Oxidative coupling of methane in a bubbling fluidized bed reactor

The oxidative coupling of methane to higher hydrocarbons (C₂₊) was studied in a bubbling fluidized bed reactor between 700°C and 820°C, and with partial pressures of methane from 40 to 70 kPa and of oxygen from 2 to 20 kPa; the total pressure was ca 100 kPa. CaO, Na₂CO₃/CaO and PbO/γ-Al₂O₃ were used as catalytic materials. C₂₊ selectivity depends markedly on temperature and oxygen partial pressure. The optimum temperature for maximizing C₂₊ selectivity varies between 720 and 800°C depending on the catalyst. Maximum C₂₊ selectivities were achieved at low oxygen and high methane partial pressures and amounted to 46% for CaO (T = 780°C; P_CH4 = 70 kPa; P_O2 = 5 kPa), 53% for Na₂CO₃/CaO (T = 760°C; P_CH4 = 60 kPa; P_O2 = 6 kPa) and 70% for PbO/γ-Al₂O₃ (T = 720°C; P_CH4 = 60 kPa; P_O2 = 5 kPa). Maximum yields were obtained at low methane-to-oxygen ratios; they amounted to 4.5% for CaO (T = 800°C; P_CH4 = 70 kPa; P_O2 = 12 kPa), 8.8% for Na₂CO₃/CaO (T = 820°C; P_CH4 = 60 kPa; P_O2 = 20 kPa) and 11.3% for PbO/γ-Al₂O₃ (T 2= 800°C; P_CH4 = 60 kPa; P_O2 = 20 kPa).     

Multi-objective optimization of simulated countercurrent moving bed chromatographic reactor for oxidative coupling of methane

A comprehensive optimization study on a simulated countercurrent moving bed chromatographic reactor (SCMCR) is reported in this article for oxidative coupling of methane (OCM) reaction. The selection of the operating parameters such as the switching time, make-up feed rate, methane to oxygen ratio in feed, length of columns and flow rates in different sections are not straightforward in an SCMCR. In most cases, conflicting requirements and constraints govern the optimal choice of the decision (operating or design) variables. An experimentally verified mathematical model was selected to optimize the performance of the SCMCR for OCM. A few multi-objective optimization problems were solved for both existing setup and at design stage. The optimization was performed using a state-of-the-art AI-based non-traditional optimization technique, non-dominated sorting genetic algorithm with jumping genes (NSGA-II-JG), which resulted in Pareto optimal solutions. It was found that the performance of the SCMCR could be improved significantly under optimal operating conditions.     

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.     

Heterogeneity analysis of gas-solid flow hydrodynamics in a pilot-scale fluidized bed reactor

Mesoscale drag model is of crucial significance for the reliability and accuracy in coarse-grid EulerianEulerian two-fluid model(TFM) simulations of gas-solid flow hydrodynamics in fluidized bed reactors.Although numerous mesoscale drag models have been reported in the literature,a systematic comparison of their prediction capability from the perspective of heterogeneity analysis is still lacking.In this study,in order to investigate the effect of several typical drag models on the hydrodynamic ...     

Gasification of coal and PET in fluidized bed reactor

Blended fuel comprising 23 wt.% polyethyleneterephthalate (PET) and 77 wt.% brown coal was gasified in an atmospheric fluidized bed gasifier of laboratory-scale. The gasification agent was composed of 10 vol.% O₂ in bulk of nitrogen. Thermal and texture analyses were carried out to determine the basic properties of the fuel components. The influence of experimental conditions, such as the fluidized bed and freeboard temperatures on major and minor gas components and tar content, as well as features of the blended fuel gasification in comparison with the single coal gasification, were studied. In the case of coal with PET gasification, only the fluidized bed temperature showed significant influence on CO, CO₂, CH₄ and H₂ content in the producer gas, whereas the effect of the freeboard temperature was insignificant. In single coal gasification both temperatures had considerable and almost the same influence. The content of minor components, such as ethane, ethylene, acetylene and benzene, was found to be more dependent on the freeboard temperature than on the fluidized bed temperature. It was observed that the higher the freeboard temperatures get, the lower is the concentration of the minor components, with the exception of acetylene. The absolute contents of almost all minor and tar components were approximately three times higher in blended fuel gasification than that in single coal gasification. Finally, partition of carbon (char) and selected metals into bottom and cyclone ash in gasification of both fuels is discussed.     

Particle growth kinetics of calcium fluoride in a fluidized bed reactor

Crystallization process in a fluidized bed reactor to remove fluoride from industrial wastewaters has been studied as a suitable alternative to the chemical precipitation in order to decrease the sludge formation as well as to recover fluoride as synthetic calcium fluoride.In the modeling, design and control of a fluidized bed reactor for water treatment it is necessary to study the particle growth kinetics. Removal of fluoride by crystallization process in a fluidized bed reactor using granular calcite as seed material has been carried out in a laboratory-scale fluidized bed reactor in order to study the particle growth kinetics for modeling, design, control and operation purposes.The main variables have been studied, including superficial velocity (SV, ), particle size of the seed material (L₀, m) and supersaturation (S). It has been developed a growth model based on the aggregation and molecular growth mechanisms. The kinetic model and parameters given by the equation fits well the experimental data for the studied range of variables.     

Numerical simulation of fixed bed reactor for oxidative coupling of methane over monolithic catalyst

A three-dimensional geometric modelwas set up for the oxidative coupling of methane (OCM) fixed bed reactor loaded with Na₃PO₄-Mn/SiO₂/cordierite monolithic catalyst, and an improved Stansch kinetic model was established to calculate the OCMreactions using the computational fluid dynamicsmethod and Fluent software. The simulation conditions were completely the same with the experimental conditions that the volume velocity of the reactant is 80 ml·min^-1 under standard state, the CH₄/O₂ ratio is 3 and the temperature and pressure is 800 ℃ and 1 atm, respectively. The contour of the characteristic parameters in the catalyst bed was analyzed, such as the species mass fractions, temperature, the heat flux on side wall surface, pressure, fluid density and velocity. The results showed that the calculated valuesmatchedwell with the experimental values on the conversion of CH₄ and the selectivity of products (C₂H₆, C₂H₄, CO,CO₂ and H₂) in the reactor outlet with an error range of ±4%. The mass fractions of CH₄ and O₂ decreased from 0.600 and 0.400 at the catalyst bed inlet to 0.445 and 0.120 at the outlet, where the mass fractions of C₂H₆, C₂H₄, CO and CO₂ were 0.0245, 0.0460, 0.0537 and 0.116, respectively. Due to the existence of laminar boundary layer, the mass fraction contours of each species bent upwards in the vicinity of the boundary layer. The volume of OCM reaction was changing with the proceeding of reaction, and the total moles of products were greater than reactants. The flow field in the catalyst bed maintained constant temperature and pressure. The fluid density decreased gradually from 2.28 kg·m^-3 at the inlet of the catalyst bed to 2.18 kg·m^-3 at the outlet of the catalyst bed, while the average velocity magnitude increased from 0.108 m·s^-1 to 0.120 m·s^-1.     

Lithium-doped sulfated-zirconia catalysts for oxidative coupling of methane to give ethylene and ethane

Li-doped sulfated-zirconia catalysts were found to be effective for oxidative coupling of methane (OCM). The catalyst performances depend on the sulfate content and calcination temperature. A maximum C₂ yield is attained over the catalysts, which contain 6 wt.% sulfate and calcined at 923–973 K, being closely related to the preparation conditions of sulfated-ZrO₂ as solid super-acids. When the performances of the Li-doped sulfated-ZrO₂ (Li/SZ) catalysts were tested at 1023 K as a function of reaction time, both the C₂ and CO_x selectivities remained constant over the range of 8 h, but the CH₄ conversion decreased from 17.5% to 11.9%. The nature of Li/SZ catalysts for the OCM was investigated by X-ray diffraction, XPS, and NH₃ and CO₂ TPD measurements. It could be postulated that the sulfated-ZrO₂ surface could play an important role in the formation of a catalytically active structure by Li-doping.     

MoO3/MgO as a catalyst in the oxidative dehydrogenation of n-butane in a two-zone fluidized bed reactor

Butadiene has been produced from butane by oxidative dehydrogenation on a MoO₃/MgO catalyst using a two-zone fluidized bed reactor (TZFBR). The effect of the main TZFBR operating variables was studied, and its performance was compared with that of conventional fluidized beds and fixed bed reactors loaded with the same catalyst. These results have been compared with those obtained on a selective V₂O₅/MgO catalyst.     

The basic study of methanol to gasoline in a pilot-scale fluidized bed reactor

A fluidized bed reactor, used for methanol to gasoline (MTG), was designed followed the theory of gas–solid two-phase flow, and the effects of some factors, such as temperature, space velocity and the regeneration process, on the performance of MTG catalyst were systematically examined. The results show that: heat and mass transfer can be effectively conducted in the fluidized bed reactor; with the reaction temperature was increased, the methanol conversion rate maintained at 100% and the yield of gasoline gradually increased, then reached its highest value of 25.22% at 410 °C, after that it began to decline; and the C₅ aromatics content increased with temperature and reached its maximum value of 49.86% at 430 °C. With the weight space velocity was increased, the yield of gasoline firstly increased and then decreased, while the C₅ aromatics content was decreased; In addition, the effect of inner-regenerated process for used catalyst is very good. Low temperature can help to generate lighter olefin polymer, the higher extent of hydrogen transfer and cracking of large molecules at middle temperature, the carbon deposition reaction and aromatization reaction of low carbon olefin occurred at higher temperature, all of these contributed the above mentioned rules. While the weight space velocity acts on the performance of catalyst mainly via influencing the contact time and the carbon deposition reaction.     

Modeling and simulation of simulated countercurrent moving bed chromatographic reactor for oxidative coupling of methane

Oxidative coupling of methane (OCM) is a reaction of industrial importance but per pass equilibrium conversion and product yield in a single reaction column is severely low. The simulated countercurrent moving bed chromatographic reactor (SCMCR) has been reported to significantly improve the methane conversion and C₂-product yield. This paper addresses the mathematical modeling of a five section SCMCR for OCM, which is particularly important for understanding the operation of this SCMCR system. In order to obtain the various process parameters, a realistic and rigorous kinetics was adopted in reactors for OCM and subsequently a kinetic model was developed which can best describe the associated kinetics of OCM in SCMCR. Adsorption isotherm parameters were then derived based on the experimental breakthrough curves acquired using single adsorption column. The proposed mathematical model demonstrated extremely good predictions of the experimental results. Finally, effects of operating parameters, such as switching time, methane/oxygen feed ratio, raffinate flow rate, eluent flow rate, etc., on the behavior of the SCMCR were studied systematically.     

Co-gasification of coal, plastic waste and wood in a bubbling fluidized bed reactor

Seven mixtures of coals, plastics and wood have been pelletized and fed into a pre-pilot scale fluidized bed gasifier in order to investigate the main aspects of the co-gasification of these materials. The main components of the obtained syngas (CO, H₂, CO₂, N₂, CH₄, C_nH_m) were measured by means of on-line analyzers and a gas cromatograph. The performance of the gasifier was evaluated on the basis of syngas composition, carbon conversion efficiency, energy content of syngas, cold gas efficiency and yield of undesired by-products (tar and soot-like particulate). The results of a first series of experimental tests showed the effect of gas fluidizing velocity and that of equivalence ratio on the main performance parameters for a specific coal-plastics mixture. A second series of tests has been carried out by changing the mixture composition keeping fixed the gas velocity and equivalence ratio. The presence of wood and coal in the mixture with plastics contributed to reduce the tar production even though it is accompanied by a lower syngas specific energy.     

The mass production of carbon nanotubes using a nano-agglomerate fluidized bed reactor: A multiscale space-time analysis

The scaled-up mass production of carbon nanotubes (CNTs) was reviewed by a multiscale analysis from the delicate catalyst control needed at the atomic level, CNT agglomerate formation at the mesoscopic scale, to the continuous mass production process on the macroscopic scale. A four level analysis that considered CNT assembly, agglomerate structure, reactor hydrodynamics and coupled processing was used. Atomic scale catalyst design concepts were used to modulate the CNT structure. On the reactor scale, the design consideration was on getting suitable CNT and catalyst agglomerates with good fluidization behavior and transport properties. A pilot plant with high yield (15 kg/h) and purity (> 99.9%) was demonstrated, which made a great stride for extensive applications of CNTs. Other nano-agglomerate structures can also be considered using the multiscale time and space analysis, which will benefit mass production and applications of nanomaterials in future.     

An Eulerian modeling approach of wood gasification in a bubbling fluidized bed reactor using char as bed material

We present an Eulerian multiphase approach for modeling the gasification of wood in fluidized beds. The kinetic theory of granular material is used to evaluate constitutive properties of the dispersed solid phase. Comprehensive models for wood pyrolysis, char gasification and homogeneous gas phase reactions are taken into account. The dispersed solid phase within the reactor is modeled as three continuous phases, i.e., one phase representing wood and two char phases with different diameters. In contrast to most other studies we investigate a fluidized bed which consists of wood and char particles without additional inert particles such as limestone or olivine. 2D simulation results for a lab-scale bubbling fluidized bed reactor are presented and compared with experimental data for product gas and tar concentrations and temperature. We investigate the influence of two different classes of parameters on product gas concentrations and temperature: (i) operating conditions such as initial bed height, wood feeding rate, and reactor throughput and (ii) model parameters like thermal boundary conditions, primary pyrolysis kinetics, and secondary pyrolysis model. Two different pyrolysis models are implemented and are compared against each other. The numerical results indicate (i) a relatively low influence of the investigated operating conditions on the main product gas components, (ii) a high sensitivity of main product gas components CO and CO₂ on the thermal boundary condition, and (iii) a very strong influence of operating conditions and model parameters on the tar content in the product gas.     

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.     

The selective oxidation of methane to ethane and ethylene in a solid oxide electrolyte reactor

A study of the selective oxidative coupling of methane (OCM) to C₂ hydrocarbons (ethane and ethylene) in a solid-state electrochemical reactor made from yttria-stabilized zirconia (YSZ) has been made. Three different catalyst–electrode systems based on silver and two trimetallic formulations of Mn modified alkali (Na and K) tungstates supported on silica were used. A comparison is made between co-fed and electrochemically-supplied oxygen. The electrochemically-supplied oxygen gave higher overall C₂ selectivities than the co-fed method under low current conditions, which was attributed to differences in local methane to oxygen ratios at the catalyst surface. The potassium tungstate supported catalyst gave the best overall C₂ selectivity (86% at 4% C₂ yield).     

Methanation in a fluidized bed reactor with high initial CO partial pressure: Part I—Experimental investigation of hydrodynamics, mass transfer effects, and carbon deposition

An extensive experimental study on the methanation reaction was carried out in a gas–solid fluidized bed reactor at 320 °C with a stoichiometric ratio of H₂/CO=3. By means of spatially resolved measurements of the axial gas species concentration and temperatures along the fluid bed the effects of different catalyst loadings, gas velocities and dilution rates were observed and analyzed. By applying this technique, it was found that most of the reaction (CO and H₂ conversion) proceeds in the first 20 mm of the bed depending on the experimental conditions. For a few cases, the temperature increases by up to 80 °C from 320 to 400 °C within the first 3 mm of the bed. By increasing the inlet volume flow only by a factor of 1.4, the temperature hotspot diminishes and isothermal behavior develops. For all experiments, a CO conversion of practically 100% was achieved. The experimental data indicate that the dense phase of the fluidized bed is probed and that mass transfer between bubble and dense phase is dominating in the upper part of the bed. It could be shown that both hydrodynamic and chemical boundary conditions influence the methanation reaction inside the fluidized bed reactor.     

Effect of louver baffles on hydrodynamics and gas mixing in a fluidized bed of FCC particles

The effect of louver baffles on the particle concentration profiles, pressure fluctuations, bed expansion, and gas mixing of a fluidized bed was investigated in a transparent 2-D column of cross-section 500×30 mm and height 6 m over a broad range of operating conditions covering both the bubbling and turbulent flow regimes. Visual observations, pressure fluctuations and steady gas tracer experiments showed that louver baffles can break bubbles, as indicted by the lower amplitudes and higher mean frequencies of differential pressure fluctuations, but they were only effective for superficial gas velocities <∼0.7 m/s for the FCC particles considered in this study. The ability of louver baffles to break bubbles reached a maximum near the onset of the turbulent flow regime. A gas cushion of low particle concentration appeared below the louver baffle, and its height increased with increasing superficial gas velocity, indicating increasing suppression of solids backmixing. Internal emulsion circulation was promoted above the louver baffle, causing an uneven distribution of gas flow. The addition of louver baffles reduced the upstream tracer gas concentrations by 80-90%, indicating a significant decrease in the backmixing fluxes of both gas and solids across the baffle layer. The tracer gas concentrations above the louver baffles increased resulting from the promoted emulsion circulation by louver baffles.     

Methanation in a fluidized bed reactor with high initial CO partial pressure: Part II— Modeling and sensitivity study

A model of a bench-scale methanation reactor was set-up by modifying the classical two-phase model approach and introducing an additional bulk flow from bubble to dense phase to consider the volume contraction of the methanation reaction. The model uses experimentally determined kinetics and hydrodynamic correlations from literature. It was satisfyingly validated by comparing the calculated gas concentration profiles with the experimental data, especially with respect to initial reaction rates and reactor exit concentrations.A sensitivity study with respect to different bubble size correlations, mass transfer rates and considering or neglecting the bulk flow (influence of volume contraction caused by the methanation reaction) was carried out. It showed that the bubble size correlation by Werther and the resulting gas concentration profiles fit the measured data better than the computed gas concentration profiles using the bubble size correlation by Rowe.Neither a variation of the mass transfer coefficient nor neglecting the bulk flow in the fluidized bed model did yield further improvement of the calculated concentration profiles.