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.

Kinetics of the direct reaction between ozone and phenol by high-gravity intensified heterogeneous catalytic ozonation

In this study,high-gravity intensified heterogeneous catalytic ozonation is utilized for treatment of phenol-containing wastewater,and the kinetics of the direct reaction between ozone and phenol in the presence of excess tertiary butanol(TBA)is investigated.It is revealed that the direct reaction between ozone and phenol in the rotating packed bed(RPB)follows the pseudo-first-order kinetics with a reaction rate constant higher than that in the conventional bubbling reactor(BR).Under different conditions of temperature,initial pH,high-gravity factor,and gaseous ozone concentration,the apparent reaction rate constant varies in the range of 0.0160–0.115 min-1.An empirical power-exponential model is established to characterize the effects of these parameters on the direct reaction between ozone and phenol by high-gravity intensified heterogeneous catalytic ozonation.

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.

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 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.

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.

Catalytic ozonation of phenol and oxalic acid with copper-loaded activated carbon

A novel heterogeneous catalytic ozonation process in water treatment was studied, with a copper-loaded activated carbon （Cu/AC） that was prepared by an incipient wetness impregnation method at low temperature and tested as a catalyst in the ozonation of phenol and oxalic acid. Cu/AC was characterized using XRD, BET and SEM techniques. Compared with ozonation alone, the presence of Cu/AC in the ozonation processes significantly improves the degradation of phenol or oxalic acid. With the introduction of the hydroxyl radical scavenger, i.e., turt-butanol alcohol （t-BuOH）, the degradation efficiency of both phenol and oxalic acid in the Cu/AC catalyzed ozonation process decreases by 22% at 30 min. This indicates that Cu/AC accelerates ozone decomposition into certain concentration of hydroxyl radicals. The amount of Cu（II ） produced during the reaction of Cu/AC-catalyzed ozonation of phenol or oxalic acid is very small, which shows that the two processes are both heterogeneous catalytic ozonation reactions.

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.

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.

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.

Optimization and Effects of Catalytic Ozonation of Actual Phenolic Wastewater by CuO/Al2O3

In order to improve the ability of ozone to catalyze the degradation of phenolic pollutants in wastewater,the CuO/Al2O3 catalysts was prepared by the impregnation precipitation method and an ozone catalytic oxidation system was constructed.The actual phenolic sewage was used as the treatment object.And the reaction conditions of the system were optimized,and the treatment effect was determined,while the non-catalytic system was used as a control group.At the same time,the influence of salt and ammonia nitrogen related water quality on the system was studied.The optimal reaction conditions for the treatment of phenolic wastewater covered:a catalyst dosage of 30 g/L,an ozone flow rate of 0.3 m3/h,a pH value of 8.80,and a reaction time of 15 minutes.Under these conditions,the phenol and COD removal rates of the system reached 98.7%and 49.4%,respectively,which were by 31.3 percentage points and 16.2 percentage points higher than that of the ozonation system alone.The salt and ammonia nitrogen in the sewage can reduce the oxidation effect of the system.When the salinity reached 10%and the ammonia nitrogen content reached 13 000 mg/L,the removal rate of phenol could be reduced by about 20%.The results of this paper have a reference value for phenol wastewater treatment engineering.

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.

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.

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.

Degradation of acephate using combined ultrasonic and ozonation method

The degradation of acephate in aqueous solutions was investigated with the ultrasonic and ozonation methods, as well as a combination of both. An experimental facility was designed and operation parameters such as the ultrasonic power, temperature, and gas flow rate were strictly controlled at constant levels. The frequency of the ultrasonic wave was 160 kHz. The ultraviolet-visible （UV-Vis） spectroscopic and Raman spectroscopic techniques were used in the experiment. The UV-Vis spectroscopic results show that ultrasonication and ozonation have a syn- ergistic effect in the combined system. The degradation efficiency of acephate increases from 60.6% to 87.6% after the solution is irradiated by a 160 kHz ultrasonic wave for 60 min in the ozonation process, and it is higher with the combined method than the sum of the separated ultrasonic and ozonation methods. Raman spectra studies show that degradation via the combined ultrasonic/ozonation method is more thorough than photocatalysis. The oxidability of nitrogen atoms is promoted under ultrasonic waves. Changes of the inorganic ions and degradation pathway during the degradation process were investigated in this study. Most final products are innocuous to the environment.

Magnéli phases TinO2n-1 as novel ozonation catalysts for effective mineralization of phenol

Magnéli phases TinO2n-1 have been demonstrated as promising environmentally friendly materials in advanced oxidation processes.In this study,Magnéli phases TinO2n-1 have been used as catalysts for the ozonation of phenol in aqueous solution for the first time.The materials exhibited excellent catalytic ozonation activities both in phenol degradation and mineralization.When Ti4O7was added,the reaction rate was six-fold higher than that of with ozone alone,while the total organic carbon removal rate was substantially elevated from around 19.2%to 92%.By virtue of the good chemical stability of the materials,a low metal leaching of less than 0.15 mg·L^-1could effectively avoid the secondary pollution by metal ions.Radical quenching tests revealed·O2^-and ^1O2to be active oxygen species for phenol degradation at p H 5.As semiconductor catalysts,TinO2n-1 materials show electronic transfer capability.Ozone adsorbed at B-acid sites of the catalyst surface can capture an electron from the conversion of Ti（Ⅲ）to Ti（Ⅳ）,and is thereby broken into the active oxygen species.It was interesting to observe that TinO2n-1 exhibit better catalytic activity for phenol degradation and mineralization with lower n value.The difference in electrical conductivity can be considered as a major factor for the catalytic performances.More highly conductive catalysts show a faster electron-transfer rate and better catalytic activity.Thus,significant evidences have been obtained for a single-electron-transfer mechanism of catalytic ozonation with Magnéli phases TinO2n-1.

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.

Sludge ozonation and its effect on performance of submerged membrane bio-reactor

To investigate the effects of ozonation on minimizing the excess sludge and enhancing the nitrogen removal in an effluent, batch and continuous experiments in two MBRs with and without sludge ozonation （ namely combined and reference run） were carried out. Through ozonation at a dose of 0. 16 mg O3/mg MLVSS, 53.1% of the treated MLVSS was solubilized, and soluble SCOD/TN ratio of ozonized sludge （OS） was about 8. 6 due to the release of cellular nitrogen-contained materials and SCOD loss by ozone mineralization. In addition, the results of batch nitrification and denitrification tests with OS supernatant indicated that solubilized sludge could act as a reducing power for denitrification and a nitrogen source for nitrification. 40-day operation of-two MBR systems demonstrated that the recirculation of OS into a bioreaetor enabled the combined system have two advantages over the control one. The observed sludge yield （Yobs） was decreased from 0. 13 to 0. 06g MLSS/g COD, while the nitrogen removal was increased from 64. 6% to 72. 3%. And sludge ozonation elevated the inorganic fraction of MLSS, but did not impact sludge activities.