Effect of hydrogen sulfide on the catalytic hydrodenitrogenation of quinoline

Satterfield, Charles N.; Gültekin, Selahattin

doi:10.1021/i200012a009

Cited by 116 publications

(71 citation statements)

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“…The relative adsorption coefficients of the reactants and intermediate products are completely different in the liquid and gas phase. For instance, the adsorption coefficient of DHQ is twice as large as those of Q, THQI, and THQ5 in the liquid phase, but six times larger in the gas phase (12,14,17). The H2S/H 2 ratio during the autoclave experiments was 2.5 × 10 -3 and 1.5 × 10 -4 during the flow experiments.…”

Section: Flow Reactor Experimentsmentioning

confidence: 94%

“…In contrast to HDS, the hydrogenation of the N-containing ring and in most cases also the hydrogenation of the benzene ring of quinoline are necessary steps in the two reaction pathways of Q-HDN via DHQ and OPA (cf. (11)(12)(13)(14)(15)(16)(17). The differences in the hydrogenation activities between various TMS will be more pronounced in the Q-HDN, which requires 8-14 H atoms to convert Q to hydrocarbons, than in the thiophene HDS which strictly needs only 4 H atoms, but may use up to 8 atoms.…”

Section: Autoclave Experimentsmentioning

confidence: 99%

“…Before discussing the selectivities of the various TMS catalysts it is useful to point out that the compounds present in the reaction product mixture can be divided into several categories with respect to their adsorption properties (14)(15)(16)(17). Because of their nonpolar character, the adsorption of the solvent and the hydrocarbon products of the Q-HDN can be neglected compared to the double-ring N-compounds.…”

Section: Autoclave Experimentsmentioning

confidence: 99%

“…The aromatic amines (THQ1, THQ5, Q, OPA) have a low basicity due to the interaction of the nitrogen lone-pair electrons with zr electrons of the aromatic ring, while the secondary alicyclic amine (DHQ) has a much higher basicity. Its adsorption coefficient was therefore assumed to be twice as large as that of the aromatic amines in the liquid phase (14). By studying the inhibition of the HDS of thiophene by these nitrogen compounds La Vopa and Satterfield (19) could actually measure their adsorption constants.…”

Section: Autoclave Experimentsmentioning

confidence: 99%

“…This difference might have led to slightly altered catalyst surfaces and thus to altered activities and selectivities. It is known that an increase in the H2S/H2 ratio may lead to an increase in NH3 removal, but a decrease in hydrogenation (14,16). In the autoclave experiments the catalyst activities are measured directly after sulfidation of the catalysts, while in the flow experiments the catalysts were aged during 27 h. The results of the flow experiments at constant (10 and 50%) HDN-conversions of Q to hydrocarbons are presented in Table 3.…”

Section: Flow Reactor Experimentsmentioning

confidence: 99%

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Hydrodenitrogenation of quinoline over carbon-supported transition metal sulfides

Eijsbouts

Beer

Prins

1991

Journal of Catalysis

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Transition metal sulfide (TMS) catalysts were prepared by impregnation of an activated carbon support with aqueous solutions of first-, second-, and third-row (group V-VIII) transition metal salts, drying and in situ sulfidation. The catalysts were tested in the hydrodenitrogenation of quinoline (653 K, 5.5 MPa) in microautoclaves and microflow reactors. The first-row transition metal sulfides had low quinoline conversions to hydrocarbons, and their periodic trend formed a U-shaped curve with a minimum at Mn/C and Fe/C and maxima at V/C and Ni/C. The quinoline conversions to hydrocarbons of the second-and third-row TMS formed volcano curves with maxima at Rh/C and Ir/C and with Mo/C and W/C having the lowest conversions. The transition metal sulfide catalysts with a low quinoline hydrogenation (first-row transition metal sulfides, Mo/C and W/C) also had a low quinoline conversion to hydrocarbons. The transition metal sulfides with the highest quinoline conversions to hydrocarbons (Rh/C, Pd/C, Os/C, Ir/C and Pt/C) had a very high quinoline hydrogenation and a high selectivity for propylcyclohexane. Ru/C and especially Re/C had a good quinoline conversion to hydrocarbons, but also an exceptionally high selectivity for propylbenzene.

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Section: Flow Reactor Experimentsmentioning

confidence: 94%

Section: Autoclave Experimentsmentioning

confidence: 99%

Section: Autoclave Experimentsmentioning

confidence: 99%

Section: Autoclave Experimentsmentioning

confidence: 99%

Section: Flow Reactor Experimentsmentioning

confidence: 99%

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Hydrodenitrogenation of quinoline over carbon-supported transition metal sulfides

Eijsbouts

Beer

Prins

1991

Journal of Catalysis

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Hydrodenitrogenation – Homogeneous

Fish

Bianchini

2002

Encyclopedia of Catalysis

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The industrial hydrodenitrogenation (HDN) process entails the removal of nitrogen from heteroaromatic nitrogen compounds in petroleum feedstocks under very high temperatures (400–600°C) and high pressures (200 bar) of hydrogen gas. In order to understand the various steps associated with this complicated HDN reaction, organometallic chemists have attempted to define each important reaction utilizing a homogeneous catalysis approach. Therefore, studies on the modeling of the HDN process, with an emphasis on the synthetic and mechanistic aspects of the homogeneous catalytic hydrogenation of model petroleum, heteroaromatic nitrogen compounds with organometallic complexes as catalysts, at low temperature and low pressures of hydrogen gas, will be reviewed in this article. A comparison of the regioselectivities under various hydrogenation conditions for these compounds will be discussed for a wide variety of transition‐metal complexes with regard to the role of substrate binding at the metal ion center. The polynuclear heteroaromatic nitrogen compounds appear to hydrogenate more readily, under similar reaction conditions, in comparison with model petroleum compounds with mononuclear ring systems, e.g., pyridine. The relative rates of hydrogenation of a variety of heteroaromatic nitrogen compounds as well as compounds that inhibit and enhance selective hydrogenation of the nitrogen‐containing ring will also be a focus of this review. A relatively new spectroscopic technique, high pressure nuclear magnetic resonance spectroscopy, will be shown to be a powerful tool to elucidate the mechanisms of the regioselective hydrogenation of polynuclear heteroaromatic nitrogen compounds. Finally, selected studies by other contributors to this nascent field will also be placed in perspective.

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