Hydrogénation sélective du 2-butyne-1,4-diol avec des catalyseurs de palladium supportés sur des matériaux filamenteux structurés

The principal objective of this thesis is the development of a palladium catalyst supported on woven fabrics of activated carbon fibers (ACF) for the reactions of hydrogenations in liquid phase and the design of multiphase reactors using the characteristics of these structures. This work was focused on Preparation, characterization and optimization of catalysts supported on the woven fabrics of activated carbon fibers; The intrinsic kinetics of the selective hydrogenation of 2-butylene-1,4-diol to 2-butyne-1,4-diol as model reaction; The comparison of the activity of our structured catalyst with that of commercial catalysts; Increase the catalyst concentration in the multiphase reactors with the design of a loop reactor containing a bubble column staged with the fiber fabrics supporting the catalyst, its characterization and the startup of this loop reactor which can operate in continuous or in batch mode. Chapter 4 presents the methods of manufacture of our palladium catalysts supported on woven structures of activated carbon fibers, their reproducibility and their homogeneous deposition. The characteristics of the support such as its handiness, its resistance to mechanical forces, the opening of its surface to liquid flow, its great specific surface area and its homogeneous distribution of micropores are defined there. The deposition of nanoparticules of active phase (0.5-5%mass) is characterized by metal surface obtained (280-87 m2/g), the dispersion of this surface (62.8-19.6%) and the average diameter of the nanoparticles (1.78-5.72 nm). The total degree of initial reduction (before reaction) was confirmed. Chapter 5 is devoted to the study of the reaction of selective hydrogenation of the 2-butyne-1,4-diol (B3) to 2-butylene-1,4-diol (B2) with a commercial palladium catalyst supported on activated carbon powder. A zero value even slightly negative was found for B3 partial order and equal to one for hydrogen. The activity obtained for this catalyst is large (37.1 mol(H2)/h gPd) but its initial selectivity is particularly low (SB3,0 = 76.8 %). Effect of support was tested and highlighted. Two supports (CaCO3 and Al2O3) gave reaction rates approximately half the size of those of the carbon support, but an initial selectivity close to 99 %. In chapter 6, selective hydrogenation in an autoclave with an agitator containing structured catalyst is tested. This reactor is first of all evaluated like a reactor working in kinetic mode for the selected reaction. Kinetics was studied and showed that the fibrous support does not change the orders of reaction compared to the commercial catalyst. Energy of activation of 30 kJ/mol was found in the studied configuration. A variation of the catalytic amount on woven structure was studied and gave a reaction rate of 19.4 (mol(H2)/h gPd) for an initial selectivity of 98 % for the best catalyst (Pd(2%)/ACF). The reuse of this catalyst with an in situ reactivation in hydrazine allowed a stabilization of the activity at 50% of the initial activity after four experiments. A constant Turn Over Frequency (TOF) for catalysts with high deposits (2-5%) was given. An increase in the TOF for the low deposits (0.5% and 1%) was found. This increase in the TOF agrees with a fall of the initial selectivity. The effect of several variables of the reaction such as pressure, temperature and pH of the solution were examined. Within the framework of the variation of pH an initial selectivity of 100% and selectivity during reaction remaining higher than 95% until a conversion of 90 % were obtained. This profit of selectivity was achieved only with the detriment to the reaction rate which decreased by a factor 2.5. Finally, experiments with even less harm to the environment were made without solvent thus allowing the avoidance of purification. The rate of hydrogenation in this configuration is very high (79.2 mol(H2)/(h gPd)). But in this configuration, this increase in activity is not done at the expense of the initial selectivity (98 %). In chapter 7, the increase in the catalyst concentration in the reactor was required for higher productivity. For that purpose, a new concept of reactor was studied. This new reactor is a loop reactor containing a bubble column staged with woven catalytical structure. The pressure drop, the emulsion crossing the bubble column and the RTD were characterized. The reactor, functioning in batch or continuous mode, was studied. The productivity in batch was improved by an order of magnitude due to the increase in the catalytic concentration. A unit worked during 50 hours continuously without deactivation of catalyst providing 160 g of B2 per hour (> 1 tons/year). The reaction led to a conversion of 85% with a selectivity of 96 %.

    Thèse École polytechnique fédérale de Lausanne EPFL, n° 3165 (2004)
    Section de chimie et génie chimique
    Faculté des sciences de base
    Institut des sciences et ingénierie chimiques
    Jury: Claude Friedli, Freek Kapteijn, Lioubov Kiwi, Felix Roessler, Francis Stoessel

    Public defense: 2005-1-21


    Record created on 2005-03-16, modified on 2016-08-08


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