The mechanism of pyridine hydrogenolysis on molybdenum-containing catalysts II. Hydrogenation of pyridine to piperidine

Sonnemans, J.W.M.

doi:10.1016/0021-9517(73)90329-1

Cited by 63 publications

(12 citation statements)

References 5 publications

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“…Reaction and adsorption studies also suggest that hydrogen and the nitrogen compounds adsorb on different, perhaps neighboring, catalyst sites, while the adsorption of hydrocarbons is relatively weak and can usually be neglected (Sonnemans et al, 1973).…”

Section: C 2 Hydrodenitrogenation Studiesmentioning

confidence: 99%

“…The rates of HDN reactions have often been adequately decribed by first order kinetics, in which the first order rate constant decreases with increased initial nitrogen concentration, or by pseudo first order kinetics (Flinn et al, 1963;Sonnemans et al, 1973;Shih et al, 1977).…”

Section: C 2 Hydrodenitrogenation Studiesmentioning

confidence: 99%

“…It is assumed that hydrogen and the nitrogen compounds adsorb on different catalyst sites, as suggested by adsorption measurements and other reaction studies (Sonnemans et al, 1973 Table 2 …”

Section: G 5 Kinetic Modellingmentioning

confidence: 99%

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Reaction network and kinetics of the vapor-phase catalytic hydrodenitrogenation of quinoline

Satterfield¹,

Cocchetto²

1981

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

131

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The reaction network and kinetics of quinoline hydrodenitogenation (HDN) were studied in a flow microreactor packed with presulfided NiMo/A1 2 0 3 catalyst. Reactor temperatures were 330 to 420 0 C, and total pressure was either 3.55 or 7.0 MPa (500.or 1000 psig).Partial pressure of the reactant compound (quinoline or one of its hydrogenated derivatives) was 13.3 or 26.7 kPa, and reactant feed rates varied from 41.7 to 667 hr g catalyst/g-mol.The results indicated that the initial ring saturation reactions of quinoline are all reversible over a wide range of HDN conditions; also, saturation of the aromatic ring is thermodynamically (but not necessarily kinetically) more favorable than saturation of the heteroring. Nitrogen removal from quinoline occurred primarily through the decahydroquinoline intermediate, and propylcyclohexane was the major hydrocarbon product. The NiMo/Al?0 3 catalyst exhibited little selectivity for the reaction pathway of minimum hydrogen consumption, due to insufficient hydrogenolysis activity.Adsorptivities of the nitrogen compounds in the quinoline HDN network varied significantly. A Langmuir-Hinshelwood kinetic model, allowing for these different adsorptivities, was developed for the hydrogenolysis and nitrogen removal reactions. On active catalyst sites, the Py-tetrahydroquinoline and decahydroquinoline reaction intermediates appeared to adsorb about six times as strongly as the less basic aromatic amines (quinoline, Bz-tetrahydroquinoline, and o-propylaniline), which in turn showed an adsorption strength approximately four times greater than that of ammonia.

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Section: C 2 Hydrodenitrogenation Studiesmentioning

confidence: 99%

Section: C 2 Hydrodenitrogenation Studiesmentioning

confidence: 99%

See 1 more Smart Citation

Reaction network and kinetics of the vapor-phase catalytic hydrodenitrogenation of quinoline

Satterfield¹,

Cocchetto²

1981

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

131

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“…In our dilute limit (Na 2 MoO 4 ≤ 8 mM) with relatively high pH (>4), Sonnemans and Mars reported that molybdate anions do not form oxometalate clusters. 31 On the basis of these studies, we assume that oxomolybdate clustering does not occur significantly in our system, and subsequently only consider eq 15 and 16 to be the molybdate equilibrium reactions.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Anodic Electrodeposition of a Cationic Polyelectrolyte in the Presence of Multivalent Anions

2016

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The electrochemical quartz crystal microbalance (QCM) was used to investigate the deposition of poly(allylamine hydrochloride) (PAH) with molybdate anions under anodic conditions. The PAH-molybdate complex was used as a model system to understand possible deposition criteria which may be relevant to the formation of proteinaceous films on CoCrMo hip implants. Data indicate that PAH deposition will occur above ∼0.60 V vs SCE if molybdate anions are present in the electrolyte above a critical concentration, and if the polymer concentration remains below a critical value. Numerical modeling and dynamic light scattering (DLS) studies were performed to understand the conditions that enable deposition to occur at these potentials. The results indicate that PAH-molybdate complexes form most efficiently when the polyvalent positive charge and polyvalent negative charge in the system are in an optimum range with respect to each other.

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“…To account for the extremely low concentration of pentylamine and dipentylamine in the product stream, reactions (I), (3), (4) and (7) would have to be much faster than the rest and hence have been shown irreversible.…”

Section: Hydrogenitrogenation Of Pyridinementioning

confidence: 99%

Hydrodenitrogenation of pyridine over a Co‐Mo‐AI₂O₃ catalyst

Gupta

Mann

Gupta

1978

J. Chem. Technol. Biotechnol.

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The vapour phase hydrogenation of pyridine was investigated in an integral flow reactor at a pressure of 5.62 MPa over an alumina-supported cobalt-molybdate catalyst. The effect of various process variables, viz. temperature, reactant ratio and space time, on the conversion of pyridine was studied. The kinetics of the hydrogenation of pyridine to form piperidine have been investigated. The reaction showed pseudo-second order behaviour and the order of the reaction rate in the initial pyridine concentration was found to vary with temperature.

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The mechanism of pyridine hydrogenolysis on molybdenum-containing catalysts II. Hydrogenation of pyridine to piperidine

Cited by 63 publications

References 5 publications

Reaction network and kinetics of the vapor-phase catalytic hydrodenitrogenation of quinoline

Reaction network and kinetics of the vapor-phase catalytic hydrodenitrogenation of quinoline

Anodic Electrodeposition of a Cationic Polyelectrolyte in the Presence of Multivalent Anions

Hydrodenitrogenation of pyridine over a Co‐Mo‐AI₂O₃ catalyst

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The mechanism of pyridine hydrogenolysis on molybdenum-containing catalysts II. Hydrogenation of pyridine to piperidine

Cited by 63 publications

References 5 publications

Reaction network and kinetics of the vapor-phase catalytic hydrodenitrogenation of quinoline

Reaction network and kinetics of the vapor-phase catalytic hydrodenitrogenation of quinoline

Anodic Electrodeposition of a Cationic Polyelectrolyte in the Presence of Multivalent Anions

Hydrodenitrogenation of pyridine over a Co‐Mo‐AI2O3 catalyst

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Hydrodenitrogenation of pyridine over a Co‐Mo‐AI₂O₃ catalyst