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Heterogeneously Catalyzed Valorization of Monoterpenes to High Value-Added Chemicals
Umeå University, Faculty of Science and Technology, Department of Chemistry. (Chemical reaction engineering)
2014 (English)Doctoral thesis, comprehensive summary (Other academic)Alternative title
Uppgradering av monoterpener till specialkemikalier med högt förädlingsvärde via heterogen katalys (Swedish)
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.
Keyword [en]
Catalysis, terpenes, alpha-pinene
National Category
Chemical Process Engineering
Identifiers
URN: urn:nbn:se:umu:diva-96205ISBN: 978-91-7601-153-9 (print)OAI: oai:DiVA.org:umu-96205DiVA: diva2:762630
Public defence
2014-12-04, KBC-huset, Stora hörsalen, KB3B1, Umeå universitet, Umeå, 13:00 (English)
Opponent
Supervisors
Available from: 2014-11-13 Created: 2014-11-12 Last updated: 2014-11-12Bibliographically approved
List of papers
1. Liquid phase acetoxylation of α-pinene over Amberlyst-70 ion-exchange resin
Open this publication in new window or tab >>Liquid phase acetoxylation of α-pinene over Amberlyst-70 ion-exchange resin
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2012 (English)In: Applied Catalysis A: General, ISSN 0926-860X, E-ISSN 1873-3875, Vol. 435-436, 43-50 p.Article in journal (Refereed) Published
Abstract [en]

Heterogeneously-catalyzed and solvent-catalyzed liquid phase acetoxylation of α-pinene with acetic acid acting as both a solvent and a reagent was studied. Both solvent-catalyzed and catalytic experiments were carried out and various reaction conditions were studied. The influence of temperature, pressure, solvent and gas milieu were taken into account. Bornyl, fenchyl, verbenyl as well as α-terpinyl acetates, limonene, camphene and γ-terpinene were found among reaction products. The addition of the catalyst allowed for maximization of the yield of bornyl acetate. The predominant products obtained were α-terpinyl, verbenyl and bornyl acetates. The reaction pathways were identified and evaluated.

The aim of this work was to study of the feasibility of batch acetoxylation of alpha-pinene. The analysis of the complex product distribution is not trivial and, consequently, resolving the reaction network was important. The optimized reaction conditions were searched for aiming at an efficient conversion of α-pinene to a mixture of valuable products.

Place, publisher, year, edition, pages
Elsevier, 2012
Keyword
Heterogeneous catalyst, Amberlyst 70, α-pinene acetoxylation, α-terpinyl acetate, biorefinery
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-55834 (URN)10.1016/j.apcata.2012.05.034 (DOI)
Available from: 2012-06-04 Created: 2012-06-04 Last updated: 2017-12-07Bibliographically approved
2. A kinetic study of the liquid phase acetoxylation of α-pinene
Open this publication in new window or tab >>A kinetic study of the liquid phase acetoxylation of α-pinene
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2012 (English)In: Topics in catalysis, ISSN 1022-5528, E-ISSN 1572-9028, Vol. 55, no 7-10, 649-656 p.Article in journal (Refereed) Published
Abstract [en]

The present study introduces kinetic modeling of liquid phase α-pinene acetoxylation with acetic acid over an ion-exchange resin catalyst. The reaction was carried out in a laboratory scale high-pressure autoclave. α-terpinyl (35 wt%) and bornyl (40 wt%) acetates were the primary products. The predominant reaction pathways were identified and evaluated.

Place, publisher, year, edition, pages
Springer, 2012
Keyword
Amberlyst 70, Acetoxylation, Batch process, Biorefinery, Liquid phase, Kinetic modeling, α-pinene, α-terpinyl acetate
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-56720 (URN)10.1007/s11244-012-9844-9 (DOI)
Available from: 2012-06-25 Created: 2012-06-25 Last updated: 2017-12-07Bibliographically approved
3. Continuous production of the renewable ρ-cymene from α-pinene
Open this publication in new window or tab >>Continuous production of the renewable ρ-cymene from α-pinene
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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
Keyword
q-Cymene, a-Pinene isomerization, Heterogeneous catalyst, Flow-through reactor
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-80681 (URN)10.1016/j.jcat.2013.08.007 (DOI)
Funder
Bio4Energy
Note

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

Available from: 2013-09-23 Created: 2013-09-23 Last updated: 2017-12-06Bibliographically approved
4. Effective dispersion of Au and Au-M (M = Co, Ni, Cu and Zn) bimetallic nanoparticles over TiO2 grafted SBA-15: their catalytic activity on dehydroisomerization of α-pinene
Open this publication in new window or tab >>Effective dispersion of Au and Au-M (M = Co, Ni, Cu and Zn) bimetallic nanoparticles over TiO2 grafted SBA-15: their catalytic activity on dehydroisomerization of α-pinene
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2013 (English)In: Microporous and Mesoporous Materials, ISSN 1387-1811, E-ISSN 1873-3093, Vol. 173, 99-111 p.Article in journal (Refereed) Published
Abstract [en]

Mesostructured siliceous SBA-15 was synthesized via direct hydrothermal crystallization from acidic solution of poly-(ethylene glycol)-block-poly(propylene glycol)-block poly(ethylene glycol)-copolymer and tetraethyl orthosilicate. The amorphous surface of the calcined Si-SBA-15 was modified with 20wt.% of TiO2 by chemical grafting method using titanium isopropoxide as the titanium source in ethanol solution. Various metal nanoparticles Au, Au-M (M = Co, Ni, Cu and Zn) were supported on TiO2/SBA-15 by deposition-precipitation method (DP) using urea as the precipitating agent. The structural features of the synthesized materials were characterized by various physico-chemical techniques such as X-ray diffraction, nitrogen sorption, XPS and HR-TEM. BET results of Si-SBA-15 revealed the formation of mesoporous structure with an average pore size of 5.9nm, pore volume of 1.12 cm3/g and the specific surface area of 846 m2/g. HR-TEM results demonstrated that metal nanoparticles were highly dispersed over TiO2/SBA-15 and long range ordering of hexagonal mesopores of Si-SBA-15 was well retained after loading of 20 wt.% TiO2 and 3 wt.% of bimetallic nanoparticles. The catalytic performances of the prepared catalysts were studied on dehydroisomerization of α-pinene under gas phase conditions using hydrogen atmosphere. The stability and catalytic activity of Au-M-TiO2/SBA-15 (DP) catalysts upon conversion of α-pinene in to p-cymene was explored in comparison with the catalysts prepared by conventional method. AuNi-TiO2/SBA-15 catalysts prepared via DP method were found to be stable upon longer reaction time as well as superior in terms of conversion and selective towards the formation of p-cymene.

Place, publisher, year, edition, pages
Elsevier, 2013
Keyword
Supported bimetal catalysts, TiO2/SBA-15, Dehydroisomerization, α-Pinene, p-Cymene
National Category
Chemical Sciences
Identifiers
urn:nbn:se:umu:diva-65772 (URN)10.1016/j.micromeso.2013.02.015 (DOI)
Available from: 2013-02-11 Created: 2013-02-11 Last updated: 2017-12-06Bibliographically approved

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