• Energy Research

Dolomite-based binders are characterised by interesting technical and environmental features. For their synthesis, sources of both CaO and MgO are required. The idea developed in this work is to couple the synthesis of dolomite-based binders, starting from a natural dolomite, through the concept of concentrated solar energy (needed to drive the endothermal dolomite calcination process) in fluidised bed reactors. To this end, a fluidised bed system, where the concentrated solar radiation is mimicked by the use of Xe-lamps (short-arc), has been set up and operated. Natural dolomite (sieved in the 420-590 ?m size range) was calcined at a nominal temperature of 850 °C, and bed temperature profiles during solar-driven calcination were investigated. Then, four binders were prepared by mixing slaked dolomite (obtained from the hydration of solar calcined dolomite) with either blast furnace slag or coal fly ash as supplementary cementitious materials. The binders were hydrated for curing times ranging from 7 to 56 days. X-ray fluorescence, X-ray diffraction and combined differential thermal and thermogravimetric analyses were employed as characterisation techniques both to analyse the chemical composition of starting materials and to investigate the evolution of the hydration in the four systems.

Dolomite-based binders are characterised by interesting technical and environmental features. For their synthesis, sources of both CaO and MgO are required. The idea developed in this work is to couple the synthesis of dolomite-based binders, starting from a natural dolomite, through the concept of concentrated solar energy (needed to drive the endothermal dolomite calcination process) in fluidised bed reactors. To this end, a fluidised bed system, where the concentrated solar radiation is mimicked by the use of Xe-lamps (short-arc), has been set up and operated. Natural dolomite (sieved in the 420-590 ?m size range) was calcined at a nominal temperature of 850 °C, and bed temperature profiles during solar-driven calcination were investigated. Then, four binders were prepared by mixing slaked dolomite (obtained from the hydration of solar calcined dolomite) with either blast furnace slag or coal fly ash as supplementary cementitious materials. The binders were hydrated for curing times ranging from 7 to 56 days. X-ray fluorescence, X-ray diffraction and combined differential thermal and thermogravimetric analyses were employed as characterisation techniques both to analyse the chemical composition of starting materials and to investigate the evolution of the hydration in the four systems.

Around 600 million m3 of wastewater and 6 million tonnes of leather solid wastes, are generated annually worldwide, with a chromium content of 1 to 4 %. In this context, the thermochemical valorisation of tannery sludge (TS) by hydrothermal liquefaction (HTL) process represents a promising route both for the reduction of the material to dispose in landfill and for the production of an energy carrier. HTL process produces bio-crude from wet biomasses in a hot pressurised water environment, thus avoiding the energy-intensive drying step commonly associated to other thermochemical processes. Moreover, HTL, not aiming at the complete oxidation of the organic component, potentially avoids the oxidation of Cr in its harmful hexavalent form. In this study, a TS was investigated as solid waste for HTL carried out in a 500 mL batch reactor to obtain a bio-crude for energy purposes. Results show that, under the best operating HTL condition (350 °C and 10 min), the H/C ratio of bio-crude was similar to that of starting biomass while the O/C ratio was about three times smaller than in the parent TS. The bio-crude yield was about 25–30 % on dry and ash-free basis, with an associated energy recovery of about 40–45 %. NMR analysis of bio-crude revealed that it is a complex mixture mainly constituted by aliphatic units. Moreover, ICP-MS, atomic absorption and UV–visible spectroscopy analyses proved that inorganic elements are mainly retrieved in the solid residue, and that Cr was present in its starting trivalent form.

Around 600 million m3 of wastewater and 6 million tonnes of leather solid wastes, are generated annually worldwide, with a chromium content of 1 to 4 %. In this context, the thermochemical valorisation of tannery sludge (TS) by hydrothermal liquefaction (HTL) process represents a promising route both for the reduction of the material to dispose in landfill and for the production of an energy carrier. HTL process produces bio-crude from wet biomasses in a hot pressurised water environment, thus avoiding the energy-intensive drying step commonly associated to other thermochemical processes. Moreover, HTL, not aiming at the complete oxidation of the organic component, potentially avoids the oxidation of Cr in its harmful hexavalent form. In this study, a TS was investigated as solid waste for HTL carried out in a 500 mL batch reactor to obtain a bio-crude for energy purposes. Results show that, under the best operating HTL condition (350 °C and 10 min), the H/C ratio of bio-crude was similar to that of starting biomass while the O/C ratio was about three times smaller than in the parent TS. The bio-crude yield was about 25–30 % on dry and ash-free basis, with an associated energy recovery of about 40–45 %. NMR analysis of bio-crude revealed that it is a complex mixture mainly constituted by aliphatic units. Moreover, ICP-MS, atomic absorption and UV–visible spectroscopy analyses proved that inorganic elements are mainly retrieved in the solid residue, and that Cr was present in its starting trivalent form.

Cement production is an energy-intensive manufacturing process with potentially large environmental burdens. Among the others, it is one of the largest industrial sources of CO2 emission. Limestone calcination is the stage responsible for most of CO2 emissions and energy requirement. This article aims at supporting the use of solar energy as non-carbogenic renewable source to sustain limestone calcination, with advantages on both the economic and environmental aspects of the process. A directly irradiated Fluidised Bed (FB) reactor was used as limestone precalciner for clinker production. Concentrated solar radiation was simulated with an array of three short-arc Xe-lamps of 4 kWel each, coupled with elliptical reflectors, capable of producing a peak flux of about 3 MW m-2 at the centre of the reactor. The total irradiated power is of approximately 3.2 kWth. Thermocouples and an IR camera were used for the analysis of the FB thermal profiles. Calcination was carried out at a nominal bulk bed temperature of 950 °C, in an atmosphere containing about 70% CO2. The reactivity of lime generated by the solar-driven calcination process has been characterised. Lime produced by the solar-driven process was used together with commercial clay as kiln feed components for the formulation of Portland cement samples. A binary mixture composed by fresh limestone and the same clay as above was employed as a reference. The key focus of the investigation was the assessment of the reactivity of the solar-generated lime toward the main clay components in the clinker production process, as compared to lime from ordinary calcination. An aspect that is specifically scrutinised is whether the different, and possibly more severe, thermal history to which limestone particles undergo during solar-driven calcination in directly irradiated FB reactors may compromise lime reactivity. Portland clinkers were produced by burning the raw meals at 1500 °C for 15 min. Clinkers were mixed with 5% natural gypsum to prepare the related Portland cements, which were then paste hydrated for times ranging from 2 to 28 days (water/cement mass ratio = 0.5, 20 °C, 95% relative humidity). Parameters as lime saturation factor, burnability, phase composition of clinkers and hydration behaviour of cement pastes were taken into consideration. Techniques as X-ray fluorescence and diffraction, and simultaneous differential thermal-thermogravimetry were used to study the materials.

Cement production is an energy-intensive manufacturing process with potentially large environmental burdens. Among the others, it is one of the largest industrial sources of CO2 emission. Limestone calcination is the stage responsible for most of CO2 emissions and energy requirement. This article aims at supporting the use of solar energy as non-carbogenic renewable source to sustain limestone calcination, with advantages on both the economic and environmental aspects of the process. A directly irradiated Fluidised Bed (FB) reactor was used as limestone precalciner for clinker production. Concentrated solar radiation was simulated with an array of three short-arc Xe-lamps of 4 kWel each, coupled with elliptical reflectors, capable of producing a peak flux of about 3 MW m-2 at the centre of the reactor. The total irradiated power is of approximately 3.2 kWth. Thermocouples and an IR camera were used for the analysis of the FB thermal profiles. Calcination was carried out at a nominal bulk bed temperature of 950 °C, in an atmosphere containing about 70% CO2. The reactivity of lime generated by the solar-driven calcination process has been characterised. Lime produced by the solar-driven process was used together with commercial clay as kiln feed components for the formulation of Portland cement samples. A binary mixture composed by fresh limestone and the same clay as above was employed as a reference. The key focus of the investigation was the assessment of the reactivity of the solar-generated lime toward the main clay components in the clinker production process, as compared to lime from ordinary calcination. An aspect that is specifically scrutinised is whether the different, and possibly more severe, thermal history to which limestone particles undergo during solar-driven calcination in directly irradiated FB reactors may compromise lime reactivity. Portland clinkers were produced by burning the raw meals at 1500 °C for 15 min. Clinkers were mixed with 5% natural gypsum to prepare the related Portland cements, which were then paste hydrated for times ranging from 2 to 28 days (water/cement mass ratio = 0.5, 20 °C, 95% relative humidity). Parameters as lime saturation factor, burnability, phase composition of clinkers and hydration behaviour of cement pastes were taken into consideration. Techniques as X-ray fluorescence and diffraction, and simultaneous differential thermal-thermogravimetry were used to study the materials.

Negative-emission technologies are largely investigated to better control atmospheric carbon dioxide concentration driving global warming. Calcium looping has been proposed in literature for direct air capture, but a comprehensive system analysis is still missing. Methanation of carbon dioxide can represent an alternative to geological storage, widely investigated within the power-to-gas framework. In this study, an integrated process considering the catalytic methanation of the concentrated carbon dioxide stream after capture from ambient air by a pure hydrogen stream from water electrolysis was proposed and numerically investigated. The system relies on packed bed reactors and uses calcium oxide as sorbent, and a nickel-based catalyst for methanation. A comprehensive study on the overall system performance was carried out, assuming a carbon dioxide capture target of 100 t y−1. Model computations suggest that roughly 50-in-parallel reactors, 0.5 m diameter each, are required for a continuous operation. The overall energy demand of the integrated process ranges within 344–370 GJ tCH4−1, or 215–293 GJ tCH4−1 if neglecting the humidifier. The methanation process requires 3-in-series reactors and can yield a continuous gas stream with a flow rate of 5 kg h−1 and a methane molar fraction of nearly 91%. If this stream is exploited for heat generation, a return of energy index of 16%, or 23% if neglecting the humidifier, is foreseen. The proposed process stems as viable solution towards a circular carbon economy.