Activation of natural mordenite by various acids: Characterization and evaluation in the transformation of limonene into p-cymene

Lycourghiotis, Sotiris; Makarouni, Dimitra; Kordouli, Eleana; Bourikas, Kyriakos; Kordulis, Christos; Dourtoglou, Vassilis

doi:10.1016/j.mcat.2018.03.013

Cited by 23 publications

(19 citation statements)

References 35 publications

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“…However, these conditions resulted in accumulation of even more oligomers (99%). Previous studies that utilized heterogeneous catalysts such as zeolites and acid‐activated clays also encountered significant oligomerization, which was attributed to regions of strong Brønsted acidity on the catalytic surface (Du et al, 2005; Fernandes et al, 2007; Golets et al, 2015; Linnekoski et al, 2014; Lycourghiotis et al, 2018; Makarouni et al, 2018). Thus, we speculated that the strong Brønsted acidity of p TsOH (pKa −1.3; Berkowitz and Grunwald, 1961) favored oligomerization over dehydroisomerization, thereby resulting in production of oligomers as opposed to the production of 1 .…”

Section: Resultsmentioning

confidence: 99%

Production of Industrially Useful and Renewable p‐Cymene by Catalytic Dehydration and Isomerization of Perillyl Alcohol

Moser

Jackson

Doll

2021

J Americ Oil Chem Soc

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We report the dehydration and isomerization of renewable perillyl alcohol to industrially useful p‐cymene in 91% yield utilizing 2.0 mol% para‐toluenesulfonic acid (pTsOH) catalyst at 110 °C as a 3.0 M solution in toluene. Lower reaction temperatures, catalyst loadings, and/or starting concentrations resulted in lower yields of p‐cymene as well as longer reaction times. Conversion of perillyl alcohol to p‐cymene yielded atom and carbon economies of 88.1% and 100% as well as an E‐factor of 2.7, thereby indicating that the process was both green and sustainable. A lower yield of 86% was observed when the reaction was performed neat, but a lower E‐factor of 0.4 indicated that neat conditions were more desirable from an environmental perspective. Application of the optimized parameters to 3.0 M solutions of dl‐limonene led predominantly to oligomerization (92%) as opposed to dehydroisomerization (5%), which was attributed to the strong Brønsted acidity of pTsOH. In addition, camphene (44%), terpinene isomers (15%), and limonene (14%) were obtained when dehydroisomerization was attempted on 3.0 M solutions of α‐ and β‐pinene, which was once again attributed to the acidity of the catalyst. Oligomerization was strongly favored when dehydroisomerization of dl‐limonene, α‐ and β‐pinene was attempted neat. In summary, synthesis of renewable p‐cymene was readily achieved from perillyl alcohol with catalytic pTsOH but competing side reactions suppressed yield when dehydroisomerization of dl‐limonene, α‐ and β‐pinene was attempted due to the strong Brønsted acidity of the catalyst.

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Section: Resultsmentioning

confidence: 99%

Production of Industrially Useful and Renewable p‐Cymene by Catalytic Dehydration and Isomerization of Perillyl Alcohol

Moser

Jackson

Doll

2021

J Americ Oil Chem Soc

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“…A rather high p-cymene yield (63%) at 140 °C, with a limonene/catalyst ratio of 15 and a reaction time of 7 hours is obtained [35]. Another achievement of the same group was the use of aqueous solutions of various acids (CH3COOH, HCl, H2SO4, HNO3) to further improve the surface area and the acidity of natural mordenite with a significant increase in the conversion of limonene to p-cymene up to 65% [80].…”

Section: Upgrading Of Limonene Into P-cymene Over Heterogeneous Catalmentioning

confidence: 99%

The Limonene Biorefinery: From Extractive Technologies to Its Catalytic Upgrading into p-Cymene

Satira¹,

Espro²,

Paone³

et al. 2021

Preprint

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A renewable cyclic monoterpene obtained from citrus peel, limonene is widely used as a fra-grance, nutraceutical ingredient, antibacterial, biopesticide, and green extraction solvent. Indus-trial demand largely exceeds supply. After reviewing recent advances in the recovery of limonene from citrus peel and residues with a particular attention to benign-by-design extractive processes, we focus on the latest results in its dehydrogenation to p-cymene via heterogeneous catalysis.

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“…This material was treated with 2 M acidic solutions of HCl, and CH 3 COOH (all purchased by Fisher scientific) at 70 °C for 4 h and mass solid to solution volume 1 g/20 mL. Full details on the acid activation process have been reported previously [41,42]. The symbols TECHNOSA-H2, and TECHNOSA-A2 stand, respectively, for the catalysts resulted by activation of natural mordenite with 2 M hydrochloric and acetic acid aqueous solutions.…”

Section: Catalyst Preparation and Characterizationmentioning

confidence: 99%

“…The symbols TECHNOSA-H2, and TECHNOSA-A2 stand, respectively, for the catalysts resulted by activation of natural mordenite with 2 M hydrochloric and acetic acid aqueous solutions. TECHNOSA-H2C catalyst was prepared by air-calcination of TECHNOSA-H2 catalyst at 500 °C for 2 h. Full characterization of TECHNOSA-H2, TECHNOSA-A2 and TECHNOSA-H2C with N 2 -physisorption, XRD, ATR-FTIR, SEM-EDS, TEM, Microelectrophoresis and Equilibrium pH measurements have been reported elsewhere [42,43]…”

Section: Catalyst Preparation and Characterizationmentioning

confidence: 99%

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Solvent-Driven Selectivity on the One-Step Catalytic Synthesis of Manoyl Oxide Based on a Novel and Sustainable “Zeolite Catalyst–Solvent” System

2021

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Application of a novel “zeolite catalyst–solvent” system for the sustainable one-step synthesis of the terpenoid manoyl oxide, the potential precursor of forskolin and ambrox. Manoyl oxide high-yield and large-scale production over a zeolite catalyst has been infeasible so far, while this system results in 90% yields at 135 °C and atmospheric pressure. Substrate-controlled methodology is used to achieve selectivity. Solvent-driven catalysis is shown, as the activation energy barrier decreases in the presence of appropriate solvents, being 62.7 and 93.46 kJmol−1 for a glyme-type solvent and dodecane, respectively. Finally, catalyst acidity is key parameter for the process. Graphic Abstract

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Activation of natural mordenite by various acids: Characterization and evaluation in the transformation of limonene into p-cymene

Cited by 23 publications

References 35 publications

Production of Industrially Useful and Renewable p‐Cymene by Catalytic Dehydration and Isomerization of Perillyl Alcohol

Production of Industrially Useful and Renewable p‐Cymene by Catalytic Dehydration and Isomerization of Perillyl Alcohol

The Limonene Biorefinery: From Extractive Technologies to Its Catalytic Upgrading into p-Cymene

Solvent-Driven Selectivity on the One-Step Catalytic Synthesis of Manoyl Oxide Based on a Novel and Sustainable “Zeolite Catalyst–Solvent” System

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