Progress and challenges in valorisation of biomass waste from ornamental trees pruning through pyrolysis processes. Prospects in the bioenergy sector.

Nowadays, the scarcity of energy resources is promoting the search for alternative energy sources, boosting interest in the use of forest lignocellulosic residue in the energy sector. In this study, the focus is on the energy recovery from two lignocellulosic residues originated during the pruning of ornamental trees (Horse Chestnut, CI, and False Acacia, FA). Both conventional and flash pyrolysis techniques were applied. The experimental pyrolysis variables were obtained from the study of the thermal behaviour of the pruning residues in thermogravimetric analysis. It was carried out under 5 heating rates and kinetic parameters were estimated using Flynn-Wall-Ozawa method. Results denoted higher maximum mass loss rate values for the same release temperature regions under FA experiments. Also, FA samples had lower final residues for the processes. However, activation energy values were so close for both species. FA was also linked to the faster reactions according frequency factor outcomes. Conventional pyrolysis of pruning residues was carried out in a horizontal oven of original design at a heating rate of 25 °C/min, at 750 °C and 60 min of permanence at that temperature; flash pyrolysis was tested in that oven at 750 and 850 °C. In these pyrolysis processes, three fractions were obtained: bio-char, bio-oil and gas. The physicochemical attributes of the bio-chars suggested their potential utility as biofuels (28.4-29.8 MJ/kg), adsorbent precursors or soil additives. Conventional pyrolysis bio-oils had a dominant monoaromatic hydrocarbons nature, with phenols being the most abundant (≥60%), while flash bio-oils contain mainly polycyclic aromatic hydrocarbons. Conventional pyrolysis gases contained up to 60 vol% of CO2; flash pyrolysis gases had high combustible gas content (CO, CH4, H2) and a low CO2 content (<25 vol%). As a result, their calorific value (18.06 MJ/kg) exhibited a threefold increase compared to the gas produced through conventional pyrolysis (6.04 MJ/kg).

Food industrial biowaste-based magnetic activated carbons as sustainable adsorbents for anthropogenic mercury emissions.

Bio-derived magnetic activated carbons from industrial chestnut shell waste have been obtained through a novel, optimized and sustainable methodology where impregnation, pyrolysis, acid washing or other intermediate steps commonly used in the activation process were eliminated saving time, energy and costs. The resulting materials (MACs) were obtained at 220-800 °C showed interesting properties: textural (SBET up to 568 m2 g-1) and magnetic (different iron species developed), depending on the activation temperature employed. Data showed outstanding results when MACs were tested for Hg removal in pollution emissions at 150 °C in lab-scale device. In MACs obtained at 500-600 °C, where the highest concentration of magnetite was found, the best Hg adsorption capacity was achieved, while it decreased when metallic iron or iron carbides were present (MACs obtained at 800 °C). Moreover, the difference of Hg0 removal/adsorption in N2+O2 and Simulated Flue Gas atmosphere between MACs obtained at 500 and 600 °C pointed out the influence on Hg removal of additional parameters, as surface chemistry and the existence of sulfur or chloride. The determination of Hg species in post-retention solids confirmed the mercury oxidation by high-valence iron ions (Fe3+) and the involvement of physisorption and chemisorption processes for the gas-solid interaction mechanism.

Biomass gasification chars for mercury capture from a simulated flue gas of coal combustion.

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.

An assessment of the environmental fate of mercury species in highly polluted brownfields by means of thermal desorption.

High contents of mercury (Hg) have been found in old mining-metallurgy sites occurring a widespread contamination and degradation of the land. The ability to identify the Hg species present in these areas is essential to clarify fate of Hg and its bioavailability and additionally, to be able to parameterize remediation techniques based on thermal desorption in order to carry out a full-scale decontamination of the land. This study has proven the usefulness of a thermal programmed desorption procedure (Hg-TPD) for identifying Hg species in contaminated samples related to mining-metallurgy activities. Hg bound to organic matter (Hg-OM) and to pyrite (Hg-FeS2), HgS red, HgCl2, Hg0 and HgO were identified in most of waste samples. The absence of mobile Hg species in soils and sediments showed both its re-emission to the atmosphere (Hg0) or of its oxidation and lixiviation (HgO and HgCl2) over the years. The results have demonstrated that most of these polluted solids can be remediated by thermal treatment at temperatures ranging between 150 and 600°C. The study evidence that Hg-TPD is useful either for parameterizing a thermal remediation or for identifying the evolution pathways of Hg species in different environmental compartments and in general, for any environmental remediation treatment.

A comparison of devices using thermal desorption for mercury speciation in solids.

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.

Application of thermal desorption for the identification of mercury species in solids derived from coal utilization.

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.

Impact of oxy-fuel combustion gases on mercury retention in activated carbons from a macroalgae waste: effect of water.

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.

Mercury compounds characterization by thermal desorption.

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

Leaching of major and trace elements from paper-plastic gasification chars: an experimental and modelling study.

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.

Differential partitioning and speciation of Hg in wet FGD facilities of two Spanish PCC power plants.

This paper evaluates the speciation and partitioning of mercury in two Spanish pulverised coal combustion power plants (PP1 and PP2), equipped with wet limestone-based flue gas desulphurisation facilities (FGD) operating with forced oxidation and re-circulation of FGD water streams. These plants are fed with coal (PP1) and coal/pet-coke blends (PP2) with different mercury contents. The behaviour, partitioning and speciation of Hg were found to be similar during the combustion processes but different in the FGD systems of the two power plants. A high proportion (86-88%) of Hg escaped the electrostatic precipitator in gaseous form, Hg2+ being the predominant mercury species (68-86%) to enter the FGD. At this point, a relatively high total Hg retention (72% and 65%) was achieved in the PP1 and PP2 (2007) FGD facilities respectively. However, during the second sampling campaign for PP2 (2008), the mercury removal achieved by the FGD was much lower (26%). Lab-scale tests point to liquid/gas ratio as the main parameter affecting oxidised mercury capture in the scrubber. The partitioning of the gaseous mercury reaching the FGD system in the wastes and by-products differed. In the low mercury input power plant (PP1) most of the mercury (67%) was associated with the FGD gypsum. Moreover in PP2 a significant proportion of the gaseous mercury reaching the FGD system remained in the aqueous phase (45%) in the 2007 sampling campaign while most of it escaped in 2008 (74%). This may be attributed to the scrubber operating conditions and the different composition and chemistry of the scrubber solution probably due to the use of an additive.

The stability of arsenic and selenium compounds that were retained in limestone in a coal gasification atmosphere.

The aim of this work was to evaluate the stability of arsenic and selenium species retained in a lime/limestone mixture obtained by using limestone as a sorbent for gas cleaning in a coal gasification atmosphere. It was found that the stability of arsenic and selenium species produced by the gas-solid reactions with lime/limestone may be affected by their exposure to air and by their contact with water. The results confirm the conclusions of a previous work in which Ca(AsO(2))(2) and CaSe was postulated as the products of the reaction between the arsenic and selenium species present in a coal gasification atmosphere with lime/limestone. Moreover it was proved that the compounds (Ca(AsO(2))(2) and CaSe) may undergo transformations when the sorbents post-retention are stored or disposed of in air. From the results obtained by XAFS it was possible to identify the Ca(3)(AsO(4))(2) produced by the oxidation of the Ca(AsO(2))(2) on the sorbent surface. The XAFS results for selenium showed that the CaSe formed on the sorbent was transformed to form several species, but mainly elemental Se. These changes in the speciation of arsenic and selenium may explain the behavior of the sorbent post-retention during the water solubility test. Although the selenium compounds and the products that may originate from their decomposition in water are not toxic, in the case of arsenic, species like Ca(AsO(2))(2) and Ca(3)(AsO(4))(2) may lixiviate, and generate toxic arsenic compounds in solution that could pose a risk when the sorbent is finally disposed of.

Stable lead isotope compositions in selected coals from around the world and implications for present day aerosol source tracing.

The phasing out of leaded gasoline in many countries around the world at the end of the last millennium has resulted in a complex mixture of lead sources in the atmosphere. Recent studies suggest that coal combustion has become an important source of Pb in aerosols in urban and remote areas. Here, we report lead concentration and isotopic composition for 59 coal samples representing major coal deposits worldwide in an attempt to characterize this potential source. The average concentration in these coals is 35 microg Pb g(-1), with the highest values in coals from Spain and Peru and the lowest in coals from Australia and North America. The 206Pb/207Pb isotope ratios range between 1.15 and 1.24, with less radiogenic Pb in coals from Europe and Asia compared to South and North America. Comparing the Pb isotopic signatures of coals from this and previous studies with those published for Northern and Southern Hemisphere aerosols, we hypothesize that coal combustion might now be an important Pb source in China, the eastern U.S., and to some extent, in Europe but not as yet in other regions including South Africa, South America, and western U.S. This supports the notion that "old Pb pollution" from leaded gasoline reemitted into the atmosphere or long-range transport (i.e., from China to the western U.S.) is important. Comparing the isotope ratios of the coals, the age of the deposits, and Pb isotope evolution models for the major geochemical reservoirs suggests that the PbIC in coals is strongly influenced by the depositional coal forming environment.