Process atmosphere reactions

Organic compounds are a major constituent of the FPM at all sites. The major sources of OC are combustion and atmospheric reactions involving gaseous VOCs. As is the case with VOCs, there are hundreds of different OC compounds in the atmosphere. A minor but ubiquitous aerosol constituent is elemental carbon. EC is the nonorganic, black constituent of soot. Combustion and pyrolysis are the only processes that produce EC, and diesel engines and wood burning are the most significant sources. 

Classify the compounds in Table 12-4 into precursors (reactants) and products of atmospheric reaction processes. 

Most petrochemical processes are essentially enclosed and normally vent only a small amount of fugitive emissions. However, the petrochemical processes that use air-oxidation-type reactions normally vent large, continuous amounts of gaseous emissions to the atmosphere (10). Six major petrochemical processes employ reactions using air oxidation. Table 30-5 lists the atmospheric emissions from these processes along with applicable control measures. 

Transition metal oxides or their combinations with metal oxides from the lower row 5 a elements were found to be effective catalysts for the oxidation of propene to acrolein. Examples of commercially used catalysts are supported CuO (used in the Shell process) and Bi203/Mo03 (used in the Sohio process). In both processes, the reaction is carried out at temperature and pressure ranges of 300-360°C and 1-2 atmospheres. In the Sohio process, a mixture of propylene, air, and steam is introduced to the reactor. The hot effluent is quenched to cool the product mixture and to remove the gases. Acrylic acid, a by-product from the oxidation reaction, is separated in a stripping tower where the acrolein-acetaldehyde mixture enters as an overhead stream. Acrolein is then separated from acetaldehyde in a solvent extraction tower. Finally, acrolein is distilled and the solvent recycled. 

In the vapor-phase process, the reaction temperature and pressure are approximately 250°C and 40 atmospheres. Phosphoric acid on Kieselguhr is a commonly used catalyst. To limit polyalkylation, a mixture of propene-propane feed is used. Propylene can be as low as 40% of the feed mixture. A high benzene/propylene ratio is also used to decrease polyalkylation. A selectivity of about 97% based on benzene can be obtained. 

Most of the trichloroethylene used in the United States is released into the atmosphere by evaporation primarily from degreasing operations. Once in the atmosphere, the dominant trichloroethylene degradation process is reaction with hydroxyl radicals the estimated half-life for this process is approximately 7 days. This relatively short half-life indicates that trichloroethylene is not a persistent atmospheric compound. Most trichloroethylene deposited in surface waters or on soil surfaces volatilizes into the atmosphere, although its high mobility in soil may result in substantial percolation to subsurface regions before volatilization can occur. In these subsurface environments, trichloroethylene is only slowly degraded and may be relatively persistent. 

Both processes are switched on by the absorption of short-wavelength radiation X < 240 nm for H20 and X < 230 nm for C02. On the assumption that H atoms escape from the atmosphere, there is a net gain in oxygen to the atmosphere. Reactions of O atoms and 02 chemistry would then lead to the formation of a small ozone layer with a low ozone concentration. 

If the primary loss mechanism of atmospheric reaction is accepted as having a 17h half-life, the D value is 1.6 x 109 mol/Pah. For any other process to compete with this would require a value of at least 108 mol/Pah. This is achieved by advection (4 x 10s), but the other processes range in D value from 19 (advection in bottom sediment) to 1.5 x 10s (reaction in water) and are thus a factor of over 100 or less. The implication is that the water reaction rate constant would have to be increased 100-fold to become significant. The soil rate constant would require an increase by 104 and the sediment by 10s. These are inconceivably large numbers corresponding to very short half-lives, thus the actual values of the rate constants in these media are relatively unimportant in this context. They need not be known accurately. The most sensitive quantity is clearly the atmospheric reaction rate. 

The reaction of ammonia and hydrogen chloride in the gas phase has been the subject of several studies in the last 30 years [56-65], The interest in this system is mainly that it represents a simple model for proton transfer reactions, which are important for many chemical and biological processes. Moreover, in the field of atmospheric sciences, this reaction has been considered as a prototype system for investigation of particle formation from volatile species [66,67], Finally, it is the reaction chosen as a benchmark on the ability, of quantum chemical computer simulations, to realistically simulate a chemical process, its reaction path and, eventually, its kinetics. 

Although the atmosphere is 78% nitrogen gas (N2), it is not available (i.e., able to be used) to plants or animals except after it has been fixed. Thus, the development of the process for making ammonia from hydrogen and atmospheric nitrogen by Haber was extremely important. The first reaction (1) in Figure 1.4 shows the reaction carried out in the Haber process. This reaction is reversible so ammonia is compressed and cooled, and liquid ammonia is removed from the reaction mixture to drive the reaction to the right. 

Related to the uptake and reaction of N02 into liquid water and at the interface is a so-called heterogeneous dark reaction of gaseous N02 with water vapor to form nitrous acid, HONO. Potential formation processes and reactions of HONO in the atmosphere have been reviewed by Lammel and Cape (1996). This is a fascinating reaction in that, despite decades of research, the mechanism is still not understood. It occurs on a variety of surfaces, including water and acid surfaces (e.g., Kleffmann et al., 1998) and, as discussed in this chapter, on soot as well. 

As we have seen, key nitroarenes found in extracts of ambient particulate matter are 1-nitropyrene (1-N02-Py), predominant in primary combustion emissions, and 2-nitrofluoranthene and 2-nitropyrene, major products of gas-phase atmospheric reactions. Here we focus simply on their atmospheric fates as particle-bound species participating in heterogeneous decay processes. Formation of such nitro-PAHs in gas-phase reactions is addressed in Section F. 

Styrene. All commercial processes use the catalytic dehydrogenation of ethylbenzene for the manufacture of styrene.189 A mixture of steam and ethylbenzene is reacted on a catalyst at about 600°C and usually below atmospheric pressure. These operating conditions are chosen to prevent cracking processes. Side reactions are further suppressed by running the reaction at relatively low conversion levels (50-70%) to obtain styrene yields about 90%. The preferred catalyst is iron oxide and chromia promoted with KzO, the so-called Shell 015 catalyst.190... 

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