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.

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.

Solar-assisted two-stage catalytic membrane reactor for coupling CO_(2) splitting with methane oxidation reaction

A two-stage catalytic membrane reactor(CMR)that couples CO_(2) splitting with methane oxidation reactions was constructed based on an oxygen-permeable perovskite asymmetric membrane.The asymmetric membrane comprises a dense SrFe_(0.9)Ta_(0.1)O_(3-σ)(SFT)separation layer and a porous Sr_(0.9)(Fe_(0.9)Ta_(0.1))_(0.9)Cu_(0.1)O_(3-σ)(SFTC)catalytic layer.In thefirst stage reactor,a CO_(2) splitting reaction(CDS:2CO_(2)→2CO+O_(2))occurs at the SFTC catalytic layer.Subsequently,the O_(2) product is selectively extracted through the SFT separation layer to the permeated side for the methane combustion reaction(MCR),which provides an extremely low oxygen partial pressure to enhance the oxygen extraction.In the second stage,a Sr_(0.9)(Fe_(0.9)Ta_(0.1))_(0.9)Ni_(0.1)O_(3-σ)(SFTN)catalyst is employed to reform the products derived from MCR.The two-stage CMR design results in a remarkable 35.4%CO_(2) conversion for CDS at 900℃.The two-stage CMR was extended to a hollowfiber configuration combining with solar irradiation.The solar-assisted two-stage CMR can operate stably for over 50 h with a high hydrogen yield of 18.1 mL min^(-1) cm^(-2).These results provide a novel strategy for reducing CO_(2) emissions,suggesting potential avenues for the design of the high-performance CMRs and catalysts based on perovskite oxides in the future.

Removal of dissolved oxygen from water using a Pd-resin based catalytic reactor

The removal of dissolved oxygen(DO)from water was studied experimentally in a Pd-resin base catalyst reactor using purified hydrogen gas as a reducing agent.The effects of various operating conditions,such as hydrogen and waterflow rates,height of the catalytic resin bed,temperature,pH value and run time,on the removal of DO,had been studied extensively.The results shows that DO could be removed by the reactor from ppm to ppb levels at ambient temperature.Increases of temperature,H2 gas rate and the height of the catalytic resin were helpful to improve the DO removal rate.The change of pH value from 4 to 12 resulted in no effect on DO removal.Reaction time was the key factor to control the DO removal efficiency.Only when the reaction time was longer than 2.3 minutes under the experimental conditions,could a very low DO level be achieved.

Reaction performance of fluidized bed catalytic reactor of Group C^(+)particles

Group C particles are often regarded as non-fluidizable but have proven to effectively fluidize with nanoparticle addition,which results in small bubbles and a high gas holdup in the dense phase during the experiments.Group C^(+)particles provide an increased surface area for gas-solid contact and improve the reaction performance,especially for gas-phase catalytic reactions.On the basis of a previous study of the ozone decomposition reaction using Group C^(+)particles,a two-phase model was used to evaluate the reactor contact efficiency,and was used to compare the partial oxidation performance of the n-butane to maleic anhydride reaction in fluidized-bed catalytic reactors of Group C^(+)and Group A particles.The reactor with Group C^(+)particles achieved a higher n-butane conversion and MAN yield compared with that using Group A particles,based on the identical catalyst quantity or on the same gas residence time.Therefore,the reactor with Group C^(+)particles can achieve the same reaction conversion and yield with fewer catalysts or a smaller reactor size,or both.Therefore,the fluidized bed catalytic reactor of Group C^(+)particles is expected to be of major significance in industrial processes,especially for gas-phase catalytic reactions.

Effect of hydrogen combustion reaction on the dehydrogenation of ethane in a fixed-bed catalytic membrane reactor

A two-dimensional non-isothermal mathematical model has been developed for the ethane dehydrogenation reaction in a fixed-bed catalytic membrane reactor. Since ethane dehydrogenation is an equilibrium reaction,removal of produced hydrogen by the membrane shifts the thermodynamic equilibrium to ethylene production.For further displacement of the dehydrogenation reaction, oxidative dehydrogenation method has been used.Since ethane dehydrogenation is an endothermic reaction, the energy produced by the oxidative dehydrogenation method is consumed by the dehydrogenation reaction. The results show that the oxidative dehydrogenation method generated a substantial improvement in the reactor performance in terms of high conversions and signi ficant energy saving. It was also established that the sweep gas velocity in the shell side of the reactor is one of the most important factors in the effectiveness of the reactor.

An efficient and innovative catalytic reactor for VOCs emission control

Efficient mixing and thermal control are important in the flow reactor for obtaining a high product yield and selectivity.Here,we report a heterogeneous chemical kinetic study of propene oxidation within a newly designed catalytic jet-stirred reactor(CJSR).To better understand the interplay between the catalytic performances and properties,the CuO thin films have been characterized and the adsorbed energies of propene on the adsorbed and lattice oxygen were calculated using density functional theory(DFT)method.Structure and morphology analyses revealed a monoclinic structure with nano-crystallite size and porous microstructure,which is responsible for holding an important quantity of adsorbed oxygen.The residence time inside the flow CJSR(1.12–7.84 s)makes it suitable for kinetic study and gives guidance for scale-up.The kinetic study revealed that using CJSR the reaction rate increases with O_2concentration that is commonly not achievable for catalytic flow tube reactor,whereas the reaction rate tends to increase slightly above 30%of O_2due to the catalyst surface saturation.Moreover,DFT calculations demonstrated that adsorbed oxygen is the most involved oxygen,and it has found that the pathway of producing propene oxide makes the reaction of C_3H_6over CuO surface more likely to proceed.Accordingly,these findings revealed that CJSR combined with theoretical calculation is suitable for kinetic study,which can pave the way to investigate the kinetic study of other exhaust gases.

Progress in catalytic membrane reactors for removing sulfur from natural gas

Increasingly high requirement driven by environmental concern leads to more rigorous standards for sulfur dosage in fuel. Natural gas desulfurization is an important unit for industrial natural gas process. Catalytic membrane reactor for sulfur compounds removal is a newly emerged and integrated membrane technology. We reviewed the current progress for desulfurization of natural gas with membrane process, and predicted that the process combined with catalytic membrane reactor and microwave irradiation for desulfurization of natural gas might be an integrated and promising unit for large scale desulfurization with high efficiency.

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.

Effect of silicon carbide-based iron catalyst on reactor optimization for non-oxidative direct conversion of methane

The conversion of methane to olefins,aromatics,and hydrogen(MTOAH)can be used to stably obtain hydrocarbons when the effect of the catalytic surface is optimized from the reaction engineering perspective.In this study,Fe/Si C catalysts were packed into a quartz tube reactor.The catalytic surfaces of Si C and the impregnated Fe species decreased the apparent activation energies(E_a)of methane consumption in the blank reactor between 965 and 1020℃.Consequently,the hydrocarbon yield increased by 2.4times at 1020℃.Based on the model reactions of ethane,ethylene,and acetylene mixed with hydrogen in the range of 500-1020℃,an excess amount of Fe in the reactor favored the C-C coupling reaction over the selective hydrogenation of acetylene;consequently,coke formation was favored over the hydrogenation reaction.The gas-phase reactions and catalyst properties were optimized to increase hydrocarbon yields while reducing coke selectivity.The 0.2Fe catalyst-packed reactor(0.26 wt%Fe)resulted in a hydrocarbon yield of 7.1%and a coke selectivity of<2%when the ratio of the void space of the postcatalyst zone to the catalyst space was adjusted to be≥2.Based on these findings,the facile approach of decoupling the reaction zone between the catalyst surface and the gas-phase reaction can provide insights into catalytic reactor design,thereby facilitating the scale-up from the laboratory to the commercial scale.

Electrifying Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ) for focalized heating in oxygen transport membranes

Industry decarbonization requires the development of highly efficient and flexible technologies relying on renewable energy resources,especially biomass and solar/wind electricity.In the case of pure oxygen production,oxygen transport membranes(OTMs)appear as an alternative technology for the cryogenic distillation of air,the industrially-established process of producing oxygen.Moreover,OTMs could provide oxygen from different sources(air,water,CO_(2),etc.),and they are more flexible in adapting to current processes,producing oxygen at 700^(-1)000℃.Furthermore,OTMs can be integrated into catalytic membrane reactors,providing new pathways for different processes.The first part of this study was focused on electrification on a traditional OTM material(Ba_(0.5)Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)),imposing different electric currents/voltages along a capillary membrane.Thanks to the emerging Joule effect,the membrane-surface temperature and the associated O_(2) permeation flux could be adjusted.Here,the OTM is electrically and locally heated and reaches 900℃on the surface,whereas the surrounding of the membrane was maintained at 650℃.The O_(2)permeation flux reached for the electrified membranes was~3.7 NmL min^(-1)cm^(-2),corresponding to the flux obtained with an OTM non-electrified at 900℃.The influence of depositing a porous Ce_(0.8)Tb_(0.2)O_(2-δ) catalytic/protective layer on the outer membrane surface revealed that lower surface temperatures(830℃)were detected at the same imposed electric power.Finally,the electrification concept was demonstrated in a catalytic membrane reactor(CMR)where the oxidative dehydrogenation of ethane(ODHE)was carried out.ODHE reaction is very sensitive to temperature,and here,we demonstrate an improvement of the ethylene yield by reaching moderate temperatures in the reaction chamber while the O_(2) injection into the reaction can be easily fine-tuned.

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.

Electrochemical Detection of Horseradish Peroxidase at Zeptomole Level

An electrochemical method for determination of horseradish peroxidase (HRP) was developed using a capillary catalytic system. HRP can be measured in several minutes with a detection limit of 4.8 x 10(-12) mol/L or 47 zmol (S/N=3).

Soft Sensor for Inputs and Parameters Using Nonlinear Singular State Observer in Chemical Processes

Chemical processes are usually nonlinear singular systems.In this study,a soft sensor using nonlinear singular state observer is established for unknown inputs and uncertain model parameters in chemical processes,which are augmented as state variables.Based on the observability of the singular system,this paper presents a simplified observability criterion under certain conditions for unknown inputs and uncertain model parameters.When the observability is satisfied,the unknown inputs and the uncertain model parameters are estimated online by the soft sensor using augmented nonlinear singular state observer.The riser reactor of fluid catalytic cracking unit is used as an example for analysis and simulation.With the catalyst circulation rate as the only unknown input without model error,one temperature sensor at the riser reactor outlet will ensure the correct estimation for the catalyst circulation rate.However,when uncertain model parameters also exist,additional temperature sensors must be used to ensure correct estimation for unknown inputs and uncertain model parameters of chemical processes.

Interlayer-confined two-dimensional manganese oxide-carbon nanotube catalytic ozonation membrane for efficient water purification

Catalytic ozonation technology has attracted copious attention in water purification owing to its favorable oxidative degradation of pollutants and mitigation of membrane fouling capacity.However,its extensive industrial application has been restricted by the low ozone utilization and limited mass transfer of the short-lived radical species.Interlayer space-confined catalysis has been theoretically proven to be a viable strategy for achieving high catalytic efficiency.Here,a two-dimensional MnO_(2)-incorporated ceramic membrane with tunable interspacing,which was obtained via the intercalation of a carbon nanotube,was designed as a catalytic ozonation membrane reactor for degrading methylene blue.Benefiting from the abundant catalytic active sites on the surface of two-dimensional MnO_(2) as well as the ultralow mass transfer resistance of fluids due to the nanolayer confinement,an excellent mineralization effect,i.e.,1.2 mg O_(3)(aq)mg^(-1) TOC removal(a total organic carbon removal rate of 71.5%),was achieved within a hydraulic retention time of 0.045 s of pollutant degradation.Further,the effects of hydraulic retention time and interlayer spacing on methylene blue removal were investigated.Moreover,the mechanism of the catalytic ozonation employing catalytic ozonation membrane was proposed based on the contribution of the Mn(III/IV)redox pair to electron transfer to generate the reactive oxygen species.This innovative twodimensional confinement catalytic ozonation membrane could act as a nanoreactor and separator to efficiently oxidize organic pollutants and enhance the control of membrane fouling during water purification.

Pushing the activity of CO2 electroreduction by system engineering

As a promising technology that may solve global environmental challenges and enable intermittent renewable energy storage as well as zero-carbon-emission energy cycling, the carbon dioxide reduction reaction has been extensively studied in the past several years. Beyond the fruitful progresses and innovations in catalysts, the system engineering-based research on the full carbon dioxide reduction reaction is urgently needed toward the industrial application. In this review, we summarize and discuss recent works on the innovations in the reactor architectures and optimizations based on system engineering in carbon dioxide reduction reaction. Some challenges and future trends in this field are further discussed, especially on the system engineering factors.