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This study investigates the potential of utilizing pyrolysis byproducts, including char and non-condensable gases, as an energy source to promote autothermal pyrolysis. A total of six pyrolysis experiments were conducted at three distinct cracking temperatures, namely, 450 °C, 500 °C, and 550 °C. The experiments utilized two types of biomasses, i.e., 100% pine chips and 75% pine chips mixed with 25% refuse-derived fuels (RDF). The findings from the experiments were subsequently incorporated into a process simulation conducted on Aspen Plus for an energy balance and a techno-economic analysis. The results of the experiments revealed that the energy produced by the byproducts utilizing only pine chips is 1.453 kW/kg, which is enough to fulfill the energy demand of the pyrolysis reactor (1.298 kW/kg). However, when 25% of RDF is added, the energy demand of the reactor decreases to 1.220 kW/kg, and the produced energy increases to 1.750 kW/kg. Furthermore, adding RDF increases bio-oil's lower heating value (LHV). The techno-economic study proposed three scenarios: optimistic, conservative, and tragic. The optimistic has a payback period (PBP) of 7.5 years and a positive net present value (NPV). However, the other two scenarios were unfavorable, resulting in unfeasibility. [ABSTRACT FROM AUTHOR]

Ca2Fe2O5-based catalysts were synthesized from siderite and calcite precursors, which were processed in the form of pelletized samples and tested as water gas shift catalysts. Catalytic tests were performed in a tubular reactor, at temperatures in the range 400–500 °C and with different H2O:CO ratios, diluted with N2; this demonstrates the positive impact of Ca2Fe2O5 on conversion of CO and H2 yield, relative to corresponding tests without catalyst. The catalytic performance was also remarkably boosted in a microwave-heated reactor, relative to conventional electric heating. Post-mortem analysis of spent catalysts showed significant XRD reflections of spinel phases (Fe3O4 and CaFe2O4), and SiO2 from the siderite precursor. Traces of calcium carbonate were also identified, and FTIR analysis revealed relevant bands ascribed to calcium carbonate and adsorbed CO2. Thermodynamic modelling was performed to assess the redox tolerance of Ca2Fe2O5-based catalysts in conditions expected for gasification of biomass and thermochemical conditions at somewhat lower temperatures (≤500 °C), as a guideline for suitable conditions for water gas shift. This modelling, combined with the results of catalytic tests and post-mortem analysis of spent catalysts, indicated that the O2 and CO2 storage ability of Ca2Fe2O5 contributes to its catalytic activity, suggesting prospects to enhance the H2 content of producer gases by water gas shift. [ABSTRACT FROM AUTHOR]

Forestry management operations that are designed to prevent wildfires while also protecting the environmental compartments that are directly affected by them, such as soil, are of major relevance. The valorization of residual forestry biomass into biochar that is then used to be turned back into forest soils is an approach that meets Circular Economy principles. However, the effects on soil of the application of biochar that is produced from low-grade forestry biomass are unknown. In this work, a soil incubation assay was performed with a sandy soil that was amended with biochar produced from residual forestry biomass (Acacia) to assess its effectiveness in terms of boosting soil quality. The factorial study comprised the effects of biochar at two pyrolysis temperatures (450 °C and 550 °C), four application rates (0%, 3%, 6%, and 10% (w/w)), and three particle size classes (S < 0.5 mm, M = [0.5; 3.15], and L > 3.15 mm). The soil pH increased for all treatments to suitable agronomic values (5–7), and the water-holding capacity increased by 69% to 325% when compared to the control soil. The bioavailability of the plant nutrient elements also increased with the application rate, especially for treatments with small particles of biochar. Biochar that is made of low-grade biomass from forestry maintenance operations can be efficiently recycled back into forest soils to improve the physicochemical properties of agronomic relevance, thus allowing for a reduced water demand and better soil quality. However, studies on biochar applications in different soils are needed in order to assess the effectiveness of this approach. [ABSTRACT FROM AUTHOR]

The present work explores the preparation of fayalite α‐Fe2SiO4, the iron‐rich end‐member of the olivine solid‐solution series, as a tar removal catalyst for biomass gasification. The synthetic procedure was developed starting from the stoichiometric mixture of hematite and micrometer size silicon carbide and employing thermal treatments in controlled atmospheres at 1000‐1100°C supported by thermodynamic modeling to assess the required redox conditions. The treatments in dry and humidified inert gas yielded phase mixtures containing metallic Fe as one of the main phases, thus emphasizing a shortage of oxygen supply. XRD and TGA studies of precursor mixtures on heating in dry CO2 demonstrated a multistep mechanism of the overall reaction including (a) fast reactivity between silicon carbide and hematite at ~920°C with formation of metallic Fe and amorphous silica followed by (b) formation of fayalite involving oxygen supplied in the form of CO2 and competing with (c) over‐oxidation to thermodynamically favorable Fe3O4+SiO2 mixture. Comparative studies of reactivity in powdered and pelletized samples emphasized the importance of the kinetic factor in the formation of Fe2SiO4 while preventing further oxidation. The preferential formation of fayalite in the CO2 atmosphere is shown to be favored by shorter treatments of compacted samples at higher temperatures. The procedure was designed (2‐step heating to 1100°C in CO2 followed by fast cooling) for the preparation of pelletized fayalite α‐Fe2SiO4 catalyst with only minor traces of surface over‐oxidation which can be suppressed by adding 10 vol.% of forming gas to CO2 flow. [ABSTRACT FROM AUTHOR]

The mining industry is one of the largest sources of environmental concern globally. Herein we report for the first time the application of highly porous 3D-printed sorbents containing high amounts (50 wt%) of red mud, a hazardous waste derived from the alumina industry, for the remediation of acid mine drainage (AMD). The sorption capacity of the inorganic polymers was initially evaluated for the simultaneous removal of five metal(loid) elements, namely Cu(II), Ni(II), Zn(II), Cd(II) and As(V) in synthetic wastewater. The effect of the initial concentration, pH and contact time were assessed, reaching removal efficiencies between 64% and 98%, at pH 4 and initial concentration of 50 mg L -1 of each cation, after 24 h of contact time. The 3D-printed lattices were then used for the remediation of the real AMD water samples, and the role of adsorption and acidic neutralization was investigated. Lattices were also successfully regenerated and reused up to five cycles without compromising their performance. This work paves the way for the use of an industrial waste derived from the production of alumina as raw material for the management of the hazardous AMD., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.)

The work describes the combination of granulated biomass fly ash (G BFA ) with Fenton process to enhance the removal of adsorbable organic halides (AOX) from pulp bleaching wastewater. At optimal operating conditions, wastewater's chemical and biochemical oxygen demand (COD and BOD 5 , respectively) and colour were also quantified, and operating cost of treatment assessed. For the first time, raw pulp bleaching wastewater was used to granulate BFA, instead of water, reducing the water footprint of the treatment. Five wastewater treatment setups were studied: (i) conventional Fenton process; (ii) G BFA application; (iii) simultaneous application of G BFA and Fenton process; (iv) sequential treatment by G BFA followed by Fenton process; (v) sequential treatment by Fenton process followed by G BFA . The latter yielded the highest AOX removal (60-70%), whilst COD was also reduced (≈15%) and wastewater biodegradability (BOD 5 /COD) was enhanced from 0.075 to a maximum of 0.134. Another positive feature of the proposed solution was that G BFA were successfully recovered and reused without regeneration, yielding similar AOX removal compared with fresh G BFA . The operating cost of removing 1 g of AOX from the pulp bleaching wastewater by the optimal treatment setup (60-70% removal of AOX) was 14-26% lower than the operating cost of conducting Fenton process alone (50% removal of AOX)., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 The Authors. Published by Elsevier Ltd.. All rights reserved.)

There is a growing need to recover degraded soils to restore their essential ecosystem services and limit damages of anthropic activities onto these systems. Safe and sustainable solutions for long-term recovery must be designed, ideally by recycling existing resources. Using ash from combustion of residual forest biomass at the pulp and paper industry is an interesting and sustainable strategy to recover mining soils. However, formulations must be found to limit the potential toxicity associated with soluble salts and chloride that ash contains. Here, we assessed the effectiveness of three field ash-based amendments for the recovery of three highly acidic soils from Portuguese abandoned mines. Three amendments were tested: an un-stabilized mixture of ash and biological sludge, granulated ash, and granulated ash mixed with composted sludge. One year after application in open field plots (in the scope of LIFE No&#95;Waste project), soil health restoration was evaluated through (i) soil physico-chemical characterization and (ii) soil habitat functions though standardized ecotoxicological tests. This study highlights that stabilized materials provided nutrients, organic matter and alkalinity that corrected soil pH and decreased metal bioavailability, while controlling the release of soluble salts and chloride from ash. This soil improvement correlated with improved soil model organisms' reproduction and survival. For similar amendment, the native soil properties studied (as soil native electrical conductivity) affected the level of organism response. This work provides evidence that ash stabilization, formulation and supplementation with organic matter could be sustainable strategies to restore highly degraded mining soils and to recover their ecological functions. It further highlights the importance of analyzing combined effects on soil physico-chemical properties and ecological function recovery to assess restoration strategy efficiencies in complex multi-stressor environments., (Copyright © 2021 Elsevier Ltd. All rights reserved.)

The increasing use of forest biomass as a fuel for power plants due to environmental concerns will certainly increase the amount of woody biomass ash produced. Because of the environmental problems derived from woody biomass ash disposal, an important aspect for the sustainable development of the energy sector is the implementation of effective ash management strategies. The purpose of this study is to assess the environmental impacts of woody biomass ash landfarming for soil amelioration through a Life Cycle Assessment. The baseline scenario corresponds to the current most common practice of woody biomass ash management (landfilling), and two different landfarming alternatives were assessed: liming and fertilisation. Credits were given to the system due to the substitution of three traditional liming products and five traditional fertilisers. Woody biomass ash landfarming presented satisfactory performance in five impact categories under study in comparison to landfilling. When woody biomass ash was used for liming, the environmental savings were more pronounced when substituting hydrated lime. For potassium supply, the substitution of potassium nitrate by woody biomass ash presented the best environmental performance, while for phosphorus supply, the environmental savings were more pronounced substituting single superphosphate. However, in four impact categories, the environmental impacts of ash landfarming exceeded the impacts of ash landfilling, due to the emission to soil of nutrients and trace elements to soil. But this does not necessarily imply increased risks for the environment, as the potential pollutants leaching depends on their bioavailability in the soil., (Copyright © 2019 Elsevier Ltd. All rights reserved.)

Fly ash (FA) from biomass combustion and biological sludge (S), both wastes from the pulp and paper industry, were granulated in different proportions (90% FA+10% S, and 70% FA+30% S w/w, dry weight basis, dw) and used to recover the functionality of soils affected by mining activities (Aljustrel, Iberian Pyrite Belt), with and without the application of municipal solid waste compost (MSWC). Application doses of both mixtures were 2.5, 5.0 and 10% (w/w, dw). These materials corrected soil acidity to circumneutral values and increased extractable P and K concentrations. A significant increase in soil organic matter (from 0.6 to 0.8-1.5% w/w, dw) and N content (from 0.04 to 0.09-0.12% w/w, dw) was also observed, but only when MSWC was applied. The soil was already heavily contaminated with Cu, Pb and Zn and the application of amendments did not increase their pseudo-total concentrations. The CaCl 2 extractable fractions of both Cu and Zn decreased to very low values. The improvement in soil quality, compared to fertilizer only treatment, was further evidenced by the increase in some soil enzymatic activities (dehydrogenase, β-glucosidase and cellulase), with a better response for the granules with the higher proportion of biological sludge, as well as by the decrease in the soil-water extract toxicity towards different organisms (Daphnia magna, Thamnocephalus platyurus, and Pseudokirchneriella subcapitata). Agrostis tenuis germinated and grew during the first month only in the amended pots, but, after that, a considerable phytotoxic effect was evident. This was mainly attributed to salt stress or to some specific ionic toxicity. In conclusion, to establish a long-term plant cover in mining soils amended with biomass ash-based materials, the selection of plants with higher resistance to salinity and/or the stabilization of the amendments, to reduce their soluble salt content, is recommended., (Copyright © 2019. Published by Elsevier B.V.)

Four types of pellets and three agro-fuels were chemically characterised and burned in a pellet stove. To assess the influence of the material composing the firebox and the combustion efficiency of distinct biomass heating devices in the composition of the bottom ashes, three of the pellets were also burned in a conventional woodstove and in a fireplace. Ashes were analysed for their C, H and N contents by an elemental analyser, whilst major and trace elements were quantified by inductively coupled plasma atomic-emission spectrometry and inductively coupled plasma mass spectrometry, respectively. The mineralogy of ashes was determined by X-ray powder diffraction. The European standard test was applied to samples to determine the leaching potential of major, minor and trace elements. The contents of major and trace elements in the different types of biomass presented enormous variations, which are reflected in dissimilar mineralogical and chemical compositions of the respective ashes. The leachable potential of several elements of environmental concern present in oxy-anionic form at the alkaline pH of biomass ashes were generally high in all samples. Concentrations of some elements in the leachates were in the range of values with classification of "hazardous materials" by the European legislation in what respects the acceptance of these wastes at landfills. Pellets made up of wood wastes and containing preservatives (chromated copper arsenate and ammoniacal copper arsenate) are of concern. Due to lower combustion efficiencies, the leachable potential for most of the trace elements in ashes from the woodstove, and especially from the fireplace, was lower than that of the pellet stove.

Although bottom ash (BA) [or mixtures of bottom and fly ash (FA)] from clean biomass fuels is currently used as liming agent, additive for compost, and fertilizer on agricultural and forest soils in certain European countries, in several other countries most of the ashes are currently disposed in landfills. This is due to both a lack of a proper classification of the materials and of regulatory barriers.Chemical characterization including analysis of an array of potentially toxic elements (PTEs) proved that over 100,000 tons of BA currently landfilled every year in Portugal actually complied with legal limits for PTEs for soil fertilizers applied in other countries. Pot experiments were conducted, testing three dosages of BA and FA (1, 2.5, and 5%, in weight) in three mining soils with different properties. Additions of ash materials to soils led to an increase in the pore water pH relative to control pots (0% of ash added) and had a clear impact on DOC and on the solubilization of both macro- and micronutrients (notably Cu).The results from the case study using BA and FA from a Portuguese biomass thermal power plant demonstrate that it is imperative to further develop a regulatory framework to alleviate technological and environmental barriers for biomass ash utilization as raw material for fertilizers and/or soil liming agent, in accordance with the goals of the circular economy. A more harmonized view on how to assess the merits and risks of the re-use of these materials is also needed.

Combustion of residual forest biomass (RFB) derived from eucalypt (Eucalyptus globulus), pine (Pinus pinaster) and golden wattle (Acacia longifolia) was evaluated in a pilot-scale bubbling fluidised bed reactor (BFBR). During the combustion experiments, monitoring of temperature, pressure and exhaust gas composition has been made. Ash samples were collected at several locations along the furnace and flue gas treatment devices (cyclone and bag filter) after each combustion experiment and were analysed for their unburnt carbon content and chemical composition. Total suspended particles (TSP) in the combustion flue gas were evaluated at the inlet and outlet of cyclone and baghouse filter and further analysed for organic and elemental carbon, carbonates and 57 chemical elements. High particulate matter collection efficiencies in the range of 94-99% were observed for the baghouse, while removal rates of only 1.4-17% were registered for the cyclone. Due to the sand bed, Si was the major element in bottom ashes. Fly ashes, in particular those from eucalypt combustion, were especially rich in CaO, followed by relevant amounts of SiO 2 , MgO and K 2 O. Ash characteristics varied among experiments, showing that their inorganic composition strongly depends on both the biomass composition and combustion conditions. Inorganic constituents accounted for TSP mass fractions up to 40 wt%. Elemental carbon, organic matter and carbonates contributed to TSP mass fractions in the ranges 0.58-44%, 0.79-78% and 0.01-1.7%, respectively.

Bottom and fly ashes streams collected along a year in several biomass thermal plants were studied. The bulk composition of ashes and other chemical characteristics that may impact soil application showed a high variability depending on the ash stream, combustion technology and ash management practice at the power plants. The acid neutralization capacity (ANC) and metal's availability for leaching at fixed pH 7 and 4 was performed according with EA NEN 7371, as a quick evaluation method to provide information on the long-term behavior of ashes, regarding heavy metals and also plant nutrients release. Also the pH dependence leachability study was performed according to CEN/TS 14429 for predicting the leaching behavior under different scenarios. Leachability profiles were established between pH 3 and 12, allowing to distinguish different solubility control phenomena of toxic heavy metals (Cu, Cr, Mn, Ni, Zn, Pb) as well as other salts (Ca, K, Mg, Na, Cl). The ANC of fly ashes at pH 4 (3.6-9.6 molH(+)/kg) were higher than that observed for the bottom ashes (1.2-2.1 molH(+)/kg). Ashes were also characterized for persistent organic pollutants (POP), such as polycyclic aromatic hydrocarbons (PAH) and paradibenzodioxines and furanes (PCDD/F). Contents were found to be much higher in fly ash than in bottom ash streams. None of the PAH levels did reach the current national limit value of sewage sludge application in soils or the guide value for ash in north European countries. However, PCDD/F contents, which are not regulated, varied from non-detectable levels to high amounts, regardless the level of loss on ignition (LOI) or unburned carbon content in fly ashes. Given the current ash management practices and possible use of blends of bottom and fly ash streams as soil conditioners resembles clear the urgent need to regulate ash utilization in soils, incorporating limit values both for heavy metals, PAH and PCDD/F., (Copyright © 2015. Published by Elsevier Ltd.)

This paper presents results about the characterisation of the biomass fly ashes sourced from a thermal power plant and from a co-generation power plant located in Portugal, and the study of new cement formulations incorporated with the biomass fly ashes. The study includes a comparative analysis of the phase formation, setting and mechanical behaviour of the new cement-fly ash formulations based on these biomass fly ashes. Techniques such as X-ray diffraction (XRD), X-ray fluorescence spectroscopy (XRF), thermal gravimetric and differential thermal analysis (TG/DTA), X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM) and environmental scanning electron spectroscopy (ESEM) were used to determine the structure and composition of the formulations. Fly ash F1 from the thermal power plant contained levels of SiO(2), Al(2)O(3) and Fe(2)O(3) indicating the possibility of exhibiting pozzolanic properties. Fly ash F2 from the co-generation plant contained a higher quantity of CaO ( approximately 25%). The fly ashes are similar to class C fly ashes according to EN 450 on the basis of chemical composition. The hydration rate and phase formation are greatly dependant on the samples' alkali content and water to binder (w/b) ratio. In cement based mortar with 10% fly ash the basic strength was maintained, however, when 20% fly ash was added the mechanical strength was around 75% of the reference cement mortar. The fly ashes contained significant levels of chloride and sulphate and it is suggested that the performance of fly ash-cement binders could be improved by the removal or control of these chemical species.