Catalytic hydrogenation of nitrobenzene by use of a mixture of carbon monoxide and water

Takemura, Yasuhiro; Onodera, Kiyoshi; Ōuchi, Koji

doi:10.1021/i300012a005

Cited by 10 publications

(4 citation statements)

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“…As much as 60% desulfurization of benzothiophene with a commercial -03/ -1203 catalyst at 68 atm and 583-633 K was obtained. Other work by Takemura et al (1983) showed that hydrogenation of nitrobenzene could be accomplished with in situ hydrogen generation from the water gas shift reaction. However, these reactions are known to be faster and easier to accomplish than DBT hydrodesulfurization.…”

mentioning

confidence: 99%

Desulfurization of dibenzothiophene by in-situ hydrogen generation through a water gas shift reaction

Hook¹,

Akgerman²

1986

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

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Global depletion of sweet crude necessitates greater use of high sulfur content hydrocarbon resources.Because of this and the prohibitive cost of producing pure hydrogen, hydrodesulfurization is becoming a major cost factor in petroleum and coal liquid refining. This study indicates that hydrodesulfurization can be achieved by generating the hydrogen necessary for the reaction in situ with the water gas shift reaction. For this work, a sulfided commerical -03/ -203 catalyst is used in a trickle-bed reactor at 58-69 atm of pressure and 595-648 K temperature. Dibenzothiophene is chosen for this work since it is representative of the heterocyclic sulfur molecules present in oil which are rather difficult to desulfurize. Significant desulfurization of dibenzothiophene by in situ hydrogen generation is observed. The pseudo-first-order rate constants calculated appear to be an order of magnitude higher than those reported in the literature for pure hydrogen feed. Zero-, first-, and second-order rate expressions are tested with the data analysis program developed previously, and activation energies and rate constants are calculated for each case. The three expressions have comparable validity based on the sum of the squares of deviations between predicted and experimental conversions. The activation energies calculated agree well with literature values published.

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confidence: 99%

Desulfurization of dibenzothiophene by in-situ hydrogen generation through a water gas shift reaction

Hook¹,

Akgerman²

1986

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

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“…A number of supported transition metal catalysts have reportedly been used for the in situ generation of hydrogen via the WGSR in the hydroprocessing of model and nonmodel feeds. − ,,, Takemura et al reported that hydroprocessing using H 2 generated in situ greatly reduced the tendency for cracking and coking with alumina-supported MoO 3 compared with using an external supply of H 2 . The authors postulated that the occurrence of the shift reaction on the Mo catalyst resulted in surface coverage by nascent hydrogen that subsequently participated in the hydrogenolysis reaction.…”

Section: Resultsmentioning

confidence: 99%

“…The supported transition metal oxides widely used in hydroprocessing have been shown to catalyze the WSGR in studies investigating the in situ generation of hydrogen for subsequent use in the hydrogenation and hydrogenolyses of model compounds. − Sulfided forms of these metal oxides, which are reportedly more active in hydrotreatment processes, − have also be shown to catalyze the WGSR as well as HDS. − Hook and Akgerman 12 used hydrogen generated in situ via the WGSR to study the desulfurization of dibenzothiophene (DBT), which is reported to be one of the polycyclic thiophenes most resistant to sulfur removal. − The observed HDS rate constants for DBT were an order of magnitude greater than those reported from work using H 2 feed. They suggested that the hydrogen formed on the catalyst surface during the water gas shift reaction is nascent and possibly more active than diatomic H 2 .…”

Section: Introductionmentioning

confidence: 99%

“…If successful, such a process would obviate the need for the separation and purification stages in hydrogen production; partial oxidation flue gases could be fed directly to the hydrotreater and, if necessary, additional steam could be supplied to consume the CO. 12 The supported transition metal oxides widely used in hydroprocessing have been shown to catalyze the WSGR in studies investigating the in situ generation of hydrogen for subsequent use in the hydrogenation and hydrogenolyses of model compounds. [13][14][15] Sulfided forms of these metal oxides, which are reportedly more active in hydrotreatment processes, [16][17][18] have also be shown to catalyze the WGSR as well as HDS. [19][20][21][22] Hook and Akgerman 12 used hydrogen generated in situ via the WGSR to study the desulfurization of dibenzothiophene (DBT), which is reported to be one of the polycyclic thiophenes most resistant to sulfur removal.…”

Section: Introductionmentioning

confidence: 99%

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Hydrodesulfurization of Cold Lake Diesel Fraction Using Dispersed Catalysts: Influence of Hydroprocessing Medium and Sources of H₂

Siewe

1998

Energy Fuels

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The hydrodesulfurization (HDS) of a straight-run diesel fraction of a Cold Lake crude was investigated using ammonium tetrathiomolybdate (ATTM) and phosphomolybdic acid (PMA) as dispersed catalysts. The experiments were performed in an autoclave at 340 °C using different hydrotreating media such as H2, H2/H2O, and H2 generated in situ from CO/H2O via the water gas shift reaction (WGSR). The external supply of molecular hydrogen proved to be the most effective medium for HDS with both catalysts, while similar levels of sulfur removal were achieved using either the H2/H2O or the CO/H2O medium. Desulfurization using molecular H2 was thus apparently inhibited by the addition of water to the feed, while H2 generated in situ proved to be at least as efficient at removing sulfur from diesel as using molecular H2 in the presence of water. Under our reaction conditions, ATTM exhibited greater activity for HDS and for the WGSR than PMA. This work demonstrates that Mo-based dispersed catalysts and partial oxidation flue gases containing CO, H2O, CO2, and H2 can be used to achieve satisfactory levels of sulfur removal from an industrial-type feedstock, as well as the feasibility of using dispersed catalysts and recycle streams for the treatment of heavy oil emulsions.

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Die Wassergas‐Shift‐Reaktion in der organischen Synthese

Ambrosi

Denmark

2016

Angewandte Chemie

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Seit ihrer Entdeckung vor mehr als hundert Jahren hat die Wassergas‐Shift‐Reaktion (WGSR) entscheidende Bedeutung in der industriellen Chemie, indem sie den Wasserstoff zur Beschickung grundlegender großtechnischer Prozesse wie der Haber‐Bosch‐Synthese von Ammoniak liefert. Obwohl die Produktion von Wasserstoff immer noch die Hauptanwendung der WGSR ist, markierte die Einführung der homogenen Katalyse in den 1970er Jahren den Beginn einer Synergie zwischen der WGSR und der organischen Chemie. Dabei wurde das Reduktionsvermögen des CO/H2O‐Paars in der Synthese von Feinchemikalien nicht nur für Hydrierungsreaktionen genutzt, sondern auch für katalytische Prozesse, deren Umsatz einen Reduktionsschritt im Katalysezyklus erfordert. Ungeachtet des Potenzials und der einzigartigen Eigenschaften der WGSR sind ihre Anwendungen in der organischen Synthese bisher noch wenig entwickelt. Dieses Thema wird hier kritisch besprochen in der Hoffnung, dass eine erhöhte Wahrnehmung zu neuen, kreativen Arbeiten auf dem Gebiet anregt.

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Catalytic hydrogenation of nitrobenzene by use of a mixture of carbon monoxide and water

Cited by 10 publications

References 3 publications

Desulfurization of dibenzothiophene by in-situ hydrogen generation through a water gas shift reaction

Desulfurization of dibenzothiophene by in-situ hydrogen generation through a water gas shift reaction

Hydrodesulfurization of Cold Lake Diesel Fraction Using Dispersed Catalysts: Influence of Hydroprocessing Medium and Sources of H₂

Die Wassergas‐Shift‐Reaktion in der organischen Synthese

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Catalytic hydrogenation of nitrobenzene by use of a mixture of carbon monoxide and water

Cited by 10 publications

References 3 publications

Desulfurization of dibenzothiophene by in-situ hydrogen generation through a water gas shift reaction

Desulfurization of dibenzothiophene by in-situ hydrogen generation through a water gas shift reaction

Hydrodesulfurization of Cold Lake Diesel Fraction Using Dispersed Catalysts: Influence of Hydroprocessing Medium and Sources of H2

Die Wassergas‐Shift‐Reaktion in der organischen Synthese

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Hydrodesulfurization of Cold Lake Diesel Fraction Using Dispersed Catalysts: Influence of Hydroprocessing Medium and Sources of H₂