Performance of photocatalytic reactors using immobilized TiO2 film for the degradation of phenol and methylene blue dye present in water stream

TiO2 thin film photocatalyst was successfully synthesized and immobilized on glass reactor tube using sol-gel method. The synthesized TiO2 coating was transparent, which enabled the penetration of ultra-violet (UV) light to the catalyst surface. Two photocatalytic reactors with different operating modes were tested: (a) tubular photocatalytic reactor with re-circulation mode and (b) batch photocatalytic reactor. A new proposed TiO2 synthesized film formulation of 1 titanium isopropoxide: 8 isopropanol: 3 acetyl acetone: 1.1 H2O: 0.05 acetic acid (in molar ratio) gave excellent photocatalytic activity for degradation of phenol and methylene blue dye present in the water. The half-life time, t1/2 of photocatalytic degradation of phenol was 56 min at the initial phenol concentration of 1000 microM in the batch reactor. In the tubular photocatalytic reactor, 5 re-circulation passes with residence time of 2.2 min (single pass) degraded 50% of 40-microM methylene blue dye. Initial phenol concentration, presence of hydrogen peroxide, presence of air bubbling and stirring speed as the process variables were studied in the batch reactor. Initial methylene blue concentration, pH value, light intensity and reaction temperature were studied as the process variables in the tubular reactor. The synthesized TiO2 thin film was characterized using SEM, XRD and EDX analysis. A comparative performance between the synthesized TiO2 thin film and commercial TiO2 particles (99% anatase) was evaluated under the same experimental conditions. The TiO2 film was equally active as the TiO2 powder catalyst.     

固载型TiO2光催化反应器对富营养水体杀藻作用研究

以泡沫镍作为载体，利用电沉积技术将纳米TiO₂负载在泡沫镍上，制成固载型TiO₂光催化反应器。研究表明，经过光催化反应器处理的富营养水体，30 h内叶绿素a由96.2 mg/m³降至2.2mg/m³，下降率达97.6％，而未负载纳米TiO₂普通泡沫镍材料，在同样光强的紫外灯照射下，叶绿素a下降率为74.3％，表明紫外光照射虽然也具有一定的杀藻功能，但是光催化反应才是藻类被杀灭的主要原因。利用9.54 m³景观喷水池进行杀藻中试，光催化反应器也同样表现出优异的杀藻性能，12 d内叶绿素a由18.7 mg/m³降至1.9mg/m³，下降率达到89.8％，水体由浓绿变为清澈见底，这表明光催化反应器具有很强的杀藻能力，通过有效杀灭富营养水体中藻类、控制藻类基数，对应急处理城市景观水、湖泊等富营养水体和突发性藻华，提高生物-生态法处理效率，改善城市水环境具有十分重要的意义。     

Photocatalytic degradation of phenol using Ag core-TiO<Subscript>2</Subscript> shell (Ag@TiO<Subscript>2</Subscript>) nanoparticles under UV light irradiation

Ag@TiO₂ nanoparticles were synthesized by one pot synthesis method with postcalcination. These nanoparticles were tested for their photocatalytic efficacies in degradation of phenol both in free and immobilized forms under UV light irradiation through batch experiments. Ag@TiO₂ nanoparticles were found to be the effective photocatalysts for degradation of phenol. The effects of factors such as pH, initial phenol concentration, and catalyst loading on phenol degradation were evaluated, and these factors were found to influence the process efficiency. The optimum values of these factors were determined to maximize the phenol degradation. The efficacy of the nanoparticles immobilized on cellulose acetate film was inferior to that of free nanoparticles in UV photocatalysis due to light penetration problem and diffusional limitations. The performance of fluidized bed photocatalytic reactor operated under batch with recycle mode was evaluated for UV photocatalysis with immobilized Ag@TiO₂ nanoparticles. In the fluidized bed reactor, the percentage degradation of phenol was found to increase with the increase in catalyst loading.     

活性炭纤维负载TiO_2光催化降解甲醛的影响因素

利用自制光催化气体反应器体系,以活性炭纤维负载TiO2作催化剂,在紫外光照射下模拟降解室内污染气体甲醛,测试了活性炭纤维负载TiO2催化剂的催化活性,探讨了紫外光光强、催化剂的酸度、反应器内湿度及反应时间等控制反应的主要因素对甲醛降解率的影响.结果表明,活性炭纤维与TiO2的协同作用大大提高了对甲醛的降解效果;紫外光强增倍对甲醛降解率有一定提高,但提高幅度仅为11.71%;活性炭纤维用pH=5的TiO2溶胶浸泡做催化剂对甲醛的降解效果最好,60 min内降解率达到68.37%;反应器内的湿度为81%甲醛降解率最高,反应60 min后达82.2%;随着反应时间的延长,甲醛降解率的上升幅度不断减小,最高只能达到94.59%.     

Photocatalytic degradation of methyl orange by a multi-layer rotating disk reactor

Introduction

Solar wastewater treatment based on photocatalytic reactions is a green process that utilizes renewable energy resources and minimizes secondary pollution. Reactor design plays an important role in promoting treatment efficiency and throughput density (based on unit volume of the reactor).

Experimental

A rotating disk reactor that significantly increases the process efficiency has been designed and evaluated for application to photocatalytic decomposition of dye pollutants in aqueous solutions. In this process, a novel multi-layer rotating disk reactor (MLRDR) was presented. Photocatalyst (TiO₂) particles are immobilized on the surfaces of disks. Within each layer of the reactor, methyl orange aqueous solution is allowed to flow from the center of the disk in a radial direction along the surface of the disk, which is rotating at high speed and is irradiated with UV lamps. The effluent is then directed to the center of another layer that lies underneath. Up to four stacked layers have been tested in this study, and the effects due to the number of the layers and volumetric flow rate on reaction conversion are investigated.

Results and discussion

The efficiency of this photocatalytic reactor exhibits complex dependence on these parameters. With selected operating conditions, conversions greater than 95% can be achieved within seconds of residence time. Design equations of the reactor have been derived based on fluid dynamics and kinetic models, and the simulation results show promising scale-up potential of the reactor.     

3种染料化合物在UV-TiO2/H2O2和UV-TiO2体系中的光催化降解研究

采用自制的TiO2膜和平板式固定床型光催化氧化反应装置,对甲基橙、茜素红和罗丹明B 3种含有不同生色基团的染料化合物进行了TiO2光催化氧化降解研究,通过对照测定降解过程中吸光度、电导率、pH的变化,分析了在加入和不加入H2O22种情况下降解过程的异同,比较了3种染料化合物脱色的难易程度,揭示了降解产物中无机离子的变化规律及某些可能的产物类型.     

Isovaleraldehyde elimination by UV/TiO2 photocatalysis: comparative study of the process at different reactors configurations and scales

A proposal for scaling-up the photocatalytic reactors is described and applied to the coated catalytic walls with a thin layer of titanium dioxide under the near ultraviolet (UV) irradiation. In this context, the photocatalytic degradation of isovaleraldehyde in gas phase is studied. In fact, the removal capacity is compared at different continuous reactors: a photocatalytic cylindrical reactor, planar reactor, and pilot unit. Results show that laboratory results can be useful for reactor design and scale-up. The flowrate increases lead to the removal capacity increases also. For example, with pilot unit, when flowrate extends four times, the degradation rate varies from 0.14 to 0.38 g h^?1 m_cat ^?2. The influence of UV intensity is also studied. When this parameter increases, zboth degradation rate and overall mineralization are enhanced. Moreover, the effects of inlet concentration, flowrate, geometries, and size of reactors on the removal capacity are also studied.     

TiO2/β-SiC foam-structured photoreactor for continuous wastewater treatment

Introduction

This study of photocatalytic degradation of wastewater was carried out in alveolar cell ??-SiC foam-structured photocatalytic reactors working in a recirculation mode. The immobilization of TiO2 on ??-SiC foams was efficiently obtained through a sol?Cgel technique in acidic conditions.

Discussion

In order to optimize degradation yields obtained by the foam-structured prototype reactor for the photocatalytic water treatment, the operating conditions of the photoreactor have been investigated and the efficiency of the process was evaluated by measuring the photocatalytic degradation of Diuron (3-(3,4-dichlorophenyl)-1,1-dimethyl-urea)) under UV irradiation. Kinetic studies were carried out by investigating the influence of different parameters controlling the reaction (TiO2 loading and ??-SiC foam cell size). The ageing of TiO2/??-SiC foam photocatalytic materials and the mineralization (TOC, Cl?, NO3? and NH4+) of Diuron were investigated.     

活性炭纤维负载TiO2光催化降解甲醛的影响因素

利用自制光催化气体反应器体系,以活性炭纤维负载TiO2作催化剂,在紫外光照射下模拟降解室内污染气体甲醛,测试了活性炭纤维负载TiO2催化剂的催化活性,探讨了紫外光光强、催化剂的酸度、反应器内湿度及反应时间等控制反应的主要因素对甲醛降解率的影响。结果表明,活性炭纤维与TiO2的协同作用大大提高了对甲醛的降解效果;紫外光强增倍对甲醛降解率有一定提高,但提高幅度仅为11.71%;活性炭纤维用pH=5的TiO2溶胶浸泡做催化剂对甲醛的降解效果最好,60 min内降解率达到68.37%;反应器内的湿度为81%甲醛降解率最高,反应60 min后达82.2%;随着反应时间的延长,甲醛降解率的上升幅度不断减小,最高只能达到94.59%。     

Removal of methanol from pulp and paper mills using combined activated carbon adsorption and photocatalytic regeneration

Methanol is one of the major hazardous air pollutants emitted from chemical pulp mills. Its collection and treatment is required by the Maximum Achievable Control Technology portion of the 1998 Cluster Rule. The objective of this study is to investigate the technical feasibility of combined adsorption and photocatalytic regeneration for the removal and destruction of methanol. To facilitate the regeneration, activated carbon (AC) was coated with commercially available photocatalyst by a spray desiccation method. Laboratory-scale experiments were conducted in a fixed-bed reactor equipped with an 8 W black light UV lamp (peak wavelength at 365 nm) at the center. The photocatalyst loaded onto AC had no significant impact on the adsorption capacity of the carbon. High humidity was found to greatly reduce the material's capacity in the adsorption and simultaneous adsorption and photocatalytic oxidation of methanol. The photocatalytic regeneration process is limited by the desorption of the adsorbate. Increasing desorption rate by using purge air greatly increased the regeneration capacity. When the desorption rate was greater than the photocatalytic oxidation rate, however, part of the methanol was directly desorbed without degradation.     

Photodegradation of Diquat and Paraquat in aqueous solutions by titanium dioxide: evolution of degradation reactions and characterisation of intermediates

The titanium dioxide assisted photodegradation of Diquat and Paraquat herbicides solutions has been the subject of the present investigation, considering its direct application in the treatment of contaminated waters and soils. To have a better understanding of the photodegradation process, different types of TiO2, commercial and 'home prepared' Ti(1-x)FexO2 (x = 0% and 4%), were used as catalysts, using an UV light as radiation source. The degradation reactions were followed by UV spectroscopy and the intermediates and reaction products were characterised by electrospray ionisation mass spectrometry (ESIMS) combined with collision-induced dissociation (CID) and tandem mass spectrometry (MS/MS). The present study shows that, for photocatalytic degradation of Diquat and Paraquat solutions, a basic pH can be determinant, as well as the type of catalyst. The type of catalyst can also strongly influence the degradation pattern of the herbicide. Regarding complete degradation, we were able to show that Diquat is more persistent than Paraquat. During the photocatalytic processes, several intermediate and reaction products are sequentially formed, to which structures are proposed.     

Evaluation of relative photonic efficiency in heterogeneous photocatalytic reactors

The evaluation of photonic efficiency in heterogeneous photocatalysis remains elusive because the number of absorbed photons is difficult to assess experimentally. The photonic efficiency of heterogeneous photocatalytic reactors depends on the reactor geometry, irradiation source, and photocatalyst properties. In this work, the relative photonic efficiency of heterogeneous photocatalytic reactors to degrade an azo dye was evaluated using phenol as the standard system. The experimental tests were carried out in a batch reactor under different conditions of pH, catalyst dosage, initial concentration, and ultraviolet (UV) lamps. The kinetics of disappearance of both phenol and azo dye were studied using the initial rate method and were described according to the Langmuir-Hinshelwood (L-H) kinetic model. It was observed that the relative photonic efficiency depends on the adsorption/desorption properties of the photocatalyst.     

活性炭纤维负载TiO2光催化降解甲醛的影响因素

利用自制光催化气体反应器体系,以活性炭纤维负载TiO₂作催化剂,在紫外光照射下模拟降解室内污染气体甲醛,测试了活性炭纤维负载TiO₂催化剂的催化活性,探讨了紫外光光强、催化剂的酸度、反应器内湿度及反应时间等控制反应的主要因素对甲醛降解率的影响。结果表明,活性炭纤维与TiO₂的协同作用大大提高了对甲醛的降解效果;紫外光强增倍对甲醛降解率有一定提高,但提高幅度仅为11.71%;活性炭纤维用pH=5的TiO₂溶胶浸泡做催化剂对甲醛的降解效果最好,60 min内降解率达到68.37％;反应器内的湿度为81%甲醛降解率最高,反应60 min后达82.2%;随着反应时间的延长,甲醛降解率的上升幅度不断减小,最高只能达到94.59%。     

改性TiO2/浮石光催化去除二级出水中有机物

为了实现城市污水厂二级出水的回用,将La3+、Fe3+共掺杂TiO2/浮石光催化用于二级出水中有机物的去除。在优化工艺条件下,该方法对TOC的去除率为49.0%,对UV254的去除率为76.5%;出水BDOC/DOC值大幅度提高,由最初的0.21提高到0.56,增加了出水的可生化性;二级出水中存在着影响光催化去除有机物的因素,其中阴离子对有机物的去除有一定的抑制作用;光催化反应在通过O3强化后对有机物的去除率得到提高,TOC的去除率达到75.0%,光催化和O3氧化对有机物的去除具有协同效应;随着光催化反应次数的增加,催化剂活性有下降趋势,使用10次后TOC去除率下降到第一次使用时的16.7%,再生能够使催化活性恢复到使用前的95%,催化剂在使用15次以内稳定性较好。     

Chemical identification and acute biotoxicity assessment of gaseous chlorobenzene photodegradation products

In order to evaluate the ecological safety and feasibility of UV photodegradation processes for the treatment of halogenated aromatic hydrocarbons, the chemical composition and acute biotoxicity of gaseous chlorobenzene photodegradation products were investigated. Results showed that the main products of chlorobenzene photodegradation included hydrochloric acid, acetic acid, formic acid, phenol and chlorophenol. Roughly 64% of the removed chlorobenzene was converted into phenol, making it the most significant product formed. The types of byproducts suggested that two distinct reaction pathways might compete during the photodegradation process. Interestingly, it appeared that one of these pathways did not involve the direct photocatalytic oxidation of chlorobenzene. An acute biotoxicity assay measuring the inhibition of bioluminescence indicated that gaseous exhaust with overall higher toxicity was emitted after UV irradiation. The acute toxicity of the UV reactor exhaust gas was as high as EC(50)=13.5mg-Zn(2+)m(-3-)-gas. The increased toxicity mainly resulted from the conversion of chlorobenzene to more soluble toxic products and ozone production during the photodegradation process.     

Photodecomposition of o-cresol by UV-LED/TiO2 process with controlled periodic illumination

This study investigated the effect of controlled periodic illumination on the photonic efficiency and temporal decomposition behavior of o-cresol by UV/TiO2 process in a slurry reactor using light emitting diodes as the light source. Based on the same UV light intensity of 6.7 W m(-2), the calculated photonic efficiencies increased from 1.5% to 6.3% with the decreasing duty cycle from 1.0 to 0.1 possibly ascribed to the decreasing electron-hole recombination. Actually, the calculated photonic efficiency under periodic illumination at sufficiently intermittence was inferior to, but approached, those under continuous illumination at equivalent average UV light intensity. The calculated electric energy per order increased from 32 to 37 k W h m(-3)order(-1) for experiments conducted with the increasing duty cycle from 0.1 to 1.0, and the electric energy consumption decreased significantly due to the lower duty cycle and average UV light intensity. The photocatalytic decomposition of o-cresol with the UV-light emitting diodes light could be well modeled by the Langmuir-Hinshelwood kinetic equation.     

Kinetics and mechanism of TNT degradation in TiO2 photocatalysis

The photocatalytic degradation of TNT in a circular photocatalytic reactor, using a UV lamp as a light source and TiO(2) as a photocatalyst, was investigated. The effects of various parameters such as the initial TNT concentration, and the initial pH on the TNT degradation rate of TiO(2) photocatalysis were examined. In the presence of both UV light illumination and TiO(2) catalyst, TNT was more effectively degraded than with either UV or TiO(2) alone. The reaction rate was found to obey pseudo first-order kinetics represented by the Langmuir-Hinshelwood model. In the mineralization study, TNT (30 mg/l) photocatalytic degradation resulted in an approximately 80% TOC decrease after 150 min, and 10% of acetate and 57% of formate were produced as the organic intermediates, and were further degraded. NO(-)(3) NO(-)(2), and NH(+)(4) were detected as the nitrogen byproducts from photocatalysis and photolysis, and more than 50% of the total nitrogen was converted mainly to NO(-)(3)in the photocatalysis. However, NO(-)(3) did not adsorbed on the TiO(2) surface. TNT showed higher photocatalytic degradation efficiency at neutral and basic pH.     

Photocatalytic oxidation of xenobiotics in water with immobilized TiO2 on agitator

A novel photocatalytic oxidation reactor, using Degussa P-25 TiO2 as a stationary phase with a thickness of 1.5-2.0 um on the blades of agitator, was developed to study the photocatalytic oxidation of xenobiotics. Particularly in this device, separation of photocatalyst from the purified water after oxidation reaction was not necessary, and no other aeration equipment was required to supply oxygen. To examine the efficiency of this device, photocatalytic degradation of xenobiotic organics such as carbofuran was studied as an example. Results indicated that carbofuran could be degraded completely with mineralization efficiency of 20% after 6 hours of oxidation under the imposed conditions. The mineralization rate of carbofuran was found to follow the pseudo-first order reaction kinetics. Moreover, the rate constant of mineralization was found to be proportional to TiO2 film area and the square root of UV light intensity. These results implied the mineralization efficiency of carbofuran could be improved through increasing TiO2 film area and UV light intensity. Accordingly, this novel device showed potential application for degrading xenobiotics in water.     

Solar photocatalytic decolorization of methylene blue in water

In this study, a photocatalytic decolorization system equipped with immobilized TiO2 and illuminated by solar light was used to remove the color of wastewater. To examine the decoloring efficiency of this system, photocatalytic decolorization of an organic dye such as methylene blue was studied as an example. The effects of light source, pH, as well as the initial concentration of dye were also investigated. It was observed that the solution of methylene blue could be almost completely decolorized by the solar light/TiO2 film process while there was about 50% color remaining with solar irradiation only. In addition, it was found that the decoloring efficiency of solution was higher with solar light irradiation than with artificial UV light irradiation, even though the artificial UV light source supplied higher UV intensity at 254 nm. The color removal rate of methylene blue with solar light irradiation was almost twice that of artificial UV light irradiation. This phenomena was mainly attributed to that some visible light range of solar light was useful for exciting the methylene blue molecules adsorbed on TiO2 film, leading to a photosensitization process undergoing and decoloring efficiency promoted. This solar-assisted photocatalytic device showed potential application for decoloring organic dyes in wastewater.     

光催化-膜分离三相流化床循环反应装置处理酸性红B废水

耦合光催化氧化和有机膜分离技术,设计了一种新型光催化氧化-有机膜分离三相流化床循环反应装置（循环反应装置）;并对循环反应装置光催化降解酸性红B时的影响因素进行了研究。结果表明,减小膜出水通量和降低酸性红B废水浓度均有利于膜出水降解率的提高;循环反应装置中废水降解率随光催化反应器底部曝气量的增加而先增加再降低,膜分离器中废水降解率的波动则随曝气量的增加而总是在增大,其最佳曝气量为1．00m^3／h;光催化反应器中多光源布置有利于循环反应装置的稳定运行;循环反应装置可有效地处理酸性红B废水。