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.

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.

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.

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.

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.

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 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.

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.

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.

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.

Biosorption characteristics of unicellular green alga Chlorella sorokiniana immobilized in loofa sponge for removal of Cr(Ⅲ)

Loofa sponge （LS） immobilized biomass of Chlorella sorokiniana （LSIBCS）, isolated from industrial wastewater, was investigated as a new biosorbent for the removal of Cr（Ⅲ） from aqueous solution. A comparison of the biosorption of Cr（Ⅲ） by LSIBCS and free biomass of C. sorokiniana （FBCS） from 10-300 mg Cr（Ⅲ）/L aqueous solutions showed an increase in uptake of 17.79% when the microalgal biomass was immobilized onto loofa sponge. Maximum biosorption capacity for LSIBCS and FBCS was found to be 69.26 and 58.80 mg Cr（Ⅲ）/g biosorbent, respectively, whereas the amount of Cr（Ⅲ） ions adsorbed onto naked LS was 4.97 mg/g. The kinetics of Cr（Ⅲ） biosorption was extremely rapid and equilibrium was established in about 15 and 20 min by LSIBCS and FBCS, respectively. The biosorption equilibrium was well defined by Langmuir adsorption isotherm model. The biosorption kinetics followed the pseudo-second order kinetic model. The biosorption was found to be pH dependent and the maximum sorption occurred at the solution pH 4.0. Desorption studies showed that 98% of the adsorbed Cr（Ⅲ） could be desorbed with 0.1 mol/L HNO3, while other desorbing agents were less effective in the order： EDTA 〉 H2SO4 〉 CH3COOH 〉 HCl. The regenerated LSIBCS retained 92.68% of the initial Cr（Ⅲ） binding capacity up to five cycles of reuse in continuous flow-fixed bed columns. The study revealed that LSIBCS could be used as an effective biosorbent for the removal of Cr（Ⅲ） from wastewater.

Modeling the oxidative coupling of methane: Heterogeneous chemistry coupled with 3D flow field simulation

The oxidative coupling of methane （OCM） over titanate perovskite catalyst has been developed by three-dimensional numerical simulations of flow field coupled with heat transfer as well as heterogeneous kinetic model. The reaction was assumed to take place both in the gas phase and on the catalytic surface. Kinetic rate constants were experimentally obtained using a ten step kinetic model. The simulation results agree quite well with the data of OCM experiments, which were used to investigate the effect of temperature on the selectivity and conversion obtained in the methane oxidative coupling process. The conversion of methane linearly increased with temperature and the selectivity of C2 was practically constant in the temperature range of 973-1073 K. The study shows that CFD tools make it possible to implement the heterogeneous kinetic model even for high exothermic reaction such as OCM.

Comprehensive study of nanostructured supports with high surface area for Fischer-Tropsch synthesis

An extensive study of Fischer-Tropsch synthesis on nanostructure supports with high surface area such as nanostructure -y-alumina, single wall carbon nanotubes （SWNTs）, and the hybrid of SWNTs/nanostructure -y-alumina has been investigated. The nanostructure γ-alumina was promoted with lanthanum to obtain better performance of catalyst and 15 wt% cobalt loading was the basis of our investigation. Fischer- Tropsch synthesis was performed in a fixed bed reactor under different reaction conditions （220-240 ℃, 15-25 bar, H2/CO ratio of 2, GHSV of 900-1400） in order to study the effects of temperature, pressure and gas hourly space velocity （GHSV） changes on hydrocarbon selec- tivity and catalyst activity. The catalysts were extensively characterized by different methods including X-ray diffraction （XRD）, scanning electron microscopy （SEM）, transmission electron microscopy （TEM）, inductively coupled plasma （ICP）, hydrogen （H2） chemisorption and temperature-programmed reduction （TPR）. The results showed that the yield of hybrid supported catalyst （55.4%） is higher than that of nanos- tructure -y-alumina supported catalyst （55.0%） and lower than that of SWNTs supported cobalt catalyst （71.0%）. The hybrid supported catalyst showed higher reduction degree and dispersion of cobalt particles. The temperature, pressure and GHSV effects on hybrid supported catalyst were studied and results showed that higher pressure favors the chain growth and temperature increase leads to the increases in methane selec- tivity and CO conversion. Higher hydrocarbon selectivity and CO conversion showed positive relationship with increasing GHSV while lower hydrocarbon selectivity diminishes.

The green fuel from carbon waste： optimization and product selectivity model studies

Increase in greenhouse gases, has made scientists to substitute alternative fuels for fossil fuels. Nowadays, converting biomass into liquid by Fischer-Tropsch synthesis is a major concern for alternative fuels （gasoline, diesel etc.）. Selectivity of Fischer-Tropsch hydrocarbon product （green fuel） is an important issue. In this study, the experimental data has been obtained from three factors; temperature, H2/CO ratio and pressure in the fixed bed micro reactor. T = 543-618 （K）, P = 3-10 （bar）, H2/CO = 1-2 and space velocity = 4500 （l/h） were the reactor conditions. The results of product modeling for methane （CH4）, ethane （C2H6）, ethylene （C2H4） and CO conversion with experimental data were compared. The effective parameters and the interaction between them were investigated in the model. H2/CO ratio and pressure and interaction between pressure and H2/CO in ethane selectivity model and CO conversion and interaction between temperature and H2/CO ratio in methane selectivity model and ethylene gave the best results. To determine the optimal conditions for light hydrocarbons, ANOVA and RSM were employed. Finally, products optimization was done and results were concluded.

Effects of temperature on pyrolysis products of oil sludge

Temperature is the determining factor of pyro-lysis,which is one of the alternative technologies for oil sludge treatment.The effects of final operating temper-ature ranging from 350 to 550uC on pyrolysis products of oil sludge were studied in an externally-heating fixed bed reactor.With an increase of temperature,the mass fraction of solid residues,liquids,and gases in the final product is 67.00%–56.00%,25.60%–32.35%,and 7.40%–11.65%,and their corresponding heat values are 34.4–13.8 MJ/kg,44.41–46.6 MJ/kg,and 23.94–48.23 MJ/Nm 3,respectively.The mass and energy tend to shift from solid to liquid and gas phase(especially to liquid phase)during the process,and the optimum temperature for oil sludge pyrolysis is 500uC.The liquid phase is mainly com-posed of alkane and alkene(C_(5)–C_(29)),and the gas phase is dominantly HC S and H 2.