in BECCS systems are much stricter. This article reviews the latest progress in mercury control under oxy-fuel biomass co-firing conditions, clarifies the impact of biomass co-firing on mercury species transformation, reveals the influence mechanisms of various flue gas components on elemental mercury oxidation under oxy-fuel combustion conditions, evaluates the advantages and disadvantages of various mercury removal methods, and finally provides an outlook for mercury control in BECCS systems. Research shows that after biomass co-firing, the concentrations of chlorine and alkali metals in the flue gas increase, which is beneficial for homogeneous and heterogeneous mercury oxidation. The changes in the particulate matter content could affect the transformation of gaseous mercury to particulate mercury. The high concentrations of CO₂ and H₂O in oxy-fuel flue gas inhibit mercury oxidation, while the effects of NO_x and SO₂ are dual-sided. Higher concentrations of fly ash in oxy-fuel flue gas are conducive to the removal of Hg⁰. Additionally, under oxy-fuel conditions, CO₂ and metal ions such as Fe²⁺ can inhibit the re-emission of mercury in WFGD systems. The development of efficient adsorbents and catalysts is the key to achieving deep mercury removal. Fully utilizing the advantages of chlorine, alkali metals, and CO₂ in oxy-fuel biomass co-firing flue gas will be the future focus of deep mercury removal from BECCS systems. Full article

4-nitrophenol (4-NPh) is a harmful compound produced in large amounts in the chemical industry, and its reduction to aminophenol (4-APh) using noble metals as catalysts is one of the most studied processes. The development of noble metal-free catalysts represents an economic advantage in large-scale applications and contributes to the sustainability of raw materials. Coal fly ash (FA), a major waste stream from coal combustion, contains an easily recoverable magnetic fraction (FA_mag sample) composed of Fe-rich particles that could substitute noble metal catalysts in 4-NPh reduction, with the concomitant advantage of being easily recovered via magnetic separation. For this purpose, a new composite material containing copper ferrite nanoparticles (FA_mag@CS@CuFe) was prepared via a facile, environmentally friendly and cost-effective method based on three components: FA_mag as the core, a biobased polymer chitosan (CS) as the linker and copper ferrite CuFe₂O₄ nanoparticles (CuFe) as the active sites. The structure, morphology, composition and magnetic properties of the FA_mag@CS@CuFe material were studied to assess the efficiency of the preparation. It was found that the biopolymer prevented the aggregation of CuFe nanoparticles and enabled a synergistically outstanding activity towards the reduction of 4-NPh in comparison to the pristine FA_mag and bare CuFe nanoparticles. The FA_mag@CS@CuFe catalyst showed efficiency and stability in the conversion of 4-NPh of up to 95% in 3 min over four consecutive cycles. Such remarkable catalytic results demonstrate the potential of this catalyst as a substitute for expensive noble metals. Full article

In this study, coal fly ash was functionalized, using a simple one-step process (loading with Al³⁺ and sulfonation), to yield a solid acid catalyst (S/Al-CFA) with strong acid sites. The catalyst was then used to produce furfural from xylose in a biphasic system (H₂O_(NaCl)/tetrahydrofuran). The furfural yield reached 82% at 180 °C–60 min with catalyst/xylose ratio of 0.2:1.0 (w/w). With the reaction completed, all of the components could be effectively separated, and the furfural was 97.6% pure. The cycle and regeneration of the catalyst were evaluated, and the catalyst deactivation mechanism was investigated. Full article

In order to realize the high value-added reuse of coal fly ash, a reusable Fe-modified fly ash catalyst was synthesized for ozone catalysis degradation of chemical oxygen demand (COD) in wastewater. Through enhancement of the pretreatment procedure and FeO_x modification, the resulting fly ash with Fe modification demonstrated increased specific surface area and porosity. The presence of Fe loading significantly enhances the reactivity of surface oxidizing reactive species, particularly oxygen vacancy, leading to improved adsorption and activation properties towards ozone molecules. Sodium acetate is chosen as a probe for contaminants due to its status as a small organic substance that remains resistant to further direct oxidation by ozone. This makes it suitable for evaluating the catalyst’s effectiveness in degrading chemical oxygen demand (COD). The quantitative detection of free radicals revealed the generation of •O₂⁻ was nearly 10 times that of •OH and dominated the reaction. This study showcases the potential of fly ash, an industrial byproduct, to be utilized as a cost-effective and easily prepared catalyst with consistent physical and chemical characteristics. Full article

Supported ozone catalysts usually take alumina, activated carbon, mesoporous molecular sieve, graphene, etc. as the carrier for loading metal oxide via the impregnation method, sol–gel method and precipitation method. In this work, a Mn-modified fly ash catalyst was synthesized to reduce the consumption and high unit price of traditional catalyst carriers like alumina. As a solid waste discharged from coal-fired power plants fueled by coal, fly ash also has porous spherical fine particles with constant surface area and activity, abd is expected to be applied as the main component in the synthesis of ozone catalyst. After the pretreatment process and modification with MnOx, the obtained Mn-modified fly ash exhibited stronger specific surface area and porosity combined with considerable ozone catalytic performance. We used sodium acetate as the contaminant probe, which is difficult to directly decompose with ozone as the end product of ozone oxidation, to evaluate the performance of this Mn-modified fly. It was found that ozone molecules can be transformed to generate ·OH, ·O₂⁻ and ¹O₂ for the further oxidation of sodium acetate. The oxygen vacancy produced via Mn modification plays a crucial role in the adsorption and excitation of ozone. This work demonstrates that fly ash, as an industrial waste, can be synthesized as a potential industrial catalyst with stable physical and chemical properties, a simple preparation method and low costs. Full article

High amounts of coal combustion products, such as fly ash and bottom ash, are generated every year; however, only 64% are used, which means that a significant part is landfilled despite containing valuable materials such as ferrospheres, which may be used as catalysts, substituting critical raw materials (e.g., platinoids). In commercial coals, pyrite contents are reduced as a pre-combustion S-emissions control measure, so low amounts of ferrospheres are expected in the respective ashes. However, given the large amounts of ash being generated from these coals, it may provide a reliable source of catalysts, with ferrospheres being easily recovered via magnetic separation. Several studies have been conducted regarding these morphotypes; however, there is a lack of investigation considering the ash derived from highly beneficiated coals and the variations with location and time. In this study, bottom ash, economizer grits, and fly ash samples from a Portuguese power plant burning Colombian commercial coal were fractionated using ferrite (Fe-MC fraction) and Nd (Nd-MC fraction) magnets, and a multi-technique approach was used to assess their properties (magnetic parameters, particle size distribution, mineralogy, particle morphology, microtexture, and chemical composition). The Fe-MC presented higher Fe concentrations (up to 44 wt.% Fe₂O₄) than the Nd-MC (up to 7 wt.% Fe₂O₄). Once it was a sequential process, Nd magnets essentially collected Fe-bearing aluminosilicate glass, and Fe-bearing minerals were residual when compared to the Fe-MC, where magnetite, magnesioferrite, hematite, and maghemite accounted for up to 30 wt.%. Among the Fe-MC, the sample collected from electrostatic precipitator fly ash (ESP FA), despite having a lower yield, presented higher Fe concentrations than the ones from bottom ash and economizer grits, which was related to the mode of occurrence of Fe-bearing phases: in the Fe-MC from ESP FA, discrete ferrospheres predominated, while in the remaining Fe-bearing phases, they were often embedded in aluminosilicate glass. All Fe-MC samples showed an increase of Fe-substituting elements (e.g., Mn and Ni) and their concentration tended to increase with decreasing particle size along with Fe. The integrated study of cross-sections enabled the identification of oxidation rims, martitization aspects, and the co-existence of hematite and magnesioferrite. Full article

In the present study, zeolite X (FANaX) was synthesized from coal fly ash (FA) by a two-step high-temperature method. In order to follow the effect of different contaminants in the starting coal ash, zeolite X was also synthesized from pure chemicals according to a classical recipe (NaX). Iron was loaded on this reference zeolite with the amount which was contained in the coal FA. The final catalytic samples were obtained by wet impregnation of Pt nanoparticles on both types of zeolite crystals. The most active samples in the benzene oxidation were the platinum-modified ones and, among them, the Pt-impregnated FA zeolite (Pt FANaX). The comparison of the catalytic activity of Pt FANaX with the reference PtFe NaX zeolite showed a temperature difference of 10 °C in favor of Pt FANaX at 50% benzene conversion. From these results, it can be concluded that FA zeolites are a good, cheaper and environmentally friendly alternative to traditional zeolites, synthesized from pure chemicals, which can be applied in the preparation of catalysts for the purification of gaseous mixtures from harmful organic compounds. Full article

Nitric oxide (NO) can pose a severe threat to human health and the environment. Many catalytic materials that contain noble metals can oxidize NO into NO₂. Therefore, the development of a low-cost, earth-abundant, and high-performance catalytic material is essential for NO removal. In this study, mullite whiskers on a micro-scale spherical aggregate support were obtained from high-alumina coal fly ash using an acid–alkali combined extraction method. Microspherical aggregates and Mn(NO₃)₂ were used as the catalyst support and the precursor, respectively. A mullite-supported amorphous manganese oxide (MSAMO) catalyst was prepared by impregnation and calcination at low temperatures, in which amorphous MnO_x is evenly dispersed on the surface and inside of aggregated microsphere support. The MSAMO catalyst, with a hierarchical porous structure, exhibits high catalytic performance for the oxidation of NO. The MSAMO catalyst, with a 5 wt% MnO_x loading, presented satisfactory NO catalytic oxidation activity at 250 °C, with an NO conversion rate as high as 88%. Manganese exists in a mixed-valence state in amorphous MnO_x, and Mn⁴⁺ provides the main active sites. The lattice oxygen and chemisorbed oxygen in amorphous MnO_x participate in the catalytic oxidation of NO into NO₂. This study provides insights into the effectiveness of catalytic NO removal in practical industrial coal-fired boiler flue gas. The development of high-performance MSAMO catalysts represents an important step towards the production of low-cost, earth-abundant, and easily synthesized catalytic oxidation materials. Full article

The effect of different cathode strategies (mullite/MnO₂, Plexiglas/Gore-Tex/MnO₂, mullite/coal fly ash, mullite/biochar, mullite/activated carbon) on the performance of air-cathode microbial fuel cells (MFCs) was investigated. The highest maximum power output was observed using MnO₂ catalyst pasted on Gore-Tex cloth (7.7 mW/m³), yet the highest coulombic efficiencies (CEs) were achieved using MnO₂ (CE 23.5 ± 2.7%) and coal fly ash (CE 20 ± 3.3%) pasted on ceramic. The results showed that the utilization of coal fly ash and biochar as catalysts in MFC technology can be a sustainable and cost-effective solution. Full article

Increases in biodiesel prices remains a challenge, mainly due to the high cost of conventional oil feedstocks used during biodiesel production and the challenges associated with using homogeneous catalysts in the process. This study investigated the conversion of waste-derived black soldier fly (BSF) maggot oil feedstock over hydroxy sodalite (HS) zeolite synthesized from waste coal fly ash (CFA) in biodiesel production. The zeolite product prepared after fusion of CFA followed by hydrothermal synthesis (F-HS) resulted in a highly crystalline, mesoporous F-HS zeolite with a considerable surface area of 45 m²/g. The impact of post-synthesis modification of the parent HS catalyst (F-HS) by ion exchange with an alkali source (KOH) on its performance in biodiesel production was investigated. The parent F-HS zeolite catalyst resulted in a high biodiesel yield of 84.10%, with a good quality of 65% fatty acid methyl ester (FAME) content and fuel characteristics compliant with standard biodiesel specifications. After ion exchange, the modified HS zeolite catalyst (K/F-HS) decreased in crystallinity, mesoporosity and total surface area. The K/F-HS catalyst resulted in sub-standard biodiesel of 51.50% FAME content. Hence, contrary to various studies, the ion exchange modified zeolite was unfavorable as a catalyst for biodiesel production. Interestingly, the F-HS zeolite derived from waste CFA showed a favorable performance as a heterogeneous catalyst compared to the conventional sodium hydroxide (NaOH) homogeneous catalyst. The zeolite catalyst resulted in a more profitable process using BSF maggot oil and was economically comparable with NaOH for every kilogram of biodiesel produced. Furthermore, this study showed the potential to address the overall biodiesel production cost challenge via the development of waste-derived catalysts and BSF maggot oil as low-cost feedstock alternatives. Full article