WO2017012274A1 - 一种同步去除土壤中多氯联苯和重金属的混合洗脱剂及其制备与应用 - Google Patents

一种同步去除土壤中多氯联苯和重金属的混合洗脱剂及其制备与应用 Download PDF

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WO2017012274A1
WO2017012274A1 PCT/CN2015/099287 CN2015099287W WO2017012274A1 WO 2017012274 A1 WO2017012274 A1 WO 2017012274A1 CN 2015099287 W CN2015099287 W CN 2015099287W WO 2017012274 A1 WO2017012274 A1 WO 2017012274A1
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heavy metals
soil
polychlorinated biphenyls
concentration
elution
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French (fr)
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卢桂宁
廖侃
孙国胜
党志
郭楚玲
易筱筠
王霁欣
林青
陈晨咏
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Guangdong Yue Gang Water Supply Co Ltd
South China University of Technology SCUT
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Guangdong Yue Gang Water Supply Co Ltd
South China University of Technology SCUT
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    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K17/00—Soil-conditioning materials or soil-stabilising materials
    • C09K17/14—Soil-conditioning materials or soil-stabilising materials containing organic compounds only

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  • the invention belongs to the technical field of soil pollution remediation, and particularly relates to a mixed eluent for simultaneously removing polychlorinated biphenyls and heavy metals in soil, and preparation and application thereof.
  • the concentration of pollutants is relatively high, and it is usually repaired by chemical elution.
  • Chemical elution technology to repair contaminated soil is through complexation and acid dissolution, so that heavy metals (Cu, Pb, Cd, etc.) are transferred from the solid phase soil to the liquid phase eluent, and then through solubilization and curling So that the hydrophobic organic pollutants (PCBs, PBDEs, etc.) adsorbed on the soil are desorbed from the soil and distributed into the water phase.
  • PCBs, PBDEs, etc. hydrophobic organic pollutants
  • Commonly used surfactants are polyoxyethylene sorbitan monooleate (Tween-80), octyl phenyl polyoxyethylene ether (Turaton X-100), sodium dodecyl benzene sulfonate (SDBS) ), sodium dodecyl sulfate (SDS), cetyltrimethylammonium bromide (CTMAB), ⁇ -cyclodextrin, etc.
  • commonly used heavy metal chelating agents are ethylenediaminetetraacetic acid (EDTA), citric acid , tartaric acid, etc., however, these eluents can only be used to remove hydrophobic organic substances or one of the heavy metals.
  • the Chinese invention patent application with the application number 201210257460.3 discloses an integrated method for groundwater treatment-soil ectopic leaching and repair of contaminated sites, wherein an anionic, nonionic surfactant or a mixture of both surfactants is applied to the soil. DDT and BaP are removed;
  • the Chinese invention patent application No. 201410158901.3 discloses a method for eluting heavy metal contaminated soil, which is mixed with heavy metal contaminated soil to remove heavy metal pollution.
  • the eluent is usually treated with a single object, and it is difficult to achieve simultaneous elution of heavy metals and hydrophobic organic substances, so further development of a composite eluent capable of simultaneously eluting heavy metals and hydrophobic organic substances is required.
  • surfactants such as betaine surfactants and imidazoline surfactants in amphoteric surfactants, saponins in biosurfactants, rhamnolipids, surfactants, etc.
  • Their structure is complex, with both surface-active functions and carboxyl groups in the molecule, which can form complexes with heavy metals.
  • surfactants can achieve simultaneous elution of heavy metals with hydrophobic organics.
  • a method of simultaneous elution of heavy metals and hydrophobic organics by mixing a mixture of two or more eluents in a certain ratio. It may be a combination of a surfactant and a chelating agent, or a combination of two surfactants.
  • Another object of the present invention is to provide a process for the preparation of a mixed eluent for the simultaneous removal of polychlorinated biphenyls and heavy metals from soil.
  • a mixed eluent for simultaneously removing polychlorinated biphenyls and heavy metals in soil prepared by dissolving an active ingredient comprising saponin and Tween 80 (TW-80) in water.
  • the concentration of saponin is 5-20 g/L
  • the concentration of Tween 80 is 5-20 g/L
  • the concentration of saponin is preferably 12 g/L
  • the concentration of Tween 80 is 10 g/ L.
  • the active ingredient further comprises citric acid; the concentration of citric acid is 2-10 g/L, preferably 5 g/L.
  • Saponin a generic term for plant glycosides composed of saponins and sugars, uronic acids or other organic acids, which can form aqueous or colloidal solutions and form soapy foams. It is a biosurfactant that can be used as an emulsifier. Agent, detergent.
  • Tween 80 which is polyoxyethylene (20)-sorbitan monooleate, is a nonionic surfactant that can be used as an emulsifier or detergent.
  • Citric acid a natural organic acid, also known as tannic acid, the chemical name 2-hydroxypropane-1,2,3-tricarboxylic acid, is A commonly used high efficiency heavy metal chelating agent.
  • the above preparation method for simultaneously removing the mixed eluent of polychlorinated biphenyls and heavy metals in the soil comprises the following preparation steps: taking saponin, Tween 80 and citric acid into water, and fully dissolving to obtain the polychlorination in the soil simultaneously A mixed eluent of benzene and heavy metals.
  • the application process is preferably as follows: taking a mixed contaminated soil containing polychlorinated biphenyls and heavy metals, and adding a mixed eluent for simultaneously removing polychlorinated biphenyls and heavy metals in the soil for elution, thereby completing the polychlorinated biphenyls and Repair of heavy metal composite contaminated soil.
  • the concentration of polychlorinated biphenyls in the polychlorinated biphenyls and heavy metal combined contaminated soil is 11.79 mg/kg, the concentration of copper is 5021.63 mg/kg, the concentration of lead is 2092.39 mg/kg, and the concentration of cadmium is 52.86. Mg/kg.
  • the mixed eluent is added in an amount of 2 x 10 4 L of mixed eluent per ton of the contaminated soil.
  • the elution means oscillating elution at a pH of 3 to 7 for 0.5 to 24 hours; preferably, the mixture is vortexed and eluted for 6 hours at a pH of 5.
  • the mixed eluent of the present invention can achieve simultaneous elution of heavy metals and polychlorinated biphenyls, and the elution effect is greatly improved compared to the use of a single eluent;
  • Example 1 is a washing of polychlorinated biphenyls and heavy metals in contaminated soil by the mixed eluent of Example 1 of the present invention; Off rate graph;
  • Example 2 is a graph showing the elution rate of polychlorinated biphenyls and heavy metals in contaminated soil by the mixed eluent of Example 2 of the present invention
  • Example 3 is a graph showing the elution rate of polychlorinated biphenyls and heavy metals in contaminated soil by the mixed eluent of Example 3 of the present invention
  • Example 4 is a graph showing the elution rate of polychlorinated biphenyls and heavy metals in contaminated soil by the mixed eluent of Example 4 of the present invention
  • Figure 5 is a graph showing the elution rate of polychlorinated biphenyls and heavy metals in contaminated soil by the mixed eluent of Example 5 of the present invention
  • Fig. 6 is a graph showing the elution rate of polychlorinated biphenyls and heavy metals in contaminated soils of mixed eluents according to Example 7 of the present invention at different pH values.
  • the heavy metal concentrations in the following examples were determined by the following methods:
  • the measurement was carried out in 3 parallels, and 20 ml of distilled water was used instead of the above supernatant as a blank control.
  • the saponin and the different amounts of Tween 80 were added to the water, and the saponin concentration was 5 g/L and the Tween 80 concentrations were 5 g/L, 8 g/L, 10 g/L, 15 g/L, respectively.
  • a mixed eluent of PCB and heavy metals in the soil was simultaneously removed at 20 g/L.
  • the concentration of polychlorinated biphenyls and heavy metals in the supernatant was determined, and the elution rate was calculated and compared with the elution rate and theoretical value of the saponin solution alone as an eluent.
  • the results are shown in Fig. 1 (in the figure)
  • the dotted line indicates the theoretical value of the elution rate).
  • TW-80 when used alone, part of the TW-80 is adsorbed on the surface of the soil particles due to the action of the surfactant and the soil particles, and the PCBs cannot be sufficiently eluted.
  • saponin When TW-80 is mixed with saponin, saponin is separated from the soil particles by complexation with heavy metals, and then forms a micelle together with TW-80 in solution, prompting more TW-80 to break away.
  • Soil particles on the one hand, better reduce the oil-water interfacial tension, making PCBs easier to remove; on the other hand, when PCBs
  • the molecules enter the micelles formed by TW-80 and saponin, and the solubility of the PCBs in the aqueous phase is improved by the distribution of the micelles to the PCBs, thereby causing the elution of the PCBs.
  • the saponin and the different amounts of Tween 80 were added to the water, and the saponin concentration was 10 g/L and the Tween 80 concentrations were 5 g/L, 8 g/L, 10 g/L, 15 g/L, respectively.
  • a mixed eluent of PCB and heavy metals in the soil was simultaneously removed at 20 g/L.
  • Example 1 The application of the mixed eluent of the present embodiment in repairing contaminated soils of polychlorinated biphenyls and heavy metals is as in Example 1.
  • the concentration of polychlorinated biphenyls and heavy metals in the supernatant was determined, and the elution rate was calculated and compared with the elution rate and theoretical value of the saponin solution alone as an eluent.
  • the results are shown in Fig. 2 (in the figure)
  • the dotted line indicates the theoretical value of the elution rate).
  • the saponin and the different amounts of Tween 80 were added to the water, and the saponin concentration was 12 g/L and the Tween 80 concentrations were 5 g/L, 8 g/L, 10 g/L, 15 g/L, respectively.
  • a mixed eluent of PCB and heavy metals in the soil was simultaneously removed at 20 g/L.
  • Example 1 The application of the mixed eluent of the present embodiment in repairing contaminated soils of polychlorinated biphenyls and heavy metals is as in Example 1.
  • the concentration of polychlorinated biphenyls and heavy metals in the supernatant was determined, and the elution rate was calculated and compared with the elution rate and theoretical value of the saponin solution alone as an eluent.
  • the results are shown in Fig. 3 (in the figure)
  • the dotted line indicates the theoretical value of the elution rate).
  • the saponin and the different amounts of Tween 80 were added to the water, and the saponin concentration was 15 g/L and the Tween 80 concentrations were 5 g/L, 8 g/L, 10 g/L, 15 g/L, respectively. 20g/L synchronous removal of soil A mixed eluent of PCBs and heavy metals in the soil.
  • Example 1 The application of the mixed eluent of the present embodiment in repairing contaminated soils of polychlorinated biphenyls and heavy metals is as in Example 1.
  • the concentration of polychlorinated biphenyls and heavy metals in the supernatant was determined, and the elution rate was calculated and compared with the elution rate and theoretical value of the saponin solution alone as an eluent.
  • the results are shown in Fig. 4 (in the figure)
  • the dotted line indicates the theoretical value of the elution rate).
  • the theoretical and actual values of the elution rates of Cu and Pb are basically Flat, but for Cd, the theoretical value is greater than the actual value, because when only TW-80, TW-80 can elute a small portion of Cd due to the presence of hydroxyl groups, but when TW-80 is mixed with saponin, Then, the complexation of the carboxyl group of the saponin molecule with Cd causes Cd to be eluted, and the elution rate of Cd is substantially the same as the elution rate of Cd when saponin is used alone at the same concentration.
  • the elution rate of PCBs when the concentration of TW-80 is less than or equal to 10g/L, the elution rate of PCBs increases rapidly, the increase is larger, and the difference between the actual value of PCBs elution rate and the theoretical value is larger.
  • the saponin and the different amounts of Tween 80 were added to the water, and the saponin concentration was 20 g/L and the Tween 80 concentrations were 5 g/L, 8 g/L, 10 g/L, 15 g/L, respectively.
  • a mixed eluent of PCB and heavy metals in the soil was simultaneously removed at 20 g/L.
  • Example 1 The application of the mixed eluent of the present embodiment in repairing contaminated soils of polychlorinated biphenyls and heavy metals is as in Example 1.
  • the concentration of polychlorinated biphenyls and heavy metals in the supernatant was determined, and the elution rate was calculated and compared with the elution rate and theoretical value of the saponin solution alone as an eluent.
  • the results are shown in Fig. 5 (in the figure)
  • the dotted line indicates the theoretical value of the elution rate).
  • Saponin, Tween 80 and different amounts of citric acid were added to the water, and the saponin concentration was 12 g/L, the Tween 80 concentration was 10 g/L, and the citric acid concentrations were 2 g/L and 5 g/L, respectively. Simultaneous removal of mixed eluents of polychlorinated biphenyls and heavy metals in the soil at 8g/L and 10g/L.
  • Example 1 The application of the mixed eluent of the present embodiment in repairing contaminated soils of polychlorinated biphenyls and heavy metals is as in Example 1.
  • this implementation considers the elution cost. For example, when the concentration of saponin is 12g/L, the concentration of TW-80 is 10g/L, and the concentration of citric acid is 5g/L, the elution rates for Cu, Pb, Cd and PCBs are 87.86% and 82.52%, respectively. , 94.83% and 80.51%, both reached 80%.
  • Saponin, Tween 80 and citric acid were separately added to water, and fully dissolved to obtain saponin concentration of 12 g / L, Tween 80 concentration of 10 g / L and citric acid concentration of 5 g / L of synchronous removal of polychlorinated soil A mixed eluent of biphenyl and heavy metals.
  • the concentration of saponin is 12 g/L
  • the concentration of TW-80 is 10 g/L
  • the concentration of citric acid is 5 g/L
  • the elution pH is 5, elution of Cu, Pb, Cd and PCBs.
  • the rates were 89.93%, 83.50%, 96.23%, and 81.04%, respectively.
  • Saponin, Tween 80 and citric acid were separately added to water, and fully dissolved to obtain saponin concentration of 12 g / L, Tween 80 concentration of 10 g / L and citric acid concentration of 5 g / L of synchronous removal of polychlorinated soil A mixed eluent of biphenyl and heavy metals.
  • the elution rate of each pollutant increases rapidly.
  • the heavy metal in the reducible state is gradually washed out, and the two surfactants start to separate from the surface of the soil particles to form a gel.
  • Beams that promote the elution of PCBs. 2 to 6 hours the rate of increase of the elution rate of each pollutant slows down, and the equilibrium tends to be balanced at 6 to 24 hours.
  • the oxidizable and residual heavy metals are difficult to wash out, and the saponin complexation is weakened. Start to tend to adsorb in The soil particles are not conducive to the formation of micelles with TW-80, so the rate of increase of the elution rate of PCBs is slowed down.
  • the concentration of saponin was 12g/L
  • the concentration of TW-80 was 10g/L
  • the concentration of citric acid was 5g / L
  • the elution pH of 5, elution time of 6 hours the elution rates of Cu, Pb, Cd and PCBs were 88.32%, 82.75%, 94.89% and 80.56%, respectively.

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  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
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Abstract

本发明属于土壤污染修复技术领域，公开了一种同步去除土壤中多氯联苯和重金属的混合洗脱剂及其制备与应用。所述混合洗脱剂由包括皂素和吐温80的有效成分溶于水中制备而成。该混合洗脱剂可应用于修复多氯联苯和重金属复合污染土壤，其应用步骤如下：取含有多氯联苯和重金属的复合污染土壤，加入本发明的混合洗脱剂进行洗脱，即可完成对多氯联苯和重金属复合污染土壤的修复。本发明的混合洗脱剂的原料来源广泛、价格低廉、绿色环保；而且洗脱效果好、洗脱率高，对复合污染土壤中各污染物的洗脱率均可达到80％以上。

Description

一种同步去除土壤中多氯联苯和重金属的混合洗脱剂及其制备与应用 技术领域
本发明属于土壤污染修复技术领域，具体涉及一种同步去除土壤中多氯联苯和重金属的混合洗脱剂及其制备与应用。
背景技术
当今世界已经进入一个信息化、智能化的时代，电子产品和设备推陈出新、更新换代，造成越来越多旧的电子产品和设备被丢弃淘汰，从而形成巨量的电子垃圾。在电子垃圾中，包含各种电路板、电子原件、塑料外壳等，而电子器件又包含多种贵金属成分，所以电子垃圾中的污染物种类非常多。在电子垃圾的拆解、焚烧过程中，电子垃圾中的铜、铅、镉等重金属和多氯联苯(PCBs)、多溴联苯醚(PBDEs)等持久性有机物进入环境，使得在电子垃圾拆解场地周边土壤中同时具有重金属和疏水性有机物的污染，使得周围的生态环境和人类健康受到严重的影响。
随着经济的快速发展，我国电子废弃物产生的速度十分惊人。据2010联合国环境规划署发布的报告，我国已成为世界第二大电子垃圾生产国。由于技术与设备的不完善，我国目前对于电子垃圾的处理还处于初级的阶段，在广东贵屿、清远等电子垃圾污染严重地，一些家庭小作坊对于废弃的电子产品和设备采取简单的手工拆解方法，再用酸性液体对金属进行置换，这样的方法极容易造成电子垃圾拆解场区环境污染。有研究显示，在电子垃圾拆解场区土壤中，PCBs浓度范围为3.34～458mg/kg，远远超出正常背景值(0.42mg/kg)，而重金 属Cu、Pb、Cd的含量分别达到4850.6mg/kg、1714.5mg/kg和10.5mg/kg，远远超过了国家土壤环境质量标准(GB15618-1995)规定的三级土壤标准。
对于电子垃圾污染土壤，其污染物浓度相对较高，通常使用化学洗脱的方法来对其进行修复。化学洗脱技术修复污染土壤是通过络合作用和酸溶作用，使得重金属(Cu、Pb、Cd等)从固相的土壤转移到液相淋洗液中，再通过增溶作用和卷缩作用，使得吸附在土壤上的疏水性有机污染物(PCBs、PBDEs等)从土壤上解吸下来而分配到水相中。常用的表面活性剂有聚氧乙烯脱水山梨醇单油酸酯(吐温-80)、辛基苯基聚氧乙烯醚(曲拉通X-100)、十二烷基苯磺酸钠(SDBS)、十二烷基硫酸钠(SDS)、十六烷基三甲基溴化铵(CTMAB)、β-环糊精等，常用的重金属螯合剂有乙二胺四乙酸(EDTA)、柠檬酸、酒石酸等，然而这些洗脱剂往往只能针对疏水性有机物或者重金属其中一种污染物起去除作用。如申请号为201210257460.3的中国发明专利申请公开了一种污染场地地下水处理-土壤异位淋洗修复一体化方法，其中应用了阴离子、非离子表面活性剂或两者混合表面活性剂对土壤中的DDT、BaP进行去除处理；申请号201410158901.3的中国发明专利申请公开了一种重金属污染土壤的洗脱方法，采用酸洗脱剂与重金属污染土壤混合，以去除重金属污染。目前常用洗脱剂处理对象单一，难以实现重金属和疏水性有机物的同步洗脱，所以需要进一步开发可以同步洗脱重金属和疏水性有机物的复合洗脱剂。
有一些结构较为特殊的表面活性剂，如两性表面活性剂中的甜菜碱类表面活性剂和咪唑啉类表面活性剂、生物表面活性剂中的皂素、鼠李糖脂、表面活性素等，他们的结构较为复杂，既有表面活性的功能，同时在分子中都存在羧基，可以与重金属形成络合物。理论上这类表面活性剂可以实现重金属与疏水性有机物的同步洗脱。
此外，还有一种方法是通过两种或两种以上的洗脱剂按照一定比例的混合，来实现重金属与疏水性有机物的同步洗脱。可以是表面活性剂与螯合剂的组合，也可以是两种表面活性剂的组合。
目前对于复合污染土壤重金属与多氯联苯的同步洗脱的研究不多，有必要进一步开发新型高效的洗脱剂。
发明内容
为了解决以上现有技术的缺点和不足之处，本发明的首要目的在于提供一种同步去除土壤中多氯联苯和重金属的混合洗脱剂。
本发明的另一目的在于提供上述同步去除土壤中多氯联苯和重金属的混合洗脱剂的制备方法。
本发明的又一目的在于提供上述同步去除土壤中多氯联苯和重金属的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用。
本发明目的通过以下技术方案实现：
一种同步去除土壤中多氯联苯和重金属的混合洗脱剂，由包括皂素和吐温80(TW-80)的有效成分溶于水中制备而成。
所述的混合洗脱剂中，皂素的浓度为5～20g/L，吐温80的浓度为5～20g/L；优选皂素的浓度为12g/L，吐温80的浓度为10g/L。
所述的有效成分还包括柠檬酸；柠檬酸的浓度为2～10g/L，优选为5g/L。
皂素，是由皂苷元和糖、糖醛酸或其他有机酸组成的，能形成水溶液或胶体溶液并能形成肥皂状泡沫的植物糖苷的统称，是一种生物表面活性剂，可用作乳化剂、洗涤剂。
吐温80，即为聚氧乙烯(20)-山梨醇酐单油酸酯，是一种非离子型表面活性剂，可用作乳化剂、洗涤剂。
柠檬酸，天然有机酸，又名枸橼酸，化学名称2-羟基丙烷-1,2,3-三羧酸，是 一种常用的高效重金属螯合剂。
上述同步去除土壤中多氯联苯和重金属的混合洗脱剂的制备方法，包括以下制备步骤：取皂素、吐温80和柠檬酸加入到水中，充分溶解后得到同步去除土壤中多氯联苯和重金属的混合洗脱剂。
上述同步去除土壤中多氯联苯和重金属的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用。
所述的应用过程优选如下：取含有多氯联苯和重金属的复合污染土壤，加入同步去除土壤中多氯联苯和重金属的混合洗脱剂进行洗脱，即可完成对多氯联苯和重金属复合污染土壤的修复。
所述的多氯联苯和重金属复合污染土壤中，含有多氯联苯的浓度为11.79mg/kg，铜的浓度为5021.63mg/kg，铅的浓度为2092.39mg/kg，镉的浓度为52.86mg/kg。
优选的，所述混合洗脱剂的加入量为：每吨复合污染土壤中添加2×104L混合洗脱剂。
所述的洗脱是指在pH为3～7的条件下进行振荡洗脱0.5～24h；优选在pH为5的条件下振荡洗脱6小时。
本发明的制备方法及所得到的产物具有如下优点及有益效果：
(1)本发明的混合洗脱剂可对重金属和多氯联苯实现同步洗脱，且相比使用单一洗脱剂的洗脱效果大大提高；
(2)本发明的混合洗脱剂对复合污染土壤中的重金属Cu、Pb、Cd和多氯联苯的洗脱率分别能达到88.32％、82.75％、94.89％和80.56％。
附图说明
图1为本发明实施例1的混合洗脱剂对污染土壤中多氯联苯和重金属的洗 脱率曲线图；
图2为本发明实施例2的混合洗脱剂对污染土壤中多氯联苯和重金属的洗脱率曲线图；
图3为本发明实施例3的混合洗脱剂对污染土壤中多氯联苯和重金属的洗脱率曲线图；
图4为本发明实施例4的混合洗脱剂对污染土壤中多氯联苯和重金属的洗脱率曲线图；
图5为本发明实施例5的混合洗脱剂对污染土壤中多氯联苯和重金属的洗脱率曲线图；
图6为本发明实施例7的混合洗脱剂在不同pH值条件下对污染土壤中多氯联苯和重金属的洗脱率曲线图。
具体实施方式
下面结合实施例及附图对本发明作进一步详细的描述，但本发明的实施方式不限于此。
以下实施例中重金属浓度通过以下方法测定：
取5mL上清液于20ml容量瓶中，加入蒸馏水定容至刻度线，摇匀后倒入样品瓶中，用原子吸收分光光度仪测定溶液中Cu、Pb、Cd的浓度。
多氯联苯的浓度通过以下方法测定：取10ml上清液于30ml玻璃离心管中，加入20mL萃取剂(正己烷:丙酮＝9:1,V:V)，用聚四氟乙烯垫片盖子盖紧后，放入温度为25℃(±2℃)的恒温震荡培养箱中，以150r/min的转速震荡6小时，离心20min(3500r/min)，取上清液1mL于色谱瓶中，用GC-MS测定洗脱液中的多氯联苯的浓度。
测定采用3个平行，用20ml的蒸馏水代替上述上清液作为空白对照。
实施例1
取皂素和不同量的吐温80分别加入到水中，充分溶解后得到皂素浓度为5g/L、吐温80的浓度分别为5g/L、8g/L、10g/L、15g/L和20g/L的同步去除土壤中多氯联苯和重金属的混合洗脱剂。
本实施例的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用，具体过程如下：
称取1g多氯联苯和重金属复合污染土壤(多氯联苯的浓度为11.79mg/kg，铜的浓度为5021.63mg/kg，铅的浓度为2092.39mg/kg，镉的浓度为52.86mg/kg)到30mL玻璃离心管中，分别加入上述混合洗脱剂20mL，调节pH值为5，用聚四氟乙烯垫片盖子盖紧后，放入温度为25℃(±2℃)的恒温震荡培养箱中，以150r/min的转速震荡24小时后，离心20min(3500r/min)，分离上清液，完成对多氯联苯和重金属复合污染土壤的修复。
测定上清液中的多氯联苯和重金属的浓度，计算洗脱率，并与单独的皂素溶液作为洗脱剂的洗脱率和理论值进行比较，结果如图1所示(图中虚线表示洗脱率的理论值)。
由图1可以看出：当混合洗脱剂中皂素的浓度固定为5g/L时，随着TW-80浓度的增加，Cu、Pb、Cd的洗脱率并没有明显增加，而且理论值与实际值是基本持平状态，说明TW-80的加入并不会影响混合洗脱剂中皂素与土壤重金属的络合作用。而PCBs的洗脱率则随着TW-80的浓度增加而增加，且PCBs洗脱率的理论值小于实际值，这说明皂素与TW-80混合之后，对于PCBs的洗脱有相互促进作用。这是因为当单独使用TW-80时，由于表面活性剂与土壤颗粒的作用，部分的TW-80吸附在土壤颗粒表面，不能充分对PCBs进行洗脱。当TW-80与皂素混合之后，皂素由于与重金属进行络合作用，从土壤颗粒上分离开来，而后又与TW-80在溶液中共同形成胶束，促使更多的TW-80脱离土壤颗粒，一方面，更好的降低油-水界面张力，使得PCBs更易脱除；另一方面，当PCBs 分子进入到TW-80与皂素所形成的胶束中，通过胶束对PCBs的分配作用，提高了其在水相中的溶解度，从而致使PCBs的洗脱去除。
实施例2
取皂素和不同量的吐温80分别加入到水中，充分溶解后得到皂素浓度为10g/L、吐温80的浓度分别为5g/L、8g/L、10g/L、15g/L和20g/L的同步去除土壤中多氯联苯和重金属的混合洗脱剂。
本实施例的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用，具体应用过程如同实施例1。
测定上清液中的多氯联苯和重金属的浓度，计算洗脱率，并与单独的皂素溶液作为洗脱剂的洗脱率和理论值进行比较，结果如图2所示(图中虚线表示洗脱率的理论值)。
实施例3
取皂素和不同量的吐温80分别加入到水中，充分溶解后得到皂素浓度为12g/L、吐温80的浓度分别为5g/L、8g/L、10g/L、15g/L和20g/L的同步去除土壤中多氯联苯和重金属的混合洗脱剂。
本实施例的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用，具体应用过程如同实施例1。
测定上清液中的多氯联苯和重金属的浓度，计算洗脱率，并与单独的皂素溶液作为洗脱剂的洗脱率和理论值进行比较，结果如图3所示(图中虚线表示洗脱率的理论值)。
实施例4
取皂素和不同量的吐温80分别加入到水中，充分溶解后得到皂素浓度为15g/L、吐温80的浓度分别为5g/L、8g/L、10g/L、15g/L和20g/L的同步去除土 壤中多氯联苯和重金属的混合洗脱剂。
本实施例的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用，具体应用过程如同实施例1。
测定上清液中的多氯联苯和重金属的浓度，计算洗脱率，并与单独的皂素溶液作为洗脱剂的洗脱率和理论值进行比较，结果如图4所示(图中虚线表示洗脱率的理论值)。
由图2、图3和图4可以看出：当混合洗脱剂中皂素的浓度固定为10g/L、12g/L和15g/L时，重金属的洗脱率随着皂素浓度的增加而不断增加，但不论皂素浓度是多少，TW-80的加入都几乎不会影响重金属Cu、Pb、Cd的洗脱率变化，Cu、Pb的洗脱率的理论值与实际值都是基本持平的，但对于Cd，理论值大于实际值，这是因为当只有TW-80时，由于羟基的存在，TW-80能洗脱一小部分Cd，但当TW-80与皂素混合后，则主要由皂素分子的羧基与Cd的络合作用致使Cd的洗出，且得到Cd的洗脱率基本与同浓度下单独使用皂素时Cd的洗脱率一致。对于PCBs的洗脱率，当TW-80浓度小于等于10g/L时，PCBs的洗脱率增长较快，增幅较大，且PCBs洗脱率的实际值与理论值之差越来越大，说明TW-80与皂素直接对PCBs的洗脱的相互促进作用越来越明显；而当TW-80浓度大于10g/L时，PCBs洗脱率的实际值依然大于理论值，但是实际值与理论值之差越来越小，说明这个时候TW-80与皂素之间相互促进作用逐渐减小，同时，PCBs的洗脱率也逐渐趋于平衡。
实施例5
取皂素和不同量的吐温80分别加入到水中，充分溶解后得到皂素浓度为20g/L、吐温80的浓度分别为5g/L、8g/L、10g/L、15g/L和20g/L的同步去除土壤中多氯联苯和重金属的混合洗脱剂。
本实施例的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用，具体应用过程如同实施例1。
测定上清液中的多氯联苯和重金属的浓度，计算洗脱率，并与单独的皂素溶液作为洗脱剂的洗脱率和理论值进行比较，结果如图5所示(图中虚线表示洗脱率的理论值)。
由图5可以看出：当混合洗脱剂中皂素的浓度固定为20g/L时，对于重金属的洗脱率与上述浓度时的情况相似，而对PCB的洗脱率，当TW-80浓度小于等于10g/L时，PCBs的洗脱率增长较快，增幅较大，但PCBs洗脱率的实际值与理论值之差越来越小，TW-80与皂素直接对PCBs的洗脱的相互促进作用逐渐减弱；而当TW-80浓度大于10g/L时，PCBs洗脱率逐渐趋于平衡，且实际值小于理论值，说明在这个浓度配比下，皂素与TW-80对于PCBs的洗脱相互之间出现抑制作用，这是由于两种表面活性剂的浓度都过高，使得表面活性剂偏向于吸附在土壤颗粒表面，不利于其对于PCBs的洗脱。
实施例6
取皂素、吐温80和不同量的柠檬酸分别加入到水中，充分溶解后得到皂素浓度为12g/L、吐温80浓度10g/L和柠檬酸浓度分别为2g/L、5g/L、8g/L和10g/L的同步去除土壤中多氯联苯和重金属的混合洗脱剂。
本实施例的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用，具体应用过程如同实施例1。
测定上清液中的多氯联苯和重金属的浓度，计算洗脱率，并与未添加柠檬酸的洗脱剂的洗脱率进行比较，结果如表1所示。
表1 不同浓度柠檬酸的洗脱剂的洗脱率结果
浓度 0g/L 2g/L 5g/L 8g/L 10g/L
Cu 54.35％ 77.61％ 87.86％ 94.12％ 97.38％
Pb 61.13％ 71.84％ 82.52％ 83.26％ 85.97％
Cd 86.33％ 91.58％ 94.83％ 97.08％ 99.33％
PCBs 80.27％ 80.59％ 80.51％ 80.63％ 80.65％
由表1结果可以看出：随着柠檬酸的加入，对于混合洗脱剂对PCBs的洗脱效果并没有影响，这是由于柠檬酸由于分子碳链短，且有多个羧基，是极亲水性的，没有表明活性。而对于Cd的洗脱率，随着柠檬酸的浓度增加而增加，但提升幅度不大，很快就趋于平衡，但洗脱率极高，当柠檬酸浓度增加到10g/L时，Cd洗脱率接近100％。对于Cu和Pb的洗脱率，在没有柠檬酸存在的情况下，主要由于皂素的络合作用，且Pb的洗脱率大于Cu的洗脱率，说明皂素对于Pb的洗脱效果比Cu更好；而加入柠檬酸后，在有机酸与表面活性剂混合的情况下，更促进土壤重金属的释放，因而Cu和Pb的洗脱率都有增加，且由于柠檬酸具有一定的酸溶性和络合作用，因此对于主要以酸可提取态形式存在的Cu有更好的洗脱效果，Cu的洗脱率随着柠檬酸浓度增加而不断增加；对于Pb的洗脱率则由于其残渣态和可氧化态形式存在的较多，因此当柠檬酸浓度从5g/L到10g/L时，Pb的洗脱率趋于平衡。
当柠檬酸浓度大于5g/L时，除了Cu的洗脱率增加幅度较大，对于Pb和Cd的洗脱率提高很微小，对于PCBs洗脱率毫无影响，所以考虑洗脱成本，本实施例当皂素的浓度为12g/L、TW-80的浓度为10g/L、柠檬酸的浓度为5g/L时，对Cu、Pb、Cd和PCBs的洗脱率分别为87.86％、82.52％、94.83％和80.51％，均达到了80％。
实施例7
取皂素、吐温80和柠檬酸分别加入到水中，充分溶解后得到皂素浓度为12g/L、吐温80浓度为10g/L和柠檬酸浓度为5g/L的同步去除土壤中多氯联苯和重金属的混合洗脱剂。
本实施例的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用，具体过程如下：
称取1g多氯联苯和重金属复合污染土壤(多氯联苯的浓度为11.79mg/kg，铜的浓度为5021.63mg/kg，铅的浓度为2092.39mg/kg，镉的浓度为52.86mg/kg)到30mL玻璃离心管中，分别加入上述混合洗脱剂20mL，分别调节pH值为3、4、5、6和7，用聚四氟乙烯垫片盖子盖紧后，放入温度为25℃(±2℃)的恒温震荡培养箱中，以150r/min的转速震荡24小时后，离心20min(3500r/min)，分离上清液，完成对多氯联苯和重金属复合污染土壤的修复。
测定上清液中的多氯联苯和重金属的浓度，计算洗脱率，结果如图6所示。
由图6可以看出：当pH从3到5时，混合洗脱剂对Cu、Pb、Cd的洗脱率并没有明显变化，而当pH从5到7时，Cu、Pb、Cd的洗脱率明显下降，pH从5到7，Cu、Pb、Cd的洗脱率分别从88.32％、82.75％、94.89％下降到52.64％、59.41％、45.27％，这个变化是由于当溶液偏中性时，重金属发生水解，不利于与皂素和柠檬酸发生络合作用，因此洗脱率明显下降。而同样的，当pH从3到5时，PCBs的洗脱率也没有明显变化，但是当pH从5到7时，PCBs的洗脱率稍微下降，pH从5到7，PCBs的洗脱率从80.56％下降到68.33％，这是由于在这个pH范围内，不利于土壤重金属的释放和重金属的络合作用，因此皂素吸附于土壤颗粒表面，不利于与TW-80形成胶束，从而使得PCBs的洗脱率下降。
本实施例当皂素的浓度为12g/L、TW-80的浓度为10g/L、柠檬酸的浓度为5g/L、洗脱pH为5时，对Cu、Pb、Cd和PCBs的洗脱率分别为89.93％、83.50％、96.23％和81.04％。
实施例8
取皂素、吐温80和柠檬酸分别加入到水中，充分溶解后得到皂素浓度为12g/L、吐温80浓度为10g/L和柠檬酸浓度为5g/L的同步去除土壤中多氯联苯和重金属的混合洗脱剂。
本实施例的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用， 具体过程如下：
称取1g多氯联苯和重金属复合污染土壤(多氯联苯的浓度为11.79mg/kg，铜的浓度为5021.63mg/kg，铅的浓度为2092.39mg/kg，镉的浓度为52.86mg/kg)到30mL玻璃离心管中，分别加入上述混合洗脱剂20mL，调节pH值为5，用聚四氟乙烯垫片盖子盖紧后，放入温度为25℃(±2℃)的恒温震荡培养箱中，分别以150r/min的转速震荡洗脱0.5h、1h、2h、4h、6h、12h和24h后，离心20min(3500r/min)，分离上清液，完成对多氯联苯和重金属复合污染土壤的修复。
测定上清液中的多氯联苯和重金属的浓度，计算洗脱率，结果如表2所示。
表2 不同洗脱时间的洗脱率结果
时间(h) 0.5 1 2 4 6 12 24
Cu 72.41％ 76.29％ 84.13％ 88.07％ 88.32％ 89.56％ 89.93％
Pb 53.22％ 67.27％ 75.35％ 81.68％ 82.75％ 83.28％ 83.50％
Cd 81.45％ 89.64％ 93.29％ 94.54％ 94.89％ 96.11％ 96.23％
PCB 56.87％ 65.32％ 73.19％ 78.25％ 80.56％ 80.88％ 81.04％
由表2可以看出：在洗脱半小时后，对于Cu、Pb、Cd和PCBs的洗脱率就达到一定的水平，Cu、Pb、Cd和PCBs的洗脱率分别为72.41％、53.22％、81.45％和56.87％，在这个时间内，主要洗出的是容易去除的酸可提取态形式的三种重金属，而对于PCBs的洗脱，由于两种表面活性剂还吸附于土壤颗粒表面，还没相互形成胶束，因此PCBs的洗脱率还不高。而随着洗脱时间增加，从0.5到2小时，各污染物洗脱率迅速增加，此时，可还原态的重金属也逐渐被洗出，而两种表面活性剂开始脱离土壤颗粒表面形成胶束，促进PCBs的洗脱。2到6小时，各污染物洗脱率增加速度减缓，而6到24小时则基本趋于平衡，此时，可氧化态和残渣态重金属较难洗出，而皂素的络合作用减弱，开始趋向于吸附在 土壤颗粒，则不利于与TW-80形成胶束，从而PCBs的洗脱率增加速度减缓。
由于6小时之后各污染物的洗脱率提高幅度很小，综合考虑洗脱成本，本实施例当皂素的浓度为12g/L、TW-80的浓度为10g/L、柠檬酸的浓度为5g/L、洗脱pH为5，洗脱时间为6小时，对Cu、Pb、Cd和PCBs的洗脱率分别为88.32％、82.75％、94.89％和80.56％。
上述实施例为本发明较佳的实施方式，但本发明的实施方式并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。

Claims (10)

  1. 一种同步去除土壤中多氯联苯和重金属的混合洗脱剂，其特征在于：由包括皂素和吐温80的有效成分溶于水中制备而成。
  2. 根据权利要求1所述的一种同步去除土壤中多氯联苯和重金属的混合洗脱剂，其特征在于：所述皂素的浓度为5～20g/L，吐温80的浓度为5～20g/L。
  3. 根据权利要求2所述的一种同步去除土壤中多氯联苯和重金属的混合洗脱剂，其特征在于：所述皂素的浓度为12g/L，吐温80的浓度为10g/L。
  4. 根据权利要求1所述的一种同步去除土壤中多氯联苯和重金属的混合洗脱剂，其特征在于：所述的有效成分还包括柠檬酸，柠檬酸的浓度为2～10g/L。
  5. 根据权利要求4所述的一种同步去除土壤中多氯联苯和重金属的混合洗脱剂，其特征在于：所述柠檬酸的浓度为5g/L。
  6. 权利要求4或5所述的一种同步去除土壤中多氯联苯和重金属的混合洗脱剂的制备方法，其特征在于包括以下制备步骤：取皂素、吐温80和柠檬酸加入到水中，充分溶解后得到同步去除土壤中多氯联苯和重金属的混合洗脱剂。
  7. 权利要求1～5任一项所述的一种同步去除土壤中多氯联苯和重金属的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用。
  8. 根据权利要求7所述的一种同步去除土壤中多氯联苯和重金属的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用，其特征在于所述的应用过程如下：取含有多氯联苯和重金属的复合污染土壤，加入同步去除土壤中多氯联苯和重金属的混合洗脱剂进行洗脱，即可完成对多氯联苯和重金属复合污染土壤的修复。
  9. 根据权利要求8所述的一种同步去除土壤中多氯联苯和重金属的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用，其特征在于：所述的多氯联苯和重金属复合污染土壤中，含有多氯联苯的浓度为11.79mg/kg，铜的浓 度为5021.63mg/kg，铅的浓度为2092.39mg/kg，镉的浓度为52.86mg/kg；所述混合洗脱剂的加入量为：每吨复合污染土壤中添加2×104L混合洗脱剂；所述的洗脱是指在pH为3～7的条件下进行振荡洗脱0.5～24h。
  10. 根据权利要求9所述的一种同步去除土壤中多氯联苯和重金属的混合洗脱剂在修复多氯联苯和重金属复合污染土壤中的应用，其特征在于：所述的洗脱是指在pH为5的条件下振荡洗脱6小时。
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