The Decomposition of the Paraffin Hydrocarbons

Egloff, Gustav; Schaad, R.; Lowry, C. D.

doi:10.1021/j150314a001

Cited by 31 publications

(29 citation statements)

References 40 publications

(91 reference statements)

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“…This fact contradicts data reported in [1]. Equilibrium C + 2H 2 ↔ CH 4 is shifted to the right [31] at temperatures up to 700°C, but in case of graphite and diamond under such conditions is not achieved because of negligibly small reaction rate. We think that the hydrogenolysis of fullerene black found in this work is the first example of reaction of this type without any hydrogenation catalyst.…”

Section: Hydrogenolysis Of Fullerene Blackcontrasting

confidence: 79%

Fullerene Black: Relationship between Catalytic Activity in n-alkanes Dehydrocyclization and Reactivity in Oxidation, Bromination and Hydrogenolysis

Kushch

Фурсиков

Kuyunko

et al. 2017

Eurasian Chem. Tech. J.

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The reactivity of fullerene black in oxidation (by air oxygen or ions MnO4– or Cr2O72– in solution), bromination (by Br2 or (C4H9)4NBr3) and hydrogenolysis (without hydrogenation catalyst) are studied. The dehydrocyclization of n-alkanes over fullerene black is realized via the monofunctional mechanism, i.e. the dehydrogenation and cyclization stages proceed on the same catalytic center. The addition of alumina to the catalyst transforms dehydrocyclization mechanism to bifunctional one, when fullerene black acts as dehydrogenation agent. Reactivity studies and ESR spectroscopy data for initial and annealed fullerene black show the presence in fullerene black structure of both non-conjugated multiple and dangling bonds. Nonconjugated bonds determine catalytic activity and reactivity of fullerene black. They are localized in amorphous part of fullerene black. Technological aspects of fullerene black as alkanes dehydrocyclization catalyst are discussed.

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Section: Hydrogenolysis Of Fullerene Blackcontrasting

confidence: 79%

Fullerene Black: Relationship between Catalytic Activity in n-alkanes Dehydrocyclization and Reactivity in Oxidation, Bromination and Hydrogenolysis

Kushch

Фурсиков

Kuyunko

et al. 2017

Eurasian Chem. Tech. J.

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“…The results of methane conversion over vacuum black in mixtures with hydrogen are consistent with the data of homogeneous methane pyrolysis at the temperature of 1000°C (see for example [12,14]) that confirms the observed insignificant contribution of heterogeneous reactions at this temperature. The maximum selectivity with respect to alkenes in ternary CH 4 /Ar/H 2 mixtures pyrolysis over catalyst based on fullerene black subjected to non-catalytic hydrogenolysis, is observed at methane/hydrogen molar ratio equal to 1.…”

Section: Resultssupporting

confidence: 88%

Methane Conversion over Vacuum Carbon Black: Influence of Hydrogen

Kushch

Muradyan

Kuyunko

2017

Eurasian Chem. Tech. J.

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Methane pyrolysis over vacuum carbon black has been studied in the temperature range 550–1000 °C. The methane conversion degree and selectivity with respect to ethene and propene do not depend on the initial concentration of methane i.e. the process order with respect to methane is first. The selectivity with respect to pyrolytic carbon is antibate to the methane initial concentration. Hydrogen introduced to methane inhibits formation of pyrolytic carbon and aromatics especially in methane pyrolysis. The methane conversion degree in pyrolysis of methane/hydrogen mixture is inversely proportional to the initial concentration of hydrogen while the selectivity with respect to ethene being symbate to the one. A hypothesis on the reason of inhibition of pyrolytic carbon formation by hydrogen is proposed. Methane pyrolysis is a homogeneous-heterogeneous reaction up to 850°C, but homogeneous reaction is prevalent at the temperature range of maximal selectivity with respect to alkenes.

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“…The Pyrex glass valves, V , have been described (@). Adjustment of screw B regulated the feed rate between 10 …”

Section: Apparatusmentioning

confidence: 99%

Thermal Decomposition of n-Octane

Marschner¹

1938

Ind. Eng. Chem.

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Because of the lack of complete and accurate thermal decomposition data upon normal paraffins between hexane and hexadecane, the behavior of n-octane in the neighborhood of 570" C. and at atmospheric pressure was studied. The noctane was isolated from petroleum in quantities large enough to permit the determination of the amounts of essentially all its pyrolysis products. The effect of temperature, extent of decomposition, and nature of the apparatus in which pyrolysis was effected were studied. A slight revision of the free-radical theory improves somewhat its agreement with the experimental data. The effect of a carbonized surface upon the pyrolysis was studied, and the bearing of these results upon the theory of thermal decomposition is discussed. The liquid products obtained were thoroughly examined for evidences of rearrangement of olefins and of isomerization of the carbon skeleton. A semiquantitative analysis of all the chemical individuals found among the liquid hydrocarbons is presented. The probable manner in which they were produced, as indicated by the evidence available, is outlined. M ANY thorough researches upon the thermal decomposition of alkanes a t atmospheric pressure have been published recently, but nearly all of this work has been carried out upon the relatively simple gaseous members of the series. A certain amount of attention has been given to much larger alkanes. Hexadecane was extensively studied by Gault (1 7) and an approximately thirty-carbon paraffin by Waterman (50). However, because of the large number of gaseous and particularly of liquid products which result, complete and accurate analyses of all products have not been obtained as in the case of the small homologs. With the notable exception of the investigations of Frey and Hepp (15), little work has been done upon the pyrolysis of alkanes of intermediate carbon content. This is somewhat surprising, since efficient columns for the fractionation of gases (36) and liquids (IS), permitting analysis of the complex mixtures resulting from the decomposition of relatively small amounts of hydrocarbon, have been available for several years. To bridge this gap, the present work was undertaken; the compound chosen was n-octane.Several workers have reported preliminary studies upon n-octane pyrolysis; their results are condensed in Table I.The data are of little value because of the few accurate determinations of time and extent of decomposition. Such gas analyses as are reported show little concordance. Moldavskir (SO) observed that pressure exerted a marked influence on the pyrolysis and that iron exhibited a catalytic effect. Hugel and Szayna (19) obtained evidence of splitting at all carbon-to-carbon linkages of the molecule in nickel and iron apparatus. Decomposition in the presence of added catalysts has also been reported (IO, 28, 99, 35, 64). Much more thorough work by Dintzes and associates (6-8) coincided with the present study; similar experimental conditions were employed, with the single exception that decomposition was car...

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The Decomposition of the Paraffin Hydrocarbons

Abstract: 2 Propane and butane dissolved in gasoline (given as percentage of liquid volume) are calculated to equivalent volumes as free gas.

Cited by 31 publications

References 40 publications

Fullerene Black: Relationship between Catalytic Activity in n-alkanes Dehydrocyclization and Reactivity in Oxidation, Bromination and Hydrogenolysis

Fullerene Black: Relationship between Catalytic Activity in n-alkanes Dehydrocyclization and Reactivity in Oxidation, Bromination and Hydrogenolysis

Methane Conversion over Vacuum Carbon Black: Influence of Hydrogen

Thermal Decomposition of n-Octane

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