Pyrolysis of Methane to Higher Hydrocarbons: A Thermodynamic Study

1989 ◽  
Vol 42 (10) ◽  
pp. 1655 ◽  
Author(s):  
FP Larkins ◽  
AZ Khan
Keyword(s):  
Gas Phase ◽  
Pressure Range ◽  
Solid Carbon ◽  
Free Energies ◽  
Oxidation Of Methane ◽  
Conversion Of Methane ◽  
Equilibrium Conversion ◽  
Benzene Toluene ◽  
Higher Hydrocarbons ◽  
The Individual

Some basic thermodynamic parameters such as Gibbs free energies, enthalpies of reactions and equilibrium compositions of products from the pyrolysis and partial oxidation of methane to higher hydrocarbons in the gas phase have been determined within a consistent framework for the temperature range 800-1500 K and the pressure range 0.1-3 MPa , by using the CSIRO-SGTE THERMODATA system. It has been established that the pyrolysis of methane to higher hydrocarbons, e.g. acetylene, ethylene, ethane, prop-1-ene, propane, benzene, toluene, naphthalene, 1-methylnaphthalene and 2-methylnaphthalene, considered as separate reactions, is a highly endothermic reaction with the Gibbs free energies for the individual reactions being positive until 1300 K. The aromatics are thermodynamically most favoured with the equilibrium yields increasing with temperature. Addition of O2 lowers the heats of synthesis and the free energies for methane conversion but no enhancement in the equilibrium yields of hydrocarbons is observed. When solid carbon is allowed, it is the dominant product in all cases with the equilibrium yields for all hydrocarbons becoming negligible. Increasing the pressure at a particular temperature has more effect on the lowering of the equilibrium conversion of methane than on the suppression of solid carbon. Such data are valuable for understanding the conversion limits for methane into higher hydrocarbons.

Stabilization of Organic Carbon and Nitrogen in Consolidating Benthal Deposits

1985 ◽  
Vol 17 (6-7) ◽  
pp. 929-940 ◽  
Author(s):  
C. W. Bryant ◽  
L. G. Rich
Keyword(s):  
Organic Carbon ◽  
Model Verification ◽  
Volatile Acid ◽  
Free Energies ◽  
Organic Loading ◽  
Carbon And Nitrogen ◽  
Loading Rates ◽  
Degradation Reactions ◽  
The Individual ◽  
Organic Deposits

The objective of this research was to develop and validate a predictive model of the benthal stabilization of organic carbon and nitrogen in deposits of waste activated sludge solids formed at the bottom of an aerated water column, under conditions of continual deposition. A benthal model was developed from a one-dimensional, generalized transport equation and a set of first-order biological reactions. For model verification, depth profiles of the major interstitial carbon and nitrogen components were measured from a set of deposits formed in the laboratory at 20°C and a controlled loading rate. The observed sequence of volatile acid utilization in each benthal deposit was that which would be predicted by the Gibbs free energies of the individual degradation reactions and would be controlled by the reduction in interstitial hydrogen partial pressure with time. Biodegradable solids were solubilized rapidly during the first three weeks of benthal retention, but subsequent solubilization occurred much more slowly. The benthal simulation effectively predicted the dynamics of consolidating, organic deposits. Simulation of organic loading rates up to 250 g BVSS/(m2 day) indicated that the stabilization capacity of benthal deposits was far above the range of organic loading rates currently used in lagoon design.

2-Deoxyribose Radicals in the Gas Phase and Aqueous Solution. Transient Intermediates of Hydrogen Atom Abstraction from 2-Deoxyribofuranose

2005 ◽  
Vol 70 (11) ◽  
pp. 1769-1786 ◽  
Author(s):  
Luc A. Vannier ◽  
Chunxiang Yao ◽  
František Tureček
Keyword(s):  
Aqueous Solution ◽  
Hydrogen Atom ◽  
Gas Phase ◽  
Computational Study ◽  
Hydrogen Atom Abstraction ◽  
Oh Radical ◽  
Free Energies ◽  
Intramolecular Hydrogen ◽  
Solvation Free Energies ◽  
Transient Intermediates

A computational study at correlated levels of theory is reported to address the structures and energetics of transient radicals produced by hydrogen atom abstraction from C-1, C-2, C-3, C-4, C-5, O-1, O-3, and O-5 positions in 2-deoxyribofuranose in the gas phase and in aqueous solution. In general, the carbon-centered radicals are found to be thermodynamically and kinetically more stable than the oxygen-centered ones. The most stable gas-phase radical, 2-deoxyribofuranos-5-yl (5), is produced by H-atom abstraction from C-5 and stabilized by an intramolecular hydrogen bond between the O-5 hydroxy group and O-1. The order of radical stabilities is altered in aqueous solution due to different solvation free energies. These prefer conformers that lack intramolecular hydrogen bonds and expose O-H bonds to the solvent. Carbon-centered deoxyribose radicals can undergo competitive dissociations by loss of H atoms, OH radical, or by ring cleavages that all require threshold dissociation or transition state energies >100 kJ mol-1. This points to largely non-specific dissociations of 2-deoxyribose radicals when produced by exothermic hydrogen atom abstraction from the saccharide molecule. Oxygen-centered 2-deoxyribose radicals show only marginal thermodynamic and kinetic stability and are expected to readily fragment upon formation.

THEORETICAL CALCULATION OF pKb VALUES FOR ANILINES AND SULFONAMIDE DRUGS IN AQUEOUS SOLUTION

2012 ◽  
Vol 11 (02) ◽  
pp. 283-295 ◽  
Author(s):  
BAHRAM GHALAMI-CHOOBAR ◽  
ALI GHIAMI-SHOMAMI ◽  
PARIA NIKPARSA
Keyword(s):  
Gas Phase ◽  
Continuum Model ◽  
Correlation Equation ◽  
Polarizable Continuum Model ◽  
Free Energies ◽  
Pcm Model ◽  
Solvation Models ◽  
Polarizable Continuum ◽  
Better Than ◽  
Good Agreement

In this work, calculations of p K b values have been performed for aniline and its substituted derivatives and sulfonamide drugs by using Gaussian 98 software package. Gas-phase energies were calculated with HF /6-31 G ** and B3LYP /6-31 G ** levels of theory. Free energies of solvation have been computed using the polarizable continuum model (PCM), conductor-like polarizable continuum model (CPCM) and the integral equation formalism-polarizable continuum model (IEFPCM) at the same levels which have been used for geometry determination in the gas-phase. The results show that the calculated p K b values using the B3LYP /6-31 G ** are better than those using the corresponding HF /6-31 G **. At first, the correlation equation was found to determine the p K b values of the investigated anilines. Then, this correlation equation was used to calculate the p K b values of the sulfonamide drugs. The results obtained indicate that the PCM model is a suitable solvation model for calculating p K b values in comparison to the other solvation models. For the investigated compounds a good agreement between the experimental and the calculated p K b values was also observed.

Experimental and Modeling Study of the Selective Homogeneous Gas Phase Oxidation of Methane to Methanol

1995 ◽  
Vol 34 (4) ◽  
pp. 1044-1059 ◽  
Author(s):  
Rune Lodeng ◽  
Odd A. Lindvaag ◽  
Paal Soraker ◽  
Per T. Roterud ◽  
Olav T. Onsager
Keyword(s):  
Gas Phase ◽  
Oxidation Of Methane ◽  
Phase Oxidation ◽  
Gas Phase Oxidation ◽  
Modeling Study

Optimization of C1-Oxygenates for the Selective Oxidation of Methane in a Gas-Phase Reaction of CH4−O2−NO at Atmospheric Pressure

2001 ◽  
Vol 15 (1) ◽  
pp. 44-51 ◽  
Author(s):  
Tetsuya Takemoto ◽  
Kenji Tabata ◽  
Yonghong Teng ◽  
Shuiliang Yao ◽  
Akira Nakayama ◽  
...  
Keyword(s):  
Gas Phase ◽  
Selective Oxidation ◽  
Atmospheric Pressure ◽  
Phase Reaction ◽  
Gas Phase Reaction ◽  
Oxidation Of Methane

DIRECT CATALYTIC CONVERSION OF METHANE TO HIGHER HYDROCARBONS

1987 ◽  
Vol 5 (2) ◽  
pp. 169-183 ◽  
Author(s):  
Prasad S. Yarlagadda ◽  
Lawrence A. Morton ◽  
Norman R. Hunter ◽  
Hyman D. Gesser
Keyword(s):  
Catalytic Conversion ◽  
Conversion Of Methane ◽  
Higher Hydrocarbons

scholarly journals The effect of ultraviolet lasers on conversion of methane into higher hydrocarbons

2013 ◽  
Vol 31 (3) ◽  
pp. 481-486 ◽  
Author(s):  
H.A. Navid ◽  
E. Irani ◽  
R. Sadighi-Bonabi
Keyword(s):  
Conversion Efficiency ◽  
Nd:Yag Laser ◽  
Important Variable ◽  
Reaction Products ◽  
Third Harmonic ◽  
Effect Of Pressure ◽  
Laser Parameters ◽  
Conversion Of Methane ◽  
Ultraviolet Lasers ◽  
Higher Hydrocarbons

AbstractConversion of CH4molecule into higher hydrocarbons using two different wavelengths of 248 nm KrF laser and 355 nm of third harmonic of Nd:YAG laser is studied experimentally and theoretically. The stable products are analyzed and the effect of pressure on conversion of methane is measured. The detected reaction products are C2H2, C2H4, and C2H6. The conversion efficiency of 33.5% for 355 nm in comparison to 2.2% conversion for 248 nm for C2H2is achieved. The potential of laser parameters as an important variable in controlling of final products is investigated.

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