Mechanism of hydrogenolysis and isomerization of oxacycloalkanes on metals, XVI. Transformation of tetrahydrofuran on platinum catalysts

Bartók, Mihály; Szöllösi, Gy.; Apjok, J.

doi:10.1007/bf02475365

Cited by 5 publications

(5 citation statements)

References 17 publications

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“…It is interesting that whereas 1‐butanol formation was observed in the hydrogenation of 2,3‐DHF and 2,5‐DHF over 10 wt % Pt/TiO 2 , it was not detected under flow conditions if THF was used as a substrate with the same catalyst, similar to the results reported by Smith and Fuzek . However, there are also reports on successful ring opening in THF with formation of 1‐butanol over Pt catalysts, including Pt/TiO 2 . The conversion levels and selectivity data for the hydrogenation of 2,5‐DHF over all of the catalysts utilized in this study are presented in Table S3.…”

Section: Resultssupporting

confidence: 70%

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Mechanistic Insight into the Heterogeneous Hydrogenation of Furan Derivatives with the use of Parahydrogen

et al. 2018

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Parahydrogen‐induced polarization (PHIP) was shown to be a useful and unique technique to study the mechanisms of catalytic reactions involving hydrogen. In this paper, PHIP was utilized for mechanistic investigation of the gas‐phase hydrogenation of furan, 2,3‐dihydrofuran, and 2,5‐dihydrofuran over titania‐supported Rh, Pd, and Pt catalysts. In the hydrogenation of all three substrates over the Rh/TiO2 catalyst, the PHIP technique revealed the possibility of pairwise addition of two H atoms from the same H2 molecule with the formation of tetrahydrofuran molecules while retaining spin correlation between the added protons. In the hydrogenation of 2,3‐dihydrofuran over the Rh/TiO2 catalyst, PHIP effects were detected not only for tetrahydrofuran but also for the reactant (2,3‐dihydrofuran) at positions 2 and 3 of the heterocyclic ring. Such unexpected results are direct evidence for the pairwise replacement of the hydrogen atoms in 2,3‐dihydorfuran. A probable mechanism for this pairwise replacement includes sequential steps of addition and elimination of hydrogen atoms. In contrast, if the hydrogenation of 2,5‐dihydrofuran was performed over Rh/TiO2, PHIP effects were detected for all protons of 2,3‐dihydrofuran, implying that 2,3‐dihydrofuran could be formed from 2,5‐dihydrofuran not only through isomerization of the C=C bond but also through dehydrogenation of 2,5‐dihydrofuran to furan with subsequent semihydrogenation.

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Section: Resultssupporting

confidence: 70%

“…[49] However,t here are also reports on successful ring openingi nT HF with formation of 1butanol over Pt catalysts, including Pt/TiO 2 . [50,51] The conversion levels and selectivity data for the hydrogenation of 2,5-DHF over all of the catalysts utilized in this study are presented in Ta ble S3.…”

Section: Resultsmentioning

confidence: 99%

Mechanistic Insight into the Heterogeneous Hydrogenation of Furan Derivatives with the use of Parahydrogen

et al. 2018

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“…Furans have then to be taken into consideration for HDT coprocessing option. The furan ring hydrogenation occurs efficiently at typical conditions of hydroprocessing, with the formation of tetrahydrofuran, which suffers 48,49 CoMo/Al 2 O 3 high phenol; o-cresol; benzene Ni−Cu/supports phenol 50−58 CoMo/Al 2 O 3 most refractory cyclohexanol; cyclohexanona; cyclohexane; benzene Ni/Y zeolite or silica cresols 50,59−61 CoMo/Al 2 O 3 high, effective at mild conditions toluene; cyclohexane Pt/carbon aldehydes and ketones 63−65 noble metals/zeolites high diphenylmethane; toluene esters 66,67 NiMo,CoMo/γ-Al 2 O 3 high C3−C5 alkanes and alkenes; methanol; carboxylic acids acids 68,69 NiMo,CoMo/Al 2 O 3 high alkanes Pd/carbon furans [70][71][72][73][74][75][76]79 NiMo HDO much faster than furan. In fact, classical CoMo and NiMo supported on Al 2 O 3 or carbon catalysts were extensively used for furans HDO.…”

Section: Hydrodeoxygenation (Hdo)mentioning

confidence: 99%

“…Dibenzofuran can be transformed into single-ring hydrocarbons, mainly cyclohexane . Detailed mechanisms for furan, tetrahydrofuran, benzofuran, and dibenzofuran transformations are described elsewhere. ,− More recent studies report the use of Pt-supported catalysts, , butane being preferentially formed with Pt/TiO 2 . Other studies on benzofuran HDO pointed out that reduced Mo and NiMO catalysts are able to activate benzofuran, promoting, in a first step, its hydrogenation.…”

Section: Hydrodeoxygenation (Hdo)mentioning

confidence: 99%

Bio-oils Upgrading for Second Generation Biofuels

Grac̀a

Lopes

Cerqueira³

et al. 2013

Ind. Eng. Chem. Res.

190

102

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The envisaged upgrading of lignocellulosic biomass derived feedstocks (bio-oils) in dedicated units or by coprocessing in existing units of the refinery, to partially replace crude oil in the production of transportation fuels, is a topic that has been receiving much attention from both industry and academia in recent years. Regardless of lignocellulosic biomass origin, these feedstocks are complex mixtures of many oxygenated hydrocarbons. Therefore, their upgrading toward liquid fuels must include oxygen removal. So far, two main routes have been proposed, considering many studies at laboratory scale and others from industry: catalytic hydrotreatment (HDT), mainly hydrodeoxygenation (HDO), and catalytic cracking, technologies that are already present in today's refineries configuration. HDO has been performed at high hydrogen pressure, using catalysts based on those typically applied in conventional hydrotreating, as well as a new type of supported noble metal and transition metal catalysts. Catalytic cracking occurs at atmospheric pressure, using acid catalysts, mainly the active phases of fluid catalytic cracking (FCC) catalysts (HY and HZSM-5 zeolites). The present review is then focused on the upgrading possibilities of renewable nonedible feedstocks, obtained from biomass fast pyrolysis or liquefaction, in petroleum refineries, toward the production of second generation biofuels. It includes the recent studies concerning the alternative of bio-oils coprocessing together with crude oil feedstocks. In fact, although all these feedstocks have the potential to be directly converted into transportation fuels in dedicated units, it seems more attractive to upgrade them in combination with conventional feedstocks.

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“…The reactant has a six-member ether ring with a methyl group attached to one alpha-carbon. Analogous compounds with five-member ether rings such as furan and furan derivatives were investigated on various catalysts including conventional hydrotreating catalysts, − noble metals, − metals, − and metal phosphides. − …”

Section: Introductionmentioning

confidence: 99%

Reactions of 2-Methyltetrahydropyran on Silica-Supported Nickel Phosphide in Comparison with 2-Methyltetrahydrofuran

et al. 2016

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The reactions of 2-methyltetrahydropyran (2-MTHP, C6H12O) on Ni2P/SiO2 provide insights on the interactions between a cyclic ether, an abundant component of biomass feedstock, with a transition-metal phosphide, an effective hydrotreating catalyst. At atmospheric pressure and a low contact time, conditions similar to those of a fast pyrolysis process, 70% of products formed from the reaction of 2-MTHP on Ni2P/SiO2 were deoxygenated products, 2-hexene and 2-pentenes, indicating a good oxygen removal capacity. Deprotonation, hydrogenolysis, dehydration, and decarbonylation were the main reaction routes. The reaction sequence started with the adsorption of 2-MTHP, followed by ring-opening steps on either the methyl substituted side (Path I) or the unsubstituted side (Path II) to produce adsorbed alkoxide species. In Path I, a primary alkoxide was oxidized at the α-carbon to produce an aldehyde, which subsequently underwent decarbonylation to 2-pentenes. The primary alkoxide could also be protonated to give a primary alcohol which could desorb or form the final product 2-hexene. In Path II, a secondary alkoxide was oxidized to produce a ketone or was protonated to a secondary alcohol that was dehydrated to give 2-hexene. The active sites for the adsorption of 2-MTHP and O-intermediates were likely to be Ni sites.

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Mechanism of hydrogenolysis and isomerization of oxacycloalkanes on metals, XVI. Transformation of tetrahydrofuran on platinum catalysts

Cited by 5 publications

References 17 publications

Mechanistic Insight into the Heterogeneous Hydrogenation of Furan Derivatives with the use of Parahydrogen

Mechanistic Insight into the Heterogeneous Hydrogenation of Furan Derivatives with the use of Parahydrogen

Bio-oils Upgrading for Second Generation Biofuels

Reactions of 2-Methyltetrahydropyran on Silica-Supported Nickel Phosphide in Comparison with 2-Methyltetrahydrofuran

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