Partially oxidized

The original method for the manufacture of ethyne, the action of water on calcium carbide, is still of very great importance, but newer methods include the pyrolysis of the lower paraffins in the presence of steam, the partial oxidation of natural gas (methane) and the cracking of hydrocarbons in an electric arc. 

Here again, this is not a refining process, properly speaking. Partial oxidation is one of the processes for the ultimate conversion of heavy residues, asphalts, coke and even coal. 

Table 10.14 provides some essential information concerning the production of hydrogen by partial oxidation of a VR. By-products are carbon dioxide and hydrogen sulfide. 

The needs for hydrogen being considerably accentuated, the introduction of partial oxidation of at least a part of the ultimate residues is foreseen, in spite of its high cost. 

Strelzoff, S. (1974), Partial oxidation for syngas and fuel (comparaison des precedes Texaco, Shell et Union Carbide) . Hydrocarbon processing, Vol. 53, No. 12, p. 79. 

When a solution of, say, 1 g. of hydroquinone in 4 ml. of rectified spirit is poured into a solution of 1 g. of quinone in 30 ml. of water, qulnhydrone C,HA.C,H (0H)3, a complex of equimolecular amounts of the two components, is formed as dark green crystals having a gfistening metallic lustre, m.p. 172°. In solution, it is largely dissociated into quinone and hydroquinone. Quinhydrone is more conveniently prepared by the partial oxidation of hydroquinone with a solution of iron alum. 

Acetaldehyde, first used extensively during World War I as a starting material for making acetone [67-64-1] from acetic acid [64-19-7] is currendy an important intermediate in the production of acetic acid, acetic anhydride [108-24-7] ethyl acetate [141-78-6] peracetic acid [79-21 -0] pentaerythritol [115-77-5] chloral [302-17-0], glyoxal [107-22-2], aLkylamines, and pyridines. Commercial processes for acetaldehyde production include the oxidation or dehydrogenation of ethanol, the addition of water to acetylene, the partial oxidation of hydrocarbons, and the direct oxidation of ethylene [74-85-1]. In 1989, it was estimated that 28 companies having more than 98% of the wodd s 2.5 megaton per year plant capacity used the Wacker-Hoechst processes for the direct oxidation of ethylene. 

Since 1960, the Hquid-phase oxidation of ethylene has been the process of choice for the manufacture of acetaldehyde. There is, however, stiU some commercial production by the partial oxidation of ethyl alcohol and hydration of acetylene. The economics of the various processes are strongly dependent on the prices of the feedstocks. Acetaldehyde is also formed as a coproduct in the high temperature oxidation of butane. A more recently developed rhodium catalyzed process produces acetaldehyde from synthesis gas as a coproduct with ethyl alcohol and acetic acid (83—94). 

Oxidation Step. A review of mechanistic studies of partial oxidation of propylene has appeared (58). The oxidation process flow sheet (Fig. 2) shows equipment and typical operating conditions. The reactors are of the fixed-bed shell-and-tube type (about 3—5 mlong and 2.5 cm in diameter) with a molten salt coolant on the shell side. The tubes are packed with catalyst, a small amount of inert material at the top serving as a preheater section for the feed gases. Vaporized propylene is mixed with steam and ak and fed to the first-stage reactor. The feed composition is typically 5—7% propylene, 10—30%... 

One possible route is to make formaldehyde direcdy from methane by partial oxidation. This process has been extensively studied (106—108). The incentive for such a process is reduction of raw material costs by avoiding the capital and expense of producing the methanol from methane. 

Separation, combustion, pyrolysis, hydrogena-tion, anaerobic fermen-tation, aerobic fermen-tation, biophotolysis, partial oxidation, steam reforming, chemical hy-drolysis, enzyme hydrol-ysis, other chemical conversions, natural processes... 

The electrons undergo the equivalent of a partial oxidation process ia a dark reaction to a positive potential of +0.4 V, and Photosystem I then raises the potential of the electrons to as high as —0.7 V. Under normal photosynthesis conditions, these electrons reduce tryphosphopyridine-nucleotide (TPN) to TPNH, which reduces carbon dioxide to organic plant material. In the biophotolysis of water, these electrons are diverted from carbon dioxide to a microbial hydrogenase for reduction of protons to hydrogen ... 

Medium Heat- Value Gas. Medium heat-value (medium Btu) gas (6,7) has a heating value between 9 and 26 MJ/m (250 and 700 Btu/fT). At the lower end of this range, the gas is produced like low heat-value gas, with the notable exception that an air separation plant is added and relatively pure oxygen (qv) is used instead of air to partially oxidize the coal. This eliminates the potential for nitrogen in the product and increases the heating value of the product to 10.6 MJ /m (285 Btu/fT). Medium heat-value gas consists of a mixture of methane, carbon monoxide, hydrogen, and various other gases and is suitable as a fuel for industrial consumers. 

Partial Oxidation. It is often desirable to augment the supply of naturally occurring or by-product gaseous fuels or to produce gaseous fuels of well-defined composition and combustion characteristics (5). This is particularly tme in areas where the refinery fuel (natural gas) is in poor supply and/or where the manufacture of fuel gases, originally from coal and more recently from petroleum, has become well estabHshed. 

As in the case of coal, synthetic natural gas can be produced from heavy oil by partially oxidizing the oil to a mixture of carbon monoxide and hydrogen... 

Emissions from methanol vehicles are expected to produce lower HC and CO emissions than equivalent gasoline engines. However, methanol combustion produces significant amounts of formaldehyde (qv), a partial oxidation product of methanol. Eormaldehyde is classified as an air toxic and its emissions should be minimized. Eormaldehyde is also very reactive in the atmosphere and contributes to the formation of ozone. Emissions of NO may also pose a problem, especiaHy if the engine mns lean, a regime in which the standard three-way catalyst is not effective for NO reduction. 

Dia ene deductions. Olefins, acetylenes, and azo-compounds are reduced by hydrazine in the presence of an oxidizing agent. Stereochemical studies of alkene and alkyne reductions suggest that hydrazine is partially oxidized to the transient diazene [3618-05-1] (diimide, diimine) (9) and that the cis-isomer of diazene is the actual hydrogenating agent, acting by a concerted attack on the unsaturated bond ... 

Synthesis Gas Chemicals. Hydrocarbons are used to generate synthesis gas, a mixture of carbon monoxide and hydrogen, for conversion to other chemicals. The primary chemical made from synthesis gas is methanol, though acetic acid and acetic anhydride are also made by this route. Carbon monoxide (qv) is produced by partial oxidation of hydrocarbons or by the catalytic steam reforming of natural gas. About 96% of synthesis gas is made by steam reforming, followed by the water gas shift reaction to give the desired H2 /CO ratio. 

Elastomers. Elastomers are polymers or copolymers of hydrocarbons (see Elastomers, synthetic Rubber, natural). Natural mbber is essentially polyisoprene, whereas the most common synthetic mbber is a styrene—butadiene copolymer. Moreover, nearly all synthetic mbber is reinforced with carbon black, itself produced by partial oxidation of heavy hydrocarbons. Table 10 gives U.S. elastomer production for 1991. The two most important elastomers, styrene—butadiene mbber (qv) and polybutadiene mbber, are used primarily in automobile tires. 

Flame or Partial Combustion Processes. In the combustion or flame processes, the necessary energy is imparted to the feedstock by the partial combustion of the hydrocarbon feed (one-stage process), or by the combustion of residual gas, or any other suitable fuel, and subsequent injection of the cracking stock into the hot combustion gases (two-stage process). A detailed discussion of the kinetics for the pyrolysis of methane for the production of acetylene by partial oxidation, and some conclusions as to reaction mechanism have been given (12). 

There has been considerable research into the production of substitute natural gas (SNG) from fractions of cmde oil, coal, or biomass (see Euels SYNTHETIC, Euels frombiomass Euels fromwaste). The process involves partial oxidation of the feedstock to produce a synthesis gas containing carbon... 

Parameter Steam reforming (SR) Partial oxidation (POX) Texaco gasification (TG) Water electrolysis... 

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