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.     

Intensified Fischer–Tropsch synthesis process with microchannel catalytic reactors

A microchannel catalytic reactor with improved heat and mass transport has been used for Fischer–Tropsch synthesis. It was demonstrated that this microchannel reactor based process can be carried out at gas hourly space velocity (GHSV) as high as 60,000 h⁻¹ to achieve greater than 60% of single-pass CO conversion while maintaining relatively low methane selectivity (<10%) and high chain growth probability (>0.9). In this study, performance data were obtained over a wide range of pressure (10–35 atm) and hydrogen-to-carbon monoxide ratio (1–2.5). The catalytic materials were characterized using BET, scanning electron microcopy (SEM), transmission electron microcopy (TEM), and H₂ chemisorption. A three-dimensional pseudo-homogeneous model was used to simulate temperature profiles in the exothermic reaction system in order to optimize the reactor design. Intraparticle non-isothermal characteristics are also analyzed for the FT synthesis catalyst.     

Electrocatalytic hydrogenation of soybean oil in a radial flow-through Raney nickel powder reactor

Soybean oil has been hydrogenated electrocatalytically on Raney nickel powder catalyst at atmospheric pressure and moderate temperatures in a novel undivided packed bed radial flow-through reactor. The reactor consisted of a single anode/cathode tubular element, where Raney nickel catalyst powder was contained in the annular space between two concentric porous ceramic tubes and the flow of the reaction medium (a dispersion of oil in a water/t-butanol/tetraethylammonium p-toluenesulfonate electrolyte) was either in the inward or outward radial direction. The innovative design of this reactor allows for a thin nickel bed and a high anode/cathode interfacial area without the normal problems associated with electrolyte flow distribution. The total size of the reactor can be increased without changing the relative anode/cathode position and the electrolyte flow pattern by simply increasing the length and/or number of anode/cathode elements in a single common shell (similar to a shell-and-tube heat exchanger). For the brush hydrogenation of soybean oil, current efficiencies of 90–100% were achieved with a single element reactor when the electrolyte oil content was 10 or 25 wt/vol %, the apparent current density was 10 or 15 mA cm^–2, the temperature was 75 °C, and the electrolyte flowed in the inward radial direction. The electrohydrogenated oil product was characterized by a high stearic acid content and low concentrations of linolenic acid and trans fatty acid isomers, as compared to the traditional high temperature chemical catalytic oil hydrogenation route with hydrogen gas.     

Development of a catalytic heating system for external combustion engines

A catalytic heater design was proposed for an external combustion engine. This design is based on the partial oxidation or autothermal conversion of hydrocarbon fuel to syngas and its further oxidation with heat generation in a radial catalytic reactor integrated with a tubular heat exchanger. The theoretical analysis of operational regimes for a catalytic heater with a thermal power of 25–50 kW was performed with regard to the distribution of gas and the mathematical modeling of processes in a catalyst bed integrated with a heat exchanger, and some estimates were given for the performance of an external combustion engine. The conditions providing a uniform distribution of gas along the length of a radial reactor with suction of a reaction mixture into the catalyst bed were determined. A design of catalytic heating system elements was developed, and some layout solutions that provide a rational mutual arrangement of system components were created.     

Computational fluid dynamics modeling of hydrogen production in an autothermal reactor: Effect of different thermal conditions

A numerical model was developed and validated to simulate and improve the reforming efficiency of methane to syngas (CO+H₂) in an autothermal reactor. This work was undertaken in a 0.8 cm diameter and 30 cm length quartz tubular reactor. The exhaust gas from combustion at the bottom of reactor was passed over a Ru/γ-Al₂O₃ catalyst bed. The Eddy Dissipation Concept (EDC) model for turbulence-chemistry interaction in combination with a modified standard k-? model for turbulence and a reaction mechanism with 23 species and 39 elementary reactions were considered in the combustion model. The pre-exponential factors and activation energy values for the catalyst (Ru) were obtained by using the experimental results. The percentage of difference between the predicted and measured mole fractions of the major species in the exhaust gas from combustion and catalyst bed zones was less than 5.02% and 7.73%, respectively. In addition, the results showed that the reforming efficiency, based on hydrogen yield, was increased with increase in catalyst bed’s thermal conductivity. Moreover, an enhancement of 4.34% in the reforming efficiency was obtained with increase in the catalyst bed wall heat flux from 0.5 to 2.0 kW/m².     

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.     

Effect of micropores diffusion on kinetics of CH4 decomposition over a wood-derived carbon catalyst

In order to optimise hydrogen production from biomass gasification, catalytic conversion of methane contained in a surrogate biomass syngas (CH₄ 14%; CO 19%; CO₂ 14%; H₂ 16%; H₂O 30%; N₂ 7%) is investigated over a fixed bed of porous wood char as a function of temperature (800–1000 °C) and space time (1.6–6.2 min g L⁻¹). Determination of Thiele modulus evidences a change of kinetic regime from chemically- to diffusion-controlled when the temperature increases; this finding is particularly relevant when porous chars having an average pore width of 1 nm are used as catalysts. Mass diffusion transfers are accounted for by a model introducing an internal effectiveness factor. Knudsen diffusion in micropores is shown to limit the conversion rate of methane per unit mass of catalyst, and explains why such a rate is not proportional to the BET surface area, especially when the latter is higher than typically 300 m²/g. It is concluded that diffusion limitations in micropores should be taken into account, otherwise underestimated activation energy and intrinsic kinetic constant are obtained in some experimental conditions.     

Liquid flow texture analysis in trickle bed reactors using high-resolution gamma ray tomography

Trickle bed reactor performance and safety may suffer from radial and axial liquid maldistribution and thus from non-uniform utilization of the catalyst packing. Therefore, experimental analysis and fluid dynamic simulation of liquid–gas flow in trickle bed reactors is an important topic in chemical engineering. In the present study for the first time a truly high-resolution gamma ray tomography technique was applied to the quantitative analysis of the liquid flow texture in a laboratory cold flow trickle bed reactor of 90 mm diameter. The objective of this study was to present the comparative analysis of the liquid flow dynamics for two different initial liquid distributions and two different types of reactor configurations. Thus, the hydrodynamic behavior of a glass bead packing was compared to a porous Al₂O₃ catalyst particle packing using inlet flow from a commercial spray nozzle (uniform initial liquid distribution) and inlet flow from a central point source (strongly non-uniform initial liquid distribution), respectively. The column was operated in downflow mode at a gas flow rate of 180 L h⁻¹ and at liquid flow rates of 15 and 25 L h⁻¹.     

N2O Decomposition Catalysed by Transition Metal Ions

The ignition processes for the catalytic partial oxidation of methane (POM) to synthesis gas over oxidic nickel catalyst (NiO/Al₂O₃), reduced nickel catalyst (Ni⁰/Al₂O₃), and Pt-promoted oxidic nickel catalyst (Pt–NiO/Al₂O₃) were studied by the temperature-programmed surface reaction (TPSR) technique. The complete oxidation of methane usually took place on the NiO catalyst during the CH₄/O₂ reaction, even with a pre-reduced nickel catalyst, and Ni⁰ is inevitably first oxidized to NiO if the temperature is below the ignition temperature. It is above a certain temperature that Ni⁰ is formed again, which leads to the start of the POM. The POM can be initiated at a much lower temperature on a Pt–NiO catalyst because of Pt promotion of the reduction of NiO. The POM in a fluidized bed can be easily initiated due to the addition of Pt.     

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.     

A mathematical model for the dehydrogenation of methylcyclohexane in a packed bed reactor

A model for the dehydrogenation of methylcyclohexane in a tubular reactor over an industrial catalyst Pt-Sn/Al₂O₃ has been established. This model takes into account the axial dispersion at the inlet of the catalytic bed reactor as well as the heat transfer at the wall of the reactor. The heat transfer at the wall is satisfactorily represented by using a heat transfer coefficient correlation for which the parameters are obtained by fitting to the experimental data. The model provides a good representation of the radial and axial temperature profiles in the packed bed and can be also used to calculate the conversion.     

The selective catalytic oxidation of methane to methyl bisulfate at ambient pressure

The selective catalytic oxidation of methane in 25 wt.% oleum to methyl bisulfate at ambient pressure in presence of PtCl₄ catalyst was investigated. The reaction between methane and sulfuric acid took place at atmospheric pressure if the mass transfer between gas and liquid was sufficient. The process was carried out at 130–220 °C in absorption reactor packed with glass balls 1.5–7 mm in diameter.     

Electrochemical treatment of human wastes in a packed bed reactor

There is an increasing interest in the use of electrochemical methods for dealing with pollution problems. This paper deals with the mass balance and the use of a packed bed reactor for the electrochemical incineration of human wastes. Parametric studies were carried out to determine the effect of: (i) anodic particle size, (ii) flow rate of faeces/urine mixture, (iii) height of packed bed, (iv) current density and (v) cathode to anode spacing arrangement, on the rate of oxidation of human waste. It is shown that particles of Ebonex (0.5–1.0 mm diam.) coated with a catalyst layer, comprising SnO₂/Sb₂O₃, a solution flow rate of 0.9–1.4 cm s^–1 through the packed bed based on the cross sectional area of the reactor, a bed height of 5–8 cm and a current density based on the geometric area of the particles of 5 mA cm^–2 comprise an optimum set of parameters for the scale-up of a packed-bed electrochemical reactor system. A preliminary design for the further scale up of the process is also described.     

Oxidative coupling of methane to C2-hydrocarbons over La-promoted CaO catalysts

La₂O₃ promoted CaO [La/Ca (mol/mol) = 0.05] catalyst shows very high activity and selectivity (methane conversion: 25%, C₂-selectivity: 66% and C₂-space-time-yield: 864 mmol ·g^–1 (cat.)·h^–1) with no catalyst deactivation in oxidative coupling of methane to C₂-hydrocarbons at 800 ° C.     

Study on the catalytic synthesis of diethyl carbonate from CO and ethyl nitrite over supported Pd catalysts

A vapor phase synthesis of diethyl carbonate (DEC) from carbon monoxide and ethyl nitrite (EN) was studied in a continuous flow micro fixed-bed reactor at atmospheric pressure. PdCl₂–CuCl₂/AC (activated carbon) catalyst exhibited better catalytic activity compared with other binary catalyst systems. The suitable Pd-loading is about 2.0 wt%, and some additives (LaCl₃, CeCl₃, PrCl₃) are benefit for the DEC yield and selectivity. Influences of various reaction parameters on the DEC yield and selectivity were tested. The optimum reaction temperature lies in 378–388 K and the suitable gas hourly space velocity (GHSV) range is 2500–3000 h⁻¹ considering both factors of DEC production and CO conversion. An optimum CO/C₂H₅ONO mole ratio exists for catalytic activity, which is about 1/1. The stability of PdCl₂–CuCl₂/AC catalyst and PdCl₂–CuCl₂–CeCl₃/AC catalyst was also investigated. The possible reason of the deactivation behavior of catalysts was discussed with the help of XRD.     

Comparative studies on direct conversion of methane to methanol/formaldehyde over La–Co–O and ZrO2 supported molybdenum oxide catalysts

The selective oxidation of methane with molecular oxygen over MoO_x/La–Co–O and MoO_x/ZrO₂ catalysts to methanol/formaldehyde has been investigated in a specially designed high-pressure continuous-flow reactor. The properties of the catalysts, such as crystal phase, structure, reducibility, ion oxidation state, surface composition and the specific surface area have been characterized with the use of XRD, LRS, TPR, XPS and BET methods. MoO_x/La–Co–O catalysts showed high selectivity to methanol formation while MoO_x/ZrO₂ revealed the property for the formation of formaldehyde in the selective oxidation of methane. 7 wt MoO_x/La–Co–O catalyst gave 6.7 methanol yield (ca. 60 methanol selectivity) at 420°C and 4.2 MPa. On the other hand, the maximal yield of formaldehyde ca. 4 (47.8 formaldehyde selectivity) was obtained over 12wt MoO_x/ZrO₂ catalyst at 400 °C and 5.0MPa. 7MoO_x/La–Co–O catalyst showed higher modified H₂-consumption than 12MoO_x/ZrO₂ catalyst. The reducibility and the O^–/O^2– ratio of the catalysts may play important roles on the catalytic performance. The proper reducibility and the O^–/O^2– ratio enhanced the production of methanol in selective oxidation of methane. [MoO₄]^2– species in MoO_x/ZrO₂ catalysts enable selective oxidation of methane to formaldehyde.     

Development of a CH4 dehydroaromatization–catalyst regeneration fluidized bed system

A pilot-scale methane dehydroaromatization–H₂ regeneration fluidized bed system (MDARS) was developed. In the MDARS, the catalyst circulation between a fluidized bed reactor and a fluidized bed regenerator with the help of a catalyst feeder allowed methane dehydroaromatization (MDA) and H₂ regeneration to be carried out simultaneously, which is good for maintaining a stable MDA catalytic activity. A fixed bed reactor (FB) and a single fluidized bed reactor (SFB) were also used for a comparative study. The experimental results showed that the catalytic activity in the MDARS was more stable than that in the FB and SFB reactors. The effects of some parameters of MDARS on the CH₄ conversion and product selectivity were investigated. To verify the feasibility and reliability of the MDARS, an eight-hour long-term test was carried out, which demonstrated that the operation of the MDARS was stable and that the catalytic activity remained stable throughout the entire experimental period.     

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     

Electrodeposited Cu–ZnO and Mn–Cu–ZnO nanowire/tube catalysts for higher alcohols from syngas

Cu–ZnO and Mn–Cu–ZnO catalysts have been prepared by electrodeposition and tested for the synthesis of higher alcohols via CO hydrogenation. The catalysts were prepared in the form of nanowires and nanotubes using a nanoporous polycarbonate membrane, which served as a template for the electrodeposition of the precursor metals from an aqueous electrolyte solution. Electrodeposition was carried out using variable amounts of Zn(NO₃)₂, Cu(NO₃)₂, Mn(NO₃)₂ and NH₄NO₃ at different galvanostatic conditions. A fixed bed reactor was used to study the reaction of CO and H₂ to produce alcohols at 270 °C, 10–20 bar, H₂/CO = 2/1, and 10,000–33,000 scc/h g_cat. In addition to methane and CO₂, methanol was the main alcohol product. The addition of manganese to the Cu–ZnO catalyst increased the selectivity toward higher alcohols by reducing methane formation; however, CO₂ selectivity remained high. Maximum ethanol selectivity was 5.5%, measured as carbon efficiency.     

Effect of EDTA on hydrotreating activity of CoMo/γ-Al2O3 catalyst

γ-Al₂O₃ supported Co (0–4.5 wt%) Mo (9.0 wt%) sulfide catalysts were prepared in the presence and the absence of ethylenediaminetetraacetic acid (EDTA). The hydrodenitrogenation (HDN) activity of these catalysts was studied in the model reaction of 2,6-dimethylaniline (DMA) at 300 °C under 4 MPa. The CoMo/Al₂O₃ catalysts prepared with the EDTA showed higher HDN of DMA than those prepared without EDTA. The maximum of 36% increase in rate constant of HDN of DMA was observed over the catalyst with 3% Co prepared using EDTA. The FT-IR spectroscopy of adsorbed CO on CoMo catalysts showed that EDTA addition promoted the formation of catalytically active “CoMoS” phase as evidenced from increases in intensity of band at 2070 cm⁻¹, which is maximum for 3% Co loaded catalysts. The HDN and hydrodesulfurization (HDS) activity of 3% Co loaded catalyst prepared using EDTA was tested and compared with those catalyst prepared without EDTA in a trickle bed reactor using heavy gas oil derived from Athabasca bitumen in the temperature range 370–400 °C and 8.8 MPa. Improved HDN and HDS conversion of heavy gas oil was obtained for the catalyst prepared with EDTA.