Oxidation products residence time

Aluminum-containing propellants deflver less than the calculated impulse because of two-phase flow losses in the nozzle caused by aluminum oxide particles. Combustion of the aluminum must occur in the residence time in the chamber to meet impulse expectations. As the residence time increases, the unbumed metal decreases, and the specific impulse increases. The soHd reaction products also show a velocity lag during nozzle expansion, and may fail to attain thermal equiUbrium with the gas exhaust. An overall efficiency loss of 5 to 8% from theoretical may result from these phenomena. However, these losses are more than offset by the increase in energy produced by metal oxidation (85—87). 

At still higher temperatures, when sufficient oxygen is present, combustion and "hot" flames are observed the principal products are carbon oxides and water. Key variables that determine the reaction characteristics are fuel-to-oxidant ratio, pressure, reactor configuration and residence time, and the nature of the surface exposed to the reaction 2one. The chemistry of hot flames, which occur in the high temperature region, has been extensively discussed (60-62) (see Col ustion science and technology). 

Chemical Reaction Measurements. Experimental studies of incineration kinetics have been described (37—39), where the waste species is generally introduced as a gas in a large excess of oxidant so that the oxidant concentration is constant, and the heat of reaction is negligible compared to the heat flux required to maintain the reacting mixture at temperature. The reaction is conducted in an externally heated reactor so that the temperature can be controlled to a known value and both oxidant concentration and temperature can be easily varied. The experimental reactor is generally a long tube of small diameter so that the residence time is well defined and axial dispersion may be neglected as a source of variation. Off-gas analysis is used to track both the disappearance of the feed material and the appearance and disappearance of any products of incomplete combustion. 

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. 

Figure 2 illustrates the three-step MIBK process employed by Hibernia Scholven (83). This process is designed to permit the intermediate recovery of refined diacetone alcohol and mesityl oxide. In the first step acetone and dilute sodium hydroxide are fed continuously to a reactor at low temperature and with a reactor residence time of approximately one hour. The product is then stabilized with phosphoric acid and stripped of unreacted acetone to yield a cmde diacetone alcohol stream. More phosphoric acid is then added, and the diacetone alcohol dehydrated to mesityl oxide in a distillation column. Mesityl oxide is recovered overhead in this column and fed to a further distillation column where residual acetone is removed and recycled to yield a tails stream containing 98—99% mesityl oxide. The mesityl oxide is then hydrogenated to MIBK in a reactive distillation conducted at atmospheric pressure and 110°C. Simultaneous hydrogenation and rectification are achieved in a column fitted with a palladium catalyst bed, and yields of mesityl oxide to MIBK exceeding 96% are obtained. 

Fresh butane mixed with recycled gas encounters freshly oxidized catalyst at the bottom of the transport-bed reactor and is oxidized to maleic anhydride and CO during its passage up the reactor. Catalyst densities (80 160 kg/m ) in the transport-bed reactor are substantially lower than the catalyst density in a typical fluidized-bed reactor (480 640 kg/m ) (109). The gas flow pattern in the riser is nearly plug flow which avoids the negative effect of backmixing on reaction selectivity. Reduced catalyst is separated from the reaction products by cyclones and is further stripped of products and reactants in a separate stripping vessel. The reduced catalyst is reoxidized in a separate fluidized-bed oxidizer where the exothermic heat of reaction is removed by steam cods. The rate of reoxidation of the VPO catalyst is slower than the rate of oxidation of butane, and consequently residence times are longer in the oxidizer than in the transport-bed reactor. 

Because of the formation of nitrogen oxides, a steady-state ozone concentration cannot be obtained instead, due to the buHdup of nitrogen oxides, an increase in residence time in the discharge results in a decrease in ozone concentration beyond the maximum value. Thus, there is an optimum residence time for maximum ozone production. 

Acetaldehyde can be used as an oxidation-promoter in place of bromine. The absence of bromine means that titanium metallurgy is not required. Eastman Chemical Co. has used such a process, with cobalt as the only catalyst metal. In that process, acetaldehyde is converted to acetic acid at the rate of 0.55—1.1 kg/kg of terephthahc acid produced. The acetic acid is recycled as the solvent and can be isolated as a by-product. Reaction temperatures can be low, 120—140°C, and residence times tend to be high, with values of two hours or more (55). Recovery of dry terephthahc acid follows steps similar to those in the Amoco process. Eastman has abandoned this process in favor of a bromine promoter (56). Another oxidation promoter which has been used is paraldehyde (57), employed by Toray Industries. This leads to the coproduction of acetic acid. 2-Butanone has been used by Mobil Chemical Co. (58). 

ButylatedPhenols and Cresols. Butylated phenols and cresols, used primarily as oxidation inhibitors and chain terrninators, are manufactured by direct alkylation of the phenol using a wide variety of conditions and acid catalysts, including sulfuric acid, -toluenesulfonic acid, and sulfonic acid ion-exchange resins (110,111). By use of a small amount of catalyst and short residence times, the first-formed, ortho-alkylated products can be made to predominate. Eor the preparation of the 2,6-substituted products, aluminum phenoxides generated in situ from the phenol being alkylated are used as catalyst. Reaction conditions are controlled to minimise formation of the thermodynamically favored 4-substituted products (see Alkylphenols). The most commonly used is -/ fZ-butylphenol [98-54-4] for manufacture of phenoHc resins. The tert-huty group leaves only two rather than three active sites for condensation with formaldehyde and thus modifies the characteristics of the resin. 

Methanol oxidation on Pt has been investigated at temperatures 350° to 650°C, CH3OH partial pressures, pM, between 5-10"2 and 1 kPa and oxygen partial pressures, po2, between 1 and 20 kPa.50 Formaldehyde and C02 were the only products detected in measurable concentrations. The open-circuit selectivity to H2CO is of the order of 0.5 and is practically unaffected by gas residence time over the above conditions for methanol conversions below 30%. Consequently the reactions of H2CO and C02 formation can be considered kinetically as two parallel reactions. 

Release of superoxide during ORR catalysis indicates that the ferric-superoxo intermediate (Fig. 18.20) has a substantial residence time at 0.2 V (the potential of the maximum production of superoxide), suggesting that the potential of the ferric-superoxo/ferric-peroxo couple, (Fig. 18.20), is more reducing than 0.2 V. The fraction of superoxide detected at potentials >0.2 V probably reflects the fact that 02, which is a strong outer-sphere reductant [Huie and Neta, 1999], was oxidized by the mostly ferric catalytic film before it could escape the film. There are two plausible explanations for the decrease in the fraction of superoxide byproduct released at... 

Continuous Multicomponent Distillation Column 501 Gas Separation by Membrane Permeation 475 Transport of Heavy Metals in Water and Sediment 565 Residence Time Distribution Studies 381 Nitrification in a Fluidised Bed Reactor 547 Conversion of Nitrobenzene to Aniline 329 Non-Ideal Stirred-Tank Reactor 374 Oscillating Tank Reactor Behaviour 290 Oxidation Reaction in an Aerated Tank 250 Classic Streeter-Phelps Oxygen Sag Curves 569 Auto-Refrigerated Reactor 295 Batch Reactor of Luyben 253 Reversible Reaction with Temperature Effects 305 Reversible Reaction with Variable Heat Capacities 299 Reaction with Integrated Extraction of Inhibitory Product 280... 

Figure 6. Reservoir sizes, residence times, and 5 Fe values for aqueous Fe(II), as calculated for DIR assuming first-order rate laws. Timescale arbitrarily set to 100 days. Calculations based on rate constant determined for a 23 day DIR experiment involving hydrous ferric oxide (HFO) by S. algae (Beard et al. 1999). The percent total reduction at 100 days is shown in the grey box on the lower right side of the lower diagrams, based on the value of k. Parts A-C assume a 2/ 1 ratio of 10, whereas parts D-F assume Bikjki ratio of 1000. As constrained by first-order rate laws, the proportion of the intermediate products Fe(III)-L, followed by Fe(II)-L, increase before substantial accumulation of the final Fe(II)aq product (Parts A and D). Tlie fraction of Fe(III)-L in the exchangeable pool of Fe (Fe(III)-L + Fe(II)-L + Fe(II)aq) decreases with time, primarily due to accumulation of the Fe(II)aq end product, where the rate of change is a function of the kjk ratio.

Phenol methylation to 2,6-xylenol has been widely studied for the past few deeades owing to the room for improvisation from the viewpoint of product selectivity. Generally during phenol methylation to 2,6-xylenol, occurs via sequential methylation of phenol to o-cresol to 2,6-xylenol, various reaction parameters mediate the selectivity between the two. For instance, when the reaetants stoichiometry of methanol to phenol molar ratio > 2, and significant residence time of o-cresol may favor 2,6-xylenol selectivity. However, excess methanol is often used, sinee some amount of methanol tend to undergo oxidation into various reformate produets [71] under vapor phase condition. Similarly, reaction temperature, catalyst acid-base property, and space velocity of the reaetant are the parameters that govern the selectivity to 2,6-xylenol. 

Results of an experimental program in which aluminum particles were burned with steam and mixtures of oxygen and argon in small-scale atmospheric dump combustor are presented. Measurements of combustion temperature, radiation intensity in the wavelength interval from 400 to 800 nm, and combustion products particle size distribution and composition were made. A combustion temperature of about 2900 K was measured for combustion of aluminum particles with a mixture of 20%(wt.) O2 and 80%(wt.) Ar, while a combustion temperature of about 2500 K was measured for combustion of aluminum particles with steam. Combustion efficiency for aluminum particles with a mean size of 17 yum burned in steam with O/F) / 0/F)st 1-10 and with residence time after ignition estimated at 22 ms was about 95%. A Monte Carlo numerical method was used to estimate the radiant heat loss rates from the combustion products, based on the measured radiation intensities and combustion temperatures. A peak heat loss rate of 9.5 W/cm was calculated for the 02/Ar oxidizer case, while a peak heat loss rate of 4.8 W/cm was calculated for the H2O oxidizer case. 

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