Kinetic Study of Light Mercaptans in the Presence of Merox Catalyst and Caustic Soda

Ehsani, Mohammad Reza; Mirjani, Peyman; Safadoost, Alireza

doi:10.1515/ijcre-2012-0005

Cited by 8 publications

(9 citation statements)

References 13 publications

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“…One of the most demanded industrial applications of metal phthalocyanines is their use as catalysts in the oxidative demercaptanization process [13][14][15], often named in the literature as the Merox reaction. In this reaction, metal phthalocyanines behave as biomimetic catalysts (inorganic mimics of cytochrome P450), because they are capable of limited oxidation of mercaptans into disulfides by molecular oxygen under mild conditions.…”

Section: Introductionmentioning

confidence: 99%

“…In this reaction, metal phthalocyanines behave as biomimetic catalysts (inorganic mimics of cytochrome P450), because they are capable of limited oxidation of mercaptans into disulfides by molecular oxygen under mild conditions. The catalytic oxidative demercaptanization is widely used for eliminating offensive odors from industrial wastewaters and petroleum products [14,16] and to reduce the corrosion activity of mercaptans in motor fuel [15]. The Merox process was used in the present work as a model reaction to compare the catalytic performance of transition metal complexes of petroleum porphyrins, synthesized for the first time from high-purity petroleum vanadyl porphyrins obtained by the sulfocationite-based chromatographic method [11].…”

Section: Introductionmentioning

confidence: 99%

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Complexes of Transition Metals with Petroleum Porphyrin Ligands: Preparation and Evaluation of Catalytic Ability

et al. 2021

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In the present work, the first data on the catalytic activity of d-metal complexes of petroleum porphyrins obtained via two-stage re-metallization (acid demetallization with subsequent metalation) of high-purity petroleum vanadyl porphyrins are presented. During acid demetallization of petroleum vanadyl porphyrins, the highest yield (49%) and spectral purity of free petroporphyrin bases were achieved with concentrated sulfuric acid and a diluted solution of vanadyl porphyrins in chloroform. In the series of divalent cations of Mn, Fe, Co, Ni, Cu, and Zn, only the last four metals are complexed with demetallated petroporphyrins without significant changes in their component composition, whereas the interaction with Mn and Fe cations causes an evident structural transformation or even full degradation of petroporphyrin macrocycles, respectively. The composition and spectral purity of petroleum porphyrin-containing reactants and products were analyzed by FT-IR, UV-Vis, NMR, and MALDI-TOF mass spectroscopic methods. The obtained petroporphyrin-based d-metal complexes were assayed by the reaction of 2-mercaptoethanol oxidative dimerization, in which the copper porphyrins exhibited the highest catalytic activity.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Complexes of Transition Metals with Petroleum Porphyrin Ligands: Preparation and Evaluation of Catalytic Ability

et al. 2021

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“…For fast reactions, g > 2, for slow reactions, g ranges from 0.02 to 2, whereas for very slow reactions, g < 0.02 [19]. In the case of thiol oxidation for uncatalysed or catalysed reactions with low catalyst concentrations, g was estimated to fall in the range of 0.05 to 1.758 and, hence, it is a slow reaction [20][21][22][23]. In such cases, reaction happens both in the film and bulk.…”

Section: Gas Liquid Reactionsmentioning

confidence: 99%

“…To be able to determine the true kinetics representing industrial conditions, it is necessary to establish hydrodynamics which ensures maximum transport of oxygen to the bulk. Substantial literature is available on mass transfer effects and reaction kinetics studies on thiol oxidation by Van de Vusse [20], Pal and Sharma [25], Leitao and Rodrigues [21], Xia et al [22,26,27], Ganguly et al [16,[28][29][30][31], and Ehsani et al [23,32]. They studied the mass transfer, kinetics, and mechanism of catalytic co-oxidation of pure and mixed thiols (ethanethiol, iso-propanethiol, 1-butanethiol, 1-octanethiol, and 2-methyl-2-propanethiol) in gas-liquid and gas-solid-liquid systems.…”

Section: Gas Liquid Reactionsmentioning

confidence: 99%

A Review on Gas‐Liquid Reactions in Light Oil Sweetening: Kinetics and Reactor Design Aspects

et al. 2014

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Thiols in liquefied petroleum gas are undesirable due to their foul odor and corrosive nature. The process of removing these thiols is termed as sweetening. Metal phthalocyanines are reported to be the most effective sweetening catalyst. However, the solubility of metal phthalocyanine is low in aqueous medium. Thus, in an effort to further improve upon the existing catalysts, a novel cobalt phthalocyanine sulfonamide catalyst was developed. Laboratory and commercial evaluation of this catalyst showed enhanced activity as compared to a commercial catalyst with comparable stability. With proven higher activity, comparable stability, design of grass root oxidizer using this catalyst is the next step. Design of oxidizers for an extractive sweetening process based on this catalyst in grass root refineries requires a rigorous kinetic model. The paper reviews the literature on sweetening kinetics and focuses on the concepts of design of laboratory reactors for reaction kinetics studies for such gas-liquid reactions. Laboratory reactor systems can be useful for accurate estimation of kinetic parameters which can then be used to design industrial reactors and predict their performance.

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“…They found an increase in the reaction rate with increasing temperatures, using a catalyst supported by activated carbon. Reza et al 12 also evaluated the kinetics of oxidation of ethyl, normal propyl, isopropyl, and isobutyl mercaptans in the presence of MEROX catalysts showing a first-order reaction.…”

Section: Introductionmentioning

confidence: 99%

Process Simulation and Exergy Analysis of a Mercaptan Oxidation Unit in a Latin American Refinery

2020

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In this work, the mercaptan oxidation unit of an oil and gas refinery was simulated and assessed using exergy and parametric sensitivity analysis to identify opportunities for improvement from a technical and energy point of view. The process simulation was performed using Aspen HYSYS V10.1 to obtain extended mass and energy balances. The simulation results were validated with the data available in the literature. The effects of operating conditions on technical performance were analyzed via parametric analysis. The exergy analysis was applied to two case studies: the base case and the resulting case from technical improvements. The global exergy efficiency, irreversibilities, exergy of utilities, and efficiencies per stage were calculated to map process equipment with the highest losses of exergy. A comparison between both base and alternative cases was introduced in order to analyze increments in exergy efficiencies. An exergy efficiency of 84.21% was found for the base case, while for the alternative case after applying parametric sensitivity, it was calculated to be 81.95%. This decrease by 2.26% was attributed to the increase of irreversibilities and exergy of wastes to achieve a product with better quality standards.

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Kinetic Study of Light Mercaptans in the Presence of Merox Catalyst and Caustic Soda

Cited by 8 publications

References 13 publications

Complexes of Transition Metals with Petroleum Porphyrin Ligands: Preparation and Evaluation of Catalytic Ability

Complexes of Transition Metals with Petroleum Porphyrin Ligands: Preparation and Evaluation of Catalytic Ability

A Review on Gas‐Liquid Reactions in Light Oil Sweetening: Kinetics and Reactor Design Aspects

Process Simulation and Exergy Analysis of a Mercaptan Oxidation Unit in a Latin American Refinery

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