Simulation of fixed bed reactor for dimethyl ether synthesis

Dimethyl Ether (DME) is considered as one of the most promising candidates for a substitute for LPG and diesel fuel. We analyzed one-step DME synthesis from syngas in a shell and tube type fixed bed reactor with consideration of the heat and mass transfer between catalyst pellet and reactants gas and effectiveness factor of catalysts together with reactor cooling through reactor wall. Simulation results showed strong effects of pore diffusion. We compared two different arrangements of catalysts, mixture of catalyst pellets (methanol synthesis catalyst and methanol dehydration catalyst) and hybrid catalyst. Hybrid catalyst gave better performance than a mixture of pellets in terms of CO conversion and DME productivity, but more difficulties with reactor temperature control. Use of inert pellets and inter-cooling was also simulated as a means of controlling maximum reactor temperature.     

Experimental studies and modeling of a fixed bed reactor for Fischer-Tropsch synthesis using biosyngas

The aim of this work was to study the Fischer-Tropsch (FT) synthesis of a model biosyngas (33% H₂, 17% CO and 50% N₂) in a single tube fixed-bed FT reactor. The FT reactor consisted of a shell and tube with high-pressure boiling water circulating throughout the shell. A spherical unpromoted cobalt catalyst was used with the following reaction conditions: a wall temperature of 473 K, a pressure of 20 bars and a gas hour space velocity (GHSV) of 37 to 180 NmL.g_cat^− 1.h^− 1. The performance of the FT reactor was also validated by developing a 2D pseudo-homogeneous model that includes transport equations and reaction rate equations. Good agreement between the model predictions and experimental results were obtained. This developed model was extended to predict and quantify the influence of the FT kinetics as well as determine the influence of the tube diameter and the wall temperature. The predicted behaviors for CO and H₂ conversion, productivity of hydrocarbons (mainly CH₄ and C₅₊) and fluid temperature along the axis of the reactor have been analyzed.     

Gasification characteristics of combustible wastes in a 5 ton/day fixed bed gasifier

The gasification characteristics of combustible wastes were determined in a 5 ton/day fixed bed gasifier (1.2 m I.D. and 2.8m high). The fixed bed gasifier consisted of air compressor, oxygen tank, MFC, fixed bed gasifier, cyclone, heat exchanger, solid/gas separator, water fluidized bed reactor and blower. To capture soot or unburned carbon from the gasification reaction, solid/gas separator and water fluidized bed were used. The experiments with 10–50 hours of operation were carried out to determine the effects of bed temperature, solid/oxygen ratio and oxidant on the gas composition, calorific value and carbon conversion. The calorific values of the produced gas decreased with an increase of bed temperature because combustion reaction happened more actively. The gas composition of partial oxidation of woodchip is CO: 34.4%, H₂: 10.7%, CH₄: 6.0%, CO₂: 48.9% and that of RPF is CO: 33.9%, H₂: 26.1%, CH₄: 10.7%, CO₂: 29.2%. The average calorific values of produced gas were about 1,933 kcal/Nm³, 2,863 kcal/Nm³, respectively. The maximum calorific values were 3,100 kcal/Nm³ at RPF/oxygen ratio: 7     

Hydrogenation of CO2 over Fe-K based catalysts in a fixed bed reactors at elevated pressure

Catalytic hydrogenation of CO₂to produce hydrocarbons was conducted in a fixed bed reactor (1.6 cm-IDx60 cm-High). Fe-K based catalysts (KRICAT-A, B) were used for more than 850 hours to maintain CO₂ conversion level up to 30 C-mol% in the fixed bed micro-reactor. Effects of operating variables on the CO₂ conversion, hydrocarbon yield and its selectivity were investigated. The CO₂ conversion and total hydrocarbon yield increased with increasing reaction temperature (250-325 °C), pressure (0.5-2.5 MPa) and H₂/CO₂ mol ratio (2-5); however, they decreased with increasing space velocity (1,000-4,000 ml/g_cathr) in the reactor. The selectivities of liquid products increased with increasing reaction pressure; however, they decreased with increasing temperature, space velocity and H₂/CO₂ ratio. From the results of an experimental study, optimum operating conditions for the maximum yield of olefinic liquid products were found as T=315 °C, P=1.5 MPa, SV=2,000 ml/g_cathr and H₂/CO₂ ratio=3 in the fixed bed reactor within these experimental conditions. Presented at the Int’l Symp. on Chem. Eng. (Cheju, Feb. 8-10, 2001), dedicated to Prof. H. S. Chun on the occasion of his retirement from Korea University.     

Adsorption of chlorinated volatile organic compounds in a fixed bed of activated carbon

Adsorption isotherms of dichloromethane and 1,1,2-trichloro-1,2,2-trifluoroethane on an activated carbon pellet, Norit B4, were studied. For these chemicals, the Sips equation gave the best fit for the single component adsorption isotherm. The adsorption affinity on activated carbon was greater for dichloromethane than that of 1,1,2-trichloro-1,2,2-trifluoroethane. An experimental and theoretical study was made for the adsorption of dichloromethane and 1,1,2-trichloro-1,2,2-trifluoroethane in a fixed bed. Experimental results were used to examine the effect of operation variables, such as feed concentration, flow rate and bed height. Intraparticle diffusion was able to be explained by a surface diffusion mechanism. An adsorption model based on the linear driving force approximation (LDFA) was found to be applicable to fit the experimental data.     

Removal of Congo Red dye from aqueous solution using Amberlite IRA-400 in batch and fixed bed reactors

Removal of Congo Red (CR) azo dye by adsorption process using Amberlite IRA-400 resin was evaluated in both batch and fixed bed system. From the batch adsorption results, maximum loading efficiency (99.99%) of CR dye was obtained at the conditions pH 4.5, temp. 303?K, contact time 180?min., Amberlite IRA-400 dose 0.5?g. The isotherm study ascertained on favorability of adsorption process as the value of separation factor (K_L?=?0.88) and Freundlich constant (1/n?=?0.96?R²?=?0.99) than Freundlich model (R²?=?0.97). The kinetic data studied at three different CR dye concentration (50, 75, 100?mg) and results were fitted with both pseudo-first-order and second-order model equations. The values of R² obtained are of 0.95 and 0.99 for former and later one, respectively, ensuring on best fitting of pseudo-second-order kinetics and also suggesting about the chemisorptions type of adsorption. The bed depth service model was applied for competitive analysis of the CR dye adsorption in column variables indicating mass transfer from aqueous solution to Amberlite IRA-400 phase. Fourier transform infrared analysis of CR-loaded resin Amberlite IRA-400 showed a band shifted from 1057 to 1130?cm^?1 confirming CR adsorption with Amberlite IRA-400. Scanning electron microscope analysis of resin before and after adsorption was well evident from the phase patterns. Selective separation of CR dye from waste effluent of a textile industry bearing CR dye along with other trace heavy metal was achieved.     

Inorganic microballoon production from shinju-gan using an entrained bed reactor

Hollow inorganic microparticles were produced continuously from a volcanic glass (shinju-gan or per-lite) using an entrained bed reactor. The microparticles are called expanded perlite. The raw material was a sieved fraction (104 μm in volume average diameter) of crushed perlite, which is from China. The effects of temperature and residence time on expanded perlite yield were investigated.     

固定床法氢化萘合成十氢萘工艺研究

选用自制的镍铝加氢催化剂,在固定床加氢反应器中对氢化萘合成十氢萘的工艺进行了研究,确定了适宜的反应条件：反应温度180～200℃,反应压力6～8MPa,液时体积空速0．8～1．0mL/ (mL·h)。在此条件下,原料萘的转化率达96%以上,产物十氢萘的选择性达94%以上。     

Adsorption characteristics of 2,4-dichlorophenoxyacetic acid and 2,4-dinitrophenol in a fixed bed adsorber

The influence of temperature and initial pH of aqueous solution on adsorption has been discussed in detail using the Sips equation. Single-component adsorption equilibria of 2,4-D and 2,4-DNP dissolved in water have been measured for three kinds of GACs (F400, SLS103, and WWL). For 2,4-D, the magnitude of adsorption capacity was in the order of F400>SLS103>WWL, and that for 2,4-DNP was SLS103>F400>WWL. These results may come from the effects of the pore size distribution, surface area, surface properties, and difference in adsorption affinity. Kinetic parameters were measured in a batch adsorber to analyze the adsorption rates of 2,4-D and 2,4-DNP. The internal diffusion coefficients were determined by comparing the experimental concentration curves with those predicted from surface diffusion model (SDM) and pore diffusion model (PDM). The linear driving force approximation (LDFA) model was used to simulate isothermal adsorption behavior in a fixed bed adsorber and successfully simulated experimental adsorption breakthrough behavior under various operation conditions. Efficiency of desorption for 2,4-D and 2,4-DNP was about 80% using distilled water at pH of 6.     

Reactivity of a CaSO<Subscript>4</Subscript>-oxygen carrier in chemical-looping combustion of methane in a fixed bed reactor

Chemical-looping combustion (CLC) is a promising technology for the combustion of gas or solid fuel with efficient use of energy and inherent separation of CO₂. A reactivity study of CaSO₄ oxygen carrier in CLC of methane was conducted in a laboratory scale fixed bed reactor. The oxygen carrier particles were exposed in six cycles of alternating reduction methane and oxidation air. A majority of CH₄ reacted with CaSO₄ to form CO₂ and H₂O. The oxidation was incomplete, possibly due to the CaSO₄ product layer. The reactivity of CaSO₄ oxygen carrier increased for the initial cycles but slightly decreased after four cycles. The product gas yields of CO₂, CH₄, and CO with cycles were analyzed. Carbon deposition during the reduction period was confirmed with the combustible gas (CO+H₂) in the product gas and slight CO₂ formed during the early stage of oxidation. The mechanism of carbon deposition and effect was also discussed. SO₂ release behavior during reduction and oxidation was investigated, and the possible formation mechanism and mitigation method was discussed. The oxygen carrier conversion after the reduction decreased gradually in the cyclic test while it could not restore its oxygen capacity after the oxidation. The mass-based reaction rates during the reduction and oxidation also demonstrated the variation of reactivity of CaSO₄ oxygen carrier. XRD analysis illustrated the phase change of CaSO₄ oxygen carrier. CaS was the main reduction product, while a slight amount of CaO also formed in the cyclic test. ESEM analysis demonstrated the surface change of particles during the cyclic test. The reacted particles tested in the fixed bed reactor were not uniform in porosity. EDS analysis demonstrated the transfer of oxygen from CaSO₄ to fuel gas while leaving CaS as the dominant reduced product. The results show that CaSO₄ oxygen carrier may be an interesting candidate for oxygen carrier in CLC. This work was presented at the 7 ^th China-Korea Workshop on Clean Energy Technology held at Taiyuan, China, June 26–28, 2008.     

Axial gas phase dispersion in a molten salt oxidation reactor

Gas phase axial dispersion characteristics were determined in a molten salt oxidation reactor (air-molten sodium carbonate salt two phase system). The effects of the gas velocity (0.05–0.22 m/s) and molten salt bed temperature (870–970 °C) on the gas phase axial dispersion coefficient were studied. The amount of axial gas-phase dispersion was experimentally evaluated by means of residence time distribution (RTD) experiments using an inert gas tracer (CO). The experimentally determined RTD curves were interpreted by using the axial dispersions model, which proved to be a suitable means of describing the axial mixing in the gas phase. The results indicated that the axial dispersion coefficients exhibited an asymptotic value with increasing gas velocity due to the plug-flow like behavior in the higher gas velocity. Temperature had positive effects on the gas phase dispersion. The effect of the temperature on the dispersion intensity was interpreted in terms of the liquid circulation velocity using the drift-flux model.     

Modelling of a photocatalytic reactor with a fixed bed of supported catalyst

This work intends to develop a mathematical model of a fixed bed reactor and tests this model with experimental data. For this reason, we introduce some specific knowledge about light absorption from the catalyst, about the hydrodynamic interpretation of the reactor and the kinetic behaviour of photocatalytic reactions. Afterwards, we summarise this information and set up a complex mathematical model. We use this model in order to identify the kinetic constants of some reactions. We also formulate some simplified models to be used in particular circumstances and we compare the results of the complex model and the simplified models. Moreover, we compare experimental data of conversion and the results estimated with our model.     

Studies on the preparation of C/SiC composite as a catalyst support by CVI in a fluidized bed reactor

In this research, in order to improve the mechanical strength and oxidation resistance of a catalyst support, we studied the formation of SiC layer on the pore surfaces of activated carbons by permeating and depositing SiC from a reaction between hydrogen and dichlorodimethylsilane (DDS). The porous structure should be kept during deposition. A fluidized bed reactor and activated carbons of size of 20-40 mesh were used. By studying characteristics of deposits under various deposition conditions, we confirmed that the best conditions of manufacturing catalyst support are a lower pressure and a lower concentration. In this work, at the conditions of 5 torr of total pressure and 3% of DDS concentration, during the 10 hr processing time, deposition occurred on the pore walls before plugging pores. The results from the mathematical modeling were compared with the experimental results.     

Numerical analysis of fixed bed adsorption kinetics using orthogonal collocation

Fixed bed adsorption kinetics is analyzed to test the validity of the simplified model based on the linear driving force approximation by comparison with the exact model by using the orthogonal collocation method. The axial dispersion, the external film diffusion, and the intraparticle diffusion are considered to be the major mass transfer phenomena involved with the fixed bed adsorption kinetics in this study. It is assumed that a local equilibrium is attained at the fluid-solid interface and the equilibrium can be described by the Langmuir isotherm. A homogeneous particle diffusion model is employed to describe the intraparticle diffusion.     

Cooling exothermic catalytic fixed bed reactors: Co-current versus countercurrent operation in a methanol conversion reactor

A comparison between two possible designs of exothermic catalytic fixed bed reactors, fully co-current and fully countercurrent flow, was performed for the process of methanol transformation into hydrocarbons. The fully co-current operation proved more appropriate, yielding, under low parametric sensitivity, higher productivities and allowing higher inlet methanol partial pressures. The co-current design showed, in a wide range of operating conditions, the Pseudoadiabatic Regime, a useful mode of operation. The countercurrent design did not allow Pseudoadiabatic Operation and had drawbacks such as multiple steady states and reactor ignition.     

Oxidation of Benzene to Maleic Anhydride in a Fluidized Bed Reactor

In this project, the selective oxidation of benzene to maleic anhydride (MAN) was studied. Gas phase catalytic oxidation of benzene was carried out in a laboratory scale fluidized bed reactor on six different types of catalysts, which have different compositions. Effects of temperature, flow rates of benzene and air and catalyst type on the reaction selectivity were investigated at atmospheric pressure. The experiments were performed over a temperature range of 325 to 400 °C, a space‐time (W/F_A0) range from 11.28 × 10⁵ to 31.9 × 10⁵ g s mol^–1, and benzene/air mole ratio changes between 0.0109 and 0.0477. It was seen that conversion of benzene to MAN increased with increasing temperature for the catalysts supported by silica gel, aluminum oxide and titanium oxide. From the results it was found that conversion increased with increasing flow rate of air. When the comparison of the catalysts were made, it could be said that catalysts supported by silica gel showed higher MAN conversions. So it can be concluded that catalysts supported by silica gel were more suitable catalysts for benzene oxidation to MAN in a fluidized bed reactor.     

Modeling of photocatalytic oxidation of VOCs in a packed bed reactor under continuous and discontinuous illuminations

In this paper, a mathematical model is presented to describe the photocatalytic degradation of VOCs in a packed bed reactor. Here, the adsorption of VOCs on the wall of the reactor is taken into account and the diffusion of VOCs in the axial direction is neglected. First-order kinetics is used to describe the photocatalytic oxidation of VOCs. The analytical solution of the present model is obtained by traveling wave method. The solution shows that the reactor performance is totally dependent on the inlet concentration of VOCs when the time is large enough. The present model is validated through the experimental result of the photocatalytic oxidation of trichloroethylene in a packed bed and the predicted results accord well with the experimental data. The influence of flow rate and inlet concentration on the performance of the reactor is discussed in detail. High flow rate offers high reaction rate and low conversion efficiency. The different inlet conditions and different reaction patterns are also investigated. The model would be useful to estimate the rate constant and help to the design of the reactor.     

Oxidation of cyanide in a hydrocyclone reactor by chlorine dioxide

The greatest amounts of cyanide-containing wastes are produced by precious metals milling operations, the electroplating industry and coal processing or coking effluents processes. Because of high toxicity and to comply with federal and state regulations, the treatment of wastewater is required before safe discharge of cyanide wastes. In this regard, the gas-sparged hydrocyclone (GSH) has been tested as a reactor for the treatment of cyanide solutions for cyanide destruction by oxidation with the use of chlorine dioxide gas (ClO₂). The results show oxidation efficiencies of free cyanide approached 99% at all pH values in 5 min. The use of NaCl was also considered for the generation of chlorine dioxide. Excellent performance appears to offer operational and cost advantages over conventional processes.     

A two-phase compartments model for the selective oxidation of n-butane in a circulating fluidized bed reactor

A phenomenological model for the partial oxidation of n-butane to maleic anhydride (MAN) in a gas–solid riser reactor is proposed. The model captures the main transport–kinetic interactions at both the particle and reactor scale. Two different kinetic models from the literature that either include or neglect the role of solid-state diffusion of oxygen in the catalyst bulk are compared in terms of their impact on overall reactor performance. The use of computational fluid dynamics (CFD) as a means of defining a macroscopic cell-type model for describing the flow patterns in an industrial-scale gas–solids riser is also described. Predictions for the conversion of n-butane and yield of MAN are presented as a function of selected operating variables, and the impact of the variable model parameters on the predictions is briefly assessed. It is shown that the predictions are particularly sensitive to the kinetic model. The relative importance of the interactions between the chemical kinetics and the hydrodynamics is also highlighted.     

Reactive bed materials for improved biomass gasification in a circulating fluidised bed reactor

Reactive bed materials for the optimisation of the biomass gasification in a fast internally circulating fluidised bed (FICB) reactor system were tested under sulphur-free (S-free) and H₂S enriched conditions in a micro-scale fluidised bed reactor. In the experiments, the bed materials (natural olivine, (Fe_xMg_1-x)₂SiO₄, perovskite-type oxides, Ba_0.3Sr_0.7Fe_0.9Mn_0.1O_3-δ and La_0.65Sr_0.35Cr_0.5Mn_0.5O_3-δ, Gd_0.1Ce_0.9O₂ and a natural calcite, CaCO₃) were examined under realistic redox-cycling conditions to study their oxygen capacity and release, their catalytic activity towards toluene reforming as well as their mechanical and chemical stability.It was found that the synthesised materials outperform the natural materials as reactive bed materials for the FICFB process under S-free atmosphere. Gd_0.1Ce_0.9O₂ has better catalytic properties, perovskites show a higher oxygen storage capacity. However, in the presence of H₂S, the perovskite loose their oxygen capacity, while calcite can form a sulphide/sulphate cycle which allows for significant oxygen capacity. Additionally, the catalytic activity goes up. Therefore, under real conditions, the two natural materials, calcite and to a lower extent olivine, have clear advantages with respect to price, catalytic activity and oxygen capacity.