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Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) are efficient processes to degrade organic pollutants in water. In this paper, the influence of different reaction parameters in WAO, such as temperature, oxygen pressure, pH, stirring speed are analyzed in detail. Homogenous and heterogeneous catalysts including carbon materials, transitional metal oxides and noble metals are extensively discussed in CWAO. Three different kinds of the reactor in the CWAO (autoclave, packed bed and membrane reactors) are illustrated and compared. To enhance the degrada [Detail] ...
Different reaction parameters are emphasized in the WAO process. Homogenous catalysts and heterogeneous catalysts are extensively discussed. Mechanism and kinetic of WAO are elaborated. Three kinds of the reactors for CWAO are compared. Integration of CWAO with biological degradation is discussed.
Wet air oxidation (WAO) and catalytic wet air oxidation (CWAO) are efficient processes to degrade organic pollutants in water. In this paper, we especially reviewed the WAO and CWAO processes for phenolic compounds degradation. It provides a comprehensive introduction to the CWAO processes that could be beneficial to the scientists entering this field of research. The influence of different reaction parameters, such as temperature, oxygen pressure, pH, stirring speed are analyzed in detail; Homogenous catalysts and heterogeneous catalysts including carbon materials, transitional metal oxides and noble metals are extensively discussed, among which Cu based catalysts and Ru catalysts were shown to be the most active. Three different kinds of the reactor implemented for the CWAO (autoclave, packed bed and membrane reactors) are illustrated and compared. To enhance the degradation efficiency and reduce the cost of the CWAO process, biological degradation can be combined to develop an integrated technology.
Tunisian clay has been successfully pillared with Al and Fe by microwave irradiation. Microwave method reduces considerably the synthesis time and the water consumption. AlFe-pillared clays are highly stable in the severe operating conditions of CWAO. Oxidation takes place through a heterogeneous mechanism. Microwave pillared-clays are good candidate for CWAO industrial water treatment.
Microwave irradiation has been used to prepare Al, Fe-pillared clays from a natural Tunisian smectite from the El Hicha deposit (province of Gabes). Chemical analysis, XRD spectra and surface properties evidenced the success of pillaring process. The obtained solids present higher surface area and pore volume than conventionally prepared Al-Fe pillared clays. The main advantages of the microwave methodology are the considerable reduction of the synthesis time and the consumption of water. The microwave-derived Al-Fe pillared clays have been tested for catalytic wet air oxidation (CWAO) of phenol in a stirred tank at 160°C and 20 bar of pure oxygen pressure. These materials are efficient for CWAO of phenol and are highly stable despite the severe operating conditions (acidic media, high pressure, high temperature). The catalyst deactivation was also significantly hindered when compared to conventionally prepared clays. Al-Fe pillared clays prepared by microwave methodology are promising as catalysts for CWAO industrial water treatment.
• Catalytic reduction technology for water treatment was reviewed. • Hydrodehalogenation for wastewater treatment was covered. • Hydrogenation of nitrate for groundwater remediation was introduced. • Combination of water splitting with catalytic reduction was illustrated.
Treating water contaminants via heterogeneously catalyzed reduction reaction is a subject of growing interest due to its good activity and superior selectivity compared to conventional technology, yielding products that are non-toxic or substantially less toxic. This article reviews the application of catalytic reduction as a progressive approach to treat different types of contaminants in water, which covers hydrodehalogenation for wastewater treatment and hydrogenation of nitrate/nitrite for groundwater remediation. For hydrodehalogenation, an overview of the existing treatment technologies is provided with an assessment of the advantages of catalytic reduction over the conventional methodologies. Catalyst design for feasible catalytic reactions is considered with a critical analysis of the pertinent literature. For hydrogenation, hydrogenation of nitrate/nitrite contaminants in water is mainly focused. Several important nitrate reduction catalysts are discussed relating to their preparation method and catalytic performance. In addition, novel approach of catalytic reduction using in situ synthesized H2 evolved from water splitting reaction is illustrated. Finally, the challenges and perspective for the extensive application of catalytic reduction technology in water treatment are discussed. This review provides key information to our community to apply catalytic reduction approach for water treatment.
Deposition Au nanoparticles on both TiO2 and RGO to fabricate Au/TiO2/RGO. Au/TiO2/RGO displayed a high H2O2 and •OH production in photocatalytic process. RGO is a good collector to transfer electrons from TiO2 to Au.
A new type of Au/TiO2/reduced graphene oxide (RGO) nanocomposite was fabricated by the hydrothermal synthesis of TiO2 on graphene oxide followed by the photodeposition of Au nanoparticles. Transmission electron microscopy images showed that Au nanoparticles were loaded onto the surface of both TiO2 and RGO. Au/TiO2/RGO had a better photocatalytic activity than Au/TiO2 for the degradation of phenol. Electrochemical measurements indicated that Au/TiO2/RGO had an improved charge transfer capability. Meanwhile, chemiluminescent analysis and electron spin resonance spectroscopy revealed that Au/TiO2/RGO displayed high production of hydrogen peroxide and hydroxyl radicals in the photocatalytic process. This high photocatalytic performance was achieved via the addition of RGO in Au/TiO2/RGO, where RGO served not only as a catalyst support to provide more sites for the deposition of Au nanoparticles but also as a collector to accept electrons from TiO2 to effectively reduce photogenerated charge recombination.
The adsorption behavior of DB BN on microwave catalyst MgFe2O4-SiC was investigated and the effects of concentration, temperature and pH on the adsorption process were discussed in this study. The microwave-induced catalytic degradation rate of DB BN decreased even more than ten percent after the adsorption equilibrium were attained. The degradation intermediate products of DB BN were identified and analyzed by GC-MS and LC-MS. The proposed degradation pathways of direct black BN (DB BN) were described by combining with the microwave-induced catalytic reaction mechanism of MgFe2O4-SiC.
The novel microwave catalyst MgFe2O4-SiC was synthesized via sol-gel method, to remove azo dye Direct Black BN (DB BN) through adsorption and microwave-induced catalytic reaction. Microwave-induced catalytic degradation of DB BN, including adsorption behavior and its influencing factors of DB BN on MgFe2O4-SiC were investigated. According to the obtained results, it indicated that the pseudo-second-order kinetics model was suitable for the adsorption of DB BN onto MgFe2O4-SiC. Besides, the consequence of adsorption isotherm depicted that the adsorption of DB BN was in accordance with the Langmuir isotherm, which verified that the singer layer adsorption of MgFe2O4-SiC was dominant than the multi-layer one. The excellent adsorption capacities of MgFe2O4-SiC were kept in the range of initial pH from 3 to 7. In addition, it could be concluded that the degradation rate of DB BN decreased over ten percent after the adsorption equilibrium had been attained, and the results from the result of comparative experiments manifested that the adsorption process was not conducive to the process of microwave-induced catalytic degradation. The degradation intermediates and products of DB BN were identified and determined by GC-MS and LC-MS. Furthermore, combined with the catalytic mechanism of MgFe2O4-SiC, the proposed degradation pathways of DB BN were the involution of microwave-induced ·OH and holes in this catalytic system the breakage of azo bond, hydroxyl substitution, hydroxyl addition, nitration reaction, deamination reaction, desorbate reaction, dehydroxy group and ring-opening reaction.
SPAC significantly enhanced the efficacyof catalytic ozonation. Large external surface reduced the diffusionresistance. Surface reaction was dominant for SPAC-basedcatalytic ozonation. Simple ball milling brought favorablematerial characteristics for catalysis.
In this study, super-fine powdered activated carbon (SPAC) hasbeen proposed and investigated as a novel catalyst for the catalyticozonation of oxalate for the first time. SPAC was prepared from commercialgranular activated carbon (GAC) by ball milling. SPAC exhibited highexternal surface area with a far greater member of meso- and macropores(563% increase in volume). The catalytic performances of activatedcarbons (ACs) of 8 sizes were compared and the rate constant for pseudofirst-order total organic carbon removal increased from 0.012 min-1 to 0.568 min-1 (47-fold increase) withthe decrease in size of AC from 20 to 40 mesh (863 mm) to SPAC (~1.0 mm). Furthermore, the diffusion resistance of SPAC decreased17-fold compared with GAC. The ratio of oxalate degradation by surfacereaction increased by 57%. The rate of transformationof ozone to radicals by SPAC was 330 times that of GAC. The resultssuggest that a series of changes stimulated by ball milling, includinga larger ratio of external surface area, less diffusion resistance,significant surface reaction and potential oxidized surface all contributedto enhancing catalytic ozonation performance. This study demonstratedthat SPAC is a simple and effective catalyst for enhancing catalyticozonation efficacy.
The applicability of FeVO4 extended the optimum pH range for heterogeneous Fenton process towardsneutral conditions. The datas for the removal of OG in FeVO4 systems conform to the Langmuir–Hinshelwood model. The irradiation of FeVO4 by visible light significantly increases the degradation rate ofOG due to the enhanced rates of the iron and vanadium cycles.
In this study, FeVO4 was prepared andused as Fenton-like catalyst to degrade orange G (OG) dye. The removalof OG in an aqueous solution containing 0.5 g·L-1 FeVO4 and 15 mmol·L-1 hydrogen peroxide at pH 7.0 reached 93.2%. Similar rates were achievedat pH 5.7 (k = 0.0471 min-1), pH 7.0 (k = 0.0438 min-1), and pH 7.7 (k = 0.0434 min-1). The FeVO4 catalyst successfullyovercomes the problem faced in the heterogeneous Fenton process, i.e.,the narrow working pH range. The data for the removal of OG in FeVO4 systems containing H2O2 conform to the Langmuir–Hinshelwood model (R2 = 0.9988),indicating that adsorption and surface reaction are the two basicmechanisms for OG removal in the FeVO4–H2O2 system. Furthermore, the irradiationof FeVO4 by visible light significantly increasesthe degradation rate of OG, which is attributed to the enhanced ratesof the iron cycles and vanadium cycles.
Fe2O3-CeO2-Bi2O3/γ-Al2O3, an environmental friendly material, was investigated. The catalyst exhibited good catalytic performance in the CWAO of cationic red GTL. The apparent activation energy for the reaction was 79 kJ·mol−1. HO2· and O2·− appeared as the main reactive species in the reaction.
The Fe2O3-CeO2-Bi2O3/γ-Al2O3 catalyst, a novel environmental-friendly material, was used to investigate the catalytic wet air oxidation (CWAO) of cationic red GTL under mild operating conditions in a batch reactor. The catalyst was prepared by wet impregnation, and characterized by special surface area (BET measurement), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Fe2O3-CeO2-Bi2O3/γ-Al2O3 catalyst exhibited good catalytic activity and stability in the CWAO under atmosphere pressure. The effect of the reaction conditions (catalyst loading, degradation temperature, solution concentration and initial solution pH value) was studied. The result showed that the decolorization efficiency of cationic red GTL was improved with increasing the initial solution pH value and the degradation temperature. The apparent activation energy for the reaction was 79 kJ·mol−1. Hydroperoxy radicals (HO2·) and superoxide radicals (O2−·) appeared as the main reactive species upon the CWAO of cationic red GTL.
Electrochemical removal is promising in nitrate elimination from wastewater. Influencing factors of nitrate electrochemical removal are critically reviewed. Electroreduction pathways of nitrate undergo electron transfer and hydrogenation. Electrocoagulation pathways of nitrate undergo coagulation, reduction, flotation. Electrodialysis pathways of nitrate undergo dialysis, reduction and oxidation.
A number of recent studies have demonstrated that electrochemical technologies, including electroreduction (ER), electrocoagulation (EC), and electrodialysis (ED), are effective in nitrate elimination in wastewater due to their high reactivity. To obtain the maximal elimination efficiency and current efficiency, many researchers have conducted experiments to investigate the optimal conditions (i.e., potential, current density, pH value, plate distance, initial nitrate concentration, electrolyte, and other factors) for nitrate elimination. The mechanism of ER, EC and ED for nitrate removal has been fully elucidated. The ER mechanism of nitrate undergoes electron transfer and hydrogenation reduction. The EC pathways of nitrate removal include reduction, coagulation and flotation. The ED pathways of nitrate include redox reaction and dialysis. Although the electrochemical technology can remove nitrate from wastewater efficiently, many problems (such as relatively low selectivity toward nitrogen, sludge production and brine generation) still hinder electrochemical treatment implementation. This paper critically presents an overview of the current state-of-the-art of electrochemical denitrification to enhance the removal efficiency and overcome the shortages, and will significantly improve the understanding of the detailed processes and mechanisms of nitrate removal by electrochemical treatment and provide useful information to scientific research and actual practice.
N2O release variesin response to enzyme-catalyzed nitrogen imbalances. The enzymology involved in N2O production and consumption are introduced. The pathways of N2O production and consumption are summarized. Key factors affecting N2O release and enzymatic mechanisms are summarized/revealed. Enzymatic strategies are proposed tomitigate N2O emissions.
Nitrous oxide (N2O), a potent greenhousegas, is emitted during nitrogen removal in wastewater treatment, significantlycontributing to greenhouse effect. Nitrogen removal generally involvesnitrification and denitrification catalyzed by specific enzymes. N2O production and consumption vary considerably in responseto specific enzyme-catalyzed nitrogen imbalances, but the mechanismsare not yet completely understood. Studying the regulation of relatedenzymes’ activity is essential to minimize N2O emissions during wastewater treatment. This paper aims to reviewthe poorly understood related enzymes that most commonly involvedin producing and consuming N2O in terms oftheir nature, structure and catalytic mechanisms. The pathways ofN2O emission during wastewater treatment arebriefly introduced. The key environmental factors influencing N2O emission through regulatory enzymes are summarizedand the enzyme-based mechanisms are revealed. Several enzyme-basedtechniques for mitigating N2O emissions directlyor indirectly are proposed. Finally, areas for further research onN2O release during wastewater treatment arediscussed.
Nitrobenzene degraded rapidly and was removed completely in native sediments. Indigenous microorganisms in native sediments are abundant. Proteobacteria and Firmicutes might play important roles in nitrobenzene removal. P. australis could provide a more suitable environment for Thauera.
The feasibility of using Phragmites australis-JS45 system in removing nitrobenzene from sediments was conducted. However, it was observed that nitrobenzene degraded rapidly and was removed completely within 20 days in native sediments, raising the possibility that indigenous microorganisms may play important roles in nitrobenzene degradation. Consequently, this study aimed to verify this possibility and investigate the potential nitrobenzene degraders among indigenous microorganisms in sediments. The abundance of inoculated strain JS45 and indigenous bacteria in sediments was quantified using real-time polymerase chain reaction. Furthermore, community structure of the indigenous bacteria was analyzed through high throughput sequencing based on Illumina MiSeq platform. The results showed that indigenous bacteria in native sediments were abundant, approximately 1014 CFU/g dry weight, which is about six orders of magnitude higher than that in fertile soils. In addition, the levels of indigenous Proteobacteria (Acinetobacter, Comamonadaceae_uncultured, Pseudomonas, and Thauera) and Firmicutes (Clostridium, Sporacetigenium, Fusibacter, Youngiibacter, and Trichococcus) increased significantly during nitrobenzene removal. Their quantities sharply decreased after nitrobenzene was removed completely, except for Pseudomonas and Thauera. Based on the results, it can be concluded that indigenous microorganisms including Proteobacteria and Firmicutes can have great potential for removing nitrobenzene from sediments. Although P. australis - JS45 system was set up in an attempt to eliminate nitrobenzene from sediments, and the system did not meet the expectation. The findings still provide valuable information on enhancing nitrobenzene removal by optimizing the sediment conditions for better growth of indigenous Proteobacteria and Firmicutes.
PM2.5 in Chengdu showed clear seasonal and diurnal variation. 5, 5, 5 and 3 mean clusters are generated in spring, summer, autumn, and winter. Short-distance air masses are important pathways in Chengdu. Emissions within the Sichuan Basin contribute significantly to PM2.5 pollution. Long-range transport from Southern Xinjiang is a dust invasion path to Chengdu.
Seasonal pattern of transport pathways and potential sources of PM2.5 in Chengdu during 2012–2013 were investigated based on hourly PM2.5 data, backward trajectories, clustering analysis, potential source contribution function (PSCF), and concentration-weighted trajectory (CWT) method. The annual hourly mean PM2.5 concentration in Chengdu was 97.4 mg·m–3. 5, 5, 5 and 3 mean clusters were generated in four seasons, respectively. Short-distance air masses, which travelled within the Sichuan Basin with no specific source direction and relatively high PM2.5 loadings (>80 mg·m–3) appeared as important pathways in all seasons. These short pathways indicated that emissions from both local and surrounding regions of Chengdu contributed significantly to PM2.5 pollution. The cities in southern Chengdu were major potential sources with PSCF>0.6 and CWT>90 mg·m–3. The northeastern pathway prevailed throughout the year with higher frequency in autumn and winter and lower frequency in spring and summer. In spring, long-range transport from southern Xinjiang was a representative dust invasion path to Chengdu, and the CWT values along the path were 30-60 mg·m–3. Long-range transport was also observed in autumn from southeastern Xinjiang along a northwesterly pathway, and in winter from the Tibetan Plateau along a westerly pathway. In summer, the potential source regions of Chengdu were smaller than those in other seasons, and no long-range transport pathway was observed. Results of PSCF and CWT indicated that regions in Qinghai and Tibet contributed to PM2.5 pollution in Chengdu as well, and their CWT values increased to above 30 mg·m-3 in winter.
Performance of CMAQ-Hg is better usingModel-driven BCs than default BC. Model-VAT provides a better user experienceto convert Model-driven BCs. Model-VAT is designed to efficientlyaccess and analyze the results of multi-models.
Atmospheric models are essential tools to study the behaviorof air pollutants. To interpret the complicated atmospheric modelsimulations, a new-generation Model Visualization and Analysis Tool(Model-VAT) has been developed for scientists to analyze the modeldata and visualize the simulation results. The Model-VAT incorporatesanalytic functions of conventional tools and enhanced capabilitiesin flexibly accessing, analyzing, and comparing simulated resultsfrom multi-scale models with different map projections and grid resolutions.The performance of the Model-VAT is demonstrated by a case study ofinvestigating the influence of boundary conditions (BCs) on the ambientHg formation and transport simulated by the CMAQ model over the PearlRiver Delta (PRD) region. The alternative BC options are taken from(1) default time-independent profiles, (2) outputs from a CMAQ simulationof a larger nesting domain, and (3) concentration files from GEOS-Chem(re-gridded and re-projected using the Model-VAT). The three BC inputsand simulated ambient concentrations and deposition were comparedusing the Model-VAT. The results show that the model simulations basedon the static BCs (default profile) underestimates the Hg concentrationsby ~6.5%, dry depositions by ~9.4%, and wet depositions by ~43.2%compared to those of the model-derived (e.g. GEOS-Chem or nestingCMAQ) BCs. This study highlights the importance of model nesting approachand demonstrates that the innovative functions of Model-VAT enhancesthe efficiency of analyzing and comparing the model results from variousatmospheric model simulations.
Peak of surface runoff was lagged andclipped by BRU with turf grass and B. Sinica. Lag of peak and extent of clipping wasinfluenced flow regime of inflow and plants grown. TN, TP and COD were removed by filtrationof the media and bio-degradation of reservoir layer. Infiltration rate and storage depth couldbe transferred key parameters for engineering design.
A bioretention unit (BRU) or cell is a green infrastructurepractice that is widely used as a low impact development (LID) techniquefor urban stormwater management. Bioretention is considered a goodfit for use in China’s sponge city construction projects. However,studies on bioretention design, which incorporates site-specific environmentaland social-economic conditions in China are still very much needed.In this study, an experimental BRU, consisted of two cells plantedwith Turf grass and Buxus sinica,was tested with eighteen synthesizedstorm events. Three levels (high, median, low) of flows and concentrationsof pollutants (TN, TP and COD) were fed to the BRU and the performanceof which was examined. The results showed that the BRU not only delayedand lowered the peak flows but also removed TN, TP and COD in variousways and to different extents. Under the high, medium and low inflowrate conditions, the outflow peaks were delayed for at least 13 minutesand lowered at least 52%. The two cells stored a maximum of 231 mmand 265 mm for turf grass and Buxus sinica, respectively. For both cells the total depth available for storagewas 1,220 mm, including a maximum 110 mm deep ponding area. The largestinfiltrate rate was 206 mm/h for both cells with different plants.For the eighteen events, TP and COD were removed at least 60% and42% by mean concentration, and 65% and 49% by total load, respectively.In the reservoir layer, the efficiency ratio of removal of TN, TPand COD were 52%, 8% and 38%, respectively, within 5 days after runoffevents stopped. Furthermore, the engineering implication of the hydrologicaland water quality performances in sponge city construction projectsis discussed.
Fe-BEA with zirconia binder has higher SCR activity in high temperature. Alumina enhances the low-temperature activity for greater NO oxidation and storage. The SCR activity of Fe-BEA/Al decreases in high temperature.
Fe-BEA catalysts are active for the NH3-SCR of NO. For industrial application, a binder should be added to the Fe-BEA catalysts to make them tightly adhere to the monoliths. The addition of alumina and zirconia as binders to the Fe-BEA led to a different effect on NO conversion. The catalytic activity of the mixed samples was evaluated by the temperature programmed procedure in a flow-reactor system, and the mechanism was analyzed via SEM, BET, XRD and XPS. It was found that larger iron particles were formed by the migration of parent iron particles in the Fe-BEA catalyst with alumina. This led to the increase of Fe3+ magnitude and iron cluster, enhancing the abilities of NO oxidation and storage. Accordingly, the SCR activity increased slightly in low temperature but decreased sharply in high temperature. For the Fe-BEA with zirconia sample, NO oxidation and storage abilities decreased due to the less iron clusters. The increase of Fe3+ magnitude resulted in higher catalytic oxidation ability, which gave rise to little change in the SCR activity compared with the Fe-BEA.
There is a rapidly emerging and potentially huge market for the remediation of contaminated groundwater in China. The Chinese government published a Water Action Plan in April 2015, a Soil Action Plan in May 2016, and a draft Soil Pollution Prevention and Control Law in June 2017. All of these new policies and regulations put pressures on local governments and contaminated site owners, obliging them to conduct site investigation and to cleanup contaminated groundwater. The Chinese population in northern regions heavily depend on groundwater, with nearly 70% of water supply coming from aquifer sources in the Beijing-Tianjin-Hebei region. However, poor groundwater quality due to natural geochemical background and anthropogeic pollution is a serious concern, with poor or very poor quality water observed in nearly 80% of groundwater monitoring wells in 17 northern provinces. Shallow groundwater in many areas has been contaminated by toxic pollutants such as heavy metals and chlorinated organic compounds. There is an urgent need to better understand the situation and to conduct groundwater remediation at contaminated sites. The Chinese government is investing heavily in the research and development for groundwater remediation, which is expected to greatly add to the quality and quantity of groundwater remediation projects in the near future.