Optimization of a flow reversal reactor for the catalytic combustion of lean methane mixtures

This paper describes a parametric study of a catalytic flow reversal reactor used for the combustion of lean methane in air mixtures. The effects of cycle time, velocity, reactor diameter, insulation thickness, thermal mass and thermal conductivity of the inert sections are studied using a computer model of the system. The effects on the transient behaviour of the reactor are shown. Emphasis is placed on the effects of geometry from a scale-up perspective. The most stable system is obtained when the thermal mass of the inert sections is highest, while thermal conductivity has only a minor effect on reactor temperature. For a given operation, the stationary state depends on the combination of velocity and switch time. Provided that complete conversion is achieved, highest reactor temperature is achieved with the highest switch time. The role of the insulation is not only to prevent heat loss to the environment, but also to provide additional thermal mass. During operation heat is transfer to and from the insulation. The insulation effect leads to higher reactor temperature up to a maximum thickness. The insulation effect diminishes as the reactor diameter increases, and results in higher temperatures at the centreline.     

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.     

A novel particle/monolithic two-stage catalyst bed reactor and their catalytic performance for oxidative coupling of methane

A novel two-stage catalyst bed reactor was constructed comprising of the 5%Na₂WO₄-2%Mn/SiO₂ particle catalyst and the 5%Na₃PO₄-2%Mn/SiO₂/cordierite monolithic catalyst. The reaction performance of the oxidative coupling of methane (OCM) in the two-stage bed reactor system was evaluated. The effects of the bed height and operation mode, as well as the reaction parameters such as reaction temperature, CH₄/O₂ ratio and flowrate of feed gas on the catalytic performance were investigated. The results indicated that the two-stage bed reactor system exhibited a good performance for the OCM reaction when the feed gases were firstly passed through the particle catalyst bed and then to the monolithic catalyst bed. The CH₄ conversion of 32.6% and C₂ selectivity of 67.5% could be obtained with a particle catalyst bed height of 10 mm and a monolithic catalyst bed height of 50 mm in the two-stage bed reactor. Both of the CH₄ conversion and C₂ selectivity have been increased by 4.8% and 2.5%, respectively, as compared with the 5%Na₂WO₄-2%Mn/SiO₂ particle catalyst in a single-bed reactor and by 7.7% and 16.1%, respectively, as compared with the 5%Na₃PO₄-2%Mn/SiO₂/cordierite monolithic catalyst in a single-bed reactor. The catalytic performance of the OCM in the two-stage bed reactor system has been remarkably improved. The TPR results indicate the high temperature reduction oxygen species in the monolithic catalyst might be favorable to the formation of C₂ products.     

Cu/γ-Al2O3 catalyst for the combustion of methane in a fluidized bed reactor

The applicability of a catalyst based on copper dispersed on γ-Al₂O₃ spheres (1 mm diameter) for fluidized bed catalytic combustion of methane has been assessed. Catalyst properties have been determined by physico-chemical characterization techniques and fixed bed activity tests revealing the presence of a surface CuAl₂O₄ spinel phase, still active and stable in methane combustion after repeated thermal ageing treatments at 800 °C. Methane catalytic combustion experiments have been performed in a 100 mm premixed fluidized bed reactor under lean conditions (0.15–3% inlet methane concentration), showing that complete CH₄ conversion can be attained below 700 °C in a fluidized bed of 1 mm solids with a gas superficial velocity about twice the incipient fluidization velocity.     

Influence of feedstock source on the biocatalyst stability and reactor performance in continuous biodiesel production

A biodiesel process in a packed bed reactor was used as a model system to show the strong dependence of the reactor behavior on the developing of chemical environment within the reactor. Ethanolysis runs of babassu and macaw palm oils were carried out in a solvent-free system using Burkholderia cepacia lipase immobilized on silica–PVA matrix. The best performance was found for the reactor running on macaw palm oil, which resulted in a stable operating system and an average yield of 87.6 ± 2.5%. This strategy also gave high biocatalyst operational stability, revealing a half-life of 478 h.     

Flow distribution and velocity measurement in a radial flow fixed bed reactor using electrical resistance tomography

Electrical resistance tomography is a relatively simple and inexpensive technique for imaging electrically conducting systems. It has been applied to visualise the flow pattern and distribution inside a radial flow packed bed of novel design for improving reactor performance with lower pressure drop. The density of information yielded by electrical tomography is suitable for validation of Computational fluid dynamics. Sets of tomographic images representing slices through a packed bed have been obtained for a 8-plane × 16-electrode sensor configuration which produces of the order 10³ conductivity measurements in three-dimensions. Pulse injections of high conductivity tracer, both uniformly in the feed and localised, can be imaged as multiple tomographic images or 3D solid-body images, revealing the internal flow pattern. Differentiation of the motion of the tracer peak conductivity within pixels in the sensing planes and between the planes allows the local flow velocities and directions to be determined. This quantifies the flow pattern for uniformity and radial distributive properties.     

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.     

Hydrothermal synthesis of LA-MN-Hexaaluminates for the catalytic combustion of methane

Hydrothermal synthesis by using urea hydrolysis at 1.0-3.0 MPa and 120-130 ‡C was employed to prepare Mn-substituted hexaaluminate catalysts for methane combustion. The results from DTA-MS demonstrated that CO_3- and Off anions co-exist in the hydrothermal reaction. XRD reveals that the components of carbonates and hydroxides in the hydrothermal reaction are more favorable than those in the (NH₄)₂CO₃ co-precipitation for the formation of the Mn-substituted hexaaluminate phase. After calcination at 1,200 ‡C for 2 h, LaMnAl₁₁O₁₉ is the major phase of the catalyst prepared by the hydrothermal synthesis method while LaAlO₃ is the major one of the catalysts prepared by NH₄OH and (NH₄)₂CO₃ co-precipitation. The catalyst prepared by hydrothermal synthesis has higher activity than that prepared by NH₄OH and (NH₄)₂CO₃ co-precipitation. The major reason is that more Mn²⁺ ions have incorporated into the hexaaluminate lattice. The effect of drying methods on the formation of hexaaluminate phase was also discussed.     

Design and demonstration of an experimental membrane reactor set-up for oxidative coupling of methane

In this experimental research, the performance of the oxidative coupling of methane (OCM) reactions in a porous packed bed membrane reactor was investigated. A commercially available porous alpha-alumina membrane was modified to obtain the characteristics needed for a stable and catalytically inert OCM membrane reactor. The silica-sol impregnation–calcination method and a new silicon oxycarbide (SiOC) coating-calcination approach were applied to modify the membrane. The characteristics of the resulted membrane and its typical performance as OCM membrane reactor are reported.     

Effect of the wall Nusselt number on the simulation of catalytic fixed bed reactors

Literature correlations for the apparent wall heat transfer coefficient (h_w) in fixed bed catalytic reactors are compared. At low to moderate values of the Reynolds number (Re), different correlations can produce estimates of the dimensionless wall Nusselt number (Nu_w = h_wd_p/k_f) that differ by an order of magnitude or more. Some correlations give Nu_w as a function of Re only, others allow for the effects of tube-to-particle diameter ratio and particle and fluid thermal conductivities. The value of Nu_w that is used in a simulation of a fixed bed catalytic reactor can have a strong effect on the predicted behavior. Two examples of fixed bed reactors are simulated and show that the more general correlations for Nu_w are to be preferred.     

Bimetallic catalysts for the catalytic combustion of methane using microreactor technology

Pt–W and Pt–Mo based catalysts were evaluated for methane combustion using a sandwich-type microreactor. Alumina washcoated microchannels were impregnated with platinum in combination with and promoted with tungsten and molybdenum and compared with commercially available Pt/Al₂O₃ catalysts. Catalysts were tested in the range of 300–700 °C with flow rates adjusted to GHSV of 74,000 h⁻¹ and WHSV of 316 L h⁻¹ g⁻¹. Catalysts containing tungsten were found to be the most active and the most stable possibly due to a metal interaction effect. A Pt–W/γ-Al₂O₃ containing 4.6 wt% Pt and 9 wt% W displayed the highest activity with full conversion at 600 °C and a selectivity to CO₂ of 99%.     

Production of hydrogen and carbon nanotubes from methane decomposition in a two-stage fluidized bed reactor

Methane decomposition over a Ni/Cu/Al₂O₃ catalyst is studied in a two-stage fluidized bed reactor. Low temperature is adopted in the lower stage and high temperature in the upper stage. This allows the fluidized catalysts to decompose methane with high activity in the high temperature condition; then the carbon produced will diffuse effectively to form carbon nanotubes (CNTs) in both low and high temperature regions. Thus the catalytic cycle of carbon production and carbon diffusion in micro scale can be tailored by a macroscopic method, which permits the catalyst to have high activity and high thermal stability even at 1123 K for hydrogen production for long times. Such controlled temperature condition also provides an increased thermal driving force for the nucleation of CNTs and hence favors the graphitization of CNTs, characterized by high resolution transmission electron microscopy (HRTEM), Raman spectroscopy and XRD. Multistage operation with different temperatures in a fluidized bed reactor is an effective way to meet the both requirements of hydrogen production and preparation of CNTs with relatively perfect microstructures.     

Catalytic combustion of methane over bimetallic catalysts a comparison between a novel annular reactor and a high-pressure reactor

The effects of adding a co-metal, Pt or Rh, to Pd/γ-Al₂O₃ catalysts were studied with respect to the catalytic activity for methane combustion and compared to a Pd/γ-Al₂O₃ catalyst, using both a pressurized pilot-scale and a lab-scale annular reactor. Temperature programmed oxidation (TPO) experiments were also carried out to investigate the oxygen release/uptake of the catalyst materials. Palladium showed an unstable behavior both in the pilot and lab-scale experiments at temperatures well below the PdO to Pd transformation. An addition of Pt to Pd stabilized, and in some cases increased, the catalytic activity for methane combustion.

The TPO experiments showed that the oxygen release peak was shifted to lower temperatures even for low additions of Pt, i.e. Pd:Pt=2:1. For additions of rhodium only small beneficial effects were seen. The steady-state behavior of the lab-scale annular reactor correspond well to the pressurized pilot-scale tests.     

Improving selectivity during methane partial oxidation by use of a membrane reactor

A reactant-swept catalytic membrane reactor for partial oxidation of methane to formaldehyde has been modeled. Kinetic parameters were taken from the literature for a V₂O₅/Sio₂ methane partial oxidation catalyst, and membrane parameters characteristic of commercially available materials were used. The models show that the selectivity for formaldehyde can be significantly improved by using a membrane reactor.     

Control of a nonadiabatic packed bed reactor under periodic flow reversal

A full parametric study of the open-loop behavior of a packed bed reactor-recuperator system operating under periodic flow reversal produced a series of parametric maps which slow regions of operating conditions for which the system exhibits runaway, stable operation or extinction of the reaction. The reaction is CO oxidation over a Pt/alumina catalyst. A set of optimal operating conditions in terms of cycle time and heat transfer coefficient can be directly extracted from the parametric maps. A preliminary study on the control of periodic flow reversal tested and compared two strategies. 1) feedback PID control of the exit CO concentration and 2) model based feedforward control.     

Modelling channel interactions in a non-adiabatic multichannel catalytic combustion reactor

The development of a mathematical model to account for channel interactions in a multichannel monolith with square shaped channels is described. As an example of the application of the code, channel interactions are modelled that result from a maldistribution in fuel supply into a catalytic monolith combustor. The response of a metal and a ceramic monolith are compared, demonstrating the advantages of conduction as a method of dissipating heat in the radial direction.     

Effect of structural, thermal and flow parameters on steam reforming of methane in a catalytic microreactor

Steam reforming of methane in microchannels, embedded in a monolith is numerically modelled. Horizontal heating layers at equal intervals within the monolith are maintained at constant temperature. The channels are coated internally with catalyst to enhance gas–solid heterogeneous reaction. The numerical method combines the analytical solution for heat transfer through a fin, extended to a stack of fins, and the reactive flow of gases through an iterative procedure. The method offers a tool for quick design of a micro-structure, without considering detailed CFD-based model. In addition, the method can be suitably modified to address thermal management in electronic chip.The temperature within a stack between two heating layers drops near the centre of the stack, in case of an endothermic reaction. This drop, signifying the deviation from isothermal behaviour is found more near the heating layer, and tapers off near the centre of the stack. When the feed temperature is significantly less than the temperature of the heating layer, the portion of the reactor, away from the heating layer remains at a substantially lower temperature, particularly when the number of channels between two heating layers is large. Accordingly, the conversions in the individual channels at the outlet are affected. If the channel wall becomes thicker, the drop in fluid temperature away from the heating layer is more. The increase in feed velocity leads to larger drop in temperature and overall conversion. The decrease in thermal conductivity and the increase in number of channels between two heating layers enhance the temperature drop. None of these functionalities appears to be linear.     

Control of a reverse flow reactor for VOC combustion

A flow reversal reactor for VOC combustion is controlled by the linear quadratic regulator (LQR), which uses dilution and internal electric heating as controls to confine the hot spot temperature within the two temperature limits, in order to ensure complete conversion of the VOC and to prevent overheating of the catalyst. Three phases of operation, i.e., dilution phase, heating phase and inactive phase, are identified. In dilution and heating phases, the cost functions of the LQR control are defined in quadratic forms. In the inactive phase, the controllers are inactivated. A linear model is derived by linearization of a countercurrent pseudo-homogeneous model at two nominal operating conditions in the dilution phase and the heating phase, respectively. The feed concentration and the temperature profile are estimated on-line by using a high-gain observer with three temperatures measurements and are used in the LQR feedback control. Experiments are carried out on a medium-scale reversed flow reactor to demonstrate the proposed LQR control strategy. Results show that the LQR controller is highly efficient in maintaining normal operation of the reactor.     

The effect of fixed-bed reactor configuration on the oxidative coupling of methane over a Li/Pb/Ca catalyst

Introduction of additional O₂ at the midpoint of the catalyst bed of a methane oxidative coupling, fixed bed reactor, increases the C₂ STY more than the CO _x . STY over a Li/Pb/Ca catalyst. This observation is not only a consequence of kinetics but may also be attributed to increased methyl radical generation on the O₂ replenished catalyst surface.     

Experimental demonstration of the reverse flow catalytic membrane reactor concept for energy efficient syngas production. Part 1: Influence of operating conditions

In this contribution the technical feasibility of the reverse flow catalytic membrane reactor (RFCMR) concept with porous membranes for energy efficient syngas production is investigated. In earlier work an experimental proof of principle was already provided [Smit, J., Bekink, G.J., van Sint Annaland, M., Kuipers, J.A.M., 2005a. A reverse flow catalytic membrane reactor for the production of syngas: an experimental study. International Journal of Chemical Reactor Engineering 3 (A12)], but compensatory heating was required and problems related to the mechanical strength of the powder-based YsZ catalyst and the steel filter were reported. Therefore, in Part 1 the performance of a Rh-Pt/Al₂O₃ catalyst with improved mechanical strength and porous Al₂O₃ membranes with excellent temperature resistance was tested in an isothermal membrane reactor. For this purpose a novel sealing technique was developed that could withstand sufficiently high pressure differences and temperatures. Very high syngas selectivities close to the thermodynamic equilibrium could be achieved for a considerable period of time without any increase in pressure drop and without any decrease in syngas selectivity. Using the Rh-Pt/Al₂O₃ catalyst, several experiments were performed in a RFCMR demonstration unit and the influence of different operating conditions and design parameters on the reactor behaviour was investigated. It is shown that very high syngas selectivities (up to 95%) can be achieved with a maximal on-stream time of 12 h, without using any compensatory heating and despite inevitable radial heat losses. In Part 2 a reactor model is discussed that can well describe the experimental results presented in this part.