An Improved Model for Analyzing the Performance of Photocatalytic Oxidation Reactors in Removing Volatile Organic Compounds and Its Application

Abstract

An improved photocatalytic oxidation (PCO) reactor model was developed to analyze the removal of volatile organic compounds (VOCs) in indoor air. One new parameter, the average total removing factor K _t, together with the other two parameters, the number of mass transfer units NTU_m and the fractional conversion e, are found to be the main parameters influencing the photooxidation performance of PCO reactors. Three new parameters, the ideal reaction number of mass transfer units, NTU_m,ir; the ideal reaction fractional conversion, ε_ir; and the reaction effectiveness, η, also are defined. These concepts are helpful to the structural design and optimization for PCO reactors. The application of the model in designing a plate-type PCO reactor is demonstrated. This study shows that the present model is an effective tool for designing PCO reactors and for evaluating VOC removal performance of available PCO reactors.     

Influence of mass transfer resistance on overall nitrate removal rate in upflow sludge bed reactors

A kinetic model with intrinsic reaction kinetics and a simplified model with apparent reaction kinetics for denitrification in upflow sludge bed (USB) reactors were proposed. USB-reactor performance data with and without sludge wasting were also obtained for model verification. An independent batch study showed that the apparent kinetic constants k' did not differ from the intrinsic k but the apparent Ks' was significantly larger than the intrinsic Ks suggesting that the intra-granule mass transfer resistance can be modeled by changes in Ks. Calculations of the overall effectiveness factor, Thiele modulus, and Biot number combined with parametric sensitivity analysis showed that the influence of internal mass transfer resistance on the overall nitrate removal rate in USB reactors is more significant than the external mass transfer resistance. The simulated residual nitrate concentrations using the simplified model were in good agreement with the experimental data; the simulated results using the simplified model were also close to those using the kinetic model. Accordingly, the simplified model adequately described the overall nitrate removal rate and can be used for process design.     

Photocatalytic purification of volatile organic compounds in indoor air: A literature review

Volatile organic compounds (VOCs) are prevalent components of indoor air pollution. Among the approaches to remove VOCs from indoor air, photocatalytic oxidation (PCO) is regarded as a promising method. This paper is a review of the status of research on PCO purification of VOCs in indoor air. The review and discussion concentrate on the preparation and coating of various photocatalytic catalysts; different kinetic experiments and models; novel methods for measuring kinetic parameters; reaction pathways; intermediates generated by PCO; and an overview of various PCO reactors and their models described in the literature. Some recommendations are made for future work to evaluate the performance of photocatalytic catalysts, to reduce the generation of harmful intermediates and to design new PCO reactors with integrated UV source and reaction surface.     

Development of a continuously stirred flow cell for investigating sorption mass transfer

This paper introduces a new reversible-flow design for a continuously stirred reactor used to study sorption mass transfer in soil and solvent systems. The stirred reactor has potential advantages over conventional packed column or batch reactors because it isolates intraparticle sorption rate limitations from advective-dispersive transport, yet allows changes to flux through the reactor for analysis of sorption kinetics under dynamic conditions. Previously, stirred reactors have often failed due to clogging of sediment on the effluent frit. The reverse-flow backwashing design allows longer life and higher confidence in maintaining mixed conditions than previous designs. Mass transfer 'rate coefficients estimated from stirred and column experiments are compared; both techniques produced results consistent with a published correlation. The data also show that fitted sorption mass transfer coefficients can be strongly dependent on the choice of equilibrium partition coefficient (i.e. batch or first-moment derived values), and that the conventional two-site sorption kinetics model fails to accurately predict sorption mass transfer in the presence of changing solvent velocity through the reactor.     

Heat transfer analysis of cylindrical anaerobic reactors with different sizes: a heat transfer model

The temperature is the essential factor that influences the efficiency of anaerobic reactors. During the operation of the anaerobic reactor, the fluctuations of ambient temperature can cause a change in the internal temperature of the reactor. Therefore, insulation and heating measures are often used to maintain anaerobic reactor’s internal temperature. In this paper, a simplified heat transfer model was developed to study heat transfer between cylindrical anaerobic reactors and their surroundings. Three cylindrical reactors of different sizes were studied, and the internal relations between ambient temperature, thickness of insulation, and temperature fluctuations of the reactors were obtained at different reactor sizes. The model was calibrated by a sensitivity analysis, and the calibrated model was well able to predict reactor temperature. The Nash-Sutcliffe model efficiency coefficient was used to assess the predictive power of heat transfer models. The Nash coefficients of the three reactors were 0.76, 0.60, and 0.45, respectively. The model can provide reference for the thermal insulation design of cylindrical anaerobic reactors.     

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.     

Development and performance of an alternative biofilter system

Step tracer tests were carried out on lab-scale biofilters to determine the residence time distributions (RTDs) of gases passing through two types of biofilters: a standard biofilter with vertical gas flow and a modified biofilter with horizontal gas flow. Results were used to define the flow patterns in the reactors. "Non-ideal flow" indicates that the flow reactors did not behave like either type of ideal reactor: the perfectly stirred reactor [often called a "continuously stirred tank reactor" (CSTR)] or the plug-flow reactor. The horizontal biofilter with back-mixing was able to accommodate a shorter residence time without the usual requirement of greater biofilter surface area for increased biofiltration efficiency. Experimental results indicated that the first bed of the modified biofilter behaved like two CSTRs in series, while the second bed may be represented by two or three CSTRs in series. Because of the flow baffles used in the horizontal biofilter system, its performance was more similar to completely mixed systems, and hence, it could not be modeled as a plug-flow reactor. For the standard biofilter, the number of CSTRs was found to be between 2 and 9 depending on the airflow rate. In terms of NH3 removal efficiency and elimination capacity, the standard biofilter was not as good as the modified system; moreover, the second bed of the modified biofilter exhibited greater removal efficiency than the first bed. The elimination rate increased as biofilter load increased. An opposite trend was exhibited with respect to removal efficiency.     

Method for predicting photocatalytic oxidation rates of organic compounds

In designing a photocatalytic oxidation (PCO) system for a given air pollution source, destruction rates for volatile organic compounds (VOCs) are required. The objective of this research was to develop a systematic method of predicting PCO rate constants by correlating rate constants with physical-chemical characteristics of compounds. Accordingly, reaction rate constants were determined for destruction of volatile organics over a titanium dioxide (TiO2) catalyst in a continuous mixed-batch reactor. It was found that PCO rate constants for alkanes and alkenes vary linearly with gas-phase ionization potential (IP) and with gas-phase hydroxyl radical reaction rate constant. The correlations allow rates of destruction of compounds not tested in this research to be predicted based on physical-chemical characteristics.     

Control of Organic Emissions from Surface Coating Operations

ABSTRACT

Step tracer tests were carried out on lab-scale biofilters to determine the residence time distributions (RTDs) of gases passing through two types of biofilters: a standard biofilter with vertical gas flow and a modified biofilter with horizontal gas flow. Results were used to define the flow patterns in the reactors. “Non-ideal flow” indicates that the flow reactors did not behave like either type of ideal reactor: the perfectly stirred reactor [often called a "continuously stirred tank reactor" (CSTR)] or the plug-flow reactor.

The horizontal biofilter with back-mixing was able to accommodate a shorter residence time without the usual requirement of greater biofilter surface area for increased biofiltration efficiency. Experimental results indicated that the first bed of the modified biofilter behaved like two CSTRs in series, while the second bed may be represented by two or three CSTRs in series. Because of the flow baffles used in the horizontal biofilter system, its performance was more similar to completely mixed systems, and hence, it could not be modeled as a plug-flow reactor. For the standard biofilter, the number of CSTRs was found to be between 2 and 9 depending on the airflow rate. In terms of NH₃ removal efficiency and elimination capacity, the standard biofilter was not as good as the modified system; moreover, the second bed of the modified biofilter exhibited greater removal efficiency than the first bed. The elimination rate increased as biofilter load increased. An opposite trend was exhibited with respect to removal efficiency.     

Comparative granule characteristics and biokinetics of sucrose-fed and phenol-fed UASB reactors

Two upflow anaerobic sludge bed (UASB) reactors were fed with a non-inhibitory substrate sucrose and an inhibitory substrate phenol, respectively, to compare granule characteristics and biokinetics. The average size of biomass granules in the sucrose-fed UASB reactor was slightly larger than that of the phenol-fed reactor. The average microbial density was significantly higher in the phenol-fed reactor. The intrinsic biokinetics of sucrose-acidogenesis and phenol-acidogenesis followed Monod and Haldane kinetics, respectively. By comparing half-saturation constants for sucrose and phenol (Ks1,s; Ks1,p), the affinity of phenol to the granule should be much higher. The mass fraction of methanogens (f) in the sucrose-fed reactor decreased with increasing volumetric loading rate (VLR) because of the accumulation of volatile fatty acids (VFAs); the f of the phenol-fed reactor decreased with increasing VLR because acidogenesis was the rate-limiting step. The mass transfer resistance in overall substrate removal in the sucrose-fed reactor was greater than that in the phenol-fed reactor.     

Influence of reactor configuration on reliability of activated sludge process

The effect of uncertainty in system parameters and the accuracy of the mathematical model used on the design and reliability of the activated sludge process is investigated by Monte Carlo simulations. Simulations indicate that the coefficient of variation for a reactor volume varies from 0.56 for a single mixed tank reactor to 0.44 for a plug flow reactor. The coefficient of variation for effluent for reactors designed on nominal values was found to be 0.56 for a mixed-tank reactor, 1.28 for two reactors in series, 1.56 for three reactors in series and 1.6 for a plug flow reactor. Significant contributing parameters to the reliability of the process are established. Reactor volumes for desired reliability levels are also calculated.     

ANAEROBIC TREATMENT OF ATRAZINE BEARING WASTEWATER

Performance of mixed microbial anaerobic culture in treating synthetic wastewater with high Chemical Oxygen Demand (COD) and varying atrazine concentration was studied. Performance of hybrid reactors with wood charcoal as adsorbent, with a dose of 10 g/l and 40 g/l, along with the microbial mass was also studied. All the reactors were operated in sequential mode with Hydraulic Retention Time (HRT) of 5 days. In all the cases, COD removal after 5 days was found to be above 81%. Initial COD was above 1000 mg/l. From a hybrid reactor COD removal after 2 days was observed to be 90%. Atrazine reduction after 5 days by microbial mass alone was 43.8%, 40% and 33.2% with an initial concentration of 0.5, 1.0 and 2.0 mg/l respectively. MLSS on all the cases were almost same. Increasing MLSS concentration by about 2 fold did not increase the atrazine removal efficiency significantly. Maximum atrazine removal was observed to be 64% from the hybrid reactor with 10 g/l of wood charcoal and 69.4% from the reactor with 40 g/l of wood charcoal. Atrazine removal from the hybrid reactors after 15 days were observed to be 35.7% and 38.7%, which showed that the higher dose of wood charcoal in hybrid reactor did not improve the atrazine removal efficiency significantly. Specific methanogenic activity test showed no inhibitory effect of atrazine on methane producing bacteria. The performance of anaerobic microorganisms in removing atrazine with no external carbon source and inorganic nitrogen source was studied in batch mode. With an initial concentration of 1.0 mg/l, reduction of atrazine by the anaerobic microorganisms in absence of external carbon source after 35 days was observed to be 61.8% where as in absence of external carbon and inorganic nitrogen source the reduction was only 44.2% after 150 days. Volatilization loss of atrazine was observed to be insignificant.     

Anaerobic treatment of atrazine bearing wastewater.

Performance of mixed microbial anaerobic culture in treating synthetic waste-water with high Chemical Oxygen Demand (COD) and varying atrazine concentration was studied. Performance of hybrid reactors with wood charcoal as adsorbent, with a dose of 10 g/l and 40 g/l, along with the microbial mass was also studied. All the reactors were operated in sequential mode with Hydraulic Retention Time (HRT) of 5 days. In all the cases, COD removal after 5 days was found to be above 81%. Initial COD was above 1,000 mg/l. From a hybrid reactor COD removal after 2 days was observed to be 90%. Atrazine reduction after 5 days by microbial mass alone was 43.8%, 40% and 33.2% with an initial concentration of 0.5, 1.0 and 2.0 mg/l respectively. MLSS on all the cases were almost same. Increasing MLSS concentration by about 2 fold did not increase the atrazine removal efficiency significantly. Maximum atrazine removal was observed to be 64% from the hybrid reactor with 10 g/l of wood charcoal and 69.4% from the reactor with 40 g/l of wood charcoal. Atrazine removal from the hybrid reactors after 15 days were observed to be 35.7% and 38.7%, which showed that the higher dose of wood charcoal in hybrid reactor did not improve the atrazine removal efficiency significantly. Specific methanogenic activity test showed no inhibitory effect of atrazine on methane producing bacteria. The performance of anaerobic microorganisms in removing atrazine with no external carbon source and inorganic nitrogen source was studied in batch mode. With an initial concentration of 1.0 mg/l, reduction of atrazine by the anaerobic microorganisms in absence of external carbon source after 35 days was observed to be 61.8% where as in absence of external carbon and inorganic nitrogen source the reduction was only 44.2% after 150 days. Volatilization loss of atrazine was observed to be insignificant.     

Relative efficacy of intrinsic and extant parameters for modeling biodegradation of synthetic organic compounds in activated sludge: dynamic systems.

The utility of intrinsic and extant kinetic parameters for simulating the dynamic behavior of a biotreatment system coupled with a distributed, unstructured, balanced microbial growth model were evaluated against the observed response of test reactors to transient loads of synthetic organic compounds (SOCs). Biomass from a completely mixed activated-sludge (CMAS) system was tested in fed-batch reactors, while a sequencing batch reactor (SBR) was tested by measuring SOC concentrations during the fill and react period. Both the CMAS system and the SBR were acclimated to a feed containing biogenic substrates and several SOCs, and the transient loading tests were conducted with biogenic substrates along with one or more SOCs. Extant parameters more closely reflect the steady-state degradative capacity of activated-sludge biomass than intrinsic parameters and, hence, were expected to be better predictors of system performance. However, neither extant nor intrinsic parameters accurately predicted system response and neither parameter set was consistently superior to the other. Factors that may have contributed to the inability of the model to predict system response were identified and discussed. These factors included the role of abiotic processes in SOC removal, disparity in the bases used to evaluate parameter estimates (substrate mineralization) and reactor performance (substrate disappearance), inhibitory substrate interactions under the severe loading conditions of the SBR, changes in the physiological state of the biomass during the transient loading tests, and the presumed correlation between the competent biomass concentration and the influent SOC concentration.     

Influence of phosphorus and trace metals in biofilters treating gaseous VOCs using a novel irrigation system

ABSTRACT

Although the appropriate supply of nutrients has been extensively researched, more information is required on the effects of nutrients in treating gaseous volatile organic compounds (VOCs) in biofiltration. In this study, the effects of phosphorous and trace metals on gaseous toluene and methyl ethyl ketone (MEK) removal were investigated. The transfer of nutrients from the irrigation liquid to the packed bed, and the consumption and holding amount of nutrients in the packing material were observed during biofiltration. Under conditions of 20–24 s of empty bed residence time, MEK removal was 95% or more in all conditions of the biofiltration reactors, whereas toluene removal was affected by the operating conditions of the reactors. Consumption ratio of phosphorus to carbon was from 1.7 × 10^?4 to 1.1 × 10^?3 in the steady state of VOC removal under the conditions of this study. When gaseous VOC treatment was restarted after nine days of shutdown, a significant decline in toluene removal was observed by the reactor in which phosphorus supply was approximately one fifth of the amount in another reactor. Two types of irrigation systems, soaking and spraying, were compared and soaking irrigation achieved a more even distribution of nutrients held inside the packed bed. Soaking irrigation was expected to lead to higher VOC removal capacity by this distribution effect of nutrients, but toluene removal in the reactor with this irrigation was lower than that in the reactor with spraying irrigation. One of the possible reasons for this was the inhibition of nutrients transfer in the bottom part of the reactor. The trend of transfer in all ingredients from the irrigation liquid to the packed bed was synchronized on the whole; however, this transfer relatively tended to be high in nitrate and sodium and low in ammonium and phosphate.

Implications: A major concern about using biofiltration systems to treat VOCs is the uncertainty regarding the appropriate nutrient supply to the filter bed to preserve microbial activity. This study showed that all the elements, except nitrogen, were retained sufficiently in the filter bed when a proper composition of nutrient solution was used for irrigation; however, phosphate addition may be needed when restarting a reactor from a prolonged period of shutdown. Distinct differences in the amount of transfer to the filter bed for different ingredients are probable, and may have to be taken into account when operating biofiltration reactors.     

三维电极电化学反应器深度处理焦化废水

为探索焦化废水深度处理新途径,采用了焦粒、活性炭负载Mn（NO3）2和Zn（NO3）2化合物粒子电极为第3极的三维电极反应器对二级生化处理后的焦化废水进行深度处理。考察了焦化废水中有机物去除的影响因素及处理效果,并探讨了有机物的降解动力学。结果表明,以焦粒为载体的粒子电极三维电极系统在pH为6.5,电导率为4 580μS/cm,电流密度为16 mA/cm2,投加量大于25 g/L时,降解20 min,COD去除率超过35%以上。焦化废水的降解的动力学研究表明,焦化废水降解符合表观一级反应动力学规律。该研究可为三维电极反应器在焦化废水深度处理工程应用中提供参数依据。     

UASB performance for bleached and unbleached kraft pulp synthetic wastewater treatment

This paper presents the performance of two bench scale Upflow Anaerobic Sludge Blanket reactors (UASB) used for the treatment of synthetic substrates that simulate bleached and unbleached cellulose pulp plant wastewaters. The control reactor was fed with diluted black liquor and the treatment reactor with the same substrate plus a mixture of chlorinated organics. The total concentration of the chlorinated compounds was gradually increased from 2.5 mg l-1 to 15.0 mg l-1. The average COD removal efficiency during the last phase of the experiment was 81% in the control reactor and 76% in the treatment reactor. These results indicate the capability of UASB reactors to treat this kind of wastewater and the low impact of the chlorinated organics on COD removal efficiency. The minimum overall chlorinated organics removal efficiency was 71% and the maximum was 99.7%. The experiment indicates that under the conditions used in this research the presence of chlorinated organics does not negatively impact the treatment process.     

2种UASB的ANAMMOX与反硝化协同作用对比研究

采用2套UASB-ANAMMOX反应器处理垃圾渗滤液,其中反应器2具有生物膜,对反应器在有机环境下的ANAMMOX与反硝化协同作用进行对比研究。在稳定期,反应器1和反应器2对氨氮、亚硝氮、TIN、COD的平均去除率分别为95.7%、95.9%、77.3%、70.3%和97.4%、96.4%、87.2%、74.8%。反应器1对TIN和COD最大容积去除率为112.2和107.7 g/(m3.d),反应器2对TIN和COD最大容积去除率为120.5和119.9 g/(m3.d)。结果表明,过高的负荷会对反应器产生抑制作用,且当抑制产生后协同作用难以恢复到原来水平。在厌氧氨氧化与反硝化协同作用良好时,pH值和碱度均存在特征性变化。总体上,反应器2比反应器1具有更强的厌氧氨氧化与反硝化协同作用和抗负荷冲击能力。     

Mass transfer resistance in ASFF reactors for waste water treatment

Analysis of mass transfer resistances was performed for an aerated submerged fixed-film reactor (ASFF) for the treatment of waste water containing a mixture of sucrose and ammonia. Both external and internal mass transfer resistances were considered in the analysis, and characterized as a function of feed flow-rate and concentration. Results show that, over a certain operating regime, external mass transfer resistance in the system was greater for sucrose removal than ammonia. This is because the reaction rates for carbon removal were much larger than those of nitrogen. As a result, existence of any form of mass transfer resistance caused by inadequate mixing or diffusion limitations, strongly affects the overall removal rates of carbon more than nitrogen. Effects of the internal m?ss transfer resistance were virtually non-existent for ammonia removal. This behaviour was found over two orders of magnitude range for the effective diffusivity for ammonia, and one order of magnitude for the film specific surface area. However, over the same parameters' range, it is found that sucrose removal was strongly affected upon lowering its effective diffusivity and increasing the film specific surface area.     

造粒流化床颗粒污泥对溶解性有机物的吸附机理研究

造粒流化床对污染物的去除是由混凝沉淀和物理吸附协同作用完成的,然而对于溶解性污染物,混凝沉淀的效果不明显,根据作者的实验分析,物理吸附在溶解性污染的去除中发挥了重要的作用。作者利用静态实验的方法对流化床颗粒对葡萄糖的吸附和扩散传质过程进行了分析,并采用Langmuir方程、Freudlich方程和Weber-Morris颗粒扩散模型对实验数据进行了拟合。结果表明,颗粒对葡萄糖的吸附等温过程与Langmuir方程有很好的吻合性;颗粒对葡萄糖的吸附速度与颗粒内部的扩散过程有很好的相关性。