反渗透膜有机污染机理及其渗透反洗控制的研究
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摘要
膜污染问题是制约反渗透膜广泛应用的瓶颈之一,它导致产水水质降低、产水量减少、操作压力增大,同时污染腐蚀膜材料、增加化学试剂量,从而缩短了膜的使用寿命。而其中有机污染是目前反渗透行业最难解决的问题。
本实验主要研究以多聚糖类物质(海藻酸钠)为代表的有机污染物对于反渗透膜分离过程的影响,探索其与腐殖酸混合污染的机理。同时,提出了采用商用阻垢剂和反洗的新方法来减缓反渗透膜的有机污染。此外实验还研究了应用Fenton法来处理水溶液中的海藻酸钠。
研究结果表明海藻酸钠会在反渗透膜表面形成致密的凝胶层,致使膜通量快速衰减,特别是当进水溶液中含有Ca~(2+)时,由于Ca~(2+)的聚合作用以及有机物分子链之间的交联使得膜污染更严重。同时,料液的化学组成(污染物的浓度、离子强度、pH值等)、温度等都会对污染过程产生较强的影响。当海藻酸钠与腐殖酸进行混合污染时,在低盐度条件下,随着海藻酸钠比例增加,通量下降增大;在海水条件下,腐殖酸污染比海藻酸钠污染严重,随着腐殖酸比较增加,通量下降增大。
本实验将两种方法创新性地应用于缓解有机污染,并取得了良好的效果。同时引入阻滞效率(Inhibition efficiency)来评价不同参数对阻滞效率的影响,由此推测两种方法缓解有机污染的内在机理。
研究表明阻垢剂在反渗透膜有机污染过程中起到了有效缓解膜通量衰减的作用。通过分析认为这主要与以下三方面的作用有关:首先,阻垢剂与Ca~(2+)的螯合作用使得Ca~(2+)可以稳定地分散在溶液中,从而减少了Ca~(2+)和海藻酸钠通过络合作用形成高聚物的量。其次,阻垢剂、海藻酸钠和Ca~(2+)所形成的亲水性复合物吸附在膜表面会增强其亲水性,从而减缓膜污染。最后,阻垢剂本身对海藻酸钠具有较好的分散作用,可以将海藻酸钠稳定地分散于溶液中。因此,利用阻垢剂减缓膜污染是一种便捷、有效的方法。
同时,本研究表明在反渗透膜海藻酸钠污染过程中反洗起到了有效缓解膜通量衰减的作用。这主要是因为反洗时瞬间强大的驱动力可以解除和清除膜表面的污染物,随后污染物被水流带走。本实验将阻垢剂和反洗联用,较好地抑制了有机污染,PASP-Ca-SA聚合物的存在使得反渗透膜表面形成的污染层较薄,此时进行反洗,膜表面的污染物容易被冲散,大部分污染物被随即而来的剪切流冲走。
此外,研究应用Fenton法来处理水溶液中的海藻酸钠,从而减缓反渗透膜污染。实验结果表明Fenton法处理后,海藻酸钠从大分子分解为小分子物质,且该小分子物质不能和Ca~(2+)发生络合反应,从而减轻了膜污染。
Membrane fouling is one of the most serious obstacle to restrict its widespread application. One of the critical issues is organic fouling, which not only reduces the permeate flux of a membrane and requires more frequent cleaning, but also shortens its life .
Fouling of RO membrane by polysaccharides(alginate) was systematically investigated. Commercial antiscalant and backwash were adopted to alleviate the organic fouling of RO membrane. In addition, Fenton method was used to oxidize alginate so as to alleviate the fouling of RO membrane.
Pilot study demonstrated that alginate could form compact gel layer on membrane surface, which leads to a severe flux decline. Especially, permeate flux decreased dramatically in the presence of calcium ions. This behavior can be attributed to calcium bridges between adjacent organic matter and the formation of organic macromolecule complexation. In addition, the effects of chemical composition (foulant concentration, ionic strength and solution pH) and temperature on the membrane fouling mechanisms were investigated. Combined fouling by both alginate and humic acid were studied, in the low salinity conditions, with the increase of sodium alginate, flux decline increased; in seawater conditions, with the increase of humic acid, flux decline increased.
Antiscalant and the way of backwash are mainly used in the field of inorganic scaling control of RO technology. We innovatively use the two methods to decrease the organic fouling, and it turns out to be effective. We define the Inhibition Efficiency to evaluate how different parameters affect the fouling, and then speculate the mechanism of how the two methods alleviate the organic fouling.
The introduction of antiscalant to feed water was found very effective for relieving organic-fouled RO membrane in the presence of calcium ions. Antiscalant relieves organic fouling by the following three ways. Firstly, it is proposed that Ca~(2+) can be stably dispersed in solution by chelation between Ca~(2+) and antiscalant , which could decrease the quantity of macromolecule complexation. Secondly, antiscalant, organic foulant and calcium ions could form a kind of hydrophilic compound, which could be removed by the shear easily. Thirdly, antiscalant is also a kind of very excellent disperser to organic matters.
The way of backwash was also found effective for lessening organic-fouled RO membrane in the presence of calcium ions. This is mainly because there can be a powerful driving force to lift and sweept foulants on the membrane surface . The PASP-Ca-SA molecules formed still have relatively high hydrophilia, and hence can be removed by the shear easily. Moreover, while the antiscalant and the way of backwash are combined, the organic fouling is inhibited efficiently. The presence of PASP-Ca-SA complex molecules leads to a thinner foulant layer, and the following backwash process can disperse the foulant in the layer. Then most of the foulant is removed by the shear.
In addition, Fenton method was used to oxidize alginate. The experiment result showed that the sodium alginate may be decomposed into small molecules, which could not have complex reaction with Ca~(2+).
本实验主要研究以多聚糖类物质(海藻酸钠)为代表的有机污染物对于反渗透膜分离过程的影响,探索其与腐殖酸混合污染的机理。同时,提出了采用商用阻垢剂和反洗的新方法来减缓反渗透膜的有机污染。此外实验还研究了应用Fenton法来处理水溶液中的海藻酸钠。
研究结果表明海藻酸钠会在反渗透膜表面形成致密的凝胶层,致使膜通量快速衰减,特别是当进水溶液中含有Ca~(2+)时,由于Ca~(2+)的聚合作用以及有机物分子链之间的交联使得膜污染更严重。同时,料液的化学组成(污染物的浓度、离子强度、pH值等)、温度等都会对污染过程产生较强的影响。当海藻酸钠与腐殖酸进行混合污染时,在低盐度条件下,随着海藻酸钠比例增加,通量下降增大;在海水条件下,腐殖酸污染比海藻酸钠污染严重,随着腐殖酸比较增加,通量下降增大。
本实验将两种方法创新性地应用于缓解有机污染,并取得了良好的效果。同时引入阻滞效率(Inhibition efficiency)来评价不同参数对阻滞效率的影响,由此推测两种方法缓解有机污染的内在机理。
研究表明阻垢剂在反渗透膜有机污染过程中起到了有效缓解膜通量衰减的作用。通过分析认为这主要与以下三方面的作用有关:首先,阻垢剂与Ca~(2+)的螯合作用使得Ca~(2+)可以稳定地分散在溶液中,从而减少了Ca~(2+)和海藻酸钠通过络合作用形成高聚物的量。其次,阻垢剂、海藻酸钠和Ca~(2+)所形成的亲水性复合物吸附在膜表面会增强其亲水性,从而减缓膜污染。最后,阻垢剂本身对海藻酸钠具有较好的分散作用,可以将海藻酸钠稳定地分散于溶液中。因此,利用阻垢剂减缓膜污染是一种便捷、有效的方法。
同时,本研究表明在反渗透膜海藻酸钠污染过程中反洗起到了有效缓解膜通量衰减的作用。这主要是因为反洗时瞬间强大的驱动力可以解除和清除膜表面的污染物,随后污染物被水流带走。本实验将阻垢剂和反洗联用,较好地抑制了有机污染,PASP-Ca-SA聚合物的存在使得反渗透膜表面形成的污染层较薄,此时进行反洗,膜表面的污染物容易被冲散,大部分污染物被随即而来的剪切流冲走。
此外,研究应用Fenton法来处理水溶液中的海藻酸钠,从而减缓反渗透膜污染。实验结果表明Fenton法处理后,海藻酸钠从大分子分解为小分子物质,且该小分子物质不能和Ca~(2+)发生络合反应,从而减轻了膜污染。
Membrane fouling is one of the most serious obstacle to restrict its widespread application. One of the critical issues is organic fouling, which not only reduces the permeate flux of a membrane and requires more frequent cleaning, but also shortens its life .
Fouling of RO membrane by polysaccharides(alginate) was systematically investigated. Commercial antiscalant and backwash were adopted to alleviate the organic fouling of RO membrane. In addition, Fenton method was used to oxidize alginate so as to alleviate the fouling of RO membrane.
Pilot study demonstrated that alginate could form compact gel layer on membrane surface, which leads to a severe flux decline. Especially, permeate flux decreased dramatically in the presence of calcium ions. This behavior can be attributed to calcium bridges between adjacent organic matter and the formation of organic macromolecule complexation. In addition, the effects of chemical composition (foulant concentration, ionic strength and solution pH) and temperature on the membrane fouling mechanisms were investigated. Combined fouling by both alginate and humic acid were studied, in the low salinity conditions, with the increase of sodium alginate, flux decline increased; in seawater conditions, with the increase of humic acid, flux decline increased.
Antiscalant and the way of backwash are mainly used in the field of inorganic scaling control of RO technology. We innovatively use the two methods to decrease the organic fouling, and it turns out to be effective. We define the Inhibition Efficiency to evaluate how different parameters affect the fouling, and then speculate the mechanism of how the two methods alleviate the organic fouling.
The introduction of antiscalant to feed water was found very effective for relieving organic-fouled RO membrane in the presence of calcium ions. Antiscalant relieves organic fouling by the following three ways. Firstly, it is proposed that Ca~(2+) can be stably dispersed in solution by chelation between Ca~(2+) and antiscalant , which could decrease the quantity of macromolecule complexation. Secondly, antiscalant, organic foulant and calcium ions could form a kind of hydrophilic compound, which could be removed by the shear easily. Thirdly, antiscalant is also a kind of very excellent disperser to organic matters.
The way of backwash was also found effective for lessening organic-fouled RO membrane in the presence of calcium ions. This is mainly because there can be a powerful driving force to lift and sweept foulants on the membrane surface . The PASP-Ca-SA molecules formed still have relatively high hydrophilia, and hence can be removed by the shear easily. Moreover, while the antiscalant and the way of backwash are combined, the organic fouling is inhibited efficiently. The presence of PASP-Ca-SA complex molecules leads to a thinner foulant layer, and the following backwash process can disperse the foulant in the layer. Then most of the foulant is removed by the shear.
In addition, Fenton method was used to oxidize alginate. The experiment result showed that the sodium alginate may be decomposed into small molecules, which could not have complex reaction with Ca~(2+).
引文
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