Gasoline oxidation

Isobutyric acid, dimethylacetic acid, 2-methylpropanoic acid, (CHjjjCH COOH, colourless syrupy liquid with an unpleasant odour b.p. 154°C. Prepared by oxidation of 2-methylpropanol with K2Cr207 and H2SO4. Salts soluble in water. Used in alkaline solution for sweetening gasoline. 

In the petroleum industry the term gum refers to the dark coloured polymer formed by the oxidation of certain unsaturated compounds of cracked or reformed gasolines. 

The crankcase of a gasoline or diesel engine is in reality a hydrocarbon oxidation reactor oil is submitted to strong agitation in the presence of air at high temperature (120°C) furthermore, metals such as copper and iron, excellent catalysts for oxidation, are present in the surroundings. 

Oxidation stability (gasoline) (induction period) NFM 07-012 ISO/DlS 7536 ASTM D 525 Time necessary for a sample bomb under oxygen pressure to reach the critical induction point... 

Isobutyl alcohol [78-83-1] forms a substantial fraction of the butanols produced by higher alcohol synthesis over modified copper—zinc oxide-based catalysts. Conceivably, separation of this alcohol and dehydration affords an alternative route to isobutjiene [115-11 -7] for methyl /-butyl ether [1624-04-4] (MTBE) production. MTBE is a rapidly growing constituent of reformulated gasoline, but its growth is likely to be limited by available suppHes of isobutylene. Thus higher alcohol synthesis provides a process capable of supplying all of the raw materials required for manufacture of this key fuel oxygenate (24) (see Ethers). 

Another ASTM test method. Potential Gum (D873), combines the existent gum and the oxidation stabihty tests to measure potential gum. A sample of gasoline is subjected to the oxidation stabihty test for 960 min, filtered to remove particulates, and then subjected to an existent gum test. The potential gum is expressed as the total (unwashed) gum in this test. 

Other tests to predict stabihty of gasoline have been developed and reported in the hterature. One, developed by the U.S. military, stores gasoline at elevated (43°C) temperatures for up to 12 weeks and measures existent gum at the end of that period (26). Another measures existent gum in the presence of copper. The copper catalyzes oxidation and may be a better estimator of the stabihty of gasoline at high temperature/low residence time conditions. 

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. 

Lubricants. Glycerol can be used as a lubricant in places where an oil would fad. It is recommended for oxygen compressors because it is more resistant to oxidation than mineral ods. It is also used to lubricate pumps and bearings exposed to fluids such as gasoline and benzene, which would... 

Total consumption of lead in the United States in 1993 reached 1,318,800 t. Of this, 766,000 t (58%) is allocated to battery use suppHed as either a mixed oxide or as metal. Approximately 95% of batteries are recycled and the lead recovered. In 1993, 908,000 t of lead came from secondary smelters and refiners compared to 350,000 t originating in primary mines and smelters (39). Approximately 51,000 t of lead was consumed in U.S. production of all oxides and chemicals appHcable to all industries other than batteries. Estimates include 8000 t for plastics, 6000 t for gasoline additives, 2000 t for mbber, and 30,000 t for ceramics, glass, and electronics. Lead is not used to any extent in dispersive appHcations such as coatings. 

Propjiene [115-07-17, CH2CH=CH2, is perhaps the oldest petrochemical feedstock and is one of the principal light olefins (1) (see Feedstocks). It is used widely as an alkylation (qv) or polymer—ga soline feedstock for octane improvement (see Gasoline and other motor fuels). In addition, large quantities of propylene are used ia plastics as polypropylene, and ia chemicals, eg, acrylonitrile (qv), propylene oxide (qv), 2-propanol, and cumene (qv) (see Olefin POLYMERS,polypropylene Propyl ALCOHOLS). Propylene is produced primarily as a by-product of petroleum (qv) refining and of ethylene (qv) production by steam pyrolysis. 

The hydroperoxide process involves oxidation of propjiene (qv) to propylene oxide by an organic hydroperoxide. An alcohol is produced as a coproduct. Two different hydroperoxides are used commercially that result in / fZ-butanol or 1-phenylethanol as the coproduct. The / fZ-butanol (TBA) has been used as a gasoline additive, dehydrated to isobutjiene, and used as feedstock to produce methyl tert-huty ether (MTBE), a gasoline additive. The 1-phenyl ethanol is dehydrated to styrene. ARCO Chemical has plants producing the TBA coproduct in the United States, Erance, and the Netherlands. Texaco has a TBA coproduct plant in the United States. Styrene coproduct plants are operated by ARCO Chemical in the United States and Japan, Shell in the Netherlands, Repsol in Spain, and Yukong in South Korea. 

The / f/-butanol (TBA) coproduct is purified for further use as a gasoline additive. Upon reaction with methanol, methyl tert-huty ether (MTBE) is produced. Alternatively the TBA is dehydrated to isobutylene which is further hydrogenated to isobutane for recycle ia the propylene oxide process. 

Neutral aqueous salt solutions react slowly with tin when oxygen is present but oxidizing salt solutions, such as potassium peroxysulfate, ferric chloride and sulfate, and aluminum and stannic chlorides dissolve tin. Nonaqueous organic solvents, lubricating oils, and gasoline have Httle effect. 

Stannic Chloride. Stannic chloride is available commercially as anhydrous stannic chloride, SnCl (tin(IV) chloride) stannic chloride pentahydrate, SnCl 5H20 and in proprietary solutions for special appHcations. Anhydrous stannic chloride, a colorless Aiming Hquid, fumes only in moist air, with the subsequent hydrolysis producing finely divided hydrated tin oxide or basic chloride. It is soluble in water, carbon tetrachloride, benzene, toluene, kerosene, gasoline, methanol, and many other organic solvents. With water, it forms a number of hydrates, of which the most important is the pentahydrate. Although stannic chloride is an almost perfect electrical insulator, traces of water make it a weak conductor. 

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