Transient modeling of combined catalytic combustion/CH4 steam reforming

This paper presents an investigation into the complex interactions between catalytic combustion and CH₄ steam reforming in a co-flow heat exchanger where the surface combustion drives the endothermic steam reforming on opposite sides of separating plates in alternating channel flows. To this end, a simplified transient model was established to assess the stability of a system combining H₂ or CH₄ combustion over a supported Pd catalyst and CH₄ steam reforming over a supported Rh catalyst. The model uses previously reported detailed surface chemistry mechanisms, and results compared favorably with experiments using a flat-plate reactor with simultaneous H₂ combustion over a γ-Al₂O₃-supported Pd catalyst and CH₄ steam reforming over a γ-Al₂O₃-supported Rh catalyst. Results indicate that stable reactor operation is achievable at relatively low inlet temperatures (400 °C) with H₂ combustion. Model results for a reactor with CH₄ combustion indicated that stable reactor operation with reforming fuel conversion to H₂ requires higher inlet temperatures. The results indicate that slow transient decay of conversion, on the order of minutes, can arise due to loss of combustion activity from high-temperature reduction of the Pd catalyst near the reactor entrance. However, model results also show that under preferred conditions, the endothermic reforming can be sustained with adequate conversion to maintain combustion catalyst temperatures within the range where activity is high. A parametric study of combustion inlet stoichiometry, temperature, and velocity reveals that higher combustion fuel/air ratios are preferred with lower inlet temperatures (≤500 °C) while lower fuel/air ratios are necessary at higher inlet temperatures (600 °C).     

Comparison among structured and packed-bed reactors for the catalytic partial oxidation of CH4 at short contact times

Three types of catalyst support (foams, honeycomb monoliths with square channels and spheres with approximately equal values of specific geometric surface a_v) were examined and compared by simulation with a 1D, dynamic heterogeneous mathematical model for application to the autothermal partial oxidation of methane. Both cold start-up and steady-state behaviours were investigated.

It was found that mass and, particularly, heat transfer properties markedly affect the reactor behaviour, both at start up and at steady state. Thus, the choice of the catalyst support can lead to greatly different reactor performances. Concerning the reactor start-up, simulations revealed that better interphase heat transport properties and lower bed heat capacity are useful to minimize the total start-up time; on the other hand, more favourable transport properties reduce the maximum flow rate which allows to achieve and maintain an ignited steady state. At steady state, oxygen conversion is strictly governed by interphase mass transfer, while methane conversion depends on a more complex, mixed chemical-diffusional regime.     

Catalytic combustion of CH4 and CO on La1−xMxMnO3 perovskites

The activities of perovskites depend on compositions and preparation methods. Various perovskites, La_1−xM_xMnO₃ (M=Ag, Sr, Ce, La), have been prepared by two different methods (co-precipitation and spray decomposition). The new preparation method, spray decomposition, produced perovskites of a high surface area of over 10 m²/g. The catalytic activities for CH₄ and CO oxidation have been studied on a series of catalysts, La_1−xM_xMnO₃. The perovskite-type oxide, La_0.7Ag_0.3MnO₃, shows the highest catalytic activity: the complete conversion of CO and CH₄ at 370 and 825 K, respectively.     

Catalytic reduction of NOx with H2/CO/CH4 over PdMOR catalysts

Conversion of NO_x with reducing agents H₂, CO and CH₄, with and without O₂, H₂O, and CO₂ were studied with catalysts based on MOR zeolite loaded with palladium and cerium. The catalysts reached high NO_x to N₂ conversion with H₂ and CO (>90% conversion and N₂ selectivity) range under lean conditions. The formation of N₂O is absent in the presence of both H₂ and CO together with oxygen in the feed, which will be the case in lean engine exhaust. PdMOR shows synergic co-operation between H₂ and CO at 450–500 K. The positive effect of cerium is significant in the case of H₂ and CH₄ reducing agent but is less obvious with H₂/CO mixture and under lean conditions. Cerium lowers the reducibility of Pd species in the zeolite micropores. The catalysts showed excellent stability at temperatures up to 673 K in a feed with 2500 ppm CH₄, 500 ppm NO, 5% O₂, 10% H₂O (0–1% H₂), N₂ balance but deactivation is noticed at higher temperatures. Combining results of the present study with those of previous studies it shows that the PdMOR-based catalysts are good catalysts for NO_x reduction with H₂, CO, hydrocarbons, alcohols and aldehydes under lean conditions at temperatures up to 673 K.     

Effect of alternate CH4-reducing/lean combustion treatments on the reactivity of fresh and S-poisoned Pd/CeO2/Al2O3 catalysts

This work investigates the effect of treatments under different CH₄-containing atmospheres on the reactivity of fresh and S-poisoned 2% w/w Pd/Al₂O₃/CeO₂ catalysts for methane combustion.

Over the fresh catalyst the decomposition/reformation processes of PdO occurring during cycles of CH₄-reducing/lean combustion pulses allowed the complete recovery of activity losses possibly associated with H₂O poisoning which were observed during prolonged exposure under lean combustion conditions. The presence of CeO₂ markedly enhances both the activity losses under lean combustion conditions and the rate of PdO reoxidation/reactivation upon Pd redox cycle.

Under lean combustion conditions, regeneration of catalyst deactivated by exposure to SO₂-containing atmosphere required very high temperatures (above 750 °C) in order to decompose stable sulphate species adsorbed on the support. Treatments consisting of alternate CH₄-reducing/lean combustion pulses allowed a complete recovery of activity at much lower temperatures (550–600 °C) due to the reduction of sulphates by CH₄ activated on the surface of Pd metal. A protecting role of CeO₂ on Pd poisoning due either to exposure to SO₂-containing atmosphere or to spill-back of support sulphates species was also evidenced.     

Al18B4O33 aluminium borate: A new efficient support for palladium in the high temperature catalytic combustion of methane

Well crystallised aluminium borate Al₁₈B₄O₃₃ has been synthesised from alumina and boric acid with a BET area of 18 m²/g after calcination at 1100 °C. Afterwards, 2 wt.% Pd/Al₁₈B₄O₃₃ was prepared by conventional impregnation of Pd(NO₃)₂ aqueous solution and calcination in air at 500 °C. The catalytic activity of Pd/Al₁₈B₄O₃₃ in the complete oxidation of methane was measured between 300 and 900 °C and compared with that of Pd/Al₂O₃. Pd/Al₁₈B₄O₃₃ exhibited a much lower activity than Pd/Al₂O₃ when treated in hydrogen at 500 °C or aged in O₂/H₂O (90:10) at 800 °C prior to catalytic testing. Surprisingly, a catalytic reaction run up to 900 °C in the reaction mixture induced a steep increase of the catalytic activity of Pd/Al₁₈B₄O₃₃ which became as active as Pd/Al₂O₃. Moreover, the decrease of the catalytic activity observed around 750 °C for Pd/Al₂O₃ and attributed to PdO decomposition into metallic Pd was significantly shifted to higher temperatures (820 °C) in the case of Pd/Al₁₈B₄O₃₃. The existence of two distinct types of PdO species formed on Al₁₈B₄O₃₃ and being, respectively, responsible for the improvement of the activity at low and high temperature was proposed on the basis of diffuse reflectance spectroscopy and temperature-programmed desorption of O₂.     

ZrO2/SiO2- and La2O3/Al2O3-supported platinum catalysts for CH4/CO2 reforming

Surface-phase ZrO₂ on SiO₂ (SZrOs) and surface-phase La₂O₃ on Al₂O₃ (SLaOs) were prepared with various loadings of ZrO₂ and La₂O₃, characterized and used as supports for preparing Pt/SZrOs and Pt/SLaOs catalysts. CH₄/CO₂ reforming over the Pt/SZrOs and Pt/SLaOs catalysts was examined and compared with Pt/Al₂O₃ and Pt/SiO₂ catalysts. CO₂ or CH₄ pulse reaction/adsorption analysis was employed to elucidate the effects of these surface-phase oxides.

The zirconia can be homogeneously dispersed on SiO₂ to form a stable surface-phase oxide. The lanthana cannot be spread well on Al₂O₃, but it forms a stable amorphous oxide with Al₂O₃. The Pt/SZrOs and Pt/SLaOs catalysts showed higher steady activity than did Pt/SiO₂ and Pt/Al₂O₃ by a factor of three to four. The Pt/SZrOs and Pt/SLaOs catalysts were also much more stable than the Pt/SiO₂ and Pt/Al₂O₃ catalysts for long stream time and for reforming temperatures above 700 °C. These findings were attributed to the activation of CO₂ adsorbed on the basic sites of SZrOs and SLaOs.     

Effect of Pd precursor salt on the activity and stability of Pd-doped hexaaluminate catalysts for the CH4 catalytic combustion

This study reports the influence of palladium salt precursor on the catalytic activity of palladium-doped hexaaluminate catalysts for the combustion of 1 vol% CH₄ in the presence of CO₂ and H₂O as inhibitors. Thermal stability of the catalysts is evaluated in long-term catalytic test at 700 °C. The hexaaluminate supports were synthesized using two different procedures: conventional coprecipitation and solid/solid diffusion procedure. Palladium impregnation was carried out by two different routes using Pd(NO₃)₂ in water or Pd(acac)₂ in toluene as impregnation solution. It was observed that using Pd(acac)₂ as precursor allows to attain higher dispersion of the active phase (Pd particles size <3 nm). Compared to the catalysts obtained by impregnation of Pd(NO₃)₂, higher catalytic activities are then obtained. Nevertheless, a deactivation of the samples obtained using Pd(acac)₂ is observed. At the end of the stability test, almost similar catalytic activity is obtained whatever the palladium precursor. Reduction–reoxidation experiment showed that this deactivation is irreversible, and TEM analysis suggest that this deactivation is related to the sintering of Pd particles under reaction over samples synthesized using Pd(acac)₂ as precursor.     

Kinetic measurements of CH4 combustion over a 10% PdO/ZrO2 catalyst using an annular flow microreactor

A kinetic study on CH₄ combustion over a PdO/ZrO₂ (10%, w/w) catalyst has been performed in a temperature range between 400 and 550 °C by means of an annular catalytic microreactor.

The role of mass transfer phenomena including diffusion in the catalyst pore, gas–solid diffusion and axial diffusion in the gas phase, has been preliminary addressed by means of mathematical modeling. Simulation results have pointed out the key role of internal diffusion showing that thicknesses of the active catalyst layer as thin as 10–15 μm are required to minimize the impact of mass transfer limitations. The thermal behavior of the reactor has been also addressed by means of catalytic combustion tests with CH₄ and CO–H₂ mixtures as fuels. The results have demonstrated the possibility to obtain nearly isothermal temperature profiles under severe conditions (up to 3% of CH₄) thanks to effective dissipation of reaction heat by radiation from the catalyst outer skin.

Finally the effect of reactants (CH₄ and O₂) and products (H₂O and CO₂) on CH₄ combustion rate has been addressed. The results have shown that both H₂O and CO₂ markedly inhibit the reaction up to 550 °C. The data have been fitted by the following simple power law expression r=k_rP_CH4P_H2O^−0.32P_CO2^−0.25 with an apparent activation energy of 108 kJ/mol.

Evidences have been found and discussed indicating a key role of the support on the extent of such inhibition effects.     

低浓度甲烷流向变换催化燃烧反应研究

将制备的整体式催化剂应用于小型流向变换催化燃烧反应系统上,在甲烷初始浓度为0.2%,气量为30 L·min-1,换向半周期为10 min的工况条件下考察了不同预热温度对甲烷催化燃烧活性的影响以及反应系统床层轴向温度分布情况。结果表明,随着预热温度升高,甲烷催化燃烧活性呈现升高的趋势,同时,在催化剂中添加助剂元素Pt可以提高催化剂催化活性;催化剂的预热温度对反应器床层温度分布影响较大,特别是反应系统的催化段。     

Importance of palladium dispersion in Pd/Al2O3 catalysts for complete oxidation of humid low-methane–air mixtures

The catalytic oxidation is considered as an environmental benign method for utilization of various methane-poor gas mixtures, including humid post-ventilation air of coal mines. The small crystallites of palladium phase in the Pd/Al₂O₃ catalyst decrease temperatures necessary to ignite the methane oxidation reaction and to achieve complete conversion of methane. The isotopic exchange of oxygen between the catalyst and the gas phase, the temperature-programmed reduction (TPR) with methane and the X-ray photoelectron spectroscopy studies suggest that it can result from a higher number of the Pd–PdO sites present on the catalysts with small palladium crystallites. The inhibiting effect of water vapour present in the reaction mixture increases with lower dispersion of palladium phase as well as with the water concentration in the feed. The larger palladium crystallites are more significantly affected by the presence of water. It is suggested that water vapour blocks the Pd–PdO active sites. The catalysts with small crystallites (<6.6 nm) of palladium can be successfully used for mitigation of the emission of methane from coal mine post-ventilation air and, after increasing of the methane concentration to 1–2 vol.%, for its utilization for the energy production. In the case of such catalysts even a high concentration of water vapour has the least negative influence on the catalyst activity and it will not interfere with obtaining of the 100% conversion of methane below 650 °C.     

The effect of water on the activity of supported palladium catalysts in the catalytic combustion of methane

Supported palladium catalysts are very active in the combustion of methane, but still little is known about the kinetic parameters. In this paper a rate expression is presented for an alumina-supported palladium oxide catalyst in the temperature range 180–515°C. Special care was taken to ensure differential conditions during the experiments. In this way, an apparent activation energy of 151±15 kJ/mol was found. The orders in methane, oxygen and water were 1.0±0.1, 0.1±0.1 and −0.8±0.2, respectively. For carbon dioxide a zero order was observed under all conditions. Inhibition by water produced during the reaction was demonstrated to cause non-differential conditions, when a dry feed was used. The rate constant that corrects for this effect could be derived.     

Regeneration of S-poisoned Pd/Al2O3 catalysts for the combustion of methane

Regeneration of S-poisoned Pd/Al₂O₃ catalysts for the abatement of methane emissions from natural gas vehicles was addressed in this work.

Investigations were devoted to determine the temperature threshold allowing for catalyst reactivation under different CH₄ containing atmospheres. Under lean combustion conditions in the presence of excess O₂, partial regeneration took place only above 750 °C after decomposition of stable sulphate species adsorbed on the support. Short CH₄-reducing, O₂-free pulses led to partial catalyst reactivation already at 550 °C and to practically complete regeneration at 600 °C. Also in this case reactivation was associated with SO₂ release due to the decomposition of stable support sulphates likely promoted by CH₄ activation onto the reduced metallic Pd surface. Rich combustion pulses with CH₄/O₂ = 2 were equally effective to CH₄-reducing pulses in catalyst regeneration.

These results suggest that a regeneration strategy based on periodical natural gas pulses fed to the catalyst by a by-pass line might be efficient in limiting the effects of S-poisoning of palladium catalysts for the abatement of CH₄ emissions from natural gas engine.     

NO removal by CH4 on Co-NaX-CO and Ag-NaX catalysts in a dual-bed system

NO removal using CH₄ as a reductant in a dual-bed system has been investigated with Co-NaX and Ag-NaX catalysts, which were prepared by Co²⁺-, Ag⁺-ion exchange into zeolite NaX, respectively, and activation for 5 h at 500 °C. The experimental result has been compared with that of a Co-NaX-CO catalyst, additionally pre-treated under CO flow for the Co-NaX catalyst. The cobalt crystal structure of a Co-NaX-CO catalyst is Co₃O₄, which promotes NO oxidation to NO₂ by excess O₂ at a low temperature (523 K). The mechanical mixture of Co-NaX-CO and Ag-NaX catalysts shows a synergy effect on NO reduction to N₂ by CH₄ in the presence of excess O₂ and H₂O, but the NO reduction decreases quickly as time passes. However, the NO reduction to N₂ in a deNO bed at 523 K and a deNO₂ bed at 423 K, which are relatively lower than the reaction temperatures for common SCR systems, still remained at 67% even in a H₂O 10% gas mixture after 160 min.     

Structured reactors for kinetic measurements under severe conditions in catalytic combustion over palladium supported systems

The collection of chemical kinetics data in catalytic combustion over very active palladium catalysts under conditions relevant to practical applications (e.g. gas turbine combustors) is extremely difficult, mainly due to strong exothermicity and very fast rate of combustion reactions. Within this purpose in this paper two types of laboratory structured reactors, which closely resemble industrial monolith catalysts, are investigated: (a) the annular reactor, consisting of a catalyst coated ceramic tube, co-axially placed in a quartz tube; (b) the metallic plate-type reactor, consisting of an assembled packet of metallic slabs coated with a ceramic catalytic layer.

The design of the annular reactor configurations for kinetic investigations is first addressed by mathematical modeling. The resulting advantages, including: (i) negligible pressure drops; (ii) minimal impact of diffusional limitations in high temperature–high GHSV experiments; (iii) effective dissipation of reaction heat are then experimentally demonstrated for the case of CH₄ combustion over a PdO/γ-Al₂O₃ catalyst with high noble metal loading (10% (w/w) of Pd).

The feasibility of a near-isothermal operation with the metallic plate-type reactor by an extremely effective dissipation of reaction heat through proper selection of highly conductive support material and of the geometry of the metallic slabs is finally discussed and experimentally demonstrated for the case of combustion of CO at high concentrations over a PdO/γ-Al₂O₃ (3% (w/w) of Pd) catalyst.     

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.     

Deactivation of palladium catalyst in catalytic combustion of methane

Catalytic combustion of natural gas, for applications such as gas turbines, can reduce NO_x emissions. Palladium-on-stabilised alumina has been found to be the most efficient catalyst for the complete oxidation of methane to carbon dioxide and water. However, its poor durability is considered to be an obstruction for the development of catalytic combustion. This work was aimed at identifying the origin of this deactivation: metal sintering, support sintering, transformation or coking.

Catalytic combustion of methane was studied in a 15 mm i.d. and 50 mm length lab reactor and in a 25 mm i.d. pilot test rig on monolithic honeycomb substrates. Experiments were performed at GHSV of 50 000 h⁻¹ in lab test and 500 000 h⁻¹ in pilot test. The catalysts used were palladium on different supports on cordierite substrate. The catalysts were characterised by XRD, STEM, ATG and XPS.

In steady-state conditions, deactivation has been found to be dependent on the air/methane ratio, the palladium content on the washcoat and the amount of washcoat on the substrate. An oscillating behaviour of the methane conversion was even observed under specific conditions, due to the reducibility of palladium oxide PdO to Pd. The influence of the nature of the support on the catalyst deactivation was also investigated. It has been shown that some supports can surprisingly eliminate this oscillating behaviour. However, in pilot test, deactivation was found to be very rapid, even with stabilised alumina supports. Furthermore, successive tests performed on the same catalyst revealed that the activity (light-off temperature, conversion) falls strongly from one test to another.

Then, the stabilised alumina support was calcined at 1230°C for 16 h prior to its impregnation by palladium, in order to rule out its sintering. Experiments carried out on precalcined catalysts point out that deactivation is mostly correlated to the metal transformation under reaction conditions: activity decreases gradually as PdO sinters, but it dropped much more steeply in relation to appearance of metallic palladium.     

CH4-SCR of NO over Co and Pd ferrierite catalysts: Effect of preparation on catalytic performance

Selective catalytic reduction of NO with methane (CH₄-SCR) in the presence of oxygen excess and water vapour was studied over two bimetallic cobalt/palladium-based FER catalysts, which differ on the order of introduction of metal ions. H₂-TPR and UV–vis analysis showed that the simple change in the order of addition of metals to catalyst, gives rise to totally diverse species (Co²⁺ ions, Co oxides, Co-oxo cations and Pd species) both in type and quantity but also in location within zeolite framework. Experiments of TPD and TPSR of NO and NO₂ provided important information to establish a relation between the various active sites formed on both catalysts and their function in the reaction mechanism. The importance of NO₂ in the mechanism of NO reaction with CH₄ and O₂ was explored and the catalyst with a higher capacity to retain adsorbed NO₂ is the less active for deNO_x. The preparation of a bimetallic catalyst active for NO reduction must provide the proximity between Co and Pd species, and the presence of Co-oxo cations together with palladium species seem to be essential. Furthermore, a suitable amount of cobalt oxides must exist in order to originate NO₂ that is the main reaction intermediate. Nevertheless, an excessive amount of these Co species can lead to an increase of adsorbed NO₂, which reduces the rate of the reaction of some of the mechanism steps.     

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.     

Chlorobenzene total oxidation over palladium supported on ZrO2, TiO2 nanostructured supports

Two series of supported Pd catalysts were synthesized on new mesoporous–macroporous supports (ZrO₂, TiO₂) labelled M (Zr and Ti). The deposition of palladium was carried out by wet impregnation on the calcined TiO₂ and ZrO₂ supports at 400 °C (Pd/Zr₄, Pd/Ti₄) and 600 °C (Pd/Zr₆, Pd/Ti₆) and followed by a calcination at 400 °C for 4 h. The pre-reduced Pd/MX catalysts were investigated for the chlorobenzene total oxidation and their catalytic properties where compared to those of a reference catalyst Pd/Ti-Ref (TiO₂ from Huntsman Tioxide recalcined at 500 °C) and of a palladium supported on the fresh mesoporous–macroporous TiO₂ (Pd/Ti). Based on the activity determined by T₅₀, the Pd/Ti and Pd/Ti₄ catalysts have been found to be more active than the reference one. Moreover activity decreased owing to the sequence: Pd/TiX  Pd/ZrX and in each series when the temperature of calcination of the support was raised. The overall results clearly showed that the activity was dependant on the nature of the support. The better activity of Pd/TiX compared to Pd/ZrX was likely due to a better reducibility of the TiO₂ support (Ti⁴⁺ into Ti³⁺) leading to an enhancement of the oxygen mobility. Production of polychlorinated benzenes PhCl_x (x = 2–6) and of Cl₂ was also observed. Nevertheless at 500 °C the selectivity in HCl was higher than 90% for the best catalysts.