On how mild oxidation affects the structure of carbons: Comparative analysis by different techniques

Abstract Understanding how the structure of carbonaceous materials changes upon oxidation at mild temperature as a function of the graphitic order is of great importance for the development of clean combustion technologies, such as carbon fuel cells. The micro- and nanostructures of a range of carbon materials at room temperature and upon mild oxidation at 300 °C have been analysed by means of mercury porosimetry, Nitrogen adsorption, X-Ray Diffraction, Raman spectroscopy and Electron Paramagnetic Resonance. The samples included carbons with increasing level of graphitic order: three chars derived from two bituminous coals and a lignite, a synthetic carbon and a graphitized coke. The experimental characterization allows to classify the materials according to different structural parameters, including porosity, surface area, degree of graphitization and paramagnetic activation of the carbonaceous surface. A correlation with the rank of the analysed materials is observed. For the graphitized coke, oxidation leads to more crystalline order and enhancement of the paramagnetic signal. A similar increase in the paramagnetic activity is observed for the Lignite char. On the other hand, for the higher rank, bituminous and synthetic chars, mild oxidation leads to a slight expansion of the amorphous carbon and loss of paramagnetic activity. The differences are rationalized in terms of formation of new carbon-oxygen complexes on the graphitized coke and on the Lignite char, and redistribution of already existing complexes for the higher-rank coals. This investigation complements previous X-ray photoelectron spectroscopy measurements

Fragmentation of biomass-templated CaO-based pellets

The use of biomass templating materials with a cheap production method as an enhanced sorbent for CO2 uptake has been proposed recently. However, the attrition and fragmentation behaviour of this type of material, which is a vital parameter for calcium looping sorbents, has not yet been investigated in detail. In this work the fragmentation behaviour of biomass-templated sorbents is investigated. Three types of materials were prepared using a mechanical pelletiser: 1. lime and cement (LC); 2. lime and flour (LF); and 3. lime, cement and flour (LCF). These samples were heat treated in a pressurised heated strip reactor (PHSR) and in a bubbling fluidised bed (BFB) and changes in particle size distribution were measured to assess fragmentation. Results indicated that the addition of biomass enhances the propensity to undergo fragmentation. Upon heat treatment in the PHSR the particle size of LC was not modified significantly; on the contrary the mean particle diameter of LF decreased from 520 μm to 116 μm and that of LCF from 524 μm to 290 μm. Fragmentation tests in the BFB confirmed the trend: 67% of the particles of LF fragmented, against 53% of LCF and 18% of LC samples. The addition of cement to the LF samples partially counteracts this performance degradation with respect to attrition. However, calcium aluminate pellets (LC) showed the lowest rate of fragmentation amongst all of the samples tested

Predictors of abdominal pain severity in patients with constipation-prevalent irritable bowel syndrome

Symptoms of irritable bowel syndrome (IBS) have been associated to altered colonic motility and sensation. Smoking affects pain perception and is a risk factor in the development of post-infectious IBS, but its effect on abdominal pain and colonic transit remains to be elucidated in IBS. Forty patients with IBS-C and 28 with IBS-M were selected based on Rome IV criteria. Colonic transit time was studied and smoking habit was recorded. Presence of mild or severe abdominal pain and the prevalent pain characteristics (diffuse or localized, chronic or acute, with cramps or gradually distending) were recorded. Data were analyzed by univariate and stepwise multiple logistic regression analysis to verify the risk association between pain and all other variables. IBS-C patients had a longer transit time in the right colon and scored more chronic pain than IBS-M patients. When severity of abdominal pain was used as discriminating factor, a significant number of subjects reporting severe pain were males and smokers (16/30 vs. 4/38 and 20/30 vs. 4/38, both ƿ <0.001). Multivariate analysis confirmed that smoking was an independent factor associated with severe abdominal pain (OR 14.3, CI 2-99, p=0.007). Smoking was not associated with colonic transit times and colonic transit was not associated with IBS symptoms' severity (both ƿ =N.S.) Smoking was the only factor independently associated with severe abdominal pain. As smoking does not seem to affect colonic transit time, we suggest that smoking may influence visceral perception and symptoms severity in IBS patients

Dependency of the combustion behavior of energy grass and three other types of biomass upon lignocellulosic composition

The combustion characteristics of four kinds of biomass fuels (energy grass, sawdust, corn cob, and walnut shell) are investigated in this article. All the samples are heated from room temperature to 800°C at multiple heating rates of 10, 20, and 30°C/min. The effect of hemicellulose, cellulose, and lignin components on the pyrolysis and combustion processes of energy grass is explored by comparison to those of the other three types of biomass. The hemicellulose and cellulose content of samples could improve the devolatilization performance during biomass combustion. Furthermore, the comprehensive combustion index suggested herein indicates that the combustion performance of energy grass or walnut shell is limited by their high ash content or their low ratio of cellulose to lignin. Kinetic parameters are obtained by combining the isoconversional method (OFW and KAS models) and the method of master-plots. The apparent activation energy of the devolatilization stage is higher than that of the char oxidization stage, which is mainly influenced by the lignocellulosic composition

LES and RANS of air and oxy-coal combustion in a pilot-scale facility: predictions of radiative heat transfer

The development of carbon capture and storage (CCS) technology is important to permit the use of fossil fuels while honouring commitments to curb greenhouse gas emissions. Coal is a valuable global resource, which is widely available around the world, however its detrimental e ect on climate change will limit its use in a future with strict controls over carbon emissions. Oxyfuel combustion is a promising CCS technology that is being actively pursued in the development of large scale demonstration projects. Under the oxyfuel process for CCS, the combustion gas is replaced with a mixture of recycled ue gas and enriched oxygen. The resulting combustion environment can vary signi cantly from traditional air- red combustion. The development of modelling capabilities will greatly improve the optimisation process to develop oxyfuel technology into an economically viable prospect. This study evaluates the use of large eddy simulation (LES) and Reynoldsaveraged Navier Stokes (RANS) models on the prediction of thermal radiation during coal combustion for both air- red and oxyfuel operation in a pilot-scale 250 kWth furnace. The furnace is part of the UKCCSRC Pilot-scale Advanced Capture Technology (PACT) facilities and was designed for detailed analysis of the combustion process. Two radiation models were evaluated during the RANS calculations, the widely used weighted sum of grey gases (WSGG) andthe full-spectrum correlated k (FSCK) model, while the LES case was calculated using the FSCK radiation model. The results show that the LES solutions are in better agreement with measured values than the RANS predictions for both air- red and oxyfuel coal combustion, however LES demands considerably more computational resources

Thermogravimetric and reaction kinetic analysis of biomass samples from an energy plantation

The products of a Hungarian experimental plantation for energy crops were investigated. Young shoots of poplar clones (Populus x euramericana and Populus x interamericana), black locust (Robinia pseudoacacia), willow (Salix alba), and an herbaceous plant (Miscanthus sinensis) revealed unexpectedly similar thermal behavior in inert and oxidative atmospheres, as well. An 8-fold difference in the level of grinding did not result in substantial differences in the thermal decomposition. The effect of oxygen in the ambient gas was studied at low sample masses (0.2-0.4 mg) that excluded the overheating due to the high reaction heat of the combustion process. The presence of oxygen affects the decomposition from ca. 220 degreesC. Nevertheless, the extrapolated onset temperature of the hemicellulose decomposition is practically the same at 0, 5, and 21 V/V% oxygen. A group of 12 experiments, representing two grinding levels, three plant genera and four different heating programs were evaluated simultaneously by the method of least squares employing the model of independent pseudocomponents. All evaluated experiments were well described by the same set of kinetic parameters; only the parameters describing the peak area of the partial processes differed. A technique was recommended for the appropriate handling of the nonrandom errors in the simultaneous evaluation of experiment series