Mass Transfer-Promoted Fe^(2+)/Fe^(3+)Circulation Steered by 3D Flow-Through Co-Catalyst System Toward Sustainable Advanced Oxidation Processes

Realizing fast and continuous generation of reactive oxygen species(ROSs)via iron-based advanced oxidation processes(AOPs)is significant in the environmental and biological fields.However,current AOPs assisted by co-catalysts still suffer from the poor mass/electron transfer and non-durable promotion effect,giving rise to the sluggish Fe^(2+)/Fe^(3+)cycle and low dynamic concentration of Fe^(2+)for ROS production.Herein,we present a three-dimensional(3D)macroscale co-catalyst functionalized with molybdenum disulfide(MoS_(2))to achieve ultra-efficient Fe^(2+)regeneration(equilibrium Fe^(2+)ratio of 82.4%)and remarkable stability(more than 20 cycles)via a circulating flow-through process.Unlike the conventional batch-type reactor,experiments and computational fluid dynamics simulations demonstrate that the optimal utilization of the 3D active area under the flow-through mode,initiated by the convectionenhanced mass/charge transfer for Fe^(2+)reduction and then strengthened by MoS_(2)-induced flow rotation for sufficient reactant mixing,is crucial for oxidant activation and subsequent ROS generation.Strikingly,the flow-through co-catalytic system with superwetting capabilities can even tackle the intricate oily wastewater stabilized by different surfactants without the loss of pollutant degradation efficiency.Our findings highlight an innovative co-catalyst system design to expand the applicability of AOPs based technology,especially in large-scale complex wastewater treatment.

UV-Based Advanced Oxidation Processes for Antibiotic Resistance Control: Efficiency, Influencing Factors, and Energy Consumption

Antibiotic resistant bacteria(ARB)with antibiotic resistance genes(ARGs)can reduce or eliminate the effectiveness of antibiotics and thus threaten human health.The United Nations Environment Programme considers antibiotic resistance the first of six emerging issues of concern.Advanced oxidation processes(AOPs)that combine ultraviolet(UV)irradiation and chemical oxidation(primarily chlorine,hydrogen peroxide,and persulfate)have attracted increasing interest as advanced water and wastewater treatment technologies.These integrated technologies have been reported to significantly elevate the efficiencies of ARB inactivation and ARG degradation compared with direct UV irradiation or chemical oxidation alone due to the generation of multiple reactive species.In this study,the performance and underlying mechanisms of UV/chlorine,UV/hydrogen peroxide,and UV/persulfate processes for controlling ARB and ARGs were reviewed based on recent studies.Factors affecting the process-specific efficiency in controlling ARB and ARGs were discussed,including biotic factors,oxidant dose,UV fluence,pH,and water matrix properties.In addition,the cost-effectiveness of the UV-based AOPs was evaluated using the concept of electrical energy per order.The UV/chlorine process exhibited a higher efficiency with lower energy consumption than other UV-based AOPs in the wastewater matrix,indicating its potential for ARB inactivation and ARG degradation in wastewater treatment.Further studies are required to address the trade-off between toxic byproduct formation and the energy efficiency of the UV/chlorine process in real wastewater to facilitate its optimization and application in the control of ARB and ARGs.

Mechanism of microarc oxidation on AZ91D Mg alloy induced byβ-Mg_(17)Al_(12) phase

This work proposed a strategy of indirectly inducing uniform microarc discharge by controlling the content and distribution ofβ-Mg_(17)Al_(12)phase in AZ91D Mg alloy.Two kinds of nano-particles(ZrO_(2)and TiO_(2))were designed to be added into the substrate of Mg alloy by friction stir processing(FSP).Then,Mg alloy sample designed with different precipitated morphology ofβ-Mg_(17)Al_(12)phase was treated by microarc oxidation(MAO)in Na_(3)PO_(4)/Na2SiO3electrolyte.The characteristics and performance of the MAO coating was analyzed using scanning electron microscopy(SEM),energy dispersive spectrometer(EDS),X-ray diffraction(XRD),X-ray photoelectron spectroscopy(XPS),contact angle meter,and potentiodynamic polarization.It was found that the coarseα-Mg grains in extruded AZ91D Mg alloy were refined by FSP,and theβ-Mg_(17)Al_(12)phase with reticular structure was broken and dispersed.The nano-ZrO_(2)particles were pinned at the grain boundary by FSP,which refined theα-Mg grain and promoted the precipitation ofβ-Mg_(17)Al_(12)phase in grains.It effectively inhibited the“cascade”phenomenon of microarcs,which induced the uniform distribution of discharge pores.The MAO coating on Zr-FSP sample had good wettability and corrosion resistance.However,TiO_(2)particles were hardly detected in the coating on TiFSP sample.

Treatment of Domestic Sewage by Two-Stage-Bio-Contact Oxidation Process

Effects of hydraulic retention time (HRT ) and gas volume on efficiency of wastewater treatment are dis- cussed based on a simulation experiment in which the domestic swage was treated by the two-stage-bio-contact oxida- tion process. The result shows that the average CODCr, BOD5 , suspended solid (SS), and ammonia-nitrogen removal rate are 94.5 %, 93.2 %, 91.7 % and 46.9 %, respectively, under the conditions of a total air/water ratio of 5∶1 , an air/water ratio of 3:1 for oxidation tank 1 and 2:1for oxidation tank 2and a hydraulic retention time of 1 h for each stage. This method is suitable for domestic sewage treatment of residential community and small towns as well.

Microstructure and high temperature oxidation resistance of Si-Y co-deposition coatings prepared on TiAl alloy by pack cementation process

In order to improve the high temperature oxidation resistance of TiAl alloy, Y modified silicide coatings were prepared by pack cementation process at 1030, 1080 and 1130 °C, respectively, for 5 h. The microstructures, phase constitutions and oxidation behavior of these coatings were studied. The results show that the coating prepared by co-depositing Si?Y at 1080 °C for 5 h has a multiple layer structure: a superficial zone consisting of Al-rich (Ti,Nb)5Si4 and (Ti,Nb)5Si3, an out layer consisting of (Ti,Nb)Si2, a middle layer consisting of (Ti,Nb)5Si4 and (Ti,Nb)5Si3, and aγ-TiAl inner layer. Co-deposition temperature imposes strong influences on the coating structure. The coating prepared by Si?Y co-depositing at 1080 °C for 5 h shows relatively good oxidation resistance at 1000 °C in air, and the oxidation rate constant of the coating is about two orders of magnitude lower than that of the bare TiAl alloy.

Effects of vacuum pre-oxidation process on thermally-grown oxides layer of CoCrAlY high temperature corrosion resistance coating

The influence of the certain specific vacuum pre-oxidation process on the phase transformation of thermally-grown oxides（TGO） was studied.The CoCrAlY high temperature corrosion resistance coatings were produced onto the nickel-based superalloy substrate by high velocity oxygen fuel（HVOF）.It suggests that the TGO usually consists of a great number of chromium oxides,cobalt oxides and spinel oxides besides alumina during the initial period of the high temperature oxidation if the specimens are not subjected to the appropriate vacuum pre-oxidation process.Furthermore,the amount of alumina is strongly dependent on the partial pressure of oxygen;while the CoCr2O4 spinel oxides are usually formed under the conditions of higher partial pressure of oxygen during the initial period and the lower partial pressure of oxygen during the subsequent period of the isothermal oxidation.After the appropriate vacuum pre-oxidation process,the TGO is mainly composed of alumina that contains lower Y element,while alumina that contains higher Y element sporadically distributes,and the spinel oxides cannot be found.After a longer period of the isothermal oxidation,a small amount of porous CoCr2O4 and the chrome oxide sporadically distribute near the continuous alumina.Additionally,after the appropriate vacuum pre-oxidation process,the TGO growth rate is relatively slow.

Effects of Co_3O_4 nanocatalyst morphology on CO oxidation:Synthesis process map and catalytic activity

This study focuses on drawing a hydrothermal synthesis process map for Co3O4 nanoparticles with various morphologies and investigating the effects of Co3O4 nanocatalyst morphology on CO oxidation.A series of cobalt-hydroxide-carbonate nanoparticles with various morphologies（i.e.,nanorods,nanosheets,and nanocubes） were successfully synthesized,and Co3O4 nanoparticles were obtained by thermal decomposition of the cobalt-hydroxide-carbonate precursors.The results suggest that the cobalt source is a key factor for controlling the morphology of cobalt-hydroxide-carbonate at relatively low hydrothermal temperatures（≤ 140℃）.Nanorods can be synthesized in CoCl2 solution,while Co（NO3）2 solution promotes the formation of nanosheets.Further increasing the synthesis temperature（higher than 140 ℃） results in the formation of nanocubes in either Co（NO3）2 or CoCl2 solution.The reaction time only affects the size of the obtained nanoparticles.The presence of CTAB could improve the uniformity and dispersion of particles.Co3O4 nanosheets showed much higher catalytic activity for CO oxidation than nanorods and nanocubes because it has more abundant Co^（3＋） on the surface,much higher reducibility,and better oxygen desorption capacity.

Oxidation kinetics of oxide film on bubble surface of aluminum foams produced by gas injection foaming process

In the range of 620？710 °C, air was blown into A356 aluminum alloy melt to produce aluminum foams. In order to study the influence of temperature on the thickness of oxide film on bubble surface, Auger electron spectroscopy （AES） was used. Based on the knowledge of corrosion science and hydrodynamics, two oxidation kinetics models of oxide film on bubble surface were established. The thicknesses of oxide films produced at different temperatures were predicted through those two models. Furthermore, the theoretical values were compared with the experimental values. The results indicate that in the range of 620？710 °C, the theoretical values of the thickness of oxide film predicted by the model including the rising process are higher than the experimental values. While, the theoretical values predicted by the model without the rising process are in good agreement with the experimental values, which shows this model objectively describes the oxidation process of oxide film on bubble surface. This work suggests that the oxidation kinetics of oxide film on bubble surface of aluminum foams produced by gas injection foaming process follows the Arrhenius equation.

Application of advanced oxidation processes for removing salicylic acid from synthetic wastewaters

In this study,advanced oxidation processes(AOPs) such as anodic oxidation(AO),UV/H_2O_2 and Fenton processes(FP) were investigated for the degradation of salicylic acid(SA) in lab-scale experiments.Boron-doped diamond(BDD) film electrodes using Ta as substrates were employed for AO of SA.In the case of FP and UV/H_2O_2,most favorable experimental conditions were determined for each process and these were used for comparing with AO process.The study showed that the FP was the most effective process under aci...

Chemical oxygen demand reduction in coffee wastewater through chemical flocculation and advanced oxidation processes

The removal of the natural organic matter present in coffee processing wastewater through chemical coagulation-flocculation and advanced oxidation processes （AOP） had been studied. The effectiveness of the removal of natural organic matter using commercial flocculants and UV/H202, UV/O3 and UV/H2O2/O3 processes was determined under acidic conditions. For each of these processes, different operational conditions were explored to optimize the treatment efficiency of the coffee wastewater. Coffee wastewater is characterized by a high chemical oxygen demand （COD） and low total suspended solids. The outcomes of coffee wastewater treatment using coagulation-flocculation and photodegradation processes were assessed in terms of reduction of COD, color, and turbidity. It was found that a reduction in COD of 67% could be realized when the coffee wastewater was treated by chemical coagulation-flocculation with lime and coagulant T-1. When coffee wastewater was treated by coagulation-flocculation in combination with UV/H2O2, a COD reduction of 86% was achieved, although only after prolonged UV irradiation. Of the three advanced oxidation processes considered, UV/H2O2, UV/O3 and UV/H2O2/O3, we found that the treatment with UV/H2O2/O3 was the most effective, with an efficiency of color, turbidity and further COD removal of 87%, when applied to the flocculated coffee wastewater.

Advanced Oxidation Process for DNAN Using UV/H2O2

2,4-Dinitroanisole(DNAN)is an important component of insensitive munitions that is anticipated to replace 2,4,6-trinitrotoluene(TNT)in munitions formulations.Photocatalyzed hydrogen peroxide(H2O2)oxidation experiments and chemical analyses were conducted to study the effect of initial pH and H2O2 dosage on the kinetics of DNAN decomposition and the reaction pathways.The results show that DNAN degradation followed zero-order kinetics when a 250 ppm DNAN solution was treated with ultraviolet(UV)light and 1500–4500 ppm H2O2 in an initial pH range of 4–7.However,when the H2O2 concentration was 750 ppm,DNAN degradation followed pseudo-first-order kinetics.The results indicate that DNAN can easily be oxidized by UV/H2O2 treatment.When the H2O2 dosage was 1500 ppm and the initial pH was 7,DNAN was reduced from 250 ppm to less than 1 ppm in 3 h.However,the total organic carbon(TOC)and total carbon(TC)concentrations were reduced slowly from 100 to less than 70 ppm carbon(C)in 3 h,and decreased to about 5 ppm after 9 h of treatment,suggesting the formation of other organic compounds.Those reaction intermediates were oxidized to carbon dioxide(CO2)at a slower rate than the oxidation of DNAN.CO2 was emitted from the solution because the solution pH decreased rapidly to about 3 during the UV/H2O2 oxidation.Most of the nitrogen in DNAN was converted to nitrate by UV/H2O2 oxidation after 9 h of treatment.The research results indicate that UV/H2O2 oxidation is a promising technique for the treatment of DNAN in wastewater.

Multi-objective Optimization of Industrial Purified Terephthalic Acid Oxidation Process

Multi-objective optimization of a purified terephthalic acid (PTA) oxidation unit is carried out in this paper by using a process modei that has been proved to describe industrial process quite well. The modei is a semi-empirical structured into two series ideal continuously stirred tank reactor (CSTR) models. The optimal objectives include maximizing the yield or inlet rate and minimizing the concentration of 4-carboxy-benzaldhyde, which is the main undesirable intermediate product in the reaction process. The multi-objective optimization algorithra applied in this study is non-dominated sorting genetic algorithm Ⅱ (NSGA-Ⅱ). The performance of NSGA-Ⅱ is further illustrated by application to the title process.

Degradation of Organic Pollutants by the Advanced Oxidation Processes

A kinetic model has been developed for the degradation of organic pollutants concerning with hydroperoxide ion as the initial step for generation of hydroxyl radical and its subsequent reaction mechanisms. Rate equations were derived for depletion of ozone and pollutants in the peroxone oxidation process using ozone and hydrogen peroxide as combined oxidants. Kinetic data obtained experimentally from the hydrogen peroxide-ozone reaction and peroxone oxidation of nitrobenzene were analyzed by using the proposed rate equations.

Processing-Microstructure Relationships in the Plasma Electrolytic Oxidation (PEO) Coating of a Magnesium Alloy

In the plasma electrolytic oxidation (PEO) coating of light metal alloys, changing the electrical parameters and electrolytic composition can change the discharge behaviour and, ultimately, the thickness, surface morphology and porosity of the coating. In the present study a combination of cathodic and anodic current pulses with suitable Ton and Toff periods were used to control the porosity and other structural defects of PEO coatings of an AM60B magnesium alloy. In order to investigate the effect of a current mode on the plasma discharge behaviour and coating microstructure during the PEO treatment of magnesium alloy, the emission intensities of six different spectral lines from the plasma species were recorded simultaneously as a function of both time and current mode using optical emission spectroscopy (OES) system. The fluctuations in signal intensities and temperature during the coating process reflect differences in location of both the discharge initiation, and discharge type. The coating surface morphology and microstructure that are obtained can be linked to the plasma discharge behavior. These results are discussed in relation to the discharge behaviour, and how such changes in discharge behaviour relate to the coating mechanisms.

Growth process and corrosion resistance of micro-arc oxidation coating on Mg-Zn-Gd magnesium alloys

A Mg-6Zn-3Gd(mass fraction,%) alloy,noted as ZG63,was coated by different micro-arc oxidation(MAO) processes,and the coating structure and corrosion resistance of the alloy were studied using scanning electron microscopy(SEM),glancing angle X-ray diffractometry(GAXRD) and various electrochemical methods.The micro-arc oxidation process consists of three stages and corresponds with different coating structures.In the initial stage,the coating thickness is linearly increased and is controlled by electrochemical polarization.In the second stage,the coating grows mainly inward and accords with parabolic regularity.In the third stage,the loose coating forms and is controlled by local arc light.The looser coating is mainly composed of MgSiO3 and the compact coating is mainly composed of MgO.From micro-arc oxidation stage to local arc light stage,the corrosion resistance of the coated alloy firstly increases and then decreases.The satisfied corrosion resistance corresponds to the coating time ranging from 6 to10 min.

Methanol oxidation in acidic and alkaline electrolytes using PtRuIn/C electrocatalysts prepared by borohydride reduction process

PtRuIn/C electrocatalysts( 20% metal loading by weight) were prepared by sodium borohydride reduction process using H_2PtCl6·6H_2O,RuCl_3·xH_2O and InCl_3·xH_2O as metal sources,borohydride as reducing agent and Carbon Vulcan XC72 as support. The synthetized PtRuIn/C electrocatalysts were characterized by X-ray diffraction( XRD),energy dispersive analysis( EDX),transmission electron microscopy( TEM),cyclic voltammetry( CV),chronoamperommetry( CA) and polarization curves in alkaline and acidic electrolytes( single cell experiments). The XRD patterns showPtpeaks are attributed to the face-centered cubic( fcc) structure,and a shift of Pt( fcc) peaks indicates that Ru or In is incorporated into Ptlattice. TEMmicrographs showmetal nanoparticles with an average nanoparticle size between 2.7 and 3.5 nm. Methanol oxidation in acidic and alkaline electrolytes was investigated at room temperature,by CV and CA. PtRu/C( 50 ∶ 50) shows the highest activity among all electrocatalysts in study considering methanol oxidation for acidic and alkaline electrolyte. Polarization curves at 80 ℃ showPtRuIn/C( 50 ∶ 25 ∶ 25)with superior performance for methanol oxidation,when compared to Pt/C,PtIn/C and PtRu/C for both electrolytes. The best performance obtained by PtRuIn/C( 50 ∶ 25 ∶ 25) in real conditions could be associated with the increased kinetics reaction and/or with the occurrence simultaneously of the bifunctional mechanism and electronic effect resulting from the presence of Ptalloy.

Explosion limits estimation and process optimization of direct propylene epoxidation with H2 and O2

Direct propylene epoxidation with H2 and O2,an attractive process to produce propylene oxide(PO),has a potential explosion danger due to the coexistence of flammable gases(i.e.,C3 H6 and H2)and oxidizer(i.e.,O2).The unknown explosion limits of the multi-component feed gas mixture make it difficult to optimize the reaction process under safe operation conditions.In this work,a distribution method is proposed and verified to be effective by comparing estimated and experimental explosion limits of more than 200 kinds of flammable gas mixture.Then,it is employed to estimate the explosion limits of the feed gas mixture,some results of which are also validated by the classic Le Chatelier’s Rule and flammable resistance method.Based on the estimated explosion limits,process optimization is carried out using commercially high and inherently safe reactant concentrations to enhance reaction performance.The promising results are directly obtained through the interface called gOPT in gPROMS only by using a simple,easy-constructed and mature packed-bed reactor,such as the PO yield of 13.3%,PO selectivity of 85.1%and outlet PO fraction of 1.8%.These results can be rationalized by indepth analyses and discussion about the effects of the decision variables on the operation safety and reaction performance.The insights revealed here could shed new light on the process development of the PO production based on the estimation of the explosion limits of the multi-component feed gas mixture containing flammable gase s,inert gas and O2,followed by process optimization.

Influence of MnO_(x)deposition on TiO_(2)nanotube arrays for electrooxidation

TiO_(2)has demonstrated outstanding performance in electrochemical advanced oxidation processes(EAOPs)due to its structural stability and high oxygen overpotential.However,there is still much room for improving its electrochemical activity.Herein,narrow bandgap manganese oxide(MnO_(x))was composited with TiO_(2)nanotube arrays(TiO_(2)NTAs)that in-situ oxidized on porous Ti sponge,forming the MnO_(x)-TiO_(2)NTAs anode.XANES and XPS analysis further proved that the composition of MnO_(x)is Mn2O3.Electrochemical characterizations revealed that increasing the composited concentration of MnO_(x)can improve the conductivity and reduce oxygen evolution potential so as to improve the electrochemical activity of the composited MnO_(x)-TiO_(2)NTAs anode.Meanwhile,the optimal degradation rate of benzoic acid(BA)was achieved using MnO_(x)-TiO_(2)NTAs with a MnO_(x)concentration of 0.1 mmol L^(-1),and the role of MnO_(x)was proposed based on DFT calculation.Additionally,the required electrical energy(EE/O)to destroy BA was optimized by varying the composited concentration of MnO_(x)and the degradation voltage.These quantitative results are of great significance for the design and application of high-performance materials for EAOPs.

Direct oxidation of methane at low temperature using Pt/C,Pd/C,Pt/C-ATO and Pd/C-ATO electrocatalysts prepared by sodium borohydride reduction process

The main objective of this paper was to characterize the voltammetric profiles of the Pt/C,Pt/C-ATO,Pd/C and Pd/CATO electrocatalysts and study their catalytic activities for methane oxidation in an acidic electrolyte at 25 ℃ and in a direct methane proton exchange membrane fuel cell at 80 ℃. The electrocatalysts prepared also were characterized by X-ray diffraction( XRD) and transmission electron microscopy( TEM). The diffractograms of the Pt/C and Pt/C-ATO electrocatalysts show four peaks associated with Pt face-centered cubic( fcc) structure,and the diffractograms of Pd/C and Pd/C-ATO show four peaks associated with Pd face-centered cubic( fcc) structure. For Pt/C-ATO and Pd/C-ATO,characteristic peaks of cassiterite( SnO_2) phase are observed,which are associated with Sb-doped SnO_2( ATO) used as supports for electrocatalysts. Cyclic voltammograms( CV) of all electrocatalysts after adsorption of methane show that there is a current increase during the anodic scan. However,this effect is more pronounced for Pt/C-ATO and Pd/C-ATO. This process is related to the oxidation of the adsorbed species through the bifunctional mechanism,where ATO provides oxygenated species for the oxidation of CO or HCO intermediates adsorbed in Pt or Pd sites. From in situ ATR-FTIR( Attenuated Total Reflectance-Fourier Transform Infrared) experiments for all electrocatalysts prepared the formation of HCO or CO intermediates are observed,which indicates the production of carbon dioxide. Polarization curves at 80 ℃in a direct methane fuel cell( DMEFC) show that Pd/C and Pt/C electroacatalysts have superior performance to Pd/C-ATO and Pt/C-ATO in methane oxidation.

Degradation of Dyestuff Pollutant Sudan I Using Advanced Oxidation Process

Due to an increasing environmental pollution, a search for the cost effective treatment and disposal of the dyes from the textile effluents is getting more and more importance. Oxidation and reduction processes play important roles in the degradation treatments of the azo dyes. The latter process is more effective and in consequence its mechanism is also better understood. The mechanism of the oxidation processes, the intermediates involved in these reactions and their role in the effectiveness of the oxidative degradation of the azo dyes, viz, phenyl azo b-naphthol (PAN), Sudan I. On exposure to sunlight at 2 1/2 hours for various samples in different concentrations of PAN mixed with Fenton reagent, when the reactive intermediate?reacted with the colour, the pH vs. absorbance generally showed significant degradation in between pH 5 and 6. The results were compared with the same samples on exposure to uv-light of 254 nm and irradiated at 20 minutes. The degradation occurred in samples of relatively high concentrations, viz, 10-3 and 5 × 10-4 mol· dm-3 at near neutral pH 6 whereas. Low concentration samples such as 10-4 and 5 × 10-5 mol·dm-3 showed degradation towards more acidic range of pH 2 to 4. In advanced oxidation process (AOP), generally reactive, strongly oxidizing ·OH radicals play a main role in destruction of the dye molecules. The proposed mechanisms and the rate coefficients for the reactions of ·OH intermediates with the dye molecules and with model compounds are summarized.