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.

Simulation of biodiesel industrial production via solid base catalyst in a fixed-bed reactor

Biodiesel industrial production based on a solid base catalyst in a fixed-bed was simulated. The lab and bench scale experiments were carded out effectively, in which the kinetic model is established and it can describe the transesterification reaction well. The Antoine equation of biodiesel is regressed with the vapor-liquid data cited of literature. The non-random two liquid （NRTL） model is applied to describe the system of fatty acid methyl ester （FAME）, methanol and glycerol and parameters are obtained. The Ternary phase map is obtained from Aspen Plus via the liquid-liquid equilibrium （LLE） data. In order to describe the production in a fixed-bed performs in industrial scale after being magnified 1 000 times, the Aspen Plus simulation is employed, where two flowsheets are simulated to predict material and energy consumption. The simulation results prove that at least 350. 42 kW energy consumption can be reduced per hour to produce per ton biodiesel compared with data reported in previous references.

Carbon Dioxide Captured from Flue Gas by Modified Ca-based Sorbents in Fixed-bed Reactor at High Temperature

Four kinds of Ca-based sorbents were prepared by calcination and hydration reactions using different precursors： calcium hydroxide, calcium carbonate, calcium acetate monohydrate and calcium oxide. The CO2 absorption capacity of those sorbents was investigated in a fixed-bed reactor in the temperature range of 350-650 ℃. It was found that all of those sorbents showed higher capacity for CO2 absorption when the operating temperature higher than 450 ℃. The CaAc2-CaO sorbent showed the highest CO2 absorption capacity of 299 mg.g-1. The mor- phology of those sorbents was examined by scanning electron microscope （SEM）, and the changes of composition before and after carbonation were also determined by X-ray diffraction （XRD）. Results indicated that those sorbents have the similar chemical compositions and crystalline phases before carbonation reaction [mainly Ca（OH）2], and CaCO3 is the main component after carbonation reaction. The SEM morphology shows clearly that the sorbent pores were filled with reaction products after carbonation reaction, and became much denser than before. The N2 adsorption-desorption isotherms indicated that the CaAc2-CaO and CaCO3-CaO sorbents have higher specific surface area. lar2er oore volume and anoropriate pore size distribution than that of CaO-CaO and Ca（OH）2-CaO.

Modeling-based optimization of a fixed-bed industrial reactor for oxidative dehydrogenation of propane

An industrial scale propylene production via oxidative dehydrogenation of propane （ODHP） in multi-tubular re- actors was modeled. Multi-tubular fixed-bed reactor used for ODHP process, employing 10000 of small diameter tubes immersed in a shell through a proper coolant flows. Herein, a theory-based pseudo-homogeneous model to describe the operation of a fixed bed reactor for the ODHP to correspondence olefln over V2O5/γ-Al203 catalyst was presented. Steady state one dimensional model has been developed to identify the operation parameters and to describe the propane and oxygen conversions, gas process and coolant temperatures, as well as other pa- rameters affecting the reactor performance such as pressure. Furthermore, the applied model showed that a double-bed multitubular reactor with intermediate air injection scheme was superior to a single-bed design due to the increasing of propylene selectivity while operating under lower oxygen partial pressures resulting in propane conversion of about 37.3%. The optimized length of the reactor needed to reach 100% conversion of the oxygen was theoretically determined. For the single-bed reactor the optimized length of 11.96 m including 0.5 m of inert section at the entrance region and for the double-bed reactor design the optimized lengths of 5.72 m for the first and 7.32 m for the second reactor were calculated. Ultimately, the use of a distributed oxygen feed with limited number of injection points indicated a significant improvement on the reactor performance in terms of propane conversion and propylene selectivity. Besides, this concept could overcome the reactor run- away temperature problem and enabled operations at the wider range of conditions to obtain enhanced propyl- ene production in an industrial scale reactor.

Experimental Study and Modeling of an Adiabatic Fixed-bed Reactor for Methanol Dehydration to Dimethyl Ether

One-dimensional heterogeneous plug flow model was employed to model an adiabatic fixed-bed reactor for the catalytic dehydration of methanol to dimethyl ether.Longitudinal temperature and conversion profiles predicted by this model were compared to those experimentally measured in a bench scale reactor.The reactor was packed with 1.5mm γ-Al2O3 pellets as dehydration catalyst and operated in a temperature range of 543-603K at an atmospheric pressure.Also,the effects of weight hourly space velocity(WHSV)and temperature on methanol conversion were investigated.According to the results,the maximum conversion is obtained at 603.15K with WHSV of 72.87h-1.

Changes in char reactivity due to char-oxygen and char-steam reactions using Victorian brown coal in a fixed-bed reactor

This study was to examine the influence of reactions of char–O2and char–steam on the char reactivity evolution.A newly-designed fixed-bed reactor was used to conduct gasification experiments using Victorian brown coal at800 °C. The chars prepared from the gasification experiments were then collected and subjected to reactivity characterisation(ex-situ reactivity) using TGA(thermogravimetric analyser) in air. The results indicate that the char reactivity from TGA was generally high when the char experienced intensive gasification reactions in 0.3%O2in the fixed-bed reactor. The addition of steam into the gasification not only enhanced the char conversion significantly but also reduced the char reactivity dramatically. The curve shapes of the char reactivity with involvement of steam were very different from that with O2 gasification, implying the importance of gasifying agents to char properties.

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.

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.

Suiting Dynamic Models of Fixed-Bed Catalytic Reactors for Computer-Based Applications

This work investigated the applicability of heterogeneous and pseudo-homogeneous models to predict the dynamic behavior of a fixed-bed catalytic reactor. Some issues concerning the dynamic behavior of the system were discussed, such as the prediction of the inverse response phenomenon. The proposed models (Het- erogeneous I and II and Pseudo-homogeneous) were able to predict with qualitative similarity the main characteristics of the dynamic behavior of a fixed-bed catalytic reactor, including the inverse response. The computational time demanded for the solution of the heterogeneous models was 10 to 50% longer than in the case of the pseudo-homogeneous model, making the use of the former suitable for applications where computational time is not the major restriction (off-line applications). On the other hand, when on-line applications are required, the simplified model (Pseudo-homogeneous model) showed to be a good alternative because this model was able to predict (qualitatively) the dynamics of the reactor using a faster and easier numerical solution.

Enhanced lithium leaching from lepidolite in continuous tubular reactor using H_(2)SO_(4)+H_(2)SiF_(6) as lixiviant

An acidic mixture of sulfuric and fluosilicic acid(H_(2)SO_(4)+H_(2)SiF_(6))was employed as lixiviant to enhance leaching of lithium from lepidolite.The H_(2)SiF_(6) was obtained as a byproduct of anhydrous hydrofluoric acid production,aiming to provide HF molecules.It was found that the HF molecules were the main reaction component and played a key role in strengthening the dissolution of lepidolite.Different factors,including mass ratio of ore/H_(2)SO_(4)/H_(2)SiF_(6),concentrations of H_(2)SO_(4) and H_(2)SiF_(6),leaching temperatures(40−80℃)and time(15−75 min),were investigated.Moreover,an efficient tubular reactor was employed to improve this acid leaching system.Under the optimal conditions(ore/H_(2)SO_(4)/H_(2)SiF_(6) mass ratio of 1:0.8:1.6,80 wt.% H_(2)SO_(4),15 wt.% H_(2)SiF_(6),80℃,15 min),97.9% of Li,96.4% of K,97.6% of Rb,96.7% of Cs and 81.4% of Al(mass fraction)were leached.Additionally,a two-step thermal process was proposed to remove fluorine of leaching slurry.This acid treatment using an acidic mixture of H_(2)SO_(4) and H_(2)SiF_(6) in a continuous tubular reactor shows potential as an alternative process to extract lithium from lepidolite.

Performance of a tubular oxygen-permeable membrane reactor for partial oxidation of CH_4 in coke oven gas to syngas

A gas-tight BaCo 0.7 Fe 0.2 Nb 0.1 O 3-δ（BCFNO） tubular membrane was fabricated by hot pressure casting.And a membrane reactor with BCFNO tubular membrane and Ag-based sealant was readily constructed and applied to partial oxidation of CH4 in coke oven gas.At 875 ℃,95% of methane conversion,91% of H 2 and as high as 10 ml cm-2·min-1 of oxygen permeation flux were obtained.There was a good match in the coefficient of thermal expansion between Ag-based alloy and BCFNO membrane materials.The tubular BCFNO membrane reactor packed with Ni-based catalysts exhibited not only high activity but also good stability in hydrogen-enriched coke oven gas（COG） atmosphere.

Continuous Production of Biodiesel from Soybean Oil Using Supercritical Methanol in a Vertical Tubular Reactor：I.Phase Holdup and Distribution of Intermediate Product along the Axial Direction

Production of biodiesel with supercritical methanol is a green synthesis process.A study was carried out in a vertical tubular reactor with a length of 3700 mm and a diameter of 20 mm at 275-375°C,15 MPa,and molar ratio of methanol to soybean oil of 40︰1.The phase holdup,intermediate product,yield and axial distribution of methyl ester(ME) were investigated.Methanol and oil were mixed non-uniformly due to the formation of biodiesel and difference in their densities,even when the reaction system was in the supercritical state.From top to bottom,the phase holdup of methanol increased and that of oil decreased.As temperature increased,the concentrations of monoglyceride and diglyceride decreased gradually and the ME yield increased.When the temperature reached 300°C,the critical temperature of the system,the ME yield was 50%.Further increase in temperature led to a sharp in-crease of ME yield.However,at 375°C after 1200 s of reaction time,the decomposition rate of ME was greater than its formation rate,reducing the ME yield.

Modeling and Optimization of Ethane Steam Cracking Process in An Industrial Tubular Reactor with Improved Reaction Scheme

Ethane steam cracking process in an industrial reactor was investigated.An one-demsional(1D)steady-state model was developed firstly by using an improved molecular reaction scheme and was then simulated in Aspen Plus.A comparison of model results with industrial data and previously reported results showed that the model can predict the process kinetics more accurately.In addition,the validated model was used to study the effects of different process variables,including coil outlet temperature(COT),steam-to-ethane ratio and residence time on ethane conversion,ethylene selectivity,products yields,and coking rate.Finally,steady-state optimization was conducted to the operation of industrial reactor.The COT and steam-to-ethane ratio were taken as decision variables to maximize the annual operational profit.

Synthesis of Biodiesel Using ZrO_2 Polycrystalline Ceramic Foam Catalyst in a Tubular Reactor

With the help of the ceramic foam research efforts and preparation techniques, the ZrO2 polycrystalline ceramic foam catalyst was synthesized, and its characteristics, including the crystal structure, the phase composition, the acid–base properties, and the microstructure, were analyzed by XRD, SEM, Py-IR, and BET techniques. The performance of the ZrO2 polycrystalline ceramic foam catalyst in a tubular reactor was investigated via biodiesel synthesis using S. wilsoniana oil and methanol. The effects of reaction conditions(i.e., reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil) on transesterification efficiency were investigated, and the reaction conditions were optimized using RSM. The optimum reaction temperature, reaction pressure, and volume ratio of methanol to S. wilsoniana oil were determined to be 290 ℃, 10 MPa, and 4:1, respectively. Under this condition, the FAME content in the product oil reached 98.38%. The performance of the ZrO2 polycrystalline ceramic foam catalyst synthesized in this work for biodiesel synthesis from S. wilsoniana oil with a moisture content of 7.1% and an acid value of 130.697 mg KOH/g was examined, and the FAME content in the product oil was found to be 93% and 97.67%, respectively. The FAME content in the product oil exceeded 97% after five consecutive cycles(12 h per cycle of use) of the catalyst. The proposed catalyst represents a new type of solid catalyst with excellent acid resistance, water resistance, esterification efficiency, and catalytic stability.

Computational simulation of fluid dynamics in a tubular stirred reactor

The flow and concentration fields in a new style tubular stirred reactor were simulated by simulating the fluids dynamics(CFD),in which FLUENT software was used and the standard k-ε model and multiple reference frame(MRF) were adopted. The various values of initial rotating speed and inlet flow rate were adopted. Simulations were validated with experimental residence time distribution(RTD) determination. It is shown that the fluid flow is very turbulent and the flow pattern approaches to the plug flow. The velocity increases from shaft to the end of impeller,and the gradient is enlarged by increasing the rotating speed. Comparison between RTD curves shows that agitation can improve the performance of reactor. As the flow rate increases,the mean residence time decreases proportionally,and the variance of RTD lessens as well. When rotating speed increases to a certain value,the variance of RTD is enlarged by increasing rotating speed,but the mean residence time has no obvious change.

Computational Modelling of the Hydride Generation Reaction in a Tubular Reactor and Atomization in a Quartz Cell Atomizer

In this study, we present a model whereby the centre of the atomization channel is shown to be the optimal location for the spectrometric data acquisition in a quartz cell atomizer. The study aims to explore the hydride generation technique which is normally coupled with efficient thermal source to apply determination of heavy metals in water samples via spectrometric analysis. The arsenic hydride generation process and the atomization of the generated hydride in a quartz cell atomizer were studied analytically as model case studies. The hydride generation (HG) process was analyzed by adopting two hypotheses, the nascent hydrogen and formation of intermediate hydroboron species, where the results based on the second hypothesis are found to be more realistic for design purposes. Moreover, the release of the generated hydride from the liquid phase and their transport to the gas phase is simulated in a helical tubular section, in which the actual tubular section length required for separation is deduced. The analytical results have been verified experimentally by measuring the signal intensity for the free arsenic atoms against several reaction tube lengths, in which increasing the tubular section length from 12 cm to 100 cm results in signal amelioration by no more than 6.6%. Furthermore, the atomization of the hydride and the distribution of the generated free atoms are deduced in two configurations of tubular quartz atomizers. The results obtained from both studied cases illustrate that a high concentration of the free analyte atoms is generated in the first part of the atomization channel, saturates to a maximum in a position at the atomizer centre, and dissipates at the inside wall of the tubular atomizer before reaching the atomizer outlet edge, which is found to be in total agreement with the current understanding of atomization mechanism in tubular atomizer and emphasizes the fact that the centre of the quartz cell atomizer is the best location for the spectrometric data acquisition.

Modeling and experimental studies of methyl methacrylate polymerization in a tubular reactor

In this study, rheological examination of the mixture of a tubular reactor in which methyl methacrylate was polymerized has been studied. The n(flow behavior index) value of Power Law Model of mixture contained in the reactor has been determined within the span of 0.3492 to 0.9889 by curve fitting. Employing these numerical data for velocity profile, the reactor has been modeled. Moreover, the functions of the reactor have been compared in the three modes of plug, mixed and laminar flow. The results obtained in this research indicate that the polymethyl methacrylate mixture contained in the reactor is pseudo-plastic. Moreover, as the conversion grows, the velocity profile starts as a parabolic profile and approaches the plug mode; although it never reaches the plug. The other conclusions borne in this study indicate that when the reactor's radius is decreased, the conversion rate grows. However, as decreasing the radius would also reduce the productions rate, this procedure is not economical. Finally, in this modeling, the amount of conversion is equal to 56.47% at the end and according to its laboratory proportion which is 55.88%, it has reached the conclusion that the modeling duly undertaken is applicable and valid.

STUDY ON THE PERFORMANCE OF VERTICAL TUBULAR LEACHING REACTOR

Hydrodynamics in vertical tubular leaching reactor was studied in this work. Based on the observation of particle saltation in curved and square return bends, the inclined return bend was developed and examined. For the narrow and wide size distribution particle system, the method for calculating the particle holdup in upflow and downflow tubes was derived on the basis of generalized fluidization equation. The model of unit pressure drop was given and examined by experiments.

VLDPE Synthesis by Radical Ethylene Polymerization in Tubular Reactors–Negative Factor or Unrealized Opportunities

This paper presents the results of polymeric deposit analysis in HP recycling system on two ethylene polymerization trains in tubular reactors when using mixed initiation (organic peroxides and oxygen) in the process of various grade production. It is demonstrated that polymers belong to the very low density type (with ρ in 0,860 to 0,900 g/cm3 range), due to ultra high branching. Consideration is given to known processes of that kind polymer production. There discussed the alternatives of different approaches to special process features found. It is stated that 80-year high pressure PE synthesis history has been keeping potential for the development.