Kinetics of the liquid-phase hydrogenation of (-)-.alpha.-pinene over electrolessly deposited nickel-phosphorus/.gamma.-alumina catalyst

Ko, Sun Hua; Chou, Tse‐Chuan

doi:10.1021/ie00020a008

Cited by 14 publications

(11 citation statements)

References 16 publications

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“…At the surface of the nickel atoms, the adsorption of the pinene molecule produces two different π‐complexes via its two faces. The bulky C(CH 3 ) 2 group is oriented in the opposite direction to the nickel surface, which dominates the geometrical arrangement because the steric hindrance is lower in this direction (the adsorption of the pinene molecule is in the exo direction), which agrees with the structure proposed by Semikolenov et al This condition results in the endo product, i.e. cis‐pinane.…”

Section: Resultssupporting

confidence: 87%

“…The cis‐trans ratio was 11.17 for this amount of catalyst. If too much catalyst is used for hydrogenation, problems such as high cost and the possibility of shifting the reaction to the diffusion‐controlled region exist . Therefore, the experiment was conducted using 0.05 g/g catalyst as the optimal amount.…”

Section: Resultsmentioning

confidence: 99%

“…If too much catalyst is used for hydrogenation, problems such as high cost and the possibility of shifting the reaction to the diffusion-controlled region exist. [8] Therefore, the experiment was conducted using 0.05 g/g catalyst as the optimal amount. Additionally, we can see from Figure 4a that the cis-trans ratio as a function of catalyst amount appears to be rather constant.…”

Section: Effect Of the Amount Of Catalystmentioning

confidence: 99%

“…Both cis‐ and trans‐pinane are products of pinene hydrogenation. However, cis‐pinane is more easily oxidized to pinane hydroperoxide, which can be further used for the synthesis of linalool …”

Section: Introductionmentioning

confidence: 99%

“…However, cis-pinane is more easily oxidized to pinane hydroperoxide, which can be further used for the synthesis of linalool. [8] Traditionally, for the hydrogenation of pinenes to pinane on the supported precious metal catalysts Pd/C and Pt/C, the yield of cispinane ranges from 48.5-98.5 % depending on the various reaction conditions. [9,10] US Patent 4310714 proposed that higher pressures favour a faster hydrogenation rate and stereo-selectivity, and the result was hydrogenation selectivity for cis-pinane in the range of 94.3-99.1 % over a ruthenium precious metal catalyst.…”

Section: Introductionmentioning

confidence: 99%

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Kinetic study of the hydrogenation of a monoterpene over spent FCC catalyst‐supported nickel

et al. 2015

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A feasible route toward the sustainable synthesis of chemicals was provided via the transformation of monoterpene pinenes into pinane. This article discusses the conversion of pinenes to pinane over spent fluid catalytic cracking catalyst (SFCCC)‐supported nickel (Ni/SFCCC) at 110–130 °C and 2–6 MPa. The Ni/SFCCC catalyst was characterized by BET, XRD, SEM‐EDS, ICP, and FTIR. These measurements revealed that not only did the noble metal‐free catalyst Ni/SFCCC enhance the hydrogenation of pinenes to pinane, but a high cis‐trans ratio was also obtained: the conversion of pinenes and the cis‐trans ratio reached 98.48 % and 13.89, respectively. By fitting the kinetic data via the power‐law model, the hydrogenation of pinenes followed first‐order reaction kinetics, with the apparent activation energies for the hydrogenation of pinenes to cis‐ and trans‐pinane being 59.42 kJ/mol and 98.38 kJ/mol, respectively. The kinetic models described the formation of cis‐ and trans‐pinane well, with satisfactory accuracy compared to experimental observations. Furthermore, the reaction mechanism was derived via the Langmuir–Hinshelwood (L‐H) approach.

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Section: Resultssupporting

confidence: 87%

Section: Resultsmentioning

confidence: 99%

Section: Effect Of the Amount Of Catalystmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Kinetic study of the hydrogenation of a monoterpene over spent FCC catalyst‐supported nickel

et al. 2015

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Hydrogenation of (—)‐α‐pinene over nickel—phosphorus/aluminum oxide catalysts prepared by electroless deposition

Chou

1994

Can J Chem Eng

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Liquid-phase hydrogenation of (-)-a-pinene was investigated using a new type of amorphous nickel-phosphorus catalyst supported on aluminum oxide. The catalyst was prepared by the electroless deposition of nickel on the solid support at atmospheric pressure and moderate temperature from an aqueous solution. Two types of supports, aluminum oxide powder and pellet, were used. Electron probe micro-analysis (EPMA) indicated that the nickel profile on the aluminum oxide powder was uniform throughout the whole particle of the powdery support; however, the nickel deposition on the catalyst supported by pellet aluminum oxide exhibited an eggshell-type profile with a thickness about 8 pm. The amorphous structure of the nickel was confirmed by X-ray diffraction (XRD). The procedure by which the catalysts were prepared involved four steps: etching, sensitization, activation and deposition. The conditions employed for the sensitization, activation and deposition steps significantly affected the composition, structure, metal profile and activities of the catalysts. Etching, however, had a negligible effect on the properties of the catalysts. Very high selectivity was found for hydrogenation of (-)-a-pinene to cis-pinane.On a etudie I'hydrogenation en phase liquide du (-)-a-pinhe au moyen d'un nouveau type de catalyseur amorphe au nickel-phospore supportC sur de I'oxyde d'aluminium. Le catalyseur a CtC prtpare par un dip& de nickel sur le support solide a la pression atmospherique et B temperature modCree B partir d'une solution aqueuse par une technique non-electrique. Deux types de supports, poudre et granules d'oxyde d'aluminium, ont ete utilises. La micro-analyse par sonde des electrons (EPMA) indique que le profil du nickel sur la poudre d'oxyde d'aluminium est uniforme sur la totalit6 de la particule du support poudreux; cependant, le dCp6t de nickel sur le catalyseur supporte par l'oxyde d'aluminium sous forme de granules montre un profil en forme de coquille d'oeuf avec une epaisseur d'environ 8 pm. La structure amorphe du nickel est confirmee par la diffraction des rayons X (DRX). La procedure ayant servi a la mise au point des catalyseurs comprend quatre Ctapes: dtcapage, sensibilisation, activation et deposition. Les conditions employees pour les etapes de sensibilisation, d'activation et de deposition influent considerablement sur la composition, la structure, le profil mktallique et les activitts des catalyseurs. Toutefois, le dtcapage a un effet negligeable sur les proprittks du catalyseur. On a trouve une trks grande stlectivite pour I'hydrogenation de (-)-a-pinkne en cis-pinane.

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Selective hydrogenation of α‐pinene on a nickel supported aluminophosphate catalyst: Process optimization and reaction kinetics

Yang

Xiang

Jiang

et al. 2020

Int J of Chemical Kinetics

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cis‐Pinane, the hydrogenation product of pinene, is a key chemical intermediate and its production is an important forest chemical process. In this study, α‐pinene was hydrogenated using a nickel‐supported aluminophosphate catalyst (Ni/APO‐PT) in the batch mode of operation. The pore structure of the catalyst was characterized, the process parameters were studied, the hydrogenation process was optimized, and the kinetic study was conducted. The results showed that the conversion of pinene was positively correlated with temperature, duration, and catalyst dosage. In contrast, the selectivity of cis‐pinane was negatively correlated with temperature and catalyst dosage. An optimization was performed using the response surface methodology (RSM). A selectivity of 96.2% was obtained with α‐pinene conversion of 98.5% under optimal conditions, that is, a temperature of 405 K, reaction time of 60 min, hydrogen pressure of 3 MPa, and catalyst loading of 3.32 wt%. The reusability of the catalyst was studied, and the catalyst was found to maintain efficient activity for seven cycles. The kinetics of hydrogenation were investigated using both linear and nonlinear methods in the absence of diffusional limitation. In the temperature range from 403 to 433 K, the hydrogenation of α‐pinene to pinane was compatible with the pseudo‐first‐order process, and the activation energies for the formation of cis‐pinane and trans‐pinane were 41.8 and 56.1 kJ/mol, respectively. This study shows that the performance of the Ni/APO‐PT catalyst is similar to that of noble metals and the catalyst has the potential for industrial applications.

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Kinetics of the liquid-phase hydrogenation of (-)-.alpha.-pinene over electrolessly deposited nickel-phosphorus/.gamma.-alumina catalyst

Cited by 14 publications

References 16 publications

Kinetic study of the hydrogenation of a monoterpene over spent FCC catalyst‐supported nickel

Kinetic study of the hydrogenation of a monoterpene over spent FCC catalyst‐supported nickel

Hydrogenation of (—)‐α‐pinene over nickel—phosphorus/aluminum oxide catalysts prepared by electroless deposition

Selective hydrogenation of α‐pinene on a nickel supported aluminophosphate catalyst: Process optimization and reaction kinetics

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