胶团强化超滤法(MEUF)去除废水中氯苯的研究

研究了3种单一表面活性剂十二烷基硫酸钠(SDS)、十六烷基三甲基溴化铵(CTMAB)、聚氧乙烯失水山梨脂肪酸酯醇醚(TW80)和混合表面活性剂TW80-SDS对氯苯(CB)的强化超滤,以期为有机废水胶团强化超滤技术提供参考。结果表明,进料液静置时间对去除率无显著影响,而振荡时间在1 h后对去除率影响不大。氯苯的去除率随进料液中表面活性剂浓度的增大而增大,单一的表面活性剂对氯苯的去除效果顺序为TW80CTMABSDS,且表面活性剂对氯苯的去除效果与表面活性剂的临界胶束浓度值(CMC)、亲水-亲油平衡值(HLB)呈负相关。阴-非混合表面活性剂TW80-SDS对氯苯的去除效果明显强于单一的SDS,且去除率随着非离子表面活性剂质量分数的增加而增加。渗透通量随着进料液中表面活性剂浓度的增加而下降,单一表面活性剂种类对渗透通量的影响顺序为SDSTW80CTMAB,混合表面活性剂中随着非离子表面活性剂质量分数的增加而渗透液的渗透通量越低。     

胶束强化超滤去除水中双酚A

采用截留分子量(MWCO)为5000 Dalton、1000 Dalton的聚砜超滤膜,MWCO为1 kDa的再生纤维素超滤膜;采用十二烷基苯磺酸钠(SDBS)、曲拉通100(TritonX-100)、吐温80(Tween-80)、烷基多苷(APG)为表面活性剂,用胶团强化超滤工艺去除水中双酚A。研究了不同材质和截留分子量的超滤膜、表面活性剂浓度、膜操作压力、溶液pH和溶液中电解质等因素对该工艺的影响。结果表明,SDBS对双酚A有较好的去除效果,去除率在80%以上。在H+和Na+存在的条件下,双酚A的截留率增加,透过液中SDBS浓度降低。SDBS与非离子表面活性剂的复配可以提高双酚A截留率,降低透过液中SDBS的浓度,复配效果优劣顺序为Tween-80TritonX-100APG。     

醇对柴油微乳体系性能的影响

采用AOT为表面活性剂,不同碳链长度正构醇为助表面活性剂,通过稀释法制备了AOT/柴油/正构醇/水微乳体系。考察了醇与表面活性剂的质量比(r)和正构醇的碳链长度对柴油微乳体系的影响,对不同条件下制备的微乳体系的电导率(δ)、界面张力(γ)及运动粘度(μ)进行了表征。结果表明,采用正丁醇时,微乳体系会出现渗滤现象。采用其他醇时,微乳体系的最大增溶水量(W0)随碳链长度增加而减小,随r增大先增大后减小;随增溶水量(W)增加,δ增大直至达到稳定,γ减小,μ增大;随醇碳链长度增大,δ减小,γ、μ增大;随r增大,δ增大,γ、μ减小。采用正戊醇(r=0.4)时,微乳体系的W0最大,γ、μ均较小,柴油微乳液体系的性能较佳。     

表面活性剂对黄土中石油污染物的解吸影响研究

研究了用表面活性剂去除黄土中柴油类污染物。选用阴离子表面活性剂十二烷基苯磺酸钠和十二烷基硫酸钠 (LAS和SDS)和阳离子表面活性剂十六烷基三甲基溴化铵 (CTAB)对污染的土壤进行解吸实验 ,表明阴离子表面活性剂浓度从 0 .1%增加到 1.0 %时 ,其柴油的去除率可达 2 0 % ,而阳离子表面活性剂去除作用不甚明显。利用摩尔增溶比MSR值求得LAS和SDS的logKm 值为 4.5 5 2和 3 .63 0 ,这和理论的计算值很接近     

表面活性剂改性4A分子筛对Cr(VI)的吸附行为

采用浸渍法对4A分子筛进行表面改性,通过引入阳离子表面活性剂,使4A分子筛表面附着季铵型阳离子,并与反离子Br-形成"阴离子交换膜",从而促使更多的Cr(VI)阴离子通过离子交换吸附到改性4A分子筛上,通过X-射线衍射(XRD)和傅里叶变换红外光谱(FTIR)对样品的物相结构和组成进行表征分析。研究表明,表面活性剂的类型和疏水碳氢链结构会影响4A分子筛的吸附能力,十八烷基三甲基溴化铵(OTAB)碳氢链长,在分子筛表面形成的双分子层密,对Cr(VI)的吸附量最大。采用准一级、准二级、Elovich和Bangham动力学模型对六价铬的吸附数据进行拟合,其中准一级动力学方程最符合十八烷基三甲基溴化铵改性分子筛的吸附行为。同时,分别从Langmuir和Redlich-Peterson等温吸附模型获得六价铬的最大吸附量为13.98 mg/g,且改性分子筛以均一表面吸附为主。     

表面活性剂CMC对石油烃污染土壤的增溶

研究了表面活性剂羧甲基纤维素钠(carboxyl methyl cellulose,CMC)对土壤中石油污染物的增溶作用。通过批实验,对比研究了CMC和十二烷基苯磺酸钠SDBS 2种表面活性剂的增溶效果,探究了CMC浓度、pH、盐度及回用次数对土壤中石油烃增溶效果的影响。研究结果表明,当CMC浓度为0.5%,增溶时间为24 h时,对TPHs浓度为17 695 mg·kg~(-1)的污染土样,TPHs洗脱率高达60%以上。碱性环境有利于石油烃的洗脱,酸性体系会抑制石油烃的洗脱;增溶作用随盐度的增大而显著增大。在利用CMC对污染土壤进行增溶洗脱时,对于TPHs高浓度污染土壤,可以选择将其洗脱液回用1次或者2次;对于TPHs较低浓度污染土壤,可以选择将其洗脱液回用于较高浓度的污染土壤。     

两种生物表面活性剂对污染塿土中苯酚的淋洗修复研究

为探讨两种生物表面活性剂皂苷和鼠李糖脂对污染塿土中苯酚的淋洗修复机制,采用批次试验方法,初步探究了塿土对苯酚及两种生物表面活性剂的吸附特征、两种生物表面活性剂在不同淋洗条件(生物表面活性剂浓度、时间、温度)下对塿土中苯酚的淋洗效果。结果表明:(1)塿土对苯酚的吸附量较低,吸附等温线符合Langmuir等温方程;(2)在较低浓度范围,塿土对皂苷和鼠李糖脂的吸附属于单分子层物理吸附,能较好地用Langmuir等温方程拟合;(3)塿土对鼠李糖脂的吸附与其对苯酚的吸附在相同的数量级,在研究鼠李糖脂对塿土中苯酚的淋洗时应予以考虑,塿土对皂苷的吸附与其对苯酚的吸附相比可以忽略;(4)室温(25℃)下,塿土对皂苷和鼠李糖脂两种生物表面活性剂的吸附量最小;(5)两种生物表面活性剂对塿土中苯酚的最佳淋洗条件为:淋洗时间8h,温度25℃,皂苷和鼠李糖脂的质量浓度分别为0.5、0.6g/L;对于轻度污染塿土,两者对苯酚的淋洗率均可达到100.00%,而对中度和重度污染塿土修复效果相对不佳。     

超声辅助烷基糖苷去除电解锰渣中金属离子

以电解锰渣为研究对象,采用淋洗法研究超声辅助非离子型表面活性剂烷基糖苷(APG)对电解锰渣中有害金属的去除效果,为矿渣的无害化处理提供理论基础。水浴振荡实验中探究了反应时间、pH、APG浓度及转速对金属离子去除率的影响,超声辅助水浴振荡实验中优化了超声时间及超声功率2个条件,并用BCR连续提取法对表面活性剂处理前后矿渣中金属的存在形态进行分析。结果表明,在超声功率为450 W、超声时间为40 min的辅助处理下,当淋洗液pH为5.0,APG浓度为80 g·L~(-1),转速为180 r·min~(-1),处理24 h后电解锰渣中Mn、Cd、Co和Ni的去除率分别可达85.17%、78.29%、68.25%和71.34%。且比较表面活性剂处理前后电解锰渣中金属赋存形态发现,APG对不同形态的金属离子的去除能力存在差异,其中以弱酸提取态和可还原态重金属的去除效果最为明显。通过分析可知超声辅助烷基糖苷洗脱是一种有效的电解锰渣中金属离子无害化处理技术,具有环境、经济的双重效益。     

电动力学技术修复苯酚污染土壤的研究

用电动力学技术对苯酚污染砂土的修复进行了实验研究.探讨了苯酚污染砂土电动力学修复的可行性及在不同电场强度下苯酚的迁移特征和机制.研究了采用添加阴离子表面活性剂十二烷基苯磺酸钠(LAS)和控制液(柠檬酸和NaOH)等对迁移效果的影响,以及苯酚在砂土中的迁移和分布规律.实验结果表明,在电场作用下苯酚在砂土中发生富集.在电场强度为2.0V/cm时的苯酚富集效果明显,比在电场强度为0.5 V/cm时苯酚多增加30%,且向阳极的迁移距离增大了12 cm;在阴极添加不同浓度的LAS,苯酚在砂土中的富集效果不同,LAS浓度越大向阳极迁移得越快富集效果越明显,当LAS为0.046 0 mol/L时苯酚最高增加了143%;向阳极添加NaOH,苯酚在阳极区增加了136%,比向阴极添加柠檬酸的效果明显.     

糖脂类生物表面活性剂去除污染含水层中石油烃的研究

研究了糖脂类生物表面活性剂对石油烃的增溶,并将其用于污染含水层中石油烃的去除。结果表明:石油烃溶解度随着糖脂类生物表面活性剂浓度的增大而增大,糖脂类生物表面活性剂质量浓度为1 200mg/L时,石油烃溶解度达10 077.7mg/L;界面张力随着糖脂类生物表面活性剂浓度的增加而减小,糖脂类生物表面活性剂质量浓度为1mg/L时,界面张力为34.3mN/m,糖脂类生物表面活性剂质量浓度为800mg/L时,界面张力为5.2 mN/m。采用糖脂类生物表面活性剂对污染含水层进行清洗处理,在固液比(质量体积比)为1g∶2mL的体系中,糖脂类生物表面活性剂质量浓度为3 000mg/L,120r/min、10℃下振荡12h,石油烃去除率达70.82%。污染含水层柱冲洗结果表明,糖脂类生物表面活性剂质量浓度分别为1 200、3 000mg/L时,10倍孔隙体积的表面活性剂冲洗后,分别从污染砂样中去除41.81%和63.30%的石油烃。     

厌氧—好氧反应系统处理含酚废水的研究

利用好氧污泥转厌氧驯化方法在厌氧复合床内接种培养，处理浓度为1000mg／L左右的含酚废水。研究结果表明，在水力停留时间1d，酚容积负荷1．06kg／（m3·d）的条件下，厌氧复合床内培养出颗粒污泥，处理效果明显提高，本酚去除率达98．7％，COD去除率达98．3％。此时后接一个好氧接触氧化柱，最终出水中检不出酚。     

不同尾水输送方案对尾水水质的影响研究

通过管道实验和明渠实验模拟尾水输送过程,研究不同输送方案对尾水中COD、BOD5、SS、TN、氨氮、TP、DO、雌酮(E1)、辛基酚(OP)、壬基酚(4-n-NP)等指标的去除规律,为徐州市截污导流工程尾水输送方案的选取提供理论依据.结果表明:(1)除DO、TP和SS外,管道输送方案对其他指标的控制能力均优于明渠;管道输送过程中,除SS和TN外,污染物的浓度变化主要发生在0～48 h.(2)在选择管道输送方案的基础上,可以考虑在实际输送时提高流速,缩短尾水在管道中的停留时间.     

Combined biological and photocatalytic treatment for the mineralization of phenol in water

Phenol is degraded by biological treatment, however mineralization requires long time. To decrease the time and operational cost necessary for the mineralization of phenol, an optimum operation condition of the combined biological–photocatalytical treatment was investigated. The mineralization of phenol (50 mg l⁻¹) was conducted in a flow-type biomembrane tank combined with a batch-type TiO₂-suspended photocatalytic reactor. Phenol was degraded biologically to the concentration of 6.8 mg l⁻¹, an effective concentration for further photocatalytic treatment. After the biological treatment, the biotreated phenol was treated photocatalytically to complete the mineralization of phenol. The combined treatment shortened the mineralization time compared to the biological treatment and electric cost compared to the photocatalytic treatment only. The combined treatment may be suitable for a short-time mineralization of phenol in wastewater.     

Application of HYDRUS 1D model for assessment of phenol–soil adsorption dynamics

Laboratory-scale batch, vertical, and horizontal column experiments were conducted to investigate the attenuative capacity of a fine-grained clayey soil of local origin in the surrounding of a steel plant wastewater discharge site in West Bengal, India, for removal of phenol. Linear, Langmuir, and Freundlich isotherm plots from batch experimental data revealed that Freundlich isotherm model was reasonably fitted (R ²?=?0.94). The breakthrough column experiments were also carried out with different soil bed heights (5, 10, and 15 cm) under uniform flow to study the hydraulic movements of phenol by evaluating time concentration flow behavior using bromide as a tracer. The horizontal migration test was also conducted in the laboratory using adsorptive phenol and nonreactive bromide tracer to explore the movement of solute in a horizontal distance. The hydrodynamic dispersion coefficients (D) in the vertical and horizontal directions in the soil were estimated using nonlinear least-square parameter optimization method in CXTFIT model. In addition, the equilibrium convection dispersion model in HYDRUS 1D was also examined to simulate the fate and transport of phenol in vertical and horizontal directions using Freundlich isotherm constants and estimated hydrodynamic parameters as input in the model. The model efficacy and validation were examined through statistical parameters such as the coefficient of determination (R ²), root mean square error and design of index (d).     

Electrochemical destruction of p-chlorophenol and p-nitrophenol -- Influence of surfactants and anode materials

The electrochemical oxidative removal of p-chlorophenol and p-nitrophenol was studied by cyclic voltammetry (CV) and constant current electrolysis on commercially available graphite and titanium substrate insoluble anodes (TSIA). The effect of cationic cetyl trimethylammonium bromide (CTAB), anionic sodium dodecyl sulphate (SDS) and non-ionic polyoxyethylene(23)lauryl ether (Brij-35) surfactants, which prevent adherent film formation on the electrode surface were also studied. CV experiments indicate that p-chlorophenol exhibits a relatively higher tendency for film formation on graphite and that sodium chloride is a better medium for the destruction of phenols. The electrochemical oxidation of phenols under galvanostatic conditions in chloride medium with CTAB enhanced the detoxification process with significantly lower fouling effects on TSIA. The surfactants, however, did not improve phenol removal on graphite under identical experimental conditions. A charge of 2.5F per mol was found to be sufficient to achieve 44-48% removal of phenol on both the electrodes in the absence of the surfactants. A 55-65% removal was achieved in the presence of the cationic surfactant on the TSIA electrode. Phenol was removed as a low molecular weight polymer (MW approximately 4450).     

Leaching of atrazine, metolachlor and diuron in the field in relation to their injection depth into a silt loam soil

A field experiment was conducted on a Calcaric Cambisol soil to study the consequences of the penetration depth and properties of pesticides on the risk of subsequent leaching. Three pesticides with different mobility characteristics and bromide were injected at 30 cm (where soil organic matter (OM) was 2%) and 80 cm (soil OM 0.5%) on irrigated plots without a crop. The migration of injected solutes was assessed for two years by sampling the soil solution using six porous cups installed at 50 and 150 cm depth and by relating solute contents to drainage water flux estimated by the STICS model (Simulateur mulTIdisciplinaire pour les Cultures Standard). Pesticides injected at 30 cm were strongly retained so that no metolachlor or diuron was detected at 50 and 150 cm. The ratio of atrazine peak concentration in the soil solution to concentration in the injected solution (C/C₀) was 1 × 10⁻³ and 0.2 × 10⁻³, respectively, at 50 and 150 cm. When injected at 80 cm, (C/C₀) of atrazine, metolachlor and diuron were 10 × 10⁻³, 1 × 10⁻³ and 0.3 × 10⁻³ at 150 cm, respectively; 1/(C/C₀) was correlated with K_oc values reported from databases. The ratio of drainage volume to the amount of water at field capacity in the soil layer between the injection point at 30 cm and the water sampling level (V/V₀) at 50 and 150 cm was 0.6 and 0.9, respectively, for bromide and 1.6 and 1.0 for atrazine. V/V₀ of the injected solutes at 80 cm was for bromide, atrazine, metolachlor and diuron 0.6, 0.9, 1.2 and 1.7, respectively; pesticide V/V₀ was correlated with K_oc. The retardation factor was a good indicator of migration risk, but tended to overestimate retardation of molecules with high K_oc. Atrazine desorption represented an additional leaching risk as a source of prolonged low contamination. The large variability in soil solution of bromide and pesticide concentrations in the horizontal plane was attributed to flow paths and clods in the tilled soil layer. This heterogeneity was assumed to channel water fluxes into restricted areas and thereby increase the risk of groundwater contamination. The methodology used in the field proves to provide consistent results.     

Chlorination of dibenzofuran and dibenzo-p-dioxin vapor by copper (II) chloride

Dibenzofuran (DF) is formed from phenol and benzene in combustion gas exhaust streams prior to particle collection equipment. Subsequent chlorination at lower temperatures on particle surfaces is a potential source of chlorinated dibenzofuran (CDF). Gas streams containing 8% O₂ and approximately 0.1% DF vapor were passed through particle beds containing copper (II) chloride (0.5% Cu, mass) at temperatures ranging from 200 to 400 °C to investigate the potential for CDF formation during particle collection. Experiment duration was sufficient to provide an excess amount of DF (DF/Cu=3). The efficiency of DF chlorination by CuCl₂ and the distribution of CDF products were measured, with effects of temperature, gas velocity, and experiment duration assessed. Results of a more limited investigation of dibenzo-p-dioxin (DD) chlorination by CuCl₂ to form chlorinated DD (CDD) products are also presented.

The efficiency of DF/DD chlorination by CuCl₂ was high, both in terms of CuCl₂ utilization and DF/DD conversion. Total yields of Cl on CDF/CDD products of up to 0.5 mole Cl per mole CuCl₂ were observed between 200 and 300 °C; this suggests that nearly 100% CuCl₂ was utilized, assuming a conversion of two moles of CuCl₂ to CuCl per mole Cl added to DD/DF. In a short duration experiment (DF/Cu=0.3), nearly 100% DF adsorption and conversion to CDF was achieved. The degree of CDF chlorination was strongly dependent on gas velocity. At high gas velocity, corresponding to a gas–particle contact time of 0.3 s, mono-CDF (MCDF) yield was largest, with yields decreasing with increasing CDF chlorination. At low gas velocity, corresponding to a gas–particle contact time of 5 s, octa-CDF yield was largest. DF/DD chlorination was strongly favored at lateral sites, with the predominant CDF/CDD isomers within each homologue group those containing Cl substituents at only the 2,3,7,8 positions. At the higher temperatures and lower gas velocities studied, however, broader isomer distributions, particularly of the less CDD/CDF products, were observed, likely due to preferential destruction of the 2,3,7,8 congeners.     

Synergetic effects of anodic-cathodic electrocatalysis for phenol degradation in the presence of iron(II)

A novel electrocatalysis method for phenol degradation was described using a β-PbO₂ anode modified with fluorine resin and a Ni–Cr–Ti alloy cathode. In case of air sparging at the cathodic zone, the techniques of anodic–cathodic electrocatalysis (ACEC) and ferrous ion catalyzed anodic–cathodic electrocatalysis (FACEC) in the presence of iron(II) were developed. Both of ACEC and FACEC were more effective than anodic electrocatalysis (AEC). The percentage of phenol eliminated by FACEC could increase by nearly 30% compared with that of AEC, and the current efficiency could reach to 70%. Important operating factors such as ferrous ion concentration, air-sparging rate and applied current were investigated and it was found that such beneficial effects could be achieved at a suitable current and ratio of the concentration of ferrous ion to the air sparged. The mechanism of phenol degradation is proposed to be the generation of hydroxyl radicals concerned with the two electrodes. Results also indicated that the process provided an efficient way to regenerate ferrous ion compared with the conventional Fenton's system.     

Comparison of modified montmorillonite adsorbents. Part I: Preparation,characterization and phenol adsorption

This study concerns with the development of modified montmorillonites as adsorbents for water treatment. Polymeric aluminium and iron intercalated forms of montmorillonites have been prepared in the absence and presence of an alkylammonium cationic surfactant (Hexdecyl-trimethyl-ammonium bromide, HDTMA). Montmorillonites intercalated with polymeric Al, Fe, Fe/Al (2:1 Fe to Al ratio in solution), possess large N2 Brunauer-Emmett-Teller (BET) surface areas. XRD data also shows trace amounts of illite and plagioclase within the clay materials. Montmorillonites intercalated with HDTMA, polymeric Fe/HDTMA, polymeric Al/HDTMA and polymeric Fe/Al/HDTMA (1:1 metal to surfactant molar ratio in solution) undergo some losses of N2 BET surface areas. Preliminary adsorption studies on phenol have shown that polymeric Al/HDTMA- and HDTMA-only-modified montmorillonites possess a good affinity for phenol, whereas the polymeric Al/Fe modified- and starting montmorillonites have little affinity for phenol adsorption.     

Transport of creosote compounds in a large, intact, macroporous clayey till column

The transport in macroporous clayey till of bromide and 25 organic compounds typical of creosote was studied using a large intact soil column. The organic compounds represented the following groups: polycyclic aromatic hydrocarbons (PAHs), phenolic compounds, monoaromatic hydrocarbons (BTEXs), and heterocyclic compounds containing oxygen, nitrogen or sulphur in the aromatic ring structure (NSO-compounds). The clayey till column (0.5 m in height and 0.5 m in diameter) was obtained from a depth of 1–1.5 m at an experimental site located on the island of Funen, Denmark. Sodium azide was added to the influent water of the column to prevent biodegradation of the studied organic compounds. For the first 24 days of the experiment, the flow rate was 219 ml day⁻¹ corresponding to an infiltration rate of 0.0011 m day⁻¹. At this flow rate, the effluent concentrations of bromide and the organic compounds increased very slowly. The transport of bromide and the organic compounds were successfully increased by increasing the flow rate to 1353 ml day⁻¹ corresponding to 0.0069 m day⁻¹. The experiment showed that the transport of low-molecular-weight organic compounds was not retarded relative to bromide. The high-molecular-weight organic compounds were retarded significantly. The influence of sorption on the transport of the organic compounds through the column was evaluated based on the observed breakthrough curves. The observed order in the column experiment was, with increasing retardation, the following: benzene=pyrrole=toluene=o-xylene=p-xylene=ethylbenzene=phenol=benzothiophene=benzofuran<naphthalene<1-methylpyrrole<1-methylnaphthalene=indole=o-cresol=quinoline<3,5-dimethylphenol=2,4-dimethylphenol<acridine<carbazole<2-methylquinoline<fluorene<dibenzofuran<phenanthrene=dibenzothiophene. This order could not be predicted from regularly characteristics as octanol/water-distribution coefficients of the organic compounds but only from experimentally determined data. The results indicate that a thin clayey till cover of the type described in this paper does not protect groundwater against contamination by low-molecular-weight organic compounds.