Oxidation methane exploitation

One of the most important challenges in the modern chemical industry is represented by the development of new processes aimed at the exploitation of alternative raw materials, in replacement of technologies that make use of building blocks derived from oil (olefins and aromatics). This has led to a scientific activity devoted to the valorization of natural gas components, through catalytic, environmentally benign processes of transformation (1). Examples include the direct exoenthalpic transformation of methane to methanol, DME or formaldehyde, the oxidation of ethane to acetic acid or its oxychlorination to vinyl chloride, the oxidation of propane to acrylic acid or its ammoxidation to acrylonitrile, the oxidation of isobutane to... 

The industrially important direct methane conversion processes comprise oxidative coupling, reductive coupling including pyrolysis reactions, partial oxidation, halogenation and oxyhalogenation,26 and ammoxidation. Other direct conversions include alkylation, electrophilic substitution, and C-H bond activation over various complex and super acid catalysts. Several of these direct conversion technologies remain to be exploited to achieve their full commercial potentials. 

Single pulse, shock tube decomposition of acetic acid in argon inv olves the same pair of homogeneous, molecular first-order reactions as thermolysis (19). Platinum on grapliite catalyzes the decomposition at 500—800 K at low pressures (20). Ketene, methane, carbon oxides, and a variety of minor products are obtained. Photochemical decomposition yields methane and carbon dioxide and a number of free radicals, wliich have complicated pathways (21). Electron impact and gamma rays appear to generate these same products (22). Electron cyclotron resonance plasma made from acetic acid deposits a diamond [7782-40-3] film on suitable surfaces (23). The film, having a polycrystalline stmcture, is a useful electrical insulator (24) and widespread industrial exploitation of diamond films appears to be on the horizon (25). 

Within this setting, in shallow coastal water conditions, consortia of bacteria set up microbial mat columns to exploit the supply of sulphate and nitrate from water. In the muds below the mats, methanogens were active, and above them methane-oxidizing bacteria. The waters were enriched chemically by contributions from hydro-thermal water plumes, either from the laterally equivalent beginnings of Reliance Fm volcanism elsewhere in the basin, or from more distant oceanic sources. Photosynthetic green sulphur bacteria may have oxidized H2S to S°, whereas sulphate and sulphur reducers operated in the reverse direction. 

As shown above, oxidized diamond exhibited considerable activity in the oxidative dehydrogenation of alkanes, hence further studies on the oxidized diamond supported catalysts were exploited. Nickel-loaded alumina is generally used for the partial oxidation of methane (reaction 5). However, carbon deposition onto the nickel is the major problem in the commercialization of this process. 

An important breakthrough in PPy chemistry was the discovery by Lee and coworkers95 in 1995 of a chemical polymerization route to an unsubstituted PPy that was soluble in organic solvents. They exploited the surfactant-like qualities of added dodecylbenzenesulfonate (DBSA 9) as a dopant anion to solubilize PPy formed during oxidation of pyrrole by aqueous (Nn4)2S208. The PPy/DBSA product, isolated as a black powder in 42% yield after 40 h reaction at 0°C, was very soluble in m-cresol, and could be dissolved in weakly polar solvents such as chloroform and dichloro-methane by the addition of an equimolar amount of dodecylbenzenesulfonic acid. A film cast from chloroform solution exhibited an electrical conductivity of 5 S cm-1, and its UV-visible spectrum was similar to that of electrochemically deposited PPy. 

The combustion process is initiated by an ignition source converting some number of methane molecules into free radicals. Free radicals are in turn converted to OH free radical. Possible oxygenated compounds include aldehyde, alcohol, carboxylic acid, and oxide. The hydroxyl free radical then reacts with methane and is regenerated. The successive (chain type) combustion reaction is impeded by destruction of the OH radicals. Solid surfaces often destroy the OH radicals before they can react with hydrocarbons. The same effect is exploited in a porous-bed flame arrestor. In general, the combustion rates are very fast and nearly measurable with a few exceptional situations where time scales can be expanded to microseconds (KT6 s). The... 

The majority of methods for the continuous optical monitoring of gases can be divided into two groups. In the flrst, the intrinsic optical property of the gas is exploited to sense it. lypical examples include chlorine, methane, carbon monoxide, and nitrogen oxides. In the second method, an indicator is used to transduce the gas concentration into a measurable optical parameter. This approach has frequently been applied when the gas has no useful intrinsic optical property or when it is dissolved in water. Typical examples include oxygen, carbon dioxide, and sulfur dioxide. 

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