RICERCA ITALIANA     

INNOVATIVE CATALYTIC PROCESSES FOR THE SELECTIVE OXIDATION AND REDUCTION OF GLYCEROL IN WATER: STUDIES OF REACTION MECHANISMS AND KINETICS FOR THE PROCESS OPTIMISATION

Università degli Studi di Palermo

Abstract

The aim of this Research Project is the development of innovative processes for the selective production of organic species of great added value by following the principles of Green Chemistry and Green Engineering.
The selective transformation of alcohols is an important preparative method in organic chemistry and the resulting products (as aldehydes, ketones, etc.) are extensively used in pharmaceutical, fine chemical and fibers industries. In the field of transformation processes an important area of Green Chemistry concerns the selection of the medium in which to carry out chemical reactions. In fact, many of the solvents commonly used are dangerous and/or volatile so that they may cause contamination and smog when released to atmosphere. Then, the general trend is the utilization of environmentally benign solvents.
On the basis of previous considerations, the present Research Project is focused on the selective transformation of glycerol in water for the production of chemical intermediates of industrial interest such as 1,3-propanediol, 1,3-dihydroxyacetone, glyceraldehyde and glyceric acid. The study will be carried out by using processes which use innovative methods as heterogeneous photocatalysis, electrocatalysis and photoelectrocatalysis coupled with an innovative separation method as pervaporation. The investigation will concern with the preparation and characterisation of nanostructured semiconductor photocatalysts able to determine high quantum >>>

Principal Investigator

Vincenzo Augugliaro Università degli Studi di PALERMO

Research Objectives

The main objective of this research program is the development of a novel process able to perform the selective oxidation or reduction of glycerol in water under mild reaction conditions. This process is of great interest since some of the reaction products, such as dihydroxyacetone, glyceric acid, 1,3-propanediol and glyceraldehyde, are potentially useful as chemical intermediates. The novel process will be developed by following the principles of Green Chemistry (environmentally benign chemistry) and Green Engineering areas, i.e. the process will not use or generate hazardous substances but it will minimize the associated environmental impacts trying to reduce the amount of energy used in the process or to use cheap and clean solar energy. The novel process will be a catalytic one so that its development will concern: a) the catalyst; b) the reactor; and c) the operative conditions of the process.
By employing the following methods:
(i) heterogeneous photocatalysis,
(ii) electrocatalysis and
(iii) electrophotocatalysis
an optimal process able to maximize the production of the desired intermediate product and also to minimize the energy requirement will be identified.
As to concern the catalyst, objective of this research is that of obtaining photocatalysts able to perform the glycerol transformation with high quantum yield or under near-UV irradiation or under visible light irradiation. Moreover, this optimal catalysts will be >>>

First Results

The most important result expected from this research program is the successful application of Green Chemistry and Green Engineering principles for performing an important preparative method in organic chemistry such as the selective transformation of alcohols to products to be used as precursors and intermediates for the pharmaceutical, fine-chemical and fiber industries. The novel process, get in working order at the accomplishment of the research program, allows to eliminate or drastically reduce severe environmental problems of traditional methods mainly related to waste generation from the use of heavy metals or stoichiometric amounts of reagents and to the production of undesirable coproducts.
Specifically the process, whose realization and characterization will be the result of this research program, concerns the selective oxidation or reduction of glycerol in water under mild reaction conditions. The oxidation of glycerol is a process of industrial interest since some of the partial oxidation products, dihydroxyacetone, glyceric acid and glyceraldehyde, are used as chemical intermediates. The reduction process of glycerol is also of great industrial importance as it allows the production of 1,3-propanediol, a starting material in the fiber industry.
For the realization of the process of selective transformation of glycerol in water the following methods will be employed: (i) heterogeneous photocatalysis ; (ii) electrocatalysis; (iii >>>

Timescale

24 months

National and international background

With an increase in environmental consciousness throughout the world, there is a challenge for chemists and chemical engineers to develop new products, processes and services that achieve necessary social, economical and environmental objectives. The Green Chemistry (environmentally benign chemistry) and Green Engineering areas, developed in these last years, are the answers of the scientific community to that challenge. Green Chemistry is the utilization of set of principles that reduces or eliminates the use or generation of hazardous substances in the design, manufacture and application of chemical products and Green Engineering is the design, commercialisation and use of processes that are feasible and economic, reduce and prevent the generation of pollution at the source and minimise the risk to human health and the environment. As well as using and producing better chemicals with less waste, the challenge also involves reducing other associated environmental impacts including reduction in the amount of energy used in chemical processes [1-3].
An important area of green chemistry investigations concerns the selection of a medium in which to carry out a synthetic transformation. Many of the solvents commonly used are dangerous and volatile organic compounds known to cause contamination and smog when released in air so that there is an increased emphasis, both in the chemical industry and academic research, on utilization of environmentally benign solvents.
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