Simultaneous generation of electricity, ethylene and decomposition of nitrous oxide via protonic ceramic fuel cell membrane reactor

Ethylene,one of the most widely produced building blocks in the petrochemical industry,has received intense attention.Ethylene production,using electrochemical hydrogen pump-facilitated nonoxidative dehydrogenation of ethane(NDE)to ethylene,is an emerging and promising route,promoting the transformation of the ethylene industry from energy-intensive steam cracking process to new electrochemical membrane reactor technology.In this work,the NDE reaction is incorporated into a BaZr_(0.1)Ce_(0.7)Y_(0.1)Yb_(0.1)O_(3-δ)electrolyte-supported protonic ceramic fuel cell membrane reactor to co-generate electricity and ethylene,utilizing the Nb and Cu doped perovskite oxide Pr_(0.6)Sr_(0.4)Fe_(0.8)Nb_(0.1)Cu_(0.1)O_(3-δ)(PSFNCu)as anode catalytic layer.Due to the doping of Nb and Cu,PSFNCu was endowed with high reduction tolerance and rich oxygen vacancies,showing excellent NDE catalytic performance.The maximum power density of the assembled reactor reaches 200 mW cm^(-2)at 750℃,with high ethane conversion(44.9%)and ethylene selectivity(92.7%).Moreover,the nitrous oxide decomposition was first coupled in the protonic ceramic fuel cell membrane reactor to consume the permeated protons.As a result,the generation of electricity,ethylene and decomposition of nitrous oxide can be simultaneously obtained by a single reactor.Specifically,the maximum power density of the cell reaches 208 mW cm^(-2)at 750℃,with high ethane conversion(45.2%),ethylene selectivity(92.5%),and nitrous oxide conversion(19,0%).This multi-win technology is promising for not only the production of chemicals and energy but also greenhouse gas reduction.

PREPARATION OF PVA/CHITOSAN LIPASE MEMBRANE REACTOR AND ITS APPLICATION TO SYNTHESIS OF MONOGLYCERIDE

PVA/ Chitosan (CS) composite membrane was studied in this paper, which could be used for enzyme processing of fat and oils. The parameters such as concentration of lipase, pH, and cross-linking agent as well as metal ions, which influence the immobilization of lipase in membrane, were optimized. The immobilized lipase was 0.66 u/cm2 and the recovery of immobilized lipase activity was 24%. The membrane reactor could be used to synthesize monoglyceride (MG) with many batches.

Methane Aromatization Upgraded by Oxygen-Permeable Membrane Reactor

Recently the CAS Qingdao Institute of Bioenergy and Processes in collaboration with the Leibniz Universit?t Hannover,Forschungszentrum Jülich and Bayer AG has made attempts to carry out methane aromatization reaction in an oxygen-permeable membrane reactor to

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.

Multi-objective optimization for membrane reactor for steam methane reforming heated by molten salt

A membrane reactor for steam methane reforming heated by molten salt(MS-SMRMR)is studied based on finite time thermodynamics for decreasing carbon emissions and improving hydrogen production rate(HPR).Effects of flow directions of sweep gas and molten salt on MS-SMRMR are researched.Profiles of temperatures,HPR,and local entropy generation rates(EGRs)of MS-SMRMR are analyzed.Hybrid particle swarm optimization algorithm is utilized to obtain the minimum of specific EGR(SEGR),ratio of EGR to HPR.Multi-objective optimization about HPR maximization and EGR minimization is performed by utilizing NSGA-II.The EGR caused by the mass transfer process is the largest among all irreversible processes in the MS-SMRMR.The membrane length should be slightly shorter than the reactor length when the flow direction of sweep gas is different from that of reaction mixture.When flow directions of molten salt and sweep gas are opposite to that of reaction mixture,SEGR is the smallest.Compared with SEGR calculated by utilizing initial parameters,SEGRs after primary,twice and triple optimizations reduce by 1.2%,5.5%and 5.7%,respectively.SEGR can be further decreased by adjusting other operating parameters.Pareto front provides many optimization results,and it contains SEGR minimization.In Pareto front,an optimum decision point is obtained based on decision-making of TOPSIS,and its EGR and HPR,respectively,increase by 7.12%and13.24%,compared with those obtained by using initial parameters.The results have certain theoretical guiding significance for optimization designs of MS-SMRMR.

Total entropy generation rate minimization configuration of a membrane reactor of methanol synthesis via carbon dioxide hydrogenation

The total entropy generation rate,internal exergy loss and exergy efficiency of the membrane reactor of methanol synthesis via carbon dioxide hydrogenation are compared,and the results show that the total entropy generation rate minimization is equivalent to the internal exergy loss minimization and the exergy efficiency maximization under the fixed inlet exergy.Therefore,this paper optimizes the membrane reactor with total entropy generation rate minimization as an optimization objective under a fixed methanol production rate.The optimal temperatures curves of exterior walls for three optimal membrane reactors with different boundary conditions are obtained by using optimal control theory and nonlinear programming.The influences of other geometric and operating parameters on optimization results of optimal membrane reactors are analyzed.The results indicate that when inlet temperatures of the reaction mixture and mixture in the permeable tube are unfixed,the optimizing curve of exterior wall temperature makes the total entropy generation rate of membrane reactor reduce by 12.39%compared with the total entropy generation rate of a reference membrane reactor with a linear exterior wall temperature.Decreasing the inlet molar flow rate of sweep gas and gas hourly space velocity and increasing inlet pressure of reaction mixture,the inlet pressure of mixture in the permeable tube and heat transfer coefficients are favorable for decreasing the total entropy generation rate in the membrane reactor.As the porosity of catalyst bed and reactor length increases,the minimum total entropy generation rate decreases first and then increases.From the perspective of engineering application,this paper establishes two membrane reactors(membrane reactor heated by three-stage furnaces of the same length and membrane reactor heated by threestage furnaces of different lengths),respectively.The minimum total entropy generation rates of the two reactors are reduced by11.67%and 11.79%compared with the total entropy generation rate in the reference membrane reactor,respectively.The obtained results are beneficial to the optimal design of energy-efficient membrane reactors.

Hydroxyl radical intensified Cu2O NPs/H2O2 process in ceramic membrane reactor for degradation on DMAc wastewater from polymeric membrane manufacturer

High-concentration industrial wastewater containing N,N-dimethylacetamide(DMAc)from polymeric membrane manufacturer was degraded in Cu2O NPs/H2O2 Fenton.process.In the membrane assisted Fenton process DMAc removal rate was up to 98%with 120 min which was increased by 23%over the batch reactor.It was found that:OH quench time was extended by 20 min and the maximum:0H productivity was notably 88.7%higher at 40 min.The degradation reaction rate constant was enhanced by 2.2 times with membrane dispersion(k=0.0349 min^-1).DMAc initial concentration(C0)and H202 flux (Jp)had major influence on mass transfer and kinetics,meanwhile,membrane pore size(rp)and length(L)also affected the Treaction rate.The intensifed radical yield,fast mass transfer and nanoparticles high activity all contributed to improve pollutant degradation eficiency.Time-resolved DMAC degradation pathway was analyzed as hydroxylation,demethylation and oxidation leading to the finai products of CO2;H20 and NO3^-(rather.than NH,from biodegradation).Continuous process was operated in the dual-membrane configuration with in situ reaction and separation.After five cycling,tests,DMAc removal was all above 95%for the initial[DMAc]0=14,000 mg/L in wastewater and stability of the catalyst and the membrane maintained weil.

Cyclohexane Dehydrogenation in Solar-Driven Hydrogen Permeation Membrane Reactor for Efficient Solar Energy Conversion and Storage

Cyclohexane dehydrogenation in the solar-driven membrane reactor is a promising method of directly producing pure hydrogen and benzene from cyclohexane and storing low-grade solar energy as high-grade chemical energy.In this paper,partial pressure of gases,conversion rate of cyclohexane,and energy efficiency of the reactor are analyzed based on numerical simulation.The process of cyclohexane dehydrogenation under four temperatures(200℃,250℃,300℃,and 350℃)and four permeate pressures(0.050 MPa,0.025 MPa,0.010 MPa,and 0.001 MPa)were studied.A complete conversion rate(99.9%)of cyclohexane was obtained as the reaction equilibrium shifts forward with hydrogen separation.The first-law thermodynamic efficiency,solar-to-fuel efficiency,and exergy efficiency could reach as high as 94.69%,46.93%and 93.08%,respectively.This study indicates that it is feasible to combine solar energy supply technology with cyclohexane dehydrogenation reaction integrated with membrane reactor.

Conceptual Process and Analysis of Water-Gas-Shift Membrane Reactor

A new conceptual water-gas-shift(WGS) process is designed for integrated gasification combined cycle(IGCC), using membrane reactor(MR) equipped with H2-permselective zeolite membranes for the WGS reaction.The new process makes it possible to capture CO2 before power generation process by converting CO in the syngas to CO2 which can be collected after WGS reaction. The new process also produces purer H2 for combustion in gas turbine. Conceptual design of the MR, mass and heat balance analysis, and cost estimation of the new process are also provided in this paper.

Integration of nine steps for producing ammonia and liquid-fuel synthesis gases in one membrane reactor

Subject Code:B03With the support by the National Natural Science Foundation of China and the Chinese Academy of Sciences,the research team led by Prof.Yang Weishen(杨维慎)and Prof.Zhu Xuefeng(朱雪峰)at the State Key Laboratory of Catalysis,Dalian Institute of Physical Chemistry,Chinese Academy of Sciences,proposed a new catalytic membrane reactor for one-step producing the ammonia synthesis gas(ASG,H_2/

Different efficiency toward the biomimetic aerobic oxidation of benzyl alcohol in microchannel and bubble column reactors: Hydrodynamic characteristics and gas–liquid mass transfer

The selective aerobic oxidation of benzyl alcohol to benzaldehyde has attracted considerable attention because benzaldehyde is a high value-added product. The rate of this typical gas–liquid reaction is significantly affected by mass transfer. In this study, CoTPP-mediated(CoTPP: cobalt(II) mesotetraphenylporphyrin) selective benzyl alcohol oxidation with oxygen was conducted in a membrane microchannel(MMC) reactor and a bubble column(BC) reactor, respectively. We observed that 83% benzyl alcohol was converted within 6.5 min in the MMC reactor, but only less than 10% benzyl alcohol was converted in the BC reactor. Hydrodynamic characteristics and gas–liquid mass transfer performances were compared for the MMC and BC reactors. The MMC reactor was assumed to be a plug flow reactor,and the dimensionless variance was 0.29. Compared to the BC reactor, the gas–liquid mass transfer was intensified significantly in MMC reactor. It could be ascribed to the high gas holdup(2.9 times higher than that of BC reactor), liquid film mass transfer coefficient(8.2 times higher than that of BC reactor), and mass transfer coefficient per unit interfacial area(3.8 times higher than that of BC reactor). Moreover,the Hatta number for the MMC reactor reached up to 0.61, which was about 15 times higher than that of the BC reactor. The computational fluid dynamics calculations for mass fractions in both liquid and gas phases were consistent with the experimental data.

Catalyst-modified perovskite hollow fiber membrane for oxidative coupling of methane

The catalytic oxidative cou pling of methane(OCM)to C_(2) hydrocarbons(C_(2)H_(6) and C_(2)H_(4))represents one of the most effective ways to convert natural gas to more useful products,which can be performed effectively using La_(0.6)Sr0.4Co_(0.2)Fe_(0.8)O_(3-δ)(LSCF)perovskite hollow fiber membrane microreactor.In this work,the effects of adding a thin BaCe_(0.8)Gd_(0.2)O_(3-δ)(BCG)catalyst film onto the inner LSCF fiber surface as the OCM catalyst and a porous Ba0.5Sr_(0.5)Co_(0.8)Fe_(0.2)O_(3-δ)(BSCF)perovskite layer onto the outer LSCF surface to improve the oxygen permeation were evaluated.Between 700℃and 1000℃,methane conversion increased in the order of uncoated,BCG and BSCF-coated,and BCG-coated LSCF hollow fiber while Coselectivity and C_(2)-yield increased in the order of BCG and BSCF-coated,uncoated,and BCG-coated LSCF hollow fiber.Oxygen permeation flux at the same temperature range,on the other hand,was enhanced in the order of uncoated,BCG-coated,and BCG and BSCF-coated LSCF hollow fiber.This finding demonstrates the complex interplay between oxygen permeation and OCM performance.The BCG and BSCFcoated hollow fiber was also subjected to thermal cycles between 850℃and 900℃for up to 175 hours during which the fiber showed minor degradation in oxygen permeation fluxes and relatively stable OCM performance.

An Alternative to Flare Gas Processing:A Feasibility Study of Natural Gas to Liquid Processes

The quantities of gas released into the environment during the extraction and processing of crude oil,by flaring,constitute a vast source of mineral wealth which can be used to produce other useful products.The processes studied in this paper,as alternatives to the above problem,are the ones used in Shell Pearl Qatar project and Oryx GTL project.Both projects produce liquid fuels,mainly naphtha and diesel,in addition to more special fuel such as kerosene.This paper is a feasibility study of a project that makes use of the flare gas from the State of Texas,U.S.A.,as a feedstock to a process similar to either Shell Pearl Qatar project,or Oryx GTL project.The objective of this study is to determine the price range for crude oil over which an investment to similar projects can be profitable.An MS Excel Model was developed in order to perform calculations having as a variable the crude oil price and taking into account all the process and project’s financial data.The results of this model showed that a project similar to Shell Pearl Qatar remains profitable in crude oil price above$57.76/barrel,while a project similar to Oryx GTL remains viable for crude oil price over$31.4/bbl.In the price range$55-$60/barrel,the payout of the corresponding to Shell Pearl Qatar project will be in about 15.2 years and 3.3 years for a project similar to Oryx GTL.Finally,using the financial principles of this study we can apply them to any process in order to determine under what conditions will remain viable.

Bioreduction of nitrate in groundwater using a pilot-scale hydrogen-based membrane biofilm reactor

A long-term pilot-scale H_(2)-based membrane biofilm reactor(MBfR)was tested for removal of nitrate from actual groundwater.A key feature of this secondgeneration pilot MBfR is that it employed lower cost polyester hollow fibers and still achieved high loading rate.The steady-state maximum nitrate surface loading at which the effluent nitrate and nitrite concentrations were below the Maximum Contaminant Level(MCL)was at least 5.9 g·N·(m^(2)·d)^(–1),which corresponds to a maximum volumetric loading of at least 7.7 kg·N·(m^(3)·d)^(–1).The steady-state maximum nitrate surface area loading was higher than the highest nitrate surface loading reported in the firstgeneration MBfRs using composite fibers(2.6 g·N·(m^(2)·d)^(–1)).This work also evaluated the H_(2)-utilization efficiency in MBfR.The measured H_(2)supply rate was only slightly higher than the stoichiometric H_(2)-utilization rate.Thus,H_(2)utilization was controlled by diffusion and was close to 100%efficiency,as long as biofilm accumulated on the polyester-fiber surface and the fibers had no leaks.

Nitrifying population dynamics in a redox stratified membrane biofilm reactor(RSMBR)for treating ammonium-rich wastewater

Nitrogen removal performance and nitrifyingpopulation dynamics were investigated in a redox stratifiedmembrane biofilm reactor(RSMBR)under oxygen limitedcondition to treat ammonium-rich wastewater.When theNH_(4)^(+)-N loading rate increased from 11.1±1.0 to 37:2±3:2 gNH_(4)^(+)-N·m^(-2)·d^(-1),the nitrogen removal inthe RSMBR system increased from 18.0±9.6 mgN·d^(-1)to 128.9±61.7 mgN·d^(-1).Shortcut nitrogen removal wasachieved with nitrite accumulation of about22:3±5:3 mgNO_(2)^(-)-N·L-1.Confocal micrographsshowed the stratified distributions of nitrifiers anddenitrifiers in the membrane aerated biofilms(MABs)atday 120,i.e.,ammonia and nitrite oxidizing bacteria(AOBand NOB)were dominant in the region adjacent to themembrane,while heterotrophic bacteria propagated at thetop of the biofilm.Real-time qPCR results showed that theabundance of amoA gene was two orders of magnitudehigher than the abundance of nxrA gene in the MABs.However,the nxrA gene was always detected during theoperation time,which indicates the difficulty of completewashout of NOB in MABs.The growth of heterotrophicbacteria compromised the dominance of nitrifiers inbiofilm communities,but it enhanced the denitrificationperformance of the RSMBR system.Applying a highammonia loading together with oxygen limitation wasfound to be an effective way to start nitrite accumulation inMABs,but other approaches were needed to sustain orimprove the extent of nitritation in nitrogen conversion inMABs.

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.

Direct GHG emissions from a pilot scale MBR-process treating municipal wastewater

To evaluate direct greenhouse gas emissions from Membrane Biological Reactor(MBR),measurements of nitrous oxide(N_(2)O)and methane(CH_(4))were made at a pilot-scale MBR treating municipal wastewater Measurements were conducted during two campaigns with some changes in processes,i.e.introducing a pre-aeration tank in the second measurement,different distributions of aeration in the treatment line,not the same wastewater inflow rate,two types of ultrafiltration membrane.It was found that about 0.004% and 0.07% of the total ammonium loads were emitted as N_(2)O,CH_(4) emissions were 0.026% and 0.12% of incoming TOC(0.008% and 0.04% of incoming COD)in 2014 and 2018.The obtained N_(2)O emission values were relatively low.The study suggested that a high aeration at the beginning of the treatment line may result in significantly high emissions of both N_(2)O and CH_(4).A significant change in aeration in the membrane ultrafiltration tank did not have the same impact.The MBR process is known for high quality effluent but have been questioned due to its higher carbon footprint due to energy consumption.This study gave a reference case about direct GHG emissions from MBR process and provide information for the further evaluation of MBR processes.