Oxidation temperature

Figure C2.8.7. Principal oxide growth rate laws for low- and high-temperature oxidation inverse logarithmic, linear, paralinear and parabolic.

In the presence of strong oxidizing agents at elevated temperatures oxidation of tertiary alcohols leads to cleavage of the various carbon-carbon bonds at the hydroxyl bearing carbon atom and a complex mixture of products results... 

Oxidation. Acetaldehyde is readily oxidised with oxygen or air to acetic acid, acetic anhydride, and peracetic acid (see Acetic acid and derivatives). The principal product depends on the reaction conditions. Acetic acid [64-19-7] may be produced commercially by the Hquid-phase oxidation of acetaldehyde at 65°C using cobalt or manganese acetate dissolved in acetic acid as a catalyst (34). Liquid-phase oxidation in the presence of mixed acetates of copper and cobalt yields acetic anhydride [108-24-7] (35). Peroxyacetic acid or a perester is beheved to be the precursor in both syntheses. There are two commercial processes for the production of peracetic acid [79-21 -0]. Low temperature oxidation of acetaldehyde in the presence of metal salts, ultraviolet irradiation, or osone yields acetaldehyde monoperacetate, which can be decomposed to peracetic acid and acetaldehyde (36). Peracetic acid can also be formed directiy by Hquid-phase oxidation at 5—50°C with a cobalt salt catalyst (37) (see Peroxides and peroxy compounds). Nitric acid oxidation of acetaldehyde yields glyoxal [107-22-2] (38,39). Oxidations of /)-xylene to terephthaHc acid [100-21-0] and of ethanol to acetic acid are activated by acetaldehyde (40,41). 

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). 

At low temperatures, oxidation with chromic acid gives propynal [624-67-9] C2H2O (14), or propynoic acid [471-25-0] C2H2O2 (15), which can also be prepared in high yields by anodic oxidation (16). 

Perfluoroepoxides have also been prepared by anodic oxidation of fluoroalkenes (39), the low temperature oxidation of fluoroalkenes with potassium permanganate (40), by addition of difluorocarbene to perfluoroacetyl fluoride (41) or hexafluoroacetone (42), epoxidation of fluoroalkenes with oxygen difluoride (43) or peracids (44), the photolysis of substituted l,3-dioxolan-4-ones (45), and the thermal rearrangement of perfluorodioxoles (46). 

Propane. The VPO of propane [74-98-6] is the classic case (66,89,131—137). The low temperature oxidation (beginning at ca 300°C) readily produces oxygenated products. A prominent NTC region is encountered on raising the temperature (see Fig. 4) and cool flames and oscillations are extensively reported as compHcated functions of composition, pressure, and temperature (see Fig. 6) (96,128,138—140). There can be a marked induction period. Product distributions for propane oxidation are given in Table 1. 

The equiHbrium approach should not be used for species that are highly sensitive to variations in residence time, oxidant concentration, or temperature, or for species which clearly do not reach equiHbrium. There are at least three classes of compounds that cannot be estimated weU by assuming equiHbrium CO, products of incomplete combustion (PlCs), and NO. Under most incineration conditions, chemical equiHbrium results in virtually no CO or PlCs, as required by regulations. Thus success depends on achieving a nearly complete approach to equiHbrium. Calculations depend on detailed knowledge of the reaction network, its kinetics, the mixing patterns, and the temperature, oxidant, and velocity profiles. 

Metallurgy. The strong affinity for oxygen and sulfur makes the rare-earth metals useflil in metallurgy (qv). Mischmetal acts as a trap for these Group 16 (VIA) elements, which are usually detrimental to the properties of steel (qv) or cast iron (qv). Resistance to high temperature oxidation and thermomechanical properties of several metals and alloys are thus significantly improved by the addition of small amounts of mischmetal or its siUcide (16,17). 

Galvalume has been shown to have two to six times the life of an equivalent thickness of 2inc, including marine atmospheres. Eor high temperature oxidation resistance up to 700°C, Galvalume is equivalent to pure aluminum. 

There is also a two-step process of chromizing foUowed by aluminizing. Above 900°C the chromizing begins to rediffuse and the protective oxide changes to Al O from Cr202. Aluminum oxide is less volatile than chromium oxide and better for high temperature oxidation resistance above 1000°C. 

N. Birks and G. H. Meir, Introduction to High Temperature Oxidation of Metals, E. Arnold, London, 1983. 

Eastman Chemical Co. uses only cobalt and bromine, and lower temperature oxidations are held at 175—230°C (83). Solution of 4-formylbenzoic acid is obtained by using hydroclones to replace the mother hquor from the first oxidation with fresh acetic acid. A residence time of up to 2 h is used in order to allow for sufficient digestion to take place and to reduce the 4-formylbenzoic acid content to 40—270 ppm (83). Recovery of dry terephthahc acid is as described above. 

High Temperature Properties. There are marked differences in the abihty of PGMs to resist high temperature oxidation. Many technological appHcations, particularly in the form of platinum-based alloys, arise from the resistance of platinum, rhodium, and iridium to oxidation at high temperatures. Osmium and mthenium are not used in oxidation-resistant appHcations owing to the formation of volatile oxides. High temperature oxidation behavior is summarized in Table 4. 

A. Alper, ed., ELigh Temperature Oxides (1 -4), Vol. 5, Eefractoy Materials, Academic Press, Inc., New York, 1970. 

High Temperature Oxidation Resistant Coatings, Materials Advisory Board, National Academy of Science, Washington, D.C., 1970. 

Table 1. High Temperature Oxidation Resistant Beryllides...

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