The role of H2S addition on Pt/Al2O3 catalyzed propane dehydrogenation: a mechanistic study

Wang, Haizhi; Zhang, Wei; Jiang, Jinchun; Sui, Zhi‐Jun; Zhu, Yi‐An; Ye, Guanghua; Chen, De; Zhou, Xin; Wang, Yuan

doi:10.1039/c8cy02393j

Cited by 23 publications

(17 citation statements)

References 67 publications

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“…238 On the basis of COchemisorption and Bader charge analysis, Wang et al explain that the improved selectivity in the presence of H 2 S is due to the electron transfer from adsorbed sulfur species to Pt atoms, thereby resulting in weaker Pt−C 3 H 6 interactions. 239 Of note, H 2 S can inhibit the conversion and adversely affect the selectivity of propylene at higher concentrations (about 850 ppm) over Pt/Al 2 O 3 underlining the dual role of H 2 S as an inhibitor and promoter depending on H 2 S concentration in the feed. 238 Subsequently, Shan et al show that the exposure of metal oxides to sulfur feed can lead to the formation of corresponding metal sulfides (or surface sulfur species) and reported improved isobutane dehydrogenation yield, suggesting that the sulfur can play a key role in modifying the active phase of the catalyst.…”

Section: Oxidative Dehydrogenation Of Propane With Sulfur-/halogen-co...mentioning

confidence: 99%

Oxidative Dehydrogenation of Propane to Propylene with Soft Oxidants via Heterogeneous Catalysis

et al. 2021

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Oxidative dehydrogenation of propane to propylene can be achieved using conventional, oxygen-assisted dehydrogenation of propane (O2–ODHP) or via the use of soft oxidants, such as CO2, N2O, S-containing compounds, and halogens/halides. The major roles of soft oxidants include inhibiting overoxidation and improving propylene selectivity, which are considered to be current challenges in O2-assisted dehydrogenation. For both CO2– and N2O–ODHP reactions, significant efforts have been devoted to developing redox-active (e.g., chromium, vanadate, iron, etc.), nonredox-type main group metal oxide (e.g., group IIIA, gallium), and other transition metal/metal oxide catalysts (e.g., molybdenum, palladium platinum, rhodium, ruthenium, etc.), as well as zeolite-based catalysts with adjustable acid–base properties, unique pore structures, and topologies. Metal sulfides have shown promising performance in DHP, whereas the development of suitable catalysts has lagged for SO2- or S-assisted ODHP. Recently, significant efforts have been focused on homogeneous and heterogeneous ODHP using halogens (e.g., Br2, I2, Cl2, etc.) and hydrogen halides (e.g., HCl and HBr) for the development of facile processes for C3H6 synthesis. This Review aims to provide a critical, comprehensive review of recent advances in oxidative dehydrogenation of propane with these soft oxidants, particularly highlighting the current state of understanding of the following factors: (i) relationships between composition, structure, and catalytic performance, (ii) effects of the support, acidity, and promoters, (iii) reaction pathway and mechanistic insights, and (iv) the various roles of soft oxidants. Theoretical and computational insights toward understanding reaction mechanisms and catalyst design principles are also covered. Future research opportunities are discussed in terms of catalyst design and synthesis, deactivation and regeneration, reaction mechanisms, and alternative approaches.

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Section: Oxidative Dehydrogenation Of Propane With Sulfur-/halogen-co...mentioning

confidence: 99%

Oxidative Dehydrogenation of Propane to Propylene with Soft Oxidants via Heterogeneous Catalysis

et al. 2021

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“…Ni and Co weakens the Mo–S bond by donating electrons to Mo and thereby creating the active Mo sites and labile sulfur. Sulfided catalysts were used instead of native catalysts to decrease the rate of catalyst deactivation due to coke formation . Acidic supports are more prone to coke formation, thereby reducing the lifetime of catalysts.…”

Section: Product Distributions Of Hdosmentioning

confidence: 99%

“…Sulfided catalysts were used instead of native catalysts to decrease the rate of catalyst deactivation due to coke formation. 170 Acidic supports are more prone to coke formation, thereby reducing the lifetime of catalysts. Hence, support with proper acidity should be prepared or chosen for the reaction to overcome the problem of deactivation.…”

Section: Product Distributions Of Hdosmentioning

confidence: 99%

Lignin Biorefinery: New Horizons in Catalytic Hydrodeoxygenation for the Production of Chemicals

et al. 2021

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Lignin is a byproduct of the paper mill and second-generation (2G) ethanol biorefinery and the largest naturally available source of aromatic building blocks. It can serve as a feedstock to produce bulk, fine, and functionalized aromatic compounds along with aliphatic cyclic alcohols, jet fuel, and aliphatic hydrocarbons. Hydrodeoxygenation (HDO) is one of the promising strategies to produce these compounds from lignin-derived phenolics. Many reactions occur during the HDO; hence, it is very crucial to design active, selective, and long-life catalysts and choose the optimal reaction conditions to synthesize targeted end products. Herein, we first survey the conventional and new lignin fractionation techniques and determine the lignin structure, composition, and bonding with cellulose and hemicellulose. After this, we review the recent advances in the production of alkanes, arenes, cyclic alcohols, jet fuel range hydrocarbons, and HDO of raw lignin bio-oil. This review exclusively discusses the product distribution during HDO based on catalyst composition, solvent, and reaction parameters. Moreover, the review also underlines the selectivity of various catalytic systems to yield specific products such as BTX, important petrochemical materials, aliphatic hydrocarbons, cyclic alcohols, and jet fuel range hydrocarbons.

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“…[ 11 ] Besides hydrophobicity, these supports should not contain active groups that could catalyze undesirable side reactions, like isomerization. [ 5 ] Platinum is commonly deposited as a complex [ 12 ] or fine dispersion on silica, [ 12,13 ] alumina, [ 14 ] ceramic, [ 14 ] glass, [ 12 ] metallic, [ 15 ] or carbon [ 16,17 ] substrates, but the active carbon (simple [ 7 ] or fluorinated [ 5 ] ) is also preferred. In specific hydrosilylation reactions, the styrene‐divinylbenzene (SDVB) copolymers have been used as alternatives, [ 7,18 ] due to their hydrophobicity, [ 5 ] pore diameters larger than those of active carbon‐supported catalysts, [ 7 ] high specific surface area, and easy accessibility.…”

Section: Introductionmentioning

confidence: 99%

One‐pot reduction‐hydrophobization of heterogenized platinum with 1,1,3,3‐tetramethyldisiloxane

Stoica¹,

Damoc²,

Baltag³

et al. 2021

Applied Organom Chemis

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An original approach for the design of hydrophobized heterogeneous platinum‐based catalytic systems is reported here. Heterogenization was performed by depositing the platinum precursor (H2PtCl6) on macroporous styrene‐divinylbenzene (SDVB) beads with a high surface area, ∼330 m2 g−1, as determined by N2 sorption data, followed by treating with 1,1,3,3‐tetramethyldisiloxane (TMDS) as Pt(IV) reducing agent without the need of special conditions. Simultaneously, the coupling by SiOSi bonds of the TMDS oxidation or hydrolysis intermediates endowed the SDVB‐Pt systems with an enhanced hydrophobicity (up to 10 times higher than that of SDVB support). In addition, to obtain an optimum catalytic system, which stabilize the supported platinium against leaching, several mixtures of TMDS with other methylsiloxane precursors, namely, methyltrimethoxysilane (MTMS), α,ω‐bis(trimethylsiloxy)poly(dimethylsiloxane‐H‐methylsiloxane) (PDMHS), and α,ω‐bis(trimethylsiloxy)poly(dimethylsiloxane‐co‐vinylmethylsiloxane) (PDMVS), have been systematically investigated. The reduction of platinum, visible by an instant change in the color from yellow to black, was confirmed by X‐ray photoelectron spectroscopy analysis, while its total content in the samples was determined quantitatively by atomic absorption spectroscopy. The obtained systems have been preliminarily assessed for catalytic activity in the hydrosilylation of 1,3‐bis(vinyl)tetramethyldisiloxane and allyl alcohol with TMDS, and 1‐hexene with trimethoxysilane, as model reactions. The results indicate the high suitability of these systems as catalysts for the selective anti‐Markovnikov hydrosilylation of alkenes, as well as for the very fast oxidation‐condensation homocoupling of H‐silanes in presence of a green oxidation agent (air), under mild conditions, with the release of hydrogen and its in situ addition to the double bond.

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The role of H₂S addition on Pt/Al₂O₃ catalyzed propane dehydrogenation: a mechanistic study

Abstract: Effects of H2S addition on the Pt/Al2O3 catalyzed propane dehydrogenation.

Cited by 23 publications

References 67 publications

Oxidative Dehydrogenation of Propane to Propylene with Soft Oxidants via Heterogeneous Catalysis

Oxidative Dehydrogenation of Propane to Propylene with Soft Oxidants via Heterogeneous Catalysis

Lignin Biorefinery: New Horizons in Catalytic Hydrodeoxygenation for the Production of Chemicals

One‐pot reduction‐hydrophobization of heterogenized platinum with 1,1,3,3‐tetramethyldisiloxane

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