Sviluppo di processi catalitici sostenibili per la conversione di oli non-edibili di origine indiana in composti ad alto valore aggiunto

Responsabili di progetto

Matteo Guidotti, Vijay Bokade

Accordo

INDIA - CSIR-expired - Council of Scientific and Industrial Research

Bando

CNR-CSIR 2016-2018

Dipartimento

Scienze chimiche e tecnologie dei materiali

Area tematica

Scienze chimiche e tecnologie dei materiali

Stato del progetto

Nuovo

Proposta di ricerca

Thanks to an increasing level of awareness regarding environment, the development and the exploitation of sustainable raw materials and green chemicals, as reagents, is a leading theme in various domains. For instance, petrochemistry-based resin such as epoxy, polyester and vinyl ester find various engineering applications because of their advantageous material properties, such as high stiffness and strength. However, these resins suffer from serious drawbacks in terms of biodegradability, initial processing cost, energy consumption and health hazards. Consequently, there is a requirement to develop novel bio-based products from renewable feedstock. Several research groups are studying vegetable oils as alternative feedstock as a substitute for petroleum, thanks to their lower inherent toxicity and better biodegradability. The presence of unsaturations on the alkyl chain of fatty acids and oil derivatives opens the structure of the molecule to the attack by free radicals and reagents. Chemically, the polyunsaturated fraction of these oils and fats makes these compounds very sensitive to undesired transformation and degradations.
Unsaturated triglycerides are found in very high concentrations in many seeds and in the fats of animals fed on a diet containing them. Such unsaturations present in vegetable oils can be chemically modified and the pristine compounds converted into added-value products by a functionalization reaction, such as epoxidation of the C=C bond. Then, exploiting the high reactivity of oxirane rings, fatty acids epoxides are versatile building blocks for the synthesis of a broad variety of chemicals such as alcohols, polyols, glycols, which find use as lubricants, plasticizer and stabilizer for polymers, whose demand is increasing day by day.
The use of environmentally sustainable pathways for the epoxidation of fatty acid derivatives is still an object of interest, since the conventional methods rely on the use of large and stoichiometric amounts of hazardous and high-impact oxidizing agents (in particular, peroxocarboxylic acids in over-stoichiometric ratios).
Therefore, non-edible vegetable oils represent a cheap and abundant natural feedstock available and the selection of varieties rich in unsaturated components offers numerous advantages for their use as starting oleochemicals. Their transformation into epoxidised vegetable oil via sustainable synthesis pathways, moreover, increases the economic value of the starting material itself.
In India, there is a abundant availability of non-edible oil such as Jatropha and Karanja, having high percentage of unsaturated fatty acids. There is a little number of studies in the current literature about the epoxidation of these oils or their derivatives over solid metal-based peracid-free catalysts. Moreover, only few of them have planned and concerted a direct subsequent transformation of the intermediate epoxides into alcohols, polyols and glycols. These epoxides, alcohols and glycol are useful for the synthesis of resins and show the advantage of sustainability, biodegradability and eco-friendly character in comparison with resins from petrochemical source.

The present proposal will merge the expertise of two research teams in Italy and India to develop catalytic renewable processes for converting unsaturated non-edible oil (as triglycerides or as fatty acid methyl ester derivatives) to epoxides and to alcohols having wide applications, according to the "biorefinery" vision, and for proposing economically and environmentally sustainable alternatives to non-catalytic or conventional homogeneous catalytic methods still widely adopted by the oleochemical industry worldwide.
The use of raw materials poorly known in the European (and specifically Italian) context, but autochthonous to the Indian sub-continent, is the most specific reason justifying such bilateral transnational partnership.

CNR-ISTM has a deep expertise in designing and developing inorganic oxide and metal nanoparticle-based heterogeneous catalysts. The application of such know-how to a broader class of substrates and starting chemicals, difficult to be found on the Italian/European market, is an important reason for the set-up of a bilateral exchange of materials and experience between the two Units.
Analogously, CSIR-NCL, Pune-India has a broad and long-term expertise in developing heterogeneous catalysts for the transformation of natural products and bio-based substrates to bio-chemicals and bio-fuels. The application of such know-how to epoxidised derivatives and intermediates to obtain high-added value functionalised oleochemicals is the main driving force for the set-up of such bilateral collaboration.

The collaboration between CNR-ISTM and CSIR-NCL has just started and has not led to joint publications or communications so far, as the joint efforts are at an initial stage only. However, the present bilateral project will foster a narrow exchange of information, data and researchers between the two Units and will improve their capability to achieve successful results in short times and dissemination of the results across the top-level international scientific community.
In addition, the potential applicability and the number of medium/long-term benefits, not only for the local Indian productive scenario, but also at global level, can be very high.

Obiettivi della ricerca

The objective of this proposal is to develop and optimize solid heterogeneous catalysts for the two main reaction steps:
1) the conversion of unsaturated fatty acid derivatives and triglycerides, obtained from vegetable oils, especially non-edible ones, such as Jatropha (Jatropha curcas) oil or Karanja (Millettia pinnata) oil, abundantly available in India, into their epoxidised derivatives; and
2) the transformation of the obtained epoxides into fatty derivatives functionalized on the alkyl chain, namely alcohols, glycols and polyols.

The successful application and use of environmentally friendly oxidants (hydrogen peroxide or oxygen) in these epoxidation reactions is another major aim of the present proposal. A constant attention will be paid to the choice of environmentally and economically sustainable reagents, solvents and techniques in each step of the research activity.

At the same time, another relevant objective is to establish long-term linkages between CNR-ISTM, Italy and CSIR-NCL, Pune-India for further extensive international collaborations.

Ultimo aggiornamento: 21/05/2024