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.     

Macro kinetic studies for photocatalytic degradation of benzoic acid in immobilized systems

Semiconductor photocatalytic process has been studied extensively in recent years due to its intriguing advantages in environmental remediation. In this study, a two-phase swirl-flow monolithic-type reactor is used to study the kinetics of photocatalytic degradation of benzoic acid in immobilized systems. Transport contributions into the observed degradation rates were determined when catalyst is immobilized. Intrinsic kinetic rate constants and its dependence on light intensity and catalyst layer thickness, values of adsorption equilibrium constant, internal as well as external mass transfer parameters were determined. The simultaneous effect of catalyst loading and light intensity and optimum catalyst layer thickness were also determined experimentally. Reaction rate constants and overall observed degradation rates were compared with slurry systems.     

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%。     

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。     

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%。     

添加壳聚糖溶胶-凝胶法制备的TiO2光催化剂及其光催化性能研究

采用添加壳聚糖（CTS）的溶胶-凝胶法制备了具有较高光催化活性的TiO2光催化剂,并用XRD、TEM、BET和IR等手段对其进行表征。结果表明,CTS的添加使TiO2衍射强度增强、分散性提高、比表面积增大从而使光催化活性提高;用所制备的催化剂光催化降解甲基橙反应60min后,其去除率由不添加CTS所制备TiO2的32％提高到48％,TOC去除率由14％提高到23％。     

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.     

添加壳聚糖溶胶-凝胶法制备的TiO_2光催化剂及其光催化性能研究

采用添加壳聚糖(CTS)的溶胶-凝胶法制备了具有较高光催化活性的TiO_2光催化剂,并用XRD、TEM、BET和IR等手段对其进行表征。结果表明,CTS的添加使TiO_2衍射强度增强、分散性提高、比表面积增大从而使光催化活性提高;用所制备的催化剂光催化降解甲基橙反应60 min后,其去除率由不添加CTS所制备TiO_2的32%提高到48%,TOC去除率由14%提高到23%。     

光催化降解模拟室内挥发性有机污染物研究

用浸渍-提拉法制备玻璃弹簧负载型TiO2薄膜催化剂,在自制的反应器中进行光催化降解由丙酮、甲苯、对二甲苯组成的模拟室内挥发性有机污染物VOCs研究.研究发现:催化剂中掺杂金属离子能影响催化剂的降解效果,降解效果依次为掺铈TiO2＞纯TiO2＞掺银TiO2;气体流量显著影响降解效果,丙酮、甲苯和对二甲苯的最佳降解流量分别为3、5、7 L/min;混合气体中非对称性的极性分子的降解效率高于对称性分子,导致丙酮、对二甲苯组分降解率降低,甲苯降解率增高.     

太阳能固定膜光催化去除双酚A的特性与效果

以太阳能固定膜光催化中试装置,研究了光解、初始浓度和平均光强等对双酚A(BPA)光催化去除的影响及BPA的矿化和在自来水中的处理效果.试验结果表明,BPA在日光照射下很难光解,其光催化降解呈表观一级反应,在平均光强介于5.7～23.5 W/m2时,表观反应速率常数和平均光强呈线性关系.太阳能光催化对BPA具有良好的矿化作用,但其降解与以UV254为光源的降解有不同的机理.太阳能光催化对自来水中BPA也具有较好的处理效果.     

氮掺杂TiO_2可见光光催化剂的制备及性能

以尿素和钛酸丁酯为原料,通过溶胶-凝胶法低温下制备了高可见光催化活性的氮掺杂TiO2（NDT）光催化剂,采用XRD、TEM、BET和UV-Vis DRS等测试手段对其进行了表征,并在自制光催化反应器中降解甲基橙评价了样品的光催化活性。结果表明,当氮与钛的摩尔比为0.5∶1时,350℃焙烧的样品（NDT350）具有最佳的可见光光谱吸收和光催化活性,该催化剂为锐钛矿晶相,平均粒径为21 nm,比表面积为89.13 m2/g。可见光辐照下,NDT350降解甲基橙的表观反应速率常数为1.381×10-2min-1,是商业P25催化剂的16.85倍。NDT350优良的可见光催化活性与其大的比表面积和强烈的可见光光谱吸收有关。     

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%.     

纳米RuO2－TiO2光电催化处理农药废水研究

采用自制的负载型纳米RuO₂－TiO₂光催化剂对农药厂生产废水进行光电催化降解试验。考察了煅烧时间、催化剂用量、光辐照强度、电流密度、废水初始pH值和反应时间对废水COD和色度去除率的影响。结果表明，自制光催化剂光电催化性能显著，最佳光电催化活性是同样降解条件下、同样含量的Degussa P－25 TiO₂的1.38倍，是Ru_0.3Ti_0.7O₂的1.81倍。其COD和色度去除率分别为64.3%和95.2%。     

Decomposition of low-concentration gas-phase toluene using plasma-driven photocatalyst reactor

Plasma-driven photocatalysis system was prepared and performed. To overcome the treatment difficulty of volatile organic compounds, non-thermal plasma was used as a light source of photocatalysis. The removal of low-concentration toluene was investigated and secondary products were analyzed by gas chromatograph–mass spectroscopy. The plasma-driven photocatalyst reactor using direct current as a light source and titanium dioxide catalyst loaded on activated carbon fiber (TiO₂/ACF) as photocatalyst was studied. It was found that plasma-driven photocatalysis system could significantly increase the removal effect of toluene. The number of secondary products was largely decreased. It means that plasma-driven photocatalysis hybrid system was an effective method for the removal of volatile organic compounds.     

Carbofuran removal in continuous-photocatalytic reactor: Reactor optimization,rate-constant determination and carbofuran degradation pathway analysis

Carbofuran (CBF) removal in a continuous-flow photocatalytic reactor with granular activated carbon supported titanium dioxide (GAC-TiO₂) catalyst was investigated. The effects of feed flow rate, TiO₂ concentration and addition of supplementary oxidants on CBF removal were investigated. The central composite design (CCD) was used to design the experiments and to estimate the effects of feed flow rate and TiO₂ concentration on CBF removal. The outcome of CCD experiments demonstrated that reactor performance was influenced mainly by feed flow rate compared to TiO₂ concentration. A second-order polynomial model developed based on CCD experiments fitted the experimental data with good correlation (R² ～ 0.964). The addition of 1 mL min^?1 hydrogen peroxide has shown complete CBF degradation and 76% chemical oxygen demand removal under the following operating conditions of CBF ～50 mg L^?1, TiO₂ ～5 mg L^?1 and feed flow rate ～82.5 mL min^?1. Rate constant of the photodegradation process was also calculated by applying the kinetic data in pseudo-first-order kinetics. Four major degradation intermediates of CBF were identified using GC-MS analysis. As a whole, the reactor system and GAC-TiO₂ catalyst used could be constructive in cost-effective CBF removal with no impact to receiving environment through getaway of photocatalyst.     

Feasibility of ultraviolet-light-emitting diodes as an alternative light source for photocatalysis

The objective of this study was to determine whether ultraviolet-light-emitting diodes (UV-LEDs) could serve as an efficient photon source for heterogeneous photocatalytic oxidation (PCO). An LED module consisting of 12 high-power UV-A (lambda max = 365 nm) LEDs was designed to be interchangeable with a UV-A fluorescent black light blue (BLB) lamp for a bench scale annular reactor packed with silica-titania composite (STC) pellets. Lighting and thermal properties of the module were characterized to assess its uniformity and total irradiance. A forward current (I(F)) of 100 mA delivered an average irradiance of 4.0 mW cm(-2) at a distance of 8 mm, which is equivalent to the maximum output of the BLB, but the irradiance of the LED module was less uniform than that of the BLB. The LED and BLB reactors were tested for the oxidization of ethanol (50 ppm(v)) in a continuous-flow-through mode with 0.94 sec residence time. At the same average irradiance, the UV-A LED reactor resulted in a lower CO2 production rate (19.8 vs. 28.6 nmol L(-1) s(-1)), lower ethanol removal (80% vs. 91%), and lower mineralization efficiency (28% vs. 44%) than the UV-A BLB reactor. Ethanol mineralization was enhanced with the increase of the irradiance at the catalyst surface. This result suggests that reduced ethanol mineralization in the LED reactor relative to the BLB reactor at the same average irradiance could be attributed to the nonuniform irradiance over the photocatalyst, that is, a portion of the catalyst was exposed to less than the average irradiance. The potential of UV-A LEDs may be fully realized by optimizing the light distribution over the catalyst and utilizing their instantaneous "on" and "off" feature for periodic irradiation. Nevertheless, our results also showed that the current UV-A LED module had the same wall plug efficiency (WPE) of 13% as that of the UV-A BLB, demonstrating that UV-A LEDs are a viable photon source both in terms of WPE and PCO efficiency.     

膜生物反应器处理甲苯废气的降解特性及传质过程强化

设计了一种气相空间带方形扰流柱结构的平板膜生物反应器,进行了甲苯降解废气净化实验,并与未加入方形扰流柱结构的反应器进行了对比。实验研究了甲苯入口浓度和气体流量对甲苯降解效率和传质速率的影响,结果表明,随着甲苯入口浓度和气体流量的增加,膜生物反应器降解效率降低,甲苯的传质速率增大,气相空间加入方形扰流柱后,甲苯在反应器中的传输得到了强化,降解效率最大提高了8%。     

黄铁矿催化H2O2氧化降解水中三氯生

以三氯生为目标污染物,研究了黄铁矿催化H2O2非均相类Fenton体系对污染物的去除效果,并利用SEM、EDS等手段对天然黄铁矿进行了表征。考察了催化剂、H2O2投加量、溶液初始pH、反应时间等重要因素对催化氧化反应的影响。在H2O2投加量5 mg/L,黄铁矿用量0.1 g/L,溶液初始pH为8,反应10 min后,三氯生的去除率达90%以上。相对于传统Fenton反应,pH对本非均相催化反应的影响较小,在2～10的pH范围内,仍有较高的催化活性。利用GC-MS分析显示,三氯生降解过程能够产生包括2,4-二氯苯酚在内的多种中间产物。     

Optimizing nutrient supply in a rotatory-switching biofilter for toluene vapor treatment

The influence of nutrient conditions on the degradation of toluene vapor in a rotatory-switching biofilter (RSB) was investigated. The biofilter consists of four segments connected in series, each with a packing layer made of polyvinyl formal. The influent airstreams including toluene vapors were passed through segments 1-3 as up-flow with a toluene concentration of 0.9-1.2 g m(-3) and with an empty-bed retention time of 26-52 sec. Nutrient solutions were fed to all packed segments once a day by means of immersion. The nutrient solution was used repeatedly and replenished by the addition of (NH4)2SO4. The result at 155 days showed nitrogen depletion was particularly obvious and the lack of nitrogen affected toluene removal. By adding 161 g of nitrogen solution per volumetric cubic meter of reactor, toluene removal efficiency was immediately increased to greater than 99%. With long-term biofilter operation, 21%-32% of ammonium was utilized for nitrification because of the growth of nitrifying bacteria such as Nitrosomonas sp. Based on the carbon-nitrogen balance, the daily nitrogen demand for toluene removal was estimated 2.1 g day(-1) at a toluene load of 70 g m(-3) hr(-1).     

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。