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CARBONYLATION REACTIONS OF INDUSTRIAL INTEREST CATALYSED BY SUPPORTED METAL

Objectif

The main objective concerns the production of higher carboxylic acids by catalytic of methanol in the presence of supported Rh.
This work demonstrated the possibility of creating chains in the reaction to carbonylate methanol in the presence of iodised promoters in heterogeneous catalysis, using supported rhodium catalysts. The crucial problem in this state is the loss of rhodium from the catalytic support. This project established that the use of polymeric carbon and resins as the support, are capable of greatly reducing such losses through their strong anchoring of rhodium. The chosen resins could be used at high temperature (230 C) and at high pressures (21 MPa) without altering their properties. It was apparent that the rhodium was fused in 2 site types on the resins. The first was a high anchorage site where the rhodium was bound, whereas the rhodium in the second site was more poorly anchored through deposition. Preliminary treatment of the catalyst allowed the majority of the more weakly retained rhodium to be eliminated and therefore to reduce subsequent losses. An exhaustive thermodynamic study allowed the elucidation of the vapour phase conditions in which the condensation of either the reactants or the products can be avoided, thereby eliminating possible later losses of rhodium. The problem of recovering rhodium when it has passed into solution has also been tackled. A second route of obtaining higher acids (from 2-carbon to 6-carbon) using hydrocarbonylation was proposed. The second stage of this process consists of the esterification of the resultant acids. This is complete if the choice of esterification agent recovered and recycled is judicious. The hydrogenation of esters has been optimised and is quantitative with a commercial catalyst based on copper-chromium or manganese. A comprehensive outline of the process was proposed in the view of the overall results of the project.
Direct conversion of synthesis gas to chemicals is not presently commercialized in any homogeneously catalyzed process. On the other hand, the heterogeneously the catalyzed Fischer-Tropsch reaction converts synthesis gas directly to mixtures of variously functionalized compounds. With the notable exception of methanol synthesis however, such heterogeneously catalyzed processes have thus so far been rather nonselective to discourage further application.

As a result of this project, a new preparative route to short-chain aliphatic carboxylic acids may be developed where the products are optionally based upon syngas feedstocks alone. Alternatively by conventional esterification and hydrogenolysis of the reaction mixtures containing variable blends of acids and alcohols may be obtained which are useful as octane boosters.

The first will be devoted to the development of innovative techniques for supporting Rh, to the chemical and physical characterization of the catalysts and to batch catalytic tests under various conditions. In the second year optimization will be performed through kinetic modelling while investigating on the esterification of reaction mixtures obtained and their hydrogenation to alcohols to assess their potential as octane boosters. The third year will study the transportation as a continuous process othe optimum conditions identified in batches while evaluating the recovery of the metal from the reaction and the economic potential of the defined process.

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Coordinateur

Politecnico di Milano
Contribution de l’UE
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Adresse
Piazza Leonardo da Vinci 32
20133 Milano
Italie

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