Academic literature on the topic 'Carbonised'

The main purpose of this project was to synthesise, characterise and evaluate metal organic frameworks (MOFs) and MOF-derived carbons for different applications. Carbon is widely used in the structure of electrodes of electrochemical energy conversion/storage devices. In order to control the pore size distribution of such carbons, the pyrolysis of MFOs under inert atmosphere was considered. MOFs are highly porous crystalline materials constructed from metal ions linked together by different organic ligands. When MOFs are pyrolysed, the resulting carbon material inherits the pore structure of the precursor MOF. By combining different metal ions and organic linkers, it is possible to create MOFs with different pore sizes. In this research, we aimed to take advantage of this property and derive carbons from MOFs to produce porous carbons with controlled pore size distributions and evaluate their behaviour in electrochemical energy conversion/storage devices to improve the performance of the latter. Three different MOFs were selected in terms of their pore sizes (ZIF-8, MOF-5 and MIL-100(Fe)) and were hydrothermally synthesised and characterised with Brunauer–Emmet–Teller (BET) and powder X-ray diffraction. These MOFs were then carbonised under an argon atmosphere and characterised with BET and energy dispersive spectroscopy analysis. The electrocatalyst was made by loading platinum on the carbonised ZIF-8 and characterised with EDS to measure the amount of platinum loaded and assess the homogeneity of the platinisation process for fuel cell application. The Pt/CZIF-8 was electrochemically characterised by cyclic voltammetry, oxygen reduction reaction and durability tests to evaluate its electrochemical behaviour. For the supercapacitor applications, all MOF-derived carbons were characterised by cyclic voltammetry and the cyclic charge–discharge curve. The separation ability of the MOFs was also assessed by immersion calorimetry, and when any unexpected behaviour was observed, the assessment was applied to the replica MOF (carbonised MOFs), and their behaviour was observed. After evaluating the results, the best MOF/carbonised MOF for each application was introduced. Four different MOFs, ZIF-8, HKUST, UiO-66 and UiO-67, were synthesised and characterised with BET and X-ray diffraction, and their separation ability was investigated using immersion calorimetry in xylene isomers. Since HKUST and UiO-66 had unexpected adsorption behaviour, the replicas of these MOFs were also produced under argon, and their separation ability was evaluated in m-xylene.

Ever since the development of farming humans have been implicitly linked with the landscape. Influences include the manipulation of natural environments by woodland clearance, field developments and animal husbandry. Development can also be determined by the identification and distribution of soils developed and modified by the addition of organic and inorganic components. Anthropogenic or amended soils have been identified in many forms across north west Europe that retain distinctive physical and chemical indications of historical agrarian and settlement history. This thesis researched the on-site distribution of anthropogenic and amended soils across different landuse areas and identified and quantified a range of black carbonised particles in order to investigate their role in the soils ability to retain high elemental concentrations of manuring and elements associated with domestic activity and industrial processes. Three sites in contrasting environments were chosen for analysis; in Fair Isle, the Netherlands and Ireland on the basis of an excellent agararian and settlement history and previous analysis of anthropogenic soils. The fieldwork results showed extremly deep plaggen soils in the Netherlands but considerably shallower horizons of amended arable soils on Fair Isle and in Ireland contrary to previous analysis. There was however, clear evidence of a reduction in anthropogenic and amended soils with increased distance from the farm centres as a result of less manuring. The soil pH, organic matter, particle size, magnetic susceptibility and bulk elemental analysis results showed unexpected increases in the amended soils of Fair Isle and Ireland and reflected a similar manuring process. In the Netherlands the deep plaggen soils had very low results reflecting modern arable farming. The micromorphology results illustrated distinctive characteristics associated with localised manuring techniques. On Fair Isle and in Ireland the main organic manuring material was peat and burnt peat, whereas in the Netherlands the plaggen soils were predominantly composed of meadowland and heathland turf. At all three sites there was a large number of black carbonised and black amorphous inclusions and point counting and image analysis results showed a decrease with depth and distance from settlement nucleii mirroring the fieldwork observations. The elemental analysis conducted has proved to be an extremly useful tool for the identification of various forms of black carbon and for identifying the provenance of high elemental concentrations. The oxygen:carbon ratios confirmed the origins of organic components used in the development of the amended and anthropogenic soils and the elemental analysis showed that at each site over 80% of visually unidentifiable amorphous black carbon particles were heavily decomposed carbonised inclusions. Overall the elemental concentrations within the black carbonised particles was very low but this reflected the elemental results found in the bulk soils and the inclusions contained higher concentrations of P, Ca, K, Fe and Al and considerably lower concentrations of elements associated with domestic activity or industry Zn, Cu, Ba, Cr, As and Pb.

Kyoto University (京都大学)<br>0048<br>新制・課程博士<br>博士(農学)<br>甲第13127号<br>農博第1632号<br>新制||農||942(附属図書館)<br>学位論文||H19||N4253(農学部図書室)<br>UT51-2007-H400<br>京都大学大学院農学研究科森林科学専攻<br>(主査)教授 今村 祐嗣, 教授 矢野 浩之, 教授 杉山 淳司<br>学位規則第4条第1項該当

<p>Pitches are used on a large scale in the manufacture of carbon anodes for the production of primary aluminium. The role of the pitch is to act as a binder between the petroleum coke grains. The structure of the carbonized pitch binder (pitch coke) has an important impact on the overall performance of the anode. Even though the binder pitch is the minor constituent in an anode, it is impossible to make a good quality anode without a good quality binder pitch.</p><p>Pitch is an extremely complex mixture of numerous, essentially aromatic and heterocyclic compounds derived from pyrolysis of organic material or tar distillation. Upon heat treatment pitches form cokes in relatively high yields. Physical and chemical properties of the anode such as mechanical strength, electrical resistivity, thermal conductivity and resistance towards oxidation by air and CO2 are dependent on the structure of the aggregate material as well as the carbonized binder pitch. The properties of the pitch coke is in turn mainly dependent on the chemical characteristics of the parent pitch.</p><p>Coal-tar pitch is the preferred choice of binder material in anode manufacture today. However, the availability of high quality coal-tar is in decline and at least partial replacement by alternative binder sources will become increasingly important in the future. Due to environmental regulations, petroleum pitches are interesting as they generally have lower PAH emissions than coal-tar pitches during baking. Blends of coal-tar pitches and petroleum pitches are in use today on an industrial scale. The aluminium industry must be prepared to meet the challenges involved in adapting binder pitches from new sources which may be of inferior quality to the pitches available on the market today. An increased understanding of the processes involved in the transformation of a pitch into a coke and the link between raw material composition and properties and the final artifact is thus highly relevant.</p><p>Traditionally, the suitability of a binder pitch for use in anodes, has been defined from parameters like softening point, insolubility in toluene (TI) and quinoline (QI), coke yield, H/C atomic ratio, ash content and density. Although these parameters, which are mostly empirical in nature, give an indication of the pitch quality, more information on the chemical characteristics and carbonization behavior of pitches is certainly valuable. The present work aims to describe and explain the link between “classical” pitch properties, hydrogen transfer properties, information derived from NMR spectroscopy and the structure of the carbonized binder pitch.</p><p>Coal-tar and petroleum pitches pass through a fluid stage during carbonization. In the early stages of carbonization, free radicals are formed due to thermal rupture of C-C and C-H bonds in reactive components. Polymerization occurs mainly via a free radical mechanism leading to molecular size enlargement (aromatic growth)and the formation of oligomeric systems (mesogens). If the intermolecular reactivity of the pitch constituents is too high, extensive cross-linking and a rapid transformation of pitch molecules through polymerization will occur at a relatively low temperature. In this case, either mesophase will not be formed or the growth and coalescence of mesophase will take place under low fluidity/high viscosity conditions leading to a premature solidification of the pyrolysis system. An isotropic coke or a pitch coke of small optical domains will then be formed. On the other hand, if the pitch has a low thermal reactivity, aromatic growth is constrained and the mesogens will have sufficient mobility to stack parallel to each other and establish a liquid crystal system (mesophase). The growth and coalescence of mesophase take place at a higher temperature where the viscosity of the pyrolysis system is at a low level. Eventually, the system will solidify and an anisotropic coke of large well-developed optical domains is formed.</p><p>In particular, the presence of alkyl side chains and oxygenated functional groups are considered to lead to an increased thermal reactivity. If free radicals formed by thermal rupture of bonds in reactive pitch species can be stabilized by hydrogen transfer from within the system, extensive cross-linking at a too early stage is prevented. The initiation, growth and coalescence of mesophase are facilitated and consequently a coke of large well-developed optical domains is formed. Hydroaromatic rings and naphthenic rings in hydroaromatic species are considered to be principal hydrogen donor groups. Oxygen acceptor sites are believed to deplete the supply of donatable hydrogen and leave radicals free to recombine. The thermal reactivity of a pitch is thus dependent on both the amount of reactive species and the ability of the pitch to stabilize free radicals by hydrogen transfer.</p><p>In the present work, the subject of study was five coal-tar pitches and four petroleum pitches. In addition, a QI-free coal-tar pitch supplied by GrafTech International was studied. The pitches were characterized by 1H NMR and 13C NMR spectroscopy, hydrogen transfer properties, elemental analysis and the release of volatiles during carbonization. In addition, the pitches were characterized by more “traditional” pitch parameters like insolubility in quinoline (QI), insolubility in toluene (TI), softening point and coking value. The structure of the carbonized pitches was examined by optical microscopy and X-ray diffraction.</p><p>The hydrogen transfer properties of the pitches were evaluated from their ability to donate hydrogen to an acceptor compound, anthracene, or abstract hydrogen from a donor compound, 1,2,3,4-tetrahydronaphthalene (tetralin). A mixture of pitch and anthracene or tetralin was heat treated in sealed glass tubes filled with argon gas at 400 ºC. Two different heat treatment procedures were tested. In the first, the sample was kept at 400 ºC for 8 hours while in the second, the sample was heated at a rate of 5 ºC/min to 400 ºC with no soaking time. The major hydrogenated products from the reaction between anthracene and pitch were 9,10-dihydroanthracene (DHA) and 1,2,3,4-tetrahydroanthracene (THA). After the reaction, the semi-coke residue was dissolved in carbon disulphide and analyzed by gas chromatography. The hydrogen donor ability (HDa) was calculated from the amounts of DHA and THA formed and expressed as milligrams of hydrogen transferred to anthracene per gram of pitch. For the hydrogen donor ability test, the less severe heat treatment (5ºC/min to 400 ºC, no soaking time) was found to be the most appropriate. The reaction between tetralin and pitch gave one major dehydrogenated product, naphthalene. The hydrogen acceptor ability (HAa) was calculated from the ratio of naphthalene to tetralin as determined by gas chromatography and expressed as milligrams of hydrogen transferred per gram of pitch. For the acceptor ability test, the heat treatment at 400 ºC with 8 hours soaking time was found to be the most appropriate.</p><p>The release of volatiles during carbonization was studied by thermogravimetric analysis. The amount of volatiles released between 300 and 500 ºC (VM300-500)relative to the total amount of volatiles released at 1000 ºC was selected as a parameter reflecting the thermal behavior of pitches during the critical stages of carbonization.</p><p>Carbonization of pitches was performed under inert gas pressure (15 bar) and the green cokes obtained at 550 ºC were studied by optical microscopy. Computerized image analysis was performed to quantify the optical texture. The output parameters from the image analysis were the mosaic index, which is a measure of the optical domain size, and the fiber index, which is a measure of the parallel alignment of optical domains. The green cokes were further heat treated to 1150 ºC and the microstructure of the resulting calcined pitch cokes was characterized by X-ray diffraction.</p><p>The carbon disulphide soluble part of the pitches was investigated by 1H NMR and 13C NMR spectroscopy. Results from elemental analysis of the pitches were used in conjunction with the results obtained from the NMR spectroscopy. The main objective of the NMR analysis was to identify and quantify structures in the pitch which are considered either to increase or decrease the thermal reactivity. The coal-tar pitches were as expected found to be more aromatic than the pitches of petroleum origin. A relationship was found between the aromaticity of the pitches and the H/C atomic ratio as determined from elemental analysis. Elemental analysis is a rapid and convenient method to estimate the aromaticity of pitches. Due to a more hydroaromatic structure, the petroleum pitches were in general found to have a higher estimated concentration of donatable hydrogen which will suppress intermolecular reactivity. However, the petroleum pitches also had a high concentration of alkyl side chains which are generally believed to give increased thermal reactivity. Carbon connected to oxygen could not be distinguished in the NMR spectra. Pitch constituents containing heteroatoms are generally concentrated in the heavier pitch fractions which may not be soluble in carbon disulphide. This could be an explanation for the failure in the detection of aromatic carbon connected to heteroatoms. However,the oxygen content was determined by elemental analysis.</p><p>The pitches could be distinguished due to their ability to donate hydrogen to anthracene or abstract hydrogen from tetralin. The hydrogen donor ability was not found to correlate with the concentration of donatable hydrogen (NMR) which might have been expected. A likely explanation for this apparent inconsistency is that potential donatable hydrogen in reactive pitches will be preferentially consumed by free radicals and oxygenated acceptor sites instead of being transferred to anthracene.</p><p>A correlation between the hydrogen donor (HDa) and acceptor ability (HAa) was not found. This indicates that the two parameters represent two separate properties where both are linked to the thermal reactivity of the pitch. The ratio between the hydrogen donor and acceptor ability, HDa/HAa, was used as a parameter reflecting the thermal reactivity of pitches. Pitches which exhibit a high HDa/HAa ratio (low thermal reactivity) are expected to form an anisotropic coke of large optical domains. On the other hand, pitches with a relatively low HDa/HAa ratio are expected to have a high thermal reactivity and form a more isotropic (small optical domains) coke. Despite the higher concentration of donatable hydrogen, the petroleum pitches were not generally considered to have a lower thermal reactivity than the coal-tar pitches expressed by the HDa/HAa ratio.</p><p>The processes taking place during thermal treatment of pitches are reflected in the release of volatiles. A correlation was observed between the HDa/HAa ratio and the relative amount of volatiles released between 300 and 500 ºC (VM300-500). Thermally reactive pitches exhibiting a low HDa/HAa ratio will have a high activity at low temperatures and release low boiling point molecules and fragmentation species. If on the other hand the pitch has a low thermal reactivity, fragmentation species will be stabilized by hydrogen transfer and retained in the pyrolysis system.</p><p>The resulting thermally stable molecules of relatively low molecular weight may then act as solvating vehicles maintaining a low viscosity in the system and may also be important as hydrogen shuttling agents. When the system has reached a critical stage for mesophase growth and coalescence, these smaller thermally stable molecules (non-mesogens) are eventually released at higher temperatures.</p><p>The petroleum pitches developed cokes of relatively large optical domains (coarse mosaic). A correlation was observed between the HDa/HAa ratio and the mosaic index (size of optical texture) for the petroleum pitches. As expected, a high thermal reactivity (low HDa/HAa ratio) resulted in a pitch coke of small optical domains (high mosaic index). The HDa/HAa ratio was, however, not successful in predicting the size of optical texture in the cokes obtained from the coal-tar pitches. This was mainly due to the influence of QI material on the pitch coke structure. It is recognized that particulate matter (primary QI material) hinders the growth and coalescence of mesophase. This was found for the coal-tar pitches. Scanning electron (SEM) and polarized light microscopy images taken at a high magnification revealed how the QI particles were arranged and clustered around smaller anisotropic domains. The detrimental effect of QI material on the development of anisotropic texture in the resulting coke was demonstrated by comparing the structure of the coke obtained from a QI-free coal-tar pitch and a coal-tar pitch containing QI. The QI-free pitch developed a coke of large optical domains whereas the coke obtained from the pitch containing QI material had mainly a fine mosaic texture (small optical domains).</p><p>However, some large anisotropic domains were present in between the QI clusters. It is also not to be excluded that the QI fraction not only acts physically by obstructing the growth and coalescence of mesophase but may also be chemically active. Findings indicate that the oxygen is concentrated in the QI fraction. Solid QI particles with oxygenated functional groups or heteroatomic structures containing oxygen, which due to their large size are insoluble in quinoline, may act as acceptor sites for hydrogen thus increasing the thermal reactivity.</p><p>The average coherent stacks of the calcined (1150 ºC) pitch cokes was found to consist of between 7 and 8 graphene layers (Lc divided by d002). The average crystallite size (Lc) was fairly similar for all the calcined pitch cokes but significant differences were found. The coal-tar pitches generally developed cokes of slightly higher average crystallite sizes than the pitches of petroleum origin. The microstructure of the coal-tar pitch cokes is probably influenced by the amount and nature of the QI fraction. For the petroleum pitches there was a tendency that a high average crystallite size was connected to a more well-developed structure (larger domains) at the green coke stage.</p><p>The evaluation of hydrogen donor and acceptor abilities provides a rapid and relatively simple method to differentiate pitches which can be linked to the development of structure during carbonization. These properties thus reflect the thermal reactivity of pitches and can be connected to the release of volatiles during pyrolysis. However, for coal-tar pitches the QI content was found to be the most influential factor on the development of optical texture and must be considered in addition to the hydrogen transfer properties. Considerations on thermal reactivity from NMR spectroscopy and elemental analysis were found to generally support the results from the hydrogen donor and acceptor ability tests.</p>

Kolmaterial, såsom kolfibrer och kolskum, används som värmeisolatorer i applikationer vid höga temperaturer. För närvarande härleds dessa material från fossilbaserade källor, vilket tyder på ett behov av att hitta alternativa kandidater baserade på förnybara källor. Detta examensarbete undersökte möjligheten att använda kraftlignin som ett förnyelsebart startmaterial för framställning av kolskum med värmeisoleringsegenskaper. Två kraftligniner av barrträd med olika molekylvikter och ett kraftlignin av lövträd användes. De tre kraftligninerna karboniserades vid 1000°C efter att ha blandats i olika förhållanden och kombinationer (formuleringen av råmaterialet). Formuleringen av råmaterialet påverkade densiteten och porositeten hos de erhållna materialen, vilket i sin tur ledde till skillnader i kompressionsstyrkan och värmeledningsförmågan hos de erhållna kolskummen. Kolskummen hade olika värmeledningsförmåga (0,11-0,35 W/mK), porositet (80,55-97,53%) och densitet (0,08-0,42 g/cm3). För skummet med den högsta densiteten uppskattades krossstyrkan till cirka 10,03 MPa vilket är jämförbart med kommersiellt använda kolskum för högtemperaturisolerande applikationer. Kolskummens värmeledningsförmåga var inom omfånget för kommersiellt använda kolskum för högtemperaturapplikationer. Detta arbete visar möjligheten att tillverka kolskum från 100% kraftlignin som har liknande egenskaper som kommersiellt tillgängliga termiska isoleringsmaterial för högtemperaturapplikationer.<br>Carbon materials, such as carbon fibres and carbon foams, are used as thermal insulators in high-temperature applications. At present, these materials are derived from fossil-based sources, which suggests a need of finding alternatives candidates based on renewables. This thesis work investigated the possibility of using kraft lignin as a renewable starting material for the preparation of carbon foams with thermal insulation properties. Two softwood kraft lignins with different molecular weights and a hardwood kraft lignin were used. The three kraft lignins were carbonized at 1000°C after being mixed in different ratios and combinations (precursor formulation). The precursor formulation affected the density and porosity of the obtained materials, which in turn led to differences in compression strength and thermal conductivity of the carbon foams derived. The obtained carbon foams had different thermal conductivities (0.11-0.35 W/mK), porosity (80.55-97.53%) and density (0.08-0.42 g/cm3). For the foam with the highest density, the crushing strength was estimated to approximately 10.03 MPa which is comparable to commercially used carbon foams for high-temperature insulating applications. The thermal conductivity of the prepared carbon foams was in the range of commercially used carbon foams for high-temperature applications. This work demonstrates the possibility of preparing carbon foams from 100% kraft lignin which has properties similar of commercially available insulating materials for high-temperature applications.

Kyoto University (京都大学)<br>0048<br>新制・課程博士<br>博士(農学)<br>甲第14954号<br>農博第1795号<br>新制||農||976(附属図書館)<br>学位論文||H21||N4503(農学部図書室)<br>27392<br>UT51-2009-M868<br>京都大学大学院農学研究科森林科学専攻<br>(主査)教授 今村 祐嗣, 教授 中野 隆人, 教授 渡邊 隆司<br>学位規則第4条第1項該当

Kyoto University (京都大学)<br>0048<br>新制・課程博士<br>博士(農学)<br>甲第13138号<br>農博第1643号<br>新制||農||943(附属図書館)<br>学位論文||H19||N4264(農学部図書室)<br>UT51-2007-H411<br>京都大学大学院農学研究科森林科学専攻<br>(主査)教授 今村 祐嗣, 教授 中野 隆人, 教授 橋本 弘藏<br>学位規則第4条第1項該当

Hydrothermally treated biomass could not only be used as a fuel or a fertilizer but it can also be refined into high-value products. Activated carbons are one of those. In the studies of this thesis, four different hydrothermally carbonized (HTC) biomasses, including horse manure, grass cuttings, beer waste and biosludge, have been successfully made into activated carbons. The activated carbon materials were in the forms of powdered activated carbons, powdered composites of activated carbon and iron oxide nano-crystals, and activated carbon discs. The HTC biomasses and the activated carbons were characterized and analyzed using several methods. The biomasses were carbonized to different extent during the hydrothermal treatment, which depended on the different natures of the biomasses. The HTC biomasses were activated into powdered activated carbons by both physical activation, using CO2, and by chemical activation, using H3PO4. Full factorial design matrices were applied to design experiments and study the influence of different parameters used during both physical and chemical activation. Activated carbons with embedded iron oxide nanoparticles were synthesized through hydrothermal carbonization followed by CO2 activation. These composites had high surface areas and showed a strong magnetism, and the powders could be separated from liquid phase by applying a magnetic field. Strong and dense activated carbon discs were also prepared from powdered HTC beer waste by pulsed current processing (PCP) and a subsequent CO2 activation procedure. The potential for carbon dioxide separation from nitrogen, and methylene blue adsorption in aqueous solution, were assessed for the powdered activated carbons produced from HTC biomasses. They showed good performance in both applications.<br><p>At the time of the doctoral defense, the following paper was unpublished and had a status as follows: Paper 1: In press.</p>