剩余污泥制备吸附材料处理重金属废水研究
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摘要
随着城市化进程的加快,污水排放总量逐年提高,随之而来产生大量的剩余污泥,其安全处理和处置成为亟待解决的重要问题。近年来,学者研究发现剩余污泥通过添加化学物质在一定条件下可以转化为吸附材料,这使得剩余污泥变废为宝,为污泥的去向开辟了新的途径。与此同时,重金属废水是当前水污染的突出问题,控制重金属废水排放成为当前研究重点。相比传统的重金属废水处理方法,利用廉价吸附材料处理重金属受到研究者亲睐,成为当前研究的主题。
本文以城市污水处理厂的剩余污泥为原料,通过添加活化剂和表面活性剂改性后,利用化学活化法制备得到吸附材料。实验研究了活化温度、活化时间、活化剂浓度、固液比、浸泡时间和活化前污泥粒径等制备条件的影响;利用表面活性剂对吸附材料进行改性,研究表面活性剂添加种类、用量及配比,改性后对活化条件的影响;结合形貌分析、比表面积、氮气吸附等温线及谱图分析等,对吸附材料进行性能评价,对制备过程和机理进行初步探讨。此外,制备完的吸附材料,对铬、镍单纯溶液和二者混合溶液进行分析,研究吸附材料在不同用量、pH、吸附时间、振荡频率、静置时间、吸附温度等条件对重金属去除率的影响。通过实验,得出如下结论:
添加氯化锌活化剂,以碘值、亚甲基蓝和铬去除率表征吸附性能,确定吸附材料的最佳制备条件:活化温度为550℃,活化时间0.5h,活化剂浓度3mol/L,固液比1:2,浸泡时间1h,活化前污泥粒径100目。改性材料为十二烷基硫酸钠和聚丙烯酰胺,复配比为1:1,二者质量均为0.01g。制备的吸附材料,其铬吸附值为5.80mg/g,亚甲基蓝吸附值114.64mg/g,碘值503.20mg/g。从形貌分析、比表面积、氮气吸附等温线及谱图分析等微观方面对污泥制备的吸附材料性能进行表征,得出改性后的吸附材料性能比改性前的吸附材料和商用活性炭都高,这与实验结论相一致。
利用污泥制备的吸附材料,经改性前后对铬、镍及二者的混合溶液的重金属去除率在用量、pH、吸附时间、振荡频率、静置时间、吸附温度等吸附条件进行分析,结果表明常温下的单独溶液中,铬与镍溶液适合的pH范围不同;对于混合溶液而言,吸附材料用量增加的同时,去除率也有所升高,其他影响条件变动不大,这说明混合溶液的存在能够促进重金属离子的去除。通过对铬、镍离子的吸附热力学和动力学研究,得出铬离子吸附过程符合Freundlich热力吸附模型,镍离子吸附过程符合Langmuir热力吸附模型,且二者均符合二级动力吸附模型。
With the accelerated process of urbanization, the total wastewater increase year after year, the following excessive sludge’s treatment and disposal problems urgently need to be solved. These years, the researchers find that the excess sludge can be transformed into adsorption material by adding chemical substances under certain conditions, so that, this method makes the remaining sludge turning waste into treasure, and has opened a new way to the whereabouts of the sludge. Meanwhile, heavy metal waste water which is the current outstanding problem in the field of water pollution, becomes the focus of research in the controlling field. Compared to traditional heavy metal waste water treatment method, using low-cost adsorption material in the field of treatment of heavy metal becomes the subject of current research focus.
The adsorption material chemical activation making is this topic research focus which uses municipal sewage treatment plant sludge as raw material, by adding activator and surfactant modification. In the experiment, the effects of preparation conditions are studied on activation temperature, activation time, activator concentration, solid-liquid ratio, soaking time and activated sludge particle size before modification; By using surfactant modification to the adsorption material, researching on the surfactant types, dosage, ratio and the influence to the activated conditions after modification; combined with morphology, specific surface area, nitrogen adsorption isotherms and the spectrum analysis, performance evaluation on the adsorption material, discussion on the preparation process and the mechanism. In addition, the prepared adsorption material analyses on the Cr(VI), Ni(II) simple solution and mixed solution, by researching on the removal of heavy metals impact through different adsorption material dosage, pH of solution, adsorption hour, oscillation frequency, holding time, adsorption temperature, etc. The conclusions are as following through the experiment:
Adding ZnCl2 as the activator, studies the best preparation conditions by iodine, methylene blue and Cr(VI) removal ratio: the activation temperature is 550℃, the activation time is 0.5 hour, the concentration of activator is 3 mol/L, the ratio between solid and liquid is 1:2, the hour to immerse sludge is 1 hour, and the sludge particle before activation is 100 mesh. The modification materials are SDS and PAM, the complex ratio of 1:1, both qualities of 0.01g. Through the prepared adsorption material, adsorption performance contains 5.80mg/g of Cr(VI), 114.64mg/g of MB adsorption, 503.20mg/g iodine. From the research on the morphology, specific surface area, nitrogen adsorption isotherms and the spectrum of the micro level, character adsorption material properties, obtained the adsorption material property after modification higher than the adsorption material before modification and commercial activated carbon which is consistent with the experimental results.
The removal ratio of heavy metal in Cr(VI), Ni(VI) solution and mixed solution is researched by the sludge-making adsorption material before or after modification on the adsorption conditions of dosage, pH of solution, adsorption hour, oscillation frequency, frequency, holding time, adsorption temperature, etc. The results show that Cr(VI) and Ni (VI) solution have different pH range in the simple solution and in the room temperature; for the mixed solution, the removal ratio has also increased with the increasing of adsorption material dosage except other influent conditions, so that, it shows that the heavy metal removal ratio can be propelled by the other heavy metal solution’s existence.
Through the studying of adsorption thermodynamics and kinetics to Cr6+ and Ni2+, the Cr6+ adsorption model is consistent with Freundlich adsorption, while the Ni2+ adsorption model is consistent with Langmuir adsorption, meanwhile the both heavy metals’thermal models fit Lagergren second dynamic adsorption model.
本文以城市污水处理厂的剩余污泥为原料,通过添加活化剂和表面活性剂改性后,利用化学活化法制备得到吸附材料。实验研究了活化温度、活化时间、活化剂浓度、固液比、浸泡时间和活化前污泥粒径等制备条件的影响;利用表面活性剂对吸附材料进行改性,研究表面活性剂添加种类、用量及配比,改性后对活化条件的影响;结合形貌分析、比表面积、氮气吸附等温线及谱图分析等,对吸附材料进行性能评价,对制备过程和机理进行初步探讨。此外,制备完的吸附材料,对铬、镍单纯溶液和二者混合溶液进行分析,研究吸附材料在不同用量、pH、吸附时间、振荡频率、静置时间、吸附温度等条件对重金属去除率的影响。通过实验,得出如下结论:
添加氯化锌活化剂,以碘值、亚甲基蓝和铬去除率表征吸附性能,确定吸附材料的最佳制备条件:活化温度为550℃,活化时间0.5h,活化剂浓度3mol/L,固液比1:2,浸泡时间1h,活化前污泥粒径100目。改性材料为十二烷基硫酸钠和聚丙烯酰胺,复配比为1:1,二者质量均为0.01g。制备的吸附材料,其铬吸附值为5.80mg/g,亚甲基蓝吸附值114.64mg/g,碘值503.20mg/g。从形貌分析、比表面积、氮气吸附等温线及谱图分析等微观方面对污泥制备的吸附材料性能进行表征,得出改性后的吸附材料性能比改性前的吸附材料和商用活性炭都高,这与实验结论相一致。
利用污泥制备的吸附材料,经改性前后对铬、镍及二者的混合溶液的重金属去除率在用量、pH、吸附时间、振荡频率、静置时间、吸附温度等吸附条件进行分析,结果表明常温下的单独溶液中,铬与镍溶液适合的pH范围不同;对于混合溶液而言,吸附材料用量增加的同时,去除率也有所升高,其他影响条件变动不大,这说明混合溶液的存在能够促进重金属离子的去除。通过对铬、镍离子的吸附热力学和动力学研究,得出铬离子吸附过程符合Freundlich热力吸附模型,镍离子吸附过程符合Langmuir热力吸附模型,且二者均符合二级动力吸附模型。
With the accelerated process of urbanization, the total wastewater increase year after year, the following excessive sludge’s treatment and disposal problems urgently need to be solved. These years, the researchers find that the excess sludge can be transformed into adsorption material by adding chemical substances under certain conditions, so that, this method makes the remaining sludge turning waste into treasure, and has opened a new way to the whereabouts of the sludge. Meanwhile, heavy metal waste water which is the current outstanding problem in the field of water pollution, becomes the focus of research in the controlling field. Compared to traditional heavy metal waste water treatment method, using low-cost adsorption material in the field of treatment of heavy metal becomes the subject of current research focus.
The adsorption material chemical activation making is this topic research focus which uses municipal sewage treatment plant sludge as raw material, by adding activator and surfactant modification. In the experiment, the effects of preparation conditions are studied on activation temperature, activation time, activator concentration, solid-liquid ratio, soaking time and activated sludge particle size before modification; By using surfactant modification to the adsorption material, researching on the surfactant types, dosage, ratio and the influence to the activated conditions after modification; combined with morphology, specific surface area, nitrogen adsorption isotherms and the spectrum analysis, performance evaluation on the adsorption material, discussion on the preparation process and the mechanism. In addition, the prepared adsorption material analyses on the Cr(VI), Ni(II) simple solution and mixed solution, by researching on the removal of heavy metals impact through different adsorption material dosage, pH of solution, adsorption hour, oscillation frequency, holding time, adsorption temperature, etc. The conclusions are as following through the experiment:
Adding ZnCl2 as the activator, studies the best preparation conditions by iodine, methylene blue and Cr(VI) removal ratio: the activation temperature is 550℃, the activation time is 0.5 hour, the concentration of activator is 3 mol/L, the ratio between solid and liquid is 1:2, the hour to immerse sludge is 1 hour, and the sludge particle before activation is 100 mesh. The modification materials are SDS and PAM, the complex ratio of 1:1, both qualities of 0.01g. Through the prepared adsorption material, adsorption performance contains 5.80mg/g of Cr(VI), 114.64mg/g of MB adsorption, 503.20mg/g iodine. From the research on the morphology, specific surface area, nitrogen adsorption isotherms and the spectrum of the micro level, character adsorption material properties, obtained the adsorption material property after modification higher than the adsorption material before modification and commercial activated carbon which is consistent with the experimental results.
The removal ratio of heavy metal in Cr(VI), Ni(VI) solution and mixed solution is researched by the sludge-making adsorption material before or after modification on the adsorption conditions of dosage, pH of solution, adsorption hour, oscillation frequency, frequency, holding time, adsorption temperature, etc. The results show that Cr(VI) and Ni (VI) solution have different pH range in the simple solution and in the room temperature; for the mixed solution, the removal ratio has also increased with the increasing of adsorption material dosage except other influent conditions, so that, it shows that the heavy metal removal ratio can be propelled by the other heavy metal solution’s existence.
Through the studying of adsorption thermodynamics and kinetics to Cr6+ and Ni2+, the Cr6+ adsorption model is consistent with Freundlich adsorption, while the Ni2+ adsorption model is consistent with Langmuir adsorption, meanwhile the both heavy metals’thermal models fit Lagergren second dynamic adsorption model.
引文
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