The interaction between silver and N2O in relation to the oxidative dehydrogenation of methanol

The interaction of N2O with pure silver at temperatures up to 900 °C has been studied using temperature-programmed reduction and desorption; the interaction is compared with that of oxygen with silver. The effect of addition of N2O, as well as of the complete replacement of oxygen by N2O, on the oxidative dehydrogenation of methanol on a silver catalyst has also been studied. It was found that the interaction of silver with N2O was much slower than that of O2; no atomic surface oxygen species were observed, probably because the formation of subsurface species was not complete; selective adsorption appears to take place on the surface defects and grain boundaries involved in the formation of the subsurface species. Addition of small amounts of N2O to the reaction mixture (CH3OH + O2) for the oxidative dehydrogenation of methanol had almost no influence on the conversion or on the product distribution measured. However, the conversions were considerably lower when oxygen was totally replaced by N2O; only above 600 °C was the N2O exhausted. At the same level of conversion of the methanol, the amount of CO2 produced was lowered compared to the case of O2. This is in agreement with the suggestion that CO2 is formed via weakly bound surface oxygen

The influence of hydrogen treatment and catalyst morphology on the interaction of oxygen with a silver catalyst

The interaction of an unsupported silver catalyst which had been pretreated by hydrogen at various temperatures with oxygen at 210°C has been studied using Temperature Programmed Reduction (TPR) over a temperature range up to 900°C. Hydrogen treatment at 500°C or above before the oxidation step causes the formation of extra species, thought to be OH groups in the sub-surface of the sample. A peak in the spectra attributable to oxygen strongly bound in the vicinity of surface defects is found to be dependent on the surface roughness and grain size of the silver sample used; hydrogen pretreatment causes the strongly bound oxygen in the vicinity of surface defects to be converted to sub-surface OH. It is also shown that the TPR measurements themselves influence the morphology of the sample and that these changes are comparable with structural changes which occur during the use of the catalysts for oxidative dehydrogenation of methanol. It is suggested that these structural changes are caused by the interaction of the sub-surface of the silver with both oxygen and hydrogen

The silver-oxygen interaction in relation to oxidative dehydrogenation of methanol

The interaction of unsupported silver with oxygen at atmospheric pressure and at temperatures between 100 and 600°C has been studied using temperature programmed reduction and desorption experiments with temperatures ranging up to 900°C. In addition, the interaction of an oxygen-loaded silver surface with methanol has been studied using both these techniques and temperature programmed reaction. It appears that the silver-oxygen chemistry is influenced strongly by hydrogen dissolved in the silver during the pretreatment of the catalyst, the hydrogen giving rise to a new type of sub-surface species, possibly sub-surface OH groups, and also to an increase of the amount of sub-surface oxygen formed. Sub-surface oxygen can be converted into a strongly bound species that is not present to a measurable extent after normal oxidation. Defects, partly generated as a consequence of the interaction between oxygen and hydrogen in the sub-surface region of the silver, probably generate this strongly bound oxygen species. The presence of the sub-surface oxygen species appears to activate the silver for methanol dehydrogenation

The oxidative dehydrogenation of methanol to formaldehyde over silver catalysts in relation to the oxygen-silver interaction

The properties of silver in the oxidative dehydrogenation of methanol were studied in a flow reactor under near industrial conditions. The influences of temperature, concentration of both reactants, gas velocity, space velocity, the form of the silver catalyst and surface composition of the catalyst were studied. A model for the reaction is proposed which is based on the experimental observations and on the nature of the interaction of silver with oxygen. It issuggested that different oxygen species on the silver surface play different roles in the reactions to CO, CO2 and H2CO. Gas phase reactions only contribute to the conversion to CO

Kinetic research on heterogeneously catalysed processes: a questionnaire on the state-of-the-art in industry

On the initiative of the Working Party `Chemical Engineering in the Applications of Catalysis¿ of the European Federation of Chemical Engineering an assessment of the issues in the determination and application of kinetic data within the European industry was performed. The basis of the analysis consisted of a questionnaire put together by researchers from Dow, DSM, Shell and Eindhoven University of Technology. The 24 companies, which have responded to the questionnaire, can be classified into four groups: chemical, oil, engineering contractors and catalyst manufacturers. From the overall input it appears that there are three, equally important, utilisation areas for kinetic data: process development, process optimisation and catalyst development. There is a wide variety of kinetic data sources. Most of the respondents make use of test units which were primarily designed for development and optimisation. Avoiding transport limitation is, certainly in the case of short range projects or for complex feedstocks, not always taken care of. With respect to the modelling approaches, a common philosophy is `as simple as possible¿. Most of the respondents state that `in principle¿ one should strive for intrinsic kinetics, but the majority nevertheless does for various reasons not separate all transport phenomena from reaction kinetics. Kinetic models are mostly simple first or nth order or Langmuir-Hinshelwood type expressions. More complex kinetic models are scarcely used. Three areas were frequently identified to offer opportunities for improvement. Gathering of kinetic data is too costly and time consuming. There is no systematic approach at all for determination and application of kinetics in case of unstable catalytic performance. Furthermore, the software available for the regression of kinetic data to rate equations based on mechanistic schemes as well as software to model reactors are insufficiently user friendly. The majority of the respondents state that the problems indicated should be solved by cooperation, e.g., between companies, between industry and academia and between the catalysis and the chemical engineering community. A workshop on the above topics was held in December 1996 with 15 companies and 6 academics attending. More information can be obtained from the secretariat of the Working Party

The influence of polydispersity and inhomogeneity on EXAFS of bimetallic catalysts

The effect of polydispersity and inhomogeneity of supported bimetallic catalysts on the EXAFS analysis is investigated with some simple model calculations. These show that EXAFS is very insensitive to polydispersity. Polydispersity and inhomogeneous distribution of the metals over the particles however have only limited influence on the ability to distinguish between core-shell particles and particles with random distribution of both metals

Influence of the Catalyst Particle Size on the Aqueous Phase Reforming of n-Butanol Over Rh/ZrO2

Butanol is a by-product obtained from biomass that can be valorized through aqueous phase reforming. Rh/ZrO2 catalysts were prepared and characterized, varying the size of the support particles. The results showed a relatively mild effect of internal mass transport on butanol conversion. However, the influence of internal transport limitations on the product distribution was much stronger, promoting consecutive reactions, i.e., dehydrogenation, hydrogenolysis, and reforming of propane and ethane. Hydrogen consuming reactions, i.e., hydrogenolysis, were more strongly enhanced than hydrogen producing reactions due to internal concentration gradients. Large support particles deactivated faster, attributed to high concentrations of butyraldehyde inside the catalyst particles, enhancing deposit formation via aldol condensation reactions. Consequently, also the local butyric acid concentration was high, decreasing the local pH, enhancing Rh leaching. The influence of internal transfer limitation on product distribution and stability is discussed based on a reaction scheme with three main stages, i.e., (1) formation of liquid intermediates via dehydrogenation, (2) formation of gas via decarbonylation/decarboxylation reactions, and (3) hydrocarbon hydrogenolysis/reforming/dehydrogenation

NO adsorption and thermal behavior on Pd surfaces. A detailed comparative study

The adsorption and thermal behavior of NO on `flat¿ Pd(111) and `stepped¿ Pd(112) surfaces has been investigated by temperature programmed desorption (TPD), high resolution electron energy loss spectroscopy (HREELS), and electron stimulated desorption ion angular distribution (ESDIAD) techniques. NO is shown to molecularly adsorb on both Pd(111) and Pd(112) in the temperature range 100¿373 K. NO thermally desorbs predominantly molecularly from Pd(111) near 500 K with an activation energy and pre-exponential factor of desorption which strongly depend on the initial NO surface coverage. In contrast, NO decomposes substantially on Pd(112) upon heating, with relatively large amounts of N2 and N2O desorbing near 500 K, in addition to NO. The fractional amount of NO dissociation on Pd(112) during heating is observed to be a strong function of the initial NO surface coverage. HREELS results indicate that the thermal dissociation of NO on both Pd(111) and Pd(112) occurs upon annealing to 490 K, forming surface-bound O on both surfaces. Evidence for the formation of sub-surface O via NO thermal dissociation is found only on Pd(112), and is verified by dissociative O2 adsorption experiments. Both surface-bound O and sub-surface O dissolve into the Pd bulk upon annealing of both surfaces to 550 K. HREELS and ESDIAD data consistently indicate that NO preferentially adsorbs on the (111) terrace sites of Pd(112) at low coverages, filling the (001) step sites only at high coverage. This result was verified for adsorption temperatures in the range 100¿373 K. In addition, the thermal dissociation of NO on Pd(112) is most prevalent at low coverages, where only terrace sites are occupied by NO. Thus, by direct comparison to NO/Pd(111), this study shows that the presence of steps on the Pd(112) surface enhances the thermal dissociation of NO, but that adsorption at the step sites is not the criterion for this decomposition

Synthesis of Carbon Nanofibers on Large Woven Cloth

This experimental study aims at the in situ growth of carbon nano-fibers (CNFs) on relatively large (25 × 30 cm2) single-layer carbon-fiber fabrics. It is shown that CNFs can be grown with the distribution potentially suitable for a future use in polymer-matrix composite materials. Details of tuning the catalyst deposition method and the CNF growth process are presented and analyzed. In particular, the Ni catalyst deposition method and the type of solvent are shown to strongly influence the uniformity of a CNF growth on carbon fibers, and sometimes even processibility of the whole specimen

Effects of Morphology of Cerium Oxide Catalysts for Reverse Water Gas Shift Reaction

Reverse water gas shift reaction (RWGS) was investigated over cerium oxide catalysts of distinct morphologies: cubes, rods and particles. Catalysts were characterized by X-ray diffraction, Raman spectroscopy and temperature programmed reduction (TPR) in hydrogen. Nanoshapes with high concentration of oxygen vacancies contain less surface oxygen removable in TPR. Cerium oxide cubes exhibited two times higher activity per surface area as compared to rods and particles. Catalytic activity of these nanoshapes in RWGS reaction exhibited a relation with the lattice microstrain increase, however a causal relationship remained unclear. Results presented in this study suggest that superior catalytic activity of ceria cubes in RWGS originates from the greater inherent reactivity of (100) crystal planes enclosing cubes, contrary to less inherently reactive (111) facets exposed at rods and particles