A comprehensive kinetic model for Cu catalyzed liquid phase glycerol hydrogenolysis

Rajkhowa, Tapas; Marin, Guy; Thybaut, Joris

doi:10.1016/j.apcatb.2016.12.042

Cited by 59 publications

(38 citation statements)

References 49 publications

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“…Different reaction parameters were optimized, such as temperature ( T lower than 120 °C did not permit a full reduction of starting precursors; see Figure S1 in the Supporting Information), Cu/polymer ratio (no significant differences were observed at different monomer/Cu ratios; see Figure S2 in the Supporting Information), and H 2 /total copper ratio (no significant effect in CuNPs morphology was observed, but an impact in catalysis could be evidenced, see catalysis discussion in the next section). Under these optimized conditions, glycerol did not exhibit hydrogenolysis …”

Section: Resultsmentioning

confidence: 99%

Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst

et al. 2017

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Dedicatedt ot he Laboratoire HØtØrochimieF ondamentale et AppliquØeo nt he occasiono fi ts 50 th anniversary.Supporting information for this article is availableunder https://doi.org/10.1002/adsc.201700535.Abstract: Small zero-valent copper nanoparticles (CuNPs) have been straightforwardly preparedf rom Cu(I) andC u(II) precursors in glycerol andi nt he presence of polyvinylpyrrolidone as stabilizer. Thanks to the negligible vaporp ressure of the solvent, these original nano-systems could be directly characterized in glycerol as well as in the solids tate, exhibiting relevantly homogeneous colloidal dispersions,a lso evena fter catalysis. CuNPs coming from the well-defined coordinationc omplex di-m-hydroxobis[(N,N,N',N'-tetramethylethylenediamine)copper(II)] chloride {[Cu(k 2 -N,N-TMEDA)(m-OH)] 2 Cl 2 } have been highly efficient in C-C andC -heteroatom bond formation processes. This newc atalytic system has proved its performance in C-Nc ouplings and in the synthesis of differently substitutedp ropargylic amines throughc ross-dehydrogenative couplings, multi-component reactions such as A 3 (aldehydealkyne-amine) and KA 2 (ketone-alkyne-amine) couplings,a sw ell as in the formationo fh eterocycles such as benzofurans,i ndolizines,a nd quinolines under smoothc onditions.N os ignificant copper amount was detected in the extracted organic compounds from the catalytic phase by inductively coupled plasma-atomic emission spectroscopic (ICP-AES)analyses,p roving ah ighly efficient immobilization of copper nanoparticles in glycerol. From am echanisticp oint of view,s pectroscopic data (infrareda nd ultraviolet-visible spectra) agreew ith asurface-like catalytic reactivity.

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Section: Resultsmentioning

confidence: 99%

Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst

et al. 2017

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“…Rajkhowa et al. applied the technique in a kinetic study of Cu‐ catalysed liquid phase glycerol hydrogenolysis. Using delplot analysis, the authors were able to identify that acetol was the primary product and propylene glycol was a secondary product …”

Section: Introductionmentioning

confidence: 99%

“…[19] The method uses ap lot of molar yield/conversion versus conversion and aids the identification of primary and non-primary reaction products.For example, Wei et al employed the delplot method in their analysiso ft he selectiveh ydrogenation of acrolein on supported silver catalysts [20] and found that while the desired product allyl alcohol was ap rimary product, propanal was both ap rimary product and as econdary product, via isomerisation of allyla lcohol. Rajkhowa et al applied the technique in ak inetic study of Cu-catalysed liquid phase glycerolh ydrogenolysis [21] .U sing delplota nalysis, the authors were able to identifyt hat acetolw as the primary product and propylene glycol was asecondary product. [21] In the present work, we investigate the effect of water addition to the feed on the oxidation of methane using N 2 Oo ver Fe-ZSM-5.…”

Section: Introductionmentioning

confidence: 99%

“…Rajkhowa et al applied the technique in ak inetic study of Cu-catalysed liquid phase glycerolh ydrogenolysis [21] .U sing delplota nalysis, the authors were able to identifyt hat acetolw as the primary product and propylene glycol was asecondary product. [21] In the present work, we investigate the effect of water addition to the feed on the oxidation of methane using N 2 Oo ver Fe-ZSM-5. Specifically,w ea pply the delplott echnique to investigate the way in which water addition affects reactionp athways.…”

Section: Introductionmentioning

confidence: 99%

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A Kinetic Study of Methane Partial Oxidation over Fe‐ZSM‐5 Using N₂O as an Oxidant

et al. 2018

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Catalytic methane oxidation using N O was investigated at 300 °C over Fe-ZSM-5. This reaction rapidly produces coke (retained organic species), and causes catalyst fouling. The introduction of water into the feed-stream resulted in a significant decrease in the coke selectivity and an increase in the selectivity to the desired product, methanol, from ca. 1 % up to 16 %. A detailed investigation was carried out to determine the fundamental effect of water on the reaction pathway and catalyst stability. The delplot technique was utilised to identify primary and secondary reaction products. This kinetic study suggests that observed gas phase products (CO, CO , CH OH, C H and C H ) form as primary products whilst coke is a secondary product. Dimethyl ether was not detected, however we consider that the formation of C products are likely to be due to an initial condensation of methanol within the pores of the zeolite and hence considered pseudo-primary products. According to a second order delplot analysis, coke is considered a secondary product and its formation correlates with CH OH formation. Control experiments in the absence of methane revealed that the rate of N O decomposition is similar to that of the full reaction mixture, indicating that the loss of active alpha-oxygen sites is the likely cause of the decrease in activity observed and water does not inhibit this process.

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“…Nonetheless, copper chromite catalysts are still being used in various catalytic processes globally [4]. Thus, various other relatively safer supports have been studied to replace chromium, e.g., alumina [18]. However, in so doing, its impact against poisons will also need consideration when compared to copper chromite.…”

Section: Introductionmentioning

confidence: 99%

Water: Friend or Foe in Catalytic Hydrogenation? A Case Study Using Copper Catalysts

Mahomed

Friedrich

2018

Catalysts

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Copper oxide supported on alumina and copper chromite were synthesized, characterized, and subsequently tested for their catalytic activity toward the hydrogenation of octanal. Thereafter, the impact of water addition on the conversion and selectivity of the catalysts were investigated. The fresh catalysts were characterized using X-ray diffraction (XRD), BET surface area and pore volume, SEM, TEM, TGA-DSC, ICP, TPR, and TPD. An initial catalytic testing study was carried out using the catalysts to optimize the temperature and the hydrogen-to-aldehyde ratio—which were found to be 160 °C and 2, respectively—to obtain the best conversion and selectivity to octanol prior to water addition. Water impact studies were carried out under the same conditions. The copper chromite catalyst showed no deactivation or change in octanol selectivity when water was added to the feed. The alumina-supported catalyst showed no change in conversion, but the octanol selectivity improved marginally when water was added.

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A comprehensive kinetic model for Cu catalyzed liquid phase glycerol hydrogenolysis

Cited by 59 publications

References 49 publications

Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst

Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst

A Kinetic Study of Methane Partial Oxidation over Fe‐ZSM‐5 Using N₂O as an Oxidant

Water: Friend or Foe in Catalytic Hydrogenation? A Case Study Using Copper Catalysts

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A comprehensive kinetic model for Cu catalyzed liquid phase glycerol hydrogenolysis

Cited by 59 publications

References 49 publications

Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst

Making Copper(0) Nanoparticles in Glycerol: A Straightforward Synthesis for a Multipurpose Catalyst

A Kinetic Study of Methane Partial Oxidation over Fe‐ZSM‐5 Using N2O as an Oxidant

Water: Friend or Foe in Catalytic Hydrogenation? A Case Study Using Copper Catalysts

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A Kinetic Study of Methane Partial Oxidation over Fe‐ZSM‐5 Using N₂O as an Oxidant