CN102448892B - 一种处理含重金属的废水的方法 - Google Patents
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- C02F1/00—Treatment of water, waste water, or sewage
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Abstract
本发明公开了一种处理含有重金属的废水的方法,该方法包括使废水在40-120psi的低压下通过芳香聚酰胺反渗透膜,该反渗透膜能够去除废水中至少90%的目标重金属。
Description
技术领域
本发明涉及一种处理含重金属的废水的方法,进一步地,本发明涉及一种在低压下通过反渗透膜除去含重金属的废水中的高含量重金属的方法。
背景技术
利用在低压下工作的低能量膜处理废水的技术近年来被发展来降低水处理系统的运行和维护费用。通过水处理系统的各种工作条件,低能量膜可以去除包括微污染物,纳米尺寸的阴离子物质和金属污染物。
和传统的醋酸纤维素膜相比,聚酰胺膜在以下方面具有更好的膜性能:对盐和水溶性有机物的有更高的截留能力,有更好的抗水解和抗微生物侵袭能力,能耐更高的温度,并在广泛的pH值范围(pH=2~10)内操作。
芳香聚酰胺膜对氯化钠有更低扩散性,对水有更高的渗透性,溶解性和扩散性,因此芳香聚酰胺膜脱盐率优于醋酸纤维素膜。
目前有关膜系统或通过反渗透处理废水或盐水的方法,有以下几种现有技术。
日本专利N0.2007105572公开了一种净水系统,该系统通过一个反渗透膜类型的过滤器将原水分离成渗透水,即纯净水,和不透明的残余水。作为一个喷射管的分支,水处理循环回路将渗透水灌入储液槽,然后通过某种控制手段根据灌溉操作向反渗透膜过滤器供水。
另一个日本专利No.2001113136公开了一种反渗透膜设备,该设备包含一个泵,一个旁路通道,该旁路通道还包含一个流量控制阀。该泵提升原水压力到一预设的可供应反渗透膜工作需要的压力值;该旁路通道分流由泵的排放口排出的原水并输入到反渗透膜组件;该流量控制阀用于调整原水的分流率。
美国专利No.2007289904公开了一种反渗透系统,该系统含一个膜室,一个助推器设备。所述膜室含一个供料线以产生一个渗透流和一个盐水流;所述助推器设备在盐水流流体窜槽处有一个涡轮机,在供料线流体窜槽处有一个泵。
在前述技术中一种操作反渗透系统的方法包含以下步骤:给供料线加压,产生对应于渗透流的一股流体的第一个流量信号,操作对应第一个流量信号的变频驱动,控制响应该变频驱动的马达,产生对应于盐水流系统的一股流体的第二个流量信号,通过对第二个流量信号的响应控制一个耦合到涡轮部分的大小可变的喷嘴的开关。
美国专利No.6162361公开了一种从废水中分离回收重金属的方法,该方法包括使废水流通过一组串联或并联安排的纳米过滤膜,产生一股渗透流和一股浓缩输出流,再使该浓缩输出流通过一个电透析设备以浓缩重金属离子。所述专利方法应进一步包括使渗透流通过一组串联或并联安排的纳米过滤膜。
在水处理系统中,典型的反渗透膜需要高工作压力。但是,想要减少系统的运行和维护费用就需要一个能在低压工作的低能量膜,所述膜同时还需能在处理废水、大量去除其中各种污染物方面有好的表现。
发明内容
本发明的主要目的是提供一种处理含重金属的废水的方法,该方法利用一种能在低压范围内操作的反渗透膜,以节省运营和维护成本,并延长膜的寿命。
本发明的另一个目的是提供了一种处理含重金属的废水的方法,该方法使废水通过一个低能量的反渗透膜,该膜具有高脱盐率和高水通量,能够去除废水中包括大量重金属在内的各种污染物。
本发明至少全部或部分达到前述一个目的,本发明实施例描述了一种处理含重金属的废水的方法,该方法包括:使废水在40-120psi的低压范围内通过一种反渗透芳香聚酰胺膜,该膜能够去除废水中至少90%的目标重金属。
本发明的反渗透芳香聚酰胺膜具有高脱盐率,能够高效脱除分子量大于100的纳米级污染物,如阴离子。该膜在低压下工作,能去除含重金属的废水中至少90%的目标重金属。使用优化后的废水处理条件,该低能量反渗透膜能够去除超过99%的砷。
附图说明
图1为一种使用低能量反渗透膜处理含重金属的废水的系统(100)的示意图。
具体实施方式
本领域技术人员将会领会到本发明非常适用于实现所述目的,且能获得所提及以及所内含的效果和优点。本发明的范围并不限于所述的实施例。
本发明公开了一种处理含重金属的废水的方法,该方法包括引导废水在40-120psi的低压范围内通过一种反渗透芳香聚酰胺膜,该膜能够去除废水中至少90%的目标重金属。
通过使用所述能在低压下工作的低能量反渗透膜,能够降低废水处理系统的操作和维护费用。该低能量膜比在高压下使用的普通反渗透膜使用寿命能够延长3-5年。
本发明的反渗透芳香聚酰胺膜有高脱盐率和高水通量或渗透流量。本发明的一个优选实施例中,在室温下,压力为80psi或552kPa,pH范围为3.4-7.6的优化条件下,所述反渗透芳香聚酰胺膜能够去除废水中至少90%的目标重金属,特别是能去除超过99%的重金属砷。
而且,所述的反渗透芳香聚酰胺膜也能够移除废水中以下重金属:镉,铬,铜,铁,镍,锌,锰,镁及其它同类重金属。本发明的一个优选实施例中:所述反渗透芳香聚酰胺膜对重金属有很高的脱除率,特别是能够从废水中去除至少99%的砷,至少98%的镍,至少97%的锰和99.9%的镁,94%的铬以及至少80%的钙、铜和锌。
此外,本发明还公开了对于500mg/L的氯化钠溶液,本发明所述的反渗透芳香聚酰胺膜,在室温,552kPa的压力,pH值为7的条件下,能够脱除至少98%的氯化钠。在本发明中,所述膜应能阻隔分子量100以上的分子以及微粒直径小于2纳米(nm)的粒子。
如本发明中声称,所述芳香聚酰胺膜应包含孔径小于2nm,且水通量或渗透通量范围在0.005m3/m2.h到0.025m3/m2.h之间的孔,具体视工作条件和给水的类型而定。优选地,水通量或渗透通量为0.013m3/m2.h。
和传统的醋酸纤维素膜相比,聚酰胺膜在以下方面具有更好的膜性能:对盐和水溶性有机物有更高的截留能力,提供更好的抗水解和抗微生物侵袭能力,能耐更高的温度,并能在pH=2~10的宽pH范围操作。
由于芳香聚酰胺膜对氯化钠的低扩散性,对水的高渗透性,高溶解性和高扩散性,芳香聚酰胺膜相对醋酸纤维素膜具有更好的脱盐率。本发明所述的芳香聚酰胺膜是超低压力反渗透膜,其具有一个瓦楞状膜层。通常情况下,芳香聚酰胺通过胺基和卤化酰基反应制备,反应式如下:
nNH2-Ar-COCl→-(NH-Ar-CO)n-+nHCl
其中n是一个数字或比例;下标n是一个数字或比例,Ar是芳烃自由基。
如本发明所述,一个处理含重金属的废水的系统100包括:一个膜池102,该膜池102内框设有芳香聚酰胺膜多层薄平板,一个给料罐101,一个低压泵106,一个压力表105,一个渗透罐103,一个流量控制阀104和一个流量计107。系统100的循环或运输管道最好由不锈钢和/或优质塑料制成。
本发明中,膜池最好采用错流模型,其中,膜池102顶框和底框上封闭设置芳香聚酰胺膜多层薄平板。该错流模型含一个60平方厘米的活性膜表面,最大工作压力为130psi,最高温度为40摄氏度。
芳香聚酰胺膜多层薄平板可在pH值2~10范围间工作。由于膜层具有带电荷的酰基和胺基基团,在pH值大于5的情况下由于羧基的解离,膜将带负电荷;而在pH值小于5的情况下由于胺基的解离,膜将带负电荷。
错流模型膜组件由高性能玻璃制成,以防止腐蚀性物质污染给料液。膜组件还应包括以下组成:如一个给水隔片,最好间隔0.7毫米;两个渗透隔片,最好分别间隔0.3毫米和1.25毫米,一个用于安装膜层且防止系统100泄漏的板形环或O型环。
膜组件或加外框的膜池102的三维结构最好是80毫米宽,210毫米长和82毫米高。然而,加外框的膜池102的三维内尺寸为46毫米宽,180毫米长和82毫米高,采用这样的三维内尺寸是为了适应包括平板芳香聚酰胺膜、给水隔片、渗透隔片、板形环或O型环的所有构成部分或组件的需要。
在一个处理含重金属的废水的系统100中,给料罐101最好能容纳2升废水。如本发明一个较佳实施例所述,含重金属的废水是从一个矿池中收集得到或是通过在蒸馏水中溶解硫酸镁和氯化铜得到。
废水的给水将从给料罐101中抽提出来,然后,通过低压泵106在特定范围的低压下泵过膜池102。所得的渗透水或纯化水收集到渗透罐103,而残余物或浓缩物返回或循环回给料罐101以保持它的容量和溶液浓度恒定。
在下文本发明的讨论中,系统100的给料液温度维持在25±2℃。系统100配有压力表105来记录给料压力、浓度,流量计107来记录给料流速和渗出流速,流量控制阀104来调节给料和渗出流量,pH探头108记录给料罐101中料液的pH值或渗透罐103中料液的pH值。
实施例
实施例1
从一份废水样品中去除的各种金属的百分含量如下表所示:
金属/参数 | 去除的百分含量(%) |
砷 | 99.4 |
镉 | 80.2 |
铬 | 94.0 |
铜 | 81.4 |
铁 | 51.5 |
镍 | 98.8 |
锌 | 86.0 |
锰 | 96.7 |
镁 | 99.9 |
由表可知去除的各种重金属的平均百分含量为87.5。
实施例2
在本发明中,处理废水的方法试用废水样品可来自一个矿池,矿池中废水的估计的组成如下表所示:
金属/参数 | 浓度(毫克/升)±0.05 |
砷 | 0.52 |
镉 | 0.33 |
铬 | 0.01 |
铜 | 0.42 |
铁 | 0.33 |
镍 | 0.10 |
锌 | 0.56 |
镁 | 2.34 |
本发明公开了一种使用低能量芳香聚酰胺膜处理废水样品的方法。如下表所示,重金属,特别是砷,在不同低操作压力和pH值下至少可以被去除90%:
测试参数 | 1 | 2 | 3 | 4 | 5 | 6 |
操作压力(psi) | 51.7 | 108.3 | 51.7 | 108.3 | 40.0 | 120.0 |
pH值 | 3.4 | 3.4 | 7.6 | 7.6 | 5.5 | 5.5 |
流速(×10-3m3/m2.h) | 8.5 | 20.5 | 7.7 | 19.3 | 6.1 | 21.8 |
去除砷含量(%) | 99.15 | 99.70 | 99.68 | 98.72 | 98.02 | 99.72 |
实施例3
为测试处理后的水样,每隔30分钟从渗透罐103中取样,测量渗出液流量和浓度,直到获得一个能够评估反渗透膜的截留能力的稳定的渗出液。蒸馏水流量数据测定方式为:使蒸馏水在80psi或552kpa压力,pH值7,稳定回收率在60%-65%的条件下通过反渗透膜4小时。膜有效性测定方式为:使用500mg/L的氯化钠溶液获得在稳定状态在工作的废水处理系统100的最小工作时间。
截留氯化钠的工作条件为552kpa压力,pH值7,氯化钠溶液浓度500mg/L。240分钟,每30分钟采样一次,8组相同氯化钠渗出流样品的渗出流量数据如下表所示:
在240分钟内,每30分钟采样一次,8组相同样品去除氯化钠的百分含量的数据如下表所示:
实施例4
以下测定稳定回收率60%-65%的条件下,氯化铜和硫酸镁在不同进水浓度、不同压力条件、给水液不同pH值条件下去除废水中重金属尤其是铜、镁和砷的情况。其中所取进水浓度包括1.00mg/L,2.00mg/L,3.00mg/L,4.0mg/L和5.0mg/L,所取压力包括40psi,60psi,80psi,100psi和120psi所取给水液pH值包括2.5,4.5,6.5和8.5。
通过一组运行20个轮次的实验获得的去除铜(%)的渗出流量相关数据如下表所示:
另一通过一组运行20轮次的实验获得的去除铜百分含量的数据如下表所示:
实施例5
为了优化低能量反渗透膜去除重金属的工艺,使用一个响应面分析法以定量识别重大的、有互动关系的影响因素。该响应面分析法是以统计学方式使用响应面设计法设计的,尤其是,中心旋转组合设计法。
此外,中心旋转组合设计法便于对非线性影响行为以及能获得最大产出的最佳实验参数的测定。
各参数之间的协同效应通过哈德玛得矩阵(Hadamard matrix)和中心点运行测定。其中非线性影响行为通过开始点和中心点运行来分析。中心点运行重复6次以更好估算实验误差。运行随机进行,以降低本研究中没有计算在内的时间依赖因子的影响。
下表显示恒定的回收率在60%-65%之间时,非随机状态下,从去除微污染物的实验中获得渗透通量值和的重金属去除百分比值:
a运行轮次 | 操作压力,psi()b | pH值()b | 浓度,mg/L()b |
1 | 56.2(-1) | 3.7(-1) | 1.8(-1) |
2 | 103.8(+1) | 3.7(-1) | 1.8(-1) |
3 | 56.2(-1) | 7.3(+1) | 1.8(-1) |
4 | 103.8(+1) | 7.3(+1) | 1.8(-1) |
5 | 56.2(-1) | 3.7(-1) | 4.2(+1) |
6 | 103.8(+1) | 3.7(-1) | 4.2(+1) |
7 | 56.2(-1) | 7.3(+1) | 4.2(+1) |
8 | 103.8(+1) | 7.3(+1) | 4.2(+1) |
9 | 40.0(-1.682) | 5.5(0) | 3.0(0) |
10 | 120.0(+1.682) | 5.5(0) | 3.0(0) |
11 | 80.0(0) | 2.5(-1.682) | 3.0(0) |
12 | 80.0(0) | 8.5(+1.682) | 3.0(0) |
13 | 80.0(0) | 5.5(0) | 1.0(-1.682) |
14 | 80.0(0) | 5.5(0) | 5.0(+1.682) |
15 | 80.0(0) | 5.5(0) | 3.0(0) |
16 | 80.0(0) | 5.5(0) | 3.0(0) |
17 | 80.0(0) | 5.5(0) | 3.0(0) |
18 | 80.0(0) | 5.5(0) | 3.0(0) |
19 | 80.0(0) | 5.5(0) | 3.0(0) |
20 | 80.0(0) | 5.5(0) | 3.0(0) |
上表中:a是基于中心旋转组合设计法设计的标准顺序;()b是中心旋转组合设计法分配的编码值。
Claims (4)
1.一种处理含重金属的废水的方法,其特征在于,该方法包括:从给料罐(101)抽提废水,在40-120psi的低压下,通过反渗透膜池(102),所得的渗透水收集到渗透罐(103)中,其中,所述的膜池采用错流模型;错流模型组件由高性能玻璃制成,膜池(102)的顶框和底框上封闭设置芳香聚酰胺膜多层薄平板,该膜具有孔径大小为能够截留粒径小于2纳米的微粒的孔,能够从废水中去除至少90%的目标重金属,从而获得渗透水,而残余物循环返回至给料罐(101)。
2.如权利要求1所述的处理含重金属的废水的方法,其特征在于,所述膜的流速在0.005m3/m2.h到0.025m3/m2.h之间。
3.如权利要求1所述的处理含重金属的废水的方法,其特征在于,所述膜能够截留至少99%的重金属砷。
4.如权利要求1所述的处理含重金属的废水的方法,其特征在于,所述膜还能够从废水中去除至少98%镍,至少97%锰,99.9%镁,94%铬,以及至少80%钙、铜和锌。
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