电动修复技术机理及去除污泥和尾砂中重金属的研究
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摘要
土壤重金属污染是国内亟待解决的环境问题。土壤污染具有累积性、滞后性、隐蔽性和不可逆性,因此,土壤污染一般极难恢复或治理。本研究在国内外研究的基础上,结合国内实际对电复技术进行了研究和探讨。
电动修复技术是国际环境科学和工程领域的前沿课题之一。它的基本机理是:土壤中的水在电场力的作用下发生电解反应,阴极产生氢气和氢氧根离子,阳极产生氧气和氢离子,阳极产生的氢离子在电场和浓度梯度的作用下,向土壤内部迁移和扩散,氢离子在迁移和扩散的过程中,置换和溶解土壤中的重金属污染物,被溶解后的重金属污染物在电场和浓度梯度的作用下,以离子迁移和电渗的方式朝阴极方向定向迁移,从而达到去除土壤污染物的目的。
本文在国内外电动修复技术研究的基础上,首先探讨了电修复对红壤的适应性分析,结果表明:电动力修复技术适用于铅污染红壤,但是必须对修复技术进行改进才能用于该土壤修复;阴极酸化法能有效的提高修复效率、降低修复成本和缩短修复周期;土壤pH值是影响电动力修复效果的关键因素,土壤pH值不但可以影响土壤中重金属的存在形态还可以通过影响土壤的电导率,土壤的温度和改变土壤的含水率来影响土壤中可以迁移的重金属含量。其次,探讨了电流密度对电修复的影响,对于红壤来说,10A/m2是相对较适合的电流密度。
在前面研究的基础上,探讨和改进了电修复技术处理污泥中重金属。实验I表明,污泥在电动力的作用下,经过5d后,Cd、Zn、Cu的总去除率分别为64.50%、65.02%;易于被植物吸收的不稳定态(可交换态、碳酸盐结合态和铁锰氧化物结合态)的处理效果明显,不稳定态的去除率分别68.60%、75.73%。电动力修复技术处理污泥中的重金属是可行的,修复后的污泥有利于土地利用。实验Ⅱ结果表明,污泥pH值是影响电动力修复效果的关键因素,污泥pH值不但可以影响污泥中重金属的存在形态还可以通过影响污泥的电导率、污泥的温度和改变污泥的含水率来影响污泥中可以迁移的重金属含量。降低污泥pH值能有效的提高修复效率、降低修复成本和缩短修复周期。实验Ⅲ分析了硫杆菌对电动力去除污泥中重金属的影响机理。硫杆菌处理后的污泥,pH值降低,部分重金属从稳定态转化为可溶态。经硫杆菌预处理后的泥样和未经预处理的泥样,在同样条件下用电动力处理,处理结果为:预处理后Cd的去除率从61.85%上升到72.54%,Cu从34.26%上升到63.51%,Zn从65.06%上升到71.22%。预处理对Cu的影响比Cd、Zn大得多。用电动力处理Cu超标污泥中重金属时,将污泥先用硫杆菌预处理,可有效地提高其去除效果,处理后的污泥有利于农用。
本研究在前面的基础上,以铅锌选矿尾砂为样品,分别用电修复技术、阴极酸化技术和生物淋滤-电修复联合基础处理样品,探索电修复技术在处理污泥中重金属的应用前景。结果表明:直接用电修复处理尾砂时,铜、铅、锌3者的处理效率为别为75.8%、37.8%和几乎无效果;应用中间循环冲洗技术处理尾砂时,铜、铅、锌3者的处理效率为别为81.4%、48.58%和36.3%;应用生物淋滤-中间循环冲洗—电修复连用技术时,效果最佳,铜、铅、锌3者的处理效率为别为82.8%、56.1%和47.5%。
Soil contaminated by heavy metals is one of the environmental problems that should be resolved urgently. Soil pollution is accumulative, lagging, dormant, and irreversible, therefore, soil pollution is usually difficult to be remedied and treated. This paper mainly studied phytoremediation and electroremediation of lead contaminated red soils. The studies based on the researches of at home and abroad and combined actual conditions.
Electroremediation technique is an advancing task of global environment science and technology. Its principle is that: application of direct electric current via electrodes immersed in a saturated soil results in oxidation at the anode, generating an acid front that cause desorption and dissolution of heavy metals. The desorped and soluted heavy metals are migrated toward cathode reservoir by electric field and ions concentration grads by the means of electromigration, electroosmosis and diffusing.
Firstly, a series of tests about lead spiked red soil sample are conducted, the results show: the electroremediation technology is efficient to remedy Pb contaminated red soil; pH value of red soil is the major factor of dominating electroremediation efficiency: pH value of red soil can not only lead to high tank voltage and high temperature of red soil by means of decreasing electro-conductivity of soil, but also reduce remediation efficiency by precipitating Pb and then decreasing mobility of Pb. Hence, electroremediation techniques should be enhanced so as to efficiently remove Pb from contaminated red soil; control pH value of the cathode reservoir with HNO3 can improve the removal efficiency. The enhanced test removal efficiency of Pb is 79.5%, and the energy consumption is 285kw/m3.soil; 10 A/m2 is the suitable current density for electroremediation.
Secondly, a series of experiments used sludge samples are conducted to research and explore electroremediation. Experiment I showed the curve of removal efficiencies of different speciation Cd and Zn. The total removal efficiencies of Cd and Zn in municipal sewage sludge were 64.5% and 52.36% after five days electroremediation. The removal efficiencies of labile state fractions of Cd and Zn were 68.6%, 60.6% correspondingly. The labile state fractions that could be easily absorbed by plants included the exchangeable, carbonate and Fe and Mn oxides fraction. The electroremediation technique was fitted for removing heavy metals from municipal sewage sludge, and the electro remedied sludge was favorable to land utilization.
ExperimentⅡshowed pH value of municipal biosolids is the major factor of dominating electroremediation; pH value of red soil can not only lead to high tank voltage and high temperature of municipal biosolids by means of decreasing electro-conductivity of soil, but also reduce remediation efficiency by precipitating Pb and then decreasing mobility of Pb. Hence, electroremediation techniques should be enhanced so as to apply to remedy heavy metals contaminated municipal biosolids. Control pH value of the cathode reservoir with HNO3 can improve the removal efficiency, decrease cost of remediation and shorten duration of remediation.
The influence of thiobacillus ferrooxidans on the Speciation of Heavy Metals in the Sewage were analyzed and the removal efficiencies of heavy metals from sewage sludge by electrokinetics in experimentⅢ.The pH value of the sludge sample which was pretreated by thiobacillus ferrooxidans reduced. Because of this, the heavy metals of the sewage sludge transformed from stable state to labile state. The samples pretreated by thiobacillus ferrooxidans and pretreated were electroremedied under the same conditions, the results were that the removal efficiencies of Cd raised from 61.85% to 72.54%,Cu from 34.26% to 63.51%, and Zn from 65.06% to71.22%, after pretreated. The effect of pretreated by thiobacillus ferrooxidans on Cu was much obviously than Cd or Zn. The sewage sludge pretreated by thiobacillus ferrooxidans could effectively enhance the removal efficiency of Cu while it is exceeded the control standards of land utilization. The electroremedied sludge which was pretreated by thiobacillus ferrooxidans was favorable to land utilization.
Based on foregoing results, sampled with nonferrous tailings, the expectation of electroremediation technique to dispose tailings are conducted using electrokinetic’s, middle recycle washing technology, bioleaching-electroremediation technology, respectively. The results shows: the removal efficiency of Cu, Pb and Zn is 75.8, 37.8 and o% in test 1, respectively; the removal efficiency of Cu, Pb and Zn is 81.4%, 48.6% and 36.3% in test 2, respectively; the removal efficiency of Cu, Pb and Zn is 82.8%, 56.1% and 47.5% in test 3, respectively.
电动修复技术是国际环境科学和工程领域的前沿课题之一。它的基本机理是:土壤中的水在电场力的作用下发生电解反应,阴极产生氢气和氢氧根离子,阳极产生氧气和氢离子,阳极产生的氢离子在电场和浓度梯度的作用下,向土壤内部迁移和扩散,氢离子在迁移和扩散的过程中,置换和溶解土壤中的重金属污染物,被溶解后的重金属污染物在电场和浓度梯度的作用下,以离子迁移和电渗的方式朝阴极方向定向迁移,从而达到去除土壤污染物的目的。
本文在国内外电动修复技术研究的基础上,首先探讨了电修复对红壤的适应性分析,结果表明:电动力修复技术适用于铅污染红壤,但是必须对修复技术进行改进才能用于该土壤修复;阴极酸化法能有效的提高修复效率、降低修复成本和缩短修复周期;土壤pH值是影响电动力修复效果的关键因素,土壤pH值不但可以影响土壤中重金属的存在形态还可以通过影响土壤的电导率,土壤的温度和改变土壤的含水率来影响土壤中可以迁移的重金属含量。其次,探讨了电流密度对电修复的影响,对于红壤来说,10A/m2是相对较适合的电流密度。
在前面研究的基础上,探讨和改进了电修复技术处理污泥中重金属。实验I表明,污泥在电动力的作用下,经过5d后,Cd、Zn、Cu的总去除率分别为64.50%、65.02%;易于被植物吸收的不稳定态(可交换态、碳酸盐结合态和铁锰氧化物结合态)的处理效果明显,不稳定态的去除率分别68.60%、75.73%。电动力修复技术处理污泥中的重金属是可行的,修复后的污泥有利于土地利用。实验Ⅱ结果表明,污泥pH值是影响电动力修复效果的关键因素,污泥pH值不但可以影响污泥中重金属的存在形态还可以通过影响污泥的电导率、污泥的温度和改变污泥的含水率来影响污泥中可以迁移的重金属含量。降低污泥pH值能有效的提高修复效率、降低修复成本和缩短修复周期。实验Ⅲ分析了硫杆菌对电动力去除污泥中重金属的影响机理。硫杆菌处理后的污泥,pH值降低,部分重金属从稳定态转化为可溶态。经硫杆菌预处理后的泥样和未经预处理的泥样,在同样条件下用电动力处理,处理结果为:预处理后Cd的去除率从61.85%上升到72.54%,Cu从34.26%上升到63.51%,Zn从65.06%上升到71.22%。预处理对Cu的影响比Cd、Zn大得多。用电动力处理Cu超标污泥中重金属时,将污泥先用硫杆菌预处理,可有效地提高其去除效果,处理后的污泥有利于农用。
本研究在前面的基础上,以铅锌选矿尾砂为样品,分别用电修复技术、阴极酸化技术和生物淋滤-电修复联合基础处理样品,探索电修复技术在处理污泥中重金属的应用前景。结果表明:直接用电修复处理尾砂时,铜、铅、锌3者的处理效率为别为75.8%、37.8%和几乎无效果;应用中间循环冲洗技术处理尾砂时,铜、铅、锌3者的处理效率为别为81.4%、48.58%和36.3%;应用生物淋滤-中间循环冲洗—电修复连用技术时,效果最佳,铜、铅、锌3者的处理效率为别为82.8%、56.1%和47.5%。
Soil contaminated by heavy metals is one of the environmental problems that should be resolved urgently. Soil pollution is accumulative, lagging, dormant, and irreversible, therefore, soil pollution is usually difficult to be remedied and treated. This paper mainly studied phytoremediation and electroremediation of lead contaminated red soils. The studies based on the researches of at home and abroad and combined actual conditions.
Electroremediation technique is an advancing task of global environment science and technology. Its principle is that: application of direct electric current via electrodes immersed in a saturated soil results in oxidation at the anode, generating an acid front that cause desorption and dissolution of heavy metals. The desorped and soluted heavy metals are migrated toward cathode reservoir by electric field and ions concentration grads by the means of electromigration, electroosmosis and diffusing.
Firstly, a series of tests about lead spiked red soil sample are conducted, the results show: the electroremediation technology is efficient to remedy Pb contaminated red soil; pH value of red soil is the major factor of dominating electroremediation efficiency: pH value of red soil can not only lead to high tank voltage and high temperature of red soil by means of decreasing electro-conductivity of soil, but also reduce remediation efficiency by precipitating Pb and then decreasing mobility of Pb. Hence, electroremediation techniques should be enhanced so as to efficiently remove Pb from contaminated red soil; control pH value of the cathode reservoir with HNO3 can improve the removal efficiency. The enhanced test removal efficiency of Pb is 79.5%, and the energy consumption is 285kw/m3.soil; 10 A/m2 is the suitable current density for electroremediation.
Secondly, a series of experiments used sludge samples are conducted to research and explore electroremediation. Experiment I showed the curve of removal efficiencies of different speciation Cd and Zn. The total removal efficiencies of Cd and Zn in municipal sewage sludge were 64.5% and 52.36% after five days electroremediation. The removal efficiencies of labile state fractions of Cd and Zn were 68.6%, 60.6% correspondingly. The labile state fractions that could be easily absorbed by plants included the exchangeable, carbonate and Fe and Mn oxides fraction. The electroremediation technique was fitted for removing heavy metals from municipal sewage sludge, and the electro remedied sludge was favorable to land utilization.
ExperimentⅡshowed pH value of municipal biosolids is the major factor of dominating electroremediation; pH value of red soil can not only lead to high tank voltage and high temperature of municipal biosolids by means of decreasing electro-conductivity of soil, but also reduce remediation efficiency by precipitating Pb and then decreasing mobility of Pb. Hence, electroremediation techniques should be enhanced so as to apply to remedy heavy metals contaminated municipal biosolids. Control pH value of the cathode reservoir with HNO3 can improve the removal efficiency, decrease cost of remediation and shorten duration of remediation.
The influence of thiobacillus ferrooxidans on the Speciation of Heavy Metals in the Sewage were analyzed and the removal efficiencies of heavy metals from sewage sludge by electrokinetics in experimentⅢ.The pH value of the sludge sample which was pretreated by thiobacillus ferrooxidans reduced. Because of this, the heavy metals of the sewage sludge transformed from stable state to labile state. The samples pretreated by thiobacillus ferrooxidans and pretreated were electroremedied under the same conditions, the results were that the removal efficiencies of Cd raised from 61.85% to 72.54%,Cu from 34.26% to 63.51%, and Zn from 65.06% to71.22%, after pretreated. The effect of pretreated by thiobacillus ferrooxidans on Cu was much obviously than Cd or Zn. The sewage sludge pretreated by thiobacillus ferrooxidans could effectively enhance the removal efficiency of Cu while it is exceeded the control standards of land utilization. The electroremedied sludge which was pretreated by thiobacillus ferrooxidans was favorable to land utilization.
Based on foregoing results, sampled with nonferrous tailings, the expectation of electroremediation technique to dispose tailings are conducted using electrokinetic’s, middle recycle washing technology, bioleaching-electroremediation technology, respectively. The results shows: the removal efficiency of Cu, Pb and Zn is 75.8, 37.8 and o% in test 1, respectively; the removal efficiency of Cu, Pb and Zn is 81.4%, 48.6% and 36.3% in test 2, respectively; the removal efficiency of Cu, Pb and Zn is 82.8%, 56.1% and 47.5% in test 3, respectively.
引文
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