Inorganic greywater matrix impact on photocatalytic oxidation: does flocculation of TiO2 nanoparticles impair process efficiency?

This study was conducted in order to clarify whether photocatalyst flocculation--as observed in biologically pretreated greywater--contributes to photocatalytic oxidation (PCO) efficiency impairment. Aqueous solutions of tetraethyleneglycol dimethylether spiked with different inorganic salts in concentrations as found in biologically treated greywater were investigated with respect to TiO2 flocculation and PCO mineralisation kinetics. Flocculation of the photocatalyst primarily depended on pH (which was affected by the salts) and how close pH was to the point of zero charge (PZC). Photocatalyst agglomeration was maximum at pH 5.5. With salt concentrations >7 mmol L(-1), flocculation was strong even at pH far above PZC due to electric double layer compression. PCO rate constants were not unequivocally related to flocculation. Increasing pH was observed as the clearest factor deteriorating PCO efficiency. This was interpreted to result from impaired adsorbability of negatively charged oxidation intermediates as well as from enhanced CO2 absorption with increasing pH and subsequent formation of HCO3(-) anions which are OH radical scavengers.     

Preliminary studies using hybrid mediated electrochemical oxidation (HMEO) for the removal of persistent organic pollutants (POPs).

This study investigates the hybrid mediated electrochemical oxidation (HMEO) technology, which is a newly developed non thermal electrochemical oxidation process for organic destruction. A combination of ozone and ultrasonication processes to the mediated electrochemical oxidation (MEO) process is termed as hybrid mediated electrochemical oxidation. The electrochemical cell was developed in this laboratory. In the present study, several organic compounds, such as phenol, benzoquinone and ethylenediaminetetraacetic acid (EDTA), were chosen as the model organic pollutants to be destructed by the hybrid process. The organic destruction was monitored based on the CO2 generation and total organic carbon (TOC) reduction. The HMEO process was found to be extremely effective in the destruction of all the target organics chosen in this study. The information obtained from this study will provide an insight in adopting this technique for dealing with more recalcitrant organics (POPs).     

Gas-phase photocatalytic oxidation of motor fuel oxygenated additives.

Methyl tert-butyl ether (MTBE) and tert-butyl alcohol (TBA) were oxidized in the gas phase by photocatalytic oxidation (PCO). Transient PCO was carried out at room temperature on TiO2 (Degussa P25), 0.2% Pt-TiO2, and 2% Pt-TiO2 catalysts. Surface-adsorbed reaction by-products were characterized by temperature-programmed desorption (TPD) and oxidation (TPO). Continuous flow PCO was also carried out at 373 K on TiO2. Acetone, H2O, and CO2 were the gas-phase products for PCO of TBA and MTBE, and formic acid was adsorbed on the TiO2 surface. Temperature-programmed desorption of TBA and MTBE formed 2-methyl-1-propene, water (TBA), and methanol (MTBE). During continuous-flow PCO, acetone desorbed in molar amounts equal to the amount of decomposed TBA and MTBE. The Pt/TiO2 catalysts had higher rates of complete oxidation during PCO and TPO. Injection of water during transient PCO increased the rates of oxidation of adsorbed TBA, formic acid, and acetone. Photocatalytic oxidation of TBA proceeded faster in humid air than dry air, but MTBE oxidation was less sensitive to humidity. The TiO2 catalyst was stable for MTBE, TBA, and acetone PCO at 373 K. The PCO at low conversions followed the Langmuir-Hinshelwood model.     

Heterogeneous photocatalytic ozonation of 2,4-D in dilute aqueous solution with TiO2 fiber

Photocatalytic ozonation (O(3)/UV/TiO2) is an emerging oxidation method for recalcitrant organic contaminants in water. However, immobilised TiO2 catalysts suffer from reduced photonic efficiency. Therefore, TiO2 catalysts with excellent mechanical and thermal properties and enhanced photonic efficiencies are sought. This paper aimed to elucidate the mineralisation of low concentration 2,4-D (45.0 microM) by O(3)/UV/TiO2 using the world's first high-strength TiO2 fibre in laboratory batch experiments. 2,4-D degradation and TOC removal followed pseudo first-order reaction kinetic. The removal rates for 2,4-D and TOC in O(3)/UV/TiO2 were 1.5 and 2.4-fold larger than the summation of the values for ozonation (O3)) and photocatalysis (UV/TiO2), respectively. O(3)/UV/TiO2 was characterised by few aromatic intermediates with low abundance, fast degradations of aliphatic intermediates and dechlorination as a major step. The significantly enhanced 2,4-D mineralisation in O(3)/UV/TiO2 was attributed to increased ozone dissolution and decomposition, and reduced electron-hole recombination resulting in large number of hydroxyl radical (*OH) formation from more than one parallel path. The discrepancies in the organic carbon mass budget were attributed to few apparently major unidentified intermediates, while chlorine mass balance was reasonably acceptable. The mineralisation efficiency of O(3)/UV/TiO2 with the TiO2 fibre can further be enhanced by optimisation of experimental design parameters. The new TiO2 fibre is very promising to overcome the problem of reduced efficiency of TiO2 catalyst in an immobilised state.     

Decolorization and mineralization of Oolong tea polyphenols in colored soft drink wastewater by photo Fenton reaction

The decolorization and the mineralization of the colored soft drink wastewater including Oolong tea polyphenols by the photo Fenton reaction have been investigated. The decolorization of the colored soft drink wastewater including Oolong tea polyphenols by the photo Fenton reaction could be divided into 3 phases. Just after H2O2 was added to the solution, the color of the solution immediately increased from absorbance of 0.247 to 0.711 at the wavelength of 400 nm, which was defined as the 1st phase. Subsequently the significant decolorization by the photo Fenton reaction occurred at the 2nd phase. Finally, complete decolorization (the color attributed to the color of Fe3+) could be achieved in 180 min at the 3rd phase. The instantaneous and considerable color increase at the 1st phase could be attributed to the formation of intermediate colored compounds like quinones and soluble iron complexes produced by the Fenton reaction. About 95% mineralization of model colored soft drink wastewater with 229 mg L(-1) initial TOC concentration was achieved after 165 min.     

Photocatalytic oxidation of low concentration 2,4-D solution with new TiO2 fiber catalyst in a continuous flow reactor.

Environmental pollution by low concentrations of 2,4-Dichlorophenoxyacetic acid (2,4-D) is a concern these days due to ever increasingly stringent regulations. Photocatalysis with immobilized TiO2 fiber is a promising oxidation method. Laboratory experiments on photocatalytic degradation of 0.045 mmol l(-1) 2,4-D with the world's first high-strength TiO2 fiber catalyst were carried out in a continuous flow reactor in which the degradations were, in general, similar to those with high 2,4-D concentrations investigated elsewhere. Degradation and mineralization of 2,4-D were significantly enhanced with no initial pH adjustments. The rate constants for total organic carbon (TOC) without pH adjustment were about two-fold bigger than the pH adjustment cases. CO2 gas measurement and carbon mass-balance were carried out for the first time, where about 34% organic carbon converted into CO2 gas during four-hour oxidation. 2,4-Dichlorophenol (2,4-DCP), phenol, benzyl alcohol and two unknowns (RT = 2.65 and 3.78 min.) were detected as aromatic intermediates while Phenol was the new aromatic in HPLC analysis. Dechlorination efficiencies were high (> 70%) in all the cases, and more than 90% efficiencies were observed in chloride mass balance. Bigger flow rates and solution temperature fixed at 20 degrees C without pH adjustment greatly enhanced 2,4-D mineralization. These results can be an important basis in applying the treatment method for dioxin-contaminated water and wastewater.     

Water matrix effect on UV photodegradation of perfluorooctanoic acid

The widespread detection of perfluorinated compounds (PFCs) in the water environment has been a concern for the last several years, while effluents from wastewater treatment facilities are the major sources of these compounds. Even advanced oxidation technologies (AOTs) are not useful for mineralization of the compounds due to their very high stability. Photochemical techniques using particularly vacuum UV (VUV) have been found to be very promising in this regard. But the use of VUV in UV-based AOTs has still not progressed much. Moreover, the impact of water quality on PFCs photomineralization is unknown. This investigation aimed to assess photomineralization potentials of perfluorooctanoic acid (PFOA) in ultrapure water (UPW), tap water (TW), surface water and treated wastewater effluent using a reactor setup enabling maximum utilization of VUV emission of low pressure lamp in laboratory batch experiments. Neya River water (NRW) and the Nakahama Wastewater Treatment Plant Effluent (NWWTPE) represented surface water and treated wastewater effluent respectively. Also, tests were carried out in 50% diluted NRW and NWWTPE. PFOA photomineralization in terms of PFOA removal, defluorination and total organic carbon (TOC) removal are discussed. The usefulness of the method for PFOA mineralization in organic-rich wastewaters, and further research needs are also highlighted.     

Photocatalytic oxidation of VX-simulation substance.

Experimental studies of photocatalytic oxidation (PCO) of VX-gas simulation substance cysteamine-S-phosphate sodium salt (NaHPO3S-CH2-CH2-NH2, CPSS) at various initial concentrations and pH were undertaken. PCO ultimately resulted in complete mineralisation of CPSS. The PCO byproducts of CPSS include acetate, oxalate and trace amounts of formate ions. The formation rates of acetate and phosphate were equal to the rate of degradation of CPSS, which indicates easy breakage of P-S, C-S and C-N bonds. Sulphate was formed more slowly due to stepwise oxidation of reduced sulphur. Amino group, generally transformed to ammonia, was partially oxidised to nitrite and nitrate in alkaline media. The fastest mineralisation in terms of both TOC degradation and phosphate formation was observed in neutral media. Under neutral media conditions, the PCO rate increased linearly with the CPSS concentration increase. The maximum efficiency by TOC degradation was observed as large as 77 mg per Wh of incident UV flux with quantum efficiency 3.8%.     

Reuse of low concentrated electronic wastewater using selected microbe immobilised cell system.

This work describes a novel technology for the reuse of low concentrated electronic wastewater using selected microbe immobilisation cell (SMIC) system. The SMIC system is an innovative technology to maximise the activity of specific microorganisms capable of decomposing tetramethyl ammonium hydroxide (TMAH) as a major organic compound in the low concentrated electronic wastewater. The versatility of the SMIC system has been studied by using continuous-flow reactors. The TOC in a SMIC system was removed completely, indicating that SMIC is a useful technology to remove TOC biologically in low concentrated wastewater. The most important advantages of this system are highly effective and stable in view of TMAH removal. These characteristics make well suited to various applications depending on targeted compounds and microorganisms and, especially, in the wastewater of electronic facilities.     

Photocatalytic degradation of di(2-ethylhexyl)phthalate adsorbed by chitin A.

Di(2-ethylhexyl)phthalate (DEHP) is a ubiquitous environmental contaminant due to its extensive use as a plasticiser and its persistence. Currently, there is no cost-effective treatment method for its removal from industrial wastewater. In a previous study, DEHP was effectively adsorbed from aqueous solution by biosorption onto chitinous materials. Biosorption can pre-concentrate DEHP from the aqueous phase for further treatment. As biosorption cannot degrade DEHP, in this study the degradation (and detoxification) of DEHP adsorbed onto chitinous material by photocatalytic oxidation (PCO) is attempted. PCO relies on hydroxyl radical (.OH), which is a strong oxidising agent, for the oxidative degradation of pollutants. It is a non-selective process which can degrade DEHP adsorbed onto chitinous material. The first part of this study is the optimisation of the degradation of adsorbed DEHP by PCO. Adsorption was carried out in the physicochemical conditions optimised in the previous study, with 500 mg/L chitin A and 40 mg/L DEHP at initial pH 2, 22+/-2 degrees C and 150 rpm agitation for 5 min. After optimisation of PCO, a 61% removal efficiency of 10 mg/L of DEHP was achieved within 45 min under 0.65 mW/cm2 of UV-A with 100 mg/L TiO2, and 10 mM of H2O2 at initial pH 12. The optimisation study showed that UV-A and TiO(2) are essential for the degradation of DEHP by PCO. The degradation intermediates/products were identified by GC-MS analysis. GC-MS results showed that the di(2-ethylhexyl) side chain was first degraded, producing phthalates with shorter side chains. Further reaction produced phathalic anhydride and aliphatic compounds such as alkanol and ester. The toxicities of parental and degradation intermediates in the solution phase and on chitinous materials were followed by the Microtox test. Results indicated that toxicity can be removed after 4 h treatment by PCO. Thus the decontamination of DEHP by integrating biosorption and PCO is feasible.     

Leachate detoxification by combination of biological and TiO2-photocatalytic processes.

Landfill leachates are a problematic wastewater due to their variable concentration, volume changing in time and presence of refractory and hazardous components. In this paper, the results of a new approach to photocatalysis assisted by biological process for the detoxification of stabilised landfill leachate are presented. The biologically pre-treated leachate still contained a significant amount of non-biodegradable COD and TOC amounting to 500 and 200 mg/L, respectively. The 300 min of photocatalytic treatment (UVC/TiO2) brought about a significant decrease in more than 80% refractory organics remaining in leachate. The effect of pH and catalyst loading on mineralisation, colour removal rate and biodegradability (BOD/COD) improvement in the photoreactor were discussed. The bio-accessibility of formed photocatalytic oxidation intermediates was confirmed by oxygen uptake rate (OUR) measurements. Consequently, a part of COD was successfully removed in post-biological treatment.     

Advanced oxidation process-biological system for wastewater containing a recalcitrant pollutant.

Two advanced oxidation processes (AOPs), ozonation and photo-Fenton, combined with a pilot aerobic biological reactor at field scale were employed for the treatment of industrial non-biodegradable saline wastewater (TOC around 200 mgL(-1)) containing a biorecalcitrant compound, alpha-methylphenylglycine (MPG), at a concentration of 500 mgL(-1). Ozonation experiments were performed in a 50-L reactor with constant inlet ozone of 21.9 g m(-3). Solar photo-Fenton tests were carried out in a 75-L pilot plant made up of four compound parabolic collector (CPC) units. The catalyst concentration employed in this system was 20 mgL(-1) of Fe2+ and the H2O2 concentration was kept in the range of 200-500mgL(-1). Complete degradation of MPG was attained after 1,020 min of ozone treatment, while only 195 min were required for photo-Fenton. Samples from different stages of both AOPs were taken for Zahn-Wellens biocompatibility tests. Biodegradability enhancement of the industrial saline wastewater was confirmed (>70% biodegradability). Biodegradable compounds generated during the preliminary oxidative processes were biologically mineralised in a 170-L aerobic immobilised biomass reactor (IBR). The global efficiency of both AOP/biological combined systems was 90% removal of an initial TOC of over 500 mgL(-1).     

光电催化技术在污水处理中的应用研究

水电工程在建设过程中有大量的污水需要处理，而有毒有机物的降解方法很多，如传统的气浮法、吸附法等，近年来发展了一些氧化技术，如化学氧化法、光化学氧化法、催化氧化法等。为了进一步提高有机物降解效率，合理利用资源，将光化学氧化(光催化)和电化学氧化方法结合起来，达到协同效应的光电结合技术是目前氧化法研究的新的热点。光电催化法能将水中有害物质完全矿化，或者通过控制条件将其分解为有用成分，这是其他方法所无法比拟的。在当今水污染日趋严重的情况下具有很好的推广应用价值。     

Electrochemical treatment of residual ammonia nitrogen in biologically pretreated coking wastewater with three-dimensional electrodes

The electrochemical oxidation of the residual ammonia nitrogen contained in biologically pretreated coking wastewater using three-dimensional electrode system was studied. The results show the Ti/RuO2/IrO2 anode plates and the coke have good surface characteristics for the purpose of this study. In addition, studies also show that the three-dimensional electrode system should be able to give a satisfied solution to the residual bio-refractory ammonia nitrogen in biologically pretreated coking wastewater in comparison to conventional two-dimensional electrodes. At coke size of 10-20 mesh, electrode distance of 1.0 cm and current density of 4.5 mA/cm2, the residual ammonia nitrogen in the three-dimensional electrode system was almost completely removed in 60 min.     

Removal of humic acid foulant from ultrafiltration membrane surface using photocatalytic oxidation process.

The experimental results indicated that without the TiO2 particles and PCO treatment, the permeate flux of ultrafiltration (UF) membrane declined to 40% of the initial permeate flux after 8 hours filtration. Feeding the humic acid solution with TiO2 particles dosage of 1 g/L with calcium ions into UF membrane, after the same filtration time and PCO reaction at 120 minutes, the permeate flux was increased to about 90% of the initial permeate flux. At longer PCO reaction times, a better water quality of UF permeate was observed. It has been found that with the coexistence of calcium ions in humic acid solution, the smaller molecular fragments of humic acid (HA) generated by PCO reaction may be transferred to the surface of TiO2 by means of adsorption. The humic acid adsorption by TiO2 in the presence of Ca2+ is also pH dependent. The adsorption rates were 21.0, 14.9 and 10.8 ppmTOC/gTiO2 for pH value of 4, 7 and 10 respectively. The combination of effects of PCO mineralization of humic acid into CO2 and adsorption of humic acid by TiO2 through the forming of HA-Ca(2+)-TiO2 aggregate particles were responsible for the removal of humic acid foulant from UF membrane surface.     

Advanced oxidation of commercial textile biocides in aqueous solution: effects on acute toxicity and biomass inhibition.

In the present study, the decomposition of two biocides used in the textile finishing process with Advanced Oxidation Processes (AOPs) has been studied. Different AOPs, i.e O3/OH-, TiO2/UV-A and Fe2+/H2O2 have been used representing mutually combined components of the chemically and photochemically driven advanced oxidation systems. The course of reaction was examined by changes in chemical oxygen demand (COD), total organic carbon (TOC) and acute toxicity towards the water flea Daphnia magna (assessed in terms of the effective dilution ratio LD50). Particular attention has been paid to determine the inhibitory effect of raw and ozonated biocides on biological activated sludge consortium at concentrations typically encountered in textile finishing effluents. Significant oxidation and mineralization of both biocides could be achieved employing ozonation at pH = 11.5 and heterogeneous photocatalysis (TiO2/UV-A) at pH = 5.0, whereas Fenton's reagent appeared to be less effective in COD and acute toxicity abatement.     

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.     

The use of catalyst to enhance the wet oxidation process.

Wet oxidation tests were performed on two pure compound streams: acetic acid and ammonia; and on two wastewater streams: acrylic acid wastewater and sulphide laden spent caustic. Test results showed that Mn/Ce and Pt/TiO2 were effective catalysts that greatly enhanced acetic acid, ammonia and acrylic acid wastewater destruction. However, the Mn/Ce catalyst performance appears to be inhibited by concentrated salts dissolved in solution. This could limit the applicability of this catalyst for the treatment of brackish wastewaters. Zr, Ce and Ce nanoparticles were also shown to exhibit some catalytic activity, however not to the extent of the Mn/Ce and the Pt/TiO2.     

Photocatalytic removal of cyanide with illuminated TiO(2)

Effects of TiO(2) dosage, pH and initial cyanide concentration on the removal efficiency of cyanide from aqueous solutions with illuminated TiO(2) have been investigated. Adsorption and oxidation were recognized as significant processes for the elimination of cyanide. From the Langmuir isotherm, the maximum adsorption capacity was determined as 17.24 mg/g at pH 7. Adsorbed amount of cyanide slightly increased as the TiO(2) dosage increased. However, as no significant increase was observed above 1 g/L TiO(2), an optimum TiO(2) dosage was determined as 1 g/L. Photocatalytic oxidation efficiency of cyanide was greatly affected by the solution pH. It increased as the solution pH decreased. The photocatalytic oxidation efficiency after 120 min was 80.4% at pH 3 while it was only 20.4% at pH 11. Photocatalytic oxidation of cyanide was well described by the second-order kinetics. Photocatalytic reaction with illuminated TiO(2) can be effectively applied to treat industrial wastewater contaminated with cyanide.     

Catalytic oxidation with Al-Ce-Fe-PILC as a post-treatment system for coffee wet processing wastewater

The effluent from the anaerobic biological treatment of coffee wet processing wastewater (CWPW) contains a non-biodegradable compound that must be treated before it is discharged into a water source. In this paper, the wet hydrogen peroxide catalytic oxidation (WHPCO) process using Al-Ce-Fe-PILC catalysts was researched as a post-treatment system for CWPW and tested in a semi-batch reactor at atmospheric pressure and 25 °C. The Al-Ce-Fe-PILC achieved a high conversion rate of total phenolic compounds (70%) and mineralization to CO(2) (50%) after 5 h reaction time. The chemical oxygen demand (COD) of coffee processing wastewater after wet hydrogen peroxide catalytic oxidation was reduced in 66%. The combination of the two treatment methods, biological (developed by Cenicafé) and catalytic oxidation with Al-Ce-Fe-PILC, achieved a 97% reduction of COD in CWPW. Therefore, the WHPCO using Al-Ce-Fe-PILC catalysts is a viable alternative for the post-treatment of coffee processing wastewater.