Vapor Phase Oxidation of Aromatic Hydrocarbons.

Jones, J. H.; Fenske, M. R.; Hutton, David G.; Allendorf, H. D.

doi:10.1021/je60011a043

Cited by 7 publications

(5 citation statements)

References 1 publication

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“…Subsequent to the development of the raining solids reactors extensive experimental research was initiated to establish the products and conversion levels obtainable under various operating conditions utilizing various hydrocarbons ranging from paraffins to aromatics (Jones, et al, 1961a(Jones, et al, ,b, 1970(Jones, et al, , 1971a. Experiments were also undertaken to establish the utility of these processes for various conversions presently being employed in the petroleum and petrochemical industries as well as the chemical industry.…”

Section: Introductionmentioning

confidence: 99%

Chemical and Physical Processes of Hydrocarbon Combustion: Chemical Processes

Geisbrecht¹,

Daubert²

1975

Ind. Eng. Chem. Proc. Des. Dev.

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An initial attempt at firmly establishing the interrelationship of vapor-phase partial oxidation processes to the associated process parameters has been undertaken. This has been specifically done for the oxidation of ethane in the presence or absence of a countercurrent rain of particulate solids which enable uniform and stable control of the extreme reaction heat. It has been shown that these systems are comprised of a coupled chemical and physical transport process. Part I of this two-part series deals with the chemical processes of ethane partial oxidation. A mechanism is developed on the bases of experimental data illustrating the effects of temperature, pressure, composition, and contact time in conjunction with estimated rate parameters. The mechanism has been found very effective in quantitatively correlating and predicting experimental behavior over substantial ranges of conditions using derived Arrhenius parameters which are consistent when compared with theoretical estimates.

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Section: Introductionmentioning

confidence: 99%

Chemical and Physical Processes of Hydrocarbon Combustion: Chemical Processes

Geisbrecht¹,

Daubert²

1975

Ind. Eng. Chem. Proc. Des. Dev.

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“…Benzene may be formed by a variation of the first propagation step such as ^~^,CH2CH2 + ch2=ch2 (9) which would follow the abstraction of a primary hydrogen from ethylbenzene, /X/CHiCHa u aCH2CH2 4-H2 (10) instead of the secondary abstraction shown in Reaction 6. Benzene could also be formed by a variation of the second propagation step, such as that suggested by Szwarc ( 22 A greater yield of ethylene than ethane was observed, but the ethyl radical from Reaction 11 could decompose to ethylene and a hydrogen atom instead of forming ethane through abstraction.…”

Section: Resultsmentioning

confidence: 99%

Pyrolysis of Ethylbenzene with and without Oxygen Initiation

Hausmann¹,

King²

1966

Ind. Eng. Chem. Fund.

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BRIEFThe effect of small quantities of oxygen (0 to 10%) on the thermal decomposition of ethylbenzene in the temperature range of 570-650° c was investigated utilizing a flow reactor with residence times on the order of 0.1 second. The runs made,with oxygen excluded fit a half order rate expression with an activation energy of 69 kcal.jg.mole. Small quantities of oxygen increase the rate of thermal decomposition but this· effect tapers off as the oxygen concentration is increased. With an oxygen . concentration of around 3% the same level of conversion is achieved at a temperature 10° C :t:ow~r than that required when oxygen is excluded. The styrene yield selectivity increases from 74 mole % 'I· without oxygen to 81 mole %with 10% oxygen. The presence of "' oxygen also lowers the apparent activation energy. SHORT SUMMARYRates of thermal decomposition of ethylbenzene. were measured· ~-· .< in an C.l second flow reactor at 570-650° c and interpreted via a Rice-Herzfeld mechanism. The effect of small quantities of oxygen on rate and product selectivity was determined., .. A reviewof investigations of oxygen-initiated pyrolysis prior to 1956 has been given by Letort, who states that one part of oxygen in 100,000 doubles the initial deqomposition rate of · acetaldehyde at 4 77° c ( 13). Niclause, .Combe; and .Letort· ·have ·-·shown that the pyrolysis threshold· of acetaldehyde. is lowered·.from 450° C to 150° C by the addition of one part oxygen in 10,000 (16 ; .., . ' ' . ., ..... :The. hydrocarbon investigated· in this ·work ·was ethylbenzene .. · · · . .The tnermal decomposition rates of alkylated aromatics have not · 415-590° C with a residence time of 5 seconds and an oxygenethylbenzene mole ratio of 0.7-1.0 (10). They found that. styrene forms essentially all the non-oxygenated aromatic product. For example with 33% conversion of ethylbenzene at 530° C a carbon balance gives a selectivity of 65% to styrene, 15% to benzaldehyde~ 8% to acetophenone, 3%. to other aromatics and the remainder to gaseous products. This raises the possibility that at a much lower oxygen content the selectivity.of styrene formation might remain high without the simultan~ous appearance of oxygenated aromatics which present a separation problem. A qualitative analysis of the gaseous pyrolysis products was made using the gas chromatograph. Hydrogen was found to I • be present in the highest concentration. Methane, ethane and ethylene were also identl.fied as products of the pyrolysis.Approximately 10 times as much ethylene as ethane was produced.Exact quantitative analyses of the gaseous products were not made because of the large amount of nitrogen diluent. Webb andCorson found approximately equal yields of ethylene and parafinnic hydrocarbons; however they employed much higher conversion levels where secondary reactions would be more important (24). The.standard error of the resulting correlation is 23%. (1)( 2) can be seen the slope of this line is 35,000° K, which corresponds ! to an apparent activation energy, E, of 70,000 ca...

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“…Product Analysis. The gaseous products were collected over saturated sodium chloride solution and analyzed either by means of an Orsat apparatus or by gas chromatography, following the procedure of Jones et al (1961). The total amount of off-gas was measured by a wettest meter using corrections for pressure, temperature, and water saturation.…”

Section: Methodsmentioning

confidence: 99%