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.     

Degradation of methyl tert-butyl ether (MTBE) in water by glow discharge plasma

This study evaluated the ability of the glow discharge plasma (GDP) technique to degrade methyl tert-butyl ether (MTBE) in an aqueous solution. The results showed that a large amount of hydrogen peroxide and highly active *OH free radicals were produced during the treatment. Various experimental parameters including discharge current, initial MTBE concentration and initial pH played significant roles on MTBE degradation. In addition, Fe2+ had a catalytic effect on the degradation of MTBE, which is potentially attributable to the reaction between Fe3+ and the hydrated electron. It was also confirmed that GDP was comparable to electrocatalytic oxidation and high-density plasma and more efficient than photocatalytic degradation techniques. These results suggest that GDP may become a competitive MTBE wastewater treatment technology.     

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.     

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.     

Photocatalytical polishing of paper-mill effluents.

Photocatalytic oxidation (PCO) is a promising technology for purification of biological pretreated wastewater or destruction of non-biodegradable compounds. For this reason PCO has been investigated as a last step of purification of biologically pre-treated paper-mill effluents. The influence of the parameters pH, TiO2-modification, TiO2-concentration, catalyst re-use, concentration of substances to be oxidised (wastewater quality) has been determined. The TOC of the biologically pretreated wasterwater was up to 55 mg L(-1). This wastewater was treated with a previously presented aerated cascade photoreactor which was modified for batch experiments. A high specific oxidation rate of up to 0.76 g TOC m(-2) h(-1) as well as a complete TOC mineralization has been achieved after the optimisation of the process parameters. The complete destruction of recalcitrant compounds will offer the opportunity to reuse the wastewater in the production process. The increase of the BOD5/TOC ratio after a short irradiation period indicates the transformation of recalcitrant organic compounds to better biodegradable intermediates. The use of PCO as a pre-treatment step for the enhancement of the biodegradability of wastewater, containing recalcitrant or inhibitory compounds is an alternative to a long and energy-intensive total pollutant mineralization.     

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.     

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.     

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.     

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.     

The catalytic and photocatalytic oxidation of organic substances using heterogeneous Fenton-type catalysts.

This paper deals with catalytic and photocatalytic oxidation of organic substances using H202 over heterogeneous Fenton-type catalysts. In the study a series of Fe-containing catalysts was experienced. A zeolite named as FeZSM-5 was selected as the most active heterogeneous Fenton-type catalyst. The FeZSM-5 reported was prepared by hydrothermal crystallization in the presence of iron salt. In contrast to the homogeneous Fenton system the catalyst prepared had minimal, if any, leaching of iron ions, was stable during 30 catalytic runs and didn't lose its activity in the presence of complexing agents, e.g. P2O7(4-). The catalyst was active in oxidation of organic substances at pH from 1.5 to 8, maximum activity was observed at pH = 3. The FeZSM-5 effectively oxidized a simulant of the warfare agent, diethylnitrophenil phosphate, which is hardly detoxified by other methods. It appeared that the rate of oxidation of formic acid, ethanol and benzene over FeZSM-5 increased under the action of visible light (lambda > 436 nm), quantum efficiency being 0.06-0.14.     

The adsorption and photodegradation of oxalic acid at the TiO2 surface.

ATR-FTIR measurements in combination with quantum chemical calculations were performed to study chemical reactions taking place at the surface of a thin TiO2 layer immersed in an aqueous oxalic acid solution under UV(A) illumination. It was found that the adsorption of oxalic acid on TiO2 in the dark can be explained in terms of two surface complexes for the anatase phase. Under UV(A) illumination, one of the adsorbed species on the anatase phase preferably undergoes photo-degradation and at the same time more molecules of oxalic acid are adsorbed at the TiO2 surface which is thus enriched in the second complexation mode. The spectral changes observed under UV(A) illumination are explained in the light of different theories: photo-desorption of water molecules as a thermal mechanism induced by the absorption of photons, surface reconstruction, and newly exposed surface area provided by the de-aggregation of the TiO2 particles.     

Photocatalytic degradation of toluene by platinized titanium dioxide photocatalysts.

A photoreactor has been set up to study the photodegradation of volatile organic compound (VOC) in situ. In the reactor, TiO2 and Pt/TiO2 photocatalysts were immobilized on to UV-transparent quartz support. Scanning electron microscope (SEM) studies and Brunauer-Emmett-Teller (BET) surface area measurements revealed that the quartz fiber support was mostly coated with catalyst with a total surface area of 4.0 +/- 0.3 m2/g. The photocatalytic activity of the photocatalysts was evaluated for the photodegradation of 160 ppm toluene-laden air. It was found that 50-70% of toluene was degraded within the first 5 min of UV illumination. Both TiO2 and Pt/TiO2 photocatalysts suffered from deactivation after 18 hours of continuous operation, and the photocatalysts' activity was significantly reduced. However, platinization doubled the photocatalyst life and delayed the onset of de-activation. The presence of moisture was found to shift the onset of catalyst de-activation to an earlier time. It is concluded that the de-activation of the photocatalyst was due to the accumulation of intermediates on the photocatalysts surface preventing the toluene being adsorbed on the photocatalyst surface for degradation.     

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%.     

Photocatalytic oxidation of methyl ethyl ketone over sol-gel and commercial TiO2 for the improvement of indoor air.

This work focuses on the photocatalytic oxidation of gaseous methyl ethyl ketone chosen as a typical indoor air pollutant. Two types of TiO coatings were prepared and deposited on glass plates: one using the commercial Degussa P25 TiO2 and the other one by sol-gel method. The first objective of this study was to compare different ways of preparing thin films of sol-gel TiO2 coated on glass plates, taking into account their general aspect and their photocatalytic efficiency. Several parameters were tested, such as the stabilising agent, the glass type of the support, the number of coatings and the calcination temperature. One of the synthesised materials was then kept to carry out the following study. The study aimed to assess the influence of TiO2 coating types on the effect of water vapour. This was achieved by performing MEK photocatalytic degradation kinetics under two levels of humidity at a fixed temperature. Experimental results were then modelled by the Langmuir-Hinshelwood equation. The obtained parameters gave specific trends in function of the considered catalyst. The second part of this work was to identify MEK degradation byproducts during its photocatalytic oxidation. The main detected intermediate was acetaldehyde, followed by methyl formate. A MEK degradation pathway was then proposed.     

Comparison of different TiO2 photocatalysts for the gas phase oxidation of volatile organic compounds.

Gas-solid photocatalyzed oxidation of air contaminants is being explored more and more for possible application to decontamination, purification and deodorization of enclosed atmospheres. Indoor air is characterized by a huge number of pollutants at low concentrations. Volatile organic compounds (VOC) represent the main indoor air pollutants category, and are of great concern since some of them can act negatively on human health. Several treatments exist to reduce VOC concentrations in gaseous effluents, but photocatalytic oxidation appears to be the most appropriate regarding indoor air specific constraints. It is then necessary to develop photocatalysts, which can possibly be used in an application such as indoor air-quality improvement. In the present work, three different TiO2-based materials were studied and compared for the photocatalytic oxidation of a typical pollutant of indoor air: methyl ethyl ketone. Kinetic studies were performed for each material in dry and humid air conditions, and the Langmuir-Hinshelwood model was satisfactorily applied in almost every case. A second approach consisted of determining methyl ethyl ketone degradation by-products. Acetaldehyde was found to be the main gaseous intermediate, and could be taken into account in the general Langmuir-Hinshelwood modeling.     

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.     

Ozone catalysed with solids as an advanced oxidation process for landfill leachate treatment.

Heterogeneous catalytic ozonation (HCO) of wastewater is gaining both research and industrial interests. It is proved to be an advanced oxidation process since it involves hydroxyl radicals as oxidation species. Few studies have been carried out to test HCO in the treatment of landfill leachates. This work has been carried out to test three types of catalysts: activated carbon (AC), expanded perlite (EP) and titanium dioxide (TiO2) combined with ozone at 80 g/m3 gas concentration for the treatment of a leachate generated by Jebel Chakir landfill site near Tunis-capital of Tunisia. The work has shown a reduction in COD of about 45% and an increase in biodegradability (BOD5/COD) from 0.1 to 0.34. A catalyst concentration of 0.7 g/L was found optimal for the treatment of the leachate.     

Catalytic wet air oxidation with Ni- and Fe-doped mixed oxides derived from hydrotalcites

Catalytic wet air oxidation of Basic Yellow 11 (BY11), a basic dye, was studied in a batch reactor. Layered double hydroxides with the hydrotalcite-like structure containing nickel or iron cations have been prepared by coprecipitation and subsequently calcined leading to Ni- and Fe-doped mixed oxides, respectively. Compared with the results in the wet air oxidation of BY11, these catalysts showed high activity for total organic carbon (TOC), toxicity and dye removal at 120 degrees C and 50 bars after 120 min. It has been demonstrated that the activity depended strongly on the presence of catalyst. The results show that catalysts containing nickel provide a higher extent of oxidation of the dye whereas the reaction carried out with the iron catalyst is faster. The Ni and Fe dispersion determined from the TPR results was higher for the catalysts with a lower Ni or Fe content and decreased for higher Ni or Fe contents. On the basis of activity and selectivity, the Ni containing catalyst with the medium (3%) Ni content was found to be the best catalyst. Finally, a relationship between metal content of the catalyst and reaction rate has been established.     

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.