Evaluation of hybrid treatments to produce high quality reuse water

Four tertiary hybrid treatments to produce high quality reused water, fulfilling Brazilian drinking water regulations, from a slaughterhouse's secondary treated effluent were evaluated. The pilot plant with a capacity of 500 L h(-1) was set up and consisted of these stages: pre-filtration system (cartridge filter 50 micron, activated carbon filter, cartridge filter 10 micron), oxidation (H2O2) or second filtration (ceramic filter, UF) followed by UV radiation (90 L h(-1)). The best combination was T4: pre-filtration followed by H2O2 addition and UV radiation (AOP H2O2/UV). Disinfection kinetics by T4 followed pseudo first-order kinetics: k(T4) = 0.00943 s(-1) or 0.00101 cm2 mJ(-1). Three different zones (A, B, C) were observed in the UV254 degradation kinetics (pseudo-first order kinetics): k' decreased over time (k'(A) > k'(B) > k'(C)).     

Photodegradation of hydrophobic disperse dyes and dye-bath effluents by silicadodecatungstate (SiW12O40(4-/5-)) nanoparticles.

Polyoxometalate (POM) silicadodecatungstic acid has been applied as a photochemical catalyst for the degradation of SETAPERS Black WNSP, a disperse dyestuff preparation widely used to dye polyester and polyamide fabrics. It could be demonstrated that the disperse dyestuff was photo-reduced by SiW12O40(5-), the one-electron reduced form of POM, as evidenced by Heteropolyblue (HPB) formation. For completion of the photochemical redox cycle, isopropanol (IsOH) was required. Acetone (Ac) served solely as an effective solute and photosensitizer; however this effect was suppressed in the presence of POM. Threshold (0.087 mM) and optimum (0.375 mM) POM concentrations existed and decolorization kinetics were inhibited upon the addition of dye auxiliary chemicals. Increasing the dyestuff concentration from 50 mg/L to 150 mg/L did not affect initial decolorization kinetics revealing that not the formation of the excited [POM-Substrate]* complex, but its reduction to HPB was the rate limiting step. POM-mediated, IsOH-assisted UV-photodegradation of disperse dyes and dye-baths is by far more effective than applying other, more well known chemical oxidation methods (O3, H202/UV, Power Ultrasound). Key to the action of POM redox catalysts is the feature that particularly heteropoly tungstates undergo facile re-oxidation to their original state, thus allowing regeneration of the photocatalyst, a feature that may become critical for real-scale application.     

Study on the treatment of Acid Red 4 wastewaters by a laminar-falling-film-slurry-type VUV photolytic process.

The purpose of this study is to develop the design equation of a laminar-falling-film-slurry-type (LFFS) photoreactor for the treatment of organic wastewaters (Acid Red 4) by 185 nm vacuum ultra-violet (VUV) related processes. The LFFS photoreactor is one of the most efficient reactor configurations for conducting heterogeneous photocatalytic reactions, particularly for wastewater treatment. The decomposition of Acid Red 4 dye wastewaters by VUV-based photo-oxidation process was studied under various UV light intensities, dosages of H2O2 and TiO2. By the treatment of the LFFS-VUV only process, it was found that the decomposition rates of the dye in aqueous solutions increased with the increasing of VUV light intensity, dosage of TiO2, dosage of H2O2. The apparent potential of OH. generation from the photolysis of used oxidants (i.e. OH. sources, H2O, H2O2, TiO2) to decompose the targeted dye wastewater was investigated and compared.     

Evaluation of the combined solar TiO2/photo-Fenton process using multivariate analysis.

The effect of combining the photocatalytic processes using TiO2 and the photo-Fenton reaction with Fe3+ or ferrioxalate as a source of Fe2+ was investigated in the degradation of 4-chlorophenol (4CP) and dichloroacetic acid (DCA) using solar irradiation. Multivariate analysis was used to evaluate the role of three variables: iron, H2O2 and TiO2 concentrations. The results show that TiO2 plays a minor role when compared to iron and H2O2 in the solar degradation of 4CP and DCA in the studied conditions. However, its presence can improve TOC removal when H2O2 is totally consumed. Iron and peroxide play major roles, especially when Fe(NO3)3 is used in the degradation of 4CP. No significant synergistic effect was observed by the addition of TiO2 in this process. On the other hand, synergistic effects were observed between FeOx and TiO2 and between H2O2 and TiO2 in the degradation of DCA.     

Ti/MCM-22/MCM-41微介孔复合材料光催化降解酸性红B模拟废水的研究

采用纳米自组装法制备了具有吸附性和光催化性的Ti/MCM-22/MCM-41微介孔复合材料,利用X射线衍射、N2吸附、扫描电镜等方法对其进行表征。将复合材料用于光催化降解酸性红B的实验,考察了催化剂用量、光照时间、pH值和染料初始浓度对光催化降解率的影响,并对光降解产物进行了紫外光谱分析。结果表明:当染料的初始浓度为50 mg/L,废水pH在6左右,催化剂投加量为0.1 g/L,光照时间120 min,酸性红B的去除率可达98%以上,光催化降解反应遵循一级反应动力学方程。降解产物的紫外光谱图表明,降解后酸性红B的两个特征吸收带消失,结构的共轭系被打破,颜色消失,说明该复合材料去除水中的酸性红B主要是通过光催化作用。     

Noble metal modified titania catalysts in the degradation of reactive black 5: a kinetic approach

The photocatalytic degradation of Reactive Black 5 (RB 5), a di-azo dye was investigated over M/TiO2 (M = Ag, Au and Pt) photocatalysts irradiated with UV and visible light. TiO2 was prepared by sol-gel technique (Syn-TiO2). Photodeposition of metal salt precursors over Syn-TiO2 was carried out so as to obtain 1 wt% of M/TiO2 catalysts. The photodecolourization and photodegradation reactions were also compared with commercial TiO2 (Degussa P25) catalyst. Kinetic studies for the decolourization of RB 5 showed that it followed pseudo first order. Recycling of catalysts was performed to check the economic feasibility of the photocatalytic process. In order to check the applicability of M/TiO2 catalyst in the treatment of industrial effluent, real textile effluent was collected from an industry and subjected to photodegradation and the results are presented. Enhanced activity of M/TiO2 catalyst under visible light irradiation highlights its importance in the field of photocatalysis.     

Decolorization and mineralization of reactive dyes by a photocatalytic process using ZnO and UV radiation

Reactive dyes are one of the major pollutants in textile wastewater and a concern because they are not easily degraded by conventional wastewater treatments. Heterogeneous photocatalysis has been considered an effective option for treating wastewater containing those dyes. This research work assesses the photocatalytic degradation of reactive dyes using UV irradiation and pure or impregnated ZnO. In addition to photocatalysis, separate photolysis and adsorption experiments were conducted but showed low efficiency. The dye degradation was monitored by UV-Vis spectroscopy and mineralization was determined by total organic carbon (TOC) analyses. Total color removal was achieved after 30 min of irradiation using pure ZnO. The Black 5 dye photocatalytic decolorization reaction followed first-order kinetics, while Yellow 145, Red 4 and Blue 21 dyes followed zero-order kinetics. TOC removals in the range of 70-80% were achieved after 240 min of individual photocatalytic treatment with ZnO. The performance of each photocatalyst was also compared when the four dyes were mixed together and the order of efficiency in the mineralization process was as follows: Fe/ZnO > ZnO > Co/ZnO. This result was explained by the crystal field theory.     

Effect of support and second metal in catalytic in-situ generation of hydrogen peroxide by Pd-supported catalysts: application in the removal of organic pollutants by means of the Fenton process

A catalytic system for the generation of H2O2 from formic acid and oxygen at ambient conditions has been developed. Pd-supported catalysts (Pd/C, Pd/TiO2 and Pd/Al2O3) have been tested, showing that for bulk purposes Pd/Al2O3 is more favourable while for in-situ applications Pd/TiO2 seems to be preferable. However, when these catalysts were tested in the in-situ H2O2 generation for the oxidation of phenol by means of the Fenton process (in the presence of ferrous ion), Pd/TiO2 did not demonstrate the expected results, whereas Pd/Al2O3 showed to be an efficient catalyst. Therefore, Pd/Al2O3 is offered as a good catalyst for Fenton's reactions with in-situ generated H2O2. In order to optimize the operating cost of the process, different initial concentrations of formic acid have been tested with Pd/Al2O3, and it has been seen that lowering the initial amount of formic acid favours the efficiency of the process. The effect of the addition of a second metallic (Pt, Au, Fe, Cu) active phase was studied. Concerning H2O2 generation, best results were obtained with a Pd-Au catalyst for bulk production (long time) while for in-situ application Pd-Fe showed interesting results. The Pd-Fe catalyst also performed similarly to the semi-heterogeneous Fenton system involving Pd/Al2O3 and ferrous ion in the degradation of phenol. Therefore, Pd-Fe catalyst offered an interesting prospect for making a full heterogeneous catalyst for Fenton reaction involving in-situ generation of H2O2.     

Fenton氧化处理甲基橙染料模拟废水的动力学研究

采用Fenton试剂降解含甲基橙染料的模拟废水,通过对甲基橙染料处理过程中UV-Vis吸收光谱的分析,证明了Fenton氧化法对甲基橙染料的处理效果。进一步研究了Fenton氧化降解甲基橙废水的反应动力学,并建立了反应动力学模型。结果表明,Fenton氧化过程中,影响甲基橙降解速率的主要因素为H2O2和甲基橙的初始浓度。H2O2和甲基橙初始浓度与反应速率常数之间的关系可分别归纳为:kRH=0.05c(H2O2)1.4和kRH=0.023c(RH)-1.3。     

Photo-Fenton reaction using a nanocomposite.

A laponite RD clay-based Fe nanocomposite (Fe-Lap-RD) has been synthesized by the so-called pillaring technique. The X-ray diffraction (XRD) results reveal that the Fe-Lap-RD mainly consists of Fe2O3 (maghemite) crystallites and Fe2SiO10(OH)2 (iron silicate hydroxide) crystallites. The photo-catalytic activity of the Fe-Lap-RD for the degradation of an organic azo dye Orange II is examined. It is found that the rate of mineralization of Orange II is slower than that of discoloration. Under optimal conditions, 100% color and 70% total organic carbon (TOC) of 0.2 mM Orange II can be removed in 45 and 90 minutes, respectively. In addition, the performance of a strongly acidic type of ion exchange resin based catalyst as a heterogeneous photo-Fenton catalyst for the degradation of salicylic acid is also discussed.     

Decolorization of anthraquinone dye Reactive Blue 19 by the combination of persulfate and zero-valent iron

Decolorization of anthraquinone dye Reactive Blue 19 (RB19) with sulfate radicals generated in situ from persulfate and zero-valent iron (ZVI) was investigated. The effects of initial solution pH, initial concentration of RB19, ZVI and persulfate, reaction temperature and common dissolved anions were studied. 100% color removal efficiency and 54% TOC removal efficiency were achieved in 45 min with an initial RB19 concentration of 0.1 mM under typical conditions (pH 7.0, 0.8 g L(-1) ZVI, 10 mM persulfate and 30 C). The decolorization efficiency of RB19 increased with higher iron dosage, higher initial persulfate concentration, and higher reaction temperature. It is also an acid driven process. The decolorization process followed pseudo-first order kinetics and the activation energy was 98.1 kJ mol-1. RB19 decolorization was inhibited by common dissolved anions such as CL-, NO3-, H2PO4- and HCO3- since they reacted with sulfate radicals that retarded the oxidation process. The experiment demonstrated that the combination of persulfate and ZVI was a promising technology for the decolorization of dye wastewater.     

Removal of pharmaceuticals using combination of UV/H(2)O(2)/O(3) advanced oxidation process

Water and wastewater effluents contain a vast range of pharmaceutical chemicals. The present study aims to determine the potential of the advanced oxidation technology UV/H(2)O(2)/O(3) and its sub-processes (i.e. UV, UV/H(2)O(2), UV/O(3), O(3) and H(2)O(2)/O(3)) for the degradation of the antibiotics ciprofloxacin (CIP) and trimethoprim (TMP), and the antineoplastic drug cyclophosphamide (CPD) from water. Creating AOP conditions improved in most cases the degradation rate of the target compounds (compared with O(3) and UV alone). H(2)O(2) concentration was found to be an important parameter in the UV/H(2)O(2) and H(2)O(2)/O(3) sub-processes, acting as (?)OH initiator as well as (?)OH scavenger. Out of the examined processes, O(3) had the highest degradation rate for TMP and H(2)O(2)/O(3) showed highest degradation rate for CIP and CPD. The electrical energy consumption for both CIP and CPD, as calculated using the E(EO) parameter, was in the following order: UV > UV/O(3) > UV/H(2)O(2)/O(3) > O(3) > H(2)O(2)/O(3). Whereas for TMP O(3) was shown to be the most electrical energy efficient. Twelve degradation byproducts were identified following direct UV photolysis of CIP.     

Heterogeneous catalytic oxidation of hypophosphite by H2O2: pH effect.

Phosphorus chemicals control key aspects of eutrophication and other environmental process. Hypophosphite (HP) originating from manmade and natural sources was evidenced as present in the environment and was investigated rarely. Recently, iron oxide has been used as a catalyst for oxidising organic contaminants with hydrogen peroxide (i.e. heterogeneous Fenton-like reaction). This study focused mainly on the oxidation of 1.0 mM HP by hydrogen peroxide in the presence of a novel iron oxide catalyst (B1 catalyst) which was prepared through a fluidised-bed Fenton reactor (FBR-Fenton). The background experiments including the oxidation experiment of HP by air only, by H2O2 only and adsorption of HP by B1 catalyst were first elucidated. It was found that HP could not be oxidised at all by air and H2O2 at pH 2.5-12 in 24 hours. On the other hand, it could be adsorbed by B1 catalyst with 89.8% removal at pH 2.5 in 5 hours and complete desorption at pH 11.0. Then, we investigated the effects of pH and Fe leaching from the catalyst on the oxidative efficiency of HP. We found that although the removal rate of HP at pH 2.5 is faster than that at pH 4.0, B1 catalyst has a higher HP oxidation efficiency at pH 4.0 than that at pH 2.5. We conclude that it is a major heterogeneous catalytic oxidation by our novel iron oxide catalyst to oxidise HP at pH 4.0. Also, B1 could be a useful and potential catalyst for the treatment of HP wastewater.     

H2O2／强化日光协同光解脱色直接湖蓝染料研究

在H2O2存在条件下,对直接湖蓝染料进行强化日光辐照处理。研究染料初始浓度、H2O2浓度、pH值、不同阴离子等因素对直接湖蓝染料的脱色效果影响。结果表明:在pH酸性媒介中直接湖蓝能有效地光解脱色。与SO42-、NO2-、Cl-相比,Br-和NO3-对脱色作用抑制最显著,而且两者能形成协同作用抑制光解脱色。染料光解脱色速率随H2O2浓度的增加而增加,但在高H2O2浓度时,降解速率增加不明显。处理前后的UV-Vis谱图分析表明直接湖蓝在H2O2/强化日光光解处理中脱色是因为染料发生光解作用。     

UV/H2O2和UV/TiO2/H2O2去除水中微量硝基苯的比较研究

研究比较了UV/H2O2和UV/TiO2/H2O2对水中微量硝基苯的降解效果,并考察了水中常见HCO-3和腐殖酸对硝基苯降解的影响.结果表明,薄膜状TiO2的存在对UV/H2O2降解硝基苯有显著的促进作用,在最佳H2O2投加量2.1 mg/L时,UV/TiO2/H2O2的反应速率常数比UV/H2O2高32.8%;2 min内UV/TiO2/H2O2对硝基苯的去除率达到80%以上.HCO-3和腐殖酸对硝基苯降解有很强的抑制作用,HCO-3和腐殖酸浓度分别为2 mmol/L和3.2 mg/L时,UV/TiO2/H2O2对硝基苯的反应速率常数分别下降84.6%和92.2%.     

Intensification of sonochemical degradation of phenol using additives at pilot scale operation

The present work reports the use of sonochemical reactors for the degradation of phenol in the presence of additives with an objective of enhancing the rates of degradation at a pilot scale operation. Process intensification studies have been carried out using additives such as hydrogen peroxide (H2O2) (0.5-2.0 g/L), sodium chloride (0.5-1.5 g/L) and solid particles viz. cupric oxide (CuO) and titanium dioxide (TiO2) (0.5-2.5 g/L). Optimum concentration for H2O2 and sodium chloride has been observed beyond which no beneficial effects are obtained even with additional loadings. Maximum extent of degradation has been observed by using ultrasound/H2O2/CuO approach at a solid loading of 1.5 g/L followed by ultrasound/H2O2/TiO2 approach at a loading of 2.0 g/L. The obtained results at pilot scale operation in the current work are very important especially due to the fact that the majority of earlier studies are at laboratory scale which cannot provide the design related information for large scale operation as required scale up ratios are quite high adding a degree of uncertainty in the design. The novelty of the present work lies in the fact that it highlights successful application of sonochemical reactors for wastewater treatment at pilot scale operation.     

Potential of UV/H2O2 oxidation for enhancing the biodegradability of municipal reverse osmosis concentrates

UVC/H2O2 and VUV/H2O2 oxidation processes were evaluated for the degradation of organic pollutants in reverse osmosis concentrate (ROC) produced from a municipal secondary effluent. It was found that the oxidation by UVC/H2O2 and VUV/H2O2 processes could be described as a pseudo first-order reaction. For UVC increased oxidation occurred with increasing H2O2 dosage up to 2 mM above which improvement in oxidation performance decreased. At the same H2O2 dosage, VUV irradiation gave better overall oxidation performance. Compared with UVC/6 mM H2O2, VUV/2 mM H2O2 gave a greater rate of reduction of chemical oxygen demand, but a lower rate for reduction of dissolved organic carbon, suggesting that oxidation of organics by the two methods followed different pathways. The change of absorbance at 254 nm and fluorescence excitation emission matrix spectra of irradiated samples indicated that the large and complex compounds were fragmented rapidly by the *OH, resulting in rapid decolourisation. The biodegradability of the organics in the ROC was increased from 11% to 35% after 1 h treatment by UVC/3 mM H2O2, whereas a greater increase (41%) was obtained with VUV/2 mM H2O2. This increase in biodegradability indicates the potential for employing a subsequent biological treatment process.     

Effective degradation of para-chloronitrobenzene through a sequential treatment using zero-valent iron reduction and Fenton oxidation

In this study, zero-valent iron (ZVI) was used to pretreat para-chloronitrobenzene (p-CNB), and the major product was para-chloroaniline (p-CAN). By adding H(2)O(2) directly, further p-CAN degradation can be attributed to Fenton oxidation because ferrous ions (Fe(2+)) released during the ZVI corrosion could be used as an activator for H(2)O(2) decomposition. In the reduction process, the reduction efficiency of p-CNB as well as Fe(2+) concentration increased with increasing iron dosage and decreasing solution pH. Under the optimal conditions, 25 mg L(-1) of p-CNB could be transformed in 3 h when initial solution pH was 3.0 and ZVI dosage was 2.0 g L(-1). A sufficient amount of Fe(2+) (50.4 mg L(-1)) was obtained after the above reaction to activate H(2)O(2). In the Fenton process, the oxidization of p-CAN was also more effective in acidic conditions and it increased with increasing H(2)O(2) concentration. The control experiments showed that the sequential treatment was more effective than Fenton oxidation alone in treating p-CNB wastewater since the removal rate of total organic carbon (TOC) was improved by about 34%. It suggested that the amino function group is more susceptible to oxidative radical attack than the nitro function group. Therefore, sequential treatment using zero-valent iron reduction followed by Fenton oxidation is a promising method for p-CNB degradation.     

Photooxidation of azo dye reactive black 5 using a novel supported iron oxide: heterogeneous and homogeneous approach.

Photooxidation of azo dye Reactive Black 5 (RB5) by H202 was performed with a novel supported iron oxide in a batch reactor in the range of pH 2.5-6.0. The iron oxide was prepared through a fluidized-bed reactor (FBR) and much cheaper than the Nafion-based catalysts. Experimental results indicate that the iron oxide can significantly accelerate the degradation of RB5 under the irradiation of UVA light (wavelength = 365 nm). An advantage of the catalyst is its long-term stability, which was confirmed through using the catalyst for multiple runs in the degradation of RB5. In addition, this study focused mainly on determining the proportions of homogeneous catalysis and heterogeneous catalysis in the batch reactor. Conclusively, although heterogeneous catalysis contributes primarily to the oxidation of RB5 during pH 4.5-6.0, the homogeneous catalysis is of increasing importance below pH 4.0 because of the Fe ions leaching from the catalyst to solution.     

Photodegradation of aqueous reactive dye using TiO(2)/zeolite admixtures in a continuous flow reactor

The photocatalytic degradation of an organic dye, i.e. reactive blue 19 (RB19), was studied by employing different TiO(2)/zeolite (TZ) photocatalysts, which have TiO(2)/(TiO(2) + zeolite) weight ratios ranging from 20 to 80%, in a continuous flow system. Three light sources including two UV lights (i.e. λ(max,254 nm) and λ(max,365 nm)) and natural sunlight were used. The results showed that the decoloring rate of RB19 increased as the amount of TiO(2) in the TZ catalyst increased. The photodegradation of RB19 exhibited pseudo-first-order kinetics with respect to the concentration of RB19. Almost 100% of initial RB19 was mineralized under the controlled conditions in this study. And the activities of the prepared photocatalysts were retained after long-term durability experiments. Compared with UV lights (i.e. λ(max,254 nm) and λ(max,365 nm)), the decoloring efficiency of RB19 was significantly increased under natural sunlight illumination, which is likely due to the long-wavelength incident light that photoexcited RB19 and accelerated the degradation rate of RB19 radicals by the UV fraction of sunlight.