Emissions of NO(x) and SO(2) from Coals of Various Ranks, Bagasse, and Coal-Bagasse Blends Burning in O(2)/N(2) and O(2)/CO(2) Environments

Oxy-coal combustion is a viable technology, for new and existing coal-fired power plants, as it facilitates carbon capture and, thereby, can mitigate climate change. Pulverized coals of various ranks, biomass, and their blends were burned to assess the evolution of combustion effluent gases, such as NO(x), SO(2), and CO, under a variety of background gas compositions. The fuels were burned in an electrically heated laboratory drop-tube furnace in O(2)/N(2) and O(2)/CO(2) environments with oxygen mole fractions of 20%, 40%, 60%, 80%, and 100%, at a furnace temperature of 1400 K. The fuel mass flow rate was kept constant in most cases, and combustion was fuel-lean. Results showed that in the case of four coals studied, NO(x) emissions in O(2)/CO(2) environments were lower than those in O(2)/N(2) environments by amounts that ranged from 19 to 43% at the same oxygen concentration. In the case of bagasse and coal/bagasse blends, the corresponding NO(x) reductions ranged from 22 to 39%. NO(x) emissions were found to increase with increasing oxygen mole fraction until similar to 50% O(2) was reached; thereafter, they monotonically decreased with increasing oxygen concentration. NO(x) emissions from the various fuels burned did not clearly reflect their nitrogen content (0.2-1.4%), except when large content differences were present. SO(2) emissions from all fuels remained largely unaffected by the replacement of the N(2) diluent gas with CO(2), whereas they typically increased with increasing sulfur content of the fuels (0.07-1.4%) and decreased with increasing calcium content of the fuels (0.28-2.7%). Under the conditions of this work, 20-50% of the fuel-nitrogen was converted to NO(x). The amount of fuel-sulfur converted to SO(2) varied widely, depending on the fuel and, in the case of the bituminous coal, also depending on the O(2) mole fraction. Blending the sub-bituminous coal with bagasse reduced its SO(2) yields, whereas blending the bituminous coal with bagasse reduced both its SO(2) and NO(x) yields. CO emissions were generally very low in all cases. The emission trends were interpreted on the basis of separate combustion observations.

Emissions from the premixed combustion of gasified polyethylene

An investigation was conducted on pollutants emitted from steady-state, steady-flow gasification and combustion of polyethylene (PE) in a two-stage furnace. The polymer, in pulverized form, was first pyrolyzed at 1000 degrees C, and subsequently, its gaseous pyrolyzates were burned, upon mixing with air at high temperatures (900-1100 degrees C). The motivation for this indirect type of burning PE was to attain nominally premixed combustion of the pyrolyzate gases with air, thereby achieving lower pollutant emissions than those emanating from the direct burning of the solid PE polymer. This work assessed the effluents of the two-stage furnace and examined the effects of the combustion temperature, as well as the polymer feed rate and the associated fuel/air equivalence ratio (0.3 < phi < 1.4). It was found that, whereas the yield of pyrolysis gas decreased with an increasing polymer feed rate, its composition was nearly independent of the feed rate. CO2 emissions peaked at an equivalence ratio near unity, while the CO emissions increased with an increasing equivalence ratio. The total light volatile hydrocarbon and semivolatile polycyclic aromatic hydrocarbon (PAH) emissions of combustion increased with an increasing equivalence ratio. The generated particulates were mostly submicrometer in size. Overall, PAH and soot emissions from this indirect burning of PE were an order of magnitude lower than corresponding emissions from the direct burning of the solid polymer, obtained previously in this laboratory using identical sampling and analytical techniques. Because pyrolysis of this polymer requires a nominal heat input that amounts to only a diminutive fraction of the heat released during its combustion, implementation of this technique is deemed advantageous.

Reaction rate and product morphology in carbon composite iron ore pellets with and without Portland cement

The aim of this work is to study the reaction rate and the morphology of intermediate reaction products during iron ore reduction when iron ore and carbonaceous materials are agglomerated together with or without Portland cement. The reaction was performed at high temperatures, and used small size samples in order to minimise heat transfer constraints. Coke breeze and pure graphite were the carbonaceous materials employed. Portland cement was applied as a binder, and pellet diameters were in the range 5.6-6.5 mm. The experimental technique involved the measurement of the pellet weight loss, as well as the interruption of the reaction at different stages, in order to submit the partially reduced pellet to scanning electron microscopy. The experimental temperature was in the range 1423-1623 K, and the total reaction time varied from 240 to 1200 s. It was observed that above 1523 K the formation of liquid slag occurred inside the pellets, which partially dissolved iron oxides. The apparent activation energies obtained were 255 kJ mol(-1) for coke breeze containing pellets, and 230 kJ mol(-1) for those pellets containing graphite. It was possible to avoid heat transfer control of the reaction rate up to 1523 K by employing small composite pellets.

Alterations in energy properties of eucalyptus wood and bark subjected to torrefaction: The potential of mass loss as a synthetic indicator

Torrefaction is a mild pyrolysis process (usually up to 300 degrees C) that changes the chemical and physical properties of biomass. This process is a possible pre-treatment prior to further processes (transport, grinding, combustion, gasification, etc) to generate energy or biofuels. In this study, three eucalyptus wood species and bark were subjected to different torrefaction conditions to determine the alterations in their structural and energy properties. The most severe treatment (280 degrees C, 5 h) causes mass losses of more than 35%, with severe damage to anatomical structure, and an increase of about 27% in the specific energy content. Bark is more sensitive to heat than wood. Energy yields are always higher than mass yields, thereby demonstrating the benefits of torrefaction in concentrating biomass energy. The overall mass loss is proposed as a relevant parameter to synthesize the effect of torrefaction conditions (temperature and duration). Accordingly, all results are summarised by analytical expressions able to predict the energy properties as a function of the overall mass loss. These expressions are intended to be used in any optimization procedure, from production in the field to the final use. (c) 2010 Elsevier Ltd. All rights reserved.

The kinetics of NO and N2O reduction over coal chars in fluidised-bed combustion

This paper presents a comprehensive and critical review of the mechanisms and kinetics of NO and N2O reduction reaction with coal chars under fluidised-bed combustion conditions (FBC). The heterogeneous reactions of NO and N2O with char/carbon surface have been well recognised as the most important processes in reducing both NOx and N2O in situ FBC. Compared to NO-carbon reactions in FBC, the reactions of N2O with chars have been relatively less understood and studied. Beginning with the overall reaction schemes for both NO and N2O reduction, the paper extensively discusses the reaction mechanisms including the effects of active surface sites. Generally, NO- and N2O-carbon reactions follow a series of step reactions. However, questions remain concerning the role of adsorbed phases of NO and N2O, and the behaviour of different surface sites. Important kinetics factors such as the rate expressions, kinetics parameters as well as the effects of surface area and pore structure are discussed in detail. The main factors influencing the reduction of NO and N2O in FBC conditions are the chemical and physical properties of chars, and the operating parameters of FBC such as temperature, presence of CO, O-2 and pressure. It is shown that under similar conditions, N2O is more readily reduced on the char surface than NO. Temperature was found to be a very important parameter in both NO and N2O reduction. It is generally agreed that both NO- and N2O-carbon reactions follow first-order reaction kinetics with respect to the NO and N2O concentrations. The kinetic parameters for NO and N2O reduction largely depend on the pore structure of chars. The correlation between the char surface area and the reactivities of NO/N2O-char reactions is considered to be of great importance to the determination of the reaction kinetics. The rate of NO reduction by chars is strongly enhanced by the presence of CO and O-2, but these species may not have significant effects on the rate of N2O reduction. However, the presence of these gases in FBC presents difficulties in the study of kinetics since CO cannot be easily eliminated from the carbon surface. In N2O reduction reactions, ash in chars is found to have significant catalytic effects, which must be accounted for in the kinetic models and data evaluation. (C) 1997 Elsevier Science Ltd.

Thermogravimetric analysis of carbon deposition over Ni/gamma-Al2O3 catalysts in carbon dioxide reforming of methane

Carbon formation on Ni/gamma-Al2O3 catalysts and its kinetics during methane reforming with carbon dioxide was studied in the temperature range of 500-700 degrees C using a thermogravimetric analysis technique. The activation energies of methane cracking, carbon gasification in CO2, as well as carbon deposition in CO2-CH4 reforming were obtained. The results show that the activation energy for carbon gasification is larger than that of carbon formation in methane cracking and that the activation energy of coking in CO2-CH4 reforming is also larger than that of methane decomposition to carbon. The dependencies of coking rate on partial pressures of CH4 and CO2 indicate that methane decomposition is the main route for carbon deposition. A mechanism and kinetic model for carbon deposition is proposed.

Carbon structure and porosity of carbonaceous adsorbents in relation to their adsorption properties

A number of carbonaceous adsorbents were prepared by carbonisation at 600 degrees C following acidic oxidation under various conditions. Effects of the chemical nature of the precursor, such as the ratio of aromatic to aliphatic carbons and oxygen content, on the chemical and structural characteristics of the resultant chars were investigated using C-13 NMR and Raman spectroscopy, respectively. The C-13 NMR spectral parameters of the coal samples show that as the severity of oxidation conditions increased, the ratio of aromatic to aliphatic carbons increased. Furthermore, it was also found that the amount of disorganised carbon affects both the pore structure and the adsorption properties of carbonaceous adsorbents. It is demonstrated that higher amount of the disorganised carbon indicates smaller micropore size. (C) 1999 Elsevier Science Ltd. All rights reserved.

Catalytic conversion to N2O to N2 over potassium catalyst supported on activated carbon

Catalytic conversion of N2O to N-2 With potassium catalysts supported on activated carbon (K/AC) was investigated. Potassium proves to be much more active and stable than either copper or cobalt because potassium possesses strong abilities both for N2O chemisorption and oxygen transfer. Potassium redispersion is found to play a critical role in influencing the catalyst stability. A detailed study of the reaction mechanism was conducted based upon three different catalyst loadings. It was found that during temperature-programmed reaction (TPR), the negative oxygen balance at low temperatures (< 50 degrees C) is due to the oxidation of the external surface of potassium oxide particles, while the bulk oxidation accounts for the oxygen accumulation at higher temperatures (below ca. 270 degrees C). N2O is beneficial for the removal of carbon-oxygen complexes because of the formation of CO2 instead of CO and because of its role in making the chemisorption of produced CO2 on potassium oxide particles less stable. A conceptual three-zone model was proposed to clarify the reaction mechanism over K/AC catalysts. CO2 chemisorption at 250 degrees C proves to be an effective measurement of potassium dispersion. (C) 1999 Academic Press.

Effects of acid treatments of carbon on N2O and NO reduction by carbon-supported copper catalysts

The influences of HCl, HNO3 and HF treatments of carbon on N2O and NO reduction with 20 wt% Cu-loaded activated carbon were studied. The order of activity in both N2O and NO is as follows: Cu20/AC-HNO3>Cu20/AC>Cu20/AC-HF>Cu20/AC-HCl. The same sequence was also observed for the amount of CO2 evolved during TPD experiments of supports acid for the catalyst dispersion. On the other hand, N2O exhibited a higher reaction rate than NO and a higher sensitivity to acid treatments, and the presence of gas-phase O-2 had opposite effects in N2O and NO reduction. The key role of carbon surface chemistry is examined to rationalize these findings and the relevant mechanistic and practical implications are discussed. The effects of oxygen surface groups on the pore structure of supports and catalysts are also analyzed, (C) 2000 Elsevier Science Ltd. All rights reserved.

Determination of activation energy distributions for chemisorption of oxygen on carbon: an improved approach

The present paper proposes an approach to obtaining the activation energy distribution for chemisorption of oxygen onto carbon surfaces, while simultaneously allowing for the activation energy dependence of the pre-exponential factor of the rate constant. Prior studies in this area have considered this factor to be uniform, thereby biasing estimated distributions. The results show that the derived activation energy distribution is not sensitive to the chemisorption mechanism because of the step function like property of the coverage. The activation energy distribution is essentially uniform for some carbons, and has two or possibly more discrete stages, suggestive of at least two types of sites, each with its own uniform distribution. The pre-exponential factors of the reactions are determined directly from the experimental data, and are found not to be constant as assumed in earlier work, but correlated with the activation energy. The latter results empirically follow an exponential function, supporting some earlier statistical and experimental work. The activation energy distribution obtained in the present paper permits improved correlation of chemisorption data in comparison to earlier studies. (C) 2000 Elsevier Science Ltd. All rights reserved.

Opposite roles of O-2 in NO- and N2O-carbon reactions: An ab initio study

Previous experimental studies showed that the presence of O-2 greatly enhances NO-carbon reaction while it depresses N2O-carbon reaction on carbon surfaces. A popular explanation for the rate increase is that the addition of O-2 results in a large number of reactive carbon-oxygen complexes, and decomposition of these complexes produces many more active sites. The explanation for the latter is that excess O-2 simply blocks the active sites, thus reducing the rate of N2O-carbon reaction. The contradiction is that O-2 can also occupy active sites in NO-carbon reaction and produce active sites in N2O-carbon reduction. By using ab initio calculation, we find that the opposite roles of O-2 are caused by the different manners of N2O and NO adsorption on the carbon surface. In the presence of excess O-2, most Of the active sites are occupied by oxygen groups. In the competition for the remaining active sites, NO is more likely to chemisorb in the form of NO2 and NO chemisorption is mon thermodynamically favorable than O-2 chemisorption. By contrast, the presence of excess O-2 makes N2O chemisorption much less thermally stable either on the consecutive edge sites or edge sites isolated by semiquinone oxygen. A detailed analysis and discussion of the reaction mechanism of N-2 formation from NO- and N2O-carbon reaction in the presence of O-2 is presented in this paper.

Determination of T1pH relaxation rates in charred and uncharred wood and consequences for NMR quantitation

The performance of three different techniques for determining proton rotating frame relaxation rates (T1pH) in charred and uncharred woods is compared. The variable contact time (VCT) experiment is shown to over-estimate T1pH, particularly for the charred samples, due to the presence of slowly cross-polarizing C-13 nuclei. The variable spin (VSL) or delayed contact experiment is shown to overcome these problems; however, care is needed in the analysis to ensure rapidly relaxing components are not overlooked. T1pH is shown to be non-uniform for both charred and uncharred wood samples; a rapidly relaxing component (T1pH = 0.46-1.07 ms) and a slowly relaxing component (T1pH = 3.58-7.49) is detected in each sample. T1pH for each component generally decreases with heating temperature (degree of charring) and the proportion of rapidly relaxing component increases. Direct T1pH determination (via H-1 detection) shows that all samples contain an even faster relaxing component (0.09-0.24 ms) that is virtually undetectable by the indirect (VCT and VSL) techniques. A new method for correcting for T1pH signal losses in spin counting experiments is developed to deal with the rapidly relaxing component detected in the VSL experiment. Implementation of this correction increased the proportion of potential C-13 CPMAS NMR signal that can be accounted for by up to 50% for the charred samples. An even greater proportion of potential signal can be accounted for if the very rapidly relaxing component detected in the direct T1pH determination is included; however, it must be kept in mind that this experiment also detects H-1 pools which may not be involved in H-1-C-13 cross-polarization. (C) 2002 Elsevier Science (USA).

Characterization of pore wall heterogeneity in nanoporous carbons using adsorption: the slit pore model revisited

In this paper, we propose a new nonlocal density functional theory characterization procedure, the finite wall thickness model, for nanoporous carbons, whereby heterogeneity of pore size and pore walls in the carbon is probed simultaneously. We determine the pore size distributions and pore wall thickness distributions of several commercial activated carbons and coal chars, with good correspondence with X-ray diffraction. It is shown that the conventional infinite wall thickness approach overestimates the pore size slightly. Pore-pore correlation has been shown to have a negligible effect on prediction of pore size and pore wall thickness distributions for small molecules such as argon used in characterization. By utilizing the structural parameters (pore size and pore wall thickness distribution) in the generalized adsorption isotherm (GAI) we are able to predict adsorption uptake of supercritical gases in BPL and Norit RI Extra carbons, in excellent agreement with experimental adsorption uptake data up to 60 MPa. The method offers a useful technique for probing features of the solid skeleton, hitherto studied by crystallographic methods.

An electron microscopic study of nickel sulfide inclusions in toughened glass

It has been known since the early sixties that nickel sulfide inclusions cause spontaneous fracture of toughened (thermally tempered) glass, but despite the considerable amount of work done on this problem in the last four decades, failures still occur in the field with regularity. In this study we have classified (by viewing through a 60x optical microscope) inclusions into two groups, which are classic and atypical nickel sulfides. The classics look like the nickel sulfide inclusions found at the initiation-of-fracture of windows that have broken spontaneously. We have compared the structure and composition of the atypical inclusions with the structure and composition of the classics. All of the classic and atypical nickel sulfide inclusions studied in this work were found to have a composition in the range of Ni52S48 to Ni48S52. Inclusions on the nickel rich side of stoichiometric NiS were found to be two-phase assemblies, and inclusions on the sulphur rich side of NiS were single phase. It had been proposed that the atypicals were passive, and of a different composition to the classics. However, we found that the difference between passive and dangerous nickel sulfide inclusions was not a difference in composition but rather a difference in the type of material in the internal pore space. The passive's had carbon char in their internal pore space, whereas the pore space of dangerous inclusions contained Na2O. The presence of Na2O and carbon char with the inclusions indicates that the formation of the inclusions results from a reaction of a nickel-rich phase with sodium sulphate and carbon. (C) 2001 Kluwer Academic Publishers.