Are 3‐D models necessary to simulate packed bed reactors? analysis and 3‐D simulations of adiabatic and cooled reactors

Simulations and analysis of transversal patterns in a homogeneous three‐dimensional (3‐D) model of adiabatic or cooled packed bed reactors (PBRs) catalyzing a first‐order exothermic reaction were presented. In the adiabatic case the simulation verify previous criteria, claiming the emergence of such patterns when (ΔT_ad/ΔT_m)/(Pe_C/Pe_T) surpasses a critical value larger than unity, where ΔT_ad and ΔT_m are adiabatic and maximal temperature rise, respectively. The reactor radius required for such patterns should be larger than a bifurcation value, calculated here from the linear analysis. With increasing radius new patterned branches, corresponding to eigenfunction of the problem emerge, whereas other branches become unstable. The maximal temperature of the 3‐D simulations may exceed the 1‐D prediction, which may affect design procedures. Cooled reactor may exhibit patterns, usually axisymmetric ones that can be characterized by two anomalies: the peak temperature may exceed the corresponding value of an adiabatic reactor and may increase with wall heat‐transfer coefficient, and the peak temperature in a sufficiently wide reactor need not lie at the center but rather on a ring away from it. In conclusions, we argue that transversal patterns are highly unlikely to emerge in practical adiabatic PBRs with a single exothermic reaction, as in practice Pe_C/Pe_T > 1. That eliminates patterns in stationary and downstream‐moving fronts, whereas patterns may emerge in upstream‐moving fronts, as shown here. This conclusion may not hold for microkinetic models, for which stationary modes may be established over a domain of parameters. This suggests that a 1‐D model may be sufficient to analyze a single reaction in an adiabatic reactor and a 2‐D axisymmetric model is sufficient for a cooled reactor. The predictions of a 2‐D cylindrical thin reactor with those of a 3‐D reactor were compared, to show many similarities but some notable differences. © 2012 American Institute of Chemical Engineers AIChE J, 2012     

Transversal thermal patterns in packed‐bed reactors with simple kinetics: Bifurcation criterion and simulations

We derive a new criterion for transversal instability of planar fronts based on the bifurcation condition dV_f/dK|_K=0 = 0, where V_f and K are the front velocity and its curvature, respectively. This refines our previously obtained condition, which was formulated as α = (ΔT_adPe_T)/(ΔT_mPe_C) > 1 to α > 1 + |δ|, where ΔT_ad and ΔT_m are the adiabatic and maximal temperature rise, respectively, Pe_C and Pe_T are the axial mass and the heat Pe numbers, respectively, and δ is a small parameter. The criterion is based on approximate relations for ΔT_m and V_f, which account for the local curvature of a propagating front in a packed bed reactor with a first‐order activated kinetics. The obtained relations are verified by linear stability analysis of planar fronts. Simulations of a simplified 2D model in the form of a thin cylindrical shell are in good agreement with the critical parameters predicted by dispersion relations. Three types of patterns were detected in simulations: “frozen” multiwave patterns, spinning waves, and complex rotating–oscillating patterns. We map bifurcation diagrams showing domains of different modes using the shell radius as the bifurcation parameter. The possible translation of the 2D cylindrical shell model results to the 3D case is discussed. © 2010 American Institute of Chemical Engineers AIChE J, 2011     

Performance of silicon‐carbide foams as supports for Pd‐based methane combustion catalysts

BACKGROUND: Cellular foam materials are a new type of catalyst support that provides improved mass and heat transport characteristics and similar pressure drops to other well‐established structured supports such as monoliths. RESULTS: A Pd‐based catalyst has been prepared using a moderate surface area (25 m² g^?1) β‐SiC foam support without further washcoating. The stability of this catalyst has been tested for methane combustion at lean conditions, showing a small decrease of activity during the first 10 h followed by stable performance. Characterization of fresh and aged catalyst shows no significant changes. The influence of the most important reaction conditions, such as reactor loading (0.25–1 g), temperature (300–550 °C) and inlet methane concentration (833 and 1724 ppm), was studied in a fixed‐bed reactor. The results were fitted to three kinetic models: Mars‐van Krevelen; Langmuir‐Hinselwood; power‐law kinetics. CONCLUSIONS: The Pd/β‐SiC foam catalyst, prepared without the previous addition of a washcoating has been demonstrated to be stable for the combustion of methane‐air lean mixtures. A Mars‐van Krevelen kinetic model provides the best fit to the results obtained. Copyright © 2011 Society of Chemical Industry     

Coupling of highly exothermic and endothermic reactions in a metallic monolith catalyst reactor: A preliminary experimental study

An LaFe_0.5Mg_0.5O₃/Al₂O₃/FeCrAl metallic monolith catalyst for the exothermic catalytic combustion of methane and an Ni/SBA-15/Al₂O₃/FeCrAl metallic monolith catalyst for the endothermic reforming of methane with CO₂ have been prepared. A laboratory-scale tubular jacket reactor with the Ni/SBA-15/Al₂O₃/FeCrAl catalyst packed into its outer jacket and the LaFe_0.5Mg_0.5O₃/Al₂O₃/FeCrAl catalyst packed into its inner tube was devised and constructed. The reactor allows a coupling of the exothermic and endothermic reactions by virtue of their thermal matching. An experimental study in which the temperature difference between the chamber of the external electric furnace and the metallic monolith catalyst bed in the jacket was kept very small, by adjusting the power supply to the furnace, confirmed that the heat absorbed in the reforming reaction does indeed partly come from that evolved in the catalytic combustion of methane, and that the direct thermal coupling of the two reactions in the reactor can be realized in practice. When the temperature of the electric furnace chamber was 1088 K, and the gas hourly space velocities (GHSVs) of the reactant mixtures passed through the inner tube and the jacket were 382 h⁻¹ and 40 h⁻¹, respectively, the conversions of methane and CO₂ in the reforming reaction were 93.6% and 91.7%, respectively, and the heat efficiency reached 81.9%. Stability tests showed that neither catalyst underwent deactivation during 150 h on stream.     

A robust mixed‐conducting multichannel hollow fiber membrane reactor

To accelerate the commercial application of mixed‐conducting membrane reactor for catalytic reaction processes, a robust mixed‐conducting multichannel hollow fiber (MCMHF) membrane reactor was constructed and characterized in this work. The MCMHF membrane based on reduction‐tolerant and CO₂‐stable SrFe_0.8Nb_0.2O_3‐δ (SFN) oxide not only possesses a good mechanical strength but also has a high oxygen permeation flux under air/He gradient, which is about four times that of SFN disk membrane. When partial oxidation of methane (POM) was performed in the MCMHF membrane reactor, excellent reaction performance (oxygen flux of 19.2 mL min^?1 cm^?2, hydrogen production rate of 54.7 mL min^?1 cm^?2, methane conversion of 94.6% and the CO selectivity of 99%) was achieved at 1173 K. And also, the MCMHF membrane reactor for POM reaction was operated stably for 120 h without obvious degradation of reaction performance. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2592–2599, 2015     

Large barocaloric effect and pressure‐mediated electrocaloric effect in Pb0.99Nb0.02(Zr0.95Ti0.05)0.08O3 ceramics

Ferroelectric materials are being actively explored for next‐generation solid‐state cooling technology. Even though bulk materials possess an advantage in terms of overall heat extraction capacity, their performance is limited due to low adiabatic temperature change. In this regard, the present article explores enhanced cooling capacity of bulk polycrystalline Pb_0.99Nb_0.02(Zr_0.95Ti_0.05)_0.08O₃ (PNZT) through external‐field mediation and coupled caloric effects. Barocaloric (BC) and electrocaloric (EC) effects were indirectly estimated using polarization versus electric field (P‐E) loops (under varying pressure and temperature). It was observed that under applied pressure of 325 MPa, ΔT_EC could be improved from 1 K to 4.5 K. Similarly, a peak unbiased ΔT_BC of 1.5 K could be enhanced to 5.3 K under an electric field of 5 MV·m^?1. These figures correspond to an improvement of ~400% over the unbiased values. The results are indicative of the multicaloric cooling capacity of bulk ferroelectric materials.     

Heat Exchangeability of a Catalytic Plate Reactor and Analysis of the Reactivity of Steam and CO2 in Methane Reforming

An assemble‐type plate reactor was developed and its intensified heat transfer compared to that of a conventional tubular reactor in methane reforming was confirmed. This characteristic enables accurate reaction kinetic analysis because of quasi‐isothermal operation with mild pressure loss. Reduced experiment cost is one of the features of the assemble‐type reactor. Simple thermal design equations applicable to plate reactors were also assessed. From experiments and accurate reaction analysis using the plate reactor it is suggested that H₂O and CO₂ have similar reactivity for a commercial Ni/α‐Al₂O₃ catalyst. The partial pressure of the oxidizing agent had much more influence on the reactivity of methane reforming than the species of this agent.     

Monoliths as suitable catalysts for reverse‐flow combustors: Modeling and experimental validation

The performance of a bench‐scale monolithic reverse‐flow reactor (RFR) for methane combustion has been experimentally studied in this work. The influence of the different operating parameters, such as total gas flow rate (2.5 × 10^?4–5 × 10^?4 m³ s^?1 (STP)), methane inlet concentration (1000–5500 ppm), and switching time (300–900 s) on the reactor performance (outlet conversion and stability), has been experimentally determined. The validation of a heterogeneous one‐dimensional dynamic model for monolithic beds with the obtained experimental data allows the use of this model to simulate the behavior of industrial‐scale reactors. In the second part of the work, a systematic comparison of particulate and monolithic RFRs is carried out through design curves. Reactor length for 99% outlet conversion and the corresponding pressure drop is determined for varying operating conditions (surface velocity and inlet methane concentration). © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Partial Oxidation of Methane to Syngas in a Packed Bed Catalyst Membrane Reactor

The planar membrane reactor configuration was explored for partial oxidation of methane (POM) to syngas. A supported membrane composed of yttria‐stabilized zirconia and La_0.8Sr_0.2Cr_0.5Fe_0.5O_3‐δ was sealed to a stainless holder, and a Ni/Al₂O₃ catalyst bed was placed under the membrane plane with a small slit between them. This reactor configuration would facilitate the POM reaction via oxidation‐reforming mechanism: the oxidation reaction occurring at the membrane surface and the reforming reaction taking place in the catalyst bed. At 800°C and a methane feed rate of 32 mL min^?1, the reactor attained methane throughput conversion over 90%, CO and H₂ selectivity both over 95%, and an equivalent oxygen permeation rate 1.4 mL cm^?2 min^?1. The membrane and catalyst remained intact after the POM testing. The planar membrane reactor configuration explored in this study may lead to the development of a compact reactor for syngas production. © 2016 American Institute of Chemical Engineers AIChE J, 62: 2170–2176, 2016     

Oxidative Coupling of Methane in a Negative DC Corona Reactor at Low Temperature

Oxidative coupling of methane (OCM) in the presence of DC corona is reported in a narrow glass tube reactor at atmospheric pressure and at temperatures below 200°C. The corona is created by applying 2200V between a tip and a plate electrode 1.5 mm apart. The C₂ selectivity as well as the methane conversion are functions of methane‐to‐oxygen ratio, gas residence time, and electric current. At CH₄/O₂ ratio of 5 and the residence time of about 30 ms, a C₂ yield of 23.1% has been achieved. The main products of this process are ethane, ethylene, acetylene as well as CO and CO₂ with CO/CO₂ ratios as high as 25. It is proposed that methane is activated by electrophilic oxygen species to form methyl radicals and C₂ products are produced by a consecutive mechanism, whereas CO_x is formed during parallel reactions.     

Chemical‐looping combustion process: Kinetics and mathematical modeling

Chemical Looping Combustion technology involves circulating a metal oxide between a fuel zone where methane reacts under anaerobic conditions to produce a concentrated stream of CO₂ and water and an oxygen rich environment where the metal is reoxidized. Although the needs for electrical power generation drive the process to high temperatures, lower temperatures (600–800°C) are sufficient for industrial processes such as refineries. In this paper, we investigate the transient kinetics of NiO carriers in the temperature range of 600 to 900°C in both a fixed bed microreactor (WHSV = 2‐4 g CH₄/h/g oxygen carrier) and a fluid bed reactor (WHSV = 0.014‐0.14 g CH₄/h per g oxygen carrier). Complete methane conversion is achieved in the fluid bed for several minutes. In the microreactor, the methane conversion reaches a maximum after an initial induction period of less than 10 s. Both CO₂ and H₂O yields are highest during this induction period. As the oxygen is consumed, methane conversion drops and both CO and H₂ yields increase, whereas the CO₂ and H₂O concentrations decrease. The kinetics parameter of the gas–solids reactions (reduction of NiO with CH₄, H₂, and CO) together with catalytic reactions (methane reforming, methanation, shift, and gasification) were estimated using experimental data obtained on the fixed bed microreactor. Then, the kinetic expressions were combined with a detailed hydrodynamic model to successfully simulate the comportment of the fluidized bed reactor. © 2010 American Institute of Chemical Engineers AIChE J, 2010     

Modelling and experimental studies on unsteady-state SO2 converters

This paper deals with experimentation of the unsteady-state fixed-bed reactor with flow reversal for SO₂ conversion. A laboratory reactor with compensatory heating coils has been set up, resulting in 96–99% conversion for SO₂ = 2.62–9.52 vol%, and u = 0.2 m/s. The results were from agreement with simulation of a really adiabatic unsteady-state reactor, but agreed well with modelling by considering the radial heat transfer. A three-stage pilot-scale converter has also been run with the M-typed temperature profile produced by heat loss from the chamber between stages. Good agreement was achieved with modelling by taking into account this feature. The results show that, while the adiabatic requirement is difficult to fulfill in the well-accepted experimental reactors, simulation and modelling are powerful means for compensation.     

Radial Reactor-Heat Exchanger for Natural Gas Combustion in a Structured Porous Metal Catalyst Bed

A compact (0.01 m³ in volume) radial reactor for deep oxidation of methane (with a heat output of 16–30 kW) that is combined with an internal water heat exchanger is designed. The reactor contains the structured porous metal catalyst 5% (0.5% Pt/γ-Al₂O₃) + 65% Ni + 5% Al. The reactor performance at different heat outputs is experimentally studied. It is demonstrated that, if catalytic methane combustion is virtually complete, the fraction of heat transferred to the internal heat exchanger (to the water) is large (31–53%) and allows the reactor to reach a specific heat output up to 130 kW/m² (on the outer surface of the catalytic heating element). The coefficients of heat transfer to the internal heat exchanger and the radial thermal conductivity of the catalyst bed are shown to theoretically strongly affect the thermal conditions in the catalyst bed. It is concluded that the proposed mathematical model fits the experimental data well.__________Translated from Teoreticheskie Osnovy Khimicheskoi Tekhnologii, Vol. 39, No. 4, 2005, pp. 432–439.Original Russian Text Copyright © 2005 by Kirillov, Kuzin, Kuz’min, Skomorokhov, Shigarov.     

Comparison of the performance of a direct-contact bubble reactor and an indirectly heated tubular reactor for solar-aided methane dry reforming employing molten salt

A theoretical approach is presented for the comparison of two different atmospheric pressure reactors—a direct-contact bubble reactor (DCBR) and an indirectly heated tubular reactor (IHTR)—to evaluate the reactor performance in terms of heat transfer and available catalytic active surface area. The model considers the catalytic endothermic reactions of methane dry reforming that proceeds in both reactors by employing molten salts at elevated temperatures (700–900 °C) in the absence of catalyst deactivation effects. The methane conversion process is simulated for a single reactor using both a reaction kinetics model and a heat transfer model. A well-tested reaction kinetics model, which showed an acceptable agreement with the empirical observations, was implemented to describe the methane dry reforming. In DCBR, the heat is internally transferred by direct contact with the three phases of the system: the reactant gas bubbles, the heat carrier molten salts and the solid catalyst (Ni-Al₂O₃). In contrast, the supplied heat in the conventional shell-and-tube heat exchanger of the IHTR is transferred across an intervening wall. The results suggest a combination system of DCBR and IHTR would be a suitable configuration for process intensification associated with higher thermal efficiency and cost reduction.     

Hydrogen production through chemical looping using NiO/NiAl2O4 as oxygen carrier

A new autothermal route to produce hydrogen from natural gas via chemical looping technology was investigated. Tests were conducted in a micro-fixed bed reactor loaded with 200 mg of NiO/NiAl₂O₄ as oxygen carrier. Methane reacts with a nickel oxide in the absence of molecular oxygen at 800 °C for a period of time as high as 10 min. The NiO is subsequently contacted with a synthetic air stream (21% O₂ in argon) to reconstitute the surface and combust carbon deposited on the surface. Methane conversion nears completion but to minimize combustion of the hydrogen produced, the oxidation state of the carrier was maintained below 30% (where 100% represents a fully oxidized surface). Co-feeding water together with methane resulted in stable hydrogen production. Although the carbon deposition increased with time during the reduction cycle, the production rate of hydrogen remained virtually constant. A new concept is also presented where hydrogen is obtained from methane with inherent CO₂ capture in an energy neutral 3-reactors CFB process. This process combines a methane combustion step where oxygen is provided via an oxygen carrier, a steam methane reforming step catalyzed by the reduced oxygen carrier and an oxidizing step where the O-carrier is reconstituted to its original state.     

Structural parameters in relation to the rheological behavior and properties of PP/EPR in‐reactor alloy synthesized by multi‐stage sequential polymerization

The morphology and molecular structure of an in‐reactor polypropylene/ethylene propylene rubber alloy, synthesized by multi‐stage sequential polymerization, were studied with respect to the rheological behavior and final properties of the alloy. The polymer alloys, based on different structural morphologies, were characterized by SEM, GPC, ¹³C NMR, DSC, rheological analysis, and mechanical testing. The scanning electron microscopy of samples showed that the size of the dispersed phase particles is decreased as the switch frequency of copolymerization timing is increased. The GPC results showed that switch frequency slightly altered the molecular weight distribution of the copolymer although it had no effect on PP homopolymer. ¹³C NMR results were used for the evaluation of compatibility between the two phases with changes in switch frequency. DSC results showed that T_m and T_c were almost independent of switch frequency, even though the size of dispersed phase was decreased and the blend crystal content increased with ΔH of about 13%. The small amplitude oscillation rheometry showed that storage modulus and viscosity shifted to higher values when switch frequency increased. In studying the mechanical properties it was revealed that, especially the impact strength increased by about 62% when the size of the dispersed particles was decreased. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Performance of an internally circulating fluidized-bed reactor for the catalytic oxidative coupling of methane

The oxidative coupling of methane to C₂-hydrocarbons (OCM) over a La₂O₃/CaO catalyst (27 at.%) was investigated in an internally circulating fluidized-bed (ICFB) reactor (ID_eff = 1.9 cm, H_riser = 20.5 cm). The experiments were performed in the following range of conditions: T = 800?900°C, p_CH4:p_O2p_N2 = 57.1–64:16–22.9:20 kPa. The obtained C₂ selectivities and C₂ yields were compared with the corresponding data from a spouted-fluid-bed reactor (ID = 5 cm) and a bubbling fluidized-bed (FIB) reactor (ID = 5 cm). The maximum C₂ yield in the internally circulating fluidized-bed (ICFB) reactor amounted to 12.2% (T = 860°C, 38.7% C₂ selectivity, 31.5% methane conversion), whereas in the FIB reactor a maximum C₂ yield of 13.8% (T = 840°C, 40.4% C₂ selectivity, 34.2% methane conversion) was obtained. The lowest C₂ yield was achieved in the spouted-bed (SFB) reactor (Y = 11.6%, T = 840°C, 36.2% C₂ selectivity, 32.0% methane conversion). The highest space-time yield of 24.0 mol/kg_cat.h was obtained in the ICFB reactor, whereas in a FIB reactor only a space-time yield of 9.6 mol/kg_catcould be obtained. The performance of the ICFB reactor was strongly influenced by gas-phase reactions. Furthermore, stable reactor operation was possible only over a narrow range of gas velocities.     

Performance of Ba0.5Sr0.5Co0.8Fe0.2O3 + δ membrane after laser ablation for methane conversion

A cross-shaped pattern was formed on the surface of Ba_0.5Sr_0.5Co_0.8Fe_0.2O_3 − δ oxygen permeation membrane by laser ablation. A membrane reactor made from this membrane was operated for partial oxidation of methane to syngas in the presence of Ni/ZrO₂ catalyst. The CH₄ conversion and CO selectivity of the membrane reactor were 98.8% and 91.5%, respectively, and the oxygen permeation flux through the membrane was 11.0 ml/cm² min at 850 °C. The effects of space velocity (SV) on CH₄ conversion and CO selectivity in such reactor were discussed. The mechanism of POM in such membrane reactor may follow the combustion and reforming mechanism.     

Determination of potential methane production capacity of a granular sludge from a pilot‐scale upflow anaerobic sludge blanket reactor using a specific methanogenic activity test

A 450 dm³ pilot‐scale upflow anaerobic sludge blanket (UASB) reactor was used for the treatment of a fermentation‐based pharmaceutical wastewater. The UASB reactor performed well up to an organic loading rate (OLR) of 10.7 kg COD m^?3 d^?1 at which point 94% COD removal efficiency was achieved. This high treatment efficiency did not continue, however and the UASB reactor was then operated at lower OLRs for the remainder of the study. Specific methanogenic activity (SMA) tests were, therefore, carried out to determine the potential loading capacity of the UASB reactor. For this purpose, the SMA tests were carried out at four different initial acetate concentrations, namely 500 mg dm^?3, 1000 mg dm^?3, 1500 mg dm^?3 and 2000 mg dm^?3 so that substrate limitation could not occur. The results showed that the sludge sample taken from the UASB reactor (OLR of 6.1 kg COD m^?3 d^?1) had a potential acetoclastic methane production (PMP) rate of 72 cm³ CH₄ g^?1 VSS d^?1. When the PMP rate was compared with the actual methane production rate (AMP) of 67 cm³ CH₄ g^?1 VSS d^?1 obtained from the UASB reactor, the AMP/PMP ratio was found to be 0.94 which ensured that the UASB reactor was operated using its maximum potential acetoclastic methanogenic capacity. In order to achieve higher OLRs with desired COD removal efficiencies it was recommended that the UASB reactor should be loaded with suitable OLRs pre‐determined by SMA tests. © 2001 Society of Chemical Industry     

Structural and Thermal Characterization of A Novel High Nitrogen Energetic Material: (NH4)2DNMT

1,4‐Dihydro‐5H‐(dinitromethylene)‐tetrazole ammonium salt ((NH₄)₂DNMT), a high nitrogen energetic compound, was synthesized and structurally characterized by single‐crystal X‐ray diffraction. The thermal behavior of (NH₄)₂DNMT was studied with DSC and TG‐DTG methods. The kinetic equation of the thermal decomposition reaction is: dα/dT=10^13.17/3β(1−α)⁻² exp(−1.388×10⁵/RT). The critical temperature of thermal explosion is 182.7 °C. The specific heat capacity of (NH₄)₂DNMT was determined and the molar heat capacity is 301 J mol⁻¹ K⁻¹ at 298.15 K. The adiabatic time‐to‐explosion of (NH₄)₂DNMT was calculated to be 277 s. The detonation velocity and detonation pressure were also estimated. All results showed that (NH₄)₂DNMT presents good performance.