Removal and Destruction of Organic Contaminants in Water Using Adsorption,Steam Regeneration,and Photocatalytic Oxidation: A Pilot-Scale Study

ABSTRACT

The overall objective of this pilot-scale study is to investigate the technical feasibility of the removal and destruction of organic contaminants in water using adsorption and photocatalytic oxidation. The process consists of two consecutive operational steps: (1) removal of organic contaminants using fixed-bed adsorption; and (2) regeneration of spent adsorbent using photocatalysis or steam, followed by decontamination of steam condensate using photocatalysis. The pilot-scale study was conducted to evaluate these options at a water treatment plant in Wausau (Wisconsin) for treatment of groundwater contaminated with tetrachloroethene (PCE), trichloroethene (TCE), cis-dichloroethene (cis-DCE), toluene, ethylbenzene (EB), and xylenes. The adsorbents used were F-400 GAC and Ambersorb 563.

In the first treatment strategy, the adsorbents were impregnated with photocatalyst and used for the removal of aqueous organics. The spent adsorbents were then exposed to ultraviolet light to achieve photocatalytic regeneration. Regeneration of adsorbents using photocatalysis was observed to be not effective, probably because the impregnated photocatalyst was fouled by background organic matter present in the groundwater matrix.

In the second treatment strategy, the spent adsorbents were regenerated using steam, followed by cleanup of steam condensate using photocatalysis. Four cycles of adsorption and three cycles of steam regeneration were performed. Ambersorb 563 adsorbent was successfully regenerated using saturated steam at 160 °C within 20 hours. The steam condensate was treated using fixed-bed photo-catalysis using 1% Pt-TiO₂ photocatalyst supported on silica gel. After 35 minutes of empty bed contact time, more than 95% removal of TCE, cis-DCE, toluene, EB, and xylenes was achieved, and more than 75% removal of PCE was observed.

In the case of activated carbon adsorbent, steam regeneration was not effective, and a significant loss in adsorbent capacity was observed.     

Method of removal of volatile organic compounds by using wet scrubber coupled with photo-Fenton reaction - Preventing emission of by-products

The photo-Fenton reaction was applied as a novel method for the removal of volatile organic compounds (VOCs) in the gas phase, and its effectiveness was experimentally examined. In conventional VOCs removal methods using a photocatalyst or ozone, VOCs are oxidized in the gas phase. Therefore, incompletely oxidized intermediates, which may have adverse effects on health, are likely to contaminate the treated air. On the other hand, in the VOCs removal method developed in this study, because the VOCs are oxidized in the liquid phase by the photo-Fenton reaction, any incompletely oxidized intermediates produced are confined to the liquid phase. As a result, the contamination of the treated air by these harmful intermediates can be prevented. Using a semi-batch process, it was found that the removal efficiency for toluene in a one-pass test (residence time of 17 s) was 61%, for an inlet toluene gas concentration of 930 ppbv, an initial iron ion concentration of 20 mg L⁻¹, and an initial hydrogen peroxide concentration of 630 mg L⁻¹. The removal efficiency was almost constant as long as H₂O₂ was present in the solution. Proton transfer reaction mass spectrometry analysis confirmed the absence of any incompletely oxidized intermediates in the treated air.     

Mathematical Model for Photocatalytic Destruction of Organic Contaminants in Air

Abstract

Photocatalytic oxidation (PCO) was investigated in a bench-scale reactor for the abatement of two airborne organic contaminants: toluene and ethanol. A mathematical model that includes the impacts of light intensity, initial contaminant concentration, catalyst thickness, and relative humidity (RH) on the degradation of organic contaminants in a photocatalytic reactor was developed to describe this process. The commercially available catalyst Degussa-PtTiO₂ was selected to compare with the MTU-PtTiO₂-350 catalyst, which was synthesized by the sol-gel process, platinized, and calcined at 350 °C. For toluene removal using the MTU-PtTiO₂-350 catalyst, the degradation rate increased with increases in light intensity from 0.2 to 2.2 mW/cm² and in catalyst thickness from 0.00037 to 0.00361 cm. However, further increases in light intensity and catalyst thickness had only slight effect on the toluene degradation rate. Increasing the initial concentration from 6.29 to 127.9 μg/L and the RH from 10 to 85% resulted in decreases in the toluene degradation rate. For ethanol removal using the MTU-PtTiO₂- 350 catalyst, the degradation rate increased more rapidly with an increase in RH from 17 to 56%; the RH had little effect on the ethanol degradation rate while it further increased from 56% to 82%. We discuss applicability of the model to estimate the influence of process variables and to evaluate photocatalyst performance.     

Solar photocatalysis for treatment of Acid Yellow-17 (AY-17) dye contaminated water using Ag@TiO2 core–shell structured nanoparticles

Wastewater released from textile industries causes water pollution, and it needs to be treated before discharge to the environment by cost effective technologies. Solar photocatalysis is a promising technology for the treatment of dye wastewater. The Ag@TiO₂ nanoparticles comprising of Ag core and TiO₂ shell (Ag@TiO₂) have unique photocatalytic property of inhibition of electron–hole recombination and visible light absorption, which makes it a promising photocatalyst for use in solar photocatalysis and with higher photocatalytic rate. Therefore, in the present work, the Ag@TiO₂ nanoparticles synthesized by one pot method with postcalcination step has been used for the degradation of Acid Yellow-17 (AY-17) dye under solar light irradiation. The Ag@TiO₂ nanoparticles were characterized using thermogravimetric–differential thermal analysis, X-ray diffraction, transmission electron microscopy, selected area electron diffraction, and energy dispersive X-ray analysis. The catalyst has been found to be very effective in solar photocatalysis of AY-17, as compared to other catalysts. The effects of pH, catalyst loading, initial dye concentration, and oxidants on photocatalysis were also studied. The optimized parameters for degradation of AY-17 using Ag@TiO₂ were found to be pH?3, dye/catalyst ratio of 1:10 (g/g), and 2 g/L of (NH₄)₂S₂O₈ as oxidant. Efficient decolorization and mineralization of AY-17 was achieved. The kinetics of color, total organic carbon, and chemical oxygen demand removal followed the Langmuir–Hinshelwood model. Ag@TiO₂ catalyst can be reused thrice without much decline in efficiency. The catalyst exhibited its potential as economic photocatalyst for treatment of dye wastewater.     

活性炭吸附和脱附-等离子体氧化净化有机废气的研究

根据滑动弧放电等离子体适于降解高浓度有机物废气的特性,结合活性炭吸附法,提出了吸附器的吸附浓缩和热脱附-等离子体氧化净化有机废气的方法。在活性炭吸附过程中,最初2 h内甲苯净化率达到100%,随着时间的增加净化率下降;在热脱附滑动弧放电等离子体净化过程中,甲苯降解效率最高为97.3%。将滑动弧放电等离子体反应器出口气相产物收集进行FT-IR检测,发现放电后有CO2、CO、H2O和NO2产生,并分析了甲苯的降解机理。     

生物过滤塔处理实验室废气

研究了生物过滤塔处理实验室排放的模拟混合废气,考察了反应器对苯、甲苯、二甲苯、乙醇、丙酮、乙酸乙酯和甲烷等废气的去除效果。运行结果表明,在设备稳定运行期间,进气中总挥发性有机物(TVOCs)的浓度为124～380 mg/m3,而出气浓度在10～40 mg/m3,去除效率保持在85%以上。实验室废气中的多种污染物在生物过滤塔中去除机理不同,亲水性污染物的去除效率高于疏水性污染物。通过系统关停后重启,污染物的去除效果在第2天就能恢复,这为生物过滤塔处理实验室废气过程的停运检修或者系统闲置提供了可行性。     

Assessment of volatile organic compound removal by indoor plants—a novel experimental setup

Indoor plants can remove volatile organic compounds (VOCs) from the air. The majority of knowledge comes from laboratory studies where results cannot directly be transferred to real-life settings. The aim of this study was to develop an experimental test system to assess VOC removal by indoor plants which allows for an improved real-life simulation. Parameters such as relative humidity, air exchange rate and VOC concentration are controlled and can be varied to simulate different real-life settings. For example, toluene diffusion through a needle gave concentrations in the range of 0.10–2.35 μg/L with deviations from theoretical values of 3.2–10.5 %. Overall, the system proved to be functional for the assessment of VOC removal by indoor plants with Hedera helix reaching a toluene removal rate of up to 66.5 μg/m²/h. The mode of toluene exposure (semi-dynamic or dynamic) had a significant influence on the removal rate obtained by H. helix.     

Significance of analytical parameters for the understanding of natural organic matter in relation to photocatalytic oxidation

In this review, special interest was devoted to provide information on the surrogate parameters expressing both quality and quantity of organic matter for the understanding of the photocatalytic oxidation of humic substances. Detailed investigation was directed to the application of photocatalysis with reference to source, origin and modeling of organic matter. Evaluation of the literature findings emphasizes that organic matter taken from natural waters are site specific and should be characterized in detail to be comparable to other studies. Taking into account the photocatalytic degradation studies of natural organic matter, humic substances, humic acids and fulvic acids in slurry systems, a procedure could be deduced that depends on the selection of a standard model sample with a representative concentration, selection of a standard photocatalyst and dose (e.g., TiO₂ Degussa P-25, 0.25 mg mL⁻¹), application of standardized reaction conditions such as light intensity, pH, and temperature. Furthermore, standardized filtration step avoiding organic leaching and selection of the most suitable analytical parameter are the crucial points to be considered. The use of such a protocol could form a basis for the determination of “relative degradation efficiency” of any sample containing natural organic matter, humic substances, humic acids and fulvic acids regardless of dependency on source and origin.     

TiO2光催化-微滤膜分离深度净化亚甲基蓝印染废水

采用悬浮式TiO2光催化膜反应器深度净化纺织工业园区含亚甲基蓝印染废水经生物处理二级出水,利用中空纤维微滤膜进行催化剂截留分离,研究催化剂投加量、运行时间、溶解氧、搅拌方式对出水水质及膜通量的影响。结果表明:光催化会消耗体系溶解氧,鼓风曝气搅拌可同时为系统供氧,优于机械搅拌;该耦合体系的催化剂最佳投加量为1 g/L,经光催化氧化-膜组合工艺处理后水质优于GB 4287-1992《纺织染整工业污染物排放标准》的I级标准,符合建设部颁布的《生活杂用水水质标准》(CJ/T 48-1999)。     

Application of photocatalysis as a post treatment method of a heterotrophic-autotrophic denitrification reactor effluent

The aim of this study is the application of photocatalysis as an effective post treatment scheme for the removal of the organic matter and bacteria released by an innovative biological denitrification process referred to as heterotrophic-autotrophic denitrification, which combines heterotrophic and autotrophic denitrification processes. Photocatalytic treatment was applied using TiO2 as a photocatalyst in the loading range of 0.25-2.00 g l(-1) for irradiation periods up to 60 min using a black light fluorescent lamp with an intensity of I(0)=1309 microW cm(-2). The photocatalytic inactivation data were modelled to pseudo first order kinetics as well as by the areal rates to evaluate the photocatalyst loading effect. Chlorination was used as a final disinfection step to attain an overall inactivation of total coliforms as well as to the formation of very low level of trihalomethanes.     

Effect of Substrate Henry’s Constant on Biofilter Performance

Abstract

Butanol, ether, toluene, and hexane, which have Henry's constants ranging from 0.0005 to 53, were used to investigate the effects of substrate solubility or availability on the removal of volatile organic compounds (VOCs) in trickle-bed biofilters. Results from this study suggest that, although removal of a VOC generally increases with a decrease in its Henry's constant, an optimal Henry's constant range for biofiltration may exist. For the treatment of VOCs with high Henry's constant values, such as hexane and toluene, the transfer of VOCs between the vapor and liquid phases or between the vapor phase and the biofilm is a rate-determining step. However, oxygen (O₂) transfer may become a rate-limiting step in treating VOCs with low Henry's constants, such as butanol, especially at high organic loadings. The results demonstrated that in a gas-phase aerobic biofilter, nitrate can serve both as a growth-controlling nutrient and as an electron acceptor in a biofilm for the respiration of VOCs with low Henry's constants. Microbial communities within the biofilters were examined using denaturing gradient gel electrophoresis to provide a more complete picture of the effect of O₂ limitation and denitrification on biofilter performance.     

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.     

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.     

Mathematical model for photocatalytic destruction of organic contaminants in air

Photocatalytic oxidation (PCO) was investigated in a bench-scale reactor for the abatement of two airborne organic contaminants: toluene and ethanol. A mathematical model that includes the impacts of light intensity, initial contaminant concentration, catalyst thickness, and relative humidity (RH) on the degradation of organic contaminants in a photocatalytic reactor was developed to describe this process. The commercially available catalyst Degussa-PtTiO2 was selected to compare with the MTU-PtTiO2-350 catalyst, which was synthesized by the sol-gel process, platinized, and calcined at 350 degrees C. For toluene removal using the MTU-PtTiO2-350 catalyst, the degradation rate increased with increases in light intensity from 0.2 to 2.2 mW/cm2 and in catalyst thickness from 0.00037 to 0.00361 cm. However, further increases in light intensity and catalyst thickness had only slight effect on the toluene degradation rate. Increasing the initial concentration from 6.29 to 127.9 microg/L and the RH from 10 to 85% resulted in decreases in the toluene degradation rate. For ethanol removal using the MTU-PtTiO2-350 catalyst, the degradation rate increased more rapidly with an increase in RH from 17 to 56%; the RH had little effect on the ethanol degradation rate while it further increased from 56% to 82%. We discuss applicability of the model to estimate the influence of process variables and to evaluate photocatalyst performance.     

CdS-TiO_2/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%。     

A new condensed toluene mechanism for Carbon Bond: CB05-TU

Toluene is ubiquitous in urban atmospheres and is a precursor to tropospheric ozone and aerosol (smog). An important characteristic of toluene chemistry is the tendency of some degradation products (e.g., cresols and methyl-catechols) to form organic nitro and nitrate compounds that sequester NOx (NO and NO₂) from active participation in smog formation. Explaining the NOx sinks in toluene degradation has made mechanism development more difficult for toluene than for many other organic compounds. Another challenge for toluene is explaining sources of radicals early in the degradation process. This paper describes the development of a new condensed toluene mechanism consisting of 26 reactions, and evaluates the performance of CB05 with this new toluene scheme (Toluene Update, TU) against 38 chamber experiments at 7 different environmental chambers, and provides recommendations for future developments. CB05 with the current toluene mechanism (CB05-Base) under-predicted the maximum O₃ and O₃ production rate for many of these toluene–NOx chamber experiments, especially under low-NOx conditions ([NOx]_t=0 < 100 ppb). CB05 with the new toluene mechanism (CB05-TU) includes changes to the yields and reactions of cresols and ring-opening products, and showed better performance than CB05-Base in predicting the maximum O₃, O₃ formation rate, NOx removal rate and cresol concentration. Additional environmental chamber simulations with xylene–NOx experiments showed that the TU mechanism updates tended to improve mechanism performance for xylene.     

Study on particulates and volatile organic compounds removal with TiO2 nonwoven filter prepared by electrospinning

In this study, polyvinyl alcohol (PVA) and titania (TiO₂) Degussa P-25 were mixed to generate TiO₂ nonwoven filters using electrospinning. The wires of titanium dioxide and the nonwoven binding titania nanofibers were formed using 14 kV voltage and a distance of 15 cm. A single-factor experimental method was used to investigate the effects of parameters such as initial concentration, retention time, and light source on acetone removal by nonwoven binding titania nanofibers. Furthermore, the effects of parameters such as gas pressure, particle size, initial concentration, and retention time on the removal of particulates were also assessed. The results showed that the degradation efficiency increased with decreasing initial concentrations and increasing retention time. The best operational conditions during this study for the removal of acetone using the TiO₂ nonwoven filters were a retention time of 100 sec, initial acetone concentration of 250 ppm, and ultraviolet (UV) light source of 254 nm. Under those conditions, 99% acetone removal efficiency was obtained. In addition, 90% particulate matter removal efficiency was reached when the particulate size was greater than 200 nm and the reaction time was longer than 5 minutes. The prepared TiO₂/nanofiber has good performance for volatile organic compounds (VOCs) and particulate removal at the same time.

Implications: In this study, polyvinyl alcohol (PVA) and titania (TiO₂) Degussa P-25 were mixed to generate TiO₂ nonwoven filters using electrospinning. The results showed that the optimum operating conditions for the removal of acetone using the TiO₂ nonwoven filters were a retention time of 100 sec, initial acetone concentration of 250 ppm, and UV light source of 254 nm. Under those conditions, 99% acetone removal efficiency was obtained.     

Decomposition of NO in automobile exhaust by plasma–photocatalysis synergy

The combination of plasma discharge and TiO₂ photocatalysis exhibits high performances in the removal of nitrogen monoxide (NO). This article is aimed at elucidating the relationships between NO decomposition efficiency and various experimental parameters, including voltages, humidity and temperature. The experimental results indicate that the efficiency of NO removal by synergic plasma-catalyst coupling is significantly higher than plasma only or photocatalyst only systems. Moreover, the NO removal efficiency improves with the increase of applied voltage. Meanwhile, a higher humidity results in a reduced number of electron–hole pairs at the surface of TiO₂ photocatalyst, leading to lower synergic purification efficiencies. Finally, the efficiency of NO removal is raised with the increase of temperature due to the fact that the adsorption of NO and water by nano-TiO₂ is affected by environmental temperature.     

Electrochemical wastewater treatment: influence of the type of carbon and of nitrogen on the organic load removal

Boron-doped diamond (BDD) and Ti/Pt/PbO₂ anodes were utilized to perform the electrodegradation of synthetic samples containing humic acid in the presence of different organic and inorganic carbon-containing and nitrogen-containing compounds. The influence of the chloride ion in the degradation process of the different synthetic samples was also assessed. The results showed that the anodic oxidation process can efficiently degrade recalcitrant compounds such as humic acid. The presence of carbonate in solution enhances the nitrogen removal, whereas it hinders the oxidation of the organic compounds. When organic nitrogen is present, it is converted to NH₄ ⁺, which in turn is oxidized to nitrate and to volatile nitrogen compounds. Hydroxyl radicals are more prone to oxidize the organic nitrogen than the ammonium nitrogen. The presence of chloride enhances the organic matter and nitrogen removal rates, BDD being the anode material that yields the highest removals.     

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.