Catalytic combustion of methane over bimetallic Pd–Pt catalysts: The influence of support materials

The effect of support material on the catalytic performance for methane combustion has been studied for bimetallic palladium–platinum catalysts and compared with a monometallic palladium catalyst on alumina. The catalytic activities of the various catalysts were measured in a tubular reactor, in which both the activity and stability of methane conversion were monitored. In addition, all catalysts were analysed by temperature-programmed oxidation and in situ XRD operating at high temperatures in order to study the oxidation/reduction properties.

The activity of the monometallic palladium catalyst decreases under steady-state conditions, even at a temperature as low as 470 °C. In situ XRD results showed that no decomposition of bulk PdO into metallic palladium occurred at temperatures below 800 °C. Hence, the reason for the drop in activity is probably not connected to the bulk PdO decomposition.

All Pd–Pt catalysts, independently of the support, have considerably more stable methane conversion than the monometallic palladium catalyst. However, dissimilarities in activity and ability to reoxidise PdO were observed for the various support materials. Pd–Pt supported on Al₂O₃ was the most active catalyst in the low-temperature region, Pd–Pt supported on ceria-stabilised ZrO₂ was the most active between 620 and 800 °C, whereas Pd–Pt supported on LaMnAl₁₁O₁₉ was superior for temperatures above 800 °C. The ability to reoxidise metallic Pd into PdO was observed to vary between the supports. The alumina sample showed a very slow reoxidation, whereas ceria-stabilised ZrO₂ was clearly faster.     

Microemulsions in the preparation of highly active combustion catalysts

Catalytic activity in combustion of toluene in toluene–air mixtures and physical–chemical properties of platinum catalysts prepared from reverse microemulsions (water-in-oil) and by classical impregnation from water solutions of H₂PtCl₆ were studied. Microemulsion catalysts were more active than those prepared classically from water solutions. Size of Pt in classically impregnated catalysts was three times higher than that of catalysts prepared from microemulsions. In case of microemulsion preparation method, platinum is located near the pellet surface or its position in the pellet can be optimised. The effect of oil used in microemulsion system seems to be negligible for the activity of the catalysts with 0.1 wt.% Pt.     

Catalytic Combustion of the Stoichiometric n-Butane/Air Mixture on Isothermally Heated Platinum Wire

The catalytic combustion of the stoichiometric n-butane–air mixture per se or diluted with N₂, on a platinum wire at different initial pressures (10–70 kPa) and temperatures (690–1,080 K) was studied. The chemical heat flow rate, dQ _r/dt, of the surface reaction was measured in isothermal and isobaric conditions and the overall kinetic parameters were evaluated for both steady state and initial transient catalytic combustion. At low total pressure (10 kPa), the temperature dependence of dQ _r/dt indicated a normal (Arrhenius) behavior for 690 < T < 900 K, while at higher temperatures, over 900 K, an anti-Arrhenius behavior was found. The obtained results are consistent with a diffusion-controlled process, accompanied by reactant depletion around the catalytic surface, at higher temperatures.     

Kinetics of methane combustion over Pt and Pt–Pd catalysts

A kinetic study was performed over thermally aged and steam-aged Pt and Pt–Pd catalysts to investigate the effect of temperature, and methane and water concentrations on the performance of catalysts in the range of interest for environmental applications. It was found that both catalysts permanently lose a large portion of their initial activity as result of exposure to 5 vol.% water in the reactor feed. Empirical power-law and LHHW type of rate equations were proposed for methane combustion over Pt and Pt–Pd catalysts respectively. Optimization was used to determine the parameters of the proposed rate equations using the experimental results. The overall reaction orders of one and zero in methane and water concentration was found for stabilized steam-aged Pt catalyst in the presence and absence of water. The apparent self-inhibition effect caused by methane over Pt–Pd catalyst in the absence of water was associated with the inhibiting effect of water produced during the combustion of methane. A significant reversible inhibition effect was also observed over steam-aged Pt–Pd catalyst when 5 vol.% water vapor was added to the reactor feed stream. A significant reduction in both activity and activation energy was observed above temperatures of approximately 550 °C for steam-aged Pt–Pd catalyst in the presence of water (the activation energy dropped from a value of 72.6 kJ/mol to 35.7 kJ/mol when temperature exceeded 550 °C).     

Pt-Al2O3 Cryogel with High Thermal Stability for Catalytic Combustion

The cryogel catalyst of platinum on alumina was prepared from aluminum sec-butoxide and H₂PtCl₆ through the sol-gel technique and subsequent freeze drying. The cryogel catalyst showed higher thermal stability of platinum than the corresponding xerogel or impregnation catalysts, which was ascribed to the more intimately developed platinum-alumina interaction accompanied by the encapsulation of the metal into the alumina cryogel. It was also shown that platinum accessibility was higher on the cryogel than on the xerogel despite the higher thermal stability of the metal on the formed than on the latter. For the VOC combustion, the cryogel exhibited higher activity than the xerogel and impregnation catalysts. Also for the methane combustion the cryogel showed higher activity, although it showed lower activity than the impregnation catalysts above 600 °C. By the addition of ceria as an additive to the cryogel catalyst, the CH₄ combustion activity was improved especially in the temperature region above 600 °C.     

The catalytic heat exchanger using catalytic fin tubes

The characteristics of a catalytic heat exchanger which integrates heat generation and heat exchange into one equipment have been investigated by the experiment and numerical simulation. The surface of the fin tubes was catalyzed by the formation of the oxide layer and the subsequent washcoating of ZrO₂, followed by the impregnation of Pd catalyst. The experimental results showed that the performance of catalytic combustion in the catalytic heat exchanger was more significantly affected by the inlet velocity of the mixture than by its inlet temperature and equivalence ratio. It was also found that the catalytic surface area was a critical parameter to obtain the complete conversion of the mixture. Numerical simulation has been performed with a commercial software FLUENT. The calculated results indicated that the performance of the catalytic combustion was influenced by the catalytic fin configuration as well as the flow pattern of the mixture over the catalytic fins. The results recommend that the number and thickness of catalytic fins should be designed above 6 pieces/inch and less than to achieve the best performance in the catalytic heat exchanger.     

Modelling catalytic combustion in monolith reactors – challenges faced

When searching for a design concept in which a catalytic combustor is utilised, or looking for areas where improvements can be made to an existing design, then mathematical modelling is an important tool. However, models are only as good as the way in which the physico-chemical processes are modelled and the quality of the physical and chemical parameters (e.g. kinetic expressions, physical properties) acquired for use in the models. When selecting a basis for a model, there are many questions that need to be asked and answered by the developer of the chemical reaction engineering model of the catalytic combustor. Many challenges arise from having to make decisions on compromises that need to be made, and in recognising the consequences of such action. Examples of such challenges are outlined and, for some, clues are offered as to where the answers may lie. The examples include challenges in: the selection of appropriate kinetic expressions, recognition of the role that intraphase diffusion may play, the choice of pressure for catalytic kinetic and pilot scale studies, the selection of heat and mass transfer correlations, and the modelling of transients.     

Catalytic destruction of chlorinated POPs—Catalytic oxidation of chlorobenzene over PtHFAU catalysts

Catalytic oxidation of monochlorobenzene (667 ppm) in wet air was investigated over PtHFAU(5) catalysts, differing by their Pt content (from 0 to 1.1 wt.%), their Pt dispersion (for identical Pt content) and the electronic state of Pt. PtHFAU(5) catalysts show a higher activity compared to more conventional PtAl₂O₃ and PtSiO₂ samples.

For a given temperature, chlorobenzene oxidation over PtHFAU(5) is independent of the platinum particles size. On the other hand, a plateau in activity is reached from 0.4 to 0.6% Pt.

Amount of polychlorinated benzenes (PhCl₂₊) were produced in the order PtAl₂O₃ > PtSiO₂ > PtHFAU(5). The formation of these compounds, especially PhCl₂, over PtHFAU(5) was function on the Pt content (PhCl₂ isomers appear only from 0.6% PtHFAU), and of the electronic state of Pt. Thus PhCl₂, were mainly found over reduced Pt⁰ particles certainly through a chlorination of platinum (formation of PtCl_x species). A reaction scheme for the PhCl₂ formation was proposed.     

Synthesis and physicochemical characterizations of nanostructured Pd/carbon-clinoptilolite-CeO2 catalyst for abatement of xylene from waste gas streams at low temperature

Xylene removal from waste gas streams was carried out via catalytic oxidation over Pd/carbon-clinoptilolite-CeO₂. The synthesized samples were characterized by XRD, FESEM, BET, FTIR and TG techniques. The XRD patterns confirmed the formation of nano ceria with an average crystallite size of 11.6 nm. FESEM results indicated a good morphology for prepared carbon with deep pores, confirmed structure modification of zeolite, and showed that nanocatalyst has nanometric particles with an average size of 60.85 nm. Reaction data illustrated 98% abatement of xylene at 250 °C. The stability test of catalyst demonstrated that the removal efficiency has remained constant for 1200 min.     

Increased combustion rate of chlorobenzene on Pt/γ-Al2O3 in binary mixtures with hydrocarbons and with carbon monoxide

The catalytic combustion of chlorobenzene on a 2 wt.% Pt/γ-Al₂O₃ catalyst in binary mixtures with various hydrocarbons (toluene, benzene, cyclohexane, cyclohexene, 1,4-cyclohexadiene, 2-butene, and ethene) and with carbon monoxide has been explored. For all binary mixtures used the (excess of) added hydrocarbon increased the rate of conversion of chlorobenzene. With 2-butene, T_50% and T_100% for chlorobenzene were reduced by 100 and 200°C, respectively. Toluene and ethene were almost equally efficient as 2-butene. Co-feeding benzene or carbon monoxide resulted in a much smaller decrease of the T_50%. The additional heat and water production in hydrocarbon combustion may contribute to some extent to the observed rate acceleration, but removal of Cl from the surface due to the hydrocarbon appears to be the major factor.

The co-feeding of hydrocarbons invariably reduced the output of polychlorinated benzenes, which are formed as byproducts in the combustion of chlorobenzene on Pt/γ-Al₂O₃. Again, especially toluene, ethene, and 2-butene were very efficient. Benzene — as well as cyclohexane, cyclohexene, and 1,4-cyclohexadiene, which were converted in situ into benzene — was much less effective, due to chlorination of the aromatic nucleus. In chlorobenzene–CO mixtures the levels of polychlorinated benzenes were almost as high as with chlorobenzene per se. Removal of Cl from the surface (mainly in the form of HCl) by (non-aromatic) hydrocarbons is responsible for reducing the formation of byproducts.     

Use of seydişehir alumina as a support for CO oxidation catalysts

An Al 2 O 3 sample obtained from Seydi y ehir Eti Alüminyum A. z was treated and characterized for its potential use as a catalyst support. Atomic absorption spectroscopy and flame photometry characterization revealed the presence of 95.52% Al 2 O 3 , 4.44% Na 2 O, and 0.043% Fe 2 O 3 in the original sample. Both n -Al 2 O 3 and f -Al 2 O 3 phases were identified in the crystalline structure by X-ray diffraction analysis. However, f -Al 2 O 3 was found to be the phase in abundance. The BET surface area of the original sample was found to be 40.85 m 2 /g. The original sample was treated in various concentrations of hydrochloric acid to remove Na 2 O impurity. The acid concentration was optimized for the Na 2 O removal efficiency and surface area enhancement. The optimum HCl concentration was found to be 1 M. 1 Pt/Al 2 O 3 catalysts prepared from these supports and a reference support (Johnson Matthey n -Al 2 O 3 ) were tested for CO oxidation reactions. Catalysts prepared fromSeydis¸ehir alumina showed reasonable activity for the CO oxidation reaction.     

Kinetics of methane combustion over CVD-made cobalt oxide catalysts

The present investigation provides the required kinetic parameters to evaluate and to predict the rate of the catalytic combustion of methane over cobalt oxide. For this purpose, monolithic cordierites with low specific surface area were uniformly coated with cobalt oxide thin films of controlled thickness using the chemical vapor deposition (CVD) process. The obtained catalysts were tested in the catalytic combustion of methane in oxygen-deficient and -rich conditions. Catalysts with loadings above 0.46 wt.% are active starting at a temperature of 250 °C and completely convert methane to CO₂ below 550 °C where the conversion rate reaches 35 μmol (CH₄)/g_cat s. The involvement of the bulk-oxide-ions in the catalytic reaction was supported by the constant value of the normalized reaction rate to the weight of deposited cobalt oxide. The experimental data fit well to the Mars–Van Krevelen redox model and can be approximated with a power rate law in oxygen-rich mixtures. The resulting activation energies and frequency factors allow the identification of the rate-limiting step and accurately reproduce the effect of the temperature and partial pressure of the reactants on the specific reaction rate.     

Combustion of CH4 over a PdO/ZrO2 catalyst: an example of kinetic study under severe conditions

A kinetic study on CH₄ combustion over a very active PdO/ZrO₂ catalyst with high Pd loading (10% w/w of Pd) is presented as an example of a demanding problem which requires both the development of appropriate experimental tools and a theoretical insight on surface chemistry.

The use of an annular catalytic reactor as a tool to collect kinetic data under unusually severe conditions (high temperature and CH₄ concentration) is described in comparison with the use of a conventional packed bed reactor. In particular, problems related to the biasing effects of mass, heat and momentum transfer are addressed.

Kinetic data addressing the effects of CH₄, O₂, H₂O and CO₂ concentration in a temperature range from 400 to 550 °C are analysed by means of a purely empirical power law model and of a formal kinetic model based on literature indication assuming methane dissociative adsorption as the rate controlling step.     

Effectiveness in catalytic washcoats with multi-step mechanisms for catalytic combustion of hydrogen

The effect of intra-phase diffusion for channel-flow oxidation reactors with washcoats ranging in thickness from 10 to is explored in combination with a detailed surface chemistry for low-temperature H₂ oxidation over supported Pd/PdO_x catalysts. A numerical model of a porous catalyst washcoat is developed to assess how local conditions influence catalyst effectiveness when considering a detailed multi-step surface mechanism, and this washcoat model is integrated into a channel flow reactor model to assess if and when effectiveness correlations may apply for channel flow reactors. The Pd-H₂-O₂ surface chemistry mechanism, which is validated against experimental measurements in an annular flow reactor, implements thermodynamically consistent interaction potentials of surface species and predicts non-linear behavior of conversion with respect to H₂ concentrations at the low equivalence ratios of the current study, particularly at lower temperatures where surface chemistry dominates overall reaction rates. The catalytic washcoat model further indicates that conversion and similarly catalyst effectiveness are strongly dependent upon the site fractions of vacancies available for H₂ adsorption, which vary strongly with flow conditions and at higher conversions with depth in the porous washcoat. This leads to difficulty in developing simple models for catalyst washcoat effectiveness based upon any parameter such as a Thiele modulus. Furthermore the results suggest that care should be taken in interpreting kinetic data for oxidation reactions even when relatively thin washcoats are employed for reaction rate studies.     

Stability of palladium-based catalysts during catalytic combustion of methane: The influence of water

The stability of methane conversion was studied over a Pd/Al₂O₃ catalyst and bimetallic Pd–Pt/Al₂O₃ catalysts. The activity of methane combustion over Pd/Al₂O₃ gradually decreased with time, whereas the methane conversion over bimetallic Pd–Pt catalysts was significantly more stable. The differences in combustion behavior were further investigated by activity tests where additional water vapor was periodically added to the feed stream. From these tests it was concluded that water speeds up the degradation process of the Pd/Al₂O₃ catalyst, whereas the catalyst containing Pt was not affected to the same extent. DRIFTS studies in a mixture of oxygen and methane revealed that both catalysts produce surface hydroxyls during combustion, although the steady state concentration on the pure Pd catalyst is higher for a fixed temperature and water partial pressure. The structure of the bimetallic catalyst grains with a PdO domain and a Pd–Pt alloy domain may be the reason for the higher stability, as the PdO domain appears to be more affected by the water generated in the combustion reaction than the alloy. Not all fuels that produce water during combustion will have stability issues. It appears that less strong binding in the fuel molecule will compensate for the degradation.