Reaction Selectivity Improvement for Reduction of Nitrobenzene in a Packed-Bed Electrode Reactor under Periodic-Current Control

Rectangular wave current control of the electrochemical reduction of nitrobenzene im-proves the selectivity for p-aminophenol(PAP) compared to direct current(d.c.) control at thesame average current density in a flow-by packed-bed reactor.Optimal increase in PAP selectivitycan be obtained at about a frequency of 50Hz and a duty cycle of 0.2.A mathematical model isset up to incorporate the effects of mass transfer,hydrogen evolution and double layer charging,and is solved using the Duhamel’s superposition principle and the modified Crank-Nicolson methodwith the upwind scheme.The conventional d.c.control cases are also calculated for comparison.Calculations can be applied to predict the reaction results under periodic current and d.c.control,but both display the same trends compared to experimental data.

Charge transfer in plasma assisted dry reforming of methane using a nanosecond pulsed packed-bed reactor discharge

This paper is aimed to investigate the effect of packing material on plasma characteristic from the viewpoint of charge transfer process.Both the charge accumulation and release processes in the dielectric barrier discharge reactor and packed-bed reactor were investigated by measuring voltage and current waveforms and taking ICCD images.The packing material was ZrO2 pellets and the reactors were driven by a parameterized nanosecond pulse source.The quantity of transferred charges in the dielectric barrier discharge reactor was enhanced when decreasing pulse rise time or increasing pulse width(within 150 ns),but reduced when the gas gap was packed with pellets.The quantity of accumulated charges in the primary discharge was larger than the quantity of released charges in the secondary discharges in the dielectric barrier discharge reactor,but they were almost equal in the packed-bed reactor.It indicates that the discharge behavior has been changed from the view of charge transfer process once the gas gap was packed with pellets,and the ICCD images confirmed it.

Electro-enhanced adsorption of As(V)by activated carbon in three-dimensional electrode reactor

This study focused on As(V)removal by electrosorption in a self-made three-dimensional electrode reactor,in which granular activated carbon(GAC)was used as the particle electrode.Under the optimal conditions,the removal efficiency of As(V)was 84%,and its residual concentration in solution was 0.08 mg/L.From kinetic investigation,the rate determining steps of the entire process may involve more than two processes:membrane diffusion,material diffusion and physical/chemical adsorption processes.During the desorption process,As(V)can be desorbed from GAC,and the GAC was able to electro-adsorb As(V)again after desorption,which means that the electrode has good cycling performance.

Feasibility and advantage of biofilm-electrode reactor for phenol degradation

The new biofilm-electrode method was used for the phenol degradation, because of its low current requirement. The biofilm-electrode reactor consisted of immobilized degrading bacteria on Ti electrode as cathode and Ti/PbO2 electrode as anode. With the biofilmelectrode reactor in a divided electrolytic cell, the phenol degradation rate could achieve 100% at 18 h which was higher than using traditional methods, such as biological or electrochemical methods. Chemical oxygen demand （COD） removal rate of the biofilmelectrode reactor was also greater than that using biological and electrochemical method, and could reach 80% at 16 h. The results suggested that the biofilm-electrode reactor system can be used to treat wastewater with phenol.

Effects of the Electrode Materials and Its Structure on Denitrification in a Bio-electrode Reactor

Experimental results of a denitrification process which is driven and controlled by the electric current are demonstrated in this paper. Hydrogen produced from a carbon cathode by denitrifying microorganisms adhered to the cathode surface was used to reduce nitrate to nitrogen gas. The denitrification results have close relationships with materials and structures of electrodes applied. The experimental results showed that denitrification can proceed steadily and efficiently by using carbon black as anode material, and surface roughened graphite can adhere much more biomass. The estimated energy required to remove 20mg nitrate nitrogen from 1 liter water is about 1.20×10 -4 kWh.

Ozone generation enhanced by silica catalyst in packed-bed DBD reactor

In this paper,three dielectric barrier discharge(DBD)configurations,which were plain DBD with no packing,DBD with packed pure quartz fibers and DBD with packed loaded quartz fibers,were employed to investigate the effect and catalytic mechanism of catalyst materials in a packed-bed ozone generator.From the experimental results,it was clear that the DBD configuration with packed pure fibers and packed loaded fibers promotes ozone generation.For the packed-bed reactor,ozone concentration and ozone yield were enhanced by an increase of electric field in the discharge gap with the packed-bed effect.Meanwhile,the enhancement of ozone concentration and yield for the DBD reactor packed by loaded fibers with silica nanoparticles was due to the catalysis of silica nanoparticles on the fiber surface.The adsorption of silica nanoparticles on the fiber surface can prolong the retention time of active species and enhance surface reactions.

Numerical simulation of packed-bed reactor for oxidative coupling of methane

A three-dimensional geometric model of the oxidative coupling of methane （OCM） packed-bed reactor loaded with Na2WO4-Mn/SiO2 partic- ulate catalyst was set up, 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 was 80 mL/min under standard state, the ratio of CH4/O2 was 3, the temperature and pressure were 800 ℃ and 1 atm, respectively. The contour of the characteristics 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 to products （C2H6, C2H4, CO2, CO） in the reactor outlet with an error range of 4-2%. The mass fractions of CH4 and O2 decreased from 0.6 and 0.4 in the catalyst bed inlet to 0.436 and 0.142 in the outlet, where the mass fractions of C2H6, C2H4, CO and CO2 were 0.035, 0.061, 0.032 and 0.106, respectively. Due to the existence of laminar boundary layer, the contours of each component bent upwards in the vicinity of the boundary layer. This OCM reaction was volume increase reaction and the total moles of products were greater than those of reactants. The flow field in the catalyst bed maintained constant temperature and pressure. The fluid density decreased gradually from 2.28 kg/m3 in the inlet of the catalyst bed to 2.22 kg/m3 in the outlet of the catalyst bed, while the velocity increased from 0.108 m/s to 0.115 m/s.

High-Con cent rat ion Electrosynthesis of Formic Acid/Formate from CO_(2):Reactor and Electrode Design Strategies

The electrochemical CO_(2)reduction reaction(CO_(2)RR),driven by renewable energy,provides a potential carbon-neutral avenue to convert CO_(2)into valuable fuels and feedstocks.Conversion of CO_(2)into formic acid/formate is considered one of the economical and feasible methods,owing to their high energy densities,and ease of distribution and storage.The separation of formic acid/formate from the reaction mixtures accounts for the majority of the overall CO_(2)RR process cost,while the increment of product concentration can lead to the reduction of separation cost,remarkably.In this paper,we give an overview of recent strategies for highly concentrated formic acid/formate products in CO_(2)RR.CO_(2)RR is a complex process with several different products,as it has different intermediates and reaction pathways.Therefore,this review focuses on recent study strategies that can enhance targeted formic acid/formate yield,such as the all-solid-state reactor design to deliver a high concentration of products during the reduction of CO_(2)in the electrolyzer.Firstly,some novel electrolyzers are introduced as an engineering strategy to improve the concentration of the formic acid/formate and reduce the cost of downstream separations.Also,the design of planar and gas diffusion electrodes(GDEs)with the potential to deliver high-concentration formic acid/formate in CO_(2)RR is summarized.Finally,the existing technological challenges are highlighted,and further research recommendations to achieve high-concentration products in CO_(2)RR.This review can provide some inspiration for future research to further improve the product concentration and economic benefits of CO_(2)RR.

Electrochemical oxidation of aniline by a novel Ti/TiO_xH_y/Sb-SnO_2 electrode

Electrochemical oxidation of aniline in aqueous solution was investigated over a novel Ti/TiOxHy/Sb-SnO2 electrode prepared by the electrodeposition method.Scanning electron microscopy,X-ray diffraction,and electrochemical measurements were used to characterize its morphology,crystal structure,and electrochemical properties.Removal of aniline by the Ti/TiOxHy/Sb-SnO2electrode was investigated by ultraviolet-Visible spectroscopy and chemical oxygen demand（COD）analysis under different conditions,including current densities,initial concentrations of aniline,pH values,concentrations of chloride ions,and types of reactor.It was found that a higher current density,a lower initial concentration of aniline,an acidic solution,the presence of chloride ions（0.2wt%NaCl）,and a three-dimensional（3D） reactor promoted the removal efficiency of aniline.Electrochemical degradation of aniline followed pseudo-first-order kinetics.The aniline（200 mL of 100mg·L-（-1）） and COD removal efficiencies reached 100%and 73.5%,respectively,at a current density of 20 mA·cm-（-2）,pH of 7.0,and supporting electrolyte of 0.5 wt%Na2SO4 after 2 h electrolysis in a 3D reactor.These results show that aniline can be significantly removed on the Ti/TiOxHy/Sb-SnO2electrode,which provides an efficient way for elimination of aniline from aqueous solution.

Electrochemical analysis and convection-enhanced mass transfer synergistic effect of MnO_x/Ti membrane electrode for alcohol oxidation

The different electrocatalytic reactors could be constructed for the electrocatalytic oxidation of 2,2,3,3-tetrafluoro-1-propanol(TFP) with two typical MnO_x/Ti electrodes, i.e.the electrocatalytic membrane reactor(ECMR) with the Ti membrane electrode and the electrocatalytic reactor(ECR) with the traditional Ti plate electrode.For the electro-oxidation of TFP, the conversion with membrane electrode(70.1%) in the ECMR was 3.3 and 1.7 times higher than that of the membrane electrode without permeate flow(40.8%) in the ECMR and the plate electrode(21.5%) in the ECR, respectively.Obviously, the pore structure of membrane and convection-enhanced mass transfer in the ECMR dramatically improved the catalytic activity towards the electro-oxidation of TFP.The specific surface area of porous electrode was 2.22 m^2·g^(-1).The surface area of plate electrode was 2.26 cm^2(1.13 cm^2× 2).In addition, the electrochemical results showed that the mass diffusion coefficient of the MnO_x/Ti membrane electrode(1.80 × 10^(-6) cm^2·s^(-1)) could be increased to 6.87 × 10^(-6) cm^2·s^(-1) at the certain flow rate with pump, confirming the lower resistance of mass transfer due to the convection-enhanced mass transfer during the operation of the ECMR.Hence, the porous structure and convection-enhanced mass transfer would improve the electrochemical property of the membrane electrode and the catalytic performance of the ECMR,which could give guideline for the design and application of the porous electrode and electrochemical reactor.

Experimental Study on Denitrification Using Coated Electrode of Immobilized Denitrifying Bacteria

Objective To develop a coated electrode of immobilized denitrificants and to evaluate the performance of a bioelectrochemical reactor to enhance and control denitrification, Methods Denitrifying bacteria were developed by batch incubation and immobilized with polyvinyl alcohol （PVA） on the surface of activated carbon fiber （ACF） to make a coated electrode. Then the coated electrode （cathode） and graphite electrode （anode） were transferred to the reactor to reduce nitrate. Results After acclimated to the mixtrophic and autotrophic denitrification stages, the denitrifying bacteria could use hydrogen as an electron donor to reduce nitrate, When the initial nitrate concentration was 30.2 mg NO3-N/L, the denitrification efficiency was 57.3% at an applied electric current of 15 mA and a hydraulic retention time （HRT） of 12 hours. Correspondingly, the current density was 0.083 mA / cm^2. The nitrate removal rate of the reactor was 34,4 g NO3-N / m^3,d, and the surface area loading was 1.34 g NO3-N / m^2.d. Conclusion The coated electrode may keep high quantity of blomass, thus achieving a high denitrification rate. Denitrification efficiencies are related to HRT, current density, oxidation reduction potential （ORP）, dissolved oxygen （DO）, pH value, and temperature,

A Mathematic Model of Gas-diffusion Electrodes in Contact with Liquid Electrolytes

A mathematic model is developed which is applied to analyze the main factors that affect electrode performance and to account for the process of reaction and mass transfer in gas-diffusion electrodes in contact with liquid electrolytes. Electrochemical Thiele modulus φ^2 and electrochemical effectiveness factor η are introduced to elucidate the effects of diffusion on electrochemical reaction and utilization of the gas-diffusion electrode. Profile of the reactant along axial direction is discussed, dependence of electrode potential V on current density J, are predicated by means of the newly developed mathematical model.

Electrosynthesis of H_(2)O_(2)via two-electron oxygen reduction over carbon-based catalysts:From microenvironment control to electrode/reactor design

The electrochemical production of hydrogen peroxide(H_(2)O_(2))by the two-electron oxygen reduction(2e^(-)-ORR)process has the advantages of high safety,low energy consumption,and environmental friendliness.For 2e^(-)-ORR,the catalyst/electrode is the key component as it strongly affects catalytic performance and cost.Carbon materials have the advantages of high electronic conductivity,good structural stability,easy control of nanostructures,and low cost.Therefore,it has been regarded as a promising catalyst/electrode material for the electrosynthesis of H_(2)O_(2)via 2e^(-)-ORR.In addition,studies have also considered the optimization of the liquid/gas interface by tuning the electrode surface,electrolyte pH,and reactor configurations for further improving the activity and selectivity of catalysts.In this review,we provide an in-depth discussion of the recent research on the carbon-based electrocatalysts for 2e^(-)ORR,especially in terms of microenvironment tuning,catalyst/electrode interface engineering,and reactor design for achieving stable and efficient production of H_(2)O_(2).The challenges that we are still facing and the future development prospects will then be concluded,which we believe should help the future development in this field.

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.

Chlorine-free emission disposal of spent acid etchant in a three-compartment ceramic membrane reactor

Electrochemical technologies for the on-site treatment of spent acid etchant have received great attention due their ease of operation and economic benefits. On the other hand, a large amount of Cl2 is generated during the electrolysis process, which leads to potential environmental risks. In the present work, a novel threecompartment ceramic membrane flow reactor, including a cathode chamber, an anode chamber, and a gas absorption chamber was developed. The three chambers were divided by an Al2O3 ceramic membrane and a breathable hydrophobic anode diffusion electrode(ADE). The Cl2 evolution onset potential of the ADE was increased to 1.19 V from 1.05 V of the graphite felt, effectively inhibiting the chlorine evolution reaction(CER).The anode-generated Cl2 diffused into the gas absorption chamber through the ADE and was eventually consumed by the H2O2 adsorbent. Cu could be recovered without emitting chlorine due to the special structure of reactor. The current efficiency of copper precipitation and cathode reduction from Cu2+to Cu+reached 97.7%at a working current of 150 m A. These results indicated that the novel membrane reactor had high potential for application in the copper recovery industry.

新型电化学反应器降解苯酚废水的研究

以自制钛基PbO_(2)电极为阳极,以碳纤维管为阴极成功开发了一种基于电磁感应无线供电技术的微型电解池填充式电化学反应器,从电解质浓度、pH值和输入电压等等方面探究了新型电化学反应器对苯酚废水的最佳降解条件,当电解质浓度为0.012 5 mol/L,pH值为5,输入电压为8 V时进行降解100 min,苯酚降解率可达92%,处理效果最佳。与传统平板式电化学反应器相比具有明显优势。

基于三维生物膜电极的难生化有机化工废水处理研究进展

近年来,难降解有机化工污染物在自然水体中被广泛检出,对水生态环境和人体健康构成了严重威胁。生物膜电极技术因具备环境友好、去除效率高、适用范围广等优点,在难降解污染物处理领域应用前景日渐广阔。对此,介绍了三维生物膜电极(3D-BERs)反应器构建方法,阐述了三维生物膜电极对有机污染物的降解机理,分析了电化学催化氧化与电活性微生物(EAMs)的协同降解作用,从电子迁移强化角度解析了污染物强化降解机制,并概述了3D-BERs的构建方法与运行参数对反应器效率的影响。本文系统综述了3D-BERs在难生化有机化工废水处理领域中的应用与优势,提出了三维生物膜电极技术的发展前景和今后研究工作的重点方向,为难生化有机化工废水的高效处理提供新思路与技术选择。

A structured packed-bed reactor designed for exothermic hydrogenation of acetone

Fixed-bed reactors randomly packed with catalysts have many disadvantages that may adversely affect the desired chemical reaction.The increasingly used monolithic reactor,in contrast,has many operational advantages;however,for a kinetically-controlled reaction,it does not contain sufficient catalyst to sustain the reaction.To address the problems associated with both randomly packed-bed reactor and the monolithic reactor,a structured packed-bed reactor was proposed and mathematical models were built for randomly packed-bed reactor and structured packed-bed reactor.Their respective performances were compared when applied to the exothermic reaction of the isopropanol-acetone-hydrogen chemical heat pump system.The results showed that the structured packed-bed reactor performed better in terms of pressure drop and heat transfer capacity,and had a lower radial temperature gradient,indicating that this reactor had a higher effective heat conductivity.Isopropanol on the catalyst particle surfaces was more concentrated near the tube wall because a wall effect existed in the boundary layer around the particle-wall contact points.

Time-resolved characteristics of a nanosecond pulsed multi-hollow needle plate packed bed dielectric barrier discharge

In this paper,self-designed multi-hollow needle electrodes are used as a high-voltage electrode in a packed bed dielectric barrier discharge reactor to facilitate fast gas flow through the active discharge area and achieve large-volume stable discharge.The dynamic characteristics of the plasma,the generated active species,and the energy transfer mechanisms in both positive discharge(PD)and negative discharge(ND)are investigated by using fast-exposure intensified charge coupled device(ICCD)images and time-resolved optical emission spectra.The experimental results show that the discharge intensity,number of discharge channels,and discharge volume are obviously enhanced when the multi-needle electrode is replaced by a multihollow needle electrode.During a single voltage pulse period,PD mainly develops in a streamer mode,which results in a stronger discharge current,luminous intensity,and E/N compared with the diffuse mode observed in ND.In PD,as the gap between dielectric beads changes from 0 to250μm,the discharge between the dielectric bead gap changes from a partial discharge to a standing filamentary micro-discharge,which allows the plasma to leave the local area and is conducive to the propagation of surface streamers.In ND,the discharge only appears as a diffusionlike mode between the gap of dielectric beads,regardless of whether there is a discharge gap.Moreover,the generation of excited states N_(2)^(+)(B^(2)∑_(u)^(+))and N2(C^(3)Π_(u))is mainly observed in PD,which is attributed to the higher E/N in PD than that in ND.However,the generation of the OH(A^(2)∑^(+))radical in ND is higher than in PD.It is not directly dominated by E/N,but mainly by the resonant energy transfer process between metastable N_(2)(A^(3)∑_(u)^(+))and OH(X^(2)Π).Furthermore,both PD and ND demonstrate obvious energy relaxation processes of electron-to-vibration and vibration-to-vibration,and no vibration-to-rotation energy relaxation process is observed.

Dielectric barrier micro-plasma reactor with segmented outer electrode for decomposition of pure CO_(2)

Four coaxial cylinder dielectric barrier discharge micro-plasma reactors were designed for the noncatalytic decomposition of pure CO_(2) into CO and O_(2) at low temperature and ambient pressure.The influence of segmented outer electrodes on the electrical characteristics and the reaction performance was investigated.Experimental results indicated that the introduction of segmented outer electrodes can significantly promote the decomposition of CO_(2).Encouragingly,the highest conversion of 13.1% was obtained at an applied voltage of 18 kV,which was a substantial increase of 39.4% compared to the traditional device.Compared with other types of dielectric barrier discharge plasma reactors,the proposed segmented outer electrode micro-plasma reactor can give a higher CO_(2) conversion and acceptable energy efficiency.The increase in conversion can be attributed mainly to the enhanced corona discharge caused by the fringe effect at electrode edges,the increase in energy density and the increase in the number of micro-discharges.In addition,detailed electrical characterization was performed to reveal some trends in the electrical behavior of proposed reactors.