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At least 397 records · Page 22

Reduction of Iron (III) Oxide in Microwaves Toward Gasification Studies

The purpose of this study is to reduce hematite (Fe2O3) using hydrogen (H2), carbon monoxide (CO), and methane (CH4) gases using microwave irradiation. Conventional temperature programmed reduction of iron phase transformation under H2, CO, and CH4 agree with the literature. Furthermore, the activation energy for the iron phase transformation in a conventional reactor was in the order of H2>CO>CH4, suggesting that CH4 was the best reductant to initiate the reduction at a much lower temperature than CO, and CO was significantly better than H2 atmosphere. Due to the uneven temperature distribution, the apparent activation energy of microwave reduction under H2 was approximately 1/4th when compared to the conventional reduction in H2. X-ray diffraction (XRD) analysis showed a mixed oxide phase in microwave reduction as opposed to the clear phase transformation in conventional studies. To combat the temperature measurement issues in microwave studies, fiber optic sensors and Forward Looking InfraRed (FLIR) sensors were used to acquire the actual temperature distribution in the catalyst bed. Therefore, a reasonably accurate activation energy estimation was achieved in the catalyst bed. Combining these with the characterization and quantification of the different iron phases in microwave reduction will provide a blueprint for future microwave-assisted gasification studies.

Aireddy, Divakar Reddy↗

Potential Risks Associated with Short-Term Hydrogen Storage in Methane Reservoirs

Hydrogen (H2) has been identified as a flexible energy carrier with zero emissions. It is possible to utilize H2 by storing Hyblend, or H2 blended with CH4, in existing natural gas infrastructure. However, the compatibility of adapting the current CH4 storage strategies to include H2 injection has not been fully demonstrated. It is essential that we understand the impact of H2 gas on the naturally occurring microbial community of subsurface storage reservoirs before deploying large-scale H2-CH4 storage. We designed a series of experiments that allowed us to identify potential challenges of HyBlend Storage in existing methane reservoirs (Figure 1). First, we characterized two field fluid samples from a methane reservoir located in Western United States. Next, we used these samples to complete a series of short-term reactor experiments at reservoir conditions for a natural gas (100% CH4) and HyBlend (80% CH4/20% H2) storage environment.

geomicrobiology↗

Upgrading Biogas through in situ Conversion of Carbon Dioxide to Biomethane in Anaerobic Digesters

Organic waste streams generated by wastewater treatment plants, agricultural operations, and food processing industries represent an important yet underutilized opportunity for renewable energy production in the United States. Through anaerobic digestion, these waste streams can produce biogas, a mixture primarily composed of methane (CH4) and carbon dioxide (CO2), that can be upgraded to pipeline-quality natural gas. However, most existing upgrading technologies remove CO2 from biogas rather than utilizing it, leaving a significant portion of the potential energy unused. This project investigates a novel biological upgrading approach that converts CO2 into additional CH4 by supplying hydrogen (H2) to specialized microorganisms capable of performing hydrogenotrophic methanation. The main challenges associated with biological biogas upgrading are related to hydrogen supply, gas-liquid mass transfer, and process stability. First, due to the high cost of hydrogen gas, it is preferable that H2 be produced on-site using renewable energy sources such as wind or solar power. Second, hydrogen has low solubility in liquids, which limits its availability to microorganisms and requires strategies to improve gas dissolution and transfer within the reactor. Third, process inhibition may occur as a result of increased pH caused by CO2 consumption or elevated H2 partial pressure, both of which can negatively affect methanogenic activity. Although research in these areas has advanced during the course of this project, these challenges have not yet been fully resolved. To date, the biological systems that have achieved the highest methane concentrations are typically ex-situ reactors, where operational conditions can be more easily controlled. For this reason, the findings of the present project remain highly relevant. The project goal was to develop an innovative system that can accomplish biogas upgrading via biological conversion of CO2 to CH4, in a novel hybrid approach that combines the advantages of both in-situ and ex-situ systems. The proposed system employs a three-phase upflow anaerobic bioreactor with H2 delivery through a gas-permeable membrane, enabling efficient hydrogen transfer and microbial conversion. Under optimized operating conditions, the system achieved 99% H2 consumption and 90% CO2 conversion. A subsequent gas cleaning stage was implemented to further improve gas quality and meet target purity standards. The upgraded gas composition reached 97.7% CH4, 2.2% CO2, and 0.97% O2, while H2S concentrations remained below detection limits. In addition, a flue gas-driven inorganic thermoelectric generator (TEG) system was designed and experimentally validated as a potential source of electricity for H2 production. The system consisted of six TEG modules connected in series and achieved an open-circuit voltage of 4.5 V and a maximum power output of 224 mW at a temperature difference of approximately 53.5 °C, demonstrating effective conversion of waste heat into electrical power under simulated flue gas conditions. Finally, a comprehensive techno-economic analysis was completed to evaluate the capital and operating costs associated with the proposed system. The results provide important insights to guide future scale-up, optimization, and potential deployment of integrated biological biogas upgrading technologies.

09 BIOMASS FUELS↗

Experimental and theoretical studies on collision-broadened lines in the nu-4 fundamental of methane.

High-resolution experimental and theoretical studies performed earlier by us on the collision-broadened rotational lines in the nu-3 and 2nu-3 bands of methane have been repeated on the lines in the nu-4 fundamental of the molecule. Line-width measurements and computations, as well as line-shape measurements, indicate that the significant differences which exist between the rotational term values of the nu-3 and nu-4 vibrational levels have no observable effect on the collision-broadening mechanism. Using the predictions of line-widths, based on the Anderson-Tsao-Curnutte theory in the extended version of Tejwani for octopolar molecules, the theoretical dependence of line-widths on temperature has been calculated for CH4-CH4, CH4-H2 and CH4-He collisions.

Varanasi, P.↗

Evaluation and characterization of the methane-carbon dioxide decomposition reaction

A program was conducted to evaluate and characterize the carbon dioxide-methane (CO2-CH4) decomposition reaction, i.e., CO2 + CH4 = 2C + 2H2O. The primary objective was to determine the feasibility of applying this reaction at low temperatures as a technique for recovering the oxygen (O2) remaining in the CO2 which exits mixed with CH4 from a Sabatier CO2 reduction subsystem (as part of an air revitalization system of a manned spacecraft). A test unit was designed, fabricated, and assembled for characterizing the performance of various catalysts for the reaction and ultraviolet activation of the CH4 and CO2. The reactor included in the test unit was designed to have sufficient capacity to evaluate catalyst charges of up to 76 g (0.17 lb). The test stand contained the necessary instrumentation and controls to obtain the data required to characterize the performance of the catalysts and sensitizers tested: flow control and measurement, temperature control and measurement, product and inlet gas analysis, and pressure measurement. A product assurance program was performed implementing the concepts of quality control and safety into the program effort.

Davenport, R. J.↗

Photosynthesis of organic compounds in the atmosphere of Jupiter

An efficient conversion of CH4 to hydrocarbons and HCN takes place when NH3 is photolysed in the presence of CH4, H2, and He using a 184.9 nm light source. The extent of NH3 decomposition after a 1 hr exposure was determined spectrophotometrically; CH4, N2, and C2 and C3 hydrocarbons were detected and analyzed by mass spectrometry. Photolysis of one molar equivalent of NH3 results in the loss of 0.84 molar equivalent of CH4, which apparently reacts with hot hydrogen atoms produced by photolysis. The 8% of the NH3 which is not converted to N2 probably is converted to organic amines and nitrile derivatives. The results indicate that NH3 photolysis is a highly probable mechanism for the conversion of methane to more complex hydrocarbons in the upper atmosphere of Jupiter, and predict the occurrence of HCN, NH2NH2, and higher hydrocarbons in the Jovian atmosphere above the NH3 clouds.

Ferris, J. P.↗

Isotope shifts in methane near 6000/cm

Isotope shifts for cleanly resolved vibrational-rotational absorption lines of CH4-12 and CH4-13 were measured by a 5-m focal length Littrow spectrometer in the 6000/cm range. The methane isotopes were held in separate absorption cells: 20 torr of CH4-13 in a 1-m cell, and 5 torr of CH4-12 in a White cell of 4-m optical path length. Measured shifts for the cleanly resolved singlets R(0), R(1), Q(1) and P(1) are summarized in tabular form.

Fox, K.↗

The structure of the atmosphere of Uranus

Models of the interior of Uranus suggest that the abundances of such substances as CH4 are greatly enhanced with respect to solar abundances of heavy elements. Such enhancement leads to a new type of model atmosphere for Uranus, which agrees with observation if the internal energy flux is small (no more than 10%) compared with the absorbed solar energy. An important feature of the models is the presence of a cloud of CH4 droplets whose top is at a temperature of approximately 90 K and a pressure of about 4 atm. Above the cloud, the atmosphere is stable because of the rapid decrease in the thermal flux with depth. Being saturated, most of the observable gaseous CH4 is near the cloud; the CH4 abundance above the cloud, of the order of 5 km-am, is a very sensitive function of the cloud-top temperature.

Danielson, R. E.↗

Titan's atmosphere: Comments on haze content, methane abundance, band shapes, and hydrogen upper limit

The existence of scatterers in Titan's atmosphere was demonstrated in a paper published in the Astrophysical Journal three years ago. This conclusion was not affected by recent laboratory investigations showing that certain CH4 bands are independent of pressure because it was shown that the reflecting layer model failed to explain Titan's CH4 absorptions regardless on which portion of the curve of growth Titan's CH4 lines lie. Saturn's atmosphere was utilized along the central meridian for studies of CH4 absorption, and to show that the conclusion is insensitive to the moderate scattering there. The quite pronounced role of scattering in Titan's atmosphere strongly suggests that Titan's surface is obscured.

Trafton, L.↗

Response of the global climate to changes in atmospheric chemical composition due to fossil fuel burning

Recent modeling of atmospheric chemical processes (Logan et al, 1978; Hameed et al, 1979) suggests that tropospheric ozone and methane might significantly increase in the future as the result of increasing anthropogenic emissions of CO, NO(x), and CH4 due to fossil fuel burning. Since O3 and CH4 are both greenhouse gases, increases in their concentrations could augment global warming due to larger future amounts of atmospheric CO2. To test the possible climatic impact of changes in tropospheric chemical composition, a zonal energy-balance climate model has been combined with a vertically averaged tropospheric chemical model. The latter model includes all relevant chemical reactions which affect species derived from H2O, O2, CH4, and NO(x). The climate model correspondingly incorporates changes in the infrared heating of the surface-troposphere system resulting from chemically induced changes in tropospheric ozone and methane. This coupled climate-chemical model indicates that global climate is sensitive to changes in emissions of CO, NO(x) and CH4, and that future increases in these emissions could augment global warming due to increasing atmospheric CO2.

Hameed, S.↗

Response of the global climate to changes in atmospheric chemical composition due to fossil fuel burning

Tropospheric ozone and methane might increase in the future as the result of increasing anthropogenic emissions of CO, NOx and CH4 due to fossil fuel burning. Since O3 and CH4 are both greenhouse gases, increases in their concentrations could augment global warming due to larger future amounts of atmospheric CO2. To test this possible climatic impact, a zonal energy-balance climate model has been combined with a vertically-averaged tropospheric chemical model. The latter model includes all relevant chemical reactions which affect species derived from H2O, O2, CH4 and NOx. The climate model correspondingly incorporates changes in the infrared heating of the surface-troposphere system resulting from chemically induced changes in tropospheric ozone and methane. This coupled climate-chemical model indicates that global climate is sensitive to changes in emissions of CO, NOx and CH4, and that future increases in these emissions could enhance global warming due to increasing atmospheric CO2.

Cess, R. D.↗

Atmospheric methane /CH4/ - Trends and seasonal cycles

On the basis of 22 months of almost continuous automated, GC/FID measurements of atmospheric CH4 and Cape Meares (45 deg N), it is shown that the concentration of CH4 is increasing at about 2% per yr (+ or - 0.5%/yr). The data also revealed stable seasonal cycles with peak concentrations in October and minimum concentrations in July. The magnitude of the seasonal variations during these months is about + or - 20 ppby from the average (+ or - 1.2%). If the current trend continues, the increased CH4 concentration may result in a 0.2 K to 0.4 K average increase in earth's surface temperature over the next 40 years or so (based on calculations of Wang et al. (1976)). The coupling of CH4 to tropospheric and stratospheric chemical processes is discussed.

Rasmussen, R. A.↗

The spectrum of Titan in the far-infrared and microwave regions

The pressure-induced absorptions of gaseous nitrogen (N2) and methane (CH4) are computed on the basis of the collisional lineshape theory of Birnbaum and Cohen (1976). Laboratory data at 300 and 124 K for N2 and at 296 and 195 K for CH4 are used to determine the collisional time constants and their temperature dependence. The spectrum of Titan from the microwave to the far-infrared region (0.1-600/cm) is then modeled using these opacities and a temperature profile of Titan's atmosphere derived from the Voyager 1 radio occultation experiment. The model atmosphere is composed of N2 and CH4, their relative proportions being determined by the vapor pressure law of CH4. A model with gaseous opacity alone is ruled out by the far-infrared observations. An additional opacity, thought to be associated with a methane cloud, is confirmed. The effective temperature of Titan is estimated at 83.2 plus or minus 1.4 K.

Courtin, R.↗

The atmosphere of the primitive earth and the prebiotic synthesis of organic compounds

The prebiotic synthesis of organic compounds is investigated using a spark discharge on various simulated prebiotic atmospheres at 25 C. It is found that glycine is almost the only amino acid produced from the model atmospheres containing CO and CO2. These results show that the maximum yield is about the same for the three carbon sources (CO, CO2, and CH4) at high H2/carbon ratios, but that CH4 is superior at low H2/carbon ratios. CH4 is found to yield a much greater variety of amino acids than either CO or CO2. If it is assumed that amino acids more complex than glycine were required for the origin of life, then these findings indicate the need for CH4 in the primitive atmosphere. The yields of cyanide and formaldehyde are shown to parallel the amino acid results, with yields of HCN and H2CO as high as 13 percent based on carbon. Ammonia is also found to be produced from N2 in experiments with no added NH3 in yields as high as 4.9 percent. These results indicate that large amounts of NH3 would have been synthesized on the primitive earth by electric discharges.

Miller, S. L.↗

The photochemistry of biogenic gases in the early and present atmosphere

The distribution of gases in the prebiologial paleoatmosphere is investigated using photochemical models. A chart of the photochemical and chemical reactions and reaction rates for CH4, NH3, H2S, N2O, and CO atmospheric gases is given. Mixing ratios and surface mixing ratios for CH4, NH3, CO, and N2O are obtained using thermodynamic equilibrium calculations; an increase in CH4 and N2O is observed. The reactions, which explain the photochemistry of the gases studied, are presented. The sources of these gases and their concentration with regards to altitude are examined. Graphs of the vertical distribution of CH4, NH3, H2S, CO, O2, and N2O in prebiological paleoatmosphere are provided. The data reveals the presence of only N2, CO2, and N2O in the early atmosphere; with the evolution of life, sources of atmospheric gases increased and their influence on the photochemistry of the troposphere and stratosphere increased.

Levine, J. S.↗

Photochemistry of methane and the formation of hydrocyanic acid (HCN) in the earth's early atmosphere

A one-dimensional photochemical model is used to analyze the photochemistries of CH4 and HCN in the primitive terrestrial atmosphere. CH4, N2, and HCN photolysis are examined. The background atmosphere and boundary conditions applied in the analysis are described. The formation of HCN as a by-product of N2 and CH4 photolysis is investigated; the effects of photodissociation and rainfall on HCN is discussed. The low and high CH4 mixing ratios and radical densities are studied.

Zahnle, K. J.↗

Methane, carbon monoxide and methylchloroform in the Southern Hemisphere

New observational data on CH4, CO and CH3CCl3 in the Southern Hemisphere are reported. The data are analyzed for long term trends and seasonal cycles. CH3CCl3 data are used to scale the OH fields incorporated in a two-dimensional model, which in turn, is used to constrain the magnitude of a global CH4 source function. The possible causes of observed seasonality of CH3CCl3, CH4 and CO are identified, and several other aspects of observed CH4 variability are discussed. Possible future research directions are also given.

Fraser, P. J.↗

Stable carbon isotope ratios in atmospheric methane and some of its sources

Ratios of C-13/C-12 have been measured in atmospheric methane and in methane collected from sites and biota that represent potentially large sources of atmospheric methane. These include temperate marshes (about -48 percent to about -54 percent), landfills (about -51 percent to about -55 percent), and the first reported values for any species of termite (-72.8 + or - 3.1 percent for Reticulitermes tibialis and -57.3 + or - 1.6 percent for Zootermopsis angusticollis). Numbers in parentheses are delta C-13 values with respect to PDB (Peedee belemnite) carbonate. Most methane sources reported thus far are depleted in C-13 with respect to atmospheric methane (-47.0 + or - 0.3 percent). Individual sources of methane should have C-13/C-12 ratios characteristic of mechanisms of CH4 formation and consumption prior to release to the atmosphere. The mass-weighted average isotopic composition of all sources should equal the mean C-13 of atmospheric methane, corrected for a kinetic isotope effect in the OH attack of CH4. Assuming the kinetic isotope effect to be small (about -3.0 percent correction to -47.0), as in the literature, the new values given here for termite methane do not help to explain the apparent discrepancy between C-13/C-12 ratios of the known CH4 sources and that of atmospheric CH4.

Tyler, Stanley C.↗