Constructing fast mass-transfer channels with efficient catalytic ozonation activity in 2D manganese dioxide membranes by intercalating Fe/Mn bimetallic MOF

Two-dimensional(2D)catalytic ozonation membranes are promising for the treatment of micropollutants in wastewater due to simultaneous ozone-catalyzed degradation and membrane filtration processes.However,it remains challenging for 2D catalytic ozonation membranes to efficiently degrade micropollutants due to low mass-transfer efficiency and poor catalytic activity.Herein,Fe/Mn bimetallic metal-organic framework(MOF)intercalated lamellar MnO_(2) membranes with fast and robust ozone-catalyzed mass-transfer channels were developed on the surface of the hollow fiber ceramic membrane(HFCM)to obtain 2D Fe/Mn-MOF@MnO_(2)-HFCM for efficiently degrading micropollutants in wastewater.The intercalation of Fe/Mn-MOF expanded the interlayer spacing of the MnO_(2) membrane,thereby providing abundant transport channels for rapid passage of water.More notably,the Fe/Mn-MOF provided enriched reactive sites as well as high electron transfer efficiency based on the redox cycling between Mn^(3+)/Mn^(4+) and Fe^(2+)/Fe^(3+),ensuring the effective catalytic oxidative degradation of micropollutants including tetracycline hydrochloride(TCH),methylene blue,and methyl blue.Moreover,the carboxyl groups on the MOF formed covalent bonds(-COO-)with the hydroxyl groups in MnO_(2) between layers,which increased the interaction between MnO_(2) nanosheets to form stable interlayer channels.Specifically,the optimal composite membrane achieved a high removal rate of TCH micropollutant(93.4%),high water treatment capacity(282 L·m^(-2)·h^(-1)·MPa^(-1)),and excellent longterm stability(1200 min).This study provides a simple and easily scalable strategy to construct fast,efficient,and stable 2D catalytic mass-transfer channels for the efficient treatment of micropollutants in wastewater.

Photocatalytic ozonation-based degradation of phenol by ZnO—TiO_(2)nanocomposites in spinning disk reactor

Spinning disk reactor(SDR)has emerged as a novel process intensification photocatalytic reactor,and it has higher mass transfer efficiency and photon utilization for the degradation of toxic organic pollutants by advanced oxidation processes(AOPs).In this study,ZnO—TiO_(2)nanocomposites were prepared by solgel method,and coated on the disk of SDR by impregnation-pull-drying-calcination method.The performance of catalyst was characterized by X-ray diffraction,scanning electron microscope,X-ray photoelectron spectroscopy,photoluminescence and ultraviolet—visible diffuse reflectance spectroscopy.Photocatalytic ozonation in SDR was used to remove phenol,and various factors on degradation effect were studied in detail.The results showed that the rate of degradation and mineralization reached 100%and 83.4%under UV light irradiation after 50 min,compared with photocatalysis and ozonation,the removal rate increased by 69.3%and 34.7%,and mineralization rate increased by 56.7%and 62.9%,which indicated that the coupling of photocatalysis and ozonation had a synergistic effect.The radical capture experiments demonstrated that the active species such as photogenerated holes(h^(+)),hydroxyl radicals(·OH),superoxide radical(·O_(2)-)were responsible for phenol degradation,and·OH played a leading role in the degradation process,while h+and·O_(2)^(-)played a non-leading role.

Effects of Coagulation and Ozonation Pretreatments on Biochemical Treatment of Fluid Catalytic Cracking Wastewater

Fluid catalytic cracking (FCC) salty wastewaters, containing quaternary ammonium compounds (QACs), are very difficult to treat by biochemical process. Anoxic/oxic (A/O) biochemical system, based on nitrification and denitrification reactions, was used to assess their possible biodegradation. Because of the negative effects of high salt concentration (3%), heavy metals and toxic organic matter on microorganisms’ activities, some techniques consisting of dilution, coagulation and flocculation, and ozonation pretreatments, were gradually tested to evaluate chemical oxygen demand (COD), ammonia-nitrogen (ammonia-N) and total nitrogen (TN) removal rates. In this process of FCC wastewater, starting with university-domesticated sludge, the ammonia-N and TN removal rates were worst. However, when using domesticated SBR’s sludge and operating with five-fold daily diluted influent (thus reducing salt concentration), the ammonia-N removal reached about 57% while the TN removal rate was less than 37% meaning an amelioration of the nitrification process. However, by reducing the dilution factors, these results were inflected after some days of operation, with ammonia-N removal decreasing and TN barely removed meaning a poor nitrification. Even by reducing heavy metals concentration with coagulation/flocculation process, the results never changed. Thereafter, by using ozonation pre-treatment to degrade the detected organic matter of di-tert-butylphenol and certain isoparaffins, COD, ammonia-N and TN removal rates reached 92%, 62% and 61%, respectively. These results showed that the activities of the microorganisms were increased, thus indicating a net denitrification and nitrification reactions improvement.

Slowing down of the summer Southern Hemisphere Annular Mode trend against the background of ozone recovery

20世纪末期,南半球热带外地区经历了显著的气候变化,包括夏季南半球环状模(SAM)的显著上升趋势,伴随着南极半岛的增暖和别林斯高晋海的海冰融化.这些趋势主要是由20世纪末期南极平流层臭氧消耗所驱动的.本文发现,自2001年左右以来,在南极平流层臭氧恢复的背景下,观测到的夏季SAM的上升趋势已经趋于平缓,验证了前人利用数值模拟预测的夏季SAM上升趋势减缓现象,与SAM在臭氧恢复后趋势只减缓但没有逆转不同,南极地表气温和海冰的趋势发生了逆转.南极半岛由变暖趋势转为降温趋势,别林斯高晋海域的海冰由融化趋势转为增多趋势.

Ozonation and Biodegradability of Lignin in Water

To convert the non biodegradable sodium lignin sulfonate into biodegradable substances, the sodium lignin sulfonate in the water was ozonized and the pH value, dissolved organic carbon(DOC), ultraviolet absorbency at λ =254 nm(UVA) and the biodegradability of the ozonation effluent were measured. The non biodegradable sodium lignin sulfonate can be partly converted into biodegradable substances by ozonation (about 38 76%). In the ozonation process, there is little DOC decrease, but much UVA decrease and obvious pH drop.

Recycle of Wastewater from Lead-Zinc Sulfide Ore Flo-tation Process by Ozone/BAC Technology

Lead-zinc sulphide ore contains lead sulphide (galena), and zinc sulphide (sphalerite). In the first flotation stage, galena is rendered hydrophobic with an organic collector such as xanthate, while sphalerite is kept from floating by depressants, and in the second flotation stage, activator was used to activated zinc flotation. Since the organic regent used are different in the two flotation stage, wastewater from the second zinc flotation stage can’t be directly recycled to the first lead flotation stage. Wastewater from flotation process for concentrating lead-zinc sulphide ore often containing organic compounds such as diethyldithiocarbamate(DDTC), xanthate, terpenic oil(2# oil) and thionocarbamate esters (Z-200), are environmentally hazardous. Their removal from contaminated water and the reuse of the water is one of the main challenges facing lead-zinc sulphide ore processing plants. In this study, synthetic wastewater containing DDTC, xanthate, 2# oil and Z-200 at concentrations ranging from 21 to 42 mg/L was fed into an Ozone/Biological activated carbon (BAC) reactor. Analyses of the effluent indicated a chemical oxygen demand (COD) removal over 86.21% and Total organic carbon (TOC) removal over 90.00% were achieved under Hydraulic retention time (HRT) of 4h and O3 feeding concentration of 33.3mg/L. The effluent was further recycled to the lab scale lead concentrating process and no significant difference was found in compare with fresh water. Furthermore, lead-zinc sulphide mineral concentrating process was carried out at lab scale. The produced wastewater was treated by Ozone/BAC reactor at O3 feeding concentration of 16.7mg/L and HRT of 4h. The effluent analysis showed that TOC removal was 74.58%. This effluent was recycled to the lab scale lead-zinc sulphide mineral concentrating process and the recovery of lead was not affected. The results showed that by using Ozone/BAC technology, the lead-zinc sulphide mineral processing wastewater could be recycled.

Degradation Mechanism of Cationic Red X-GRL by Ozonation

The degradation mechanism of Cationic Red X-GRL was investigated when the intermediates, the nitrate ion and the pH were analyzed in the ozonation. The degradation of the Cationic Red X-GRL includes the de-auxochrome stage, the decolour stage, and the decomposition of fragment stage. During the degradation process, among the six nitrogen atoms of Cationic Red X-GRL, one is transferred into a nitrate ion, one becomes the form of an amine compound, and the rest four are transformed into two molecules of nitrogen. In the course of the ozonation of Cationic Red X-GRL, the direct attack of ozone is the main decolour effect.

Pilot plant study on ozonation and biological activated carbon process for drinking water treatment

A study on advanced drinking water treatment was conducted in a pilot scale plant taking water from conventional treatment process. Ozonation-biological activated carbon process （O3-BAC） and granular activated carbon process （GAC） were evaluated based on the following parameters： CODMn, UV254, total organic carbon （TOC）, assimilable organic carbon （AOC） and biodegradable dissolved organic carbon （BDOC）. In this test, the average removal rates of CODMn, UV254 and TOC in O3-BAC were 18.2%, 9.0% and 10.2% higher on （AOC） than in GAC, respectively. Ozonation increased 19.3-57.6 μg Acetate-C/L in AOC-P17, 45.6-130.6 μg Acetate-C/L in AOC-NOX and 0.1-0.5 mg/L in BDOC with ozone doses of 2 8 mg/L. The optimum ozone dose for maximum AOC formation was 3 mgO3/L. BAC filtration was effective process to improve biostability.

Degradation of benzophenone in aqueous solution by Mn-Fe-K modified ceramic honeycomb-catalyzed ozonation

Comparative studies of ozonation alone, ceramic honeycomb-catalyzed and Mn-Fe-K modified ceramic honeycomb catalyzed ozonation processes have been undertaken with benzophenone as the model organic pollutant. The experimental results showed that the presence of Mn-Fe-K modified ceramic honeycombs significantly increased the removal rate of benzophenone and TOC compared with that achieved by ozonation alone or ceramic honeycomb-catalyzed ozonation. The electron paramagnetic resonance （EPR） experiments verified that higher benzophenone removal rate was attribute to more hydroxyl radicals generated in the Mn-Fe-K modified ceramic honeycomb-catalyzed ozonation. Under the conditions of this experiment, the degradation rate of all the three ozonation processes are increasing with the amount of catalyst, temperature and value of pH increased in the solution. We also investigated the effects of different process of ozone addition, the optimum conditions for preparing catalyst and influence of the Mn-Fe-K modified ceramic honeycomb after multiple-repeated use.

Degradation of Organic Pollutants in Water by Catalytic Ozonation

Different series of transition metal catalysts supported on Al2O3 were prepared by the impregnation method. The catalytic activity was measured in a batch reactor with ozone as the oxidizing reagent. The experimental results indicate that Cu/Al2O3 has a very effective catalytic activity during the ozonation of organic pollutants in water. The optimum conditions for preparing Cu/Al2O3 were systematically investigated with the orthogonal testing method. Furthermore, the results also show that the surface properties of catalyst are not compulsory for effective oxidation.

Removal of a type of endocrine disruptors—di-n-butyl phthalate from water by ozonation

Ozonation of synthetic water containing a type of endocrine disruptor-di-n-butyl phthalate （DBP） was examined. Key impact factors such as pH, temperature, ionic strength, ozone dosage and initial DBP concentration were investigated. In addition, the activities of radicals on uncatalysed and catalysed ozonation were studied. The degradation intermediate products were followed and the kinetic of the ozonation were assessed as well. Results revealed that ozonation of DBP followed two mechanisms. Firstly, the reaction rate of direct ozonation was slower at lower pH, temperature, and ionic strength. Secondly, when these factors were increased for indirect radical reaction, higher percentage of DBP was removed with the increase of the initial ozone dosage and the decrease of the initial DBP concentration. In addition, tea-butanol, humic substances and Fe（Ⅱ） affected DBP ozonation through the radical pathway. It was determined that ozonation was restrained by adding tea-butanol for its radical inhibition effect. Furthermore, humic substances enhanced the reaction to some extent, but a slight negative effect would be encountered if the optimum dosage was exceeded. As a matter of fact, Mn（Ⅱ） affected the ozonation by ＂active sites＂ mechanism. In the experiment, three different kinds of intermediate products were produced during ozonation, but the amount of products for each one of them decreased as pH, temperature, ionic strength and initial ozone dosage increased. A kinetic equation of the reaction between ozone and DBP was obtained.

Comparison of Ozone and PM2.5 Concentrations over Urban,Suburban,and Background Sites in China

Surface ozone(O3)and fine particulate matter(PM2.5)are dominant air pollutants in China.Concentrations of these pollutants can show significant differences between urban and nonurban areas.However,such contrast has never been explored on the country level.This study investigates the spatiotemporal characteristics of urban-to-suburban and urban-tobackground difference for O3(Δ[O3])and PM2.5(Δ[PM2.5])concentrations in China using monitoring data from 1171 urban,110 suburban,and 15 background sites built by the China National Environmental Monitoring Center(CNEMC).On the annual mean basis,the urban-to-suburbanΔ[O3]is−3.7 ppbv in Beijing-Tianjin-Hebei,1.0 ppbv in the Yangtze River Delta,−3.5 ppbv in the Pearl River Delta,and−3.8 ppbv in the Sichuan Basin.On the contrary,the urban-to-suburbanΔ[PM2.5]is 15.8,−0.3,3.5 and 2.4μg m^−3 in those areas,respectively.The urban-to-suburban contrast is more significant in winter for bothΔ[O3]andΔ[PM2.5].In eastern China,urban-to-background differences are also moderate during summer,with−5.1 to 6.8 ppbv forΔ[O3]and−0.1 to 22.5μg m^−3 forΔ[PM2.5].However,such contrasts are much larger in winter,with−22.2 to 5.5 ppbv forΔ[O3]and 3.1 to 82.3μg m^−3 forΔ[PM2.5].Since the urban region accounts for only 2%of the whole country’s area,the urban-dominant air quality data from the CNEMC network may overestimate winter[PM2.5]but underestimate winter[O3]over the vast domain of China.The study suggests that the CNEMC monitoring data should be used with caution for evaluating chemical models and assessing ecosystem health,which require more data outside urban areas.

Adsorption and Ozonation Kinetic Model for Phenolic Wastewater Treatment

A three phase fluidized bed reactor was used to investigate the combined effect of adsorption and oxidation for phenolic wastewater treatment.Aqueous solutions containing 10 mg·L 1of phenol and ozone were continuously fed co-currently as upward flow into the reactor at constant flow rate of 2 and 1 L·min 1,respectively.The phenolic treatment results in seven cases were compared：（a）O3 only,（b）fresh granular activated carbon（GAC）,（c） 1st reused GAC,（d）2nd reused GAC,（e）fresh GAC enhanced with O3,（f）1st reused GAC enhanced with O3,and （g）2nd reused GAC enhanced with O3.The phenolic wastewater was re-circulated through the reactor and its concentration was measured with respect to time.The experimental results revealed that the phenolic degradation using GAC enhanced with O3 provided the best result.The effect of adsorption by activated carbon was stronger than the effect of oxidation by ozone.Fresh GAC could adsorb phenol better than reused GAC.All cases of adsorption on GAC followed the Langmuir isotherm and displayed pseudo second order adsorption kinetics.Finally,a differential equation for the fluidized bed reactor model was used to describe the phenol concentration with respect to time for GAC enhanced with O3.The calculated results agree reasonably well with the experimental results.

Pilot Study on Nanofiltration Combined with Ozonation and GAC for Advanced Drinking Water Treatment

A pilot-scale study of advanced drinking water treatment was carried out in test site, and a combination of ozonation, granular activated carbon (GAC) and nanofiltration was employed as the experimental process. By optimizing the operational parameters of ozonation and GAC, a large quantity of micro-pollutants in drinking water was removed, which made the post-positioned nanofiltration operate more reliably. It was evident that nanofiltration shows good performance for removing residual organic matter, meantime partial minerals can also be retained by nanofiltration. Therefore the quality of drinking water can be further improved. In addition, NF membrane fouling and scaling can be solved by concentrate recycling, anti-scalant dosing and chemical rinsing effectively. By GAC adsorption for the residue chlorine and ozone self-decomposition, their oxidation on NF membrane material can be eliminated completely.

Decomposition of alachlor by ozonation and its mechanism

Decomposition and corresponding mechanism of alachlor, an endocrine disruptor in water by ozonation were investigated. Results showed that alachlor could not be completely mineralized by ozone alone. Many intermediates and final products were formed during the process, including aromatic compounds, aliphatic carboxylic acids, and inorganic ions. In evoluting these products, some of them with weak polarity were qualitatively identified by GC-MS. The information of inorganic ions suggested that the dechlorination was the first and the fastest step in the ozonation of alachlor.

Dielectric Barrier Discharge Plasma-Induced Photocatalysis and Ozonation for the Treatment of Wastewater

The physicochemical processes of dielectric barrier discharge （DBD） such as insitu formation of chemically active species and emission of ultraviolet （UV）/visible light were utilized for the treatment of a simulated wastewater formed with Acid Red 4 as the model organic contaminant. The chemically active species （mostly ozone） produced in the DBD reactor were well distributed in the wastewater using a porous gas diffuser, thereby increasing the gas-liquid contact area. For the purpose of making the best use of the light emission, a titanium oxide-based photocatalyst was incorporated in the wastewater treating system. The experimental parameters chosen were the voltage applied to the DBD reactor, the initial pH of the wastewater, and the concentration of hydrogen peroxide added to the wastewater. The results have clearly shown that the present system capable of degrading organic contaminants in two ways （photocatalysis and ozonation） may be a promising wastewater treatment technology.

Efficient ozonation of reverse osmosis concentrates from petroleum refinery wastewater using composite metal oxideloaded alumina

Novel Mn–Fe–Mg-and Mn–Fe–Ce-loaded alumina（Mn–Fe–Mg/Al2O3 and Mn–Fe–Ce/Al2O3） were developed to catalytically ozonate reverse osmosis concentrates generated from petroleum refinery wastewaters（PRW-ROC）. Highly dispersed 100–300-nm deposits of composite multivalent metal oxides of Mn（Mn^2＋）, Mn^3＋,and Mn^4＋, Fe（Fe^2＋）and Fe^3＋ and Mg（Mg^2＋）, or Ce（Ce^4＋） were achieved on Al2O3 supports. The developed Mn–Fe–Mg/Al2O3 and Mn–Fe–Ce/Al2O3 exhibited higher catalytic activity during the ozonation of PRW-ROC than Mn–Fe/Al2O3, Mn/Al2O-3, Fe/Al2O3, and Al2O3. Chemical oxygen demand removal by Mn–Fe–Mg/Al2O3-or Mn–Fe–Ce/Al2O3-catalyzed ozonation increased by 23.9% and23.2%, respectively, in comparison with single ozonation.Mn–Fe–Mg/Al2O3 and Mn–Fe–Ce/Al2O3 notably promoted áOH generation and áOH-mediated oxidation. This study demonstrated the potential use of composite metal oxide-loaded Al2O3 in advanced treatment of bio-recalcitrant wastewaters.

Reaction Kinetics of Ozonation of Trichloroethylene and Benzene in Gas and Liquid Phases

The kinetics of ozonation reactions of trichloroethylene (TCE) and benzene in gas and liquid phases at 101.3 kPa and 298 K was investigated in this paper. The ozonation of TCE is first order with respect to the ozone concentration and one and half order to TCE in the gas phase with the average rate constant 57.30 (mol·L-1)-1.5·s-1, and the TCE ozonation in aqueous medium is first order with respect to both ozone and trichloroethylene with the average rate constant 6.30 (mol·L-1)-1·-1. The ozonation of benzene in the gas phase is first order in ozone but independent of the benzene concentration with the average reaction rate constant 0.0011s-1. The overall kinetics of reaction between ozone and benzene in aqueous solution is found to be first order with one-half order in both ozone and bezene, with the average reaction rate constant 2.67s-1. It is found that the ozonation rate of pallutants is much quicker than that of self-decomposition of ozone in both gas and aqueous phase.

Preozonation of bromide-bearing source water in south China

The effectiveness of preozonation was evaluated on treating a bromide-bearing dam source water in south China through batch-scale experiments. Preozonation at ozone doses of 0.5-1.0 mg/L （at ozone consumption base） enhanced total organic carbon （TOC） removal through coagulation, and resulted in an almost linear reduction of ultraviolet absorbance at 254 nm （LW2s4）. The removals of TOC （after coagulation） and UV254 at the ozone dose of 1.0 mg/L were 36% and 70%, respectively. Preozonation at an ozone dose between 0.5 and 1.0 mg/L resulted in the removal of disinfection byproducts formation potential （DBFP） including trihalomethane formation potential （THMFP） and haloacetic acid formation potential （HAAFP） for about 50%. The removals of THMFP and HAAFP decreased with the further increase of ozone dose. Ozonation of bromide-bearing water （bromide concentration, 34 μg/L） produced a bromate concentration under the detection limit（2μg/L） at ozone doses 〈1.5 mg/L. However, bromate 〉10μg/L could be produced when the bromide concentration was increased to 96 μg/L.

Modeling of organic pollutant destruction in a stirred tank reactor by ozonation

Destruction of organic contaminants in water by ozonation is a gas-liquid process which involves ozone mass transfer and fast irreversible chemical reactions. Ozonation reactor design and process optimizing require the modeling of the gas-liquid interactions within the reactor. In this paper a theoretical model combining the fluid dynamic and reaction kinetic parameters is proposed for predicting the destruction rates of organic pollutants in a semi-batch stirred-tank reactor by ozonation. A simple expression for the enhancement factor as our previous work has been applied to evaluate the chemical mass transfer coefficient in ozone absorption. 2,4-dichlorophenol (2,4-DCP) and 2,6-DCP or their mixture are chosen as the model compounds for simulating, and the predicted DCP concentrations are compared with some measured data.