Design Approaches for a Cycling Adsorbent/Photocatalyst System for Indoor Air Purification: Formaldehyde Example

Abstract

A kinetic model for a cycling adsorbent/photocatalyst combination for formaldehyde removal in indoor air (Chin et al. J. Catalysis 2006, 237, 29-37) was previously developed in our lab, demonstrating agreement with lab-scale batch operation data of other researchers (Shiraishi et al. Chem. Engineer. Sci. 2003, 58, 929-934). Model parameters evaluated included adsorption equilibrium and rate constants for the adsorbent (activated carbon) honeycomb rotor, and catalytic rate constant for pseudo-first-order formaldehyde destruction in the titanium dioxide photoreactor. This paper explores design consequences for this novel system. In particular, the batch parameter values are used to model both adsorbent and photocatalyst behavior for continuous operation in typical residential home challenges. Design variables, including realistic make-up air fraction, adsorbent honeycomb rotation speed, and formaldehyde source emission rate, are considered to evaluate the ability of the system to achieve World Health Organization pollutant guidelines. In all circumstances, the size of the required rotating adsorbent bed and photoreactor for single-stage operation and the resultant formaldehyde concentration in the home are calculated. The ability of how well such a system might be accommodated within the typical dimensions of commercial ventilation ducts is also considered.     

Formaldehyde Release from Simulated Wall Panels Insulated with Urea-Formaldehyde Foam Insulation

An important potential source of formaldehyde in the home is ureaformaldehyde foam insulation (UFFI). This study measures the long-term release of formaldehyde through the interior wall of test panels foamed with commercial urea-formaldehyde insulation. The measurements, made approximately 16 mo after initial foaming, were conducted under both static and dynamic air conditions with air flow selected to simulate a typical air exchange found in houses. Estimated room concentrations based on a simple model of uniform mixing within a room and measured emission rates are presented. Measurements of formaldehyde in the air from within the UFFI cavities are also reported.     

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.     

Photocatalytic degradation of dyes in aqueous solution operating in a fluidised bed reactor.

This work reports a preliminary design of a new photochemical reactor and its application to photochemical degradation of two dyes, Crystal Violet and Azure B, operating in both batch and continuous processes. A novel kind of photocatalyst, consisting of ZnO immobilised in alginate gel beads, which is able to photodegrade organic dyes effectively, has been employed in the present study. When this photocatalyst, at a concentration of 1 g of ZnO per litre of alginate gel at 3%, was employed in batch process, almost total decolourisation of Crystal Violet in reaction times lower than 120 min was observed. Operating in continuous process at different residence times, it was possible to achieve a total decolourisation of both Crystal Violet and Azure B. Moreover, the total organic carbon content (TOC) was reduced to 90% in the former and to 52% in the latter. These results indicated that the photoreactor developed in the present work was able to degrade effectively dyes of different structures, revealing the non-specificity of the system.     

纳米TiO2/活性炭复合光催化剂的制备及其对甲醛气体降解

研究了纳米TiO2/活性炭复合光催化剂对空气中典型污染气体甲醛的光催化降解特性。采用扫描电镜（SEM）表征复合催化剂的表面特征。结果显示,经改性后的纳米TiO2在复合催化剂表面分布均匀,呈球状。对甲醛气体的降解实验显示TiO2负载量为1%时对甲醛的去除效果最好,6 h去除率为61.7%。结果显示复合催化剂把甲醛气体分解成CO2,可以直接排空,无二次污染。     

大尺寸大孔径TiO_2/SiO_2光催化剂的制备及甲醛去除研究

以大孔径SiO2为载体,通过钛酸丁酯溶液的浸渍、原位水解以及高温煅烧制备出大尺寸、大孔径的TiO2/SiO2光催化剂。利用自制空气净化装置对室内甲醛的清除进行研究,分别考察了TiO2的百分含量、紫外光光强、温度、湿度和空气流量等不同条件下TiO2/SiO2光催化剂对除去甲醛效率的影响。结果表明,反应温度从10～50℃依次升高,去除率逐渐下降。在相对湿度为50%,TiO2负载率为55.6%,流量为8 m3/h时,甲醛的最佳除去率达96.5%;经过7周时间的考察,发现TiO2/SiO2光催化剂的催化活性没有明显的下降。     

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.     

纳米TiO2/活性炭复合光催化剂的制备及其对甲醛气体降解

研究了纳米TiO2/活性炭复合光催化剂对空气中典型污染气体甲醛的光催化降解特性。采用扫描电镜(SEM)表征复合催化剂的表面特征。结果显示,经改性后的纳米TiO2在复合催化剂表面分布均匀,呈球状。对甲醛气体的降解实验显示TiO2负载量为1%时对甲醛的去除效果最好,6 h去除率为61.7%。结果显示复合催化剂把甲醛气体分解成CO2,可以直接排空,无二次污染。     

SAGA: a decision support system for air pollution management around a coal-fired power plant

Air quality models are currently feasible approaches to prevent air pollution episodes. From one of the first source-oriented modelling approaches for air pollution forecasting (Souto et al., 1994, 1996, 1998), a new decision support system for air quality management, SAGA, was developed to provide support to As Pontes Power Plant (APPP) staff. SAGA can provide air pollution forecasts and manage meteorological and air quality measurements. Power plant decisions are supported by the results of a non-hydrostatic meteorological model (ARPS, Xue et al., 2001) to produce Meteorological Forecasts (MFs), and to be coupled to different Lagrangian dispersion models.     

Kinetics of inorganic carbon utilization by microalgal biofilm in a flat plate photoreactor

A kinetic model was developed to describe inorganic carbon utilization by microalgae biofilm in a flat plate photoreactor. The model incorporates the fundamental mechanisms of diffusive mass transport and biological reaction of inorganic carbon by microalgal biofilm. An advanced numerical technique, the orthogonal collocation method and Gear's method, was employed to solve this kinetic model. The model solutions included the concentration profiles of inorganic carbon in the microalgal biofilm, the growths of suspended microalgae and microalgal biofilm, the effluent concentrations of inorganic carbon, and the flux of inorganic carbon from bulk liquid into biofilm. The batch kinetic test was independently conducted to determine biokinetic parameters used in the microalgal biofilm model simulation while initial thickness of microalgal biofilm were assumed. A laboratory-scale flat plate photoreactor with a high recycle flow rate was setup and conducted to verify the model. The volume of photoreactor is 60 l which yields a hydraulic retention time of 1.67 days. The model-generated inorganic carbon and the suspended microalgae concentration curves agreed well with those obtained in the laboratory-scale test. The fixation efficiencies of HCO(3)(-) and CO(2) are 98.5% and 90% at a steady-state condition, respectively. The concentration of suspended microalgal cell reached up to 12 mg/l at a maximum growth rate while the thickness of microalgal biofilm was estimated to be 104 microm at a steady-state condition. The approaches of experiments and model simulation presented in this study could be employed for the design of a flat plate photoreactor to treat CO(2) by microalgal biofilm in a fossil-fuel power plant.     

TiO2光催化涂料的制备及其降解甲醛研究

自制TiO2光催化涂料，重点对所制备的涂料在室内进行降解甲醛研究，考察了在不同分散剂、不同光催化剂以及不同甲醛初始浓度、不同光源、不同温度和不同湿度等环境因素下涂料对甲醛降解率的影响。结果表明，选用聚丙烯酸钠离子型分散剂，铜金属掺杂TiO2光催化剂制备的光催化涂料对甲醛降解率达80％以上且具有良好的耐久性，在室温（20℃左右）湿度50％日光灯照射下，甲醛初始浓度5μL时效果最佳。     

TiO_2光催化涂料的制备及其降解甲醛研究

自制TiO_2光催化涂料,重点对所制备的涂料在室内进行降解甲醛研究,考察了在不同分散剂、不同光催化剂以及不同甲醛初始浓度、不同光源、不同温度和不同湿度等环境因素下涂料对甲醛降解率的影响。结果表明,选用聚丙烯酸钠离子型分散剂,铜金属掺杂TiO_2光催化剂制备的光催化涂料对甲醛降解率达80%以上且具有良好的耐久性,在室温(20℃左右)湿度50%日光灯照射下,甲醛初始浓度5μL时效果最佳。     

Deactivation of titanium dioxide photocatalyst by oxidation of polydimethylsiloxane and silicon sealant off-gas in a recirculating batch reactor

We have studied deactivation of titanium dioxide (TiO2) photocatalyst by oxidation of polydimethylsiloxane and silicone sealant off-gas in a recirculating batch reactor. Polydimethylsiloxane vapor is a model indoor air pollutant. It does not adsorb strongly on TiO2 in the dark, but undergoes oxidation when the ultraviolet (UV) photons are also present. Commercial silicone (room-temperature vulcanizing) sealant off-gas is an actual indoor air pollutant subject to short-term spikes in concentration. It does adsorb on the TiO2 surface in the dark, but UV photons also catalyze its oxidation. The oxidation of the Si-containing vapors was monitored using a Fourier transform infrared spectroscope equipped with a gas cell. Subsequent to each incremental exposure, a hexane oxidation reaction was performed to track the titania catalyst's activity. The exposures were repeated until substantial deactivation was achieved. We have also documented the regenerative effect of washing the catalyst surface with water. Surface science techniques were used to view the topography of the catalyst and to identify the elements causing the deactivation. Procedural observations of interest in the context of our recirculating batch reactor include the following: the rate of oxidation of hexane was used to assess the activity of a photocatalyst sample; hexane is an appropriate choice of a probe molecule because it does not adsorb in the dark and it undergoes photocatalytic oxidation (PCO) completely, forming CO2; and hexane does not deactivate the photocatalyst surface.     

Thermal destruction of benzene

The thermal destruction of benzene in methane/air flue gas is studied experimentally using an atmospheric laminar flow reactor in laboratory scale. The reactor is operated at four different fuel equivalent ratios (phi = 0.06, 0.1,0.5, 3.7), and temperatures in the range from 850 to 973 K and realises a residence time of 5 s. Stable-species concentrations are measured by gas chromatography (GC) and high-pressure liquid chromatography (HPLC), where phenol, acetylene, formaldehyde, acrolein, methane and acetaldehyde are the major hydrocarbon products besides CO and CO2. The augmentation of the temperature from 850 to 973 K increases the benzene conversion rate from 55% to 99%. The experimental results for one fuel equivalent ratio (phi = 0.5) are compared to the benzene model proposed by Emdee et al. (J. Phys. Chem. 92 (1992) 2151-2161). A fair agreement is observed for the benzene consumption and the CO production throughout the temperature range considered here. The small hydrocarbons are not very well matched, which requires further research on the sub-models. Our experimental results on laboratory scale provide a database for the modelling of benzene oxidation in waste incinerators.     

Gas phase trichloroethylene (TCE) photooxidation and byproduct formation: photolysis vs. titania/silica based photocatalysis

Photooxidation of trichloroethylene (TCE) was examined in comparative study using photolysis and photocatalysis. Degussa P25 titania coated on reactor wall and deposited on silica based microporous support were used as photocatalyst. The destruction of TCE and formation of potential byproducts were investigated under steady state conditions using annular photoreactors. Experimental work involved passing polluted air containing TCE through the UV photoreactor at varying concentrations and residence times. Ultraviolet illumination was provided by low pressure mercury lamps with outputs at either 254 nm, 365 nm, or 185/254 nm. Silica supported photocatalyst yielded maximum removal capacity of up to about 6 kg TCE per m3 per hour, nearly twice that provided by the coated titania. Direct photolysis with ozone generating UV also provided very high TCE conversion of up to 6kg TCE per m3 per hour. However, major quantities of phosgene and dichloroacetyle chloride (DCAC) were produced as byproducts. TCE removal using silica based photocatalyst did not result in any detectable DCAC. Only phosgene along with trace amounts of chloroform and carbon tetrachloride were identified as oxidation byproducts with silica based photocatalyst.     

动态法测试空气净化器甲醛去除性能的研究

通过动态法测试水吸收型空气净化器A和活性炭过滤吸附型净化器B对甲醛的去除性能,探索更为合理的方法以评价空气净化器对气态污染物的去除性能.对净化器A去除甲醛的短期测试结果表明,净化器对甲醛浓度为0.3、0.5、0.8和1 mg/m3的连续空气流均有明显的净化效果,对甲醛的去除速率在0.91～2.78 mg/h之间.对净化...     

多壁碳纳米管结构对复合光催化剂催化效果的影响

采用溶胶凝胶法制备了多壁碳纳米管负载纳米TiO₂的复合光催化剂（TiO₂/MWCNTs），以偶氮类染料甲基橙为目标污染物，在自制的光催化反应器上进行了光催化降解反应实验。主要研究同一甲基橙初始浓度（C₀)下，多壁碳纳米管不同管长和管径对复合光催化剂催化效果的影响。结果表明：该降解反应可用一级反应动力学方程描述，反应速率常数k随着多壁碳纳米管管长和管径的增大而增大；与纯纳米TiO₂相比，复合光催化剂对甲基橙的降解率提高了6％～18％，反应速率常数为前者的1.19～2.11倍；采用复合光催化剂的甲基橙光降解溶液自行沉降分离效果较好，静止沉降60 min后达到沉降平衡，剩余浊度为8.5 NTU，下降了90.6％。     

Toxic Emissions from Mobile Sources: A Total Fuel-Cycle Analysis for Conventional and Alternative Fuel Vehicles

ABSTRACT

Mobile sources are among the largest contributors of four hazardous air pollutants—benzene, 1,3-butadiene, acetal-dehyde, and formaldehyde—in urban areas. At the same time, federal and state governments are promoting the use of alternative fuel vehicles as a means to curb local air pollution. As yet, the impact of this movement toward alternative fuels with respect to toxic emissions has not been well studied. The purpose of this paper is to compare toxic emissions from vehicles operating on a variety of fuels, including reformulated gasoline (RFG), natural gas, ethanol, methanol, liquid petroleum gas (LPG), and electricity. This study uses a version of Argonne National Laboratory's Greenhouse Gas, Regulated Emissions, and Energy Use in Transportation (GREET) model, appropriately modified to estimate toxic emissions. The GREET model conducts a total fuel-cycle analysis that calculates emissions from both downstream (e.g., operation of the vehicle) and upstream (e.g., fuel production and distribution) stages of the fuel cycle. We find that almost all of the fuels studied reduce 1,3-buta-diene emissions compared with conventional gasoline (CG). However, the use of ethanol in E85 (fuel made with 85% ethanol) or RFG leads to increased acetaldehyde emissions, and the use of methanol, ethanol, and compressed natural gas (CNG) may result in increased formaldehyde emissions. When the modeling results for the four air toxics are considered together with their cancer risk factors, all the fuels and vehicle technologies show air toxic emission reduction benefits.     

Photocatalytic degradation of volatile organic compounds at the gas-solid interface of a TiO2 photocatalyst

In the present work, photocatalytic degradation of volatile organic compounds including gas-phase trichloroethylene (TCE), acetone, methanol and toluene over illuminated TiO2 was closely examined in a batch photoreactor as a function of water vapor, molecular oxygen and reaction temperature. Water vapor enhanced the photocatalytic degradation rate of toluene, but was inhibitive for acetone, and, there was an optimum water vapor concentration in the TCE and methanol removal. In a nitrogen atmosphere, it showed lower photocatalytic degradation rate than in air and pure oxygen. Thus, it could be concluded that oxygen is an essential component in photocatalytic reactions by trapping photogenerated electrons on the semiconductor surface and by decreasing the recombination of electrons and holes. As for the influence of reaction temperature, it was found that photocatalytic degradation was more effective at a moderate temperature than at an elevated temperature for each compound.     

Adsorption kinetics of herbicide paraquat from aqueous solution onto activated bleaching earth

In the present study, the activated bleaching earth was used as adsorbent for the herbicide paraquat adsorption in a batch adsorber. The rate of adsorption has been investigated under the controlled process parameters like agitation speed, initial paraquat concentration, adsorbent dosage and temperature. A batch kinetic model, based on the assumption of a pseudo-second order mechanism, has been tested to predict the rate constant of adsorption, equilibrium adsorption capacity, time of half-adsorption, and equilibrium concentration by the fittings of the experimental data. The results of the kinetic studies show that the adsorption process can be well described with the pseudo-second order equation. Based on the isotherm data obtained from the fittings of the adsorption kinetics, Freundlich model appears to fit the adsorption better than Langmuir model. In addition, the effective diffusion coefficient has also been estimated based on the restrictive diffusion model.