Production of single-walled carbon nanotubes from methane over Co-Mo/MgO nanocatalyst:A comparative study of fixed and fluidized bed reactors

In this study,the performances of fixed and fluidized bed reactors in the production of single-walled carbon nanotubes（SWNTs）have been investigated.In both reactors,single-walled carbon nanotubes were grown by catalytic chemical vapor decomposition（CCVD）of methane over Co-Mo/MgO nanocatalyst under two different operating conditions.The synthesized samples were characterized by TEM,TGA and Raman spectroscopy.It is found that the performance of a fluidized bed in the synthesis of carbon nanotubes is much better than that of a fixed bed.The quality of carbon nanotubes obtained from the fluidized bed was significantly higher than that from the fixed bed and the former one with the ID/IG ratio of 0.11 while the latter one with the ID/IG ratio of 0.71.Also,the yield of SWNTs in the fluidized bed was 92 wt%,while it was 78 wt%in the fixed bed.These advantages of fluidized bed reactors for the synthesis of carbon nanotubes can be attributed to more available space for the growth of carbon nanotubes and more uniform temperature and concentration profiles.

Runaway Criterion in Fixed Bed Catalytic Reactors with Radial Temperature Profile

The discrepancy between pseudo-homogeneous one-dimensional model and pseudo-homogeneous two-dimensional model is studied. It is found that there are great differences between two models. This paper compares the maximum and minimum values of the radial temperature in the hot spot in case that a single exothermic reaction is carried out, a correlation is obtained with pseudo-homogeneous one-dimensional model to describe the entire reactor behavior. A new runaway criterion, based on the occurrence of inflection in the hot spot locus, is developed for the case of pseudo-homogeneous two-dimensional model. This criterion predicts the maximum allowable temperature for safe operation and the regions of runaway, respectively. The calculated results show that, compared with the results based on pseudo-homogeneous one-dimensional model, runaway will easily occur when the radial temperature gradient has to be considered.

Oxidative coupling of methane in a fixed bed reactor over perovskite catalyst:A simulation study using experimental kinetic model

The oxidative coupling of methane （OCM） to ethylene over a perovskite titanate catalyst in a fixed bed reactor was studied experimentally and numerically. The two-dimensional steady state model accounted for separate energy equations for the gas and solid phases coupled with an experimental kinetic model. A lumped kinetic model containing four main species CH4, O2, COx （CO2, CO）, and C2 （C2H4 and C2H6） was used with a plug flow reactor model as well. The results from the model agreed with the experimental data. The model was used to analyze the influence of temperature and feed gas composition on the conversion and selectivity of the reactor performance. The analytical results indicate that the conversion decreases, whereas, C2 selectivity increases by increasing gas hourly space velocity （GHSV） and the methane conversion also decreases by increasing the methane to oxygen ratio.

Kinetic Model of Fixed Bed Reactor with Immobilized Microorganisms for Removing Low-Concentration SO_2

On the basis of the analysis of the process of treating low concentrations of sulfur dioxide （SO2） gas in a fixed bed reactor, a kinetic model is proposed for this process after taking into consideration the effects of internal diffusion, cell concentration, and production yield of microorganisms but ignoring the effect of external diffusion. The results obtained from the model simulation show that this model can indicate the influence of the process factors, Cin, η μmax, Cx, A, h, Kin, and Q, on the removal of SO2 and that the prediction of the results by this model is also satisfactory. This kinetic model can also provide some very important indications regarding the preparation of immobilized microorganisms, selection and domestication of proper species of microorganisms, as well as the design of bioreactors.

Modeling of Isobutane/Butene Alkylation Using Solid Acid Catalysts in a Fixed Bed Reactor

A dynamic mass transfer model of isobutane/butene alkylation over solid acid catalysts in a fixed bed reactor was established. In the model, a modified equation for the relationship between point activity and effective diffusion coefficient was proposed. It is found that the simulation results fit the experimental data well and the breakthrough time of the bed layer is predicted accurately. By modeling the alkylation process, the time-space distribution of butene and point activity profiles of catalysts can be obtained. Furthermore, the reasons for the deactivation of solid acid catalysts were investigated. It indicates that the main reason for the deactivation of catalysts is the site coverage near the inlet of the reactor, while it is ascribed to the steric effect in the region far away from the inlet.

Improved Generalized Predictive Control Algorithm with Offline and Online Identification and Its Application to Fixed Bed Reactor

An improved generalized predictive control algorithm is presented in thispaper by incorporating offline identification into online identification. Unlike the existinggeneralized predictive control algorithms, the proposed approach divides parameters of a predictivemodel into the time invariant and time-varying ones, which are treated respectively by offline andonline identification algorithms. Therefore, both the reliability and accuracy of the predictivemodel are improved. Two simulation examples of control of a fixed bed reactor show that this newalgorithm is not only reliable and stable in the case of uncertainties and abnormal disturbances,but also adaptable to slow time varying processes.

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

A three-dimensional geometric model was set up for the oxidative coupling of methane(OCM) fixed bed reactor loaded with Na_3PO_4-Mn/SiO_2/cordierite monolithic catalyst,and an improved Stansch kinetic model was established to calculate the OCM reactions using the computational fluid dynamics method 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 CH_4/O_2 ratio is 3 and the temperature and pressure is800 ℃ 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 values matched well with the experimental values on the conversion of CH4 and the selectivity of products(C_2H_6,C_2H_4,CO,CO_2 and H_2) in the reactor outlet with an error range of±4%.The mass fractions of CH_4 and O_2 decreased from 0.600 and 0.400 at the catalyst bed inlet to 0.445 and0.120 at the outlet,where the mass fractions of C_2H_6,C_2H_4,CO and CO_2 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).

Conversion enhancement of tubular fixed-bed reactor for Fischer-Tropsch synthesis using static mixer

Recently, Fischer-Tropsch synthesis （FTS） has become an interesting technology because of its potential role in producing biofuels via Biomass- to-Liquids （BTL） processes. In Fischer-Tropsch （FT） section, biomass-derived syngas, mainly composed of a mixture of carbon monoxide （CO） and hydrogen （H2）, is converted into various forms of hydrocarbon products over a catalyst at specified temperature and pressure. Fixed-bed reactors are typically used for these processes as conventional FT reactors. The fixed-bed or packed-bed type reactor has its drawbacks, which are heat transfer limitation, i.e. a hot spot problem involved highly exothermic characteristics of FT reaction, and mass transfer limitation due to the condensation of liquid hydrocarbon products occurred on catalyst surface. This work is initiated to develop a new chemical reactor design in which a better distribution of gaseous reactants and hydrocarbon products could be achieved, and led to higher throughput and conversion. The main goal of the research is the enhancement of a fixed-bed reactor, focusing on the application of KenicsTM static mixer insertion in the tubular packed-bed reactor. Two FTS experiments were carried out using two reactors i.e., with and without static mixer insertion within catalytic beds. The modeled syngas used was a mixed gas composed of H2/CO in 2 ： 1 molar ratio that was fed at the rate of 30 mL（STP）·min^- 1 （GHSV ≈ 136 mL·gcat^-1 ·h^-1） into the fixed Ru supported aluminum catalyst bed of weight 13.3 g. The reaction was carried out at 180 ℃ and atmospheric pressure continuously for 36 h for both experiments. Both transient and steady-state conversions （in terms of time on stream） were reported. The results revealed that the steady-state CO conversion for the case using the static mixer was approximately 3.5 times higher than that of the case without static mixer. In both cases, the values of chain growth probability of hydrocarbon products （α） for Fischer-Tropsch synthesis were 0.92 and 0.89 for the case with and without static mixer, respectively.

Scale up and stability test for oxidative coupling of methane over Na_2WO_4-Mn/SiO_2 catalyst in a 200 ml fixed-bed reactor

The study of scale up for the oxidative coupling of methane （OCM） has been carried out in a 200 ml stainless steel fixed-bed reactor over a 5wt% Na2WO4-1.9wt% Mn/SiO2 （W-Mn/SiO2） catalyst. The effects of reaction conditions were investigated in detail. The results showed that, with increasing reaction temperature, the gas-phase reaction was enhanced and a significant amount of methane was converted into COx; with the CH4/O2 molar ratio of 5, the highest C2 （ethylene and ethane） yield of 25% was achieved; the presence of steam （as diluent） had a positive effect on the C2 selectivity and yield. Under lower methane gaseous hourly space velocity （GHSV）, higher selectivity and yield of C2 were obtained as the result of the decrease of released heat energy. In 100 h reaction time, the C2 selectivity of 66%-61% and C2 yield of 24.2%-25.4% were achieved by a single pass without any significant loss in catalytic performance.

A three dimensional CFD simulation and optimization of direct DME synthesis in a fixed bed reactor

In this study, a comprehensive three-dimensional dynamic model was developed for simulating the flow behavior and catalytic coupling reactions for direct synthesis of dimethyl ether （DME） from syngas including CO2 in a fixed bed reactor at commercial scale under both adiabatic and isothermal conditions. For this purpose, a computational fluid dynamic （CFD） simulation was carried out through which the standard κ-ε model with 10% turbulence tolerations was implemented. At first, an adiabatic fixed bed reactor was simulated and the obtained results were compared with those of an equivalent commercial slurry reactor. Then the concentration and temperature profiles along the reactor were predicted. Consequently, the optimum temperature, pressure, hydrogen to carbon monoxide ratio in the feedstock and the reactor height under different operation conditions were determined. Finally, the results obtained from this three-dimensional dynamic model under appropriate industrial boundary conditions were compared with those of others available in literature to verify the model. Next, through changing the boundary conditions, the simulation was performed for an isothermal fixed bed reactor. Furthermore, it was revealed that, under isothermal conditions, the performed equilibrium simulations were done for a single phase system. Considering the simultaneous effects of temperature and pressure, the optimum operation conditions for the isothermal and adiabatic fixed bed reactors were investigated. The results of the H2＋CO conversions indicated that, under isothermal condition, higher conversion could be achieved, in compared with that under adiabatic conditions. Then, the effects of various operating parameters, including the pressure and temperature, of the reactor on the DME production were examined. Ultimately, the CFD modeling results generated in the present work showed reasonable agreement with previously obtained data available in the literature.

PARAMETRIC SENSITIVITY IN FIXED BED REACTOR WITH CO-CURRENT COOLING

This criterion is based on the occurrence of an extremum of hot spot parameters with respect to any of the input parameters of the reactor. The critical operation trajectory, the critical isoconcentration curve and the supercritical operation trajectory are defined. Applying the relationship between the hot spot of the critical operation trajectory and the inflection point of the supercritical, an approximate expression of the critical inlet conditions is derived. The computed results show that the influence of the cooling medium on the parametric sensitivity region is related to the heat capacity ratio α. And the greater α is, the more sensitive the reaction systems would be.

Liquid-phase esterification of methacrylic acid with methanol catalyzed by cation-exchange resin in a fixed bed reactor:Experimental and kinetic studies

The kinetic behavior of esterification between methacrylic acid and methanol catalyzed by NKC-9 resin was studied in a fixed bed reactor.The reaction was conducted in the temperature range of 323.15 to 368.15 K with the molar ratio of reactants from 0.8 to 1.4 under certain pressure.The measurement data were regression with the pseudo-homogeneous(P-H),Eley-Rideal(E-R),and Langmuir-Hinshelwood(L-H)heterogeneous kinetic models.Independent adsorption experiments were implemented to gain the adsorption equilibrium constants of four components.Among the above three models,the L-H model exhibited the best fitting results.The stability of NKC-9 was evaluated by long-term running with the yield of methyl methacrylate no decrease during 3000 h operation.The structure and physicochemical properties of the new and used catalyst were performed by several characterizations including thermogravimetric analysis(TG),scanning electron microscope(SEM),X-ray diffraction(XRD)and Fourier transform infrared spectroscopy(FT-IR)and so on.

Conversion of Non-a-Tocopherols to a-Tocopherol in a Fixed Bed Reactor

Since a-tocopherol has special biological and nutritional activities, it is important to convert non-a-tocopherols to a-tocopherol. This paper focuses on the effects of residence time, pressure, temperature and the mass ratio of formaldehyde to tocopherols on the content of a-tocopherol, the conversion of non-a-tocopherols, the selectivity and yield of a-tocopherol in a fixed-bed reactor. The reactor is made from φ12 (I.D.)×360mm stainless steel pipe. It is packed with a mixture of 5% Pd/C and cation exchange resin catalysts. Preliminary results indicated the suitable operation conditions are pressure 5.0 MPa, temperature 180℃, and mass ratio of formaldehyde to tocopherols 2.0. A product of more than 50% a-tocopherol content has been obtained by using 88.85% mixed tocopherols as raw material.

EXPERIMENTAL INVESTIGATION OF KINETIC AND TRANSPORT PARAMETERS IN A WALL－COOLED FIXED－BED REACTOR

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On-Line Prediction of a Fixed-Bed Reactor Using K-L Expansion and Neural Networks

An on-line prediction scheme combining the Karhunen-Love expansion and a recurrent neural network for a wall-cooled fixed-bed reactor is presented.Benzene oxidation in a pilotscale,single tube fixed-bed reactor is chosen as a working system and a pseudo-homogeneous twodimensional model is used to generate simulation data to investigate the prediction scheme presentedunder randomly changing operating conditions.The scheme consisting of the K-L expansion andneural network performs satisfactorily for on-line prediction of reaction yield and bed temperatures.

A Simulation Study of the Steam Reforming of Methaneina Fixed-Bed Reactor

In this work a one-dimensional mathematical model was developed to simulate methane conversion and hydrogen yield in a fixed-bed reactor filled with catalyst particles. For the reason that reforming reactions are sorely endothermic process, the heat is supplied to the reactor through electrical heating. The reforming reactions have been investigated from a modelling view point considering the effect of different temperatures ranging from 500℃ and 977℃ on the conversion of methane and hydrogen yield. Simulation results show that the steam reforming of methane in a fixed-bed reactor can efficiently store high temperature end thermal energy. When the operating temperature is increased to 977℃, the conversion of methane is 97.48% and the hydrogen yield is 2.2408. As a conclusion, the maximum thermochemical efficiency will be obtained under optimal operating temperature (977℃) and the steam/methane (3.86) ratio.

Kinetic Study of Methanol Dehydration to Dimethyl Ether in Catalytic Packed Bed Reactor over Resin

Dimethyl ether (DME) is considered as a significant fuel alternative with a critical manufacturing process. Only a few authors have presented the kinetic analysis of attractive and alternative catalysts to Al2O3 and/or zeolite in DME production, despite the fact that there is a large library of kinetic studies for these commercial catalysts. The purpose of this research was to contribute to this direction by conducting a catalytic test to determine kinetic parameters for methanol dehydration over sulfonic acid catalysts (resin). However, due to the relevance of the mathematical description of this process in the industry was also studied, a study of kinetics parameters and mathematical modeling of methanol dehydration in an atmospheric gas phase in a fixed bed reactor with a temperature range (90°C - 120°C) was examined. The Langmuir-Hinshelwood (L-H) model provides the best fit to experimental data, with an excellent R2 = 0.9997, and the experimental results were compared to those predicted by these models with very small deviations. The kinetic parameters were found to be in good agreement with the Arrhenius equation, with acceptable straight-line graphs. The activation energy E was computed and found to be 27.66 kJ/mole, with an average variation of 0.32 percent between the predicted and calculated results. Simple mathematical continuum models (plug flow reactor PFR) showed an acceptable agreement with the experimental data.

Palladium nanoparticles supported on amine-functionalized glass fiber mat for fixed-bed reactors on the effective removal of hexavalent chromium by catalytic reduction

Palladium nanoparticles were deposited on the amine-grafted glass fiber mat （GFM-NH2） catalyst support by a conventional impregnation process followed by the borohydride reduction in aqueous solution at room temperature to create the designed Pd/GFM-NH2 catalyst. By the use of large size glass fiber mat without nano/mesopores as the catalyst support, the internal mass transfer limitations due to the existence of nano/mesopores on the catalyst support were eliminated and the Pd/GFM-NH2 catalyst could be easily separated from treated water due to the large size of the catalyst support. Batch experiments demonstrate its good catalytic reduction performance of Cr（VI） with formic acid as the reducing agent. It also demonstrated an efficient Cr（VI） removal and stability in a lab-prepared, packed fixed-bed tube reactor for the continuous treatment of Cr（VI）-containing water. Thus, it has a good potential for the catalytic reduction of Cr（VI） in the water treatment practice.

3D CFD modeling of acetone hydrogenation in fixed bed reactor with spherical particles

Acetone hydrogenation in a fixed bed reactor packed with spherical catalyst particles was simulated to study the effects of inlet gas velocity and particle diameter on hydrogenation reaction. Computational results show that the catalyst particles in the reactor are almost isothermal, and the high isopropanol concentration appears at the lee of the particles. With the increase of inlet velocity, the outlet isopropanol mole fraction decreases, and the total pressure drop increases drastically. Small diameter catalyst particles are favorable for acetone hydrogenation, but result in large pressure drop.

Deactivation and regeneration of TS-1/SiO2 catalyst for epoxidation of propylene with hydrogen peroxide in a fixed-bed reactor

TS-1/SiO2 catalyst for the epoxidation of propylene with hydrogen peroxide in a fixed-bed reactor has been investigated. The catalyst activity decreases gradually with the online reaction time, but the selectivity of propylene epoxide is kept at about 93%. The fresh, deactivated and regenerated catalysts were characterized with X-ray diffraction, Fourier transform infrared spectro- scopy, ultra-violet-visible diffuse reflectance, Brunner- Emmett-TeUer method and thermogravimetric analysis, and the deactivated catalyst was regenerated with H2O2/ methanol solution. Compared with the fresh catalyst, both the framework structure and the content of titanium in the framework of the deactivated and regenerated TS-1/SiO2 catalysts were not changed. The major reason of the catalyst deactivation was the blockage of the channels of the catalyst by bulky organic by-products, which covered the active centers of titanium in TS-1. The deposited materials on the deactivated TS-1/SiO2 catalyst could be removed by treatment with hydrogen peroxide/methanol solution or pure methanol; the higher the treatment temperature and the higher the concentration of H2O2 in methanol, the higher the extent of the regeneration. The regeneration treatment did not influence the product selectivity in the propylene epoxidation.