WO2019010835A1 - 一种利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法 - Google Patents

一种利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法 Download PDF

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WO2019010835A1
WO2019010835A1 PCT/CN2017/104317 CN2017104317W WO2019010835A1 WO 2019010835 A1 WO2019010835 A1 WO 2019010835A1 CN 2017104317 W CN2017104317 W CN 2017104317W WO 2019010835 A1 WO2019010835 A1 WO 2019010835A1
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heavy metal
wastewater
metal ions
surfactant
water
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French (fr)
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李英
张凯
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山东大学
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/58—Treatment of water, waste water, or sewage by removing specified dissolved compounds
    • C02F1/62—Heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

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  • the invention relates to a method for completely removing heavy metal ions in battery plant wastewater by using a water-based foam system, and belongs to the technical field of environmental chemistry.
  • the treatment measures for heavy metal pollution in water can be mainly divided into physical methods, chemical methods, biological methods, etc. according to their mechanism of action.
  • the physical method includes extraction method, adsorption method, ion exchange method, membrane separation, etc., adsorption, concentration and separation without changing the chemical form of heavy metal ions in the wastewater; the method has high efficiency, but has high input cost and large engineering quantity. It is easy to introduce secondary pollution sources and other shortcomings.
  • the biological method mainly removes heavy metal ions in polluted water by the absorption and enrichment of plants and microorganisms. However, due to its long action period and small amount of treatment, plants treated with heavy metal ions are difficult to handle, and the recovery rate of metal ions is low. Short boards also restrict their promotion in industrial applications.
  • the chemical method generally removes heavy metal ions by oxidation, reduction, precipitation, adsorption and inhibition of additives and heavy metal ions.
  • the precipitation method has become the most widely used treatment method in battery plant wastewater treatment because of its good economy and wide application range.
  • the addition of hydroxides, sulfides and chelating agents or complexes which strongly bind to heavy metal ions forms a water-insoluble precipitate with heavy metal ions, thereby purifying the water body.
  • the operation is complicated, the efficiency is not high, and the treatment of precipitates is difficult. If it is not handled properly, it will be easily reactivated, which will cause secondary pollution and it is difficult to meet national emission standards.
  • the present invention provides a method for completely removing heavy metal ions in battery plant wastewater by using a water-based foam system.
  • the invention adopts a green environmentally-friendly specific surfactant to form a water-based foam, and the selected surfactant has electrical interaction or complexation with heavy metal ions such as Pb 2+ and Zn 2+ , and the surfactant molecules are closely related to the metal cation.
  • the amphiphilic adsorption of the surfactant is carried out at the gas-liquid interface, and the heavy metal ions are carried out of the polluted water body by the floating bubbles.
  • the invention has the advantages of simple operation, low cost, low concentration of surfactant, strong adaptability to the complexity of the wastewater of the battery factory, high removal efficiency, suitable for removal of various heavy metal ions, and ensuring by using a green environmentally-friendly surfactant. There is no secondary pollution to the environment.
  • a method for completely removing heavy metal ions in battery plant wastewater by using a water-based foam system including the following steps:
  • the surfactant described in the step (1) is a surfactant having at least one negatively charged polar hydrophilic group and a hydrophobic base carbon chain having a length of from 8 to 24, which is negative.
  • the electrodepositive hydrophilic group is a sulfate group, a sulfonic acid group or a carboxylic acid group.
  • the surfactant further contains an EO, carbonyl or amide group.
  • the surfactant is one or more selected from the group consisting of an alkyl sulfate, a fatty alcohol polyoxyethylene ether sulfate, an alkyl carboxylate or an alkyl polyether carboxylate. mixing.
  • the sulfate group-containing surfactant is sodium lauryl sulfate or a fatty alcohol polyoxyethylene ether sulfate.
  • the carboxylic acid group-containing surfactant is sodium lauryl carboxylate or sodium tridecyl polyether-4-carboxylate.
  • the molar ratio of the surfactant to the total moles of all heavy metal ions in the wastewater in the step (1) is (1 to 30): 1, preferably, the total moles of all heavy metal ions in the surfactant and the wastewater.
  • the molar ratio is (3-15): 1, and most preferably, the molar ratio of the surfactant to the total moles of all heavy metal ions in the wastewater is (5-7):1.
  • the pH of the wastewater in step (1) is 5-11.
  • the flow rate of the blowing gas in the step (2) is 0.1 to 0.7 L/min, and more preferably, the flow rate of the blowing gas is 0.2 to 0.6 L/min.
  • the blowing gas in step (2) is N 2 or air.
  • the bottom of the foam processor in step (2) is filled with a porous medium quartz sand having a porosity of 35-45%, an average pore throat radius of 0.1-10 ⁇ m, and a filling height of 4-7 mm. .
  • the wastewater can be pretreated before the foam separation, that is, the pH of the wastewater is adjusted to weak acid or neutral by adding an appropriate amount of alkali solution, and The resulting precipitate was filtered. If the wastewater does not have the above characteristics, no pretreatment is required. After the treatment, the flame atomic spectrophotometer is used. The remaining water body is subjected to measurement of heavy metal ion concentration, and the removal efficiency of heavy metal ions is calculated.
  • the invention adopts a specific surfactant which interacts with heavy metal ions such as Pb 2+ , Zn 2+ , the surfactant molecule and the metal cation are tightly combined in the aqueous solution, and the gas is introduced into the solution, due to the parents of the surfactant The property will be adsorbed on the gas-liquid interface of the bubble, and the foam will be formed by the difference in density, and the heavy metal ions will be carried out of the polluted water body.
  • heavy metal ions such as Pb 2+ , Zn 2+
  • the method of the invention can completely remove the heavy metal ions such as Pb 2+ and Zn 2+ enriched in the wastewater of the battery plant, and has the advantages of rapid and high efficiency, low input, low energy consumption and simple operation.
  • the method of the invention is applied to the treatment of wastewater of a battery factory contaminated by heavy metal ions such as Pb 2+ , Zn 2+ , the amount of surfactant is small, the removal efficiency of heavy metal ions is high, and the Pb 2+ and Zn 2+ in the wastewater are high.
  • the removal efficiency can reach more than 99.8%, which does not cause secondary pollution to the water body, and achieves the effect of completely removing heavy metal ions.
  • the method of the invention can be directly applied to various battery plant wastewaters polluted by heavy metal ions to achieve an ideal removal efficiency and meet national emission standards.
  • the method of the present invention which is detached from the foam of the aqueous phase, can be recovered after treatment, and the surfactant can also be recycled.
  • the removal efficiency was calculated by measuring the concentration of heavy metal ions in the water before and after the treatment.
  • the removal efficiency ⁇ (C 1 - C 2 ) / C 1 , where C 1 is the concentration of heavy metal ions before treatment, and C 2 is the concentration of residual heavy metal ions after the end of foaming.
  • Factors influencing the removal efficiency include the type of hydrophilic group of the surfactant, the molar ratio of surfactant to metal ion, the gas flow rate, the concentration of the surfactant solution, and the bulk pH.
  • Figure 1 is a graph showing the effect of gas flow rate on the removal efficiency of Pb 2+ and Zn 2+ .
  • a method for completely removing heavy metal ions in battery plant wastewater by using a water-based foam system wherein the concentration of Pb 2+ in the wastewater to be treated is 0.5 mmol/L, the solution is weakly acidic, and the pH is 4, and the steps are as follows:
  • the wastewater is weakly acidic and does not require pretreatment.
  • Sodium dodecyl sulfate is dissolved in water to prepare a solution of sodium lauryl sulfate, which is added to the wastewater.
  • the overall concentration of sodium lauryl sulfate in the wastewater is 3.5 mmol. / L, the molar ratio of sodium lauryl sulfate to Pb 2+ is 7:1;
  • the mixture obtained in the step (1) is introduced into a foam processor filled with porous media quartz sand, and N 2 is introduced into the bottom of the foam processor at a gas flow rate of 0.1 L/min, and foaming is continued until it cannot be produced.
  • the foam is introduced into the foam collector through a pipe at the top of the treatment column for use as a surfactant and heavy metal ion recovery.
  • the wastewater is neutral, no pretreatment is required, and the sodium tridecyl polyether-4-carboxylate is dissolved in water to prepare a solution of sodium tridecyl polyether-4-carboxylate, which is added to the wastewater and mixed uniformly in the wastewater.
  • the overall concentration of sodium tridecyl polyether-4-carboxylate is 2.5 mmol/L, and the molar ratio of sodium tridecyl polyether-4-carboxylate to the total moles of Pb 2+ and Zn 2+ is 5: 1;
  • the mixture obtained in the step (1) is introduced into a foam processor filled with a porous medium quartz sand, and N 2 is introduced into the bottom of the foam processor at a gas flow rate of 0.2 L/min, and foaming is continued until it cannot be produced.
  • the foam is introduced into the foam collector through a pipe at the top of the treatment column for use as a surfactant and heavy metal ion recovery.
  • the results show that the method removes Pb 2+ and Zn 2+ . The efficiency can reach more than 99.9%.
  • a method for thoroughly removing heavy metal ions in battery plant wastewater by using a water-based foam system wherein the concentration of Pb 2+ and Zn 2+ after dilution of the treated wastewater is 0.3 mmol/L, 0.7 mmol/L, the solution is weakly acidic, and the pH is 5, the steps are as follows:
  • the wastewater is weakly acidic, no pretreatment is required, and the sodium tridecyl polyether-4-carboxylate is dissolved in water to prepare a solution of sodium tridecyl polyether-4-carboxylate, which is added to the wastewater, and uniformly mixed in the wastewater.
  • the overall concentration of sodium tridecyl polyether-4-carboxylate is 5 mmol/L, and the molar ratio of sodium tridecyl polyether-4-carboxylate to the total moles of Pb 2+ and Zn 2+ is 5:1. ;
  • the mixture obtained in the step (1) is introduced into a foam processor filled with a porous medium quartz sand, and N 2 is introduced into the bottom of the foam processor at a gas flow rate of 0.2 L/min, and foaming is continued until it cannot be produced.
  • the foam is introduced into the foam collector through a pipe at the top of the treatment column for use as a surfactant and heavy metal ion recovery.
  • a method for completely removing heavy metal ions in battery plant wastewater by using a water-based foam system wherein the concentrations of Pb 2+ and Zn 2+ in the wastewater to be treated are 1.0 mmol/L and 1.5 mmol/L, respectively, and the solution is strongly acidic and has a pH of 1.2. Proceed as follows:
  • the wastewater is strongly acidic.
  • the wastewater from the battery plant is pretreated, 1mmol/L sodium hydroxide solution is prepared, the wastewater is added to the wastewater to adjust the wastewater to neutrality, the pH is 7, the precipitate is filtered, and the filtrate is retained to measure the heavy metal ions again.
  • the mixture obtained in the step (1) is introduced into a foam processor filled with a porous medium quartz sand, and N 2 is introduced into the bottom of the foam processor at a gas flow rate of 0.3 L/min, and foaming is continued until it cannot be produced.
  • the foam is introduced into the foam collector through a pipe at the top of the treatment column for use as a surfactant and heavy metal ion recovery.
  • Comparative Example 1 The gas flow rate was 0.01 L/min.
  • Comparative Example 2 The gas flow rate was 0.05 L/min.
  • Comparative Example 4 The gas flow rate was 1.2 L/min.
  • Comparative Example 5 The gas flow rate was 1.4 L/min.
  • Comparative Example 6 The gas flow rate was 1.6 L/min.
  • Comparative Example 7 The gas flow rate was 2.0 L/min.

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  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
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Abstract

一种利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，该方法包括：调节废水的pH值为4‑11，向废水中加入表面活性剂溶液，使表面活性剂与废水中所有重金属离子总摩尔数的摩尔比为适当比例并搅拌均匀；将混合液引入泡沫处理器中，在泡沫处理器底部经石英砂芯以一定的气体流速通入发泡气体，生成的泡沫通过泡沫处理器顶部管道引入泡沫收集器中进行消泡和重金属的回收处理，直至无泡沫产生。该方法操作简单，成本低廉，适用于多种重金属离子的去除。

Description

一种利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法 技术领域
本发明涉及一种利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，属于环境化学技术领域。
背景技术
随着经济的迅猛发展，国内外水体污染日趋严重，其中，含重金属的污染源电池厂废水对水资源造成极大的破坏与污染，同时对农业、工业、人类生活及整个生态平衡影响极大。电池厂废水不仅发散衍生出土壤及大气污染，并可通过食物链严重危害动物和人类的生命健康。电池生产中的废水主要来源有电池生产线清洗浆料的废水、调配浆料中洒漏的药剂废水、清洗生产地面的废水等，含有大量的Pb2+,Zn2+,Mn2+,Hg2+等重金属离子。这些重金属离子不会通过生物降解和生物链的循环而减弱或者消失，反而极易在生物链中富集放大，长久存在于生物体内，且重金属的毒性较大，因此对人类的生存健康和环境安全造成了严重的影响，危害甚大。因此，高效快捷治理水体污染，特别是对电池厂污染废水的治理，具有重要的环境效应和深远的社会意义。
目前水中重金属污染的治理措施按其作用机制主要可以分为物理法、化学法、生物法等。物理法包括萃取法、吸附法、离子交换法、膜分离等,在不改变废水中的重金属离子化学形态下进行吸附、浓缩、分离；该类方法效率高，但存在投入费用高，工程量大，易引入二次污染源等缺点。生物法主要是通过植物、微生物的吸收富集作用来去除污染水体中的重金属离子，然而因其作用周期长，处理量小，吸附重金属离子后的植物处理困难，对金属离子的回收利用率低等短板也制约着其在工业应用中的推广。化学法一般是通过添加剂与重金属离子发生氧化、还原、沉淀、吸附、抑制等作用去除重金属离子，其中沉淀法因经济性好、适用范围广，成为电池厂废水处理中应用最多的处理方法，通过加入氢氧化物，硫化物以及与重金属离子有较强结合作用的螯合剂或络合物，与重金属离子形成不溶于水的沉淀，进而达到净化水体的目的。但对于成分复杂的工业废水，因各离子沉淀范围不同，往往需要多次调节pH或分批次多次添加不同类型的作用剂，不仅操作复杂，而且效率不高，沉淀物的处理也存在困难，若处理不当，容易再度活化，会造成二次污染，难以达到国家排放标准。
发明内容
针对现有技术的不足，本发明提供一种利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法。本发明采用绿色环保的特定表面活性剂形成水基泡沫，选择的表面活性剂与Pb2+，Zn2+等重金属离子间具有电性相互作用或络合作用，表面活性剂分子与金属阳离子紧密 结合后，利用表面活性剂的两亲性吸附在气液界面上，通过上浮的气泡将重金属离子带出污染水体。本发明操作简单，成本低廉，表面活性剂使用浓度低，对电池厂废水的复杂性适应能力强，去除效率高，适用于多种重金属离子的去除，并且通过优选绿色环保型表面活性剂，确保对环境没有二次污染。
本发明的技术方案如下：
一种利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，包括步骤如下：
(1)调节废水的pH为4-11，向废水中加入预先配制好的表面活性剂溶液，表面活性剂溶液的加入量使表面活性剂与废水中所有重金属离子总摩尔数的摩尔比为(1～50):1，搅拌均匀；
(2)将步骤(1)得到的混合液引入泡沫处理器中，在泡沫处理器底部通入发泡气体，发泡气体气流速度控制在0.1～1.0L/min，生成泡沫通过泡沫处理器顶部管道引入泡沫收集器中进行消泡和重金属的回收处理，直至无泡沫产生。
根据本发明优选的，步骤(1)中所述的表面活性剂为至少含有一个带负电的极性亲水基团、疏水基碳链长度为8-24的表面活性剂，所述的带负电极性亲水基团为硫酸基、磺酸基或羧酸基。
进一步优选的，所述的表面活性剂还含有EO、羰基或酰胺基团。
根据本发明优选的，所述的表面活性剂为烷基硫酸盐、脂肪醇聚氧乙烯醚硫酸盐、烷基羧酸盐或烷基聚醚羧酸盐中的其中一种或两种以上任意混合。
进一步优选的，含有硫酸基的表面活性剂为十二烷基硫酸钠或脂肪醇聚氧乙烯醚硫酸钠。
进一步优选的，含有羧酸基的表面活性剂为十二烷基羧酸钠或十三烷醇聚醚-4-羧酸钠。
根据本发明优选的，步骤(1)中表面活性剂与废水中所有重金属离子总摩尔数的摩尔比为(1～30):1，优选的，表面活性剂与废水中所有重金属离子总摩尔数的摩尔比为(3～15):1，最为优选的，表面活性剂与废水中所有重金属离子总摩尔数的摩尔比为(5～7):1。
根据本发明优选的，步骤(1)中废水的pH为5-11。
根据本发明优选的，步骤(2)中发泡气体气流速度为0.1～0.7L/min，进一步优选的，发泡气体气流速度为0.2～0.6L/min。
根据本发明优选的，步骤(2)中发泡气体为N2或空气。
根据本发明优选的，步骤(2)中泡沫处理器的底部填充有多孔介质石英砂，多孔介质石英砂孔隙率为35-45％，平均孔喉半径为0.1-10μm，填充高度为4-7mm。
针对部分电池厂废水重金属离子浓度极大或混合液呈强酸性的情况，在进行泡沫分离之前可先对废水做预处理，即通过加入适量的碱溶液调节废水的pH至弱酸或中性，并对产生的沉淀过滤。若废水无上述特征则无需进行预处理。处理完毕后利用火焰原子分光光度计对 剩余水体进行重金属离子浓度的测定，计算重金属离子的去除效率。
本发明利用水基泡沫去除电池厂废水中重金属离子的方法具体过程简述如下：
收集废水样品分析其中重金属元素的种类和含量，然后按照与废水中的重金属离子的摩尔比为(1～50):1的比例，以及与废水混合后的整体摩尔浓度为(1～15)mmol/L的要求，称量表面活性剂若干，与适量纯水混合，在恒温25～40℃的情况下，搅拌均匀，形成表面活性剂溶液，后将处理剂加入废水，适当搅拌混合均匀。然后将混合液引入泡沫处理器，同时将气体从泡沫处理器引入，利用气体流量计控制气流速度在0.1～1.0L/min，通过泡沫处理器顶端的引流装置将泡沫引入泡沫收集器内，进行消泡和重金属的回收。持续注入气体，直至无泡沫产生为止。
本发明的原理：
本发明采用与Pb2+，Zn2+等重金属离子间具有相互作用的特定表面活性剂，表面活性剂分子与金属阳离子在水溶液中紧密结合，将气体引入溶液后，由于表面活性剂的两亲性将吸附在气泡的气液界面上，通过密度差异上浮形成泡沫，将重金属离子带出污染水体。
本发明的优点如下：
1、本发明的方法可以彻底去除电池厂废水中富集的Pb2+，Zn2+等重金属离子，快速高效，投入低，耗能少，操作简单易行。
2、本发明方法在处理Pb2+，Zn2+等重金属离子污染的电池厂废水方面的应用，表面活性剂用量少，重金属离子去除效率高，对废水中Pb2+、Zn2+的去除效率均可达到99.8以上％，不对水体造成二次污染，达到彻底去除重金属离子的效果。
3、本发明的方法，可直接应用于被重金属离子污染的各种电池厂废水，达到理想的去除效率，满足国家排放标准。
4、本发明的方法，脱离水相的泡沫，经处理后，重金属元素可以回收，同时表面活性剂也可以回收利用。
通过对处理前后的水体进行重金属离子浓度的测定，计算去除效率。去除效率η＝(C1-C2)/C1,其中C1是处理前重金属离子的浓度，C2是发泡结束后剩余重金属离子的浓度。去除效率的影响因素包括表面活性剂的亲水基团的类型、表面活性剂与金属离子的摩尔比、气流速度、表面活性剂溶液浓度及体相pH等。
附图说明
图1为发泡气体气流速度对Pb2+、Zn2+去除效率的影响曲线图。
具体实施方式
下面结合实施例对本发明做进一步说明，但不仅限于此。
实施例1：
一种利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，待处理废水中Pb2+的浓度为0.5mmol/L，溶液呈弱酸性，pH为4，步骤如下：
(1)废水呈弱酸性，无需预处理，十二烷基硫酸钠加水溶解配制成十二烷基硫酸钠溶液加入废水中，混合均匀后废水中十二烷基硫酸钠的整体浓度为3.5mmol/L，十二烷基硫酸钠与Pb2+摩尔比为7:1；
(2)将步骤(1)得到的混合液引入底部填充有多孔介质石英砂的泡沫处理器中，在泡沫处理器底部通入N2，气流速度为0.1L/min，持续发泡直至不能产生泡沫为止，泡沫通过处理塔顶端的管道引入泡沫收集器内，用作表面活性剂和重金属离子回收再利用。然后再对处理后的废水利用火焰原子分光光度计进行重金属离子浓度的分析测定，计算去除效率η＝(C1-C2)/C1，结果显示该方法去除Pb2+的效率为99.8％。
实施例2：
一种利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，待处理废水中Pb2+和Zn2+浓度分别为0.2mmol/L,0.3mmol/L，溶液呈中性，pH为6.82，步骤如下：
(1)废水呈中性，无需预处理，十三烷醇聚醚-4-羧酸钠加水溶解配制成十三烷醇聚醚-4-羧酸钠溶液加入废水中，混合均匀后废水中十三烷醇聚醚-4-羧酸钠的整体浓度为2.5mmol/L，十三烷醇聚醚-4-羧酸钠与Pb2+和Zn2+总摩尔数的摩尔比为5:1；
(2)将步骤(1)得到的混合液引入底部填充有多孔介质石英砂的泡沫处理器中，在泡沫处理器底部通入N2，气流速度为0.2L/min，持续发泡直至不能产生泡沫为止，泡沫通过处理塔顶端的管道引入泡沫收集器内，用作表面活性剂和重金属离子回收再利用。然后再对处理后的废水利用火焰原子分光光度计进行重金属离子浓度的分析测定，计算去除效率η＝(C1-C2)/C1，结果显示该方法去除Pb2+、Zn2+的效率均可达到99.9以上％。
实施例3：
一种利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，待处理废水稀释后Pb2+和Zn2+浓度分别为0.3mmol/L，0.7mmol/L，溶液呈弱酸性，pH为5，步骤如下：
(1)废水呈弱酸性，无需预处理，十三烷醇聚醚-4-羧酸钠加水溶解配制成十三烷醇聚醚-4-羧酸钠溶液加入废水中，混合均匀后废水中十三烷醇聚醚-4-羧酸钠的整体浓度为5mmol/L，十三烷醇聚醚-4-羧酸钠与Pb2+和Zn2+总摩尔数的摩尔比为5:1；
(2)将步骤(1)得到的混合液引入底部填充有多孔介质石英砂的泡沫处理器中，在泡沫处理器底部通入N2，气流速度为0.2L/min，持续发泡直至不能产生泡沫为止，泡沫通过处理塔顶端的管道引入泡沫收集器内，用作表面活性剂和重金属离子回收再利用。然后再对处理后的废水利用火焰原子分光光度计进行重金属离子浓度的分析测定，计算去除效率η＝(C1-C2)/C1，结果显示该方法去除Pb2+、Zn2+的效率为99.8％。
实施例4：
一种利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，待处理废水Pb2+和Zn2+浓度分别为1.0mmol/L,1.5mmol/L，溶液呈强酸性，pH为1.2，步骤如下：
(1)废水呈强酸性，先对电池厂废水做预处理，配制1mmol/L的氢氧化钠溶液，加入废水中调节废水至中性，pH为7，将沉淀过滤，保留滤液再次测定重金属离子的浓度；十三烷醇聚醚-4-羧酸钠和十二烷基硫酸钠加水溶解配制成溶液加入废水中，混合均匀后废水中十三烷醇聚醚-4-羧酸钠和十二烷基硫酸钠的总浓度为12mmol/L，十三烷醇聚醚-4-羧酸钠和十二烷基硫酸钠与Pb2+和Zn2+总摩尔数的摩尔比为5:1；
(2)将步骤(1)得到的混合液引入底部填充有多孔介质石英砂的泡沫处理器中，在泡沫处理器底部通入N2，气流速度为0.3L/min，持续发泡直至不能产生泡沫为止，泡沫通过处理塔顶端的管道引入泡沫收集器内，用作表面活性剂和重金属离子回收再利用。然后再对处理后的废水利用火焰原子分光光度计进行重金属离子浓度的分析测定，计算去除效率η＝(C1-C2)/C1，结果显示该方法去除Pb2+、Zn2+的效率均达到99.8％以上。
对比例
如实施例1所述的利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，不同之处在于：
对比例1：气流速度为0.01L/min。
对比例2：气流速度为0.05L/min。
对比例3：气流速度为0.08L/min。
对比例4：气流速度为1.2L/min。
对比例5：气流速度为1.4L/min。
对比例6：气流速度为1.6L/min。
对比例7：气流速度为2.0L/min。
实验例：
上述实施例1～4及对比例1～7的处理方法不同发泡气体气流速度对Pb2+、Zn2+去除效率的影响见图1。(其中，表面活性剂浓度为3.5mmol/L，铅离子、锌离子浓度各为0.5mmol/L，溶液pH为6)

Claims (10)

  1. 一种利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，包括步骤如下：
    (1)调节废水的pH为4-11，向废水中加入预先配制好的表面活性剂溶液，表面活性剂溶液的加入量使表面活性剂与废水中所有重金属离子总摩尔数的摩尔比为(1～50):1，搅拌均匀；
    (2)将步骤(1)得到的混合液引入泡沫处理器中，在泡沫处理器底部通入发泡气体，发泡气体气流速度控制在0.1～1.0L/min，生成泡沫通过泡沫处理器顶部管道引入泡沫收集器中进行消泡和重金属的回收处理，直至无泡沫产生。
  2. 根据权利要求1所述的利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，其特征在于，步骤(1)中所述的表面活性剂为至少含有一个带负电的极性亲水基团、疏水基碳链长度为8-24的表面活性剂，所述的带负电极性亲水基团为硫酸基、磺酸基或羧酸基。
  3. 根据权利要求2所述的利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，其特征在于，所述的表面活性剂还含有EO、羰基或酰胺基团。
  4. 根据权利要求2所述的利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，其特征在于，所述的表面活性剂为烷基硫酸盐、脂肪醇聚氧乙烯醚硫酸盐、烷基羧酸盐或烷基聚醚羧酸盐中的其中一种或两种以上任意混合。
  5. 根据权利要求2所述的利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，其特征在于，含有硫酸基的表面活性剂为十二烷基硫酸钠或脂肪醇聚氧乙烯醚硫酸钠。
  6. 根据权利要求2所述的利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，其特征在于，含有羧酸基的表面活性剂为十二烷基羧酸钠或十三烷醇聚醚-4-羧酸钠。
  7. 根据权利要求1所述的利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，其特征在于，步骤(1)中表面活性剂与废水中所有重金属离子总摩尔数的摩尔比为(1～30):1，优选的，表面活性剂与废水中所有重金属离子总摩尔数的摩尔比为(3～15):1，最为优选的，表面活性剂与废水中所有重金属离子总摩尔数的摩尔比为(5～7):1，废水的pH为5-11。
  8. 根据权利要求1所述的利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，其特征在于，步骤(2)中发泡气体气流速度为0.1～0.7L/min，进一步优选的，发泡气体气流速度为0.2～0.6L/min。
  9. 根据权利要求1所述的利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，其特征在于，步骤(2)中发泡气体为N2或空气。
  10. 根据权利要求1所述的利用水基泡沫体系彻底去除电池厂废水中重金属离子的方法，其特征在于，步骤(2)中泡沫处理器的底部填充有多孔介质石英砂，多孔介质石英砂孔隙率为35-45％，平均孔喉半径为0.1-10μm，填充高度为4-7mm。
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