Low Methane Concentrations Research Articles

Auto-cyclic reactor: Design and evaluation for the removal of unburned methane from emissions of natural gas engines

A non-adiabatic fixed bed auto-cyclic reactor (ACR) consisting of two counter-current concentric compartments was designed and built for removing low concentrations of methane from exhaust gases from natural gas engines. The length was based on simulations by a simple heterogeneous one dimensional model using literature parameters and kinetic data, while the diameter was selected to assure a linear fluid velocity between 0.5 and 2 m/s. Its innovative design consists of a judicious combination of 14 longitudinal fins welded to the outlet part of inner reactor compartment to maximize the heat transfer to the inlet section and highly active pellet type catalyst filling the space between fins to lower the ignition temperature. The experimental ACR pilot unit was loaded by a combination of highly active laboratory prepared catalysts: palladium/alumina pellets and palladium/alumina coated cordierite monoliths. The efficiency of methane removal from air and from synthetic exhaust gas containing 7 vol% CO 2 and 14 vol% H 2O was evaluated under a wide range of operating conditions: temperature from 290 to 500 °C, methane concentration between 500 and 3800 ppm. The reactor performance was monitored in terms of axial temperature profiles and methane conversion both in transient and steady state conditions. Reproducible performance of the ACR was observed even after 1200 h of cumulative operation and complete methane removal was obtained at relatively low temperatures. To simulate the obtained experimental data, a heterogeneous one-dimensional model was developed to suit the final reactor configuration using actual laboratory determined kinetic data. The model described adequately the experimental temperature profiles and methane conversion when heat transfer between the reactor compartments and heat loss were taken into account.

Effects of Small Amounts of Fugitive Methane in the Air on Diesel Engine Performance and its Combustion Characteristics

Methane, which is the main component of natural and biogases, is known to be a very strong greenhouse gas with long lasting effect in the atmosphere that contributes actively to global warming. Releases of the gas commonly described as “Fugitive Gas Emissions” are an important source of methane emissions. A possible approach to reduce the harmful effects of such methane emissions is to introduce the fugitive methane into a device that can convert it through combustion to less environmentally harmful products. It has been shown that the bulk of such methane can be converted into much weaker green house gases in an IDI diesel engine. However, such applications can bring about changes to engine combustion processes and the resulting performance. The present contribution reports the results of an investigation of the effect on combustion characteristics, emissions and performance of introducing very small concentrations of methane into the intake of an operating diesel engine. It is shown that for wide ranges of gas admission concentrations in the air, unlike with other conventional combustion devices such as burners and furnaces, much of the methane added was indeed oxidized in the IDI diesel engine and increased the power output and thus saving some diesel fuel. Such methane admissions tended to increase carbon monoxide emissions, indicating that part of the methane may not have been fully oxidized. NOx emission increased slightly, but when compared to the diesel operation for the same fuel energy input, it represented a reduction. Consuming a small amount of fugitive methane in the engine could bring about reductions to the global warming effect well in excess of that due to the entire engine exhaust gases resulting from diesel fuel combustion. The introduction of low concentrations of methane into the engine air hardly affected the ignition delay and the combustion duration. However, the total gross heat released and its rate showed correspondingly an increase consistent with a positive contribution of methane to engine power.

Improved activity of Pt/γ-Al2O3 catalysts for CH4O2 reaction under lean conditions due to sulfation and catalyst loading

Abstract The catalytic oxidation of low concentration of methane (2000 ppmV) in excess oxygen was investigated over unsulfated and pre-sulfated Pt/γ-Al 2 O 3 catalysts. Over unsulfated samples, catalyst activity increased slightly with Pt concentration and with catalyst loading in the reactor. This enhancement was stronger over pre-sulfated catalyst relative to unsulfated samples. The results suggest that the new catalytic sites generated during sulfation (formed by the interaction between surface support sulfates and highly oxidized Pt atom at the edge of the platinum particle) may activate the almost non-polar C–H bonds of methane through a dissociate adsorption of CH 4 , thus the increase in the sulfated catalyst loading results in the increase in the number of the catalytic sites generated during sulfation. The probability of the initial C–H activation of CH 4 increases and may lead to the observed increase in the oxidation rate for CH 4 O 2 reaction.

Synthesis of thin diamond films from faceted nanosized crystallites

Diamond films consist of crystallites having nanometer grains were deposited using low methane concentration by hot filament chemical vapor deposition (HFCVD). The results show that films consist of nanodiamond grains with grain sizes ranging from 20 nm to 200 nm having thickness dependent size. Increasing the deposition time, the grain size increases and hence the thickness of the film increases. The diamond nucleation (nucleation density 10 10 cm −2) is comparable to that obtained by biasing the substrate. The use of low methane concentration for the formation of nano crystallites improves the quality of the film as indicated by Raman spectroscopy. The distance between the filament and substrate is increased while maintaining the substrate temperature. The effects of this large separation on the gas phase chemistry are discussed which helps to understand the reduced size of the crystallites under input gas ratios when microcrystallines are obtained.

Growth of carbon nanotubes in the microchannels of glass substrates

Carbon nanotubes (CNTs) were grown in soda-lime glass microchannels using microwave plasma enhanced chemical vapor deposition and an Fe–Si thin film catalyst. It was found that CNT growth in the microchannels is different from that on flat substrates. The growth length is proportional to t 0.5 for the CNTs grown in microchannels; whereas the length is proportional to t 1.5 for the CNTs grown on flat substrates. The former is attributed a diffusion-controlled growth mechanism where the depth of the microchannel serves a diffusion boundary layer; while the later is attributed to a reaction-control growth mechanism where the growth rate increases linearly with the methane concentration used. From Raman analysis, the CNTs grown in microchannels at low methane concentrations seem to have better crystalline structure than that grown on flat substrates. The opposite is true at high methane concentrations. The cross point is at a methane concentration of 18%.

Processing of coal mine gas with low methane concentrations for use in high-temperature fuel cells

Coal mines are emitting off-gases containing methane of varying content. For environmental as well as economical reasons the gas should be collected and put to further use, i.e., as a feed stock for gas engines or fuel cells. Certain concentration ranges of the coal mine gas require an adjustment of the methane content due to safety related and technical constraints. The application of gas permeation is one possibility to increase the methane content to the desired levels. Employing methane selective, silicone-based, high-flux membranes is currently being investigated by a German project consortium. Experimental results as well as simulation studies showed that selectivity and flux of the membrane are sufficient to increase the methane content to the desired value at a reasonable recovery.

Spectroscopic investigation of homoepitaxial CVD diamond for detection applications

Three-layer structures consisting of intrinsic/B-doped homoepitaxial CVD diamond grown onto commercial HPHT Ib substrates have been studied by means of Raman spectroscopy and photoluminescence (PL). The intrinsic layers have been deposited, at fixed methane to hydrogen ratio (1%), by systematically changing the substrate temperature (620–820 °C). Raman measurements point out the excellent crystalline quality and phase purity of the samples. Moreover, flat PL spectra in a wide energy range (1.7 eV–2.7 eV) indicate also their great purity. As the free-exciton recombination can be used to further probe the quality of synthetic diamond, measurements of free-exciton emission at room temperature have been also performed. The excitation was produced by a 5 ns pulsed tunable laser irradiation. The results have been compared with the detection characteristics of simple alpha-particle detector prototypes based on the analyzed samples. A clear correlation between excitonic emission and detector sensitivity is demonstrated. On the basis of these results, low methane concentrations (approx. 1% CH 4/H 2) in the deposition gas mixture and intermediate substrate temperatures (approx. 720 °C–770 °C) have been identified as the best working conditions of our growth reactor.

(BaxLa1-x)2In2O5+x (0.4 ≤ x ≤ 0.6) Electrolyte-Supported Mixed-Potential CO Sensors

The dense (Ba(x)La(1-x)(2))In(2)O(5+x) electrolytes with different compositions (x = 0.4, 0.5, 0.6) were synthesized by Pechini method. The obtained sintered (Ba(x)La(1-x)(2))In(2)O(5+x) electrolytes showed a high relative density of approximately 98%, and the major phase of three electrolyte compositions was indexed as a cubic phase. The CO sensing properties of as-fabricated planar-type (Ba(x)La(1-x)(2))In(2)O(5+x)-based sensors coupled with ITO and Pt as the sensing electrode and reference electrode, respectively, were investigated. The effects of factors such as gas flow rate, chemical compositions, and density of the electrolytes on the sensing performance were investigated. The sensors showed good sensitivity to different concentrations of CO from approximately 100 to approximately 500 ppm and excellent selectivity over low concentrations of methane (<500 ppm). Linear relationships between emf of the sensors and CO gas concentrations from approximately 100 to approximately 400 ppm were observed. However, the sensors indicated more sluggish response compared with the sensors coupled with a corresponding porous electrolyte. The probable reason has been discussed. The long-term stability of the sensor for the detection of CO was also investigated, which indicated a reasonably stable sensor signal after an initial decline during the incubation period.

On the Atomistic Mechanisms of Alkane (Methane−Pentane) Separation by Distillation: A Molecular Dynamics Study

Insights into the liquid-vapor transformation of methane-pentane mixtures were obtained from transition path sampling molecular dynamics simulations. This case study of the boiling of non-azeotropic mixtures demonstrates an unprejudiced identification of the atomistic mechanisms of phase separation in the course of vaporization which form the basis of distillation processes. From our simulations we observe spontaneous segregation events in the liquid mixture to trigger vapor nucleation. The formation of vapor domains stabilizes and further promotes the separation process by preferential evaporation of methane molecules. While this discrimination holds for all mixtures of different composition studied, a full account of the boiling process requires a more complex picture. At low methane concentration the nucleation of the vapor domains includes both methane and pentane molecules. The pentane molecules, however, tend to form small aggregates and undergo rapid re-condensation within picoseconds to nanoseconds scales. Accordingly, two aspects of selectivity accounting for methane-pentane separation in the course of liquid-vapor transformations were made accessible to molecular dynamics simulations: spontaneous segregation in the liquid phase leading to selective vapor nucleation and growth favoring methane vaporization and selective re-condensation of pentane molecules.

CO2 inhibition of global terrestrial isoprene emissions: Potential implications for atmospheric chemistry

Isoprene is the dominant volatile organic compound produced by the terrestrial biosphere and fundamental for atmospheric composition and climate. It constrains the concentration of tropospheric oxidants, affecting the lifetime of other reduced species such as methane and contributing to ozone production. Oxidation products of isoprene contribute to aerosol growth. Recent consensus holds that emissions were low during glacial periods (helping to explain low methane concentrations), while high emissions (contributing to high ozone concentrations) can be expected in a greenhouse world, due to positive relationships with temperature and terrestrial productivity. However, this response is offset when the recently demonstrated inhibition of leaf isoprene emissions by increasing atmospheric CO2 concentration is accounted for in a process‐based model. Thus, isoprene may play a small role in determining pre‐industrial tropospheric OH concentration and glacial‐interglacial methane trends, while predictions of high future tropospheric O3 concentrations partly driven by isoprene emissions may need to be revised.

Methane in pristine and impaired mangrove soils and its possible effect on establishment of mangrove seedlings

Pristine and impaired mangrove soils (from road construction, aquaculture, and sewage) in Baja California Sur, Mexico were investigated for methane dynamics, related soil properties, and their impact on initial establishment of black mangrove propagules. All soils (Salic Fluvisols and Histosols) had neutral to alkaline pH, were saline, and had variable organic carbon content, and redox potentials. Most pristine mangrove soils showed low methane concentration, low methane production rates, and no methane emission. Impaired mangrove soil (from aquaculture) and mangrove soil affected by sewage water showed high methane concentration, high methane production rates, and high methane emission, thus acting as a methane source. Elevated methane concentrations, similar to levels detected in the impaired mangrove soil, reduce the growth of seedlings under closed chamber conditions. Addition of sulfate to the soil reversed the trend. These results indicate that impaired mangrove soils in dry climatic regions produce and emit methane and that elevated methane concentration in the vicinity of propagules may affect establishment of mangrove seedlings in impaired mangrove soils.

Structural effects of nanocomposite films of amorphous carbon and metal deposited by pulsed-DC reactive magnetron sputtering

The relationship between metal-induced (W, Mo, Nb and Ti) structures and the surface properties of Me–DLC thin films is discussed. Nanocomposite films were deposited on c–Si wafers by pulsed-DC reactive magnetron sputtering controlling the gas ratio CH 4/Ar. The sputtering process of metals such as Ti, Nb and Mo (unlike the tungsten) in the presence of methane shows a low reactivity at low methane concentration. The deposition rate and the spatial distribution of sputtered material depend of Z-ratio of each metal. The surface contamination of metal targets by carbon, owing to methane dilution, limits the incorporation of metals into DLC films according to an exponential decay. Results of electron probe microanalysis and X-ray photoelectron spectroscopy indicate a C rich Me/C composition ratio for low relative methane flows. According to the depth profile by secondary ion mass spectrometry, the films are systematically homogeneous in depth, whereas at high carbon contents they exhibit a metal-rich interfacial layer on the substrate. Moreover, high resolution transmission electron microscopy has evidenced important structural modifications with respect to DLC standard films, with marked differences for each Me/C combination, providing nanodendritic, nanocrystallized or multilayered structures. These particular nanostructures favour the stress decrease and induce significant changes in the tribological characteristics of the films. This study shows the possibilities of controlling the amorphous carbon films structure and surface properties by introducing metal in the DLC matrix.

Chemical vapor infiltration of porous substrates with diamond by using a new designed hot-filament plant

We designed a new hot-filament plant which features some new operating states for chemical vapor infiltration with diamond. Complete infiltration of porous substrates with diamond by using standard hot filament plants is not possible. Chemical vapor infiltration with diamond is limited by the overgrowing diamond layer at the surface primarily caused by high recombination rates of atomic hydrogen on surfaces. As a consequence, the pore mouth is closed before the pore is completely infiltrated (“bottleneck” effect). Porous substrates were infiltrated by using a forced flow through the substrate. In order to achieve good infiltration results, it was necessary to use very low methane concentrations.

Influence of Methane Concentration on Crystal Growing Process in CVD Free Standing Diamond Films

The Macro-texture, grain boundary distribution and surface morphlolgy in CVD free standing diamond films deposited with different methane concentrations were observed by X ray diffraction technology, electron backscatter diffraction and SEM. The crystal growing process of {100} and {111} planes in diamond crystal was studied. It is shown that diamond films adsorb activated radical CH2 2-on {100} plane or adsorb CH3- and CH3- on {111} plane alternately. Carbon atoms stack on the film surface during dehydrogenation. At low methane concentration, the expansion ratio of {111} planes is close to, but faster than that of {100} planes because of their relative lower surface energy. The enhanced driving force induced by the increased methane concentration results in faster growth of {100} plane than that of {111} plane, which promotes the formation of {100} texture. The film surface morphology consisits of the exposured {100} planes that are parallel to the film surface and the exposured {111} planes area as the side surface that decrease during the competition growth, which is different from that of single crystal growth.

Methane and nitrous oxide in the ice core record

Polar ice cores contain, in trapped air bubbles, an archive of the concentrations of stable atmospheric gases. Of the major non-CO2 greenhouse gases, methane is measured quite routinely, while nitrous oxide is more challenging, with some artefacts occurring in the ice and so far limited interpretation. In the recent past, the ice cores provide the only direct measure of the changes that have occurred during the industrial period; they show that the current concentration of methane in the atmosphere is far outside the range experienced in the last 650,000 years; nitrous oxide is also elevated above its natural levels. There is controversy about whether changes in the pre-industrial Holocene are natural or anthropogenic in origin. Changes in wetland emissions are generally cited as the main cause of the large glacial-interglacial change in methane. However, changing sinks must also be considered, and the impact of possible newly described sources evaluated. Recent isotopic data appear to finally rule out any major impact of clathrate releases on methane at these time-scales. Any explanation must take into account that, at the rapid Dansgaard-Oeschger warmings of the last glacial period, methane rose by around half its glacial-interglacial range in only a few decades. The recent EPICA Dome C (Antarctica) record shows that methane tracked climate over the last 650,000 years, with lower methane concentrations in glacials than interglacials, and lower concentrations in cooler interglacials than in warmer ones. Nitrous oxide also shows Dansgaard-Oeschger and glacial-interglacial periodicity, but the pattern is less clear.

Geochemical characterization of the organic matter, pore water constituents and shallow methane gas in the eastern part of the Ulleung Basin, East Sea (Japan Sea)

Abstract Geochemical analyses of sediments, pore water and headspace gas of the piston cores taken from the eastern part of Ulleung Basin of the East Sea (Japan Sea) were carried out to assess the origin of the sedimentary organic matter and interstitial fluid. Several tephra layers within the core are identified as the Ulleung‐Oki (10.1 ka), the Aira‐Tanzawa (23 ka) and the Ulleung‐Yamato (30.9 ka) tephras. With the exception of these volcanic layers, the cores consist predominantly of muddy sediments that contain &gt;0.5% total organic carbon. Atomic C/N ratios and δ13Corg values suggest that the organic matter originated from marine algae rather than from land vascular plants, whereas Rock‐Eval pyrolysis suggests that the organic matter is thermally immature and comes from a land vascular plant (Type III). These conflicting results seem to be caused by the heavy oxidization of the marine organic matter. Sulphate concentration profiles of pore waters show strongly linear depletion (r2 &gt; 0.97) with sediment depth. The estimated sulphate–methane interface (SMI) depth using the sulphate concentration gradient was nearly 3.5 m below seafloor (mbsf) in the southern part of the study area, and deeper than 6 mbsf in the northern part of the area. The difference in SMI depths is likely associated with the amount of the methane flux. The methane concentration below the SMI in the two southern cores increases rapidly, implying the occurrence of methanogenesis and anaerobic methane oxidation (AMO). In contrast, the two northern cores have a low methane concentration below the SMI. values measured from all cores were in the range of −83.5 to −69.5‰, which suggests that the methane derives from a methanogenic microbe. values become decreased toward SMI, but increased below SMI; therefore, has eventually the minimum value near the SMI. The values are also decreased when the methane concentration is increased. These phenomena support the typical occurrence of AMO in the study area.

Characteristics of coal mine ventilation air flows

Coal mine methane (CMM) is not only a greenhouse gas but also a wasted energy resource if not utilised. Underground coal mining is by far the most important source of fugitive methane emissions, and ∼70% of all coal mining related methane is emitted to the atmosphere through mine ventilation air. Therefore, research and development on mine methane mitigation and utilisation now focuses on methane emitted from underground coal mines, in particular ventilation air methane (VAM) capture and utilisation. To date, most work has focused on the oxidation of very low concentration methane. These processes may be classified based on their combustion kinetic mechanisms into thermal oxidation and catalytic oxidation. VAM mitigation/utilisation technologies are generally divided into two basic categories: ancillary uses and principal uses. However, it is possible that the characteristics of ventilation air flows, for example the variations in methane concentration and the presence of certain compounds, which have not been reported so far, could make some potential VAM mitigation and utilisation technologies unfeasible if they cannot cope with the characteristics of mine site ventilation air flows. Therefore, it is important to understand the characteristics of mine ventilation air flows. Moreover, dust, hydrogen sulphide, sulphur dioxide, and other possible compounds emitted through mine ventilation air into the atmosphere are also pollutants. Therefore, this paper presents mine-site experimental results on the characteristics of mine ventilation air flows, including methane concentration and its variations, dust loadings, particle size, mineral matter of the dust, and other compounds in the ventilation air flows. The paper also discusses possible correlations between ventilation air characteristics and underground mining activities.

Atomic mechanism of twin formation in CVD diamond films

The macro-texture, grain boundary distribution and surface morphology in CVD free standing diamond films deposited with different methane concentrations were observed by X ray diffraction, electron backscatter diffraction and SEM. The atom stacking process of twins on {111} planes of diamond crystal were studied. It is shown that the twins form easily on {111} planes because of the 〈111〉 60° orientation relationship of first order twin and the stacking structure of {111} planes. At low methane concentration, carbon atoms tend to deposit on {111} planes with lower surface energy, which facilitates the formation of twins by means of rotating deposition of carbon atoms, while the high twinning frequency weakens the texture. With increasing methane concentration the {001} planes with lower growing activation energy become the main frontal growth fronts, and only those grains with 〈001〉 crystal direction which is parallel to the surface normal can continuously grow, so that the probability of twin nucleation decreases. In addition, second_order twins were found in diamond film, and their formation mechanism was analyzed.

Further improvement in high crystalline quality of homoepitaxial CVD diamond

High-quality homoepitaxial diamond (001) films with macroscopically flat surfaces have been successfully grown using a high-power microwave-plasma chemical-vapor-deposition (MWPCVD) method. In this study, further optimization of the homoepitaxial growth condition has been accomplished mainly by controlling off-angles to 5° along the <110> or <100> direction of high-pressure/high-temperature-synthesized Ib diamond (001) substrates. We have found that the homoepitaxial films deposited at reasonably high growth rates under the optimized growth condition including the off-angle of 3°–4° along the <110> direction have macroscopically flat surfaces, accompany very low or almost negligible densities of growth hillocks and yield strong free-exciton emissions in both steady-state cathodoluminescence and time-resolved photoluminescence spectra measured at room temperature. These indicate that apparent lateral growths suitable for high-quality homoepitaxial layers in the case of the high-power MWPCVD method, which are similar to those previously reported in the case of MWPCVD processes with low methane concentrations, rather quickly occur from step edges on (001) terraces and that they can be achieved more preferentially on the vicinal substrates at high temperatures and high methane concentrations.

Non-Equilibrium Potentiometric CO Sensor Using (BaxLa1-x)2In2O5 (0.4

Dense (BaxLa1-x)2In2O5 (BLIO) ceramic electrolytes with different compositions (x=0.4, 0.5, 0.6) were synthesised by Pechini method during which the obtained sintered BLIO electrolytes showed high relative density of ~98% and indicated a pure single cubic phase. The CO sensing properties of as-fabricated planar-type BLIO-based sensors coupled with ITO and Pt as the sensing electrode and reference electrode, respectively was investigated. The sensors showed good sensitivity to different concentrations of CO from 0 to 500ppm and excellent selectivity over low-concentrations of methane (<500ppm). However, the sensors with dense electrolyte indicated more sluggish response compared with the sensors coupled with corresponding porous electrolyte as previously reported. The long-term stability of the sensor for the detection of CO was also investigated which indicated a reasonably stable sensor signal after the initial declination.