Direct synthesis of hydrogen peroxide in batch reactors: understanding the kinetics and mechanisms

J. R. Hernndez Carucci1, T. Salmi1, P. Biasi1,2, J. Wrn1, K. Ernen1, K. Arve1, P. Canu2. 1 bo Akademi, Process Chemistry Centre, Industrial Chemistry and Reaction Engineering FI20500 Turku/bo, Finland. E-mail: johernan@abo.fi 2 Dipartimento di Principi e Impianti di Ingegneria Chimica I. Sorgato (DIPIC), University of Padova, via Marzolo 9, 35131, Padova, Italy. Introduction The current applied industrial process for the production of hydrogen peroxide, the anthraquinone process which is based on the successive hydrogenation and oxidation of quinonic components, is far from optimal: several process steps are needed, the use of an organic solvent is not desirable, plus the working solution is circulating in the process. The working solution is the memory of the continuous process, since impurities and by-products tend to accumulate in it. Furthermore, the anthraquinone process incorporates many units, which increase the capital cost. Catalyst deactivation is a problem in the anthraquine process, too. Ideally, the production of hydrogen peroxide has to be performed from the elements (oxygen and hydrogen). Since the pioneering work of Pospelova et al. in early 1960s [1] much research efforts have been focused on the direct synthesis of hydrogen peroxide. A lot of catalyst development work has taken place, being the most promising heterogeneous catalysts Pd and Pd-Au [2-3]. Catalyst development alone does not bring us to a success in the development of a hydrogen peroxide process based on the direct synthesis. Early attempts to apply direct synthesis failed because of low reaction rates and selectivities the catalyst enhances water formation and hydrogen peroxide decomposition, too. Thus the study of direct synthesis should always be combined to studies of the hydrogen peroxide decomposition. The introduction of methanol as solvent and the presence of carbon dioxide in the reaction environment have implied real breakthroughs in the process development. In this way, the solubilities of the reacting gases can be essentially improved and the reaction enhanced. In spite the huge interest on the direct synthesis, only few detailed kinetic studies are available for the system. There is an imperative need of understanding the kinetics if the process is going to be carried out industrially. The efforts on kinetic modelling of the direct synthesis of hydrogen peroxide, still remain scarce, and proper and systematic kinetic experiments are still to be carried out. Therefore, we constructed a special batch-semibatch reactor system to determine the very precise kinetics of hydrogen peroxide synthesis and decomposition. The reaction kinetics was determined at different temperatures and partial pressures in order to reveal the kinetic phenomena. The final goal of this work is to model the kinetics and the synthesis reactor behaviour. Experimental The direct synthesis of hydrogen peroxide from molecular hydrogen and oxygen was performed in a Parr stainless steel batch reactor with a volume of 600 ml and a maximum working pressure of 200 bar with a commercial 5 wt.% Pd/C catalyst (Evonik). Mixing was carried out with a Heidolph RZR 2021 rotor operating at 1000 rpm. During each experiment, the reactor was charged with 0.1 g of catalyst. The autoclave was initially filled with a 25 mol.% O2/CO2 mixture until reaching the desired working pressure. The addition of 400 ml of the reaction solvent (methanol) was successively done. Pure hydrogen was sequentially added, keeping the total pressure constant. The reaction

temperature was kept constant at 273 K by using ethylene glycol as a coolant. The catalyst was in a form of finely dispersed slurry in the reactor to suppress the internal and external mass transfer resistances. The concentration of the reactants (H2 and O2), as well as the total pressure of the system were systematically varied as follows: i) keeping the total pressure of the system at 20 bar and the partial pressure of hydrogen pH2=0.5 bar, the O2 partial pressure was varied between 3 and 8 bar; ii) keeping the total pressure of the system at 20 bar and the partial pressure of O2 at 5 bar, the H2 partial pressure was varied between 0 and 4 bar; and iii) keeping the partial pressures of H2 and O2 constants (0.5 and 5 bar, respectively), the total pressure of the system was varied between 10 and 30 bar. Results The specific surface area of the catalyst was measured by N2-physisorption, the metal dispersion by CO-chemisorption and the Pd oxidation state was determined by XPS analyses (before and after the experiments). Scanning electron micrographs of the powders were also taken for determining their structure. Experiments carried out under kinetic control revealed that hydrogen peroxide was successfully formed on the catalyst surface, but it was decomposed as the reaction time was prolonged. The mass balances of the components were considered in detail. A LangmuirHinshelwood rate mechanism was proposed based on the competitive adsorption of hydrogen and oxygen on the palladium surface. The adsorption and desorption steps are assumed to be rapid enough to reach quasi-equilibria, while the surface reaction steps are assumed to limit the rates. Fig. 1, left presents the reaction steps for the proposed mechanism. The surface reactions leading to the formation of hydrogen peroxide and water were assumed to be rate determining, after which the rate equations describing the system were derived and the kinetic parameters were estimated by nonlinear regression analysis. The model gave a good fit to the experimental data and it was used to predict the system behaviour under batch conditions (See Fig. 1, right).
Reaction H2 + 2* = 2H* O2 + 2* = 2O* O* + H* = OH* + * OH* + OH* = HOOH* + * OH* + H* = H2O* + * HOOH* + * =H2O* + O* HOOH* + H* = OH* + H2O* HOOH* = H2O2 + * H2O* = H2O + * Step # I II III
wt.% 0.08 0.07

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Fig. 1. Reaction steps of the proposed mechanism (left) and experimental (symbols) and predicted (lines) production rates of H2O2 (+) and H2O (o) (right). References 1. T.A. Pospelova, N.I. Kobozev, E.N. Eremin, J. Phys. Chem. (Trans.) 35 (1961) 143. 2. P. Landon, P.J. Papworth, C.J. Kiely, G.J. Hutchings, Chem. Commun. (2002) 2058. 3. J.K. Edwards, B.E. Solsona, P. Landon, A.F. Carley, A. Herzing, C.J. Kiely, G.J. Hutchings, J. Catal. 236 (2005) 69.