Gábor Veréb

Removal of organic pollutants in model water and thermal wastewater using clay minerals.

Water treatment method was developed for the removal of different anionic dyes such as methyl orange and indigo carmine, and also for thymol applying sodium bentonite and cationic surfactant - hexadecyltrimethylammonium bromide (HTAB) - or polyelectrolytes (polydiallyldimethylammonium chloride, poly-DADMAC and poly-amines). The removal efficiency of these model substrates was examined in model water using UV-Vis spectrophotometry, HPLC and TOC analysis. The clay mineral and HTAB were added in one step to the polluted model water in Jar-test experiments. The influence of the cation exchange capacity (CEC) of the applied clay mineral and the presence of polyaluminium chloride coagulant (BOPAC) were also tested for the water treatment process. The structures of the in situ produced and pre-prepared organoclay composites were compared by XRD analysis. The rapid formation of organoclay adsorbents provided very efficient removal of the dyes (65–90 % in 3–10 mg/L TOC0 range) with 200 mg/L sodium bentonite dose, however thymol was less efficiently separated. Adsorption efficiencies of the composites were compared at different levels of ion exchange such as at 40, 60 and 100 %. In the case of thymol, the elimination of inorganic carbon from the model water before the TOC analysis resulted in some loss of the analysed volatile compound therefore the HPLC analysis was found to be the most suitable tool for the evaluation of the process. This one-step adsorption method using in situ formed organoclay was better performing than the conventional process in which the montmorillonite-surfactant composite is pre-preapared and subsequently added to the polluted water. The purification performance of this method was also evaluated on raw and artificially polluted thermal wastewater samples containing added thymol.

Immobilization of crystallized photocatalysts on ceramic paper by titanium(IV) ethoxide and photocatalytic decomposition of phenol

A simple method of persistent immobilization was developed for the fixing of highly efficient precrystallized (or even doped) titania (TiO2) based photocatalysts. TiO2 nanoparticles (Aeroxide P25 and VLP7000) were immobilized on the surface of Al2O3-based ceramic paper. For the immobilization, a titanium alkoxide (Ti(OEt)4) was applied as a fixing agent. This type of immobilization resulted in a photocatalytically active surface, which was used in fixed-bed flow reactors through the application of different forms of artificial or solar irradiation to activate the TiO2. To verify the stability, the decomposition of phenol was repeatedly measured on the same TiO2-covered ceramic paper; the photocatalytic performance proved to remain constant throughout five 2-h cycles. The potential for application on an industrial scale was demonstrated by a pilot-plant-scale flow reactor. The developed immobilization method is a simple technique that can be used to investigate the long-term efficiency of novel TiO2 samples, or can be applied in real air/water treatments.

Comparison of various advanced oxidation processes for the degradation of phenylurea herbicides

ABSTRACT Various types of advanced oxidation processes (AOPs), such as UV photolysis, ozonation, heterogeneous photocatalysis and their combinations were comparatively examined at the same energy input in a home-made reactor. The oxidative transformations of the phenylurea herbicides fenuron, monuron and diuron were investigated. The initial rates of transformation demonstrated that UV photolysis was highly efficient in the cases of diuron and monuron. Ozonation proved to be much more effective in the transformation of fenuron than in those of the chlorine containing monuron and diuron. In heterogeneous photocatalysis, the rate of decomposition decreased with increase of the number of chlorine atoms in the target molecule. Addition of ozone to UV-irradiated solutions and/or TiO2-containing suspensions markedly increased the initial rates of degradation. Dehalogenation of monuron and diuron showed that each of these procedures is suitable for the simultaneous removal of chlorinated pesticides and their chlorinated intermediates. Heterogeneous photocatalysis was found to be effective in the mineralization.

Visible light driven photocatalytic elimination of organic- and microbial pollution by rutile-phase titanium dioxides: new insights on the dynamic relationship between morpho-structural parameters and photocatalytic performance

The characteristic properties and the resulted photocatalytic efficiencies of rutile-phase titanium dioxides were investigated in the present study. A series of rutile with different primary particle sizes (5.2–290 nm) were produced by a sol–gel method followed by calcination and were characterized by XRD, DRS, TEM, XPS, EPR, IR and N2 adsorption. Their photocatalytic efficiencies were determined in the decomposition of phenol, and in the inactivation of E. coli bacteria under visible light irradiation. The results were compared with the photocatalytic performance of commercial Aldrich rutile and Aeroxide P25 powders. Of the non-commercial products, the TiO2 with the smallest particle size displayed the highest efficiency, while the surface-normalized photocatalytic performance was significantly higher for the larger rutile particles. This can be explained by the red shift of light absorption at higher calcination temperatures. Although Aldrich rutile and the corresponding laboratory-made photocatalyst exhibited similar structural features (e.g. particle size, specific surface area, morphology and light absorption), the latter proved to be less efficient despite its Ti3+ content (while Aldrich rutile contains only Ti4+). The main reason for the much higher photocatalytic performance was the presence of Ti–O–O– entities on the surface of Aldrich rutile. On the basis of these results, in the case of rutile-phase titanium dioxide, the presence of Ti–O–O– entities was more beneficial, than the presence of Ti3+ and low-binding-energy oxygen (which indicates defects) in relation with the photocatalytic performance under visible light irradiation.

Treatment of model oily produced water by combined pre-ozonation–microfiltration process

Oily wastewaters are one of the major environmental pollutants in aquatic systems. This is due to the emission of a variety of industrial oily wastewaters from sources such as crude oil mining (production), refineries, petrochemical plants and transportation. The aims of this work were to investigate the treatment of oil-contaminated wastewaters with a pre-ozonation/microfiltration combined system and the effect of pre-ozonation on the microfiltration parameters. The results demonstrated that ozone pre-treatment modified the chemical nature (pH and conductivity) of oil-in-water emulsion, resulting in higher wettability of the polyethersulphone membrane. In case of salt-containing model emulsions compared to pure oil emulsions, ozone treatment was found to be more effective for membrane resistance reduction and in chemical oxygen demand retention.

Investigation of surface and filtration properties of TiO2 coated ultrafiltration polyacrylonitrile membranes

In the present work, the surface and filtration properties of TiO2 coated polyacrylonitrile ultrafiltration membranes were investigated. The membranes were coated using the physical deposition method. The appropriate TiO2 coverage proved to be 0.3 mg/cm2, which formed a hydrophilic cake layer on the membrane surface. The cleanability without chemicals and the retention of the coated membranes was compared to the neat membrane after model oily wastewater filtration. The cleaning sustained of rinsing with distilled water and ultraviolet (UV) irradiation of the fouled membranes. The coated membranes have better antifouling properties; higher flux values during oily water filtration and by the mentioned cleaning process a significantly better flux recovery can be achieved. The amount of the catalyst and the irradiation time are limiting factors to the effectiveness of the cleaning process. The UV irradiation increases the wettability of the fouled membrane surface by degrading the oil layer. The coating, the continuous use, and the cleaning process do not significantly affect the membrane retention expressed in chemical oxygen demand.

Novel Applications and Future Perspectives of Nanocomposites

As the present chapter of the book is located in the concluding section, it was important to highlight the main applications of composite materials focusing especially on applications, which exploit other peculiarities of the materials besides photocatalysis. This will be done, by introducing those materials and their composites that are most studied, or were found to exhibit interesting behavior. In many of the presented cases, the main structural, morphological, or optical property of the given composite will be discussed to understand its functioning mechanism, and its role in the current scientific approaches. Additionally, this chapter aims to give a perspective regarding the composite-based nanoscience, and points out important research directions for the further developments of composite materials.