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Continuous production of the renewable ρ-cymene from α-pinene
Umeå University, Faculty of Science and Technology, Department of Chemistry.
Umeå University, Faculty of Science and Technology, Department of Chemistry.
University of Oulu, Oulu, Finland.
Umeå University, Faculty of Science and Technology, Department of Chemistry. Åbo Akademi University, Åbo-Turku, Finland.
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2013 (English)In: Journal of Catalysis, ISSN 0021-9517, E-ISSN 1090-2694, Vol. 307, 305-315 p.Article in journal (Refereed) Published
Abstract [en]

The aim of this work was to demonstrate the feasibility to produce ρ-cymene, an important commodity chemical, in a continuous, one-pot reaction system from abundant α-pinene, available e.g. as a by-product of pulping industry. The isomerization reactions of α-pinene over bimetallic heterogeneous catalysts, 3 and 5 wt% Pd–Zn (1:1, 1:4, 4:1, 1:0, and 0:1), supported on Al-SBA15 were studied. The principal reaction products were identified as ρ- and m-cymenes, limonene, camphene, and ρ-menthene, respectively. The highest concentration of ρ-cymene reached 77 wt% under the optimized reaction conditions: 300 °C and α-pinene feed of 0.03 mL/min. Two main reaction pathways toward ρ- and m-cymenes were described, and a mechanistic kinetic model, based on a plausible reaction network in line with Langmuir–Hinshelwood approach, was developed. The catalyst characterization revealed the reduction in Pd(II) sites, catalyst coking, and decline of surface area over the course of time. The catalyst recovery and reuse was addressed.

Place, publisher, year, edition, pages
Elsevier, 2013. Vol. 307, 305-315 p.
Keyword [en]
q-Cymene, a-Pinene isomerization, Heterogeneous catalyst, Flow-through reactor
National Category
Chemical Sciences
URN: urn:nbn:se:umu:diva-80681DOI: 10.1016/j.jcat.2013.08.007OAI: diva2:650852

Continuous production of the renewable rho-cymene from alpha-pinene

Available from: 2013-09-23 Created: 2013-09-23 Last updated: 2014-11-12Bibliographically approved
In thesis
1. Heterogeneously Catalyzed Valorization of Monoterpenes to High Value-Added Chemicals
Open this publication in new window or tab >>Heterogeneously Catalyzed Valorization of Monoterpenes to High Value-Added Chemicals
2014 (English)Doctoral thesis, comprehensive summary (Other academic)
Alternative title[sv]
Uppgradering av monoterpener till specialkemikalier med högt förädlingsvärde via heterogen katalys
Abstract [en]

A potential industrial process is profitable only if it is successfully implemented by the continuously developing chemical industry. Throughout last decades heterogeneous catalysis has opened doors to the creation of various know-how products which previously were considered unfeasible. Moreover, the use of heterogeneous catalysts allows improving existing processes to shift towards more ecological and cost efficient practices. In particular, polymer or fuel compounds could be eco-friendly produced from wood extractives, as an alternative to the conventional oil resources. This goal becomes even more attractive in light of the upcoming peak-oil.

In the Nordic pulping industry turpentine is widely available as a tonnage by-product. Despite its interesting properties and promising application possibilities this fraction is commonly burned in the recovery boilers for energy. Although the chemical composition of turpentine depends strongly on the specific pulping process, α-pinene is the predominant compound and as such most studied. The general message of this thesis is the successful implementation of the heterogeneous catalysts in one-pot value-added upgrading of crude turpentine and specific terpenes, particularly α-pinene. Concepts allowing the production of fragrances, resins, plastics and pharmaceutical compounds are presented in the current study. Both commercial (Amberlyst 70) and self-prepared (Me/Al-SBA-15 or TiO2) catalysts were studied in several reactions including: acetoxylation, isomerization, dehydroisomerisation and oxidation. Both commercially purified α-pinene and crude thermo-mechanical turpentine were used as raw materials in the catalytic one-pot synthesis of value-added compounds.

The experiments were performed in both batch and continuous reactor systems depending on the studied reaction. Successful results were obtained in case of several reactions. As an example, upon acetoxylation of α-pinene valuable fragrances – α-terpinyl and bornyl acetates – were produced with yields of 35 and 40 wt-%, respectively. Furthermore, in the dehydroisomerisation reaction of α-pinene, a yield of around 80 wt-% of an important fragrance, solvent and plastics precursor, ρ-cymene, was obtained. In the last case, thermo-mechanical turpentine was also successfully utilized. Still, some α-pinene oxidation tests leading to α-pinene oxide and verbenone fragrances were also carried out. Upon this study, further oxidation of ρ-cymene lead to the formation of ρ-methyl-acetophenone, a product essential for perfumery, pharmaceutical and pesticide industry as well as a potent polymer precursor. In addition, isomerization reactions were performed. Additionally, the catalytic materials were thoroughly characterized and analyzed.

Place, publisher, year, edition, pages
Umeå: Umeå University, 2014. 57 p.
Catalysis, terpenes, alpha-pinene
National Category
Chemical Process Engineering
urn:nbn:se:umu:diva-96205 (URN)978-91-7601-153-9 (ISBN)
Public defence
2014-12-04, KBC-huset, Stora hörsalen, KB3B1, Umeå universitet, Umeå, 13:00 (English)
Available from: 2014-11-13 Created: 2014-11-12 Last updated: 2014-11-12Bibliographically approved

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Golets, MikhailSamikannu, AjaikumarWärnå, JohanMikkola, Jyri-Pekka
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