Enhanced photo-degradation of contaminants in petroleum refinery wastewater

In order to rise efficiency of the wastewater treatment in a refinery plant, several oxidation experiments were done, testing their applicability as an additional pretreatment method. The influence of treatment with low concentrations of H2O2 combined with stirring and UV light on degradation of organic compounds present in the refinery wastewater was studied. Oxidation of the total petroleum hydrocarbons occurs at relatively low concentrations of H2O2, additional UV irradiation slightly accelerates the process due to the increased formation of hydroxyl radicals. 1,2-dichloroethane and t-butyl methyl ether degrade in the similar manner and except for the lowest H2O2 concentration used (1.17 mM), the reduction after 24 h is total. The degradation rate for dichloromethane is the lowest one, depending both on hydrogen peroxide concentration and the presence of UV. Its maximum reduction of 83% was obtained using the highest applied peroxide concentration of 11.76 mM.     

氧化剂协同即时成膜型光催化反应器降解有机物

研究了“表观”即时成膜型UV／TiO2光催化反应器降解水中有机污染物的过程中,外加氧化剂与UV／TiO2体系之间的协同效应。在UV／TiO2体系中单独投加H2O2或O3可以提高光催化氧化有机污染物的速率和效率,同时投加H2O2和O3时则光催化氧化的协同作用更加显著,可大大缩短反应时间。不同反应体系的表观速率常数排序为：UV／H2O2／O3／TiO2〉UV／O3／TiO2〉UV／H2O2／TiO2〉UV／O3〉UV／H2O2〉UV／TiO2。     

Application of nano TiO(2) towards polluted water treatment combined with electro-photochemical method

A novel composite reactor was prepared and studied towards the degradation of organic pollutants in this work. In the reactor, a UV lamp was installed to provide energy to excite nano TiO(2), which served as photocatalyst, leading to the production of hole-electron pairs, and a three-electrode electrolysis system was used to accumulate H(2)O(2) which played an important role in the degradation process. The reactor was evaluated by the degradation process of rhodamine 6G (R-6G), and the data obtained in the experiments showed that the combination of the photochemical and electrochemical system raised the degradation rate of R-6G greatly; the working mechanism of the reactor was also discussed in the article. The prepared reactor was also utilized to treat polluted water from dyeing and printing process. After continuous treatment for 0.5h, chemical oxygen demand biochemical oxygen demand, quantity of bacteria and ammonia nitrogen of the polluted water were reduced by 93.9%, 87.6%, 99.9% and 67.5%, respectively, which indicated that the method used here could be used for effective organic dyes degradation.     

UV-based processes for reactive azo dye mineralization

In the present study, advanced oxidation processes, UV/H2O2, UV/O3, and UV/H2O2/O3 have been applied to bleach and degrade organic dye C.I. Reactive Red 45 in water solution. Influence of pH and hydrogen peroxide dosage on process efficiency was investigated. The rate of color removal was studied by measuring the absorbance at the characteristic wavelength while mineralization rates were obtained on the basis of total organic carbon (TOC) and adsorbable organic halides (AOX) measurements. Complete bleaching was achieved by all applied processes after 60 min while the maximal mineralization extent depended on the reaction conditions for each of the processes. It has been found that UV/H2O2/O3 process was the most efficient with 61.1% TOC removal and 72.0% AOX removal, respectively, achieved after a 1-h treatment. Time required for complete mineralization of RR45 by UV/H2O2 and UV/H2O2/O3 processes was determined as well.     

Evaluation of UV irradiation for photolytic and oxidative degradation of pharmaceutical compounds in water

A medium-pressure (MP) ultraviolet (UV) system was used to investigate the UV photolysis and UV/H(2)O(2) oxidation of pharmaceutically active compounds (PhACs) that belong to different therapeutic classes and were found to occur in the aquatic environment. The results obtained in laboratory-grade water (LGW) and surface water (SW) were compared with low-pressure (LP) results reported previously. Overall, MP lamps proved to be more efficient to maximize the bench-scale degradation of the selected group of compounds (ketoprofen, naproxen, carbamazepine, ciprofloxacin, clofibric acid, and iohexol) by both UV photolysis and UV/H(2)O(2) oxidation. Fundamental direct and indirect photolysis parameters obtained in LGW are reported and used to model the MP-UV photolysis and MP-UV/H(2)O(2) oxidation of the pharmaceuticals in SW, predicting the experimental results very well.     

Destruction of cresols by Fenton oxidation process

The present study was used to probe the treatment of simulated wastewater containing cresols by Fenton process. Experiments were conducted in a batch reactor to examine the effects of operating variables like pH, hydrogen peroxide concentration (H(2)O(2)) and ferrous ion concentration (Fe(2+)) on chemical oxygen demand (COD) removal. The progress of the degradation reaction was monitored by the decrease in COD content in the treated solution. The optimal reacting conditions were experimentally determined and it was found to be [H(2)O(2)]=31.64 mM, [Fe(2+)]=0.90 mM for o- and p-cresol while 0.72 mM for m-cresol at pH=3.0+/-0.2. The degradation efficiency for cresol isomers was as high as 82% within 120 min at optimum conditions. A pseudo-first-order kinetic model was adopted to represent the Fenton oxidation for cresols. The mineralization rate for cresols obeys the following sequence: m->p->o-. Maximum degradation occurred at 30 degrees C for the temperature range of 20-50 degrees C studied. The global activation energy for the first-order reaction was estimated to be in the range of 12.90-16.25 kJ/mol. Air/nitrogen did not play an active role in completely mineralizing the organic intermediates at the experimental conditions adopted. Irrespective of the position of methyl group in o-, m- or p-position, the maximum dissolved organic carbon (DOC) removal efficiency was 42%. Only 2/5th of cresol was mineralized to CO(2) by Fenton process. The results showed that the cresols were completely oxidized and degraded into lower molecular weight aliphatic acids. Among the acids, acetic and oxalic acids were identified as the major products formed during the degradation.     

The role of effluent nitrate in trace organic chemical oxidation during UV disinfection

Most conventional biological treatment wastewater treatment plants (WWTPs) contain nitrate in the effluent. Nitrate undergoes photolysis when irradiated with ultraviolet (UV) light in the 200-240 and 300-325 nm wavelength range. In the process of nitrate photolysis, nitrite and hydroxyl radicals are produced. Medium pressure mercury lamps emitting a polychromatic UV spectrum including irradiation below 240 nm are becoming more common for wastewater disinfection. Therefore, nitrified effluent irradiated with polychromatic UV could effectively become a de facto advanced oxidation (hydroxyl radical) treatment process. UV-based advanced oxidation processes commonly rely on addition of hydrogen peroxide in the presence of UV irradiation for production of hydroxyl radicals. This study compares the steady-state concentration of hydroxyl radicals produced by nitrate contained in a conventional WWTP effluent to that produced by typical concentrations of hydrogen peroxide used for advanced oxidation treatment of water. The quantum yield of hydroxyl radical production from nitrate by all pathways was calculated to be 0.24 ± 0.03, and the quantum yield of hydroxyl radicals from nitrite was calculated to be 0.65 ± 0.06. A model was developed that would estimate production of hydroxyl radicals directly from nitrate and water quality parameters. In effluents with >5 mg-N/L of nitrate, the concentration of hydroxyl radicals is comparable to that produced by addition of 10 mg/L of H₂O₂. Nitrifying wastewater treatment plants utilizing polychromatic UV systems at disinfection dose levels can be expected to achieve up to 30% degradation of some micropollutants by hydroxyl radical oxidation. Increasing UV fluence to levels used during advanced oxidation could achieve over 95% degradation of some compounds.     

Treatment of biorefractory organic compounds in wool scour effluent by hydroxyl radical oxidation

Wool scouring effluent that had been treated with chemical flocculation and aerobic biological treatment (Sirolan CFB effluent) was tertiary treated by hydroxyl radical oxidation to remove residual organic compounds. These compounds impart a high chemical oxygen demand of 500-3000 mg/L and dark colour. However, a H2O2/UV process was found to effectively treat the majority of residual compounds, with up to 75% COD, 85% total organic carbon, and 100% removal of colour (T(480 nm)) achieved. This was despite the effluent being strongly absorbing in the UV region, with a film thickness of 0.21 mm reducing T(254 nm) by 50%. Treatment was unaffected by pH over the range 3-9. H2O2/UV treatment increased the biodegradability of the effluent (5-day biochemical oxygen demand increased from < 10 to 86 mg/L), but a combined chemical and biological process did not increase maximum COD removal or overall process efficiency. The tertiary treated effluent had a final COD in the range 125-750 mg/L, equating to a total COD removal from raw wool scour effluent of approximately 97.5%. This degree of treatment is sufficient for discharge in many, but not all, circumstances.     

pH sequential ozonation of domestic and wine-distillery wastewaters

Domestic and wine-distillery wastewaters were treated by semi-batch and continuous pH sequential ozonations. The process involves a succession of acidic and alkaline wastewater pH conditions. The alkaline periods allow oxidation of organic matter by hydroxyl radical and produce carbonates that eventually would inhibit the oxidation. On the other hand, the acidic periods favour the development of direct ozone reactions and strip off carbonates as carbon dioxide from the wastewater. Experimental results of pH sequential ozonation showed degradation and removal rates of wastewater pollutants higher than those achieved at constant either acidic or basic pH. The most significant improvement of ozone efficiency and pollutants removal were obtained by controlling the number of cycles, pH and time of acidic and alkaline phases. Also, ozonated wastewaters showed high biodegradability as deduced from their BOD/COD ratios. The feasibility of treating domestic and wine-distillery wastewater by an integrated activated sludge (ASP)-pH sequential ozonation system was evaluated. Integrated ASP-ozonation at constant pH processes were also carried out for comparative purposes. In these combined experiments, pH sequential ozonation showed advantages compared to ozonation at constant pH in reducing global parameters such as COD, TOC and TKN, but ozonation at constant pH led to higher removal of polyphenols and UV254 absorbing compounds.     

Application of ferrous hydrogen peroxide for treatment of DSD-acid manufacturing process wastewater

A pretreatment method for the biological treatment of wastewater from 4,4'-diaminostilbene-2,2'-disulfonic acid (DSD-acid) manufacturing processes, a refractory dye intermediate wastewater, based on combined ferrous hydrogen peroxide oxidation and coagulation-flocculation, was developed. When the wastewater was treated with ferrous hydrogen peroxide oxidation ([Fe2+] = 2.7 mmol/L, [H2O2] = 0.21 mol/L) after a flocculation using an organic flocculant TS-1 at a dosage of 3 g/L, the overall COD and color removals were 64 and 62%, respectively. BOD5/COD value of the effluent was 0.3. Ferrous hydrogen peroxide oxidation treatment can reduce the solubility of organic molecules with sulfonic group and increase the efficiency of coagulation treatment. The COD and color removals were both more than 90% when FeCl3 was used as the coagulation (dosages of two-step coagulation were 0.031 and 0.012 mol/L respectively) after a ferrous hydrogen peroxide oxidation pretreatment at a H2O2 dosage of 0.06 mol/L.     

二级氧化工艺预处理对硝基苯甲酸废水的研究

以对硝基苯甲酸废水为处理对象,分别考察了O3／GAC、ClO2／GAC工艺以及二者的组合工艺对有机物的去除效率和改善废水可生化性的效果。结果表明,O3／GAC工艺的最佳O3投量为400mg／L,ClO2／GAC工艺的最佳ClO2投量为300mg／L;单级氧化工艺处理出水的有机物浓度仍较高,不能满足后续生化处理对进水水质的要求;O3／CAC-ClO2／GAC组合工艺的处理效果优于ClO2／GAC-O3／GAC组合工艺,其对COD的去除率可达75％左右,并使BOD5／COD值由原水的0．10升高到0．46,提高了废水的可生化性,减轻了后续生化处理的负荷,是对硝基苯甲酸废水的有效预处理方法。     

O3／H2O2艺去除饮用水中2-MIB的效能与机制

以2-甲基异莰醇（MIB）为嗅味物质的代表物,采用过氧化氢／臭氧氧化（O3／H2O2）工艺去除水中嗅味物质,考察了O3／H2O2工艺对水中2一MIB的去除效能与主导作用机制。研究表明,投加H2O2显著提高了单独0,氧化对2-MIB的去除效能,H2O2与O3最佳物质的量比为0．3：1,且2-MIB去除效果随pH值的升高而升高。叔丁醇对2-MIB的去除表现出显著的抑制作用,在O3氧化2-MIB过程中,除O3分子氧化2-MIB外,O3在水中自分解产生的强氧化性的羟基自由基（HO·）也具有协同氧化作用。不同浓度的天然有机物（NOM）对2-MIB去除效果的影响不同,较低浓度的NOM促进了2-MIB的去除,但随着其浓度的升高,2-MIB去除率明显降低。O3／H2O2工艺对水中2-MIB表现出良好的去除效果,是强化去除水中2-MIB等致臭微量有机物的重要工艺。     

H2O2/TiO2 photocatalytic oxidation of metol. Identification of intermediates and reaction pathways

The applicability of H2O2 to increase the efficiency of TiO2 photocatalytic degradations was investigated. The photographic developer metol [N-methyl-p-aminophenol] that does not adsorb on the surface of TiO2 particulates was used as a model for this purpose. It was proved that metol was mineralised under oxidation with H2O2/TiO2/UV through different thermal and photochemical reactions. Identification of intermediates by both HPLC-electron impact-MS and HPLC-electrospray ionisation-MS helped to elucidate the role of H2O2 and TiO2 in the degradation process and to establish degradation pathways. Intermediates yielded were partially oxygenated aromatic species and dimers, which were amenable to oxidation. The optimal degradation conditions found for mineralisation were 0.4 M H2O2, 5 mg/ml TiO2, pH 9 and irradiation centred at 360 nm (4.9 mW/cm2). The use of oxidants opens an interesting medium to the treatment of effluents containing a diversity of organics since they increase substantially the efficiency of TiO2 photocatalytic degradations.     

Advanced oxidation processes for the degradation of microplastics from the environment: A review

Microplastic pollution has rapidly become one of the major global environmental concerns because of its low biodegradability rate and threat to biota. Although many treatment methods are reported, the advanced oxidation process (AOP) is recommended because of its capacity to completely mineralize organic pollutants into carbon dioxide and water. This review gathers published investigations on recent AOP techniques (UV/solar photolysis and photocatalysis (PC), UV/H₂O₂, Fenton reaction, sonolysis, heat-activated persulphate and peroxymonosulphate) tested for the degradation of microplastics from water and wastewater. The review lists 54 studies, by far the most comprehensive collection on the AOP-driven treatment of microplastics, and is also the first to explain the methods related to the ultrasonic degradation of microplastics. We found that all the reviewed AOP techniques achieved satisfying performance in the degradation of microplastics. This paper proposes recommendations for future research based on the review.     

微波/Fe-Zr联用技术处理正丁酸模拟废水的研究

采用自制的Fe—Zr为催化剂、H2O2为氧化剂、正丁酸为模拟污染物,以TOC去除率为指标,对微波／Fe—Zr联用技术进行了研究。分别考察了Fe—Zr用量、H2O2用量、微波炉的功率、微波的作用时间及Fe—Zr重复使用的次数对TOC去除率的影响;并利用一次回归正交试验确定了微波／Fe—Zr联用技术处理正丁酸模拟废水的优化条件,即处理TOC约为490mg／L的150mL正丁酸模拟废水,Fe—Zr的用量为4g、H2O2的用量为7mL、微波炉的功率为640W、微波的作用时间为10min,此时对TOC的去除率高达95％;最后在优化条件的基础上,对6种不同的处理工艺进行了比较,结果表明微彬Fe—Zr联用技术对TOC的去除率最高。     

UV/H2O2/微曝气处理微污染水中苯胺的试验研究

采用UV/H2O2/微曝气、UV/H2O2、UV/微曝气、H2O2/微曝气四种工艺处理受苯胺污染的水源水.试验结果表明,采用UV/H2O2/微曝气工艺,H2O2投加量分别为1,2,5,10和20 mL,对苯胺均有理想的去除效果.随着投加量的增加,苯胺的去除率并没有明显的提高,反应30 min后去除率分别达到94.3%,96.4%,96.5%,97.3%和96.8%.原水苯胺为0.90 mg/L时,投加1 mL H2O2反应30 min后,出水苯胺为0.06 mg/L,满足标准要求.UV/H2O2/微曝气、UV/H2O2、UV/微曝气、H2O2/微曝气四种工艺对苯胺的去除率均随着时间的增长而提高,40 min后趋于平稳,最高去除率分别为97.9%,94.5%,64.27%和13.84%,UV/H2O2/微曝气、UV/H2O2出水苯胺均低于规定限值.     

Drinking water treatment of priority pesticides using low pressure UV photolysis and advanced oxidation processes

This study reports the efficiency of low pressure UV photolysis for the degradation of pesticides identified as priority pollutants by the European Water Framework Directive 2000/60/EC. Direct low pressure UV photolysis and advanced oxidation processes (using hydrogen peroxide and titanium dioxide) experiments were conducted in laboratory grade water, surface water, and groundwater.LP direct photolysis using a high UV fluence (1500 mJ/cm²) was found to be extremely efficient to accomplish the degradation of all pesticides except isoproturon, whereas photolysis using hydrogen peroxide and titanium dioxide did not significantly enhance their removal. In all matrices tested the experimental photolysis of the pesticides followed the same trend: isoproturon degradation was negligible, alachlor, pentachlorophenol, and atrazine showed similar degradation rate constants, whereas diuron and chlorfenvinphos were highly removed. The degradation trend observed for the selected compounds followed the decadic molar absorption coefficients order with exception of isoproturon probably due to its extremely low quantum yield.Similar direct photolysis rate constants were obtained for each pesticide in the different matrices tested, showing that the water components did not significantly impact degradation. Extremely similar photolysis rate constants were also obtained in surface water for individual compounds when compared to mixtures. The model fluence and time-based rate constants reported were very similar to the direct photolysis experimental results obtained, while overestimating the advanced oxidation results. This model was used to predict how degradation of isoproturon, the most resilient compound, could be improved.     

Formation of oxidation byproducts from ozonation of wastewater

Disinfection byproduct (DBP) formation in tertiary wastewater was examined after ozonation (O(3)) and advanced oxidation with O(3) and hydrogen peroxide (O(3)/H(2)O(2)). O(3) and O(3)/H(2)O(2) were applied at multiple dosages to investigate DBP formation during coliform disinfection and trace contaminant oxidation. Results showed O(3) provided superior disinfection of fecal and total coliforms compared to O(3)/H(2)O(2). Color, UV absorbance, and SUVA were reduced by O(3) and O(3)/H(2)O(2), offering wastewater utilities a few potential surrogates to monitor disinfection or trace contaminant oxidation. At equivalent O(3) dosages, O(3)/H(2)O(2) produced greater concentrations of assimilable organic carbon (5-52%), aldehydes (31-47%), and carboxylic acids (12-43%) compared to O(3) alone, indicating that organic DBP formation is largely dependent upon hydroxyl radical exposure. Bromate formation occurred when O(3) dosages exceeded the O(3) demand of the wastewater. Bench-scale tests with free chlorine showed O(3) is capable of reducing total organic halide (TOX) formation potential by at least 20%. In summary, O(3) provided superior disinfection compared to O(3)/H(2)O(2) while minimizing DBP concentrations. These are important considerations for water reuse, aquifer storage and recovery, and advanced wastewater treatment applications.     

高级氧化+SBR工艺处理聚乙二醇废水试验研究

研究了高级氧化+SBR组合工艺处理高浓度聚乙二醇(PEG)废水的效果及其影响因素。结果表明,采用芬顿试剂作为高级氧化剂,当FeSO4.7H2O投加量为800 mg/L,H2O2投加量为30 mL/L,反应时间为3.5 h时,CODCr去除率可达到50.5%;生化处理阶段所需采用两级SBR工艺,污泥浓度均为4 000 mg/L,一、二级厌氧及好氧反应时间分别为12和10 h;芬顿试剂氧化和厌氧处理对提高PEG废水的可生化性有明显效果;该组合工艺的出水水质可以达到《污水综合排放标准》(GB 8978—1996)中的二级排放标准。     

Inactivation of enteric microorganisms with chemical disinfectants, UV irradiation and combined chemical/UV treatments

The relative disinfection efficiencies of peracetic acid (PAA), hydrogen peroxide (H2O2) and sodium hypochlorite (NaOCl) against Escherichia coli, Enterococcus faecalis, Salmonella enteritidis and coliphage MS2 virus were studied in laboratory-scale experiments. This study also evaluated the efficiency of combined PAA/ultraviolet irradiation (UV) and H2O2/UV treatments to determine if the microbial inactivation was synergistic. Microbial cultures were added into a synthetic wastewater-like test medium and treated by chemical disinfectants with a 10 min contact time, UV irradiation or the combination of chemical and UV treatments. A peracetic acid dose of 3 mg/l resulted in approximately 2-3 log enteric bacterial reductions, whereas 7-15 mg/l PAA was needed to achieve 1-1.5 log coliphage MS2 reductions. Doses of 3-150 mg/l hydrogen peroxide achieved below 0.2 log microbial reductions. Sodium hypochlorite treatments caused 0.3-1 log microbial reductions at an 18 mg/l chlorine dose, while 2.6 log reductions of E. faecalis were achieved at a 12 mg/l chlorine dose. The results indicate that PAA could represent a good alternative to chlorine compounds in disinfection procedures, especially in wastewaters containing easily oxidizable organic matter. Hydrogen peroxide is not an efficient disinfectant against enteric microorganisms in wastewaters. The combined PAA/UV disinfection showed increased disinfection efficiency and synergistic benefits with all the enteric bacteria tested but lower synergies for the coliphage MS2. This suggests that this method could improve the efficiency and reliability of disinfection in wastewater treatment plants. The combined H2O2/UV disinfection only slightly influenced the microbial reductions compared to UV treatments and showed some antagonism and no synergies.