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.     

Chemical absorption process for degradation of VOC gas using heterogeneous gas-liquid photocatalytic oxidation: toluene degradation by photo-Fenton reaction

A novel process for degradation of toluene in the gas-phase using heterogeneous gas-liquid photocatalytic oxidation has been developed. The degradation of toluene gas by photo-Fenton reaction in the liquid-phase has experimentally examined. The photo-Fenton reaction in the liquid-phase could improve the overall toluene absorption rate by increasing the driving force for mass transfer and as a result enhance the removal of toluene in the exhaust gas. The toluene concentrations in the inlet gas were varied in the range from 0.0968 to 8.69gm(-3) with initial hydrogen peroxide concentration of 400mgl(-1) and Fe dose of 5.0mgl(-1). It was found that toluene in the inlet gas was almost completely dissolved into water and degraded in the liquid-phase for the inlet toluene gas concentration of less than 0.42gm(-3). The dynamic process of toluene gas degradation by the photo-Fenton reaction providing information for reaction kinetics and mass transfer rate was examined. Toluene removal kinetic analysis indicated that photo-Fenton degradation was significantly affected by H(2)O(2) concentration. The experimental results were satisfactorily described by the predictions simulated using the simplified tanks-in-series model combined with toluene removal kinetic analysis. The present results showed that the proposed chemical absorption process using the photo-Fenton heterogeneous gas-liquid photocatalytic oxidation is very effective for degradation of volatile organic gases.     

Kinetic study of the removal of dimethyl phthalate from an aqueous solution using an anion exchange resin

Phthalate acid esters are becoming an important class of pollutants in wastewaters. This study addresses the kinetics of removal of dimethyl phthalate (DMP) using the anion exchange resin D201-OH from an aqueous solution. The effects of various factors on the removal rate and efficiency were investigated. An overall initial removal rate (OIRR) law and a pseudo first-order kinetic (PFOK) model were also developed. The internal diffusion of DMP within the resin phase of D201-OH is the rate-controlling step. Optimization of the particle size and pore structure of the resin D201-OH, the DMP concentration, and the reaction temperature can improve the DMP removal rate. The hydrolysis reaction of DMP catalyzed by D201-OH indicates an overall reaction order of 1.76, a value that is between the first order and the second order. The apparent activation energy of the reaction is 34.6 kJ/mol, which is below the homogeneous alkaline hydrolysis activation energy of 44.3 kJ/mol. The OIRR law can quantify the initial removal rate under different conditions. The results also show that the theoretical DMP removal efficiency predicted by the PFOK model agrees well with the experimentally determined values. Our research provides valuable insights into the primary parameters influencing the kinetic process, which enables a focused improvement in the removal or hydrolysis rate for similar processes.     

Characterization of metal adsorption kinetic properties in batch and fixed-bed reactors

Copper adsorption kinetic properties in batch and fixed-bed reactors were studied in this paper. The isothermal adsorption experiments showed that the copper adsorption capacity of a granular activated carbon (Filtrasorb 200) increased when ionic strength was higher. The presence of EDTA diminished the adsorption. An intraparticle diffusion model and a fixed-bed model were successfully used to describe the batch kinetic and fixed-bed operation behaviors. The kinetics became faster when the solution pH was not controlled, implying that the surface precipitation caused some metal uptake. The external mass transfer coefficient, the diffusivity and the dispersion coefficient were obtained from the modeling. It was found that both external mass transfer and dispersion coefficients increased when the flow rate was higher. Finally effects of kinetic parameters on simulation of fixed-bed operation were conducted.     

An improved model for analyzing the performance of photocatalytic oxidation reactors in removing volatile organic compounds and its application

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 Kt, together with the other two parameters, the number of mass transfer units NTUm and the fractional conversion epsilon, 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, NTUm,ir; the ideal reaction fractional conversion, epsilonir; and the reaction effectiveness, eta, 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.     

自养反硝化菌对硝酸盐氮去除动力学及影响因素研究

为更经济有效地去除污水中的硝酸盐,从兼性污泥中分离获得6株能氧化单质硫和还原硝酸盐的自养反硝化菌。根据各菌株的降解曲线筛选出优势菌种N-I,并研究影响菌株N-I降解性能的环境因素,如pH、温度、碳源及硝酸盐的降解动力学。实验表明,菌株N-I对硝酸盐的降解符合一级反应动力学方程,反应的半衰期t_1/2为1.42 h,反应速率常数为0.488 h^-1。最佳反应pH=7,最佳反应温度为30℃,最佳NaHCO₃浓度为大于或等于2.5 g/L。     

膜基活化溶液中活化剂在回收温室气体CO2过程中的作用

将AMP和PZ作为活化剂添加于MDEA溶液中,形成活化溶液,研究了膜基活化溶液回收温室气体CO₂性能,着重考察活化剂的活化作用和对膜接触器传质加强的影响,提出一个活化机理来解释活化现象,建立了阻力层方程模型, 并模拟膜基活化溶液回收CO₂的传质过程。结果表明,活化剂对膜接触器传质的加强起到重要作用,具有双氨基环状结构的PZ对传质的加强作用高于具有空间位阻结构的AMP;活化溶液的CO2回收率和传质通量明显高于未活化的MDEA溶液,活化性能PZ＞AMP;活化剂的活化效应与分子结构有关;流体力学的改变对传质的影响有限,活化剂的反应动力学对传质的加强起主导作用;阻力层方程模型能较好地模拟膜基活化溶液回收CO₂传质过程,传质通量和总传质系数的模型值与实验值符合较好。     

Evaluation of substrate removal kinetics for UASB reactors treating chlorinated ethanes

Purpose

Lack of focus on the treatment of wastewaters bearing potentially hazardous pollutants like 1,1,2 trichloroethane and 1,1,2,2 tetrachloroethane in anaerobic reactors has provided an impetus to undertake this study. The objective of this exercise was to quantify the behavior of upflow anaerobic sludge blanket reactors and predict their performance based on the overall organic substrate removal.

Methods

The reactors (wastewater-bearing TCA (R2), and wastewater-bearing TeCA (R3)) were operated at different hydraulic retention times (HRTs), i.e., 36, 30, 24, 18, and 12?h corresponding to food-to-mass ratios varying in the range of 0.2?C0.7?mg chemical oxygen demand (COD) mg^?1 volatile suspended solids day^?1. The process kinetics of substrate utilization was evaluated on the basis of experimental results, by applying three mathematical models namely first order, Grau second order, and Michaelis-Menten type kinetics.

Results

The results showed that the lowering of HRT below 24?h resulted in reduced COD removal efficiencies and higher effluent pollutant concentrations in the reactors. The Grau second-order model was successfully applied to obtain the substrate utilization kinetics with high value of R ² (>0.95). The Grau second-order substrate removal constant (K ₂) was calculated as 1.12 and 7.53?day^?1 for reactors R2 and R3, respectively.

Conclusion

This study demonstrated the suitability of Grau second-order kinetic model over other models, for predicting the performance of reactors R2 and R3, in treating wastewaters containing chlorinated ethanes under different organic and hydraulic loading conditions.     

接种物对厌氧同步脱硫反硝化特性的影响实验研究

分别以厌氧污泥、脱氮硫杆菌菌悬液和厌氧污泥并添加脱氮硫杆菌菌悬液为接种物,以硫化物和硝酸盐为进水基质,考察不同接种物条件下,各反应器的硫化物氧化特性、反硝化特性、生化反应机理及微生物特性。结果表明,在无菌条件下,硫化物不能被硝酸盐化学氧化。接种脱氮硫杆菌菌悬液的2#反应器的硫氧化速率为1.98 g S/(m3.h),停留24 h硫化物的去除率高达97%,脱硫能力最强,该接种条件下以硝酸盐氧化硫化物为主反应,优势菌为杆菌,进水的NO3--N/S应控制在0.4以下,可以实现高效生物脱硫。接种厌氧污泥的1#和3#反应器的脱氮效果比2#反应器好,停留时间为24 h时,硝酸盐的平均去除率为96%。单独接种厌氧污泥的1#反应器的硫氧化速率为1.78 g S/(m3.h),其优势菌为球菌,该接种条件下以硝酸盐氧化硫化物和硝酸盐氧化单质硫为主反应,进水的NO3--N/S应控制在0.8左右。以厌氧污泥联合脱氮硫杆菌为接种物时,硫氧化速率为1.71 g S/(m3.h),反应器以硝酸盐氧化硫化物、硝酸盐氧化单质硫以及异养反硝化为主反应,驯化后优势菌为球形、卵圆形和短杆状,应控制进水NO3--N/S为1.2,可以实现同步脱硫反硝化,该工艺既可以用于含硫废水的处理,也可以用于C/N低的硝酸盐废水的处理。     

Nitrate reduction by green rusts modified with trace metals

A kinetic study of nitrate reduction by green rust (GR), a group of layered Fe(II)-Fe(III) hydroxide solids, was performed using a batch reactor system. The reduction rate of nitrate by GRs was affected by the anion content in the interlayer of GRs. GR containing F^- (GR-F) showed the fastest reduction rate while GR-SO₄ showed 9 times slower reaction rate than GR-F. The addition of 1 mM Pt or Cu to GR that contained 85 mM Fe(II) improved the reduction kinetics of nitrate by up to 200 times. Pt was an effective activating agent for all GRs. The sequential step reaction model that we proposed appropriately simulated the experimental data. The fastest nitrate reduction by GR-F with Pt was achieved at pH 9 among 7.5 to 11. At that condition, 1 mM nitrate transformed completely into ammonium within 23 min.     

Kinetic study and modeling on photocatalytic degradation of para-chlorobenzoate at different light intensities

In order to clarify the dependence of apparent adsorption constant Ks in the Langmuir-Hinshelwood (L-H) model on the incident light intensity, photocatalytic degradation kinetic characteristics were experimentally investigated at different light intensities using para-chlorobenzoate (4-CBA) as a model compound. In all cases 4-CBA initial degradation rates showed dependence on 4-CBA initial concentration, which can be described by the L-H model. However, the adsorption constant Ks and rate constant kr obviously varied with light intensity. To account for the experimental finding, slight modification of the classic kinetic model developed by Turchi and Ollis was tentatively proposed by assuming insufficiency of H2O/OH- available for photo-activated holes' scavenging. Such a kinetic model predicts that both k(r) and Ks(-1) are linearly proportional to the square root of the intensity in a rather large intensity range. The validity of the modified model was proved by fitting it to the experimental data.     

Kinetics of natural oxidant demand by permanganate in aquifer solids

During in situ chemical oxidation with permanganate, natural organic matter and other reduced species in the subsurface compete with the target compounds for the available oxidant and can exert a significant natural oxidant demand. This competition between target and nontarget compounds can have a significant impact on the permeation, dispersal, and persistence of permanganate in the subsurface. The kinetics of natural oxidant demand by permanganate was investigated using a composite sample made up of aquifer material collected from three different sites. The study found that although the depletion of organic carbon increased with increased permanganate dosage and increased reaction period, the mass ratio of MnO(4)(-):OC (wt/wt) was relatively constant over time (11.4+/-0.9). The reaction order and rate with respect to permanganate were found to decrease with time suggesting a continuum of reactions with the slower reactions becoming more controlling with time. However, the data also suggests that this continuum of reactions can be simplified into short- and long-term kinetic expressions representing fast and slow reactions. An independent first-order kinetic model with separate fast and slow reaction rate constants was used to successfully describe the complete kinetic expression of natural oxidant demand. The kinetic parameters used in the model are easily determined and can be used to better understand the complex kinetics of natural oxidant demand.     

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.     

The interfacial mass transfer resistances of the ozone dry deposition over the field soil of Taichung County in Taiwan

This study aims to design a dry deposition chamber and to measure ozone depletion over the Taichung field soil. This study seeks to verify the phenomena by an experimental and mathematical model. It is demonstrated that interfacial mass transfer resistances of ozone dry deposition involve reactive resistance (R(sr)) and kinetic resistance (R(sk)). It reveals the chemical reaction (O3 + NO --> NO2) to produce the reactive resistance, and verifies that the interfacial mass transfer resistances depend on nitrogen oxide emission and soil temperature. It shows that the interfacial mass transfer resistances are reduced with increasing soil temperature (T(S)). The model profiles are smaller than the observed data within a relative error of 15%. The reactive resistance decreases exponentially with increasing soil temperature; R(sr)(-1) (cm x sec(-1)) = 0.0001 exp (0.1455T(S)). The kinetic resistance decreases linearly with increasing soil temperature; R(sk)(-1)(cm x sec(-1)) = 0.0108T(S) + 1.4012. This model is more accurate with higher soil temperature and larger ozone concentration. Results are consistent with thermodynamics and reaction kinetics. Ozone dry deposition over agricultural soil causes conversion of nitrogen oxide (NO) to nitrogen dioxide (NO2).     

Corrected first-order model of DEHP degradation

Corrected first-order model was applied to describe the biological removal of di-(2-ethylhexyl) phthalate (DEHP) in sludge-amended soil along with batch and continuous-flow anaerobic reactors with different initial/influent DEHP concentrations and hydraulic retention times. Only two kinetic parameters - the first-order rate coefficient k describing the overall kinetics of the process and the coefficient alpha characterizing the fraction of non-degradable DEHP - were used to fit the array of experimental data published earlier. The values of k and alpha estimated for DEHP removal from different sludges at 35 degrees C varied within the range of 0.03-0.07 d(-1) and 0.25-0.5, respectively. In sludge-amended soil, the first-order kinetic coefficient k increased from 0.007 to 0.028 d(-1) and the fraction of non-degradable DEHP alpha decreased from 0.6 to 0.5 with the increase in incubation temperature from 5 to 20 degrees C. The rate coefficient k increased by a factor of 2 when the temperature increased from 5 to 10 degrees C or from 10 to 20 degrees C.     

臭氧氧化法处理焦化废水生化出水的反应动力学

对臭氧氧化去除焦化废水生化出水COD的反应动力学及其影响因素进行了实验研究,结果表明,在臭氧投加量为8．50mg／min,反应温度为20＇E和初始pH为10．61条件下,对COD的降解符合表观一级反应动力学模型,其相关系数R。=0．9991,表观反应速率常数k。。=1．01×10^-3s-1。该条件下,臭氧氧化对COD的降解主要来源于高活性羟基自由基的强氧化作用。在不同的臭氧投加量（4．25～12．75mg／min）、不同的反应温度（10～40℃）和不同的初始pH（3．76～12．53）下,COD的降解也同样遵循一级反应动力学规律。随着臭氧投加量的增大,COD降解的表观反应速率常数从（0．554×10^-3）s-1增加到（1．06×10＆-3）s-1;随着反应温度的升高,表观反应速率常数从（0．427×10^-3）s-1增加到（1．40×10-3）s-1,温度越高反应速率提高的幅度却越小;在初始pH3．76～10．61范围内,表观反应速率常数从（0．218×10^-3）s-1增加到（1．01×10^-3）s-1,在初始pH为12．53时表观反应速率常数下降到（0．857×10^-3）s-1。     

Kinetic studies of adsorption of lead(ll) from aqueous solution by wine-processing waste sludge.

A waste sludge produced from a wine-processing wastewater treatment process was used as an adsorbent to removal of heavy metal-lead(II) from aqueous solution. Results of kinetic experiments demonstrated that the adsorption was effective and rapid. Four different kinds of adsorption kinetic models (i.e., pseudo-first-order, pseudo-second-order, and two intra-particular mass diffusion models) were used to investigate the adsorption mechanisms. A normalized standard deviation was used to find the best adsorption kinetic model for the removal of lead(ll) by the sludge. The comparison shows that the kinetic adsorption data can be well-described by the pseudo-second-order adsorption model and that sorption might be a rate-limiting control. The adsorption-rate constant and adsorption capacity of pseudo-second-order adsorption equation were calculated. The parameters (initial lead(II) concentration, sludge-particle size, and sludge dosages), which affect the adsorption capacity of sludge, were discussed by using the pseudo-second-order adsorption equation.     

亚硝酸盐反硝化颗粒污泥的二次启动试验研究

接种0～4℃贮存2个月亚硝酸盐反硝化颗粒污泥,以甲醇为电子供体、亚硝酸盐为电子受体在USB(上流式污泥床)反应器内进行二次启动。结果显示,在逐步提高进水负荷下,约46 d完成了反应器二次启动,污泥床负荷达到3.43 g N/（L·d）,NO₂-N去除率为99%;在稳定运行阶段,当进水NO₂-N浓度为50 mg/L、负荷从1.7 g N/（L·d）逐步提高至5.1 g N/（L·d）时,NO₂-N去除率均大于98%;当表观流速为2.68 m/h、进水负荷逐步提高至8.0 g N/（L·d）时,脱氮率下降至63%,过程中污泥床最大去除速率约为5.7 g N/（L·d）。研究认为,亚硝酸盐颗粒污泥床具有稳定和去除效率高等特点。     

Implications of non-equilibrium transport in heterogeneous reactive barrier systems: evidence from laboratory denitrification experiments

Organic substrates in reactive barrier systems are often heterogeneous material mixtures with relatively large contrasts in hydraulic conductivity and porosity over short distances. These short-range variations in material properties imply that preferential flow paths and diffusion between regions of higher and lower hydraulic conductivity may be important for treatment efficiency. This paper presents the results of a laboratory column experiment where denitrification is investigated using a heterogeneous reactive substrate (sawdust mixed with sewage sludge). Displacement experiments with a non-reactive solute at three different flow rates are used to estimate transport parameters using a dual porosity non-equilibrium model. Parameter estimation from breakthrough curves produced relatively consistent values for the fraction of the porosity consisting of mobile water (β) and the mass transfer coefficient (α), with average values of 0.27 and 0.42 d(-1), respectively. The column system removes >95% of the influent nitrate at low and medium flow, but only 50-75% of the influent nitrate at high flow, suggesting that denitrification kinetics and diffusive mass transfer rates are limiting the degree of treatment at lower hydraulic residence times. Reactive barrier systems containing dual porosity media must therefore consider mass transfer times in their design; this is often most easily accommodated by adjusting flowpath length.     

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。