On photocatalytic membrane reactors in water and wastewater treatment and organic synthesis

A brief overview of hybrid photocatalysis-membrane processes and their possible applications in water/wastewater treatment and organic synthesis is presented. Moreover, a short introduction to photocatalysis is shown. The paper summarizes the main advantages and disadvantages of photocatalytic membrane reactors (PMRs) with photocatalytic membranes or a photocatalyst in suspension. Furthermore, the influence of photocatalysis on membranes performance in terms of fouling and efficiency of removal of organic contaminants during treatment of water and wastewater is discussed. In the second part of the review the examples showing the possibilities of application of PMRs in recovery of valuable compounds (benzaldehyde, vanillin) or photocatalytic partial oxidation of benzene to phenol are presented. It was concluded that PMRs exhibit numerous advantages over the conventional photoreactors, however, further investigations are still needed in order to improve the hybrid processes performance

Performance of hybrid systems coupling advanced oxidation processes and ultrafiltration for oxytetracycline removal

In this study, the efficiency of three different hybrid systems coupling ultrafiltration (UF) with (i) UVC/H2O2, (ii) UVC/TiO2, and (iii) UVC was evaluated for the treatment of a secondary effluent (SE) from a municipal wastewater treatment plant and a surface water (SW) from Miedwie Lake, both spiked with 5 mg L-1 of oxytetracycline (OTC). A ceramic membrane made of TiO2 was tested. The effect of H2O2 concentration (30 to 120 mg L-1) on the UVC/H2O2-UF system and of P25-TiO2 loading (0.5 to 1.5 g L-1) in suspension on the photocatalytic UVC/TiO2-UF system were investigated. A photonic flux of 5.1 J s(-1) was provided in all systems. The maximum pure water flux (PWF) was 111 L m(-2) h(-1). Adsorption on the photocatalyst particles and/or on the membrane surface was found to be an important contribution for the removal of OTC and dissolved organic carbon (DOC). The UF membrane contributed significantly to photocatalyst and pollutants rejection in the photocatalytic membrane reactor (PMR) with the UVC/TiO2 system; whereas when using the UVC/H2O2 process, with the highest H2O2 dose, the membrane effect was negligible. Using SE as reaction matrix in the UVC/ TiO2-UF system with 1.0 g L-1 of TiO2, the complete OTC removal was achieved in 5 h with a mineralization of 49%. For the same reaction period, a DOC removal of 52% was achieved with the UVC/H2O2-UF system (120 mg H2O2 L-1). A similar permeate flux decrease (ca. 40%) was observed in both cases. Furthermore, the highest reduction of permeate flux (60%) was observed when using the UVC-UF system. Using SW as reaction matrix, higher OTC degradation rates and percentage of mineralization were reached for the same reaction period, when compared with SE, due to the lower COD and inorganic salts concentration present in the surface water

Hybridization of Advanced Oxidation Processes with Membrane Separation for Treatment and Reuse of Industrial Laundry Wastewater

A new attempt to treat and reuse the industrial laundry wastewater using biological treatment followed by advanced oxidation processes (AOPs) and membrane separation is presented. Three various configurations of the hybrid systems were investigated: (1) biological treatment in a Moving Bed Biofilm Reactor (MBBR) – photocatalysis with suspended TiO2 P25, enhanced with in situ generated O3 – ultrafiltration (UF) – nanofiltration (NF); (2) biological treatment in MBBR– photocatalysis with immobilized TiO2 P25, enhanced with in situ generated O3 – UF - NF; (3) biological treatment in MBBR – photolysis/ozonation (with in situ generated O3) – UF – NF. For comparison purpose the wastewater was additionally treated in the MBBR – UF – NF mode (4). Application of AOPs contributed to the UF membrane fouling mitigation during treatment of the biologically pretreated laundry wastewater. The highest improvement of the UF permeate flux was found in case of the MBBR effluent treated with application of the immobilized TiO2 bed which was attributed to the highest efficiency of mineralization observed for that system. Since the applied wastewater contained significant amounts of inorganic ions, mainly Na+ and Cl-, the NF as the final polishing step was proposed. The quality of NF permeate was independent on the AOP mode applied and, moreover, significantly higher than the quality of water currently used in the laundry. It was concluded that the NF permeate could be recycled to any stage of the laundry system. Taking into consideration that application of TiO2 increases the overall treatment costs and that although the O3/UV pretreatment is less efficient than photocatalysis, it still allows to improve the UF permeate flux for ca. 35% compared to the direct UF of the MBBR effluent, the MBBR – UV/O3 – UF – NF system was proposed as the most beneficial configuration for the treatment and reuse of the industrial laundry wastewater

Generation of Useful Hydrocarbons and Hydrogen during Photocatalytic Decomposition of Acetic Acid on CuO/Rutile Photocatalysts

The presented studies have focused on a photocatalytic generation of useful hydrocarbons, mainly methane and ethane, from acetic acid under N2 atmosphere. CuO-loaded rutile, as well as unmodified rutile and anatase-phase TiO2 photocatalysts were applied in the experiments. The efficiency of the catalysts towards methane generation changed in the following order: Cu-TiO2 (10% Cu) > crude TiO2≈Cu-TiO2 (20% Cu) > Cu-TiO2 (5% Cu) > rutile. The amount of CH4 produced in the presence of the catalyst containing 10 wt% of Cu was higher for ca. 33% than in case of pure rutile. The concentration of ethane was 14–16 times lower than the amount of methane, regardless of the catalyst used. Low concentrations of hydrogen were also detected in the gaseous mixtures. After 5 hours of the process conducted with the catalyst containing 5–20 wt% of Cu the concentration of hydrogen amounted to 0.06–0.14 vol.%, respectively

Formation of Combustible Hydrocarbons and H2 during Photocatalytic Decomposition of Various Organic Compounds under Aerated and Deaerated Conditions

A possibility of photocatalytic production of useful aliphatic hydrocarbons and H2 from various organic compounds, including acetic acid, methanol, ethanol and glucose, over Fe-modified TiO2 is discussed. In particular, the influence of the reaction atmosphere (N2, air) was investigated. Different gases were identified in the headspace volume of the reactor depending on the substrate. In general, the evolution of the gases was more effective in air compared to a N2 atmosphere. In the presence of air, the gaseous phase contained CO2, CH4 and H2, regardless of the substrate used. Moreover, formation of C2H6 and C3H8 in the case of acetic acid and C2H6 in the case of ethanol was observed. In case of acetic acid and methanol an increase in H2 evolution under aerated conditions was observed. It was concluded that the photocatalytic decomposition of organic compounds with simultaneous generation of combustible hydrocarbons and hydrogen could be a promising method of “green energy” production

C-,N- and S-Doped TiO₂ Photocatalysts: A Review

This article presents an overview of the reports on the doping of TiO2 with carbon, nitrogen, and sulfur, including single, co-, and tri-doping. A comparison of the properties of the photocatalysts synthesized from various precursors of TiO2 and C, N, or S dopants is summarized. Selected methods of synthesis of the non-metal doped TiO2 are also described. Furthermore, the influence of the preparation conditions on the doping mode (interstitial or substitutional) with reference to various types of the modified TiO2 is summarized. The mechanisms of photocatalysis for the different modes of the non-metal doping are also discussed. Moreover, selected applications of the non-metal doped TiO2 photocatalysts are shown, including the removal of organic compounds from water/wastewater, air purification, production of hydrogen, lithium storage, inactivation of bacteria, or carbon dioxide reduction

Investigations on the Properties and Performance of Mixed-Matrix Polyethersulfone Membranes Modified with Halloysite Nanotubes

Ultrafiltration (UF) polyethersulfone (PES) membranes were prepared by wet phase inversion method. Commercial halloysite nanotubes (HNTs) in the amount of 0.5–4 wt % vs PES (15 wt %) were introduced into the casting solution containing the polymer and N,N-dimethylformamide as a solvent. The morphology, physicochemical properties and performance of the membranes were characterized by scanning electron microscopy (SEM) and atomic force microscopy (AFM), zeta potential, porosity and contact angle analyses, as well as permeability measurements. Moreover, the antifouling properties of the membranes were evaluated during UF of a model solution of bovine serum albumin (BSA). The research revealed a positive influence of modification with HNTs on hydrophilicity, water permeability and antifouling properties of the PES membranes. The most significant improvement of permeability was obtained in case of the membrane containing 2 wt % of HNTs, whereas the highest fouling resistance was observed for 0.5 wt % HNTs content. It was found that a good dispersion of HNTs can be obtained only at loadings below 2 wt %. Based on the results a relation between severity of membrane fouling and surface roughness was proved. Moreover, an increase of the roughness of the modified membranes was found to be accompanied by an increase of isoelectric point values

Immobilized TiO 2

Phenol degradation was carried out in a photocatalytic pilot plant reactor equipped with a UV/vis mercury lamp. The total volume of treated water was equal to 1.35 m3. TiO2 P25 was used as a photocatalyst and it was immobilized on two different supports: (i) a steel mesh and (ii) a fiberglass cloth. Moreover, the performance of commercially available Photospheres-40 was examined. In addition, an experiment in the absence of a photocatalyst was conducted. The commercially available Photospheres-40 were found to be inadequate for the presented application due to their fragility, which in connection with vigorous mixing and pumping led to their mechanical destruction and loss of floating abilities. The highest effectiveness of phenol decomposition and mineralization was observed in the presence of TiO2 supported on the fiberglass cloth. After 15 h of the process, phenol and total organic carbon concentrations decreased by ca. 80% and 50%, respectively