<p>Black liquors are presently combusted in recovery boilers where the inorganic cooking chemicals are recovered and the energy in the organic material is converted to steam and electricity. A new technology, developed by Chemrec AB, is black liquor gasification (BLG). BLG has more to offer compared to the recovery boiler process, in terms of on-site generation of electric power, liquid fuel and process chemicals. A prerequisite for both optimization of existing processes and the commercialization of BLG is better understanding of the physical and chemical processes involved including interactions with the refractory lining. The chemistry in the BLG process is very complex and to minimize extensive and expensive time-consuming studies otherwise required accurate and reliable model descriptions are needed for a full understanding of most chemical and physical processes as well as for up-scaling of the new BLG processes. However, by using these calculated model results in practice, the errors in the state of the art thermochemical data have to be considered. An extensive literature review was therefore performed to update the data needed for unary, binary and higher order systems. The results from the review reviled that there is a significant range of uncertainty for several condensed phases and a few gas species. This resulted in experimental re-determinations of the binary phase diagrams sodium carbonate-sodium sulfide (Na2CO3-Na2S) and sodium sulfate-sodium sulfide (Na2SO4-Na2S) using High Temperature Microscopy (HTM), High Temperature X-ray Diffraction (HT-XRD) and Differential Thermal Analysis (DTA). For the Na2CO3-Na2S system, measurements were carried out in dry inert atmosphere at temperatures from 25 to 1200 °C. To examine the influence of pure CO2 atmosphere on the melting behavior, HTM experiments in the same temperature interval were made. The results include re-determination of liquidus curves, in the Na2CO3 rich area, melting points of the pure components as well as determination of the extent of the solid solution, Na2CO3(ss), area. The thermal stability of Na2SO3 was studied and the binary phase diagram Na2SO4-Na2S was re-determined. The results indicate that Na2SO3 can exist for a short time up to 750 °C, before it melts. It was also proved that a solid/solid transformation, not reported earlier, occurs at 675 ± 10 °C. At around 700 °C, Na2SO3 gradually breaks down within a few hours, to finally form the solid phases Na2SO4 and Na2S. From HTM measurements a metastable phase diagram including Na2SO3, as well as an equilibrium phase diagram have been constructed for the binary system Na2SO4-Na2S. Improved data on Na2S was experimentally obtained by using solid-state EMF measurements. The equilibrium constant for Na2S(s) was determined to be log Kf(Na2S(s)) (± 0.05) = 216.28 – 4750(T/K)–1 – 28.28878 ln (T/K). Gibbs energy of formation for Na2S(s) was obtained as ΔfG°(Na2S(s))/(kJ mol–1) (± 1.0) = 90.9 – 4.1407(T/K) + 0.5415849(T/K) ln (T/K). The standard enthalpy of formation of Na2S(s) was evaluated to be ΔfH°(Na2S(s), 298.15 K)/(kJ mol–1) (± 1.0) = – 369.0. The standard entropy was evaluated to be S°(Na2S(s), 298.15 K)/(J mol–1 K–1) (± 2.0) = 97.0. Analyses of used refractory material from the Chemrec gasifier were also performed in order to elucidate the stability of the refractory lining. Scanning electron microscopy (SEM) analysis revealed that the chemical attack was limited to 250-300 μm, of the surface directly exposed to the gasification atmosphere and the smelt. From XRD analysis it was found that the phases in this surface layer of the refractory were dominated by sodiumaluminosilicates, mainly Na1.55Al1.55Si0.45O4.</p>

Black liquors are presently combusted in recovery boilers where the inorganic cooking chemicals are recovered and the energy in the organic material is converted to steam and electricity. A new technology, developed by Chemrec AB, is black liquor gasification (BLG). BLG has more to offer compared to the recovery boiler process, in terms of on-site generation of electric power, liquid fuel and process chemicals. A prerequisite for both optimization of existing processes and the commercialization of BLG is better understanding of the physical and chemical processes involved including interactions with the refractory lining. The chemistry in the BLG process is very complex and to minimize extensive and expensive time-consuming studies otherwise required accurate and reliable model descriptions are needed for a full understanding of most chemical and physical processes as well as for up-scaling of the new BLG processes. However, by using these calculated model results in practice, the errors in the state of the art thermochemical data have to be considered. An extensive literature review was therefore performed to update the data needed for unary, binary and higher order systems. The results from the review reviled that there is a significant range of uncertainty for several condensed phases and a few gas species. This resulted in experimental re-determinations of the binary phase diagrams sodium carbonate-sodium sulfide (Na2CO3-Na2S) and sodium sulfate-sodium sulfide (Na2SO4-Na2S) using High Temperature Microscopy (HTM), High Temperature X-ray Diffraction (HT-XRD) and Differential Thermal Analysis (DTA). For the Na2CO3-Na2S system, measurements were carried out in dry inert atmosphere at temperatures from 25 to 1200 °C. To examine the influence of pure CO2 atmosphere on the melting behavior, HTM experiments in the same temperature interval were made. The results include re-determination of liquidus curves, in the Na2CO3 rich area, melting points of the pure components as well as determination of the extent of the solid solution, Na2CO3(ss), area. The thermal stability of Na2SO3 was studied and the binary phase diagram Na2SO4-Na2S was re-determined. The results indicate that Na2SO3 can exist for a short time up to 750 °C, before it melts. It was also proved that a solid/solid transformation, not reported earlier, occurs at 675 ± 10 °C. At around 700 °C, Na2SO3 gradually breaks down within a few hours, to finally form the solid phases Na2SO4 and Na2S. From HTM measurements a metastable phase diagram including Na2SO3, as well as an equilibrium phase diagram have been constructed for the binary system Na2SO4-Na2S. Improved data on Na2S was experimentally obtained by using solid-state EMF measurements. The equilibrium constant for Na2S(s) was determined to be log Kf(Na2S(s)) (± 0.05) = 216.28 – 4750(T/K)–1 – 28.28878 ln (T/K). Gibbs energy of formation for Na2S(s) was obtained as ΔfG°(Na2S(s))/(kJ mol–1) (± 1.0) = 90.9 – 4.1407(T/K) + 0.5415849(T/K) ln (T/K). The standard enthalpy of formation of Na2S(s) was evaluated to be ΔfH°(Na2S(s), 298.15 K)/(kJ mol–1) (± 1.0) = – 369.0. The standard entropy was evaluated to be S°(Na2S(s), 298.15 K)/(J mol–1 K–1) (± 2.0) = 97.0. Analyses of used refractory material from the Chemrec gasifier were also performed in order to elucidate the stability of the refractory lining. Scanning electron microscopy (SEM) analysis revealed that the chemical attack was limited to 250-300 μm, of the surface directly exposed to the gasification atmosphere and the smelt. From XRD analysis it was found that the phases in this surface layer of the refractory were dominated by sodiumaluminosilicates, mainly Na1.55Al1.55Si0.45O4.

Cement production is responsible for around 7% of the global anthropogenic carbon dioxide emissions. More than half of these emissions are due to the unavoidable release of carbon dioxide upon thermal decomposition of the main raw material limestone. Many different options for carbon capture are currently being investigated to lower emissions, and one potential route to facilitate carbon capture could be the implementation of an electrified separate calcination step. However, potential effects on the phase composition of cement clinker need to be investigated, which is the aim of the present study. Phases of special interest are alite, belite, aluminate, ferrite, calcite, and lime.  The phase composition during clinker formation was examined through HT-XRD lab-scale experiments, allowing the phase transformations to be observed in situ. Two different methods of separate calcination were investigated, one method in which the raw meal was calcined separately, and one method where the limestone was calcined separately. The former yielded an alite amount similar to that of the reference experiments, whereas the latter method yielded a lower amount. It could, unfortunately, not be excluded that the difference was due to poor experimental conditions, and additional experiments are needed to investigate the matter further. The study does, however, indicate that a calcined raw meal might be used to produce a clinker of similar phase composition concerning major phases belite, aluminate, ferrite, alite, and free lime. A raw meal containing calcined limestone might, however, need longer residence time at clinkering temperature too obtain similar phase composition. In addition, a raw meal containing calcined limestone was observed to be carbonated to a greater extent upon reheating than a calcined raw meal. Further experiments are needed to fully understand the effects on clinker composition of an electrified separate calcination step, and several improvements to the experimental method are given in the study.

En raison de leurs propriétés chimiques et physiques, les oxydes mixtes d'uranium et de plutonium sont considérés comme combustibles pour les réacteurs nucléaires de quatrième génération. Dans ce cadre, des études expérimentales complémentaires sont nécessaire, notamment pour mieux comprendre les phénomènes mis en jeu lors de la fabrication ou sous irradiation. L'objet de ce travail est d'étudier le diagramme de phase U-Pu-O dans une large gamme de composition et de températures afin d'améliorer notre connaissance de ce système. La plupart des expériences ont été réalisées par diffraction des rayons X en fonction de la température. La contrôle in situ de la pression partielle en oxygène a permis de faire varier la stœchiométrie en oxygène dans le matériau. L'approche expérimentale a été couplée avec la modélisation thermodynamique par la méthode CALPHAD afin de mieux dimensionner les expériences et interpréter les résultats. Cette méthodologie a permis d'améliorer notre connaissance des équilibres de phase dans le système U-Pu-O. / Due to their physical and chemical properties, mixed uranium-plutonium oxides are considered for fuel in 4th generation nuclear reactors. In this frame, complementary experimental studies are necessary to develop a better understanding of the phenomena that take place during fabrication and operation in the reactor. The focus of this work was to study the U Pu–O phase diagram in a wide range of compositions and temperatures to ameliorate our knowledge of the phase equilibria in this system. Most of experiments were done using in situ X-ray diffraction at elevated temperatures. The control of the oxygen partial pressure during the treatments made it possible to change the oxygen stoichiometry of the sample, which gave us an opportunity to study rapidly different compositions and the processes involved. The experimental approach was coupled with thermodynamic modeling using the CALPHAD method, to precisely plan the experiments and interpret the obtained results. This approach enabled us to enhance the knowledge of phase equilibria in the U–Pu–O system.