Low-Temperature Hydrogenation of Toluene Using an Iron-Promoted Molybdenum Carbide Catalyst

As an alternative to noble metal hydrogenation catalysts, pure molybdenum carbide displays unsatisfactory catalytic activity for arene hydrogenation. Precious metals such as palladium, platinum, and gold are widely used as additives to enhance the catalytic activities of molybdenum carbide, which severely limits its potential applications in industry. In this paper, iron-promoted molybdenum carbide was prepared and characterized by various techniques, including in situ XRD, synchrotron-based XPS and TEM. while the influence of Fe addition on catalytic performance for toluene hydrogenation was also studied. The experimental data disclose that a small amount of Fe doping strongly enhances catalytic stability in toluene hydrogenation, but the catalytic performance drops rapidly with higher loading amounts of Fe.

Electrochemical Toluene Hydrogenation Using Binary Platinum-Based Alloy Nanoparticle-Loaded Carbon Catalysts

A couple of toluene (TL) and its hydrogenation product, methylcyclohexane (MCH), are promising high-density hydrogen carriers to store and transport large amounts of hydrogen. Electrochemical hydrogenation of TL to MCH can achieve energy savings compared with hydrogenation using molecular hydrogen generated separately, and development of highly active catalysts for electrochemical TL hydrogenation is indispensable. In this study, binary Pt3M (M = Rh, Au, Pd, Ir, Cu and Ni) alloy nanoparticle-loaded carbon catalysts were prepared by a colloidal method, and their activity for electrochemical TL hydrogenation was evaluated by linear sweep voltammetry. Each Pt3M electrode was initially activated by 100 cycles of potential sweep over a potential range of 0–1.2 or 0.8 V vs. reversible hydrogen electrode (RHE). For all activated Pt3M electrodes, the cathodic current density for electrochemical TL hydrogenation was observed above 0 V, that is the standard potential of hydrogen evolution reaction. Both specific activity, cathodic current density per electrochemical surface area, and mass activity, cathodic current density per mass of Pt3M, at 0 V for the Pt3Rh/C electrode were the highest, and about 8- and 1.2-times as high as those of the commercial Pt/C electrode, respectively, which could mainly be attributed to electronic modification of Pt by alloying with Rh. The Tafel slope for each activated Pt3M/C electrode exhibited the alloying of Pt with the second metals did not change the electrochemical TL hydrogenation mechanism.

Effect of Modification of Amorphous Silica with Ammonium Agents on the Physicochemical Properties and Hydrogenation Activity of Ir/SiO2 Catalysts

The modification of commercial silica with solutions of NH4F or NH4Cl salts, followed by thermal treatment, enabled generation of the acidic sites in SiO2 and changed its textural properties. The use of ammonium salts solution also caused the generation of additional porosity. Using NH4F solution caused significant decrease in the specific surface area and the increase in the average pore diameter. The number and strength of resulting acid sites depend on the nature of anion in the applied ammonium salt and the concentration of salt solution. It has been found that the sample treated with NH4F presented higher total acidity (TPD–NH3) and the amount as well as the strength of acid sites increased with the concentration of the used modifier. As modified amorphous SiO2 materials used as a support for iridium (1 wt %, Ir(acac)3) nanoparticles permitted to obtain highly active catalysts for toluene hydrogenation under atmospheric pressure. The highest activity (expressed as the apparent rate and TOF) was obtained for iridium catalysts supported on silica modified by NH4F with the highest acidity. The modification of silica with NH4F favors the generation of centers able to adsorb toluene, which results in higher activity of this catalyst.

Hydrogenation of benzene and toluene over supported rhodium and rhodium-gold catalysts

Rhodium and rhodium-gold catalysts supported on amorphous aluminosilicates (ASA), titanium dioxide (rutile, TiO2) was prepared in two different ways: absorption and colloidal method. The catalysts were characterized by an inductively coupled plasma optical emission spectrometer (ICP-OES), transmission electron microscopy (TEM) and X-ray diffraction (XRD). The activity and selectivity of the prepared catalysts were tested by the hydrogenation of benzene and toluene. Hydrogenation was conducted at a pressure of 4 MPa and a temperature 80 °C. The bimetallic Rh-Au/ASA catalyst prepared by the absorption method showed higher activity and selectivity in benzene hydrogenation reaction, the same catalyst prepared by the colloidal method demonstrated lower selectivity.

Unraveling Toluene Conversion during the Liquid Phase Hydrogenation of Cyclohexene (in Toluene) with Rh Hybrid Catalysts

Monitoring hydrogen consumption has allowed studying the progress of the liquid phase hydrogenation of cyclohexene in toluene with Rh SILP (supported ionic liquid phase) catalysts prepared by the immobilization of the [{RhCl(cod)}2] complex on different carbon materials. An excess of hydrogen consumption with respect to the required amount for cyclohexene hydrogenation was registered and related with the solvent (toluene) hydrogenation. The study carried out led to unraveling the extent of toluene hydrogenation and to determining if the rate of this reaction is affected by the properties of the carbon material used as support. The results revealed that the Rh SILP catalysts we prepared showed acceptable toluene conversion, with 100% selectivity to the total hydrogenated product, and that the effect of the carbon support is the same as for cyclohexene hydrogenation.

Approximating Catalyst Effectiveness Factors with Reaction Rate Profiles

A novel approximate solution for catalyst effectiveness factors is presented. It is based on carefully selected approximate reaction rate profiles, instead of typical assumption of composition profiles inside the catalyst. This formulation allows analytical solution of the approximate model, leading to a very simple iterative solution for effectiveness factor for general nonlinear reaction stoichiometry and arbitrary catalyst particle shape. The same model can be used with all practical Thiele modulus values, including multicomponent systems with inert compounds. Furthermore, the correct formulation of the underlying physical model equation is discussed. It is shown that an incorrect but often-used model formulation where convective mass transfer has been neglected may lead to much higher errors than the present approximation. Even with a correctly formulated physical model, rigorous discretization of the catalyst particle volume may have unexpectedly high numerical errors, even exceeding those with the present approximate solution. The proposed approximate solution was tested with a number of examples. The first was an equimolar reaction with first order kinetics, for which analytical solutions are available for the standard catalyst particle geometries (slab, long cylinder, and sphere). Then, the method was tested with a second order reaction in three cases: 1) with one pure reactant, 2) with inert present, and 3) with two reactants and non-stoichiometric surface concentrations. Finally, the method was tested with an industrially relevant catalytic toluene hydrogenation including Maxwell-Stefan formulation for the diffusion fluxes. In all the tested systems, the results were practically identical when compared to the analytical solutions or rigorous finite volume solution of the same problem.