Photo-degradation characteristics of TCE (trichloroethylene) in an annulus fluidized bed photoreactor

The effects of gas velocity, annulus gap on solid (ε_s) and gas phase holdups (ε_g), UV light transmittance and photocatalytic reduction of TCE (trichloroethylene) over TiO₂/silica gel photocatalyst have been determined in an annulus fluidized bed photoreactor. The optimum TCE reduction efficiency exhibits at ε_s/ε_g of 0.48, annulus gap of 8 mm and UV light transmittance around 0.20. The most pronounced effects on TCE conversion are found to be gas velocity (U_g) and annular gap in the photoreactor.     

Photocatalytic oxidation of ethyl alcohol in an annulus fluidized bed reactor

The photocatalytic oxidation of ethyl alcohol vapor in an annulus fluidized bed reactor of 0.06 m I.D. and 1.0 m long was examined. The TiO₂ catalyst employed was prepared by the sol-gel method and was coated on the silica gel powder. The UV lamp was installed at the center of the bed as the light source. The effects of the initial concentration of ethyl alcohol, the power of UV-lamp, the photocatalysts with different preparation methods, and the superficial gas velocity on the reaction rate of ethyl alcohol decomposition were determined. It was found that, at 1.2 U_mf of flow rate, about 80% of ethyl alcohol was decomposed with initial concentration of 10,000 ppmv and the increase of superficial gas velocity reduced the reaction rate significantly.     

Removal of paraquat in aqueous suspension of TiO<Subscript>2</Subscript> in an immersed UV photoreactor

Experiments were performed to investigate the effect of operating parameters on the photodegradation efficiency of paraquat in a TiO₂-suspended photoreactor with immersed UV lamps. TiO₂ particles were prepared by a hydrothermal method. The removal rate of paraquat in the reactor was 0.54 mg/l/h with only air-sparging. The removal rate in 24 h with both the UV radiation and air-sparging was 50% higher than that with only the UV radiation. Variations of the paraquat concentration at the UV intensities of 4 and 8 W/m₂ decreased slowly with time, but that at 12 W/m₂ decreased more rapidly. The removal efficiency at the air-sparging flow rate of 1 //min increased as a UV light intensity increased. pH value in the reactor at the UV intensity of 12 W/m₂ decreased with time until 12 h and then increased with time over 12 h.     

Application of Optical-fiber Photoreactor for CO2 Photocatalytic Reduction

An optical-fiber photoreactor, comprised of 216 catalyst-coated fibers, was designed and assembled to transmit and spread light uniformly inside the reactor. The power loss of light transmission inside an optical fiber was calculated using beam propagation method. The optimum length of optical fiber was estimated to be near 11 cm long in order to entirely spread out light energy over surface catalyst. Vapor-phase CO₂ was photocatalytically reduced to methanol using the photoreactor under UV irradiation in a steady-state flow system. The solutions of metal-loaded titania were prepared by thermal hydrolysis method. Metal-loaded TiO₂ film was coated on optical fibers by dip-coating method. TiO₂, Cu/TiO₂ and Ag/TiO₂ films were uniformly on the fibers and their thicknesses ranged from 27 to 33 nm. The films consisted of very fine spherical particles with diameters of 10–20 nm. The XRD spectra indicated anatase phase for all films. Methanol yield increased with UV irradiative intensity. Maximum methanol rate was 4.12 μmole/g-cat h using 1.0 wt%-Ag/TiO₂ catalyst at 1.13 bar of CO₂, 0.03 bar of H₂O pressures, and 5,000 s mean residence time under 10 W/cm² UV irradiation.     

UV/H2O2 treatment of Rhodamine B in aqueous solution: Influence of operational parameters and kinetic modeling

The decolorization and degradation of Rhodamine B (RB) were investigated using UV radiation in the presence of H₂O₂ in a batch photoreactor at different light intensities. H₂O₂ and UV light have a negligible effect when they were used on their own. Removal efficiency of RB was sensitive to the operational parameters such as initial concentrations of H₂O₂ and RB, initial pH and light intensity. The results indicated that efficiency of process decreased with addition of inorganic ions and alcohols to the dye solution as hydroxyl radical scavengers. The semilogarithmic graphs of the concentrations of RB versus time were linear, suggesting pseudo-first order reaction for decolorization and degradation processes. A simple kinetic model is proposed which confirms pseudo-first-order reaction. The electrical energy per order (EE/O) values for decolorization and degradation of RB solution were calculated. Results shows that applying an optimum hydrogen peroxide concentration can reduce the EE/O.     

Photooxidation of anionic surfactant (sodium lauryl sulfate) in a three-phase fluidized bed reactor using TiO2/SiO2 photocatalyst

The photooxidation of sodium lauryl sulfate (=sodium dodecyl sulfate) in two different types of three-phase fluidized bed reactors was investigated. A low concentration of sodium lauryl sulfate (0.1–0.6 mM) in aqueous solution was photocatalytically decomposed by a TiO₂ photocatalyst immobilized on a porous SiO₂ support. In order to determine the optimum operating conditions in the fluidized beds, the effects of the air flow rate, amount of catalyst, initial concentration of surfactant, light source power, and pH on the photooxidation rate were investigated. From the experimental results, it was observed that the superficial air velocity was an important parameter in determining the reaction rate for both reactors. The photooxidation reaction rate increased with increasing UV lamp power and the experimentally obtained reaction rates showed good agreement with the Langmuir adsorption model. Also, a higher reaction rate was observed when the aqueous solution was acidic.     

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.     

Parameter effect on photocatalytic degradation of phenol using TiO2-P25/activated carbon (AC)

P25 powder embedded and TiO₂ immobilized on activated carbon (TiO₂-P25/AC) was prepared by P25 powder modified sol-gel and dip-coated method. The photocatalysts were characterized by XRD, BET, SEM and their photocatalytic activities were evaluated through phenol degradation in a fluidized bed photoreactor. The addition of P25 in the photocatalysts could significantly enhance the photocatalytic activity, and the optimum loading of P25 was 3 g L^?1. The operating parameter results indicated that the optimum pH for phenol degradation was 5.2; the effect of air flow rate gave an optimal value of 2 L min^?1; the increasing of UV light intensity led to an increase of degradation efficiency due to more photons absorbed on the surface of the photocatalyst. The kinetics of the phenol degradation fitted well with the Langmuir-Hinshelwood kinetics model. Finally, the photocatalytic ability of TiO₂-P25/AC was reduced only 10% after five cycles for phenol degradation.     

Effect of water pretreatment on CO<Subscript>2</Subscript> capture using a potassium-based solid sorbent in a bubbling fluidized bed reactor

A bubbling fluidized bed reactor was used to study CO₂ capture from flue gas by using a potassium-based solid sorbent, sorbKX35 which was manufactured by the Korea Electric Power Research Institute. A dry sorbent, sorbKX35, consists of K₂CO₃ for absorption and supporters for mechanical strength. To increase initial CO₂ removal, some amount of H₂O was absorbed in the sorbent before injecting simulated flue gas. It was possible to achieve 100% CO₂ removal for more than 10 minutes at 60°C and a residence time of 2 s with H₂O pretreatment. When H₂O pretreatment time was long enough to convert K₂CO₃ of sorbKX35 into K₂CO₃ · 1.5H₂O, CO₂ removal was excellent. The results obtained in this study can be used as basic data for designing and operating a large scale CO₂ capture process with two fluidized bed reactors. This work was presented at the 6 ^th Korea-China Workshop on Clean Energy Technology held at Busan, Korea, July 4–7, 2006.     

Effect of humidity on the photocatalytic degradation of trichloroethylene in gas Phase over TiO2 thin films treated by different conditions

The effect of humidity on the photocatalytic degradation reaction of trichloroethylene (TCE) in gas phase was investigated by using pretreated TiO₂ sol-gel films. It was observed that the photocatalytic activity of the TiO₂ films depended more greatly on the pretreatment conditions, for example, UV pre-illumination, than on the moisture content. When the relative humidity was over 50%, the reaction rates decreased regardless of treatment conditions of the photocatalyst. The photocatalytic decomposition rate of TCE increased with the increase of light intensity. However, the influence of humidity on the reaction rate was less significant under the increased light intensity. The intermediates and byproducts of the reaction were not changed in different humidity conditions.     

Photoelectrocatalytic degradation of phenol using a TiO<Subscript>2</Subscript>/Ni thin-film electrode

As a new type of photoelectrode, TiO₂/Ni thin-film electrode was prepared by dip-coating technique. The structural and surface morphology of electrode was examined by X-ray diffraction (XRD) and scanning electron microscope (SEM). Effects of initial phenol concentration, pH value, number of film layers, voltage of electrical bias applied, variation of inorganic salt type and types of dissolved gas on the photoelectrocatalytic (PEC) degradation of phenol using ultraviolet (UV) illuminated TiO₂/Ni thin-film electrode were investigated. The mechanism of PEC degradation of phenol was also studied by analyzing reaction intermediates.     

Electrochemically assisted photocatalytic degradation of oxalic acid on particulate TiO2 film in a batch mode plate photoreactor

Electrochemically assisted photocatalytic degradation of oxalic acid was studied in a batch mode plate photoreactor composed of particulate TiO₂ film immobilized on Ti metal plate (Ti/TiO₂ electrode) and Pt wires immersed in a flowing film of aqueous solution (Pt counter electrode). The degradation rate of oxalic acid was followed as a function of the potential of the Ti/TiO₂ electrode, the oxygen concentration and the light intensity. The presence of oxalic acid caused an increase in the measured photocurrent by one order of magnitude which is due to its reaction with photogenerated holes. The degradation rate increased with increasing potential up to 0.5 V vs SCE, then the increase was more gradual. Electrochemically assisted photocatalytic degradation of oxalic acid also proceeded in the absence of oxygen. The photogenerated electrons caused hydrogen evolution (low oxygen concentration) or predominantely oxygen reduction (high oxygen concentration) on the Pt counter electrode.     

Dye sensitized CO<Subscript>2</Subscript> reduction over pure and platinized TiO<Subscript>2</Subscript>

TiO₂ thin and thick films promoted with platinum and organic sensitizers including novel perylene diimide dyes (PDI) were prepared and tested for carbon dioxide reduction with water under visible light. TiO₂ films were prepared by a dip coating sol–gel technique. Pt was incorporated on TiO₂ surface by wet impregnation [Pt(on).TiO₂], or in the TiO₂ film [Pt(in).TiO₂] by adding the precursor in the sol. When tris (2,2′-bipyridyl) ruthenium(II) chloride hexahydrate was used as sensitizer, in addition to visible light activity towards methane production, H₂ evolution was also observed. Perylene diimide derivatives used in this study have shown light harvesting capability similar to the tris (2,2′-bipyridyl) ruthenium(II) chloride hexahydrate.     

Modeling of the photocatalytic decomposition of gaseous benzene in a TiO2 coated optical fiber photoreactor

Photocatalytic decomposition of benzene in an air stream in a continuous TiO₂-coated optical fiber photoreactor (OFP) was demonstrated to be effective at relatively short retention times. An increase in TiO₂ coating thickness, fiber length and retention time improved the decomposition of benzene; however, excessive TiO₂ coating thickness and optical fiber length may hamper the reaction. The UV light intensity distribution on and within the optical fiber was modeled using Snell’s law and UV light energy balance. The modeled profile indicated that the UV light intensity decreased rapidly along the axial and radial directions of the optical fiber. A mathematical model combining the continuity equations and Langmuir–Hinshelwood surface kinetics was established to adequately describe the reaction behavior of benzene decomposition in the OFP with only single TiO₂-coated fiber.     

Photodegradation of benzene,toluene, ethylbenzene and xylene by fluidized bed gaseous reactor with TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> photocatalysts

The photodegradation of BTEX (benzene, toluene, ethylbenzene and xylene) in a photocatalytic fluidized bed reactor with TiO₂/SiO₂ was investigated. The TiO₂ film was prepared using the sol-gel method and coated onto silica-gel powder. The effects of the superficial gas velocity and SiO₂ size on the photodegradation of BTEX were examined in a fluidized bed reactor. At steady-state operation, above 79, 79, 99, 98, and 98% removal efficiencies were achieved for benzene, toluene, ethylbenzene, m, p-xylene and o-xylene, respectively, under optimal conditions (2.0 U _mf of superficial gas velocity and 1.43 of height/diameter ratio). The reaction product such as CO₂ was detected and intermediate products such as benzaldehyde, malonic acid, acetaldehyde, and formic acid were identified from the photocatalytic reaction. Also, small amounts of benzoic acid and benzyl alcohol were found through analyzing the intermediate species adsorbed on the photocatalysts. The experimental results can lead to the development of an efficient photocatalytic treatment system that utilizes solar energy and TiO₂/SiO₂ photocatalysts.     

Effects of microwave,UV, and O3 on propylene gas degradation via photocatalytic reaction with CVD TiO2 films

A microwave/UV/ozone/TiO₂ photocatalyst hybrid process system, which is a combination of various propylene gas treatment techniques, is evaluated for use as an advanced, efficient technology for air pollution treatment. TiO₂ photocatalyst balls were prepared using low-pressure metal-organic chemical vapor deposition. The microwave/UV/TiO₂ photocatalyst hybrid process exhibited the higher degradation efficiency than the microwave/UV/alumina ball hybrid system. The degradation efficiency increased almost linearly with increasing ozone dose. The lower the propylene inlet concentration was the higher degradation efficiency. The double bond of propylene is broken by ozone and OH, resulting in production of CH₄ and C₂H₆. These two intermediate products are mineralized into CO₂, H₂O, and CO. C₂H₄ and C₃H₈ may be produced from CH₄, whereas C₂H₆ and C₃H₆ are produced by microwave irradiation.     

Preparation of TiO<Subscript>2</Subscript>/SiO<Subscript>2</Subscript> hollow spheres and their activity in methylene blue photodecomposition

PSA [poly-(styrene-methyl acrylic acid)] latex particle has been taken into account as template material in SiO₂ hollow spheres preparation. TiO₂-doped SiO₂ hollow spheres were obtained by using the appropriate amount of Ti(SO₄)₂ solution on SiO₂ hollow spheres. The photodecomposition of the MB (methylene blue) was evaluated on these TiO₂-doped SiO₂ hollow spheres under UV light irradiation. The catalyst samples were characterized by XRD, UV-DRS, SEM and BET. A TiO₂-doped SiO₂ hollow sphere has shown higher surface area in comparison with pure TiO₂ hollow spheres. The 40 wt% TiO₂-doped SiO₂ hollow sphere has been found as the most active catalyst compared with the others in the process of photodecomposition of MB (methylene blue). The BET surface area of this sample was found to be 377.6 m²g⁻¹. The photodegradation rate of MB using the TiO₂-doped SiO₂ catalyst was much higher than that of pure TiO₂ hollow spheres.     

Statistical optimization of process conditions for photocatalytic degradation of phenol with immobilization of nano TiO<Subscript>2</Subscript> on perlite granules

Response surface methodology (RSM) using D-optimal design was applied to optimization of photocatalytic degradation of phenol by new composite nano-catalyst (TiO₂/Perlite). Effects of seven factors (initial pH, initial phenol concentration, reaction temperature, UV irradiation time, UV light intensity, catalyst calcination temperature, and dosage of TiO₂/perlite) on phenol conversion efficiency were studied and optimized by using the statistical software MODDE 8.02. On statistical analysis of the results from the experimental studies, the optimum process conditions were as follows: initial pH, 10.7; initial phenol concentration, 0.5 mM; reaction temperature, 27 °C; UV irradiation time, 6.5 h; UV light intensity, 250 W; catalyst calcination temperature, 600 °C; and TiO₂/perlite dosage, 6 g/L. Analysis of variance (ANOVA) showed a high coefficient of determination (R²) of 91.8%.     

Synergism Between Pt/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> and Au/TiO<Subscript>2</Subscript> in the Low Temperature Oxidation of Propene

CO impedes the low temperature (<170 °C) oxidation of C₃H₆ on supported Pt. Supported Au catalysts are very effective in the removal of CO by oxidation, although it has little propene oxidation activity under these conditions. Addition of Au/TiO₂ to Pt/Al₂O₃ either as a physical mixture or as a pre-catalyst removes the CO and lowers the light-off temperature (T ₅₀) for C₃H₆ oxidation compared with Pt catalyst alone by ~54 °C in a feed of 1% CO, 400 ppm C₃H₆, 14% O₂, 2% H₂O.     

Maximization of total surface area of Pt-SnO<Subscript>2</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalyst by the Taguchi method

The maximization of the total surface area of Pt-SnO₂/Al₂O₃ catalyst was studied by using the Taguchi method of experimental design. The catalysts were prepared by sol-gel method. The effects of HNO₃, H₂O and aluminum nitrate concentrations and the stirring rate on the total surface area were studied at three levels of each. L₉ orthogonal array leading nine experiments was used in the experimental design. The parameter levels that give maximum total surface area were determined and experimentally verified. In the range of conditions studied it was found that, medium levels of HNO₃ and H₂O concentration and lower levels of aluminum nitrate concentration and stirring rate maximize the total surface area.