Biomass as a reburning fuel: a specialized cofiring application

Reaction Engineering International has performed a series of combustion tests to evaluate the potential for utilizing wood biomass as a reburn fuel for nitrogen oxides (NO_x) control. Reburning is an effective NO_x reduction technology that utilizes fuel injection above the main burner zone. Studies with other hydrocarbon fuels such as coal and natural gas as reburn fuels have shown that NO_x emissions can be reduced by more than 50–60% with about 15% of the heat input coming from the reburn fuel. Two different biomasses, a hardwood and softwood, were evaluated as reburning fuels and compared to coal and natural gas. The use of wood to reduce NO_x is attractive for several reasons. First, wood contains little nitrogen, as compared with coal which is also used as a reburning fuel. This results in lower NO_x production from fuel nitrogen species for wood. In addition, wood contains virtually no sulfur, so sulfur dioxide (SO₂) emissions are reduced in direct proportion to the coal replacement. Wood is a regenerable biofuel; when a fossil fuel is replaced by a biofuel, there is a net reduction in carbon dioxide (CO₂) emissions. Finally, since the reburning fuel is normally 10–20% of the total heat input, large quantities of wood are not necessary. Experimental results showed NO_x reductions of as high as 70% were obtained with approximately 10–15% wood heat input. The stoichiometric ratio in the reburn zone was the single most important variable affecting NO_x reduction. The highest reductions were found at a reburn stoichiometric ratio of 0.85. NO_x reduction fell to about 40–50% at slightly higher stoichiometric ratios (0.9x reduction was strongly dependent on initial NO_x concentration and only slightly dependent upon temperature, where increased temperature increased NO_x reduction. Finally, the experimental results suggest that wood is as effective as natural gas or coal as a reburning fuel. In addition, REI has completed computer simulations of a full-scale boiler to evaluate the conditions that maximize the NO_x reduction efficiency using biomass as the reburn fuel. Computer modeling of the TVA Allen Station Unit 3, a 265 MW_e cyclone-fired boiler, showed that NO_x reductions as high as 50–60% could be achieved within the constraints set by the boiler and operations. The most important parameters affecting final NO_x emissions are the cyclone barrel stoichiometry, residence time in the reburn zone, and mixing in both the reburn and overfire air zones. The combination of computer simulations and experimental programs has provided the engineers with the tools needed to optimize biomass as a reburn fuel to maximize NO_x reduction.     

Evaluation of usher wood and karkadeh stem for charcoal in Sudan

Two unusual biomass materials Hibiscus sabdarifja var. sabdariffa (karkadeh) stem and Calotropis procera (usher) wood were investigated in the laboratory as potential raw materials for charcoal making in Sudan. The materials were characterized physically and chemically and despite the low density and high bark-to-wood ratio by volume, good yields and quality of charcoal were predicted. The carbonization trials with a laboratory retort at conditions close to those of field metal kiln gave very good charcoal yields (35% for karkadeh and 38% for usher) with high energy transformation (58% and 62%, respectively). The karkadeh charcoal, except for a somewhat high ash content, was good for domestic uses (79% fixed carbon and 30.3 MJ kg⁻¹ heat value). The usher charcoal was better with respect to fixed carbon (86.5%) and gross heat value (32.4 MJ kg⁻¹ ). Both charcoals were of low density (140–160 kg m⁻³) and further assessment of their economic suitability should be carried out under field conditions. The carbonization by-products were also collected and characterized by means of gas chromatography.     

Reducing the minimum load and NOx emissions for lignite-fired boiler by applying a stable-flame concept

For the purpose of improving the load range and NO_x emission level of lignite-fired power plants, a new combustion technology, called NR-LE burners (NO_x Reduction-Load Extension), has been developed in co-operation between Babcock-Hitachi and Fortum. A single-burner combustion test was performed in Japan with this new NR-LE type burner using Czech lignite. Adapting the flame-stabilization ring and a special additional air-nozzle resulted in achieving a stable flame, which enables:

• The burner minimum load to be less than 50% (Boiler load: 30–40%)

• Low NO_x emissions of less than 200 mg/m³ (6% O₂, dry base)

The first commercial full-scale application of the NR-LE burner was by the IPP power producer in the Czech Republic (Sokolovská Uhelná, a.s. at Vresová Unit2 boiler with steam parameters 325 t/h, 535 °C, 13.5 MPa). The commissioning test runs of the new burners were carried out during September to October 2001. The boiler is now in commercial operation, with (i) a 30% minimum load without supplementary fuel, and (ii) lower NO_x emission levels.     

Bio-oils from arid land plants: Flash pyrolysis of Euphorbia characias bagasse

The devolatilization of the bagasse obtained by solvent extraction of dried Euphorbia characias, a bushy plant growing in arid land of the Mediterranean area, was investigated under rapid heating conditions at atmospheric pressure using a bench-scale fluidized bed pyrolyser. Particle heating rates exceeded 10⁴°C s⁻¹. Bagasse was fed continuously at the rate of 6 g h⁻¹ directly into a sand bed fluidized by nitrogen operating in the temperature range of 400°–750°C. The yields of oils, gases and chars are reported. A maximum oil yield of 44% (wt/wt) (moisture free bagasse) was obtained at 500°C. Yields of gases, CO, CO₂, C₁–C₄ hydrocarbons increased with the rise in temperature, reaching a maximum at 750°C. Elemental analyses showed that the composition of oils and chars was dependent on pyrolysis temperature. The nitrogen content is fairly high; an upgrading process could be necessary for its remotion before the use of the bio-oil as combustible. The other characteristics of oils fall in the range of oils derived from other biomass feedstocks. Chars have a high HHV (15.36 MJ kg⁻¹ at 500°C), representing a valuable fuel.     

Kinetic study on fermentation from CO2 and H2 using the acclimated-methanogen in batch culture

Methane was produced from H₂ and CO₂ using the acclimated-mixed methanogens in a 3.71 fermentor in batch culture at pH 7.2 and 37°C. The Fermentation kinetics parameter for the growth of methanogens, overall mass transfer coefficient of the reactor, and the conversion rate of H₂ and CO₂ to CH₄ by the acclimated-mixed culture were determined using the technique of Vega et al. The maximum specific growth rate (μ_max) and H₂ specific consumption rate (q_max) were found to be 0.064(h⁻¹) and 104.8 (mmol h⁻¹ g⁻¹) respectively. Monod saturation constants for growth (Kp) and for inhibition (K′p) were found to be 3.54 (kPa) and 0.57 (kPa), respectively. These findings indicate that without very low dissolved H₂ levels, the fermentations are carried out under μ_max, and the specific uptake rate (q) was almost not affected at any dissolved H₂ level in the range studied. The yield of CH₄ (Yp/s) was calculated to be 0.245 (mol CH₄ mol⁻¹ H₂), which is near the stoichiometric value of 0.25. DH₂ was also measured using the Teflon tubing method and was in good agreement with those estimated by kinetic calculations.     

Effects of pyrolyzed semi-char blend ratio on coal combustion and pollution emission in a 0.35 MW pulverized coal-fired furnace

The effects of blend ratio on combustion and pollution emission characteristics for co-combustion of Shenmu pyrolyzed semi-char (SC), i.e., residuals of the coal pyrolysis chemical processing, and Shenhua bituminous coal (SB) were investigated in a 0.35 MW pilot-scale pulverized coal-fired furnace. The gas temperature and concentrations of gaseous species (O₂, CO, CO₂, NO_x and HCN) were measured in the primary combustion zone at different blend ratios. It is found that the standoff distance of ignition changes monotonically from 132 to 384 mm with the increase in pyrolyzed semi-char blend ratio. The effects on the combustion characteristics may be neglected when the blend ratio is less than 30%. Above the 30% blend ratio, the increase in blend ratio postpones ignition in the primary stage and lowers the burnout rate. With the blend ratio increasing, NO_x emission at the furnace exit is smallest for the 30% blend ratio and highest for the 100% SC. The NO_x concentration was 425 mg/m³ at 6% O₂ and char burnout was 76.23% for the 45% blend ratio. The above results indicate that the change of standoff distance and NO_x emission were not obvious when the blend ratio of semi-char is less than 45%, and carbon burnout changed a little at all blend ratios. The goal of this study is to achieve blending combustion with a large proportion of semi-char without great changes in combustion characteristics. So, an SC blend ratio of no more than 45% can be suitable for the burning of semi-char.     

Mechanism of soot initiation in methane systems

Thermochemical and kinetic evaluations of the very rapid elementary radical reactions consuming the C₂H₂ produced in a chlorine catalyzed polymerization of CH₄ are presented. An earlier examination of the data and mechanism leading to C₂H₂ supports a methyl and chloromethyl recombination path to C₂ hydrocarbons. The relative yield of CH₃ and CH₂Cl depends on the excess of methane.

In the CH₄, system consumption of C₂ species to ultimately form benzene is shown to proceed by a stepwise addition of CH₃ radicals to C_nH_m species. When n is even the dominant species is an unsaturated polyolefin molecule. When n is odd the dominant species is a conjugated, unsaturated radical such as allyl, pentadienyl, benzyl, etc. Mono-olefins or saturated molecules are rapidly stripped to these species by radical catalyzed dehydrogenations. In the current system chloromethyl radicals are equivalent kinetically to methyl and play a dominant role. Their addition to unsaturated species produces chlorinated radicals that dechlorinate rapidly or recombine with chloromethyl to produce dichlorohydrocarbons that dehydrochlorinate very rapidly.

A very important reaction in the sequence is the isomerization of propenyl and chloropropenyl radicals to allyl and chlorallyl by a 1–3 H (or Cl) atom shift. Its high pressure Arrhenius parameters at 1300 K are estimated to be log [k(sec⁻¹)] = 13.7 − 37/θ = 13.7 - 37/0 where 0 = 2.303 RT in kcal/mol. It appears likely that benzene conversion to soot also proceeds via a CH₃/CH₂Cl radical, sequential addition mechanism.

Stoichiometry considerations applied to the product yield distribution support the role of methyl and chloromethyl predicted by the proposed mechanism. Ionic pathways are shown to be insignificant in the formation of aromatics.     

The reactions of hydrogen and carbon monoxide with surface-bound oxides on carbon

The stability of surface oxides formed on exposure of Spherocarb to oxygen has been investigated in various atmospheres (Ar, CO, and H₂) through gravimetry and mass spectrometry. Oxide complexes, formed in oxygen (2.67 Pa) at 973 or 1073 K, were exposed to 2.67 Pa of the bath gas in the temperature range 923 to 1073 K. Changes in the population of surface complexes were identified through analysis of gas evolution (principally CO) profiles during temperature-programmed desorption (TPD) of the oxides in an inert atmosphere. Oxides formed in this work display a distribution of activation energies for their decomposition, E_des, from 300 to 420 kJ mol⁻¹. Soaking of these oxides in Ar showed the frequency factor for their thermal decomposition to be 10^{14.3 ± 0.3} s⁻¹, independent of E_des. The effect of soaking in CO was essentially the same as that of Ar, and it is concluded that no significant reaction occurs under these conditions between surface oxides and CO. However, on soaking in H₂, H₂O was evolved as a result of reaction between hydrogen and the surface oxide complex

Abstract

The kinetics of the reaction between hydrogen and surface complexes are dependent on the reaction temperature and on the thermal stability of the reacting surface oxide. Less stable oxides react more readily than do more stable oxides. If all the reaction rate variation between complexes of differing thermal stability is attributed to changes in the activation energy of the reaction, the activation energy for the reaction of H₂ with complexes may be expressed as E_H = 0.5E_des − 50 kJ mol⁻¹, 348 < E_des < 408 kJ mol⁻¹. Comparison of the apparent preexponential factor for the reaction with the expected frequency factor for gas–surface-complex collision under the experimental conditions suggests that direct reaction of hydrogen with the oxygen complex may be the limiting step in the overall reaction.     

Miscanthus sinensis ‘giganteus’ production on several sites in Austria

In Austria it is planned to use Miscanthus sinensis ‘Giganteus’ as a renewable energy source. The influence of site, age of crop and time of harvest on yield, water content, nitrogen content and quality was investigated. In the first year the yield was 0.7 to 2 t dry matter ha⁻¹, in the second year 7.9 to 15.5 t ha⁻¹ and in the third year 17.4 to 24.5 t ha⁻¹. In February of the first year the water content was 40 to 50%, in the second year 34 to 49% and in the third year 24 to 38%. Sufficient precipitation (about 800 mm) in mild climates is required for high yields. On sites with more rain the water content of the plants was higher. Water and nitrogen content decreased significantly during the six week period from January to the end of February. In February of the first year the nitrogen content was 7.8 to 16.6 g kg⁻¹ dry matter, in the second year 3.7 to 6.2 g kg⁻¹ and in the third year 2.6 to 7.5 g kg⁻¹. The calorific value was as high as that of firewood (18 to 19 MJ kg⁻¹ ). The ash content exceeded firewood but was lower than that of straw. By the third year of cultivation 60 to 150 kg N ha⁻¹, 100 to 200 kg K20 ha⁻¹, 10 to 35 kg P₂ O₅ ha⁻¹, 10 to 25 kg MgO ha⁻¹ and 20 to 35 kg CaO ha⁻¹ had to be taken up by the harvest at the end of February.     

Characterization of Cu(InxGa1−x)2Se3.5 thin films prepared by rf sputtering

Cu(In_xGa_1−x)₂Se_3.5 thin films were fabricated by rf sputtering from CuIn_xGa_1−xSe₂ and Na mixture target by controlling the mixture ratio. X-ray diffraction analyses show that the structure of Cu(In_xGa_1−x)₂Se_3.5, thin films is different from chalcopyrite structure: especially, CuIn₂Se_3.5 thin films have a defect chalcopyrite structure. The lattice parameters for Cu(In_xGa_1−x)₂Se_3.5 thin film are slightly smaller than those for CuIn_xGa_1−xSe₂ thin film and linearly decreased with increasing Ga content. The optical absorption coefficients for Cu(In_xGa_1−x)₂Se_3.5, thin films exceed 2 × 10⁴ cm⁻¹ in energy region above the fundamental band edge. The band gap for Cu(In_xGa_1−x)₂Se_3.5 thin films is larger than that for CuIn.Ga_1−x2Se₂ with the same Ga content and increased with increasing Ga content.     

NOx and H2S formation in the reductive zone of air-staged combustion of pulverized blended coals

Low NO_x combustion of blended coals is widely used in coal-fired boilers in China to control NO_x emission; thus, it is necessary to understand the formation mechanism of NO_x and H₂S during the combustion of blended coals. This paper focused on the investigation of reductive gases in the formation of NO_x and H₂S in the reductive zone of blended coals during combustion. Experiments with Zhundong (ZD) and Commercial (GE) coal and their blends with different mixing ratios were conducted in a drop tube furnace at 1200°C–1400°C with an excessive air ratio of 0.6–1.2. The coal conversion and formation characteristics of CO, H₂S, and NO_x in the fuel-rich zone were carefully studied under different experimental conditions for different blend ratios. Blending ZD into GE was found to increase not only the coal conversion but also the concentrations of CO and H₂S as NO reduction accelerated. Both the CO and H₂S concentrations inblended coal combustion increase with an increase in the combustion temperature and a decrease in the excessive air ratio. Based on accumulated experimental data, one interesting finding was that NO and H₂S from blended coal combustion were almost directly dependent on the CO concentration, and the CO concentration of the blended coal combustion depended on the single char gasification conversion.Thus, CO, NO_x, and H₂S formation characteristics from blended coal combustion can be well predicted by single char gasification kinetics.     

Optimization of excess air for the improvement of environmental performance of a 150 MW boiler fired with Thai lignite

The results of an experimental study of the excess-air-dependent heat losses, as well as gaseous emissions (NO_x, SO₂ and CO), on a 150 MW boiler firing Thai lignite are discussed. The NO_x emissions were found to increase with the higher excess air ratios; the NO_x values in the flue gas (at 6% O₂) ranged from 257 to 325 ppm, whilst the excess air ratio varied from 1.06 to 1.32 at the economizer outlet. Owing to the highly-efficient operation of the flue gas desulfurization units, the SO₂ emissions from the unit were maintained at a relatively low level, 50–76 ppm for the above excess-air ratios, whereas they accounted for about 3100–3300 ppm at the inlet of the FGD units. The CO emissions were determined for the extremely low excess air ratios. Two approaches for the optimization of the excess air ratio were analyzed in this study. For the first, i.e. the conventional approach, the optimization was carried out based on minimizing the total excess-air-dependent heat losses. The second, the environmentally friendly approach, proposed in this work, was aimed at minimizing the “external” costs (or the costs of damage done by the boiler emissions to the environment and humans). As shown in this paper, the lignite firing at the optimal excess air results in a lower environmental impact by the boiler unit.     

Economic and CO2 mitigation impacts of promoting biomass heating systems: An input–output study for Vorarlberg, Austria

This paper reports on an empirical investigation about the economic and CO₂ mitigation impacts of bioenergy promotion in the Austrian federal province of Vorarlberg. We study domestic value-added, employment, and fiscal effects by means of a static input–output analysis. The bioenergy systems analysed comprise biomass district heating, pellet heating, and automated wood chip heating systems, as well as logwood stoves and boilers, ceramic stoves, and buffer storage systems. The results indicate that gross economic effects are significant, regarding both investment and operation of the systems, and that the negative economic effects caused by the displacement of conventional decentralised heating systems might be in the order of 20–40%. Finally, CO₂ mitigation effects are substantial, contributing already in 2004 around 35% of the 2010 CO₂ mitigation target of the Land Vorarlberg for all renewable energy sources.     

Electrochemical performance of Nd0.6Sr0.4Co0.5Fe0.5O3−δ–Ag composite cathodes in intermediate temperature solid oxide fuel cells

The electrochemical performances of Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ–Ag composite cathodes have been investigated in intermediate temperature solid oxide fuel cells. The Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ–Ag cathodes prepared by ball milling followed by firing at 920 °C show the maximum performance (power density: 0.15 W cm⁻² at 800 °C) at 3 wt.% Ag. On the other hand, the Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ–Ag composite cathodes with 0.1 mg cm⁻² (0.5 wt.%) Ag that were prepared by an impregnation of Ag into Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ followed by firing at 700 °C (but the electrolyte–Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ assembly was prepared first by firing at 1100 °C) exhibit much better performance (power density: 0.27 W cm⁻² at 800 °C) than the composite cathodes prepared by ball milling, despite a much smaller amount of Ag due to a better dispersion and an enhanced adhesion. AC impedance analysis indicates that the Ag catalysts dispersed in the porous Nd_0.6Sr_0.4Co_0.5Fe_0.5O_3−δ cathode reduce the ohmic and the polarization resistances due to an increased electronic conductivity and enhanced electrocatalytic activity.     

Distributed grid-connected photovoltaic power system emission offset assessment: statistical test of simulated- and measured-based data

This study assesses the pollutant emission offset potential of distributed grid-connected photovoltaic (PV) power systems. Computer-simulated performance results were utilized for 214 PV systems located across the US. The PV systems’ monthly electrical energy outputs were based on a performance calculator called PVWATTS. Offset emissions of sulfur dioxide (SO₂), carbon dioxide (CO₂), and nitrogen oxides (NO_x) were determined from PV system outputs and average utility emissions data from each state. For validation, the simulated monthly results were statistically compared with measurement-based data (both production and corresponding emissions data) from 29 PV systems installed at different sites across the US.

While the data shows high (geographic) variability, the substantial number of measurements allows reliable statistical analysis. The methods are found to give consistent results in spite of the necessity to employ some even quite crude input approximations—such as the use of statewide rather than specific emissions data for the systems. No significant differences between simulated and measured monthly means for any of the pollutants were noted on the basis of individual monthly analyses, though the results for NO_x suggest the possible existence of some difference in that case. A more detailed statistical modeling using all monthly data in one combined analysis (allowing improved variability estimation) confirms these conclusions. Even the shorter confidence intervals for expected offsets obtained through the combined analysis show no significant differences between simulated and measured methods for SO₂ and CO₂. The differences for NO_x are statistically significant but consistent—suggesting useful prediction by the simulations via a constant correction factor. As expected, significant differences between months are evident for both simulated and measured offsets.     

Selective removal of CO from hydrogen-rich stream over CuO/CexSn1−xO2–Al2O3 catalysts

The solid solutions of Ce_xSn_1−xO₂ incorporated with alumina to form Ce_xSn_1−xO₂–Al₂O₃ mixed oxides, by the suspension/co-precipitation method, were used to prepare CuO/Ce_xSn_1−xO₂–Al₂O₃ catalysts for the selective oxidation of CO in excess hydrogen. Incorporating Al₂O₃ increased the dispersion of Ce_xSn_1−xO₂, but did not change their main structures and did not weaken their redox properties. Doping Sn⁴⁺ into CeO₂ increased the mobility of lattice oxygen and enhanced the activity of the 7%CuO/Ce_xSn_1−xO₂–Al₂O₃ catalyst in the selective oxidation of CO. The selective oxidation of CO was weakened as the doped fraction of Sn⁴⁺ exceeded 0.5. Incorporating appropriate amounts of Sn⁴⁺ and Al₂O₃ could obtain good candidates 7%CuO/Ce_xSn_1−xO₂–Al₂O₃(20%), 1–x=0.1–0.5, for a preferential oxidation (PROX) unit in a polymer electrolyte membrane fuel cell system for removing CO. Its activity was comparable with, and its selectivity was much larger than, that of the noble catalyst 5%Pt/Al₂O₃.     

NiO–ScSZ and Ni0.9Mg0.1O–ScSZ-based anodes under internal dry reforming of simulated biogas mixtures

Solid oxide fuel cells (SOFCs) with NiO–ScSZ and Ni_0.9Mg_0.1O–ScSZ-based anodes were operated by directly feeding a fuel mixture of CH₄, CO₂ and N₂ (CH₄ to CO₂ ratio of 3:2). Stable operation under constant current load (200 mA cm⁻²) was achieved with a NiO–ScSZ type anode during 200 h operating hours at 900 °C. Less stable operation occurred with a Ni_0.9Mg_0.1O–ScSZ type anode. In the case of SOFC with Ni_0.9Mg_0.1O–ScSZ as the anode, the methane reforming activity was higher than that with NiO–ScSZ. This was explained by change in the microstructure promoting reforming reactions. However, the addition of MgO resulted in degradation of electrochemical performance due to increase in ohmic resistance of the anode material during operation.     

Electron-beam flue-gas treatment for multicomponent air-pollution control

During coal combustion, different pollutants such as fly ash, sulfur oxides (SO₂ and SO₃), nitrogen oxides (NO_x=NO+NO₂) and volatile organic compounds (VOCs) are emitted. These pollutants are harmful to the environment and human health. Therefore different air-pollution-control technologies are used. Usually these technologies are designed for removing only a single pollutant. An integrated system for SO₂, NO_x and VOC simultaneous emission control is presented in the paper. The technology uses a high-energy electron-beam from an accelerator and ammonia to treat simultaneously SO₂ and NO_x, the obtained by-product can be used as a fertilizer. The industrial-demonstration plant at EPS Pomorzany in Szczecin is under optimization tests now. Moreover, the tests carried out with the pilot plant at EPS Kawêczyn have demonstrated the possibility of volatile-organic-compounds destruction and their final toxicity reduction.     

Anthropogenic emissions of CO2 and CH4 in an urban environment

Regular observations of atmospheric mixing-ratios of carbon dioxide and methane in the urban atmosphere, combined with analyses of their carbon-isotope composition (δ¹³C, δ¹⁴C), provide a powerful tool for assessing both the source strength and source partitioning of those gases, as well as their changes with respect to time. Intense surface fluxes of CO₂ and CH₄, associated with anthropogenic activities result in elevated levels of these gases in the local atmosphere as well as in modifications of their carbon-isotope compositions. Regular measurements of concentration and carbon-isotope composition of atmospheric CO₂, carried out in Krakow over the past two decades, were extended to the period 1995–2000 and also to atmospheric mixing-ratios of CH₄ and its carbon-isotope composition. Radiocarbon concentrations (δ¹⁴C) in atmospheric CO₂ recorded at Krakow are systematically lower than the regional background levels. This effect stems from the addition of ¹⁴C-free CO₂ into the local atmosphere, originating from the burning of fossil fuels. The fossil-fuel component in the local budget of atmospheric carbon calculated using a three-component mixing model decreased from ca. 27.5 ppm in 1989 to ca. 10 ppm in 1994. The seasonal fluctuations of this component (winter–summer) are of similar magnitude. A gradually decreasing difference between the ¹⁴CO₂ content in the local atmosphere and the regional background observed after 1991 is attributed to the reduced consumption of ¹⁴C-free fuels, mostly coal, in southern Poland and the Krakow municipal area. The linear regression of δ¹³C values of methane plotted versus reciprocal concentration, performed for the data available for Krakow sampling site, yields the average δ¹³C signature of the local source of methane as being equal to −54.2‰. This value agrees very well with the measured isotope signature of natural gas being used in Krakow (−54.4±0.6‰) and points to leakages in the distribution network of this gas as the main anthropogenic source of CH₄ in the local atmosphere.     

Preparation and properties of LiCoyMnxNi1−x−yO2 as a cathode for lithium ion batteries

The preparation of LiCo_yMn_xNi_1−x−yO₂ from LiOH·H₂O, Ni(OH)₂ and γ-MnOOH in air was studied in detail. Single-phase LiCo_yMn_xNi_1−x−yO₂ (0y0.3 and x=0.2) is obtained by heating at 830–900°C. The optimum heating temperatures are 850°C for y=0–0.1 and 900°C for y=0.2–0.3. Excess lithium (1z1.11 for y=0.2) and the Co doping level (0.05y0.2) do not significantly affect the discharge capacity of Li_zCo_yMn_0.2Ni_0.8−yO₂. The doping of Co into LiMn_0.2Ni_0.8O₂ accelerates the oxidation of the transition metal ion, and suppresses partial cation mixing. Since the valence of the manganese ion in LiMn_0.2Ni_0.8O₂ is determined to be 4, the formation of a solid solution between LiCo_yNi_1−yO₂ and Li₂MnO₃ is confirmed.