麦草对水中苯胺的动态吸附研究

通过对苯胺初始浓度、流速、初始pH值和吸附床高度对穿透曲线的影响进行探讨,采用BDST模型和Thomas模型对动态实验数据进行线性拟合分析,研究了麦草对水中苯胺的动态吸附性能。结果表明：麦草能够有效地去除水中的苯胺,随着吸附床高度增加,穿透时间延长;而随着苯胺初始浓度、流速和pH值的增大,穿透时间急剧缩短。BDST模型能够准确地预测新的操作条件下的穿透时间,误差均〈5％;Thomas模型能够很好地描述麦草对苯胺的动态吸附动力学,由Thomas模型获得的麦草吸附柱对苯胺的动态吸附量与实验值相符。对吸附饱和后的麦草可用0．6mol／L盐酸进行解吸。     

改性废弃皮革对U(Ⅵ)的动态吸附

以改性废弃皮革为吸附剂对U(Ⅵ)进行动态吸附实验,采用直径3 cm、高50 cm的玻璃吸附柱,在填料高度为3、4和5 cm,U(Ⅵ)溶液进水流速为0.85、1.7和2.55 m L·min~(-1),初始U(Ⅵ)浓度为6、12和18 mg·L~(-1)的条件下,考察了各因素对U(Ⅵ)吸附穿透曲线的影响。动态实验表明:柱高的降低、流速的增大和U(Ⅵ)浓度的增加均会使穿透时间提前;动态吸附穿透曲线能很好地符合Thomas模型的条件(R2 0.95),同时吸附量的预测值与实际测试值较为接近。使用穿透时间(ta)与填料高度(h)的关系式ta=220h-433(R2=0.998),在仅改变流速和初始U(Ⅵ)浓度时,穿透时间预测值与实际测试值相差较小,表明BDST模型能确定固定床的动态吸附周期。     

聚甲醛单宁酸树脂对水体中苯胺的动态吸附研究

以单宁酸为原料,甲醛为交联剂制备了聚甲醛单宁酸树脂(PFTR),利用扫描电子显微镜和氮吸附仪对其表面孔径进行了表征和分析,并对模拟废水中的苯胺浓度进行了动态吸附性能研究,采用Thomas、Yoon-Nelson和BDST 3种模型对实验数据进行拟合分析,探讨PFTR对苯胺的吸附性能和原理。结果表明,PFTR表面含有丰富的孔状结构,能有效吸附水体中的苯胺。当PFTR用量为0.1g,吸附柱填充高度为1cm,流速为0.1cm/min,苯胺初始质量浓度为1 000~2 500mg/L时,其穿透时间随苯胺初始浓度的增大而提前。Thomas模型可较好地估算饱和吸附量,Yoon-Nelson和BDST模型能预测穿透时间。     

乙二胺还原的氧化石墨烯对镉离子的动态吸附

以乙二胺(EDA)还原氧化石墨烯(GO)制得一种吸附剂材料,即还原态氧化石墨烯(RGO)。考察了动态条件下Cd2+溶液的初始浓度、流速及吸附床高度对穿透曲线的影响,同时利用Bed-Depth-Service Time(BDST)模型对吸附床高度与穿透时间的关系进行线性拟合分析,研究了RGO对Cd2+溶液的动态吸附性能。结果表明,RGO可以有效地去除水溶液中的Cd2+,随着吸附床高度的增加,离子的去除率增大,穿透时间延长;当溶液初始浓度增大时穿透时间缩短,离子的去除率减小;而溶液的流速加快,穿透时间和去除率都相应减小。吸附床高度与穿透时间的关系可用BDST模型较好地进行描述,预测新的操作条件下的穿透时间与实验值误差均小于5%。     

改性木屑对水中苯胺的动态吸附

采用β-环糊精对木屑改性用于吸附苯胺,通过固定床实验考察了吸附床高度(10~30 mm)、进水流速(2.7~8.1 m L·min-1)和苯胺初始浓度(50~200 mg·L-1)对穿透曲线的影响,同时使用BDST模型对吸附穿透曲线进行拟合。结果表明,改性木屑可以有效吸附苯胺,随着高度的增加,穿透时间延长,固定床对苯胺的去除率增大;随着苯胺进水流速和初始浓度的增加,穿透时间缩短,固定床对苯胺的去除率降低;BDST模型对穿透曲线的拟合效果较好(Ct/C0=0.7,R2=0.999 0),随着运行时间的增加,固定床的吸附速率常数(Ka)变小,对苯胺的吸附量(N0)增大;当改变流速时,运用该模型能较准确的预测吸附固定床的操作时间。     

粉状褐煤对水中草甘膦的动态吸附

采集内蒙霍林河煤矿褐煤样品,加工成粒径0.38~0.83 mm作为吸附剂,对模拟草甘膦废水进行动态吸附实验。考察了吸附柱高(3、5和10 cm)、草甘膦初始浓度(0.5%、0.75%和1.0%)、流速(1、2和3 m L/min)、pH(9、11和13)和离子强度(IS,0.001、0.01和0.1 mol/L)对草甘膦的吸附穿透曲线和传质区长度的影响。实验结果表明,降低柱高、增大初始浓度、提高流速、增加离子强度均会使穿透时间提前,pH变化对穿透时间影响很小;柱高、初始浓度、流速、IS和pH引起的传质区长度的平均变化率绝对值分别为0.675、6.300、1.625、47.727和0.263,可见,与柱高、初始浓度和流速相比,IS对传质区长度的影响较大,pH影响较小。低浓度条件下,吸附穿透曲线的实验数据符合BDST模型拟合条件(R20.99),在仅改变柱高或流速时,穿透时间理论值与实测值的最大误差均为5.71%,运用该模型能够准确地预测褐煤吸附柱的操作时间。     

改性陶粒对水中卡马西平去除的动态吸附实验及模型

用CTMAB(十六烷三甲基溴化铵)对陶粒进行改性,以卡马西平(CBZ)为目标污染物,研究了吸附去除饮用水中CBZ的性能并探讨了其应用的可行性。通过滤料吸附去除CBZ的动态实验,发现改性陶粒的去除效果优于陶粒。进水CBZ浓度为2μg·L~(-1)时,改性陶粒对CBZ的去除率最高为50%,陶粒最高的去除率为40%。研究了滤料再生对吸附性能的影响,发现陶粒和改性陶粒对CBZ的去除均随再生次数的增加而降低,改性陶粒的去除效果仍优于陶粒,改性陶粒的使用期限更长久。讨论了修正前后的Thomas模型,推导得到能更准确描述穿透曲线的Thomas模型取值范围。滤料穿透曲线用原始Thomas模型能很好地计算的速率常数kTh和平衡吸附量q0。利用原始Thomas模型也能较为准确地预测滤柱的穿透时间。     

超细粉煤灰基成型吸附剂的动态吸附实验

以粉煤灰为原料制备成型吸附剂,对水溶液中亚甲基蓝和Cr⁶⁺进行动态吸附研究,绘制穿透曲线,利用Origin软件对实验数据分析处理,得出穿透曲线的通式C_t=A₁－A₂〖〗1+(t/t₀)^p+A₁。结果表明,初始浓度C₀=25 mg/L,填料高度不同时,达到穿透点的时间随填料高度的增加而增加;填料高度h=200 mm,初始浓度不同时,达到穿透点的时间随初始浓度的增加而减小;该吸附剂对有机染料和重金属离子均有较好的吸附性能;穿透曲线通式的回归线性相关系数表明,该通式可很好地反映超细粉煤灰成型吸附剂的动态吸附过程。     

多孔镁铝复合氧化物对水溶液中Cr(Ⅵ)的吸附性能

以镁盐、铝盐、纯碱和烧碱为原料制备了一种多孔镁铝复合氧化物(P-Mg3.1AlO4.6),其比表面积、平均孔径和总孔容分别为206.3 m2/g、8.961 nm和0.4208 cm3/g。研究了这种多孔材料对水溶液中Cr(Ⅵ)的吸附性能,在25～45℃时,静态吸附量为82.32～141.7 mg/g;当初始浓度100 mg/L、流速5 mL/min、床层高度10 cm和pH=6时,半穿透时间、半穿透吸附量和饱和吸附量分别为406 min、49.28 mg/g和51.30 mg/g;拟合参数及误差分析表明,Cr(Ⅵ)在P-Mg3.1AlO4.6上的静态吸附过程符合Freundlich等温方程式和伪二级动力学方程,Yoon-Nelson模型能很好地预测Cr(Ⅵ)在P-Mg3.1AlO4.6上的动态穿透曲线。     

木质素基水凝胶对亚甲基蓝染料的吸附性能

以木质素磺酸钠(LS-Na)、2-丙烯酰胺基-2-甲基丙磺酸(AMPS)、丙烯酸(AA)为原料,采用微波辐射法,通过接枝共聚反应合成了生物质LS-g-PAMPS/AA水凝胶吸附剂,利用FTIR分析了水凝胶的结构。研究了吸附剂用量、染料初始浓度、吸附时间对亚甲基蓝(MB)染料的吸附性能的影响,结果显示,在MB初始浓度为1 000 mg/L,吸附剂为0.1 g时,吸附量和吸附率分别达1 914 mg/g和95%。平衡吸附数据满足Langmuir吸附等温模型,吸附动力学曲线较好地符合准二级动力学反应模型。木质素水凝胶对MB染料废水具有显著的吸附效果,可以作为阳离了染料废水处理用的生物质吸附剂。     

Artificial neural network (ANN) modeling of adsorption of methylene blue by NaOH-modified rice husk in a fixed-bed column system

In this study, rice husk was modified with NaOH and used as adsorbent for dynamic adsorption of methylene blue (MB) from aqueous solutions. Continuous removal of MB from aqueous solutions was studied in a laboratory scale fixed-bed column packed with NaOH-modified rice husk (NMRH). Effect of different flow rates and bed heights on the column breakthrough performance was investigated. In order to determine the most suitable model for describing the adsorption kinetics of MB in the fixed-bed column system, the bed depth service time (BDST) model as well as the Thomas model was fitted to the experimental data. An artificial neural network (ANN)-based model was also developed for describing the dynamic dye adsorption process. An extensive error analysis was carried out between experimental data and data predicted by the models by using the following error functions: correlation coefficient (R ²), average relative error, sum of the absolute error and Chi-square statistic test (χ ²). Results show that with increasing bed height and decreasing flow rate, the breakthrough time was delayed. All the error functions yielded minimum values for the ANN model than the traditional models (BDST and Thomas), suggesting that the ANN model is the most suitable model to describe the fixed-bed adsorption of MB by NMRH. It is also more rational and reliable to interpret dynamic dye adsorption data through a process of ANN architecture.     

Use of tracer tests to investigate changes in flow and transport properties due to bioclogging of porous media

Tracer tests were conducted in three laboratory columns to study changes in the hydraulic properties of a porous medium due to bioclogging. About 30 breakthrough curves (BTCs) for each column were obtained. The BTCs were analyzed using analytical equilibrium and dual-porosity models, and estimates of the hydrodynamic dispersion and mass transfer coefficients were obtained by curve fitting. The change in transport properties developed in three stages: an initial phase (I) with no significant changes in transport properties, phase II with growth of biomass near the inlet of the columns causing changes in dispersivity, and phase III with added growth of micro-colonies deeper in the columns causing mass transfer of solutes from the water phase to the biophase. Tracer transport changed from being uniform to more non-uniform with increase in mass transfer of the tracer between the mobile phase and the immobile biomass. An increase in the bulk dispersivity value of up to one order of magnitude was observed. Numerical simulations suggest that local dispersivity values may be as much as 40 times higher in the more severe clogged areas inside the column. The bulk hydraulic conductivities of the columns decreased by up to three orders of magnitude. The hydraulic conductivity and dispersivity parameters were almost recovered after disinfection of the columns. Different models relating the changes of the hydraulic conductivity to the changes in the mobile porosity due to bioclogging were reviewed, and the micro-colony relation of Thullner et al. [Thullner, M., Zeyer, J., Kinzelbach, W., 2002. Influence of microbial growth on hydraulic properties of pore networks, Transport in Porous Media, 49, 99-122.] was found to best describe the relation between the bulk hydraulic parameters.     

Modelling dissolution of multi-component non-aqueous phase liquids using Pareto distributions

A distributed-site non-aqueous phase liquid (NAPL) dissolution model that can capture the physical process of dissolution is presented. The model uses a Pareto distribution of effective interfacial area and a correlation for the mass transfer. Model parameters are obtained using a formal constrained non-linear optimisation technique. The model is applied on effluent data from two soil column experiments. The results of the Pareto distributed site model, with only two parameters to fit, were compared to two-site and multi-site models as well as the beta distributed site model. The Pareto distributed-site model produces equal or smaller error estimates than the other models.     

H4SiW12O40/TiO2/beads光催化降解亚甲基蓝的研究

以钛酸四丁酯为原料,空心微珠为载体,采用溶胶凝胶法制备TiO₂/beads光催化剂载体,然后浸渍法制备出H₄SiW₁₂O₄₀/TiO₂/beads表面负载修饰型复合光催化剂,并运用SEM、XRD、FT-IR和DRS对催化剂进行表征和分析。研究了H₄SiW₁₂O₄₀/TiO₂/beads对亚甲基蓝降解的光催化活性,考察了光强度、pH值、曝气量、底物浓度和催化剂用量等对催化效率的影响。实验结果表明,在中性条件下,H₄SiW₁₂O₄₀/TiO₂/beads催化剂的投加量为0.25 g/L,浓度为7.5 mg/L的亚甲基蓝溶液在250 W的紫外灯和600 W的可见光灯下光照60 min降解率分别可达到94.5%和55%。     

Biodegradation of petroleum hydrocarbon vapors: laboratory studies on rates and kinetics in unsaturated alluvial sand

Predictions of natural attenuation of volatile organic compounds (VOCs) in the unsaturated zone rely critically on information about microbial biodegradation kinetics. This study aims at determining kinetic rate laws for the aerobic biodegradation of a mixture of 12 volatile petroleum hydrocarbons and methyl tert-butyl ether (MTBE) in unsaturated alluvial sand. Laboratory column and batch experiments were performed at room temperature under aerobic conditions, and a reactive transport model for VOC vapors in soil gas coupled to Monod-type degradation kinetics was used for data interpretation. In the column experiment, an acclimatization of 23 days took place before steady-state diffusive vapor transport through the horizontal column was achieved. Monod kinetic parameters Ks and vmax could be derived from the concentration profiles of toluene, m-xylene, n-octane, and n-hexane, because substrate saturation was approached with these compounds under the experimental conditions. The removal of cyclic alkanes, isooctane, and 1,2,4-trimethylbenzene followed first-order kinetics over the whole concentration range applied. MTBE, n-pentane, and chlorofluorocarbons (CFCs) were not visibly degraded. Batch experiments suggested first-order disappearance rate laws for all VOCs except n-octane, which decreased following zero-order kinetics in live batch experiments. For many compounds including MTBE, disappearance rates in abiotic batch experiments were as high as in live batches indicating sorption. It was concluded that the column approach is preferable for determining biodegradation rate parameters to be used in risk assessment models.     

Numerical modeling of humic colloid borne americium (III) migration in column experiments using the transport/speciation code K1D and the KICAM model

The humic colloid borne Am(III) transport was investigated in column experiments for Gorleben groundwater/sand systems. It was found that the interaction of Am with humic colloids is kinetically controlled, which strongly influences the migration behavior of Am(III). These kinetic effects have to be taken into account for transport/speciation modeling. The kinetically controlled availability model (KICAM) was developed to describe actinide sorption and transport in laboratory batch and column experiments. Application of the KICAM requires a chemical transport/speciation code, which simultaneously models both kinetically controlled processes and equilibrium reactions. Therefore, the code K1D was developed as a flexible research code that allows the inclusion of kinetic data in addition to transport features and chemical equilibrium. This paper presents the verification of K1D and its application to model column experiments investigating unimpeded humic colloid borne Am migration. Parmeters for reactive transport simulations were determined for a Gorleben groundwater system of high humic colloid concentration (GoHy 2227). A single set of parameters was used to model a series of column experiments. Model results correspond well to experimental data for the unretarded humic borne Am breakthrough.     

黄麻纤维活性炭对亚甲基蓝和甲基橙吸附动力学

以黄麻纤维为原料,采用磷酸活化法制备活性炭。研究黄麻纤维活性炭对亚甲基蓝和甲基橙2种染料的吸附行为。结果表明,采用磷酸制备的活性炭,由于表面含有羧基和含磷官能团等酸性基团,能够促进活性炭对亚甲基蓝的吸附;黄麻纤维活性炭对2种染料的平衡吸附量、初始吸附速率均随着初始浓度的增加而升高;相同条件下,黄麻纤维活性炭对亚甲基蓝的平衡吸附量大于甲基橙;黄麻纤维活性炭对两种染料的吸附行为更符合准二级动力学模型。     

Soil column experiments used as a means to assess transport, sorption, and biodegradation of pesticides in groundwater

Soil column experiments are used to investigate the fate of three pesticides of high, intermediate, and low solubility in groundwater: N- phosphonomethyl glycine (glyphosate); O,O-diethyl-S-[(ethylthio)methyl]phosphorodithioate (phorate); (2,4-dichlorophenoxy)acetic acid (2,4-D). Feed solutions are prepared by adding each pesticide (100 mg/L glyphosate, 50 micro g/L phorate, 50 mg/L 2,4-D) along with conservative tracer, KBr, in synthetic groundwater. The concentration of the pesticides in effluents is detected by ion chromatography (glyphosate, 2,4-D) and GC-FID (phorate). The Br(-) breakthrough curves are employed to estimate the dispersion coefficient and mean pore velocity in each column. Solute transport and reactive models accounting for equilibrium/non-equilibrium sorption and biodegradation are coupled with inverse modeling numerical codes to estimate the kinetic parameters for all pesticides.     

Formation of N-nitrosodimethylamine (NDMA) by ozonation of dyes and related compounds

Formation of N-nitrosodimethylamine (NDMA) by ozonation of commercially available dyes and related compounds was investigated. Ozonation was conducted using a semi-batch type reactor, and ozone concentration in gas phase and the ozone gas flow were 10 mg L(-1) and 1.0 L min(-1), respectively. NDMA was formed by 15 min of ozonation of seven out of eight selected target compounds (0.05 mM) at pH 7. All the target compounds with N,N-dimethylamino functions were NDMA precursors in ozonation. The lowest and highest NDMA concentrations after ozonation of the target compounds were 13 ng L(-1) for N,N-dimethylformamide (DMF) and 1600 ng L(-1) for N,N-dimethyl-p-phenylenediamine (DMPD), respectively. NDMA concentrations after 15 min of ozonation of 0.05 mM methylene blue (MB) and DMPD increased with an increase in pH in its range of 6-8. The effects of coexisting compounds on NDMA concentrations after 15 min of ozonation of 0.05 mM MB and DMPD were examined at pH 7. NDMA concentrations after ozonation of MB and DMPD increased by the presence of 0.05 mM (0.7 mg L(-1) as N) nitrite (NO(2)(-)); 5000 ng L(-1) for MB and 4000 ng L(-1) for DMPD. NDMA concentration after MB ozonation decreased by the presence of 5mM tertiary butyl alcohol (TBA), a hydroxyl radical (HO.) scavenger, but that after DMPD ozonation was increased by the presence of TBA. NDMA concentrations after ozonation of MB and DMPD were not affected by the presence of 0.16 mM (5.3 mg L(-1)) hydrogen peroxide (H(2)O(2)). When 0.05 mM MB and DMPD were added to the Yodo and Tone river water samples, NDMA concentrations after 15 min of their ozonation at pH 7 increased compared with those in the case of addition to ultrapure water samples.