Thermal degradation vapors

Causes of deactivation are basically three-fold chemical, mechanical or thermal— hereby six different routes of deactivation of catalyst material are described (some have been introduced before, without further explanation) poisoning (i.e. CO on Pt), fouling (i.e. coke formation during ethene hydrogenation on Pt), thermal degradation, vapor compound formation accompanied by transport, vapor-solid and/or solid-solid reactions, and attrition/crushing [162, 163]. 

To achieve sufficient vapor pressure for El and Cl, a nonvolatile liquid will have to be heated strongly, but this heating may lead to its thermal degradation. If thermal instability is a problem, then inlet/ionization systems need to be considered, since these do not require prevolatilization of the sample before mass spectrometric analysis. This problem has led to the development of inlet/ionization systems that can operate at atmospheric pressure and ambient temperatures. Successive developments have led to the introduction of techniques such as fast-atom bombardment (FAB), fast-ion bombardment (FIB), dynamic FAB, thermospray, plasmaspray, electrospray, and APCI. Only the last two techniques are in common use. Further aspects of liquids in their role as solvents for samples are considered below. 

The question as to whether a flame retardant operates mainly by a condensed-phase mechanism or mainly by a vapor-phase mechanism is especially comphcated in the case of the haloalkyl phosphoms esters. A number of these compounds can volatilize undecomposed or undergo some thermal degradation to release volatile halogenated hydrocarbons (37). The intact compounds or these halogenated hydrocarbons are plausible flame inhibitors. At the same time, thek phosphoms content may remain at least in part as relatively nonvolatile phosphoms acids which are plausible condensed-phase flame retardants (38). There is no evidence for the occasionally postulated formation of phosphoms haUdes. Some evidence has been presented that the endothermic vaporization and heat capacity of the intact chloroalkyl phosphates may be a main part of thek action (39,40). 

Product Quality Considerations of product quahty may require low holdup time and low-temperature operation to avoid thermal degradation. The low holdup time eliminates some types of evaporators, and some types are also eliminated because of poor heat-transfer charac teristics at low temperature. Product quality may also dic tate special materials of construction to avoid met hc contamination or a catalytic effect on decomposition of the product. Corrosion may also influence evaporator selection, since the advantages of evaporators having high heat-transfer coefficients are more apparent when expensive materials of construction are indicated. Corrosion and erosion are frequently more severe in evaporators than in other types of equipment because of the high hquid and vapor velocities used, the frequent presence of sohds in suspension, and the necessary concentration differences. 

Salt accumulations and other deposits on the firetube can sometimes be detected by smelling the vapors from the still vent. A burned" odor emitted from these vapors usually indicates this type of thermal degradation. Another detection method is to observe the glycol color. It will darken quickly if the glycol degrades. These detection methods may prevent a firetube failure. 

Liquids and solids do not burn as such, but on exposure to heat vaporize or undergo thermal degradation to liberate flammable gases and vapours which burn. Some chemicals undergo spontaneous combustion (see page 214). 

Gomez et al. (1988) studied the vapor-phase pyrolysis and combustion of 2,4-D in the temperature range 200-1,000 °C. 2,4-D began to decompose at 200-250 °C. In the presence of air, 2,4-D completely degraded when the temperature exceeded 900 °C. HCl and chlorine were identified as products of thermal degradation. 

Solvent extraction processes usually run at ambient pressures and temperatures. If higher pressures are applied, it is mostly because a higher extraction temperature is required when equilibrium or mass transfer conditions are more favorable at an elevated temperature. Distillation, on the other hand, is usually carried out at higher temperatures and ambient pressures. To avoid thermal degradation, the pressure sometimes has to be lowered below ambient pressure. Distillation is based on the differences in vapor pressures of the components to be separated, whereas solvent extraction utilizes the differences in intermolecular interactions in the liquid phase. 

In extractive distillation with a supercritical solvent, extraction rather than vacuum is used to volatilize the components into the vapor phase. Operating temperatures can be lower than in conventional distillation, and the desired C8-Ci2 oxy fraction will then have been subjected to less thermal degradation. Carbon dioxide has a critical temperature that meets this goal. 

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