Intermediate operating temperatures

Various ways of overcoming the PTA oxidation problem have been incorporated into commercial processes. The predominant solution is the use of high concentrations of manganese and cobalt ions (2,248—254), optionally with various cocatalysts (204,255,256), in the presence of an organic or inorganic bromide promoter in acetic acid solvent. Operational temperatures are rather high (ca 200°C). A lesser but significant alternative involves isolation of intermediate PTA, conversion to methyl/)-toluate, and recycle to the reactor. The ester is oxidized to monomethyl terephthalate, which is subsequentiy converted to DMT and purified by distillation (248,257—264). 

Temperature. The temperature for combustion processes must be balanced between the minimum temperature required to combust the original contaminants and any intermediate by-products completely and the maximum temperature at which the ash becomes molten. Typical operating temperatures for thermal processes are incineration (750—1650°C), catalytic incineration (315—550°C), pyrolysis (475—815°C), and wet air oxidation (150—260°C at 10,350 kPa) (15). Pyrolysis is thermal decomposition in the absence of oxygen or with less than the stoichiometric amount of oxygen required. Because exhaust gases from pyrolytic operations are somewhat "dirty" with particulate matter and organics, pyrolysis is not often used for hazardous wastes. 

The reaction vessel (nitrator) is constructed of cast iron, mild carbon steel, stainless steel, or glass-lined steel depending on the reaction environment. It is designed to maintain the required operating temperature with heat-removal capabiUty to cope with this strongly exothermic and potentially ha2ardous reaction. Secondary problems are the containment of nitric oxide fumes and disposal or reuse of the dilute spent acid. Examples of important intermediates resulting from nitration are summarized in Table 3. 

For higher ambient temperatures, current capacity should be suitably reduced to maintain the same end temperature during continuous operation. Refer to Tables 28.3(a) and (b), recommending the derating factors for a higher ambient temperature or a lower temperature rise for the same end temperature of 85° or 90°C respectively. For intermediate ambient temperatures, see Figure 28.10. 

Blends with alkyd or other organic resins have, however, been preptu ed and these show heat resistance intermediate between those of the organic resins and the silicones. Of ptu ticular interest is the use of silicone-organic resin blends filled with aluminium powder for the coating of metal chimneys and furnace doors. At the operating temperatures the resins are destroyed, leaving a layer of aluminium film. 

Fuel cells such as the one shown on Fig. 3.4a convert H2 to H20 and produce electrical power with no intermediate combustion cycle. Thus their thermodynamic efficiency compares favorably with thermal power generation which is limited by Carnot-type constraints. One important advantage of solid electrolyte fuel cells is that, due to their high operating temperature (typically 700° to 1100°C), they offer the possibility of "internal reforming" which permits the use of fuels such as methane without a separate external reformer.33 36... 

According to the literature [77], a process is considered to be low hazard from the thermal standpoint if the normal operating temperature or temperature due to upset is 50°C or more lower than the ARC onset temperature, and the maximum process temperature is held for only a short period of time. However, other factors must be considered in evaluating the thermal hazard of a process such as total enthalpy of reaction or decomposition, potential for reactant accumulation, the boiling point of the reaction mass, and the rate of reaction. The testing must involve all appropriate materials including reactants, intermediates, and products. In some cases, though, the 50°C differential... 

ETEM is thus used as a nanolaboratory with multi-probe measurements. Design of novel reactions and nanosynthesis are possible. The structure and chemistry of dynamic catalysts are revealed by atomic imaging, ED, and chemical analysis (via PEELS/GIF), while the sample is immersed in controlled gas atmospheres at the operating temperature. The analysis of oxidation state in intermediate phases of the reaction and, in principle, EXELFS studies are possible. In many applications, the size and subsurface location of particles require the use of the dynamic STEM system (integrated with ETEM), with complementary methods for chemical and crystallographic analyses. 

SRE (Fig. 7) and POE (Fig. 10) reactions, a maximum yield of H2 could be attained in the OSRE reaction above 600 °C because CH4, if formed as an intermediate by ethanol decomposition could be completely converted into syngas above this temperature.7,8,10,109 The participation of reverse WGS reaction at high temperature leads to an increase in CO composition above 400 °C with a concomitant decrease in the composition of C02. Thus, at higher operating temperatures of above 600 °C, the system would produce mainly syngas rather than a mixture of H2 and C02. A comparison of equilibrium compositions of POE and OSRE reactions indicates that the presence of steam in this system increases the maximum yield of H2 from about 50% in the POE reaction (Fig. 10) to about 65% in the OSRE, and this is very close to that observed in the SRE reaction (around 70%) due to the participation of steam... 

The intermediate- and low-temperature materials exhibit both significant oxygen ion and electron conductivity. This means that the oxygen reduction can take place everywhere in the cathode and is not restricted to the TPBs as in the LSM-type cathodes. An option for compensating the relatively low oxygen ion conductivity of LSC and LSCF at operating temperatures around 600 °C is by mixing the material with (doped) ceria [79, 80],... 

Given the large number of potential beneficial effects of lowering the nominal operating temperature of the SOFC stack and their corollary affect on system cost, intermediate temperature SOFC concepts are being pursued by many organizations throughout the U.S. and the World. 

Stepwise Ce dehydrocyclization was observed over potassia-chromia-alumina as well as potassia-molybdena-alumina catalysts (9, 10). Higher operating temperatures (450°-500°C) of these catalysts facilitate the appearance of unsaturated intermediates in the gas phase. Radiotracer studies indicate a predominant Ce ring closure of C-labeled n-heptane over pure chromia (132,132a). 

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