An internal circulation iron-carbon micro-electrolysis reactor for aniline wastewater treatment:Parameter optimization,degradation pathways and mechanism

Aniline is a vital industrial raw material.However,highly-toxic aniline wastewater usually deteriorated effluent quality,posed a threat to human health and ecosystem safety.Therefore,this study reported a novel internal circulation iron-carbon micro-electrolysis(ICE)reactor to treat aniline wastewater.The effects of reaction time,pH,aeration rate and iron-carbon(Fe/C)ratio on the removal rate of aniline and the chemical oxygen demand were investigated using single-factor experiments.This process exhibited high aniline degradation performance of approximately 99.86% under optimal operating conditions(reaction time=20 min,pH=3,aeration rate=0.5 m3·h^(-1),and Fe/C=1:2).Based on the experimental results,the response surface method was applied to optimize the aniline removal rate.The Box–Behnken method was used to obtain the interaction effects of three main factors.The result showed that the reaction time had a dominant effect on the removal rate of aniline.The highest aniline removal rate was obtained at pH of 2,aeration rate of 0.5 m^(3)·h^(-1)and reaction time of 30 min.Under optional experimental conditions,the aniline content of effluent was reduced to 3 mg·L^(-1)and the removal rate was as high as 98.24%,within the 95% confidence interval(97.84%-99.32%)of the predicted values.The solution was treated and the reaction intermediates were identified by high-performance liquid chromatography,ultraviolet-visible spectroscopy,Fourier-transform infrared spectroscopy,gas chromatography-mass spectrometry,and ion chromatography.The main intermediates were phenol,benzoquinone,and carboxylic acid.These were used to propose the potential mechanism of aniline degradation in the ICE reactor.The results obtained in this study provide optimized conditions for the treatment of industrial wastewater containing aniline and can strengthen the understanding of the degradation mechanism of iron-carbon micro-electrolysis.

Micro-electrolysis technology for industrial wastewater treatment

Experiments were conducted to study the role of micro-electrolysis in removing chromaticity and COD and improving the biodegradability of wastewater from pharmaceutical, dye-printing and papermaking plants. Results showed that the use of micro-electrolysis technology could remove more than 90% of chromaticity and more than 50% of COD and greatly improved the biodegradability of pharmaceutical wastewater. Lower initial pH could be advantageous to the removal of chromaticity. A retention time of 30 minutes was recommended for the process design of micro-electrolysis. For the use of micro-electrolysis in treatment of dye-printing wastewater, the removal rates of both chromaticity and COD were increased from neutral condition to acid condition for disperse blue wastewater; more than 90% of chromaticity and more than 50% of COD could be removed in neutral condition for vital red wastewater.

Treatment of naphthalene derivatives with iron-carbon micro-electrolysis

The degradation of five naphthalene derivatives in the simulated wastewater was investigated using the iron-carbon micro-electrolysis method.The optimal initial pH of solution and adsorption of iron-carbon and removal efficiency of the total organic carbon(TOC)were investigated.The results show that the removal efficiency of the naphthalene derivatives can reach 48.9%?92.6% and the removal efficiency of TOC is 42.8%?78.0% for the simulated wastewater with 200 mg/L naphthalene derivatives at optimal pH of 2.0?2.5 after 120 min treatment.The degradation of five naphthalene derivatives with the micro-electrolysis shows the apparent first-order kinetics and the order of removal efficiency of the naphthalene derivatives is sodium 2-naphthalenesulfonate,2-naphthol,2,7-dihydroxynaphthalene,1-naphthamine,1-naphthol-8-sulfonic acid in turn.It is illustrated that the substituents of the naphthalene ring can affect the removal efficiency of naphthalene due to their electron-withdrawing or electron-donating ability.

Optimization of the N2 generation selectivity in aqueous nitrate reduction using internal circulation micro-electrolysis

The reduction of nitrate using internal circulation micro-electrolysis te chnology(ICE)was investigated.The effect of the reaction time,initial pH,Fe/C ratio,and aeration rate on the nitrate reduction was investigated using a single factor experiment.Based on the results of the single factor experiment,a response surface methodology(RSM)was applied to optimize the N2 generation selectivity.The effects and interactions of three independent variables were estimated using a Box-Behnken design.Using the RSM analysis,a quadratic polynomial model with optimal conditions at pH=8.8,Fe/C=1:1,and an aeration rate of 30 L·min-1 was developed by means of the regre ssion analysis of the experimental data.Using the RSM optimization,the optimal conditions yielded a N2 generation selectivity of 72.0%,which is in good agreement with experimental result(73.2%±0.5%)and falls within the 95%confidence interval(IC:66.8%-77.3%)of the model results.This indicates that the model obtained in this study effectively predicts the N2 generation selectivity for nitrate reduction by the ICE process,thus providing a theoretical basis for process design.

Nitrogen removal efficiency of iron-carbon micro-electrolysis system treating high nitrate nitrogen organic pharmaceutical wastewater

The nitrate nitrogen removal efficiency of iron-carbon micro-electrolysis system was discussed in treating pharmaceutical wastewater with high nitrogen and refractory organic concentration. The results show that the granularity of fillings,pH,volume ratios of iron-carbon and gas-water,and HRT. have significant effects on the nitrogen removal efficiency of iron-carbon micro-electrolysis system. The iron-carbon micro-electrolysis system has a good removal efficiency of pharmaceutical wastewater with high nitrogen and refractory organic concentration when the influent TN,NH4+-N,NO3--N and BOD5/CODCr are 823 mg/L,30 mg/L,793 mg/L and 0.1,respectively,at the granularity of iron and carbon 0.425 mm,pH 3,iron-carbon ratio 3,gas-water ratio 5,HRT 1.5 h,and the removal rates of TN,NH4+-N and NO3--N achieve 51.5%,70% and 50.94%,respectively.

Structural parameter optimization for novel internal-loop iron–carbon micro-electrolysis reactors using computational fluid dynamics

It is generally recognized that internal-loop reactors are well-developed mass and heat-transfer multiphase flow reactors. However, the internal flow field in the internal-loop reactor is influenced by the structure parameter of the reactor, which has a great effect on the reaction efficiency. In this study, the computational fluid dynamics simulation method was used to determine the influence of reactor structure on flow field, and a volume-offluid model was employed to simulate the gas–liquid, two-phase flow of the internal-loop micro-electrolysis reactor. Hydrodynamic factors were optimized when the height-to-diameter ratio was 4:1, diameter ratio was9:1, draft-tube axial height was 90 mm. Three-dimensional simulations for the water distributor were carried out, and the results suggested that the optimal conditions are as follows: the number of water distribution pipes was four, and an inhomogeneous water distribution was used. According to the results of the simulation,the suitable structure can be used to achieve good fluid mechanical properties, such as the good liquid circulation velocity and gas holdup, which provides a good theoretical foundation for the application of the reactor.

Degradation of Nitrobenzene Wastewater via Iron/Carbon Micro-electrolysis Enhanced by Ultrasound Coupled with Hydrogen Peroxide

The zero valent iron/granular active carbon(ZVI/GAC) micro-electrolysis enhanced by ultrasound(US) coupled with hydrogen peroxide(H_2O_2) was investigated for the deep degradation of nitrobenzene-containing wastewater. The results of scanning electron microscopy-energy dispersive X-rays analysis(SEM-EDS) demonstrated that continuously accelerated regeneration of ZVI and GAC in situ by US could improve the process for converting nitrobenzene(NB) to aniline(AN). H_2O_2 was decomposed catalytically by the byproduct Fe^(2+) ions generated in the micro-electrolysis process to hydroxyl radicals and the organic pollutants in the wastewater were finally mineralized to CO2 and H2O. Effects of the ZVI dosage, the ZVI/GAC mass ratio, the initial pH value and the H_2O_2 dosage on the efficiency for degradation of NB were studied in these experiments. The optimal operating conditions covered a ZVI dosage of 15 g/L, a ZVI/GAC mass ratio of 1:2,an initial pH value of 3 and a H_2O_2 dosage of 4 mL. In this case, the NB removal efficiency reached 97.72% and the total organic carbon(TOC) removal efficiency reached 73.42% at a NB concentration of 300 mg/L. The reduction of NB by USZVI/GAC followed the pseudo-first-order kinetics model, and the pseudo-first-order rate constants were given at different initial pH values. The reaction intermediates such as AN, benzoquinonimine, p-benzoquinone, p-nitrophenol and other organic acids were detected and a probable pathway for NB degradation has been proposed.

Treatment of oilfield produced water by anaerobic process coupled with micro-electrolysis

Treatment of oilfield produced water was investigated using an anaerobic process coupled with micro-electrolysis （ME）, focusing on changes in chemical oxygen demand （COD） and biodegradability. Results showed that COD exhibited an abnormal change in the single anaerobic system in which it increased within the first 168 hr, but then decreased to 222 mg/L after 360 hr. The biological oxygen demand （five-day） （BOD5）/COD ratio of the water increased from 0.05 to 0.15. Hydrocarbons in the wastewater, such as pectin, degraded to small molecules during the hydrolytic acidification process. Comparatively, the effect of ME was also investigated. The COD underwent a slight decrease and the BOD5/COD ratio of the water improved from 0,05 to 0.17 after ME. Removal of COD was 38.3% under the idealized ME conditions （pH 6.0）, using iron and active carbon （80 and 40 g/L, respectively）. Coupling the anaerobic process with ME accelerated the COD removal ratio （average removal was 53.3%）. Gas chromatography/mass spectrometry was used to analyze organic species conversion. This integrated system appeared to be a useful option for the treatment of water produced in oilfields.

Reduced graphene oxide-nano zero value iron(rGO-nZVI) micro-electrolysis accelerating Cr(Ⅵ) removal in aquifer

Nanoscale zero-valent iron （nZVI） assembled on graphene oxide （GO） （rGO-nZVI） composites were synthesized by reduction of GO and ferrous ions with potassium borohydride, for use in Cr（VI） removal from aqueous solution. The results showed that the two-dimensional structure of GO could provide a skeleton support for Fe0, thus overcoming the bottleneck of aggregation for nZVI. Also, rGO-nZVI would form a ferric-carbon micro-electrolysis system in Cr（VI）-contaminated aquifers, enhancing and accelerating electron transfer, exhibiting high rate and capacity for Cr（VI） removal. The optimum dosage of the applied rGO-nZVI was linearly correlated with the initial Cr（VI） concentration. Characterization of rGO-nZVI before and after reaction with Cr（VI） revealed the process of Cr（VI） removal： rGO-nZVI firstly transferred electrons from Fe0 cores via their Fe（II）/Fe（III） shells to the GO sheet; there, negatively charged Cr（VI） received electrons and changed into positively charged Cr（III）, which was adsorbed by the negatively charged GO sheet, avoiding the capping and passivating of nZVI rGO-nZVI formed a good electrically conductive network, and thus had long-term electron releasing properties, which was important for groundwater remediation.

Application of Fe^0/C/Clay ceramics for decoloration of synthetic Acid Red 73 and Reactive Blue 4 wastewater by micro-electrolysis

Dyes are common pollutants in textile wastewaters, and the treatment of the wastewater has now attracted much attention due to its wide application and low biodegradability. In this study, Fe^0/C/Clay ceramics, a kind of novel micro-electrolysis filler, were sintered and employed in a dynamic micro-electrolysis reactor for synthetic Acid Red 73 （AR73） and Reactive Blue 4 （RB4） wastewater treatment. The effects ofinfluent pH, hydraulic retention time （HRT）, and aeration on the decoloration efficiencies of AR73 and RB4 were studied. The optimum conditions for wastewater treatment were： AR73, influent pH of 4, HRT of 2 h and aeration; RB4, influent pH of 5, HRT of 6 h and aeration. Under the optimum conditions, decoloration efficiency of AR73 and RB4 wastewater was 96% and 83%, respectively. Results of UV-vis spectrum scanning demonstrated that the chromophores were broken. Continuous running tests showed that improvement of micro-electrolysis system with Fe^0/C/Clay ceramics for AR73 and RB4 synthetic wastewater treatment could avoid failure of micro-electrolysis reactor, which indicated great potential for the practical application of the ceramics in the field of actual industrial wastewater treatment.

Treatment of coking wastewater by a novel electric assisted micro-electrolysis filter

A newly designed electric assisted micro-electrolysis filter（E-ME） was developed to investigate its degradation efficiency for coking wastewater and correlated characteristics. The performance of the E-ME system was compared with separate electrolysis（SE） and micro-electrolysis（ME） systems. The results showed a prominent synergistic effect on COD removal in E-ME systems. Gas chromatography/mass spectrometry（GC–MS） analysis confirmed that the applied electric field enhanced the degradation of phenolic compounds.Meanwhile, more biodegradable oxygen-bearing compounds were detected. SEM images of granular activated carbon（GAC） showed that inactivation and blocking were inhibited during the E-ME process. The effects of applied voltage and initial p H in E-ME systems were also studied. The best voltage value was 1 V, but synergistic effects existed even with lower applied voltage. E-ME systems exhibited some p H buffering capacity and attained the best efficiency in neutral media, which means that there is no need to adjust p H prior to or during the treatment process. Therefore, E-ME systems were confirmed as a promising technology for treatment of coking wastewater and other refractory wastewater.

Reutilize tire in microbial fuel cell for enhancing the nitrogen removal of the anammox process coupled with iron-carbon micro-electrolysis

In this study,microbial fuel cells(MFCs)were explored to promote the nitrogen removal performance of combined anaerobic ammonium oxidation(anammox)and Fe-C micro-electrolysis(CAE)systems.The average total nitrogen(TN)removal efficiency of the modified MFC system was 85.00%,while that of the anammox system was 62.16%.Additionally,the effective operation time of this system increased from six(CAE system alone)to over 50 days,significantly promoting TN removal.The enhanced performance could be attributed to the electron transferred from the anode to the cathode,which aided in reducing nitrate/nitrite in denitrification.The H+released through the proton exchange membrane caused a decrease in the pH,facilitating Fe corrosion.The pyrolyzed waste tire used as the cathode could immobilize microorganisms,enhance electron transport,and produce a natural Fe-C micro-electrolysis system.According to the microbial community analysis,Candidatus kuenenia was the major genus involved in the anammox process.Furthermore,the SM1A02 genus exhibited the highest abundance and was enriched the fastest,and could be a novel potential strain that aids the anammox process.

High-gravity intensified iron-carbon micro-electrolysis for degradation of dinitrotoluene

The application of iron–carbon(Fe–C)micro-electrolysis to wastewater treatment is limited by the passivation potential of the Fe–C packing.In order to address this problem,high-gravity intensified Fe–C micro-electrolysis was proposed in this study for degradation of dinitrotoluene wastewater in a rotating packed bed(RPB)using commercial Fe–C particles as the packing.The effects of reaction time,high-gravity factor,liquid flow rate and initial solution pH were investigated.The degradation intermediates were determined by gas chromatography-mass spectrometry,and the possible degradation pathways of nitro compounds by Fe–C micro-electrolysis in RPB were also proposed.It is found that under optimal conditions,the removal rate of nitro compounds reaches 68.4%at 100 min.The removal rate is maintained at approximately 68%after 4 cycles in RPB,but it is decreased substantially from 57.9%to 36.8%in a stirred tank reactor.This is because RPB can increase the specific surface area and the renewal of the liquid–solid interface,and as a result the degradation efficiency of Fe–C micro-electrolysis is improved and the active sites on the Fe–C surface can be regenerated for continuous use.In conclusion,high-gravity intensified Fe–C micro-electrolysis can weaken the passivation of Fe–C particles and extend their service life.

Treatment of Wastewater from Pharmaceutical Intermittent Production by Fe/C-Fenton-Hydrolysis Acidification-A/O Process

The design and running effect of treatment of wastewater from pharmaceutical intermittent production by iron-carbon（Fe/C）-Fentonhydrolysis acidification-anoxic/aerobic（A/O）process were introduced.The results of continuous operation showed that when the flow rate of the influent wastewater was 300 m^3/d,after the influent high-concentration wastewater（CODCrand NH4＋-N concentration were 35 000 and 1 000 mg/L,respectively）and medium-concentration wastewater（CODCrand NH4＋-N concentration were 1 500 and 100 mg/L,respectively）were treated by the process,CODCrand NH4＋-N concentration in the effluent decreased to 360-410 and 20-25 mg/L,respectively,and the quality of the effluent could meet the Grade III standard of Integrated Wastewater Discharge Standard（GB 8978-1996）.The combined process was proved to be an effective method to treat wastewater from pharmaceutical intermittent production,and its operation was stable.

Enhanced removal of organic matter and typical disinfection byproduct precursors in combined iron–carbon micro electrolysis-UBAF process for drinking water pre-treatment

The organic matter and two types of disinfection byproduct(DBP) precursors in micropolluted source water were removed using an iron–carbon micro-electrolysis(ICME)combined with up-flow biological aerated filter(UBAF) process. Two pilot-scale experiments(ICME-UBAF and UBAF alone) were used to investigate the effect of the ICME system on the removal of organic matter and DBP precursors. The results showed that ICME pretreatment removed 15.6% of dissolved organic matter(DOM)and significantly improved the removal rate in the subsequent UBAF process. The ICME system removed 31% of trichloromethane(TCM) precursors and 20% of dichloroacetonitrile(DCAN) precursors. The results of measurements of the molecular weight distribution and hydrophilic fractions of DOM and DBP precursors showed that ICME pretreatment played a key role in breaking large-molecular-weight organic matter into low-molecular-weight components, and the hydrophobic fraction into hydrophilic compounds, which was favorable for subsequent biodegradation by UBAF.Three-dimensional fluorescence spectroscopy(3D-EEM) further indicated that the ICME system improved the removal of TCM and DCAN precursors. The biomass analysis indicated the presence of a larger and more diverse microbial community in the ICME-UBAF system than for the UBAF alone. The high-throughput sequencing results revealed that domination of the genera Sphingomonas, Brevundimonas and Sphingorhabdus contributed to the better removal of organic matter and two types of DBP precursors. Also, Nitrosomonas and Pseudomonas were beneficial for ammonia removal.

Enhanced remediation of Cr(Ⅵ)-contaminated groundwater by coupling electrokinetics with ZVI/Fe_(3)O_(4)/AC-based permeable reactive barrier

Although widely used in permeation reaction barrier(PRB)for strengthening the removal of various heavy metals,zero-valent iron(ZVI)is limited by various inherent drawbacks,such as easy passivation and poor electron transfer.As a solution,a synergistic system with PRB and electrokinetics(PRB-EK)was established and applied for the efficient removal of Cr(Ⅵ)-contaminated groundwater.As the filling material of PRB,ZVI/Fe_(3)O_(4)/activated carbon(ZVI/Fe_(3)O_(4)/AC)composites were synthesized by ball milling and thermal treatment.A series of continuous flow column experiments and batch tests was conducted to evaluate the removal efficiency of Cr(Ⅵ).Results showed that the removal efficiency of Cr(Ⅵ)remained above 93%even when the bed volume(BV)reached 2000 under the operational parameters(iron/AC mass ratio,2:1;current,5 m A).The mechanism of Cr(Ⅵ)removal by the PRB-EK system was revealed through field emission scanning electron microscopy images,X-ray diffraction,X-ray photoelectron spectroscopy,Fe^(2+) concentration,and redox potential(E h)values.The key in Cr(Ⅵ)reduction was the Fe^(2+)/Fe^(3+) cycle driven by the surface microelectrolysis of the composites.The application of an externally supplied weak direct current maintained the redox process by enhancing the electron transfer capability of the system,thereby prolonging the column lifetime.Cr(Ⅵ)chemical speciation was determined through sequential extraction,verifying the stability and safety of the system.These findings provide a scientific basis for PRB design and the in-situ remediation of Cr(Ⅵ)-contaminated groundwater.

Fe/C micro electrolysis and Fenton oxidation process for the removal of recalcitrant colored pollutants from mid-stage pulping effluent

The pulp and paper industry produces a large amount of colored effluent in the pulping,bleaching,and papermaking processes.The wastewater from the pulp washing and bleaching stages is also known as mid-stage pulping effluent,which is difficult to treat due to its toxicity and dark dolor.This paper reports a novel Fe/C micro-electrolysis process for the treatment of the mid-stage pulping effluent.Results show that this process is effective in removing the color under optimal reaction conditions.Scanning electron microscopy(SEM)and Fourier transform infrared spectroscopy(FTIR)analyses indicate that the colored pollutants were removed from the wastewater in the Fe/C micro-electrolysis by adsorption,collection and filtration mechanisms.The Fe2+ions produced in the micro-electrolysis process functioned as Fenton’s reagents with H2O2 in the follow-up oxidation stage,which enhanced the removal of chemical oxygen demand(COD)and color.