Modeling of radical structures in biochar using DFT calculations

Carbon is a key ingredient for producing metals used for cellphones, laptop computers, photovoltaic panels, and related solid state silicon devices employed by mankind. Thus, introduction of an alternative reductant based on bioresources into steel manufacturing without significant investments in a new technology is of high importance and wide impact. The production of iron, steel, and many other metals can employ biocarbon as the needed reductant; but because of cost, coals are usually used instead. Please click on the file below for full content of the abstract

CO2 gasification reactivity of char from high-ash biomass

Biomass char produced from pyrolysis processes is of great interest to be utilized as renewable solid fuels or materials. Forest byproducts and agricultural wastes are low-cost and sustainable biomass feedstocks. These biomasses generally contain high amounts of ash-forming elements, generally leading to high char reactivity. This study elaborates in detail how chemical and physical properties affect CO2 gasification rates of high-ash biomass char, and it also targets the interactions between these properties. Char produced from pine bark, forest residue, and corncobs (particle size 4–30 mm) were included, and all contained different relative compositions of ash-forming elements. Acid leaching was applied to further investigate the influence of inorganic elements in these biomasses. The char properties relevant to the gasification rate were analyzed, that is, elemental composition, specific surface area, and carbon structure. Gasification rates were measured at an isothermal condition of 800 °C with 20% (vol.) of CO2 in N2. The results showed that the inorganic content, particularly K, had a stronger effect on gasification reactivity than specific surface area and aromatic cluster size of the char. At the gasification condition utilized in this study, K could volatilize and mobilize through the char surface, resulting in high gasification reactivity. Meanwhile, the mobilization of Ca did not occur at the low temperature applied, thus resulting in its low catalytic effect. This implies that the dispersion of these inorganic elements through char particles is an important reason behind their catalytic activity. Upon leaching by diluted acetic acid, the K content of these biomasses substantially decreased, while most of the Ca remained in the biomasses. With a low K content in leached biomass char, char reactivity was determined by the active carbon surface area.publishedVersio

Mass flow and variability in screw feeding of biomass powders – relations to particle and bulk properties

Biomass powders are often cohesive, have low bulk density and poor material flow characteristics which causes interruptions and variations in feeding systems. In this study, a range of biomasses - commercial charcoal, torrefied Norway spruce stem wood, non-treated Norway spruce stem wood, and reed canary grass - was milled (screen size: 1 mm) using two different milling methods; cutting mill and hammer mill, to form eight types of biomass powders. Powders were analyzed for loose density, Hausner ratio, compression ratio, angle of repose and for size and shape distributions. Size and shape were determined by mechanical sieving and optical particle size and shape analysis. Additionally, yield loci and wall yield loci were determined through standard bulk solids testing methods. Screw feeding properties of the eight biomass powders were determined by feeding the materials in a twin screw feeder - at constant rpm and at a constant feeding rate of 1 kg/h. Correlation analysis and principal component loadings were used to describe relations between material properties and feeding characteristics. When materials were fed at a constant rpm, feeding variability was closely correlated to the powders’ angle of repose (long time step) and Hausner and compression ratio (short time step)

Characterization and reactivity of soot from fast pyrolysis of lignocellulosic compounds and monolignols

peer-reviewedThis study presents the effect of lignocellulosic compounds and monolignols on the yield, nanostructure and reactivity of soot generated at 1250  ° C in a drop tube furnace. The structure of soot was characterized by electron microscopy techniques, Raman spectroscopy and electron spin resonance spectroscopy. The CO2 reactivity of soot was investigated by thermogravimetric analysis. Soot from cellulose was more reactive than soot produced from extractives, lignin and monolignols. Soot reactivity was correlated with the separation distances between adjacent graphene layers, as measured using transmission electron microscopy. Particle size, free radical concentration, differences in a degree of curvature and multi-core structures influenced the soot reactivity less than the interlayer separation distances. Soot yield was correlated with the lignin content of the feedstock. The selection of the extraction solvent had a strong influence on the soot reactivity. The Soxhlet extraction of softwood and wheat straw lignin soot using methanol decreased the soot reactivity, whereas acetone extraction had only a modest effect

Aspects of alkali chloride chemistry on deposit formation and high temperature corrosion in biomass and waste fired boilers

Combustion of biomass and waste has several environmental, economical and political advantages over the use of fossil fuels for the generation of heat and electricity. However, these fuels often have a significantly different composition and the combustion is therefore associated with additional operational problems. A high content of chlorine and alkali metals (potassium and sodium) often causes problems with deposit formation and high temperature corrosion. Some different aspects of these issues are addressed in this thesis. The overall objective of this thesis was to study and highlight different means by which operational problems related to alkali chlorides can be overcome, reduced or prevented. The most important results of this thesis are: (1) A full description of the in-situ alkali chloride monitor, its operational principles, the calibration procedure, and an example of a full-scale application was made public in a scientific publication. (2) Efficient sulfation of gaseous alkali chlorides in a full-scale boiler was achieved by injecting ammonium sulfate in a water solution into the hot flue gas. (3) Reduced deposit growth and corrosion rates were achieved by lowering the alkali chloride concentration in the flue gas by sulfation. (4) Evidence of decreased deposit growth and chlorine content in deposits during peat co-combustion. (5) Results are presented from high temperature corrosion tests with different superheater steels in two different combustion environments. (6) Controlled KCl and NaCl condensation under simulated combustion conditions resulted in deposits which consisted of mostly pure phases, in contrast to the solid solution that would be expected under the prevailing conditions at chemical equilibrium

Aspects of alkali chloride chemistry on deposit formation and high temperature corrosion in biomass and waste fired boilers

Combustion of biomass and waste has several environmental, economical and political advantages over the use of fossil fuels for the generation of heat and electricity. However, these fuels often have a significantly different composition and the combustion is therefore associated with additional operational problems. A high content of chlorine and alkali metals (potassium and sodium) often causes problems with deposit formation and high temperature corrosion. Some different aspects of these issues are addressed in this thesis. The overall objective of this thesis was to study and highlight different means by which operational problems related to alkali chlorides can be overcome, reduced or prevented. The most important results of this thesis are: (1) A full description of the in-situ alkali chloride monitor, its operational principles, the calibration procedure, and an example of a full-scale application was made public in a scientific publication. (2) Efficient sulfation of gaseous alkali chlorides in a full-scale boiler was achieved by injecting ammonium sulfate in a water solution into the hot flue gas. (3) Reduced deposit growth and corrosion rates were achieved by lowering the alkali chloride concentration in the flue gas by sulfation. (4) Evidence of decreased deposit growth and chlorine content in deposits during peat co-combustion. (5) Results are presented from high temperature corrosion tests with different superheater steels in two different combustion environments. (6) Controlled KCl and NaCl condensation under simulated combustion conditions resulted in deposits which consisted of mostly pure phases, in contrast to the solid solution that would be expected under the prevailing conditions at chemical equilibrium

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Characterization of Limestone Surface Impurities and Resulting Quicklime Quality

Quicklime, rich in CaO(s), is generated by calcining limestone at high temperatures. Parallel-flow regenerative lime kilns are the most energy-effective industrial method available today. To prevent major disruptions in such kilns, a high raw material quality is necessary. Under some conditions, impurity-enriched material may adhere to limestone pebbles and enter the kiln. In this study, limestone and corresponding quicklime were analyzed to evaluate the extent and composition of surface impurities and assess the effect on quicklime product quality, here defined as free CaO. This was performed by sampling and analyzing limestone, quarry clay, laboratory-produced quicklime, and industrially produced quicklime with XRF, SEM/EDX, and XRD; interpretations were supported by thermodynamic equilibrium calculations. In the laboratory-produced quicklime, the surface impurities reacted with calcium forming Larnite, Gehlenite, Åkermanite and Merwinite, reducing the quicklime quality. The results showed that the limestone surface layer comprised 1.2 wt.-% of the total mass but possessed 4 wt.-% of the total impurities. The effect on industrially produced quicklime quality was lower; this indicated that the limestone surface impurities were removed while the material moved through the kiln. Multicomponent chemical equilibrium calculations showed that the quarry clay was expected to be fully melted at 1170 °C, possibly leading to operational problems

Impact of limestone surface impurities on quicklime product quality

Quicklime is produced through the thermal processing of limestone in industrial kilns. During quarry operations, fine particulate quarry dust adheres to limestone lump surfaces, increasing the bulk concentration of impurities in limestone products. During thermal processing in a kiln, impurities such as Si, Mg, Al, Fe, and Mn react with Ca, reducing quicklime product quality. Which reactant phases are formed, and the extent to which these result in a reduction in quality, has not been extensively investigated. The present study investigated as-received and manually washed limestone product samples from two operational quarries using elemental compositions and a developed predictive multi-component chemical equilibrium model to obtain global phase diagrams for 1000–1500 °C, corresponding to the high-temperature zone of a lime kiln, identifying phases expected to be formed in quicklime during thermal processing. The results suggest that impurities found on the surface of the lime kiln limestone feed reduce the main quality parameter of the quicklime products, i.e., calcium oxide, CaO (s), content by 0.8–1.5 wt.% for the investigated materials. The results also show that, in addition to the effect of impurities, the quantity of CaO (s) varies greatly with temperature. More impurities result in more variation and a greater need for accurate temperature control of the kiln, where keeping the temperature below approximately 1300 °C, that of Hatrurite formation, is necessary for a product with higher CaO (s)