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.     

Mechanistic analysis on the influence of humidity on photocatalytic decomposition of gas-phase chlorobenzene

The influence of humidity on the decomposition of gas phase chlorobenzene (CB) was studied in a batch photocatalytic reactor using TiO(2) (anatase). Increasing relative humidity (>7% at 25 degrees C and 1atm) resulted in an increasingly detrimental effect on the adsorption and photocatalytic decomposition rate of CB. Mechanistic analysis indicates that the relative hydrophilic/hydrophobic nature of a given chemical should dictate adsorption onto or penetration through water to the TiO(2) surface. It is suggested that multiple layers of water molecules are formed at the TiO(2) interface with air, even at low relative humidities. The multiple-layered film of water retards/prevents CB from reaching the reactive TiO(2) surface or contacting radical species in the boundary layer.     

SITE Demonstration of Slurry-Phase Biodegradation of PAH Contaminated Soil

This paper summarizes a joint Superfund Innovative Technology Evaluation (SITE) project on slurry-phase biodegradation and a project to collect information for the data base on Best Demonstrated Available Technologies (BOAT). In this 12-week study, a creosote contaminated soil from the Burlington Northern Superfund site in Brainerd, Minnesota was used to evaluate the effectiveness of the bioslurry reactors. During the demonstration, five 64-liter stainless steel bioreactors, equipped with agitation, aeration and temperature controls were used. The pilot scale study employed a 30 percent slurry, an inoculum of indigenous polynuclear aromatic hydrocarbon (PAH) degraders, and inorganic nutrients.

Total PAH degradation averaged 93.4 ± 3.2 percent over all five operating reactors in the 12 weeks with 97.4 percent degradation of the 2- and 3-ring PAHs and 90 percent degradation of the 4- to 6-ring PAHs. A study of the air emissions, both semivolatile compounds such as naphthalene, anthracene, and phenanthrene and volatile compounds such as toluene, xylene, and benzene, from the units showed that the greatest amount of emissions occurred during the loading of the reactors and during the first few days of operation. Therefore, it may not be cost-effective to require elaborate emissions controls unless there are significant quantities of volatile compounds present in the soil or water to be treated in a bioslurry reactor system.     

制备条件对不同玻璃材料负载TiO_2活性影响研究

以光催化降解苯酚为探针反应,通过正交实验,系统研究了胶液配比、涂覆次数和焙烧温度等条件对以溶胶-凝胶法分别在普通钠钙玻璃和磨砂玻璃上制备TiO2光催化性能的影响,并利用环境扫描电镜（ESEM）对TiO2催化膜形貌进行了分析。研究表明,在普通钠钙玻璃片上负载TiO2催化膜的影响因素主次顺序为：硝酸体积〉涂覆次数〉焙烧温度〉V乙醇∶V酞酸丁酯,在选定实验条件下的最优条件为：涂覆次数为4次;焙烧温度=450℃;V乙醇∶V酞酸丁酯∶V硝酸（1∶4）：V水=400∶40∶1∶4。在磨砂玻璃片上负载TiO2催化膜的的影响因素主次顺序为：涂覆次数〉硝酸体积〉焙烧温度〉V乙醇：V酞酸丁酯,在选定实验条件下的最优条件为：涂覆次数为4次;焙烧温度=500℃;V乙醇∶V酞酸丁酯∶V硝酸（1∶4）∶V水=400∶40∶2∶4。通过扫描电镜可以观察到在普通钠钙玻璃片和磨砂玻璃片表面均附着一层白色的TiO2薄膜,颗粒粒径在100 nm左右。磨砂玻璃比普通钠钙玻璃负载更多的催化剂,磨砂玻璃基TiO2活性更高。磨砂玻璃是一种非常有前景的TiO2催化剂载体材料。     

Heterogeneous photocatalysis of aromatic and chlorinated volatile organic compounds (VOCs) for non-occupational indoor air application

The current study evaluated the technical feasibility of applying TiO2 photocatalysis to the removal of low-ppb concentrations of volatile organic compounds (VOCs) commonly associated with non-occupational indoor air quality issues. A series of experiments was conducted to evaluate five parameters (relative humidity (RH), hydraulic diameter (HD), feeding type (FT) for VOCs, photocatalytic oxidation (PCO) reactor material (RM), and inlet port size (IPS) of PCO reactor) in relation to the PCO destruction efficiencies of the selected target VOCs. None of the target VOCs exhibited any significant dependence on the RH, which is inconsistent with a previous study where, under conditions of low humidity and a ppm toluene inlet level, a drop in the PCO efficiency was reported with a decreasing humidity. However, the other four parameters (HD, RM, FT, and IPS) were found to be important for better VOC removal efficiencies as regards the application of TiO2 photocatalytic technology for cleansing non-occupational indoor air. The PCO destruction of VOCs at concentrations associated with non-occupational indoor air quality issues was up to nearly 100%, and the CO generated during PCO was a negligible addition to indoor CO levels. Accordingly, a PCO reactor would appear to be an important tool in the effort to improve non-occupational indoor air quality.     

Evaluation of an In Situ,On-Line Purging System for the Cone Penetrometer

Abstract

Materials that will be used to construct an in situ, on-line purging system for the cone penetrometer were evaluated. Transfer efficiencies for volatile organic compounds (VOCs) through stainless steel, nickel, aluminum, and Teflon® tubings were determined using a gas-phase mixture of VOCs containing trichloromethane, tetrachloromethane, 1,1,1- trichloroethane, tetrachloroethene, hexane, benzene, toluene, and 1,2-dimethylbenzene. The water content of the gas stream had an insignificant effect on the quantitative transfer of VOCs through Teflon® tubing but was critical to efficiently transfer the compounds through metal tubing, particularly nickel. Transfer efficiencies for all eight analytes in moist gas streams through stainless steel were greater than 95%. Toluene, tetrachloroethene, and 1,2-dimethylbenzene were transferred with 93%, 81%, and 80% efficiency, respectively, when they were drawn through Teflon® PFA (perfluoroalkoxy) tubing. In general, the retention of the VOCs by Teflon® increases with decreasing aqueous solubility of the analyte. The efficiencies at which VOCs were purged from aqueous standards in Teflon® PFA, Type 304 stainless steel, and glass vessels were similar. Stainless steel was superior to nickel, aluminum, and the Teflon® polymers as a material for an in situ, on-line purging system for the cone penetrometer.     

TiO2/Ti转盘液膜反应器光电催化处理罗丹明B

采用溶胶-凝胶法制备了TiO2/Ti电极,X射线衍射(XRD)分析表明,TiO2主要为锐钛矿,晶粒尺寸约为46 nm.以TiO2/Ti电极作阳极,Cu电极作阴极,组装成转盘液膜反应器,考察了其光电催化处理染料罗丹明B(RhB)的影响因素(转盘转速、偏压、溶液初始pH、RhB初始浓度和电解质浓度).得到最佳处理条件为:转盘转速90 r/min,偏压0.4V,溶液初始pH2.5,电解质(硫酸钠)质量浓度0.5 g/L.在最佳处理条件下,处理20 mg/L RhB染料废水90 min的脱色率和总有机碳(TOC)去除率分别达到97.2％和72.7％.结果表明,由于同时强化了激发光源的利用率和溶液的传质效率,TiO2/Ti转盘液膜反应器可高效光电催化处理染料废水.     

Photocatalytic elimination of indoor air biological and chemical pollution in realistic conditions

The photocatalytic elimination of microorganisms from indoor air in realistic conditions and the feasibility of simultaneous elimination of chemical contaminants have been studied at laboratory scale. Transparent polymeric monoliths have been coated with sol-gel TiO(2) films and used as photocatalyst to treat real indoor air in a laboratory-scale single-step annular photocatalytic reactor. The analytical techniques used to characterize the air quality and analyze the results of the photocatalytic tests were: colony counting, microscopy and PCR with subsequent sequencing for microbial quantification and identification; automated thermal desorption coupled to gas chromatography with mass spectrometry detection for chemical analysis. The first experiments performed proved that photocatalysis based on UVA-irradiated TiO(2) for the reduction of the concentration of bacteria in the air could compete with the conventional photolytic treatment with UVC radiation, more expensive and hazardous. Simultaneously to the disinfection, the concentration of volatile organic compounds was greatly reduced, which adds value to this technology for real applications. The fungal colony number was not apparently modified.     

Decomposition of gas-phase trichloroethene by the UV/TiO2 process in the presence of ozone.

The decomposition of gas-phase trichloroethene (TCE) in air streams by direct photolysis, the UV/TiO2 and UV/O3 processes was studied. The experiments were carried out under various UV light intensities and wavelengths, ozone dosages, and initial concentrations of TCE to investigate and compare the removal efficiency of the pollutant. For UV/TiO2 process, the individual contribution to the decomposition of TCE by direct photolysis and hydroxyl radicals destruction was differentiated to discuss the quantum efficiency with 254 and 365 nm UV lamps. The removal of gaseous TCE was found to reduce by UV/TiO2 process in the presence of ozone possibly because of the ozone molecules could scavenge hydroxyl radicals produced from the excitation of TiO2 by UV radiation to inhibit the decomposition of TCE. A photoreactor design equation for the decomposition of gaseous TCE by the UV/TiO2 process in air streams was developed by combining the continuity equation of the pollutant and the surface catalysis reaction rate expression. By the proposed design scheme, the temporal distribution of TCE at various operation conditions by the UV/TiO2 process can be well modeled.     

CdS-TiO2/MWCNTs结构表征及其光催化性能

采用溶胶-凝胶法,制备了多壁碳纳米管（MWCNTs）负载的双组分复合半导体光催化剂CdS-TiO2/MWCNTs。通过透射电镜（TEM）、比表面分析（BET）、X射线衍射（XRD）和紫外-可见吸收光谱（UV-vis）等分析方法对光催化剂进行了结构表征,并考察了CdS-TiO2/MWCNTs对甲苯降解的光催化性能。结果表明：纳米活性粒子CdS-TiO2均匀负载于MWCNTs上,比表面积、光吸收阈值和强度增大,活性粒子间以及活性粒子与载体之间具有协同作用,有利于光催化性能的提高,CdS-TiO2/MWCNTs在主波长为254 nm紫外光照射下对甲苯的降解效果较好,去除率可达55.3%。     

Coupling of titania with multiwall carbon nanotubes for decomposition of gas-phase pollutants under simulated indoor conditions

This study synthesized multiwall carbon nanotube (MWNT)–titania (TiO₂) composites and examined their characteristics and photocatalytic performance for the cleaning of gas-phase benzene, toluene, ethyl benzene, and o-xylene (BTEX) under simulated indoor conditions. Optical and spectral surveys of the as-synthesized composite confirmed that the TiO₂ nanoparticles were bound intimately to the MWNT networks. The photocatalytic performance was evaluated using an annular-type reactor inner-coated with MWNT–TiO₂ or Degussa P25 TiO₂. The composite revealed gas removal ability superior to that of stand-alone TiO₂. This composite was also less affected by humidity during toluene decomposition compared to the previous result obtained from a stand-alone TiO₂. Unlike another previous result obtained from the TiO₂, the performance of the composite was not affected by changes in input concentration (IC) within a simulated indoor air quality range (0.1–1.0 ppm) but it decreased significantly when the IC was increased to 5 and 10 ppm. As the flow rate was decreased from 4.0 to 1.0 L min^?1, the average efficiency for the target compounds increased to 95% or ～100%. The MWNT–TiO₂ composite could be applied effectively to the decomposition for BTEX under certain simulated indoor conditions.

Implications: Unlike water applications, there are few reports of gas-phase applications of multiwall carbon nanotubes (MWCNT)–TiO₂ composites. This study found that MWCNT–TiO₂ composites showed performance in the removal of toxic gaseous aromatic superior to that of stand-alone TiO₂. In addition, the pollutant degradation efficiency of the composite was less affected by humidity than for a stand-alone TiO₂ unit within a simulated indoor relative humidity range. Moreover, unlike the TiO₂ unit, the composite's performance was not affected by variations in the input concentrations within the simulated indoor air quality (IAQ) range. In addition, the decomposition efficiencies increased to 100% with decreasing flow rate.     

Photocatalytic degradation of mixed gaseous carbonyl compounds at low level on adsorptive TiO2/SiO2 photocatalyst using a fluidized bed reactor

An adsorptive silica-supported titania photocatalyst TiO(2)/SiO(2) was prepared by using nanosized titania (anatase) immobilized on silica gel by the sol-gel technique with the titanium tetra isopropoxide as the main raw material and acetic acid as the acid catalyst. Meanwhile the structure and properties of the TiO(2)/SiO(2) photocatalyst were studied by means of many modern analysis techniques such as TEM, XRD, and BET. Gas-solid heterogeneous photocatalytic decomposition of four carbonyl compounds mixture at low concentration levels over ultraviolet irradiated TiO(2)/SiO(2) photocatalyst were carried out with high degradation efficiencies in a coaxial triple-cylinder-type fluidized bed photocatalytic reactor, which provided efficient continuous contact of ultraviolet photons, silica-supported titania photocatalyst, and gaseous reactants. Experimental results showed that the photocatalyst had a high adsorption performance and a good photocatalytic activity for four carbonyl compounds mixture. Some factors influencing the photocatalytic decomposition of the mixed carbonyl compounds, i.e. the gas flowrate, relative humidity, concentration of oxygen, and illumination time, were discussed in detail. It is found that the photocatalytic reaction rate of four carbonyl compounds decreased in this order: propionaldehyde, acetone, acetaldehyde and formaldehyde.     

The light transmission and distribution in an optical fiber coated with TiO2 particles

The light delivery and distribution phenomena along the optical fiber coated with the P-25 TiO(2) particles by dipping was investigated. The surface properties (coverage, roughness and thickness) of the TiO(2) layer coated on the optical fiber were characterized by SEM micrographs. For TiO(2) layer prepared from solutions containing less than 20 wt.% of TiO(2) slurry, the thickness of layer was increased linearly with the TiO(2) slurry content in solutions. The UV light intensity transmitted along a TiO(2)-coated optical fiber decreased more rapidly than that transmitted along a non-coated fiber. Based on the experimental results, the light intensity distribution around a coated optical fiber was modeled to determine the optimum configuration for the design of optical fiber reactors under various operational conditions.     

Pilot-Scale Demonstration of an Innovative Treatment for Vapor Emissions

ABSTRACT

Researchers from the National Renewable Energy Laboratory recently conducted a pilot-scale study at McClellan Air Force Base (AFB) in Sacramento, CA. The objective of the test was to determine the effectiveness of an ambient-temperature, solar-powered photocatalytic oxidation treatment unit for destroying emissions of chlorinated organic compounds from an air stripper. This paper reports test results and discusses applications and limitations of the technology.

A 10-standard-cubic-foot-per-minute (SCFM) (28.3 L/min) slip stream of air from an air stripper at Operative Unit 29-31 at McClellan AFB was passed through a reactor that contained a lightweight, perforated, inert support coated with photoactive titanium dioxide. The reactor faced south and was tilted at a 45° angle from vertical so that the light-activated catalyst received most of the available sunlight. An online portable gas chro-matograph with two identical columns simultaneously analyzed the volatile organic compounds contained in the reactor inlet and outlet air streams. Summa canister grab samples of the inlet and outlet were also collected and sent to a certified laboratory for U.S. Environmental

Protection Agency Method TO-14 analysis and verification of our field analyses. Three weeks of testing demonstrated that the treatment system's destruction and removal efficiencies (DREs) are greater than 95% at 10 SCFM with UV intensities at or greater than 1.5 milliwatts/square centimeter (mW/cm²). DREs greater than 95% at 20 SCFM were obtained under conditions where UV irradiation measured at or greater than 2 mW/cm². In Sacramento, this provided 6 hours of operation per clear or nearly clear day in April. A solar tracking system could extend operating time. The air stream also contained trace amounts of benzene. We observed no loss of system performance during testing.     

Effectiveness of photocatalytic filter for removing volatile organic compounds in the heating, ventilation, and air conditioning system

Nowadays, the heating, ventilation, and air conditioning (HVAC) system has been an important facility for maintaining indoor air quality. However, the primary function of typical HVAC systems is to control the temperature and humidity of the supply air. Most indoor air pollutants, such as volatile organic compounds (VOCs), cannot be removed by typical HVAC systems. Thus, some air handling units for removing VOCs should be added in typical HVAC systems. Among all of the air cleaning techniques used to remove indoor VOCs, photocatalytic oxidation is an attractive alternative technique for indoor air purification and deodorization. The objective of this research is to investigate the VOC removal efficiency of the photocatalytic filter in a HVAC system. Toluene and formaldehyde were chosen as the target pollutants. The experiments were conducted in a stainless steel chamber equipped with a simplified HVAC system. A mechanical filter coated with Degussa P25 titania photocatalyst and two commercial photocatalytic filters were used as the photocatalytic filters in this simplified HVAC system. The total air change rates were controlled at 0.5, 0.75, 1, 1.25, and 1.5 hr(-1), and the relative humidity (RH) was controlled at 30%, 50%, and 70%. The ultraviolet lamp used was a 4-W, ultraviolet-C (central wavelength at 254 nm) strip light bulb. The first-order decay constant of toluene and formaldehyde found in this study ranged from 0.381 to 1.01 hr(-1) under different total air change rates, from 0.34 to 0.433 hr(-1) under different RH, and from 0.381 to 0.433 hr(-1) for different photocatalytic filters.     

Photodegradation of alachlor with the TiO(2) film immobilised on the glass tube in aqueous solution

Alachlor photodegradation was performed using TiO(2), which was synthesized by a modified sol-gel method. The thickness of a TiO(2) film immobilised by a 5-time dip-coating was 174 nm and the average diameter of TiO(2) particles was about 10-15 nm in SEM images. The crystal structure of a TiO(2) film calcinated at 300 degrees C for 1 h was observed as a typical anatase type. The stability of a TiO(2) film by a modified sol-gel method was 4% better than TiO(2) by a typical sol-gel method.The removal rate of alachlor with both Fe(3+) and UV radiation in the absence of TiO(2) was 0.28 mg/l/h in 10 h and the removal rate of alachlor with Fe(3+)/UV in the presence of TiO(2) was 0.32 g/l/h, which was higher by 14% than that with Fe(3+)/UV system. TOC concentration during the alachlor degradation with both TiO(2) and UV radiation in the absence of added Fe(3+) decreased from 100%, through 81% and 51%, to 44% with time elapses of 4, 8, and 10 h, respectively, while TOC concentration with both added Fe(3+) and UV radiation in the absence of TiO(2) decreased from 100% to 70% in 10 h.     

Effectiveness of Photocatalytic Filter for Removing Volatile Organic Compounds in the Heating,Ventilation, and Air Conditioning System

Abstract

Nowadays, the heating, ventilation, and air conditioning (HVAC) system has been an important facility for maintaining indoor air quality. However, the primary function of typical HVAC systems is to control the temperature and humidity of the supply air. Most indoor air pollutants, such as volatile organic compounds (VOCs), cannot be removed by typical HVAC systems. Thus, some air handling units for removing VOCs should be added in typical HVAC systems. Among all of the air cleaning techniques used to remove indoor VOCs, photocatalytic oxidation is an attractive alternative technique for indoor air purification and deodorization. The objective of this research is to investigate the VOC removal efficiency of the photocatalytic filter in a HVAC system. Toluene and formaldehyde were chosen as the target pollutants. The experiments were conducted in a stainless steel chamber equipped with a simplified HVAC system. A mechanical filter coated with Degussa P25 titania photocatalyst and two commercial photocatalytic filters were used as the photo-catalytic filters in this simplified HVAC system. The total air change rates were controlled at 0.5, 0.75, 1, 1.25, and 1.5 hr^?1, and the relative humidity (RH) was controlled at 30%, 50%, and 70%. The ultraviolet lamp used was a 4-W, ultraviolet-C (central wavelength at 254 nm) strip light bulb. The first-order decay constant of toluene and form-aldehyde found in this study ranged from 0.381 to 1.01 hr^?1 under different total air change rates, from 0.34 to 0.433 hr^?1 under different RH, and from 0.381 to 0.433 hr^?1 for different photocatalytic filters.     

Study on the indoor volatile organic compound treatment and performance assessment with TiO2/MCM-41 and TiO2/quartz photoreactor under ultraviolet irradiation

Volatile organic compounds (VOCs) are the cause of indoor air pollution and are readily emitted from furniture and cleaning agents. In Taiwan, the concentrations of indoor VOCs range roughly from 1 to 10 ppm. It is important to effectively reduce indoor VOC emissions and establish the implementation of long-term, low-cost, controlled techniques such as those found in the ultraviolet/titanium dioxide (UV/TiO2) control systems. This study evaluates the performance of a photoreactor activated by visible irradiation and packed with TiO2/quartz or TiO2/mobile catalytic material number 41 (MCM-41). The photocatalysts tested include commercial TiO2 (Degussa P-25) and synthesized TiO2 with a modified sol-gel process. The UV light had a wavelength of 365 nm and contained an 8-W, low-pressure mercury lamp. Reactants and products were analyzed quantitatively by using gas chromatography with a flame-ionization detector. It is important to understand the influence of such operational parameters, such as concentration of pollutant, temperature, and retention time of processing. The indoor concentrations of VOCs varied from 2 to 10 ppm. Additionally, the temperatures ranged from 15 to 35 degrees C and the retention time tested from 2 to 8.2 sec. The results show that quartz with TiO2 had a better photoreductive efficiency than quartz with MCM-41. The toluene degradation efficiency of 77.4% with UV/TiO2/quartz was larger than that of 54.4% with the UV/TiO2/MCM-41 system under 10-min reaction time. The degradation efficiency of the UV/TiO2 system decreased with the increasing concentrations of indoor VOCs. The toluene degradation efficiency at 2 ppm was approximately 5 times greater than that at 10 ppm. The photoreduction rate of the VOCs was also evaluated with the Langmuir-Hinshewood model and was shown to be pseudo-first-order kinetics.     

不锈钢负载TiO2薄膜光降解印染废水

以TiO2为催化剂,将其制膜固定在不锈钢质光反应器内壁上,以125W高压汞灯为光源,对武汉市某丝绸厂的印染废水进行了处理实验.取得了脱色率100%,CODCr去除率83.4%的效果,并探讨了多种因素对光降解的影响.     

低温等离子体法去除苯和甲苯废气性能研究

对低温等离子体法去除苯和甲苯废气的性能进行了探讨,在理论分析的基础上进行实验研究。低温等离子体法去除苯和甲苯的机理是放电反应产生的高能电子与苯和甲苯分子发生非弹性碰撞并将能量全部或部分传递给目标分子,使其裂解、激化。被裂解、激化的分子与臭氧、活性基团发生一系列物理、化学反应后生成二氧化碳、一氧化碳和水。实验结果表明,苯和甲苯的去除率随着电场强度的增强而增大,随着气体流速的增大而减小。在较高电场强度下,有钛酸钡填料的反应器比无填料的反应器对苯和甲苯的去除率高得多,苯最高去除率可达92 6%,甲苯可达到96 8%。相同条件下甲苯比苯更容易去除。