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Elemental mercury (Hg 0 ) is a highly hazardous pollutant of coal combustion. The low-temperature SCR catalyst of MnO x /TiO 2 can efficiently remove Hg 0 in coal-burning flue gas. Considering its sulfur sensitivity, the effect of SO 3 on the catalytic efficiency of MnO x /TiO 2 and Fe modified MnO x /TiO 2 for Hg 0 removal was investigated comprehensively for the first time. Characterizations of Hg-TPD and XPS were conducted to explore the catalytic mechanisms of Hg 0 removal processes under different conditions. Hg 0 removal efficiency of MnO x /TiO 2 was inhibited irreversibly from 92% to approximately 60% with the addition of 50 ppm SO 3 at 150 ℃, which resulted from the transformation of Mn 4+ and chemisorbed oxygen to MnSO 4 . The existence of H 2 O would intensify the inhibitory effect. The inhibition almost disappeared and even converted to promotion as the temperature increased to 250 ℃ and above. Fe modification on MnO x /TiO 2 improved the Hg 0 removal performance in the presence of SO 3 . The addition of SO 3 caused only a slight inhibition of 1.9% on Hg 0 removal efficiency of Fe modified MnO x /TiO 2 in simulated coal-fired flue gas, and the efficiency maintained good stability during a 12 h experimental period. This work would be conducive to the future application of MnO x /TiO 2 for synergistic Hg 0 removal., (Copyright © 2022 Elsevier B.V. All rights reserved.)

Polysulfide shuttle effects, active material losses, formation of resistive surface layers, and continuous electrolyte consumption create a major barrier for the lightweight and low-cost lithium-sulfur (Li-S) battery adoption. Tuning electrolyte composition by using additives and most importantly by substantially increasing electrolyte molarity was previously shown to be one of the most effective strategies. Contrarily, little attention has been paid to dilute and super-diluted LiTFSI/DME/DOL/LiNO 3 based-electrolytes, which have been thought to aggravate the polysulfide dissolution and shuttle effects. Here we challenge this conventional wisdom and demonstrate outstanding capabilities of a dilute (0.1 mol L -1 of LiTFSI in DME/DOL with 1 wt. % LiNO 3 ) electrolyte to enable better electrode wetting, greatly improved high-rate capability, and stable cycle performance for high sulfur loading cathodes and low electrolyte/sulfur ratio in Li-S cells. Overall, the presented study shines light on the extraordinary ability of such electrolyte systems to suppress short-chain polysulfide dissolution and polysulfide shuttle effects.

This study focuses on the use of a microwave reactor that combines biomass pyrolysis, at mild temperature, with catalytic reforming of the pyrolytic gas, using activated carbon, for generating hydrogen-rich synthesis gas. The traditional pyrolysis of biomass coupled with the reforming of its pyrolytic yields were also conducted using an electrically heated reactor. The bio-oil attained from conventional pyrolysis was higher in comparison to the yield from microwave pyrolysis. The reforming of the pyrolytic gas fraction led to reductions in bio-oil yield to <3.0 wt%, with a simultaneous increase in gaseous yields. An increase in the syngas and H 2 selectivity was discovered with the reforming process such that the use of microwave pyrolysis with activated carbon reforming produced 85 vol% synthesis gas fraction containing 55 vol% H 2 in comparison to the 74 vol% syngas fraction with 30 vol% H 2 obtained without the reforming. Cracking reactions were improved with microwave heating, while deoxidation and dehydrogenation reactions were enhanced by activated carbon, which creates a reduction environment. Consequently, these reactions generated H 2 -rich syngas formation. The approach implemented in this study revealed higher H 2 , syngas yield and that the overall LHV of products has huge potential in the transformation of biomass into high-value synthesis gas., (Copyright © 2020 Shi, Yan, Menéndez, Luo, Yang, Chen, Lester and Wu.)

Because of its low concentration, its unique physico-chemical properties and the analytical difficulties associated with its measurement, the determination of mercury species in solids is not an easy task. Thermal desorption (HgTPD) is an attractive option for the identification of mercury species in solids due to its simplicity and accessibility. However, there are still issues that need to be solved for it to reach its full potential. One such issue is the availability of reference materials that will reproduce real mercury associations. The novelty of this study is the use of six uncommon mercury minerals, taken from around the world, and a sphalerite sample to expand the data base of reference materials for mercury speciation by thermal desorption at programmed temperature. In addition, by using such materials, a number of matrix effects can be ascertained. Different mercury associations were identified depending on the temperature of desorption, thereby validating the thermal desorption as a reliable technique for mercury speciation in solid samples and as a consequence improving the knowledge of the geochemistry of mercury in the environment.

A systematic study of acoustic emission avalanches in coal and charcoal samples under slow uniaxial compression is presented. The samples exhibit a range of organic composition in terms of chemical elements as well as different degrees of heterogeneity in the microstructure. The experimental analysis focuses on the energies E of the individual acoustic emission events as well as on the time correlations between successive events. The studied samples can be classified into three groups. The more homogeneous samples (group I) with pores in the micro and nanoscales, with signatures of hardening effects in the stress-strain curves, exhibit the cleanest critical power-law behavior for the energy distributions g(E)dE∼E^{-ε}dE with a critical exponent ε=1.4. The more heterogeneous samples with voids, macropores, and granular microstructures (group III), show signatures of weakening effects and a larger effective exponent close to the value ε=1.66, but in some cases truncated by exponential damping factors. The rest of the samples (group II) exhibit a mixed crossover behavior still compatible with an effective exponent ε=1.4 but clearly truncated by exponential factors. These results suggest the existence of two possible universality classes in the failure of porous materials under compression: one for homogeneous samples and another for highly heterogeneous samples. Concerning time correlations between avalanches, all samples exhibit very similar waiting time distributions although some differences for the Omori aftershock distributions cannot be discarded.

The supercritical carbon dioxide (scCO 2 ) synthesis of non-reduced graphene oxide (GO) aerogels from dispersions of GO in ethanol is here reported as a low-cost, efficient, and environmentally friendly process. The preparation is carried out under the mild conditions of 333 K and 20 MPa. The high aspect ratio of the used GO sheets (ca. 30 μm lateral dimensions) allowed the preparation of aerogel monoliths by simultaneous scCO 2 gelation and drying. Solid-state characterization results indicate that a thermally-stable mesoporous non-reduced GO aerogel was obtained by using the supercritical procedure, keeping most of the surface oxygenated groups on the GO sheets, thus, facilitating further functionalization. Moreover, the monoliths have a very low density, high specific surface area, and excellent mechanical integrity; characteristics which rival those of most light-weight reduced graphene aerogels reported in the literature., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A versatile chemical activation approach for the fabrication of sustainable porous carbons with a pore network tunable from micro- to hierarchical micro-/mesoporous is hereby presented. It is based on the use of a less corrosive and less toxic chemical, i.e., potassium oxalate, rather than the widely used KOH. The fabrication procedure is exemplified for glucose as precursor, although it can be extended to other biomass derivatives (saccharides) with similar results. When potassium oxalate alone is used as activating agent, highly microporous carbons are obtained (S BET ≈ 1300-1700 m 2 g -1 ). When a melamine-mediated activation process is used, hierarchical micro-/mesoporous carbons with surface areas as large as 3500 m 2 g -1 are obtained. The microporous carbons are excellent adsorbents for CO 2 capture at low pressure and room temperature, able to adsorb 4.2-4.5 mmol CO 2 g -1 at 1 bar and 1.1-1.4 mmol CO 2 g -1 at 0.15 bar. However, the micro-/mesoporous carbons provide record-high room temperature CO 2 uptakes at 30 bar of 32-33 mmol g -1 CO 2 and 44-49 mmol g -1 CO 2 at 50 bar. The findings demonstrate the key relevance of pore size in CO 2 capture, with narrow micropores having the leading role at pressures <1 bar and supermicropores/small mesopores at high pressures. In this regard, the fabrication strategy presented here allows fine-tuning of the pore network to maximize both the overall CO 2 uptake and the working capacity at any target pressure.

The massive production of urban and agricultural wastes has promoted a clear need for alternative processes of disposal and waste management. The potential use of municipal solid wastes (MSW) as feedstock for the production of polyhydroxyalkanoates (PHA) by a process known as syngas fermentation is considered herein as an attractive bio-economic strategy to reduce these wastes. In this work, we have evaluated the potential of Rhodospirillum rubrum as microbial cell factory for the synthesis of PHA from syngas produced by microwave pyrolysis of the MSW organic fraction from a European city (Seville). Growth rate, uptake rate, biomass yield and PHA production from syngas in R. rubrum have been analysed. The results revealed the strong robustness of this syngas fermentation where the purity of the syngas is not a critical constraint for PHA production. Microwave-induced pyrolysis is a tangible alternative to standard pyrolysis, because it can reduce cost in terms of energy and time as well as increase syngas production, providing a satisfactory PHA yield., (© 2016 The Authors. Microbial Biotechnology published by John Wiley & Sons Ltd and Society for Applied Microbiology.)

Mercury is a well-known toxic element, and flue gas streams emitted from coal-fired utilities are one of the largest anthropogenic sources of this element. This study briefly reviews the proposed technologies for reducing mercury emissions from coal combustion, focusing on an emerging process which involves the use of regenerable sorbents and especially those loaded with noble metals. Among the mercury species formed during coal combustion, elemental mercury is the most difficult to remove from the flue gases due to its low reactivity and insolubility in water. The widespread interest in using regenerable sorbents with metals is due to their ability to retain elemental mercury. With this technology, not only can efficiencies of 100 % be reached in the retention of elemental mercury but also a way to avoid the generation of new wastes loaded with mercury. This study considers the main aspects that must be taken into account when developing effective regenerable sorbents for mercury capture, with special attention to sorbents containing noble metals. The characteristics of this process are compared with those of other processes in a more advanced state of development.

A facile and environmentally friendly synthetic strategy for the production of stable and easily processable dispersions of graphene in water is presented. This strategy represents an alternative to classical chemical exfoliation methods (for example the Hummers method) that are more complex, harmful, and dangerous. The process is based on the electrochemical exfoliation of graphite and includes three simple steps: 1) the anodic exfoliation of graphite in (NH 4 ) 2 SO 4 , 2) sonication to separate the oxidized graphene sheets, and 3) reduction of oxidized graphene to graphene. The procedure makes it possible to convert around 30 wt % of the initial graphite into graphene with short processing times and high yields. The graphene sheets are well dispersed in water, have a carbon/oxygen atomic ratio of 11.7, a lateral size of about 0.5-1 μm, and contain only a few graphene layers, most of which are bilayer sheets. The processability of this type of aqueous dispersion has been demonstrated in the fabrication of macroscopic graphene structures, such as graphene aerogels and graphene films, which have been successfully employed as absorbents or as electrodes in supercapacitors, respectively., (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

Herein a new process is proposed to produce a syngas-rich gas fraction (>80vol% H2+CO) from biowaste based on microwave heating within two differentiated steps in order to avoid tars production. The first step consists of the microwave pyrolysis of biowaste induced by a char-based susceptor at 400-800°C; tars, char and syngas-rich gas fractions being produced. The tars are then fed into the second step where a portion of the char from the first step is used as a bed material in a 0.3:1wt% ratio. This bed is heated up by microwaves up to 800°C, allowing thermal cracking of tars and additional syngas (>90vol% H2+CO) being then produced. This new concept arises as an alternative technology to the gasification of biowastes for producing syngas with no need for catalysts or gasifying reagents to minimise tars production., (Copyright © 2016 Elsevier Ltd. All rights reserved.)

Sustainable synthesis schemes for the production of porous carbons with appropriate textural properties for use as supercapacitor electrodes are in high demand. In this work a greener option to the widely used but corrosive KOH is proposed for the production of highly porous carbons. Hydrochar products are used as carbon precursors. It is demonstrated that a mild alkaline potassium salt such as potassium bicarbonate is very effective to generate porosity in hydrochar to lead to materials with large surface areas (> 2000 m(2)  g(-1) ) and a tunable pore size distribution. Furthermore, the use of KHCO3 instead of KOH gives rise to a significant 10 % increase in the yield of activated carbon, and the spherical morphology of hydrochar is retained, which translates into better packing properties and reduced ion diffusion distances. These features lead to a supercapacitor performance that can compete with, and even surpass, that of KOH-activated hydrochar in a variety of electrolytes., (© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

This study evaluates some of the variables that may influence mercury retention in wet flue gas desulfurization (WFGD) plants, focusing on oxy-coal combustion processes and differences when compared with atmospheres enriched in N2. The main drawback of using WFGD for mercury capture is the possibility of unwanted reduction of dissolved Hg(2+), leading to the re-emission of insoluble elemental mercury (Hg(0)), which decreases efficiency. To acquire a better understanding of the mercury re-emission reactions in WFGD systems, this work analyses different variables that influence the behavior of mercury in slurries obtained from two limestones, under an oxy-combustion atmosphere. The O2 supplied to the reactor, the influence of the pH, the concentration of mercury in the gas phase, and the enhancement of mercury in the slurry were the variables considered. The study was performed at laboratory scale, where possible reactions between the components in the scrubber can be individually evaluated. It was found that in an oxy-combustion atmosphere (mostly CO2), the re-emission of Hg(0) is lower than under a N2-enriched atmosphere, and the mercury is mainly retained as Hg(2+) in the liquid phase.

High surface area N-doped mesoporous carbon capsules with iron traces exhibit outstanding electrocatalytic activity for the oxygen reduction reaction in both alkaline and acidic media. In alkaline conditions, they exhibit more positive onset (0.94 V vs RHE) and half-wave potentials (0.83 V vs RHE) than commercial Pt/C, while in acidic media the onset potential is comparable to that of commercial Pt/C with a peroxide yield lower than 10%. The Fe-N-doped carbon catalyst combines high catalytic activity with remarkable performance stability (3500 cycles between 0.6 and 1.0 V vs RHE), which stems from the fact that iron is coordinated to nitrogen. Additionally, the newly developed electrocatalyst is unaffected by the methanol crossover effect in both acid and basic media, contrary to commercial Pt/C. The excellent catalytic behavior of the Fe-N-doped carbon, even in the more relevant acid medium, is attributable to the combination of chemical functions (N-pyridinic, N-quaternary, and Fe-N coordination sites) and structural properties (large surface area, open mesoporous structure, and short diffusion paths), which guarantees a large number of highly active and fully accessible catalytic sites and rapid mass-transfer kinetics. Thus, this catalyst represents an important step forward toward replacing Pt catalysts with cheaper alternatives. In this regard, an alkaline anion exchange membrane fuel cell was assembled with Fe-N-doped mesoporous carbon capsules as the cathode catalyst to provide current and power densities matching those of a commercial Pt/C, which indicates the practical applicability of the Fe-N-carbon catalyst.

The effect of post-treatment upon the H₂O adsorption performance of biomass-based carbons was studied under post-combustion CO₂ capture conditions. Oxygen surface functionalities were partially replaced through heat treatment, acid washing, and wet impregnation with amines. The surface chemistry of the final carbon is strongly affected by the type of post-treatment: acid treatment introduces a greater amount of oxygen whereas it is substantially reduced after thermal treatment. The porous texture of the carbons is also influenced by post-treatment: the wider pore volume is somewhat reduced, while narrow microporosity remains unaltered only after acid treatment. Despite heat treatment leading to a reduction in the number of oxygen surface groups, water vapor adsorption was enhanced in the higher pressure range. On the other hand acid treatment and wet impregnation with amines reduce the total water vapor uptake thus being more suitable for post-combustion CO₂ capture applications.

The goal of this work is to emphasize the reliability of the thermal desorption technique in identifying mercury species. The analysis of mercury species in solids is essential for assessing the risk of disposal or re-use of mercury-contaminated materials. This study evaluates the accuracy and reliability of thermal desorption as a technique for identifying mercury species by means of different thermo-desorption devices. For this purpose, mercury species present in samples related with coal utilization processes were identified. Three devices were compared for analyzing samples free of carbon or with a low carbon content (fly ashes, gypsums and soils), and a new equipment was developed to analyze samples with a high carbon content (coal). In spite of the fact that the first three devices employ different experimental conditions (i.e., heating rate, gas flow and carrier gas), the mercury species identified in the samples were comparable in all cases. The need for new equipment for mercury speciation in materials containing carbon was a consequence of interferences produced from the pyrolysis products of the organic matter. The new device consists of two furnaces and two gas inlets to allow thermal oxidation of organic pyrolysis products and the identification of mercury species in carbonaceous samples. This new approach offers the application of thermal desorption to mercury speciation in all types of materials contaminated with mercury., (Copyright © 2015 Elsevier B.V. All rights reserved.)

Hydrothermal carbonization of cellulose in the presence of the globular protein ovalbumin leads to the formation of nitrogen-doped carbon aerogel with a fibrillar continuous carbon network. The protein plays here a double role: (i) a natural source of nitrogen functionalities (2.1 wt %) and (ii) structural directing agent (S(BET) = 38 m(2)/g). The applicability in wastewater treatment, namely, for heavy metal removal, was examined through adsorption of Cr(VI) and Pb(II) ion solely and in a mixed bicomponent aqueous solutions. This cellulose-based carbogel shows an enhanced ability to remove both Cr(VI) (∼68 mg/g) and Pb(II) (∼240 mg/g) from the targeted solutions in comparison to other carbon materials reported in the literature. The presence of competing ions showed little effect on the adsorption efficiency toward Cr(VI) and Pb(II).

Supercapacitor technology is an extremely timely area of research with fierce international competition to develop cost-effective, environmentally friendlier EC electrode materials that have real world application. Herein, nitrogen-doped carbons with large specific surface area, optimized micropore structure and surface chemistry have been prepared by means of an environmentally sound hydrothermal carbonization process using defatted soybean (i.e., Soybean meal), a widely available and cost-effective protein-rich biomass, as precursor followed by a chemical activation step. When tested as supercapacitor electrodes in aqueous electrolytes (i.e. H2SO4 and Li2SO4), they demonstrate excellent capacitive performance and robustness, with high values of specific capacitance in both gravimetric (250-260 and 176 F g(-1) in H2SO4 and Li2SO4 respectively) and volumetric (150-210 and 102 F cm(-3) in H2SO4 and Li2SO4 respectively) units, and remarkable rate capability (>60% capacitance retention at 20 A g(-1) in both media). Interestingly, when Li2SO4 is used, the voltage window is extended up to 1.7 V (in contrast to 1.1 V in H2SO4). Thus, the amount of energy stored is increased by 50% compared to H2SO4 electrolyte, enabling this environmentally sound Li2SO4-based supercapacitor to deliver ~12 Wh kg(-1) at a high power density of ~2 kW kg(-1).

Hypothesis: The synthesis process of carbon xerogels is limited, mainly due to two drawbacks that prevent their introduction onto the market: (i) the long time required for producing the material and (ii) the reagents used for the synthesis, which are costly and harmful to the environment. Microwave radiation is expected to produce a reduction in time of more than 90%, while the use of tannin instead of resorcinol will probably result in a cost-effective carbonaceous material., Experiments: Resorcinol-tannin-formaldehyde xerogels containing different amounts of tannin, either with or without a surfactant (sodium dodecyl sulphate), were synthesized by means of two different heating methods: conventional and microwave heating. The effects of the surfactant, the heating method and the addition of tannin upon the porous structure and the chemical composition of the final materials were evaluated., Findings: It was found that the addition of surfactant is essential for obtaining highly porous xerogels when using tannins. The heating method also plays an important role, as conventionally synthesized samples display a greater volume of large pores. However, tannins are less sensitive to microwave radiation and their use results in tannin-formaldehyde xerogels that have a porous structure and chemical composition similar to those of resorcinol-formaldehyde xerogels., (Copyright © 2015 Elsevier Inc. All rights reserved.)

The current energy needs have put the focus on highly efficient energy storage systems such as supercapacitors. At present, much attention focuses on graphene-like materials as promising supercapacitor electrodes. Here we show that reduced graphite oxide offers a very interesting potential. Materials obtained by oxidation of natural graphite and subsequent sonication and reduction by hydrazine achieve specific capacitances as high as 170 F/g in H2SO4 and 84F/g in (C2H5)4NBF4/acetonitrile. Although the particle size of the raw graphite has no significant effect on the physico-chemical characteristics of the reduced materials, that exfoliated from smaller particles (<75 μm) result more advantageous for the release of the stored electrical energy. This effect is particularly evident in the aqueous electrolyte. Graphene-like materials may suffer from a drop in their specific surface area upon fabrication of electrodes with features of the existing commercial devices. This should be taken into account for a reliable interpretation of their performance in supercapacitors., (Copyright © 2015 Elsevier Inc. All rights reserved.)

The aim of this study is to understand the different sorption behaviors of mercury species on activated carbons in the oxy-fuel combustion of coal and the effect of high quantities of water vapor on the retention process. The work evaluates the interactions between the mercury species and a series of activated carbons prepared from a macroalgae waste (algae meal) from the agar-agar industry in oxy-combustion atmospheres, focussing on the role that the high concentration of water in the flue gases plays in mercury retention. Two novel aspects are considered in this work (i) the impact of oxy-combustion gases on the retention of mercury by activated carbons and (ii) the performance of activated carbons prepared from biomass algae wastes for this application. The results obtained at laboratory scale indicate that the effect of the chemical and textural characteristics of the activated carbons on mercury capture is not as important as that of reactive gases, such as the SOx and water vapor present in the flue gas. Mercury retention was found to be much lower in the oxy-combustion atmosphere than in the O2+N2 (12.6% O2) atmosphere. However, the oxidation of elemental mercury (Hg0) to form oxidized mercury (Hg2+) amounted to 60%, resulting in an enhancement of mercury retention in the flue gas desulfurization units and a reduction in the amalgamation of Hg0 in the CO2 compression unit. This result is of considerable importance for the development of technologies based on activated carbon sorbents for mercury control in oxy-combustion processes., (Copyright © 2015 Elsevier Ltd. All rights reserved.)

Biomass-based highly porous carbons with excellent performances in aqueous electrolyte-based supercapacitors have been developed. The synthesis of these materials is based on the chemical activation of biomass-based hydrochar. The addition of melamine to the activation mixture leads to porous carbons with a porosity consisting of micropores/small mesopores. Furthermore, melamine promotes the introduction of nitrogen heteroatoms in the carbon framework, along with abundant oxygen functionalities, to improve the wettability. The materials produced in the presence or absence of melamine exhibit high specific capacitances in aqueous electrolytes (>270 F g(-1) in H2 SO4 and >190 F g(-1) in Li2SO4). Additionally, the mesopores present in the melamine-based micro-/mesoporous carbons notably improve the ion-transport kinetics, especially in Li2SO4. Furthermore, in Li2SO4, they remain stable up to a cell voltage of 1.6 V; thus exhibiting superior energy and power characteristics than those in H2 SO4., (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)

A straightforward one-pot approach for the synthesis of highly porous carbon nanosheets with an excellent performance as supercapacitor electrodes is presented. The procedure is based on the carbonization of an organic salt (i.e., sodium gluconate) at a temperature in the range of 700-900 °C. The carbon nanosheets have a large aspect ratio (length/thickness ≈ 10(2)-10(3)), a thickness within the range of 40-200 nm, high BET surface areas (SBET) of up to 1390 m(2) g(-1), and a porosity with a hierarchical organization in the micropore-mesopore range. Importantly, via an additional activation step, the textural properties can be substantially enhanced (SBET up to 1890 m(2) g(-1)). Both the nanosheet morphology (short diffusional paths) and the hierarchical microporous/mesoporous pore structure allow the rapid transport of ions throughout the carbonaceous matrix, leading to excellent electrochemical performance. Thus, the hierarchical nanosheets exhibit specific capacitances of up to 140 F g(-1) at an ultrahigh discharge current of 150 A g(-1) in 1 M H2SO4 and 100 F g(-1) at 120 A g(-1) in 1 M TEABF4/AN. The maximum specific power recorded in an aqueous electrolyte is ∼ 20-30 kW kg(-1) and ∼ 90-110 kW kg(-1) in an organic electrolyte. These promising power characteristics are accompanied by excellent cycling stability.

The speciation of mercury is currently attracting widespread interest because the emission, transport, deposition and behaviour of toxic mercury species depend on its chemical form. The identification of these species in low concentrations is no easy task and it is even more complex in coal combustion products due to the fact that these products contain organic and mineral matter that give rise to broad peaks and make it difficult to carry out qualitative and quantitative analysis. In this work, a solution to this problem is proposed using a method based on thermal desorption. A sequential extraction procedure was employed for the comparison and validation of the method developed. Samples of fly ashes and soils were analyzed by both of these methods, and thermal desorption was found to be an appropriate technique for mercury speciation. Even in the case of low mercury contents, recovery percentages were close to 100%. The main mercury species identified in the samples studied were HgS and, to a lesser extent, HgO and HgSO4. In addition, although the presence of mercury complexes cannot be demonstrated, the desorption behaviour and sequential extraction results suggest that this element might be associated with the mineral matrix or with carbon particles in some of the solids., (Copyright © 2014 Elsevier Ltd. All rights reserved.)

This study evaluates the effect of the gases present in a typical oxy-coal combustion atmosphere on mercury speciation and compares it with the mercury speciation produced in conventional air combustion atmospheres. The work was performed at laboratory scale at 150 °C. It was found that the minor constituents (SO2, NOx, and HCl) significantly modify the percentages of Hg(2+) in the gas. The influence of these species on mercury oxidation was demostrated when they were tested individually and also when they were blended in different gas compositions, although the effect was different to the sum of their individual effects. Of the minor constituents, NOx were the main species involved in oxidation of mercury. Moreover, it was found that a large concentration of H2O vapor also plays an important role in mercury oxidation. Around 50% of the total mercury was oxidized in atmospheres with H2O vapor concentrations typical of oxy-combustion conditions. When the atmospheres have similar concentrations of SO2, NO, NO2, HCl, and H2O, the proportion of Hg(0)/Hg(2+) is similar regardless of whether CO2 (oxy-fuel combustion) or N2 (air combustion) are the main components of the gas.

An easy, one-step procedure is proposed for the synthesis of highly porous carbon nanosheets with an excellent performance as supercapacitor electrodes. The procedure is based on the carbonization of an organic salt, i.e., potassium citrate, at a temperature in the 750-900 °C range. In this way, carbon particles made up of interconnected carbon nanosheets with a thickness of <80 nm are obtained. The porosity of the carbon nanosheets consists essentially of micropores distributed in two pore systems of 0.7-0.85 nm and 0.95-1.6 nm. Importantly, the micropore sizes of both systems can be enlarged by simply increasing the carbonization temperature. Furthermore, the carbon nanosheets possess BET surface areas in the ∼1400-2200 m(2) g(-1) range and electronic conductivities in the range of 1.7-7.4 S cm(-1) (measured at 7.1 MPa). These materials behave as high-performance supercapacitor electrodes in organic electrolyte and exhibit an excellent power handling ability and a superb robustness over long-term cycling. Excellent results were obtained with the supercapacitor fabricated from the material synthesized at 850 °C in terms of both gravimetric and volumetric energy and power densities. This device was able to deliver ∼13 Wh kg(-1) (5.2 Wh L(-1)) at an extremely high power density of 78 kW kg(-1) (31 kW L(-1)) and ∼30 Wh kg(-1) (12 Wh L(-1)) at a power density of 13 kW kg(-1) (5.2 kW L(-1)) (voltage range of 2.7 V).

A comparative study of the pyrolysis of a macroalgae industrial solid waste (algae meal) in an electrical conventional furnace and in a microwave furnace has been carried out. It was found that the chars obtained from both pyrolyses are similar and show good properties for performing as a solid bio-fuel and as a precursor of activated carbon. Bio-oils from conventional pyrolysis have a greater number of phenolic, pyrrole and alkane compounds whereas benzene and pyridine compounds are more predominant in microwave pyrolysis with a major presence of light compounds. The bio-gas fraction from microwave pyrolysis presents a much higher syngas content (H2+CO), and a lower CO2 and CH4 proportion than that obtained by conventional pyrolysis. Yields are similar for both treatments with a slightly higher gas yield in the case of microwave pyrolysis due to the fact that microwave heating favors heterogeneous reactions between the gases and the char., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Carbonaceous porous materials derived from leather skin residues have been found to have excellent CO₂ adsorption properties, with interestingly high gas selectivities for CO₂ (α > 200 at a gas composition of 15% CO₂/85% N₂, 273K, 1 bar) and capacities (>2 mmol·g -1 at 273 K). Both CO₂ isotherms and the high heat of adsorption pointed to the presence of strong binding sites for CO₂ which may be correlated with both: N content in the leather residues and ultrasmall pore sizes.

The ability to accurately determine metal mercury content and identify different mercury species in solid samples is essential for developing remediation and control strategies. The aim of the present study is to characterize mercury compounds based on thermal desorption. For this purpose a series of samples was prepared and the operational parameters-heating velocity, carrier gas-were optimized. Fifteen commercial mercury compounds were analyzed for use as fingerprints. The results of the study show that the identification of mercury species by the method of thermal desorption is possible. The temperature of desorption increased according to the following order HgI2

This work demonstrates that regenerable sorbents containing nano-particles of gold dispersed on an activated carbon are efficient and long-life materials for capturing mercury species from coal combustion flue gases. These sorbents can be used in such a way that the high investment entailed in their preparation will be compensated for by the recovery of all valuable materials. The characteristics of the support and dispersion of gold in the carbon surface influence the efficiency and lifetime of the sorbents. The main factor that determines the retention of mercury and the regeneration of the sorbent is the presence of reactive gases that enhance mercury retention capacity. The capture of mercury is a consequence of two mechanisms: (i) the retention of elemental mercury by amalgamation with gold and (ii) the retention of oxidized mercury on the activated carbon support. These sorbents were specifically designed for retaining the mercury remaining in gas phase after the desulfurization units in coal power plants., (Copyright © 2013 Elsevier B.V. All rights reserved.)

The microwave induced pyrolysis of the microalgae Scenedesmus almeriensis and its extraction residue was carried out at 400 and 800°C. The results show that it is possible to obtain a gas fraction with a high content (c.a. 50vol.%) in H2 from both materials, regardless of the pyrolysis temperature. Furthermore, an outstanding syngas production and high gas yields were achieved. The maximum syngas concentration obtained was c.a. 94 vol.%, in the case of the pyrolysis of the residue at 800°C, indicating that the production of CO2 and light hydrocarbons was minimized. The same experiments were carried out in a conventional electric furnace in order to compare the products and yields obtained. It was found that microwave induced pyrolysis gives rise not only to higher gas yields but also to greater syngas and H2 production., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

The role of micropore size and N-doping in CO2 capture by microporous carbons has been investigated by analyzing the CO2 adsorption properties of two types of activated carbons with analogous textural properties: (a) N-free carbon microspheres and (b) N-doped carbon microspheres. Both materials exhibit a porosity made up exclusively of micropores ranging in size between <0.6 nm in the case of the pristine materials and up to 1.6 nm for the highly activated carbons (47% burnoff). The N-doped carbons possess ~3 wt % of N heteroatoms that are incorporated into several types of functional groups (i.e., pyrrole/pyridone, pyridine, quaternary, and pyridine-N-oxide). Under conventional operation conditions (i.e., T ~ 0-25 °C and P(CO2) ~ 0-1 bar), CO2 adsorption proceeds via a volume-filling mechanism, the size limit for volume-filling being ~0.7-0.8 nm. Under these circumstances, the adsorption of CO2 by nonfunctionalized porous carbons is mainly determined by the volume of the micropores with a size below 0.8 nm. It was also observed that the CO2 capture capacities of undoped and N-doped carbons are analogous which shows that the nitrogen functionalities present in these N-doped samples do not influence CO2 adsorption. Taking into account the temperature invariance of the characteristic curve postulated by the Dubinin theory, we show that CO2 uptakes can be accurately predicted by using the adsorption data measured at just one temperature.

The control of soluble metal species in the sub-product leachate generated in electricity production processes is of great concern from an environmental and health point of view. Unlike fly ash, the leaching behaviour of char materials has received little attention. Yet, these solids are captured together with fly ashes in the particle control devices of power plants and are emitted in the same way as by-products. The present study was carried out using two char samples: (i) a raw char and (ii) the same type of char employed in a previous study so that it could serve as a sorbent for mercury species in gas phase. The char samples were by-products (residues) that had been generated during the gasification of plastic and paper waste. The leachates were analyzed for the following elements: Al, Ca, Si, Mg, Ba, Cu, Ni, Pb, Zn, Mo and Hg. In addition, geochemical modelling of the leaching test results was employed to identify the underlying chemical processes that led to the release of toxic elements. The results showed that at alkaline pH values, sorption on the solid surfaces of the char was negligible due to the inorganic complexation of cations in the solution. When the char was used as mercury sorbent slight changes occurred on the reactive surface resulting in the modification of the binding of some elements. As the pH increased, complexation with dissolved organic matter played a more important role in the case of some elements such as Cu because of the greater concentration of dissolved organic matter in solution., (Copyright © 2012 Elsevier B.V. All rights reserved.)

Core@shell spheres made up of a thin layer of resorcinol-formaldehyde enveloping a silica core were prepared by means of a one-step method under Stöber conditions. These spheres are used as a platform for the synthesis of carbon or polymeric capsules, and functionalized nanocomposites.

The combustion of coal can result in trace elements, such as mercury, being released from power stations with potentially harmful effects for both human health and the environment. Research is ongoing to develop cost-effective and efficient control technologies for mercury removal from coal-fired power plants, the largest source of anthropogenic mercury emissions. A number of activated carbon sorbents have been demonstrated to be effective for mercury retention in coal combustion power plants. However, more economic alternatives need to be developed. Raw biomass gasification chars could serve as low-cost sorbents for capturing mercury since they are sub-products generated during a thermal conversion process. The aim of this study was to evaluate different biomass gasification chars as mercury sorbents in a simulated coal combustion flue gas. The results were compared with those obtained using a commercial activated carbon. Chars from a mixture of paper and plastic waste showed the highest retention capacity. It was found that not only a high carbon content and a well developed microporosity but also a high chlorine content and a high aluminium content improved the mercury retention capacity of biomass gasification chars. No relationship could be inferred between the surface oxygen functional groups and mercury retention in the char samples evaluated., (Copyright © 2011 Elsevier Ltd. All rights reserved.)

The fibres that are used to reinforce tyres can be recovered as a waste in the process of grinding of scrap tyres. In this paper beneficiation through pyrolysis is studied since the fibres are made up of polymers with a small amount of rubber because the latter is difficult to separate. The experiments were performed at three temperatures (400, 550 and 900°C) in a horizontal oven. The three products - gas, oil and char - obtained from the pyrolysis were investigated. The composition of the gas was analyzed by means of gas chromatography. The oil was studied by gas chromatography and infrared spectroscopy. The char porous structure was determined by N(2) adsorption. In addition, the topography of the chars was studied by means of scanning electron microscopy (SEM). The products resulting from the pyrolysis of the fibres were compared with those obtained from scrap rubber., (Copyright © 2011 Elsevier B.V. All rights reserved.)