Terpenoids in Supercritical Solvents
New Syntheses and Transformations of Organic Compounds in Supercritical Solvents. Transformations of Mono- and Diterpene Compounds
Tech Area / Field
- CHE-SYN/Basic and Synthetic Chemistry/Chemistry
- CHE-IND/Industrial Chemistry and Chemical Process Engineering/Chemistry
3 Approved without Funding
Boreskov Institute of Catalysis, Russia, Novosibirsk reg., Akademgorodok
- Seoul National University / School of Chemical and Biological Engineering, Korea, Seoul\nUniversity of Illinois / Department of BioEngineering, USA, IL, Chicago\nUniversity of Birmingham / School of Engineering, UK, Birmingham\nNational Institute of Chemistry, Slovenia, Ljublana\nTohoku University / Institute of Multidisciplinary Research for Advanced Materials, Japan, Sendai\nGeorgia Institute of Technology / School of Chemical & Biomolecular Engineering, USA, GA, Atlanta\nHanwha Chemical R&D Center, Korea, Daejeon\nUniversity of Maribor, Slovenia, Maribor\nKRICT - Korea Research Institute of Chemical Technology, Korea, Yusong-gu\nUniversity of Michigan / Colledge of Engeneering / Department of Chemical Engineering, USA, MI, Ann Arbor
Project summaryThe Project is aimed at developing new efficient methods and technologies for transformation of phytogenic mono- and diterpene compounds to synthesize new and valuable organic compounds with the use of supercritical states of the reaction medium (solvents).
Mono- and diterpene compounds (turpentine, a-pinene (С10Н16), and sclareol (C20H36O2)) were selected as a subject of inquiry. Selective oxidation and isomerization of monoterpenes will be performed in supercritical alcohols C1-C3, water, CO2, and in some saturated hydrocarbons and mixtures used as solvents, at temperatures and pressures slightly exceeding the corresponding critical parameters of the reaction mixture. Since substances acquire special properties in the critical region of their parameters, in some cases supercritical solvents provide a manifold increase in the rate of chemical reaction and render its selectivity controllable.
Thermal isomerization of monoterpenes (natural turpentine containing ca. 60-70% of a-pinene) in supercritical alcohols, water, and their mixtures is expected to yield limonene and (neo)-alloocimenes; selective oxidation of diterpenes (sclareol) will allow synthesizing aromatic compounds of the ambrox group (II), ketal (III), diether (IV), and other compounds of this type, which are in great demand for the production of cosmetics and perfumery, polymeric materials, and household chemical goods.
In contrast to thermal isomerization of turpentine (a-pinene) performed without solvent in the liquid or gas phase at the contact time of several hours, which provides 90-95% conversion of the initial reactant, the use of supercritical solvents makes it possible to attain high degree of conversion and a required selectivity in some minutes.
Goal of the Project is to perform studies aimed at gaining new knowledge on chemical transformations of selected natural organic compounds in supercritical fluids, in particular, supercritical water, alcohols and saturated hydrocarbons, and to use this new knowledge for the development of new methods and technologies intended for synthesis of rare and valuable organic substances and compounds.
The proposed goals will be implemented via experimental studies on transformations of selected organic compounds, which are necessary to substantiate the choice of supercritical solvent and reaction conditions. The experimental studies of kinetic regularities and reaction mechanism of thermal isomerization and selective oxidation of terpene compounds along with the development of macrokinetic models of the reactions will allow us to evaluate the effect of solvent nature, temperature and pressure on the reaction rate over different routes, and reaction selectivity for target products in inpidual supercritical solvents and their mixtures.
Special attention will be paid to the effect of pressure, co-solvents and, in some cases, heterogeneous catalysts on the rate and selectivity of terpenoid transformation in supercritical solvents.
Laboratory experiments, mathematical modeling, thermodynamic and kinetic calculations concerning the basic problems of the Project will serve as main instruments to implement this part of the Project, and as an intermediate step leading to the development of new methods and technologies. Calculations and modeling will allow us to determine location and drift of the critical point of a multicomponent fluid, to calculate the chemically equilibrium composition of a mixture under the condition of its non-ideality, and to find optimal conditions (solvent concentration, temperature, pressure) for chemical reactions.
The proposed process and technology will be tested on the pilot-plant scale. For this purpose, limonene will be synthesized from turpentine in a supercritical solvent at the pilot plant of 20-30 kg/h capacity available to out research team.
The Project participants have rich experience in applied research and successful collaboration with other institutions in many countries of the world. In recent years, they have published more than 20 research works in the leading world journals. The team has created and put into operation the first Russian stationary SCWO plant intended for the oxidation and decomposition of a wide range of organic compounds with the hourly output attaining 40 kg.
The Project entirely complies with the ISTC aims and goals; it is aimed at solving national and international R&D problems and facilitates international integration of scientists and specialists in the field. The role of foreign collaborators in implementation of the proposed Project is of high importance, first, as experts, and second, as partners having experience and knowledge in the field necessary for efficient accomplishment of the Project tasks.
The International Science and Technology Center (ISTC) is an intergovernmental organization connecting scientists from Kazakhstan, Armenia, Tajikistan, Kyrgyzstan, and Georgia with their peers and research organizations in the EU, Japan, Republic of Korea, Norway and the United States.
ISTC facilitates international science projects and assists the global scientific and business community to source and engage with CIS and Georgian institutes that develop or possess an excellence of scientific know-how.