表面活性剂冲洗法治理非水卡流体污染多相流研究进展

表面活性剂冲洗法是一种治理土壤与地下水非水相流体（NAPLs）污染的有效技术。在简要介绍表面活性剂冲洗法去除作用机理的基础上，总结了近些年来与表面活性剂冲洗法多相流相关的国内外试验研究和模型研究成果，主要包括表面活性剂作用所引起的混溶驱替和不混溶驱替多相流问题，并指出目前研究中存在的问题和进一步探讨的方向。     

表面活性剂冲洗修复多氯联苯污染土壤多相流研究

多氯联苯(PCBs)是一种具有持久性、抗生物降解性、脂肪溶性和明显的生物毒性等特性的持久性有机污染物,PCBs在土壤中难于准确定位、难被分解和强烈吸附,去除土壤中PCBs比较困难.表面活性剂冲洗法可以通过提高PCBs溶解度和降低水-PCBs界面张力来实现PCBs从土壤中去除;表面活性剂冲洗PCBs污染土壤涉及气相、水相、NAPLs相和固相等物质,是多相共存并相互发生作用的过程,发生相对渗透率、饱和度和毛细压力的变化;另外,为研究表面活性剂冲洗土壤中PCBs的去除机理,并降低PCBs对研究人员的危害,采用微观孔隙结构网络模型是一种较新颖的和效果显著的研究方法.开展表面活性剂冲洗PCBs污染土壤多相流研究,可以为PCBs污染场地修复提供理论基础和实验支持,并促进我国POPs履约工作的顺利进行.     

鼠李糖脂对苯系物污染含水层的修复效果研究

通过模拟污染介质的静态脱附实验和一维模拟柱冲洗实验，对比了鼠李糖脂、Tween-80、TX-100对苯的修复效果，筛选出最优表面活性剂进行实际污染土样修复，确定最佳修复技术参数。结果表明：3种表面活性剂对苯的脱附效果为鼠李糖脂>Tween-80>TX-100。采用鼠李糖脂淋洗液进行实际污染土样动态冲洗修复时，鼠李糖脂质量分数宜为0.20%,冲洗流速不宜超过14.4 mL/d,淋洗液冲洗量宜为4倍孔隙体积(PV),在此条件下苯的出流质量浓度最低可达到0.29 mg/L。在实际污染场地修复应用时，修复后应持续注入2倍PV以上的清水冲洗出残留污染物和修复药剂，研究结果可为苯系物污染含水层的表面活性剂修复提供理论指导和技术支撑。     

一株生物表面活性剂产生菌的筛选鉴定及其特性

利用蓝色凝胶平板筛选法,从华北某油田受污染的土壤中分离筛选得到1株优良的生物表面活性剂产生菌H1.通过生理生化特征及16S rRNA基因序列相似性分析,将其鉴定为肺炎克雷伯氏菌(Klebsiella pneumoniae).薄层层析和红外光谱分析表明,该菌株所产生物表面活性剂为磷脂类生物表面活性剂.对其所产生物表面活性剂的稳定性进行研究,并考察影响该生物表面活性剂合成的因素.稳定性实验显示,该生物表面活性剂可耐受90℃的高温,对pH有较广泛的适应性(pH6.5～11.0),NaCl浓度对其生物活性影响不大.以蔗糖为碳源,硝酸铵为氮源,初始pH 6.5 ～7.0,30℃的培养条件有利于该生物表面活性剂的合成,生物表面活性剂的产量可达0.742 g/L.该研究成果可为原油的驱油降黏提供有效的菌源和理论依据.     

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。     

淋洗法去除城市生活垃圾堆肥中重金属

采用淋洗法研究了淋洗剂酸度、螯合剂与表面活性剂对生活垃圾堆肥中重金属的去除效果.结果表明,淋洗剂的酸度对堆肥中重金属的淋出效果不明显,螯合剂与表面活性剂的影响较为显著.随着螫合剂、表面活性剂浓度增加,Mn、Zn和Cu的淋出量有增加的趋势,当DL-苹果酸、柠檬酸浓度为30 mmol/L,Mn的淋出量分别为对照的87和22...     

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     

石油降解菌XD-1产表面活性剂的性能

从含油废水中筛选分离到1株原油降解菌XD-1,鉴定为假单胞菌（Pseuomonas sp.）.初步实验表明菌XD-1具有较强的产表面活性剂乳化原油的作用,对该菌的产表面活性剂性能进行了研究.实验证明,菌XD-1所产表面活性剂为脂肽类物质,菌在生长对数期产表面活性剂,表面活性剂的产生为生长相关型;充足的碳源是产表面活性剂的必需条件,菌利用原油为碳源时能持续大量地产表面活性剂;原油和尿素为产表面活性剂的最适碳源和氮源,菌XD-1产表面活性剂的最佳营养培养基组成为葡萄糖10 g,尿素4 g,磷酸二氢钾1 g,微量元素液4 mL,水1 L,pH 8.0.     

石油降解菌XD-1产表面活性剂的性能

从含油废水中筛选分离到1株原油降解菌XD-1,鉴定为假单胞菌(Pseuomonas sp.).初步实验表明菌XD-1具有较强的产表面活性剂乳化原油的作用,对该菌的产表面活性剂性能进行了研究.实验证明,菌XD-1所产表面活性剂为脂肽类物质,菌在生长对数期产表面活性剂,表面活性剂的产生为生长相关型;充足的碳源是产表面活性剂的必需条件,菌利用原油为碳源时能持续大量地产表面活性剂;原油和尿素为产表面活性剂的最适碳源和氮源,菌XD-1产表面活性剂的最佳营养培养基组成为葡萄糖10 g,尿素4 g,磷酸二氢钾1 g,微量元素液4 mL,水1 L,pH 8.0.     

汽车尾气净化催化剂涂层改性研究

汽车尾气净化催化剂的净化转化效果及其耐久性,与催化剂涂层的涂覆量以及涂层和载体的结合强度密切相关.本文研究了几种不同类型表面活性剂对浆料固体含量、涂层涂覆量以及涂层结合强度的影响.研究结果表明,不使用表面活性剂时,30%为最佳的固体含量;在使用表面活性剂的情况下,浆料的固体含量可以提高至35%.非离子型表面活性剂有助于提高催化剂涂层涂覆量,而使用离子型表面活性剂的浆料球磨过程中产生大量泡沫,无法涂覆.使用非离子型表面活性剂的催化剂涂层的结合强度最好.     

Biosurfactant-enhanced solubilization of NAPL mixtures

Remediation of nonaqueous phase liquids (NAPLs) by conventional pump-and-treat methods (i.e., water flushing) is generally considered to be ineffective due to low water solubilities of NAPLs and to mass-transfer constraints. Chemical flushing techniques, such as surfactant flushing, can greatly improve NAPL remediation primarily by increasing the apparent solubility of NAPL contaminants. NAPLs at hazardous waste sites are often complex mixtures. However, the equilibrium and nonequilibrium mass-transfer characteristics between NAPL mixtures and aqueous surfactant solutions are not well understood. This research investigates the equilibrium solubilization behavior of two- and three-component NAPL mixtures (containing akylbenzenes) in biosurfactant solutions. NAPL solubilization is found to be ideal in water (i.e., obeys Raoult's Law), while solubilization in biosurfactant solutions was observed to be nonideal. Specifically, the relatively hydrophobic compounds in the mixture experienced solubility enhancements that were greater than those predicted by ideal enhanced solubilization theory, while the solubility enhancements for the relatively hydrophilic compounds were less than predicted. The degree of nonideality is shown to be a nonlinear function of the NAPL-phase mole fraction. Empirical relationships based on the NAPL-phase mole fraction and/or micelle-aqueous partition coefficients measured in single-component NAPL systems are developed to estimate values for the multicomponent partition coefficients. Empirical relationships that incorporate both the NAPL-phase mole fraction and single-component partition coefficients yield much improved estimates for the multicomponent partition coefficient.     

颗粒层中非水相液体污染物冲洗排出速度的数值模拟简

在进行污染土壤的冲洗修复时,模型模拟是极具优势的预测净化效果的方法。本研究分别采用5种粒径的球形玻璃微珠模拟实际土壤,实验考察了玻璃微珠颗粒层中水和非水相液体的排出速度,给出了颗粒层中液含率分布函数,以及最大和最小颗粒层孔隙直径的定义,建立了一个描述颗粒层中水和非水相液体排出速度的多孔介质孔隙毛细管束模型。使用构建的模型模拟水和异辛烷在颗粒层中的排出速度,模拟结果与实验数据有很好的一致性,模型预测结果的平均相对误差小于6.4%,特别是对粒径较小颗粒层,预测的准确性更高。模型可作为进一步研究在非水相液体饱和土壤水冲洗修复时,水和非水相液体排出速度和修复效果的基础。     

Anionic surfactant remediation of soil columns contaminated by nonaqueous phase liquids

A variety of column experiments have been completed for the purpose of selecting and evaluating suitable surfactants for remediation of nonaqueous phase liquids (NAPLs). The various NAPLs tested in the laboratory experiments were tetrachloroethylene (PCE), trichloroethylene (TCE), jet fuel (JP4) and a dense nonaqueous phase liquid from a site at Hill Air Force Base, UT. Both Ottawa sand and Hill field soil were used in these experiments. Surfactant candidates were first screened using phase behavior experiments and only the best ones were selected for the subsequent column experiments. Surfactants which showed high contaminant solubilization, fast coalescence times, and the absence of liquid crystal phases and gels during the phase behavior experiments were tested in soil column experiments. The primary objective of the soil column experiments was to identify surfactants that recovered at least 99% of the contaminant. The secondary objective was to identify surfactants that show low adsorption and little or no loss of hydraulic conductivity during the column experiments. Results demonstrated that up to 99.9% of the contaminants were removed as a result of surfactant flooding of the soil columns. The addition of xanthan gum polymer to the surfactant solution was shown to increase remediation efficiency as a lower volume of surfactant was required for recovering a given volume of NAPL. Based on these experimental results, guidelines for designing highly efficient and robust surfactant floods have been developed and applied to a field demonstration.     

Effects of source zone heterogeneity on surfactant-enhanced NAPL dissolution and resulting remediation end-points

The effectiveness of removal of nonaqueous phase liquids (NAPLs) from the entrapment source zone of the subsurface has been limited by soil heterogeneity and the inability to locate all entrapped sources. The goal of this study was to demonstrate the uncertainty of degree of source removal associated with aquifer heterogeneity. In this demonstration, source zone NAPL removal using surfactant-enhanced dissolution was considered. Model components that simulate the processes of natural dissolution in aqueous phase and surfactant-enhanced dissolution were incorporated into an existing code of contaminant transport. The dissolution modules of the simulator used previously developed Gilland-Sherwood type phenomenological models of NAPL dissolution to estimate mass transfer coefficients that are upscaleable to multidimensional flow conditions found at field sites. The model was used to simulate the mass removal from 10 NAPL entrapment zone configurations based on previously conducted two-dimensional tank experiments. These entrapment zones represent the NAPL distribution in spatially correlated random fields of aquifer hydraulic conductivity. The numerical simulations representing two-dimensional conditions show that effectiveness of mass removal depends on the aquifer heterogeneity that controls the NAPL entrapment and delivery of the surfactant to the locations of entrapped NAPLs. Flow bypassing resulting from heterogeneity and the reduction of relative permeability due to NAPL entrapment reduces the delivery efficiency of the surfactant, thus prolonging the remediation time to achieve desired end-point NAPL saturations and downstream dissolved concentrations. In some extreme cases, the injected surfactant completely bypassed the NAPL source zones. It was also found that mass depletion rates for different NAPL source configurations vary significantly. The study shows that heterogeneity result in uncertainties in the mass removal and achievable end-points that are directly related to dissolved contaminant plume development downstream of the NAPL entrapment zone.     

Influence of surfactant sorption on the removal of phenanthrene from contaminated soils

Laboratory column flushing experiments were conducted to remove phenanthrene from contaminated soils by Triton X-100 (TX100) with an aim to investigating the effect of surfactant sorption on the performance of surfactant-enhanced remediation process. The effluent concentration of phenanthrene from soil columns showed strong dependence on the sorption breakthrough curves of TX100. The removal of phenanthrene from contaminated soils was enhanced only when the sorption breakthrough of TX100 occurred and the influent concentration of TX100 was greater than the critical enhanced flushing concentration (CEFC). The sorption of surfactant onto soils and the subsequent partitioning of contaminants into soil-sorbed surfactant had a significant effect on the solute equilibrium distribution coefficient (KD) and thus the flushing efficiency for phenanthrene. A model was developed to predict KD and CEFC values for simulating the performance of surfactant-enhanced flushing for contaminated soils. These results are of practical interest in developing effective and safe surfactant-enhanced remediation technologies.     

A micromodel analysis of factors influencing NAPL removal by surfactant foam flooding

A methodology to study the trichloroethylene (TCE) and dodecane removal in porous media by surfactant foams (SF) was presented by using etched-glass micromodels. The purpose of this work was to systematically evaluate the impact of various physicochemical factors such as gas fraction (GF), surfactant concentration, pore structure and nonaqueous phase liquid (NAPL) types on NAPL removal during SF flooding. The TCE displacement by SF was dependent on the gas fraction of SF. Low GFs (50% and 66%) were more efficient for TCE removal and sweep efficiencies than a high GF (85%). An increase in TCE removal was observed with increasing surfactant concentration at a fixed GF. TCE removal by SF flooding appeared to be dependent more to the value of Capillary number rather than to the concentration of surfactant solution. The effect of the pore heterogeneity was evaluated by employing two different types of micromodels. The Capillary number is an important parameter in the determination of sweep efficiency or gas saturation of SF in a nonhomogeneous porous medium. However, the TCE removal from a nonhomogeneous porous medium may not be associated with sweep efficiency. The initial configuration of residual TCE blobs in a nonhomogeneous porous medium would also be influential in displacing TCE. Sweep efficiencies and pressure responses of two NAPL systems (TCE and dodecane) were monitored to evaluate foam stability when the foam contacts the NAPLs. Stable foam contacting with TCE is implied, while it appears that dodecane cause the SF to collapse. All results indicate that the Capillary number (a ratio of viscous forces to capillary forces) is the most important parameter for TCE removal by SF flooding. Micromodel visualizations of water, surfactant and SF floods were showed and also discussed.     

Triton X-100在土壤颗粒上的吸附特征研究

采用平衡振荡法,研究了砂土对非离子表面活性剂Triton X-100的吸附特征。结果表明,砂颗粒对Triton X-100的吸附能力总体较低,单位吸附含量均＜1.1 mg/g;砂颗粒吸附Triton X-100过程中存在显著的吸附剂浓度效应,砂颗粒上Triton X-100含量随着固液比（吸附剂浓度）的增大而减小;吸附容量q_m与平衡常数K_L值随固液比变化而变化,Langmuir方程适用范围是起始浓度C₀相对较小的固液吸附体系;0.5～1 mm石英砂的吸附能力略＞0.2～0.5 mm石英砂,0.5～1 mm和0.2～0.5 mm石英砂吸附Triton X-100变化特征具有显著的一致性,采用高斯拟合模型可以反映出石英砂吸附Triton X-100的变化规律,相关系数R²均＞0.98。     

Effect of pH control at the anode for the electrokinetic removal of phenanthrene from kaolin soil

Polycyclic aromatic hydrocarbon (PAH)-contaminated soils exist at numerous sites, and these sites may threaten public health and the environment because many PAH compounds are toxic, mutagenic, and/or carcinogenic. PAHs are also hydrophobic and persistent, so conventional remediation methods are often costly or inefficient, especially when the contaminants are present in low permeability and/or organic soils. An innovative technique, electrokinetically enhanced in situ flushing, has the potential to increase soil-solution-contaminant interaction and PAH removal efficiency for low permeability soils; however, the electrolysis reaction at the anode may adversely affect the remediation of low acid buffering capacity soils, such as kaolin. Therefore, the objective of this study was to improve the remediation of low acid buffering soils by controlling the pH at the anode to counteract the electrolysis reaction. Six bench-scale electrokinetic experiments were conducted, where each test employed one of three different flushing solutions, deionized water, a surfactant, or a cosolvent. For each of these solutions, tests were performed with and without a 0.01 M NaOH solution at the anode to control the pH. The test using deionized water with pH control generated a higher electroosmotic flow than the equivalent test performed without pH control, but the electroosmotic flow difference between the surfactant and cosolvent tests with and without pH control was minor compared to that observed with the deionized water tests. Controlling the pH was beneficial for increasing contaminant solubilization and migration from the soil region adjacent to the anode, but the high contaminant concentrations that resulted in the middle or cathode soil regions indicates that subsequent changes in the soil and/or solution chemistry caused contaminant deposition and low overall contaminant removal efficiency.     

Enhanced naphthalene solubility in the presence of sodium dodecyl sulfate: effect of critical micelle concentration

Surfactants can increase the solubility of non-polar compounds, and have been applied in areas such as soil washing and treatment of non-aqueous phase liquids (NAPLs). This investigation explored the feasibility of removing vapor phase polycyclic aromatic hydrocarbon (PAH) from gases using an anionic surfactant. The solubility of vapor phase naphthalene was measured herein using gas chromatograph (GC) with a photon ionization detector (PID). The measurement results indicated that surfactant molecules were not favorable to micelle formation when temperatures increased from 25 degrees C to 50 degrees C. Regardless of whether solutions were quiescent or agitated, equilibrium naphthalene apparent solubility increased linearly with surfactant concentrations exceeding critical micelle concentration (CMC). The pH effects on naphthalene apparent solubility were small. Agitation increased naphthalene apparent solubility and lumped mass transfer coefficients. Furthermore, lumped mass transfer coefficients decreased with increasing surfactant concentration owing to increase in interfacial resistance and viscosity and decreased spherical micelle diffusion coefficients. Finally, the net absorption rate increased because the solubilization effects of micelles exceeded the reduction effects of mass transfer coefficient above the CMC. The enhanced naphthalene apparent solubility from the addition of surfactant can be expressed by an enrichment factor (EF). The EF value of naphthalene for the surfactant solution at 0.1 M with agitation at 270 rpm relative to quiescent water could reach 18.6. This work confirms that anionic surfactant can improve the removal efficiency of hydrophobic organic compound (HOC) from the gas phase.