Highly HYD Selective Pd–Pt/support Hydrotreating Catalysts for the High Pressure Desulfurization of DBT Type Molecules

Medrano, Víctor Gabriel Baldovino; Giraldo, Sonia A.; Centeno, Aristóbulo

doi:10.1007/s10562-009-9919-9

Cited by 8 publications

(7 citation statements)

References 28 publications

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“…The HDO of DBF reaction over the Pd/COK-12 catalysts was suggested to proceed via the HYD reaction route (Scheme ), which is different from the studies over metal sulfide catalysts, in which both HYD and DDO reaction routes were proposed. , Benzene rings in the DBF were hydrogenated first on the surface of Pd nanoparticles, which could be stable in the mesopores of COK-12. This assumption is consistent with the HDS of DBT over supported Pd catalysts. − Aromatic rings being partially or totally hydrogenated were detected in their work, which explained the HYD of DBT in the HDS reaction. Removal of the S atom, followed by the hydrogenation of benzene rings of DBT, was reported.…”

Section: Results and Discussionsupporting

confidence: 83%

Hydrodeoxygenation of Dibenzofuran over Mesoporous Silica COK-12 Supported Palladium Catalysts

Wang

Zhang

et al. 2013

Energy Fuels

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Hydrodeoxygenation (HDO) of dibenzofuran (DBF) with only a hydrogenation (HYD) reaction route was conducted on Pd/COK-12 catalysts with different Pd loadings, which were prepared by metal−organic chemical vapor deposition of [Pd(C 3 H 5 )(C 5 H 5 )] onto mesoporous silica COK-12. Hydrogenated intermediates with partial or full hydrogenation of the benzene ring were studied in detail. The presence of cycloketones is due to the high selectivity of Pdbased catalysts in the hydrogenation of phenols derived from the C−O bond cleavage of hydrogenated intermediates. The reaction only goes through the HYD reaction route with hardly detected biphenyl, which is further confirmed by HDO of 2phenylphenol. The increase of Pd loading on the catalysts largely promotes the deoxygenation of saturated oxygen-containing species from hydrogenation of DBF, followed by cleavage of the sp 3 C−O bond. Finally, a detailed reaction network of HDO of DBF is proposed according to the detected hydrogenated species and cycloketones.

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Section: Results and Discussionsupporting

confidence: 83%

Hydrodeoxygenation of Dibenzofuran over Mesoporous Silica COK-12 Supported Palladium Catalysts

Wang

Zhang

et al. 2013

Energy Fuels

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“…Catalytic tests . Catalytic tests were carried out in a Catatest provided with a high‐pressure fixed‐bed continuous flow reactor [23–25,27,29,52,173] . The reactor was packed with the catalyst.…”

Section: Methodsmentioning

confidence: 99%

“…Catalytic tests were carried out in a Catatest provided with a high-pressure fixed-bed continuous flow reactor. [23][24][25]27,29,52,173] The reactor was packed with the catalyst. Prior to the latter, the catalytic powders were pelletized, ground, and sieved to obtain particles with diameters ranging from 300 to 600 μm.…”

Section: Determination Of the Distribution Of Surface Hydroxyls Protonmentioning

confidence: 99%

Interplay Between Ni and Brønsted and Lewis Acid Sites in the Hydrodesulfurization of Dibenzothiophene

Valderrama‐Zapata,

García‐Sánchez,

Vargas‐Montañez

et al. 2024

ChemPhysChem

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NiMo‐S₂/γ‐Al₂O₃ catalysts are commonly used in hydrotreating to enhance fossil fuel quality. The extensive research on these catalysts reveals a gap in understanding the role of Ni, often underestimated as an inactive sulfide phase or just a MoS₂ promoter. In this work, we focused on analyzing whether well‐dispersed supported nickel nanoparticles can be active in the hydrodesulfurization of dibenzothiophene. We dispersed Ni by the Strong Electrostatic Adsorption (SEA) method over four supports with different types of acidity: silica (~ neutral acidity), γ‐Al₂O₃ (Lewis acidity), H+‐Y zeolite, and microporous‐mesoporous H+‐Y zeolite (both with Brønsted‐Lewis acidity). Our findings reveal that Ni is indeed active in dibenzothiophene hydrodesulfurization, even with alumina and silica as supports, although their catalytic activity declines abruptly in the first hours. Contrastingly, the acid nature of zeolites imparts sustained stability and performance, attributed to robust metal‐support interactions. The efficacy of the SEA method and the added mesoporosity in zeolites further amplify catalytic efficiency. Overall, we demonstrate that Ni nanoparticles may perform as a hydrogenating metal in the same manner as noble metals such as Pt and Pd perform in hydrodesulfurization. We discuss some of the probable reasons for such performance and remark on the role of Ni in hydrotreatment.

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“…Mechanistically, it is well-known that 4,6-DMDBT is desulfurized by either a hydrogenation (HYD) route or a direct desulfurization (DDS) route [4,18]. A group of researches [15,[19][20][21][22][23][24][25] proposed that 4,6-DMDBT is adsorbed following π and σ adsorptions: in the former, the aromatic ring of the 4,6-DMDBT is adsorbed on the active site, whereas in the latter the sulfur heteroatom is the one being adsorbed on. It suggests that HYD route involves both π and σ adsorptions while the DSD route involves only σ adsorption.…”

Section: Introductionmentioning

confidence: 99%

“…Jiang et al [31], Yoshimura et al [22] and Chen et al [28] observed that Pd in a Pt-Pd/γ-Al 2 O 3 catalyst leads to inhibit Pt agglomeration on the catalyst surface, increasing its hydrogenation activity and its resistance to be deactivated by surface sulfur. Baldovino-Medrano et al [24] evaluated a silica-alumina supported Pt-Pd catalyst, observing that this bimetallic catalyst is highly active in dibenzothiophene hydrodesulfurization with preferential selectivity to HYD route. Núñez et al [32] realized oxidereduction studies for Pt-Pd/TiO 2 and Pt-Pd/γ-Al 2 O 3 -TiO 2 catalytic systems during the hydrogenation of biphenyl and the HDS of 4,6-DMDBT.…”

Section: Introductionmentioning

confidence: 99%

Role of Pt–Pd/γ-Al2O3 on the HDS of 4,6-DMBT: Kinetic modeling & contribution analysis

Castillo‐Araiza

Chávez

Dutta

et al. 2015

Fuel Processing Technology

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The purpose of this study is to provide insights on the function of noble metals, namely Pt-Pd catalytic system, on the hydrodesulfurization (HDS) of alkyl-substituted dibenzothiophenes (a-DBTs) by means of kinetic modeling and contribution analyses. A series of Pt-Pd systems (1% wt. nominal loading) supported on γ-Al 2 O 3 (0-100, 20-80, 50-50, 80-20 and 100-0; %mol Pt-%mol Pd) are synthesized and evaluated during the HDS of 4,6dimethyldibenzothiophene (4,6-DMDBT) at operating conditions relevant for industry: 320°C, 500 ppm of S and an H 2 pressure of 5.5 MPa. A summary of their characterization is presented as reference herein. Kinetic model based on a Langmuir-Hinshelwood-Hougen-Watson (LHHW) mechanism and contribution analysis based on predicted reaction rates give rise to the following findings: the bimetallic catalyst 8Pt-2Pd/γ-Al 2 O 3 (80-20; %mol Pt-%mol Pd) leads to the highest activity; in all Pt-Pd/γ-Al 2 O 3 systems, Pt favors desulfurization reactions, i.e., 4,6-DMDBT to 3,3′-dimethylphenyl (3,3′-DMBP) and 4,6-dimethyltetrahydrodibenzothiophene (4,6-DM-th-DBT) to MCHT, whereas Pd favors hydrogenation of 4,6-DMDBT to 4,6-DM-th-DBT; and 4,6-DMDBT and methylcyclohexyltoluene (MCHT) are the hydrocarbons with the lowest and highest affinity to be adsorbed on the active sites from the studied Pt-Pd/γ-Al 2 O 3 systems, respectively.

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Highly HYD Selective Pd–Pt/support Hydrotreating Catalysts for the High Pressure Desulfurization of DBT Type Molecules

Cited by 8 publications

References 28 publications

Hydrodeoxygenation of Dibenzofuran over Mesoporous Silica COK-12 Supported Palladium Catalysts

Hydrodeoxygenation of Dibenzofuran over Mesoporous Silica COK-12 Supported Palladium Catalysts

Interplay Between Ni and Brønsted and Lewis Acid Sites in the Hydrodesulfurization of Dibenzothiophene

Role of Pt–Pd/γ-Al2O3 on the HDS of 4,6-DMBT: Kinetic modeling & contribution analysis

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