电镀废水纳滤膜（NF）浓缩回用研究
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摘要
随着国民经济的高速发展,我国工业废水排放量急速增加,但随之也带来了大量污染。在各种污染源中电镀废水以其毒性大,排放量大,难治理,尤其值得关注。目前膜分离法处理电镀污水以双膜法MF+RO最为主流。但RO膜易受到各种污染因素的影响,且RO膜对于进水要求高,所以限制了整个膜系统处理回用电镀废水的效率,至多只能达到50%-65%。而纳滤(简称NF)是近几年发展较快的一项膜技术。其具有筛分效应和Donnan电荷效应的分离特性,这使得NF膜对于二价或高价离子截留效果更好,加之其较强的抗污染性,因此在RO膜系统处理的基础上能应用NF膜深度浓缩电镀废水,提高整个系统的回用率达到90%左右,具有一定的优势。
本论文将考察纳滤膜浓缩处理电镀废水的可行性,研究浓差极化、操作压力和原料液浓度对截留性能的影响,揭示其规律,模拟工程效果,为纳滤膜处理实际电镀综合废水提供指导,取得的主要研究结果和结论包括：
1.本论文分别考察了陶氏NF270-400和NF90-400型纳滤膜在不同操作压力、不同进水水质等条件下的分离特性及处理效果。通过条件实验研究发现NF90和NF270膜在处理综合电镀废水的效果上有明显的差异,NF90以其表面固定电荷密度高的特性,相比NF270表现出了更高更加稳定的重金属离子截留率能力,且截留能力相对稳定在90%左右,但其产水量相比NF270却相对较小,只有NF270的1/3左右。且两种膜在进水压力为1.6Mpa时表现出最好的离子截留能力,即便在进水电导率30000μs/cm时,即原水浓缩7倍左右时,产水Zn2+浓度仍能控制1.2mg/L以下,Ni2+浓度能控制在0.4mg/L以下,符合国家排放标准。
2.论文进一步对NF90/270纳滤膜浓差极化进行分析,以实际的综合电镀废水为考察体系,在最佳操作压力1.6Mpa下考察了传质系数与浓差极化程度随膜面流速的变化关系。结果表明,两者传质系数k都随膜面流速增加而增加,浓差极化程度相应下降；同时渗透通量J对浓差极化有一定的影响,当渗透率增加时,传质系数k下降,浓差极化程度增加。而NF90相对NF270受到浓差极化的影响程度较大,即使在增加表面流速的情况下也很难降低到1.2以下,而采用的NF270膜元件,当膜面流速达到0.20m/s时浓差极化可以降到相对较小的程度,适合工程实际运行。
3.论文最后对实际工程采用NF270膜元件进行运行测试,在进水为16000μs/cm时,压力为1.6MPa时,NF产水电导率稳定低于7000μs/cm,总系统浓水即NF浓水的电导率稳定在33000μs/cm至42000μs/cm, NF系统回收率在75%左右,RO/NF组合系统可实现95%的回收率,可以满足回用水水质和水量的设计要求。
With the high-speed development of national economy, China's industrial wastewater emissions increased sharply, and it also brings large quantity of pollution. Electroplating wastewater is difficult to handle with because it has the characteristic of toxic compound and large quantity of emission. Membrane separation technology as one kind of high efficient water treatment methods has been widely used in power plant sewage treatment cycle and sea water desalination and recycling of industrial waste water treatment. And the membrane separation of MF+RO is applied mostly to deal with electroplating wastewater. But RO membrane is susceptible to many kinds of pollution factors, and the inflow water for RO membrane requires high standard, which limits the reuse efficiency of the whole membrane treatment system to only 50%-65%.
Nanofiltration is a kind of membrane technology which developed rapidly in the recent years. It has the screening effect and Donnan effects of separation electric charge, and with which the Donnan effect functioned mainly. And together with its strong resistance to pollution that makes the interception of NF membrane for divalent ion represent much better. So it has certain advantage in the application of NF membrane system which based on RO system which can make the reuse efficiency of the whole membrane treatment system to almost to 90%. This thesis studies the application of NF membrane system which based on RO system. we investigated the influence of operating pressure, concentration polarization and different nano filtration membrane modules (NF90 & NF270) on efficiency of interception. And the reuse possibility of electroplating wastewater was initially tested through the engineering case.
According to the research on working state of single nano filtration membrane that dispose the synithetical electroplating wastewater, we investigated the influence of operating pressure and different nano filtration membrane modules (NF90 & NF270) on efficiency of interception. The experiments showed remarkable differences between NF90 and NF270 when treating synithetical electroplating wastewater. NF90 with its characteristics of high fixed surface charge density showed a higher and more stable heavy metal ions interception rate compared with NF270 and interception rate was stable around 90%. But the water production rate of NF90 is relatively small compared with NF270, and only about 1/3 of NF270's. The both NF270 and NF90 system showed a high efficiency of interception when the operating pressure was about 1.6MPa. Even the inflow water conductivity is around 30000μs/cm, the concentration ofZn2+ of water production can still be controlled around 1.2mg/Land concentration of Ni2+ was around 0.4 mg/L, which accorded with the national discharge standard.
We further investigated the influence of concentration polarization of NF90 and NF270 system when treating the electroplating wastewater. In the best operating pressure under 1.6Mpa, we investigated the relationship between mass transfer coefficient and surface velocity. The results show that the mass transfer coefficient k increased with surface velocity, together with decrease of polarization degree. And at the same time, the Penetration Flux J also had a certain effect. When permeability increase, the mass transfer coefficient k decreased, and polarization degree increased. And NF90 was relatively highly influenced by the concentration polarization compared with NF270. Even we increased the surface velocity cannot control NF90's polarization degree under 1.2 while the surface velocity of NF270 membrane reached 0.20m/s the polarization can be controlled to a relatively small degree, which was suitable for the engineering practical operation.
We further tested the NF270 membrane system on an actual engineering practical operation project, in which the conductivity of inflow water was around 16000 [i s/cm, pressure was around 1.6MPa. The conductivity of water production by NF system was steadily under 7000μs/cm, The reuse efficiency of NF membrane system was about 75%, while the reuse efficiency of RO/NF combination system can reach 95%, and can reach the reuse water requirements both in quality and quantity that engineering practical operation project was designed for.
本论文将考察纳滤膜浓缩处理电镀废水的可行性,研究浓差极化、操作压力和原料液浓度对截留性能的影响,揭示其规律,模拟工程效果,为纳滤膜处理实际电镀综合废水提供指导,取得的主要研究结果和结论包括：
1.本论文分别考察了陶氏NF270-400和NF90-400型纳滤膜在不同操作压力、不同进水水质等条件下的分离特性及处理效果。通过条件实验研究发现NF90和NF270膜在处理综合电镀废水的效果上有明显的差异,NF90以其表面固定电荷密度高的特性,相比NF270表现出了更高更加稳定的重金属离子截留率能力,且截留能力相对稳定在90%左右,但其产水量相比NF270却相对较小,只有NF270的1/3左右。且两种膜在进水压力为1.6Mpa时表现出最好的离子截留能力,即便在进水电导率30000μs/cm时,即原水浓缩7倍左右时,产水Zn2+浓度仍能控制1.2mg/L以下,Ni2+浓度能控制在0.4mg/L以下,符合国家排放标准。
2.论文进一步对NF90/270纳滤膜浓差极化进行分析,以实际的综合电镀废水为考察体系,在最佳操作压力1.6Mpa下考察了传质系数与浓差极化程度随膜面流速的变化关系。结果表明,两者传质系数k都随膜面流速增加而增加,浓差极化程度相应下降；同时渗透通量J对浓差极化有一定的影响,当渗透率增加时,传质系数k下降,浓差极化程度增加。而NF90相对NF270受到浓差极化的影响程度较大,即使在增加表面流速的情况下也很难降低到1.2以下,而采用的NF270膜元件,当膜面流速达到0.20m/s时浓差极化可以降到相对较小的程度,适合工程实际运行。
3.论文最后对实际工程采用NF270膜元件进行运行测试,在进水为16000μs/cm时,压力为1.6MPa时,NF产水电导率稳定低于7000μs/cm,总系统浓水即NF浓水的电导率稳定在33000μs/cm至42000μs/cm, NF系统回收率在75%左右,RO/NF组合系统可实现95%的回收率,可以满足回用水水质和水量的设计要求。
With the high-speed development of national economy, China's industrial wastewater emissions increased sharply, and it also brings large quantity of pollution. Electroplating wastewater is difficult to handle with because it has the characteristic of toxic compound and large quantity of emission. Membrane separation technology as one kind of high efficient water treatment methods has been widely used in power plant sewage treatment cycle and sea water desalination and recycling of industrial waste water treatment. And the membrane separation of MF+RO is applied mostly to deal with electroplating wastewater. But RO membrane is susceptible to many kinds of pollution factors, and the inflow water for RO membrane requires high standard, which limits the reuse efficiency of the whole membrane treatment system to only 50%-65%.
Nanofiltration is a kind of membrane technology which developed rapidly in the recent years. It has the screening effect and Donnan effects of separation electric charge, and with which the Donnan effect functioned mainly. And together with its strong resistance to pollution that makes the interception of NF membrane for divalent ion represent much better. So it has certain advantage in the application of NF membrane system which based on RO system which can make the reuse efficiency of the whole membrane treatment system to almost to 90%. This thesis studies the application of NF membrane system which based on RO system. we investigated the influence of operating pressure, concentration polarization and different nano filtration membrane modules (NF90 & NF270) on efficiency of interception. And the reuse possibility of electroplating wastewater was initially tested through the engineering case.
According to the research on working state of single nano filtration membrane that dispose the synithetical electroplating wastewater, we investigated the influence of operating pressure and different nano filtration membrane modules (NF90 & NF270) on efficiency of interception. The experiments showed remarkable differences between NF90 and NF270 when treating synithetical electroplating wastewater. NF90 with its characteristics of high fixed surface charge density showed a higher and more stable heavy metal ions interception rate compared with NF270 and interception rate was stable around 90%. But the water production rate of NF90 is relatively small compared with NF270, and only about 1/3 of NF270's. The both NF270 and NF90 system showed a high efficiency of interception when the operating pressure was about 1.6MPa. Even the inflow water conductivity is around 30000μs/cm, the concentration ofZn2+ of water production can still be controlled around 1.2mg/Land concentration of Ni2+ was around 0.4 mg/L, which accorded with the national discharge standard.
We further investigated the influence of concentration polarization of NF90 and NF270 system when treating the electroplating wastewater. In the best operating pressure under 1.6Mpa, we investigated the relationship between mass transfer coefficient and surface velocity. The results show that the mass transfer coefficient k increased with surface velocity, together with decrease of polarization degree. And at the same time, the Penetration Flux J also had a certain effect. When permeability increase, the mass transfer coefficient k decreased, and polarization degree increased. And NF90 was relatively highly influenced by the concentration polarization compared with NF270. Even we increased the surface velocity cannot control NF90's polarization degree under 1.2 while the surface velocity of NF270 membrane reached 0.20m/s the polarization can be controlled to a relatively small degree, which was suitable for the engineering practical operation.
We further tested the NF270 membrane system on an actual engineering practical operation project, in which the conductivity of inflow water was around 16000 [i s/cm, pressure was around 1.6MPa. The conductivity of water production by NF system was steadily under 7000μs/cm, The reuse efficiency of NF membrane system was about 75%, while the reuse efficiency of RO/NF combination system can reach 95%, and can reach the reuse water requirements both in quality and quantity that engineering practical operation project was designed for.
引文
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[3]吴舜泽等.荷电NF膜对有机物的分离.水处理技术,2002,26(5)249-252
[4]高从堵等.NF[C].第二届全国膜和膜过程学术会议.杭州,1996,15.
[5]Xiao Lin, Wang, Toshinori, et al. Electrolyte transport through nanofihration membranes by the space-charge model and the comparison with Teorell-Meyer-Sievers model. Membrane Sci,1995,(103):117-133.
[6]杨月明.我国电镀废水处理现状及展望.广州化工,2011,39(15)：60-62.
[7]谢芳.浅谈目前电镀废水处理的几种方法.中国高新技术企业,2009,23(11)：103-104.
[8]朱靖.张瑶电镀废水综合治理技术及应用.水处理技术,2008,34(6)：89-91.
[9]常江.纳滤膜法处理含Ni2+电镀废水及其资源化利用与工业实践研究.硕士论文无锡：江南大学,2009.7.
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