Catalytic combustion of toluene on Cu-Mn/MCM-41 catalysts: Influence of calcination temperature and operating conditions on the catalytic activity

Catalytic combustion of toluene on Cu-Mn/MCM-41 catalyst was performed in tubular flow reactor operated at atmospheric pressure. The effect of catalyst pre-treatment temperatures on the catalytic activity and stability was investigated. Some reaction variables, such as inlet concentration of toluene and oxygen, reaction temperatures and space velocities were varied over wide ranges, and the influence of different reaction conditions on toluene conversion was discussed. It is showed that the catalytic activity was significantly affected by calcination temperatures between 300 and 800 °C, and oxygen concentration, toluene concentration and space velocity are all key experimental factors to optimize the toluene combustion activities. The objective of this study was to investigate catalytic properties of Cu-Mn/MCM-41 catalysts prepared at different calcination temperatures, in order to obtain additional information to prepare an efficient and highly active catalyst at low temperature.     

Oxygen vacancy engineering on copper-manganese spinel surface for enhancing toluene catalytic combustion: A comparative study of acid treatment and alkali treatment

Copper-manganese spinel is a low-cost VOCs catalytic combustion catalyst with good performance. Oxygen vacancy has excellent properties for oxygen activation and VOCs dehydrogenation activation, which is beneficial for the catalytic combustion of VOCs. In this study, a large number of oxygen vacancies were introduced on the copper-manganese spinel surface by selective dissolution method (acid treatment and alkali treatment) for catalytic combustion of toluene. Furthermore, the effects of acid treatment and alkali treatment on the catalytic performance, oxygen vacancy amount, physical and chemical properties, and toluene catalytic combustion mechanism of copper-manganese spinel were studied. Both acid treatment and alkali treatment can produce large quantities of oxygen vacancies on the copper-manganese spinel surface. The generation of surface oxygen vacancies can greatly improve the catalytic combustion activity of copper-manganese spinel. At 240 °C, the combustion rate of toluene increased by 8.8 times for the acid-treated catalyst and 11.2 times for the alkali-treated catalyst. The numerous surface oxygen vacancies, Mn³⁺/Mn⁴⁺ at the ratio of 1.11 and appropriate acidity result in the alkali-treated catalyst exhibiting excellent catalytic activity and stability for toluene combustion. This strategy provides a new method to further improve catalytic combustion activity of copper-manganese spinel and a reference for the development of the surface oxygen vacancy engineering of transition metal oxides.     

Effect of coke formation on catalytic activity tests for catalytic combustion of toluene: the difficulty of measuring TOF and T98 accurately

Catalytic combustion is considered as one of the most efficient routes for removing volatile organic compounds. In recent years, the catalytic activities of catalysts have usually been evaluated by the values of TOF and T₉₈. It is difficult, however, to measure the values accurately because the influencing factors are numerous and easy to be overlooked. In this work, the influence of the catalytic test procedure on TOF and T₉₈ values was investigated. Supported Pd or Pt catalysts were prepared via the incipient wetness impregnation method. The catalytic activities of the same catalyst were very different when evaluated in different catalytic test procedures. Indeed, the catalytic test procedures affected the TOF and T₉₈ values remarkably. It was found that the different coking behavior in different catalytic test procedures is the major cause. The influences on coke formation in toluene combustion – such as reaction temperature, reaction time, and catalyst type – were investigated.     

Catalytic combustion of methane over palladium exchanged zeolites

Palladium cation exchanged zeolites (ZSM-5, mordenite and ferrierite) were studied as catalysts for methane combustion. Pd-zeolites showed much higher activities than PdO/Al₂O₃. For comparable palladium loadings, PdO/Al₂O₃ requires a reaction temperature of ca. 70–80°C higher than Pd-ZSM-5 for conversions between 50–100%. The catalytic activity of Pd-ZSM-5 seems to be related to its reducibility. Temperature-programmed reduction experiments with carbon monoxide showed a lower reduction temperature (ca. 157°C) for Pd-ZSM-5 than for PdO/Al₂O₃ (225°C). Further, the positioning of the palladium by ion exchange offers a highly dispersed form of Pd^II supported on the high surface area zeolite.     

Fabrication of titanosilicate pillared MFI zeolites with tailored catalytic activity

Titanosilicate pillared MFI zeolite nanosheets were successfully synthesized by infiltrating the mixed tetraethyl orthosilicate (TEOS)/tetrabutyl orthotitanate (TBOT) solvent into the gallery space between adjacent MFI zeolite layers. The obtained zeolite catalysts were characterized using powder X-ray diffraction, N₂ adsorption/desorption isotherms, scanning electron microscopy, transmission electron microscopy, ultraviolet–visible spectroscopy, X-ray photoelectron spectroscopy, and Fourier-transform infrared spectroscopy techniques. The H₂O₂ oxidation of dibenzothiophene (DBT) was used to evaluate the catalytic performance of the obtained titanosilicate pillared MFI zeolites. The conversion of DBT and selectivity of dibenzothiophene sulfone (DBTS) were most affected by the textural properties of the zeolites. This was attributed to the DBT and DBTS molecules being larger than micropores of the MFI zeolites. The conversion of DBT and yield of DBTS could be systematically tailored by tuning the molar ratio of the TEOS/TBOT solvent. These results implied that a balance between the meso- and microporosity of zeolites and tetrahedrally coordinated Ti(IV) active sites of titanosilicate pillars can be achieved for the preparation of desired catalysts during the oxidation of bulk S compounds.     

Catalytic combustion of toluene on platinum-containing monolithic carbon aerogels

Monolithic organic aerogels were prepared by the sol–gel procedure from the polymerisation reaction of resorcinol and formaldehyde in water. The organic aerogels were heat treated in inert atmosphere at either 500 or 1000 °C to obtain the carbon aerogels. The catalysts were prepared by impregnation with an aqueous solution of [Pt(NH₃)₄]Cl₂ or by dissolving this salt in the initial aerogel mixture. Supported catalysts were pretreated in He at 400 °C or H₂ at 300 °C before their characterization by H₂ chemisorption, high-resolution transmission electron microscopy and X-ray photoelectron spectroscopy or before testing their catalytic activity. Catalyst activities in toluene combustion were evaluated by conversion versus temperature (light-off curves) and conversion versus time catalytic tests. In the case of catalysts prepared by impregnation, the light-off curves for the total combustion of toluene were shifted to lower temperatures with increasing Pt particle size. This suggests that the reaction was sensitive to the Pt structure within the dispersion range of these catalysts. However, the reverse occurred with catalysts prepared by mixing the precursor in the initial aerogel mixture. Results found could be due to the different surface Pt content of these catalysts as revealed by X-ray photoelectron spectroscopy. This difference was related to the growth of large three-dimensional Pt particles on the surface of the less dispersed catalyst. This means that there is a critical Pt particle size above which the toluene combustion activity decreases with increasing Pt particle size, due to the reduction in active surface sites available for the combustion reaction. Other effect that might influence the activity of these last catalysts is the encapsulation of some Pt particles by the carbon matrix.     

Zeolite-catalyzed chlorination of toluene by sulfuryl chloride: activity, selectivity and deactivation of NaX and NaY zeolites

Chlorination of toluene with sulfuryl chloride was studied using NaX and NaY zeolites as catalysts under conditions where ring chlorination predominates. The zeolites are more selective than conventional Lewis acid catalysts with initial para-chlorotoluene : ortho-chlorotoluene ratios of 1.2. Both faujasites studied underwent rapid deactivation under reaction conditions. The deactivation of NaX was much more rapid than that of NaY. The accumulation of polychlorinated toluenes in the pores of the catalyst may be initially responsible for the loss of activity. In the case of NaY, this lost activity can be partially recovered by soaking the catalyst in fresh toluene, whereas attempts to regenerate by burning out the deposited materials cause a rapid disintegration of the catalyst. Zeolite fouling is accompanied by a more severe dealumination process that eventually leads to structural collapse and complete loss of activity.     

Catalytic combustion of toluene over Mn, Fe and Co-exchanged clinoptilolite support

Catalytic combustion of toluene over Fe, Co, and Mn transition metal oxides catalysts supported on clinoptilolite (CLT) has been investigated. The catalysts have been characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature-programmed reduction and oxidation (TPR/TPO) and thermogravimetric analysis (TGA). 9.5MnO₂/NaCLT catalyst exhibited the catalytic activity, over which the toluene conversion reached to 93% at a temperature of 350 °C. The increase in activity was followed by increasing metal oxide content and gave a optimum at 9.5% MnO₂ loading. Addition of metal oxide into clinoptilolite support led to a measurable decrease in the onset of combustion and an increase in toluene conversion.     

Catalytic combustion assisted methane steam reforming in a catalytic plate reactor

A theoretical study of methane steam reforming coupled with methane catalytic combustion in a catalytic plate reactor (CPR) based on a two-dimensional model is presented. Plates with coated catalyst layers of order of micrometers at distances of order of millimetres offer a high degree of compactness and minimise heat and mass transport resistances. Choosing similar operating conditions in terms of inlet composition and temperature as in industrial reformer allows a direct comparison of CPRs with the latter. It is shown that short distance between heat source and heat sink increases the efficiency of heat exchange. Transverse temperature gradients do not exceed across the wall and across the gas-phase, in contrast to difference in temperature of outside wall and mean gas phase temperature inside the tube usually observed in conventional reformers. The effectiveness factors for the reforming chemical reactions are about one order of magnitude higher than in conventional processes. Minimisation of heat and mass transfer resistances results in reduction of reactor volume and catalyst weight by two orders of magnitude as compared to industrial reformer. Alteration of distance between plates in the range 1- does not result in significant difference in reactor performance, if made at constant inlet flowrates. However, if such modifications are made at constant inlet velocities, conversion and temperature profiles are considerably affected. Similar effects are observed when catalyst layer thicknesses are increased.     

Experimental and modelling studies of the catalytic combustion of methane

Ceramic honeycomb monoliths with a noble metal-alumina based washcoat were used as burners for the combustion of very lean methane-air mixtures below the conventional lower flammability limit without the emission of CO, NO_x, or unburned fuel gas. Measurements and modelling in the steady state proved that the near zero emissions could have been equally due to gas phase combustion than to catalytic combustion for the long monoliths. However, only catalytic oxidation reactions could account for the complete and clean combustion observed for the shortest burners, indicating that even in the longest monoliths, the combustion had been catalytic. Thus the onset of gas phase combustion was inhibited by catalytic combustion. This phenomenon was investigated using numerical modelling and experimental studies on a catalytic stagnation point flow reactor, with a polycrystalline Pt foil as the catalyst. These studies showed the extent of the phenomenon of inhibition of gas phase ignition and how catalytic combustion is an extremely stable and clean process.     

Changes of copper location in CuY zeolites induced by preparation methods

The location of transition ions in copper- and copper-zinc-loaded Y type zeolites prepared by different procedures has been studied by temperature-programmed reduction, infrared spectroscopy of CO adsorbed on pretreated samples and X-ray photoelectron spectroscopy. Samples outgassed at 673 K showed Cu⁺ species due likely to reduction of Cu²⁺ ions under vacuum. Over exchanged CuY zeolites copper species in exchange sites were detected, while an impregnated sample exhibited bands of CO adsorbed on both Cu²⁺ and Cu⁺ ions developed at the surface of CuO crystals, and small proportions of Cu⁺ ions located in accessible exchange sites S_II and Sn_II. Similar findings were observed in Zn- and Cu-exchanged zeolites although the relative proportion of Cu in S_I positions was decreased due to competition between Cu²⁺ and Zn²⁺ ions. Samples reduced in hydrogen at 523 K showed the appearance of Cu⁰ species in impregnated samples, whereas Cu⁺ dominated in the exchanged counterparts. Reduction at 598 K led to substantial changes in Cu-exchanged samples in water. The proportion of Cu⁺ species decreased by reduction to Cu⁰ and simultaneously migration to Cu⁺ to S_II sites occurred. While Cu²⁺ or Cu⁺ were found on outgassed samples, only Cu⁰ and intrazeolite Cu⁺ were observed after H₂-reduction at 623 K. Changes in copper exposure as a function of sample pretreatments were also revealed by X-ray photoelectron spectroscopy.     

Electrochemical promotion of toluene combustion on an inexpensive metallic catalyst

Electrochemical promotion of the complete catalytic oxidation of toluene at 310 °C is reported, using a Ag/YSZ/Ag two electrode system where Ag films were deposited on YSZ from AgNO₃ aqueous solution followed by reduction in H₂. After on-stream activation, a non-negligible conversion (about 30%) at OCV is reached and then the rate of the catalytic toluene conversion into CO₂ and H₂O can be multiplied by a factor higher than 1.5, by application of a small negative current (about—4 μA cm⁻²). The associated Faradaic efficiency is very high and may exceed −13,000.     

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.     

Flow reversal reactor for the catalytic combustion of lean methane mixtures

This paper describes an experimental investigation of a pilot scale reverse flow reactor for the catalytic destruction of lean mixtures of methane in air. It was found that using reverse flow it was possible maintain elevated reactor temperatures which were capable of achieving high methane conversion of methane in air streams at methane concentrations as low as 0.19% by volume. The space velocity, cycle time and feed concentration are all important parameters that govern the operation of the reactor. Control of these parameters is important to prevent the trapping of the thermal energy within the catalyst bed, which can limit the amount of energy that can be usefully extracted from the reactor.     

Stationary and traveling hot spots in the catalytic combustion of hydrogen in monoliths

In the course of catalytic combustion of hydrogen (1-5% H₂ in air) in monolith reactors, strongly localized stationary and traveling hot spots arise in response to a sudden and persistent rise of gas flow velocity. Such hot spots may occur, e.g. in a catalytic converter following the acceleration of a car or in a catalytic combustor as a result of a load increase. This phenomenon is illustrated by simulations using a two-phase reactor model. The temperature overshoot of the adiabatic limit is typically of the order of the adiabatic temperature rise itself.The following mechanism underlies this behavior. Light fuel is supplied to the catalytic wall by fast diffusion (in the direction perpendicular to flow), while the heat released by reaction is removed from the wall by the slower, mixture-averaged heat conduction. This leads to accumulation of heat at the catalytic surface that eventually saturates at high temperatures. The hot spots may exhibit intricate dynamics, propagating downstream or upstream, or they may remain stationary. The direction of propagation depends on the relative strength of convective downstream and conductive upstream contributions to the overall displacement of reaction fronts. Generally, the hot spot tends to drift downstream at low flow velocities, remain stationary at intermediate flow velocities, and drift upstream at high flow velocities.     

Effect of microwave absorption properties and morphology of manganese dioxide on catalytic oxidation of toluene under microwave irradiation

A large number of studies had shown that the morphology of the sample had a significant effect on the microwave absorption properties and catalytic activity of the sample. Manganese dioxide with different morphologies was synthesized by hydrothermal method through different precursors. The effects of sample morphology and microwave absorption properties on the catalytic activity of the sample in conventional thermal and microwave fields were studied. The results indicated that compared with the conventional thermal field, the catalytic activity of the samples in microwave field were obviously improved, and the activation energy of the reaction were decreased. Compared with the conventional thermal field, the conversion of toluene in microwave thermal field of MnO₂(Ac), MnO₂(S) and MnO₂(N) increased by 59%, 42% and 12%, and the mineralization rate increased by 36%,11% and 2%, respectively, when the catalytic temperature was 150 °C. Compared with the traditional thermal field, the activation energy of the sample MnO₂(Ac) in the microwave field was reduced by 88.3 KJ. A series of characterization results showed that the sample MnO₂(Ac) had good catalytic activity in the microwave field was due to: MnO₂(Ac) had proper microwave absorption properties, large amount of surface functional groups, large specific surface area and rich pore structure. The analysis results of electromagnetic parameters showed that: the reason that the sample MnO₂(Ac) had good microwave absorption performance was that the MnO₂(Ac) had proper impedance matching, high attenuation constant and Debye dipole relaxation effect.     

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.     

Homogeneous vs. catalytic combustion of lean methane—air mixtures in reverse-flow reactors

To carry out a comparative assessment of a recently proposed idea of using thermal flow-reversal reactors (TFRR) for mine ventilation air, the results for the catalytic flow-reversal reactor (CFRR) investigated within the European Project (2003) are briefly presented. Next, experimental investigations of thermal combustion are presented in this paper. These consisted of the kinetic study of homogeneous combustion in the pelletized bed and in the monolith. Kinetic equations for the two cases are derived and discussed. Experimental autothermal reverse-flow operation in a laboratory setup was performed. Due to the high heat capacity of the wall and insulation of the pelletized bed reactor, with considerable heat losses to the surroundings, autothermal operation was successful only in the monolithic reactor. It is finally concluded that the thermal combustion can be competitive compared with the catalytic oxidation.     

Influence of the exchanged cation in Pd/BEA and Pd/FAU zeolites for catalytic oxidation of VOCs

0.5 wt% palladium supported on exchanged BEA and FAU zeolites were prepared, characterized and tested in the total oxidation of volatile organic compounds (VOCs). The BEA and FAU zeolites were exchanged with different cations to study the influence of alkali metal cations (Na⁺, Cs⁺) and H⁺ in Pd-based catalysts on propene and toluene total oxidation. The exchange with different cations (Na⁺, Cs⁺) and H⁺ led to a decrease of the surface area and the micropore volume. All Pd/BEA and Pd/FAU zeolites were found to be powerful catalysts for the total oxidation of VOCs. They were active at low temperature and totally selective for CO₂ and H₂O. However, their activity depends significantly on the type of zeolite and on the nature of the charge-compensating cation. The activity order for propene and toluene oxidation on FAU catalysts, Pd/CsFAU > Pd/NaFAU > Pd/HFAU, is the reverse of the activity order on BEA catalysts: Pd/HBEA > Pd/NaBEA > Pd/CsBEA. The catalytic activities can be rationalized in terms of the influence of the electronegativity of the charge-compensating cation on the Pd particles, the Pd dispersion, the PdO reducibility and the adsorption energies for VOCs.