臭氧氧化6-APA制药厂生化处理出水的特性及动力学简

通过现场实验研究了6-APA制药厂生化处理出水的臭氧氧化特性及其动力学规律。结果表明,当臭氧浓度为27.5 mg/L,气水接触时间为80 min时,COD、UV₂₅₄、NH₃-N和色度的去除率分别可达72.95%、73.28%、72%和96.25%,达到《发酵类制药废水工业水污染物排放标准》（GB 21903-2008）排放控制要求。拟合结果表明,在0~10、10~30和30~90 min时段内,臭氧氧化过程遵循拟一级反应,但反应速率逐渐降低。当气水接触时间为30 min时,废水可生化性可由0.1提高至0.35,采用臭氧/生物处理的联合工艺也有望使出水达到相同的排放控制要求。     

MCM-41介孔分子筛的合成及其对铜离子的吸附性能简

以微硅粉为硅源,CTAB和PEG-6000为模板剂,合成MCM-41介孔分子筛。采用XRD、N₂吸附-脱附曲线、FTIR以及TEM表征了其结构、比表面积、孔径分布及晶体形貌,并且以该样品为吸附剂,对含Cu²⁺的溶液进行了静态吸附实验。结果表明,以微硅粉为硅源成功合成了具有典型六方排列孔道结构的MCM-41,其比表面积为869.5 m²/g,孔容为0.97 cm³/g,平均孔径为3.3 nm;溶液pH为5~6时,MCM-41对Cu²⁺的去除效果最好;MCM-41对Cu²⁺的最大吸附吸附容量36.3 mg/g;MCM-41对Cu²⁺的吸附性能符合Langmuir吸附方程的特征。动力学研究表明,该过程符合准二级动力学模型。     

臭氧氧化法处理焦化废水生化出水的反应动力学简

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8.50 mg/min,反应温度为20℃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R²=0.9991,表观反应速率常数k_Abs=1.01×10^-3 s^-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（4.25~12.75 mg/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。     

罐底含油泥热解动力学参数计算方法的优选

在化学反应设计中反应动力学是较重要的因素。为得到更合理的污泥热解动力学参数计算方法,利用热重分析仪,在氮气气氛下对罐底含油污泥的热解特性进行研究。根据热重实验数据,分别采用Coats-Redfern法、Kissinger法、FWO法和Popescu法计算污泥热解动力学参数,并获取罐底泥热解制油的主要阶段(第2阶段)的反应活化能E、频率因子A并分析各种方法反应机理。通过对比不同计算方法得到动力学参数及拟合曲线与实验曲线的相关性,确定了最佳罐底含油污泥热解动力学参数计算方法。研究表明,Popescu法得到罐底泥的热解过程符合Jander方程,活化能E为101.43 kJ/mol,与FWO法得到的91.20 kJ/mol相近,且预测曲线与实验曲线有较好的相关性(0.9816),说明Popescu法计算罐底泥热解动力学参数更合适。     

玉米秸秆活性炭的制备及其吸附动力学研究

以玉米秸秆为原材料,采用ZnCl2活化法制备玉米秸秆活性炭,吸附次甲基蓝染料废水,进行动力学分析。本实验用Langmuir和Freundlich模型对吸附等温线进行拟合,结果表明,玉米秸秆活性炭对次甲基蓝的吸附与Langmuir方程拟合良好,R2=0.9857。采用Lagergren准一级速率模型、Lagergren准二级速率模型、Bangham动力学方程和Elovich动力学方程分别对秸秆活性炭吸附次甲基蓝溶液进行吸附动力学拟合,通过分析得出吸附过程与Lagergren准二级速率模型拟合最好,R2=0.9979。秸秆活性炭对次甲基蓝的最大吸附量达到909.09 mg/g,具有很高的吸附能力。     

Hydrolysis and photolysis of oxytetracycline in aqueous solution

Oxytetracycline ((2Z,4S,4aR,5S,5aR,6S,12aS)-2-(amino-hydroxy-methylidene)-4-dimethylamino-5,6,10,11,12a-pentahydroxy-6-methyl-4,4a,5,5a-tetrahydrotetracene-1,3,12-trione) is a member of tetracycline antibiotics family and is widely administered to farm animals for the purpose of therapeutical treatment and health protection. Increasing attention has been paid to the environmental fate of oxytetracycline and other veterinary antibiotics with the occurrence of these antibiotics in the environment. The hydrolysis and photolysis degradation of oxytetracycline was investigated in this study. Oxytetracycline hydrolysis was found to obey the first-order model and similar rate constant values ranging from 0.094 ± 0.001 to 0.106 ± 0.003 day^{? 1} were obtained at different initial concentration ranging from 10 to 230 μ M. Solution pH and temperature were shown to have remarked effects on oxytetracycline hydrolysis. The hydrolysis in pH neutral solution appeared to be much faster than in both acidic and alkaline solutions. Oxytetracycline half-life decreased from 1.2 × 10² to 0.15 day with the increasing temperature from 4 ± 0.8 to 60 ± 1°C. The presence of Ca^{2 +} made oxytetracycline hydrolytic degradation kinetics deviate from the simple first-order model to the availability-adjusted first-order model and greatly slowed down the hydrolysis. Oxytetracycline photolysis was found to be very fast with a degradation rate constant at 3.61 ± 0.06 day^{? 1}, which is comparable to that of hydrolysis at 60°C. The presence of Ca^{2 +} accelerated oxytetracycline photolysis, implying that oxytetracycline become more vulnerable to sunlight irradiation after chelating with Ca^{2 +}. The photolysis may be the dominant degradation pathway of oxytetracycline in shallow transparent water environment.     

Kinetics study of fermentative hydrogen production from liquid swine manure supplemented with glucose under controlled pH

Kinetics of H₂ production from liquid swine manure supplemented with glucose by mixed anaerobic cultures was investigated using batch experiments under four different pH conditions (4.4, 5.0, 5.6, and uncontrolled). The temperature for the experiments was controlled at 37 ± 1°C and the length of experiments varied between 50 and 120 hours, depending upon the time needed for completion of each individual experiment. The modified Gompertz model was evaluated for its suitability for describing the H₂ production potential, H₂ production rate, and substrate consumption rate for all the experiments. The results showed that the Gompertz model could adequately fit the experimental results. The effect of pH was significant on all kinetic parameters for H₂ production including yield, production rate and lag time, and the substrate utilization rate. The optimal pH was found to be 5.0, at which a maximum H₂ production rate (0.64 L H₂/h) was obtained, and deviation from the optimal pH could result in substantial reductions in H₂ production rate (0.32 L H₂/h for pH 4.0 and 0.43 L H₂/h for pH 5.6). The results also showed that if pH was not controlled for the batch fermentation process, the substrate utilization efficiency could steeply decrease from 98.8% to 33.7%.     

Speciation and persistence of doxycycline in the aquatic environment: Characterization in terms of steady state kinetics

The aim of the present work was to establish the kinetics for the degradation of doxycycline in the aquatic environment with a view to arriving at a kinetic model that can be used to predict the persistence of antibiotic with confidence. The degradation of doxycycline in both water and sediment phases of aquatic microcosm experiments, as well as in distilled water control experiments, was studied over a period of 90 days. An initial 21% loss due to adsorption by the sediment was observed in the microcosm experiment soon after charging. Biphasic zero-order linear rates of degradation, attributed to microbial degradation of the free and sediment or colloidal particle-adsorbed antibiotic, were observed for both water phase (2.3 × 10^?2 and 4.5 × 10^?3 μgg^?1 day^?1) and sediment phase (7.9 × 10^?3 and 1.5 × 10^?3 μgg^?1 day^?1) of the microcosm experiment. The covered distilled water control experiment exhibited a monophasic zero-order linear rate (1.9 × 10^?3 μgg^?1 day^?1) attributed to hydrolysis, while the distilled water experiment exposed to natural light exhibited biphasic liner rates attributed to a combination of hydrolysis and photolysis (2.9 × 10^?3 μgg^?1 day^?1) and to microbial degradation (9.8 × 10^?3 μgg^?1 day^?1). A kinetic model that takes into account hydrolysis, photolysis, microbial degradation as well as sorption/desorption by colloidal and sediment particles is presented to account for the observed zero-order kinetics. The implications of the observed kinetics on the persistence of doxycycline in the aquatic environment are discussed.     

Adsorption of glyphosate on Brazilian subtropical soils rich in iron and aluminum oxides

Abstract

We investigated the adsorption of glyphosate onto five subtropical soils of Paraná and São Paulo states, Brazil, a region of intense agricultural activities, aiming at the determination of kinetic and isotherm adsorption parameters which enable the evaluation of the potential leaching of the herbicide. The adsorption was fast, being described by the pseudo-second order and intraparticle diffusion models, thus suggesting that mixed mechanisms are involved. The Oxisol containing the highest concentrations of metal oxides (209.5?g kg^?1 Fe₂O₃ and 160.2?g kg^?1 Al₂O₃) was the sample with the highest rate constant, indicating the adsorption sites are readily available. All the soils are rich in aluminum and iron oxides, explaining the Freundlich coefficients (K_F) between 642 and 1360?mg^1-1/n kg^?1 L^1/n, which are higher than most of the coefficients described for other soils around the world. The maximum desorption (15% of the adsorbed amount) was observed for the Oxisol. For the other soils, desorption ranged from 2 to 7%. These results suggest that the leaching of free glyphosate to nearby surface and groundwaters is unlikely unless excessive doses are used. The adsorption parameters are useful for managing the right doses applied to the crops, thus avoiding contamination of adjacent areas.     

改性粉煤灰对糖蜜废水的吸附效果及机理

采用改性粉煤灰(MCFA)吸附糖蜜废水中的有机污染物,对吸附行为和机理进行了考察和分析。结果表明,MCFA投加量为30 g/L及pH为5.0的优化条件下,COD去除率为88.6%,饱和吸附量为89.7 mg COD/g MCFA。准二级方程能更好地描述糖蜜废水在MCFA上的吸附动力学。颗粒内扩散方程结果表明孔扩散并非唯一的速度控制步骤。吸附平衡表明,Freundlich等温线最符合吸附模式,为优惠吸附。D-R模式中的吸附自由能Ea值推断更可能是物理吸附而不是化学吸附。吸附热力学参数ΔG0(<0)、ΔH0(5.130 kJ/mol)和ΔS0(19.936 J/(mol.K))表明MCFA对糖蜜废水的吸附过程为可行的,自发性的吸热反应。