Integration of Photocatalysis and Microfiltration in Removing Effluent Organic Matter from Treated Sewage Effluent

An integration of photocatalysis with low-pressure submerged membrane has attracted growing interest for its synergic advantages in water and wastewater treatment. In this study, the adsorption and photocatalytic oxidation of organic compounds by UV light responsive titanium dioxide (TiO₂) were investigated. First, the adsorption behavior of the TiO₂ was examined by the adsorption isotherm and kinetics experiments. The photocatalytic reactivity of the catalysts was then compared at different operating conditions. The results indicate that the Freundlich model described well the adsorption capacity of both materials. The photocatalytic kinetics showed that the highest removal of effluent organic matter (EfOM) was achieved at an optimum concentration of 1.0 g/L of TiO₂. In addition, it was found that the pre-photosensitization with titanium dioxide/ultra-voilet radiation (TiO₂/UV) could effectively reduce membrane fouling and enhance the permeate flux of the submerged membrane reactor when it was used as a post-treatment. An increase of 10% in organic removal efficiency was achieved by the posttreatment of membrane filtration. The sustainable flux of the membrane reactor increased from 25 up to 40 L/m²·h when the pretreatment of photocatalysis was used.     

P123 assisted morphology-engineered and hierarchical TiO<Subscript>2</Subscript> microspheres for enhanced photocatalytic activity

In this study, hierarchical titanium dioxide (TiO₂) microspheres with controlled morphology derived from calcination treatment of hierarchical titanate microspheres were fabricated. The obtained hierarchical TiO₂ microspheres with diameters of 1 to 2 µm were composed of polycrystalline anatase nanosheets with thickness of 10 nm. The morphology was manipulated by simply adjusting the molar ratio of tetrabutyl titanate/P123. At a low molar ratio of 17.04, TiO₂ microspheres composed of a large number of nanosheets closely packed together were obtained. At a high molar ratio of 34.08, TiO₂ hybrid architectures with polycrystalline anatase hierarchical microspheres and single-crystal anatase mesoporous (approximately 5 nm) nanospheres were obtained. Investigations on evolution formation revealed that P123 played a key role in the formation of a well-defined hierarchical structure. The photocatalytic performances of the obtained samples were investigated by the degradation of methylene blue and papermaking wastewater. When compared with commercial P25, the obtained hierarchical TiO₂ microspheres exhibit superior photocatalytic activity, high degradation efficiency, and good reproducibility. The product with hybrid architectures exhibited the highest photocatalytic activity. The chemical oxygen demand and the chroma removal rate of papermaking wastewater achieved 85.5 and 100%, respectively, after 12 h of photodegradation.     

A total solution for simultaneous organic degradation and particle separation using photocatalytic oxidation and submerged microfiltration membrane hybrid process

Advanced oxidation process (AOP) with reactor capacity of 150 L, using ultraviolet (UV) radiation and titanium dioxide (TiO₂) photocatalyst, was evaluated for the destruction of toxic organic chemical, bisphenol A (BPA). TiO₂ in the form of powder, was suspended as slurry in the water, as against the commonly adopted practice of immobilizing it onto a carrier material such as glass, concrete or ceramics. Adsorption of BPA by TiO₂ was evaluated and was performed as a pretreatment to AOP. The combined effect of ozone with the AOP process was also studied. Applying ozone along with UV/TiO₂, brought about a synergistic effect on BPA degradation. Within three hours, entire 10 ppm of BPA and the intermediate organic compounds were completely removed. The highlight of this study was the simultaneous degradation of BPA and separation of TiO₂ particles from water after photocatalysis, in order to obtain reusable quality water. Separation of TiO₂ particles was carried out by a unique two stage coagulation and settling process followed by submerged hollow fiber microfiltration membrane technique. With initial turbidity of 4,000 NTU, the turbidity of the final permeate water was well below 0.1 NTU. Almost complete removal of TiO₂ particles was achieved. Some of the main advantages of this hybrid treatment system include, large scale treatment, complete and efficient BPA and its organic intermediates degradation; easy separation of TiO₂ after treatment and reuse as it is free from chemical coagulant contaminants; reusable quality water, and the potential for continuous operation with simple process modifications.     

Application of Slurry Type Photocatalytic Oxidation‐Submerged Hollow Fiber Microfiltration Hybrid System for the Degradation of Bisphenol A (BPA)

Abstract

A pilot scale, slurry type photocatalytic reactor, followed by submerged hollow fiber microfiltration (MF) membrane hybrid system was evaluated for simultaneous and complete destruction of toxic organic chemical bisphenol A (BPA) and separation of photocatalyst TiO₂; in order to obtain a reusable quality water. With simple modification to the treatment operation, the effect of photocatalytic reaction at modest variations in temperature was examined. Adsorption pretreatment was carried out prior to photocatalysis (UV/TiO₂). BPA adsorption ability on TiO₂ was very less (about 15%) at 25°C. However, adsorption pretreatment followed by photocatalytic oxidation (UV/TiO₂) at an elevated nearly constant temperature (about 70°C) helped in increasing the BPA degradation efficiency. The effect of ozone introduction into the treatment stream was also analyzed. Applying ozone along with UV/TiO₂, brought about a synergistic effect on BPA degradation. Within 3 h, entire 10 ppm of BPA and the by‐product organic compounds were completely removed. TiO₂ particle separation performance using hollow fiber membrane was enhanced by adopting a two‐stage coagulation/sedimentation pretreatment. With initial turbidity of 4000 NTU, the turbidity of the final permeate water was well below 0.1 NTU. Almost complete removal of particles was achieved. Some of the main advantages of this hybrid treatment system include, large‐scale treatment, complete and efficient BPA and its organic intermediates degradation, TiO₂ easily separated after treatment and capable for reuse as it is free from chemical coagulant contaminants, reusable quality water is obtained, and the system has the potential for continuous operation with simple process modifications.     

Synthesis and characterisation of novel titania impregnated kaolinite nano-photocatalyst

Nano-sized titanium dioxide (TiO₂) has received a great attention in the field of research and development as a promising photocatalyst to promote the degradation of organic contaminants in water. One of the key technical challenges involved in separation and recovery of the photocatalyst particles from the water treatment system makes this technology unviable as an industrial process. A novel titania impregnated kaolinite (TiO₂/K) photocatalyst was synthesized by a modified two step sol–gel method: hydrolysis of titanium(IV) butoxide and heterocoagulation with pre-treated kaolinite (K) clay. The TiO₂/K photocatalysts were characterised using X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and BET specific surface area measurements (BET). The photocatalytic activity was evaluated by the degradation of Congo red in aqueous solution. The TiO₂/K photocatalyst had a rigid porous layer structure and promising nano-size properties, and demonstrated an enhanced adsorption and photocatalytic ability for the removal of Congo red. The TiO₂/K photocatalyst can be easily separated and recovered from the water treatment system. The TiO₂/K photocatalyst is expected to deliver a true engineering solution for an industrial water/wastewater treatment process.     

Preparation of photo-catalytic copolymer grafted asymmetric membranes (N-TiO<Subscript>2</Subscript>-PMAA-g-PVDF/PAN) and their application on the degradation of bentazon in water

Nitrogen-doped titanium dioxide (N–TiO₂) was prepared and supported on a novel copolymer grafted membrane matrix to avoid the problems associated with the removal of spent photocatalyst from treated water. Membranes of poly (methacrylic acid) grafted onto poly (vinylidene difluoride) and blended with poly (acrylonitrile) (PMAA-g-PVDF/PAN) were prepared through a dry–wet phase inversion technique. Methacrylic acid side chains were grafted onto an activated PVDF backbone by the method of reversible addition fragmentation chain transfer polymerization and then the novel photocatalytic asymmetric membranes of N–TiO₂–PMAA-g-PVDF/PAN were prepared. The casting solutions were blended with 1–5 % N–TiO₂ before immersion into the coagulation bath. PVDF and PAN offer several advantages which include: mechanical strength and toughness, chemical resistance, unaffected by long-term exposure to UV radiation, low weight, and thermal stability. N–TiO₂ was prepared through sol-gel synthesis. The photocatalytic membranes were evaluated by degradation process of herbicide bentazon in water. Photodegradation studies revealed that the optimum photocatalyst loading was 3 % N–TiO₂ and the optimum pH was 7 for the degradation of bentazon in water. UV–Vis, TOC and LC–MS analyses confirmed the successful photodegradation of bentazon. A bentazon removal efficiency of 90.1 % was achieved at pH 7. N–TiO₂–PMAA-g-PVDF/PAN membranes were successfully prepared and characterized. These photocatalytic membranes showed great potential as a technology for the effective removal of pesticides from water. According to literature, N–TiO₂–PMAA-g-PVDF/PAN asymmetric photocatalytic membranes have not been prepared before for the purpose of treating agricultural wastewater.     

Electrochemical treatment of ammonia in wastewater by RuO<Subscript>2</Subscript>–IrO<Subscript>2</Subscript>–TiO<Subscript>2</Subscript>/Ti electrodes

This study investigated the removal of ammonia in wastewater by an electrochemical method using titanium electrodes coated with ruthenium and iridium (RuO₂–IrO₂–TiO₂/Ti) with low chlorine evolution over-voltage. The effects of operating parameters, including chloride ion concentration, current density and initial pH, were also investigated. The results were evaluated primarily by considering the efficiency of the elimination of NH₄⁺-N. The removal of ammonia by electrochemical oxidation mainly resulted from the indirect oxidation effect of chlorine/hypochlorite produced during electrolysis. The direct anodic oxidation efficiency of ammonia was less than 5%, and the current efficiency was less than 10%. The ammonia removal followed pseudo-first-order kinetics. The electrochemical process can be applied successfully as a final polishing step, or as an alternative method to biological nitrification. The process seems to be most beneficial for small coastal cities     

Template-free preparation of TiO<Subscript>2</Subscript> microspheres for the photocatalytic degradation of organic dyes

TiO₂ microspheres were successfully synthesised by simple solution phase method by using various amount of titanium butoxide as precursor. The prepared TiO₂ were characterized by X-ray diffraction (XRD), UV-vis diffuse reflectance absorption spectra (UV-DRS), X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). XRD analysis revealed that the as-synthesized TiO₂ microsphere poses an anatase phase. The photocatalytic degradation experiments were carried out with three different dyes, such as methylene blue, brilliant black, reactive red-120 for four hours under UV light irradiation. The results show that TiO₂ morphology had great influence on photocatalytic degradation of organic dyes. The experimental results of dye mineralization indicated the concentration was reduced by a high portion of up to 99% within 4 hours. On the basis of various characterization of the photocatalysts, the reactions involved to explain the photocatalytic activity enhancement due to the concentration of titanium butoxide and morphology include a better separation of photogenerated charge carriers and improved oxygen reduction inducing a higher extent of degradation of aromatics.     

Electrospun polyamide‐6 membranes containing titanium dioxide as photocatalyst

Electrospun polyamide‐6 membranes containing titanium dioxide (TiO₂) photocatalyst were prepared and characterized. By tailoring the electrospinning parameters it was possible to obtain membranes having two different thicknesses, namely 5 and 20 µm, in which TiO₂ particles were homogeneously dispersed. As a comparison, hybrid films made with polyamide‐6 matrix and TiO₂ filler were successfully produced, with inorganic/organic ratios of 10 and 20 wt%. The photocatalytic activity of both hybrid systems was evaluated by following the degradation of methylene blue as a target molecule as a function of UV irradiation time. A smoother degradation was recorded for the electrospun membranes with respect to the hybrid films probably due to a less exposed surface because of the highly porous structure. Even if a longer photodegradation time was necessary, the degradation of the dye was successfully achieved. Copyright © 2010 Society of Chemical Industry     

Photocatalytic decolorization of rhodamine B by fluidized bed reactor with hollow ceramic ball photocatalyst

Photocatalytic degradation of organic contaminants in wastewater by TiO₂ has been introduced in both bench and pilot-scale applications in suspended state or immobilized state on supporting material. TiO₂ in suspended state gave less activity due to its coagency between particles. Recent advances in environmental photocatalysis have focused on enhancing the catalytic activity and improving the performance of photocatalytic reactors. This paper reports a preliminary design of a new immobilized TiO₂ photocatalyst and its photocatalytic fluidized bed reactor (PFBR) to apply photochemical degradation of a dye, Rhodamine B (RhB). But it was not easy to make a cost-effective and well activated immobilized TiO₂ particles. A kind of photocatalyst (named Photomedium), consisting of hollow ceramic balls coated with TiO₂-sol, which was capable of effective photodegradation of the dye, has been presented in this study. The photocatalytic oxidation of RhB was investigated by changing Photomedia concentrations, initial RhB concentrations, and UV intensity in PFBR This paper is dedicated to Professor Hyun-Ku Rhee on the occasion of his retirement from Seoul National University.     

Hollow hybrid titanate/Au@TiO2 hierarchical architecture for highly efficient photocatalytic application

Hollow hybrid titanate/Au@TiO₂ hierarchical architecture consisting of titanate and anatase titanium dioxide (TiO₂) loaded with Au nanoparticles was prepared via a sol-impregnation method combined with a hydrothermal etching process. The titanate/Au@TiO₂ architecture possesses unique hollow spherical configuration with Au nanoparticles loaded in the middle of titanate and TiO₂ shells and allows to be used as a microreactor for photocatalytic application. The hybrid titanate/Au@TiO₂ photocatalyst shows significantly enhanced photocatalytic activity on degradation of methylorange (MO) under UV light irradiation due to the lower electron–hole pairs recombination rate arisen from the synergistic effect of titanate-Au-TiO₂ in hybrid hierarchical architecture.     

Photocatalytic membrane reactor for degradation of acid red B wastewater

Nano-titanium dioxide (TiO₂) photocatalyst was prepared by acid–sol method using tetrabutyl titanate and ethanol, which appeared to be anatase by XRD analysis. The wastewater containing azo dye acid red B was then subjected to photocatalytic degradation with photocatalyst TiO₂ and UV as light source in a slurry photocatalytic membrane reactor, which included a double layer cylindrical photocatalytic reaction zone and a plate frame membrane separation part. Two kinds of ultrafiltration (UF) membranes PVDF700 and PAN700 were applied and the combined process with photocatalysis was operated by a continuous re-circulating mode during treatment. At first, the adsorption characteristic of the titanium dioxide catalyst under different pH values was analyzed and the optimal operation condition of the photocatalytic process was achieved by changing TiO₂ dose and initial concentration of the dye. Then the performance of photocatalyst separation process by ultrafiltration (UF) was investigated. It was found that the degradation of acid red B was followed by first-order kinetics and the efficiency of photocatalysis can be evaluated by the initial reaction rate. Finally, the conglomeration and hydrophilizion phenomena by TiO₂ in the coupling system and its effect to different ultrafiltration membranes were analyzed.     

Synthesis of nanocrystalline TiO<Subscript>2</Subscript>-coated coal fly ash for photocatalyst

In order to more easily separate TiO₂ photocatalyst from treated wastewater, TiO₂ photocatalyst is immobilized on coal fly ash by precipitation method. The titanium hydroxide precipitated on coal fly ash by neutralization of titanium chloride is transformed into titanium dioxide by heat treatment in the temperature range of 300–700 ‡C. The crystalline structure of the titanium dioxide shows anatase type in all ranges of heat treatment temperature. The crystal size of anatase increases with increasing heat treatment temperature, with the drawback being the lower removal ability of NO gas. When the coal fly ash coated with 10 wt% of TiO₂ was calcined at 300 and 400 ‡C for 2 hrs, the average crystal size of anatase appeared about 9 nm, and the removal rates of NO gas were 63 and 67.5%, respectively. The major iron oxide, existing in coal fly ash as impurity, is magnetite (Fe₃O₄). Phase transformation of magnetite into hematite (Fe₂O₃) by heat treatment improves the removal rate of NO gas for TiO₂-coated coal fly ash.     

Phorate degradation by TiO2 photocatalysis: Parameter and reaction pathway investigations

The photocatalytic degradation of phorate in aqueous suspensions was examined with the use of titanium dioxide (TiO₂) as a photocatalyst. About 99% of phorate was degraded after UV irradiation for 60 min. The photodegradation of phorate followed pseudo-first-order kinetics and parameters such as pH of the system, TiO₂ dosage, and presence of anions were found to influence the reaction rate. To obtain a better understanding of the mechanistic details of this TiO₂-assisted photodegradation of phorate with UV irradiation, the intermediates of the processes were separated, identified, and characterized by the solid-phase microextraction (SPME) and gas chromatography/mass spectrometry (GC/MS) techniques. The probable photodegradation pathways were proposed and discussed. To the best of our knowledge, this is the first study that reports the degradation pathways of phorate. The electrical energy consumption per order of magnitude for photocatalytic degradation of phorate was also calculated and showed that a moderated efficiency (E_EO = 96 kWh/(m³ order)) was obtained in TiO₂/UV process.     

Polyaniline modified mesoporous titanium dioxide that enhances oxo‐biodegradation of polyethylene films for agricultural plastic mulch application

Mesoporous titanium dioxide (M‐TiO₂) nanoparticles were successfully prepared followed by chemical modification with different contents of polyaniline (PANI/M‐TiO₂) and were used to accelerate the photo‐oxidation and biodegradation process of low‐density polyethylene (LDPE) film. The influence of these additives as a pro‐oxidant additive on the accelerated degradation of LDPE was investigated by photocatalytic oxidation under UV light irradiation and biodegradation with fungal strains. It was found that the as‐prepared PANI modified M‐TiO₂ particles exhibited an obvious light response from 400 to 800 nm which can improve the utilization of solar light. Compared with M‐TiO₂, PANI/M‐TiO₂ exhibited better photocatalytic performance when irradiated under UV light and the subsequent biodegradation efficiency was enhanced. Enhancement of the photocatalytic performance of PANI/M‐TiO₂ could be attributed to good dispersibility and compatibility of PANI/M‐TiO₂ in the LDPE matrix, a narrow band gap, effective separation of photogenerated electron–hole pairs and the chromophoric group of PANI which was used as a photosensitizer in the LDPE/PANI/M‐TiO₂ composite film. © 2019 Society of Chemical Industry     

Photocatalytic degradation of methylene blue and acetaldehyde by TiO<Subscript>2</Subscript>/glaze coated porous red clay tile

Nanosized TiO₂ sol synthesized by sol-gel method was successfully coated on the porous red clay tile (PRC tile) with micrometer sized pores. PRC tile was first coated with a low-firing glaze (glaze-coated PRC tile) and then TiO₂ sol was coated on the glaze layer. A low-fired glaze was prepared at various blending ratios with frit and feldspar, and a blending ratio glazed at 700 °C was selected as an optimum condition. Then TiO₂ sol synthesized from TTIP was dip-coated on the glazed layer (TiO₂/glaze-coated PRC tile), and it was calcined again at 500 °C. Here, these optimum calcination temperatures were selected to derive a strong bonding by a partial sintering between TiO₂ sol particles and glaze layer. Photocatalytic activity on the TiO₂/glaze-coated PRC tile was evaluated by the extent of photocatalytic degradation of methylene blue and acetaldehyde. Methylene blue with the high concentration of 150 mg/l on the surface of TiO₂/glaze-coated PRC tile was almost photodegraded within 5 hours under the condition of average UV intensity of 0.275 mW/cm₂, while no photodegradation reaction of methylene blue occurred on the glaze-coated PRC tile without TiO₂. Another photocatalytic activity was also evaluated by measuring the extent of photocatalytic degradation of gaseous acetaldehyde. The photodegradation efficiency in TiO₂/glaze-coated PRC tile showed about 77% photocatalytic degradation of acetaldehyde from 45,480 mg/l to 10,536 mg/l after the UV irradiation of 14 hours, but only about 16% in the case of the glaze-coated PRC tile.     

Photoassisted mineralization of remazole red F3B over NiO/TiO2 and CdO/TiO2 nanoparticles under simulated sunlight

In this work, a series of titania-supported NiO and CdO materials were synthesized by a modified sol-gel process. The prepared photocatalysts were characterized by X-ray diffraction (XRD), UV-Vis diffuse reflectance spectroscopy (DRS), and transmission electron microscopy (TEM). The activities of titania-supported NiO and CdO photocatalysts for photocatalytic degradation of Remazole Red F3B (RR) dye, under simulated sunlight, were investigated. The photocatalytic mineralization of an RR dye solution over various NiO-x/TiO₂ and CdO-x/TiO₂ photocatalysts under simulated sunlight was investigated. It was worthy noticing that the photocatalytic activity of titania improved using the prepared catalysts. The prepared TiO₂, NiO-5/TiO₂, and CdO-2/TiO₂ photocatalysts exhibited higher photocatalytic activity under simulated sunlight than did commercial TiO₂. The prepared photocatalysts were stable after photocatalytic degradation of the dye. The observed photocatalytic mineralization of the dye was 51 and 71% over NiO-10/TiO₂ and CdO-2/TiO₂ after 180 min of irradiation, respectively. Juxtaposing a p-NiO-5/TiO₂ semiconductor provided a potential approach for decreasing charge recombination. The prepared photocatalystsNiO-5/TiO₂ and CdO-2/TiO₂ are promising composites for the solar detoxification of textile wastewater.     

Effect of Hydrogen Peroxide on the Photocatalytic Degradation of Methyl tert-butyl Ether

The photocatalytic degradation of methyl tert-butyl ether (MTBE) was investigated in the aqueous slurry of titanium dioxide (TiO₂) particles irradiated with xenon lamp in a batch reactor, in the presence and absence of hydrogen peroxide. The reaction was found to follow a pseudo-first-order kinetics and the initial reaction rate constant increased by raising the TiO₂ loading and reached an apparent optimum value at 0.5 g TiO₂/L. The addition of small amounts of hydrogen peroxide to the TiO₂ slurry, which is generally known to enhance the oxidation process in treating organic pollutants, decreased the initial MTBE degradation rate by as much as nearly 50%. However, this trend was reversed and reaction rate approached a plateau at higher concentration levels of hydrogen peroxide.     

Solar photocatalytic decolorization of dyes in solution with TiO2 film

Application of TiO₂ film to solar photocatalysis of organic dyes, including Methylene Blue (MB) (λ_max, 660 nm), RR195 (λ_max, 540 nm) and RY145 (λ_max, 420 nm), was investigated. It was found that after 6-h solar irradiation, the extent of color degradation of dyes using solar photocatalytic system without TiO₂ film was quite limited. The color removal percentage for MB, RR195, and RY145 was found to be 23.3, −9.3, and −20.7%, respectively, resulting from competitions between the photosensitizing reaction and formation of colored intermediates during solar irradiation. However, as TiO₂ film was applied, the color degradation capability of solar photocatalytic system was significantly improved, in spite of the fact that only approximately 7% of solar irradiation belongs to the UV region. The color removal percentage for MB, RR195, and RY145 was up to 93.6%, 85.3%, and 71.1%, respectively, after 6-h irradiation. We believed that in such a solar photocatalytic system immobilized with TiO₂ film, both the maximum absorbance wavelength of the dye and the adsorbability of the dye on TiO₂ film played significant roles on the rate and efficiency of color removal of the dye solutions. Moreover, the possible reaction mechanism was proposed. The solar photocatalytic process with immobilized TiO₂ film was found to follow the pseudo-first order reaction kinetics. Color removal rate of MB was almost twice of that of RY145. Accordingly, the photocatalytic degradation process using solar light as an irradiation source, and immobilized TiO₂ as a photocatalyst, showed potential application for the decolorization of wastewater.     

Spherical activated carbon as an enhanced support for TiO2/AC photocatalysts

Titanium dioxide nanoparticles prepared in situ by sol–gel method were supported on a spherical activated carbon to prepare TiO₂/AC hybrid photocatalysts for the oxidation of gaseous organic compounds. Additionally, a granular activated carbon was studied for comparison purposes. In both types of TiO₂/AC composites the effect of different variables (i.e., the thermal treatment conditions used during the preparation of these materials) and the UV-light wavelength used during photocatalytic oxidation were analyzed. The prepared materials were deeply characterized (by gas adsorption, TGA, XRD, SEM and photocatalytic propene oxidation). The obtained results show that the carbon support has an important effect on the properties of the deposited TiO₂ and, therefore, on the photocatalytic activity of the resulting TiO₂/AC composites. Thus, the hybrid materials prepared over the spherical activated carbon show better results than those prepared over the granular one; a good TiO₂ coverage with a high crystallinity of the deposited titanium dioxide, which just needs an air oxidation treatment at low-moderate temperature (350–375 °C) to present high photoactivity, without the need of additional inert atmosphere treatments. Additionally, these materials are more active at 365 nm than at 257.7 nm UV radiation, opening the possibility of using solar light for this application.