去除重金属的纳米净水材料、制备方法及应用.pdf

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摘要
申请专利号:

CN200310110076.1

申请日:

2003.11.19

公开号:

CN1544352A

公开日:

2004.11.10

当前法律状态:

终止

有效性:

无权

法律详情:

未缴年费专利权终止IPC(主分类):C02F 1/62申请日:20031119授权公告日:20051102终止日期:20091221|||授权|||实质审查的生效|||公开

IPC分类号:

C02F1/62; C08J5/08; B01J20/28; B01J20/08; B01J20/26; //(C02F1/62,101:20)

主分类号:

C02F1/62; C08J5/08; B01J20/28; B01J20/08; B01J20/26; //

申请人:

吉林大学;

发明人:

韩炜; 李素文; 李鱼; 王珩; 赵晖; 王月

地址:

130023吉林省长春市朝阳区前卫路10号

优先权:

专利代理机构:

长春吉大专利代理有限责任公司

代理人:

张景林

PDF下载: PDF下载
内容摘要

本发明属于水的净化领域,具体涉及一系列以高分子材料为填充剂、纳米材料为过滤体,能够对水中的重金属进行有效处理的高分子纳米净水材料以及该材料的制备方法。其形状包括层状圆形、卷曲筒状及片状,其主要成分为铝的氧化-氢氧化相:30-60%,玻璃纤维:10-35%,纤维素:15-40%,其中氧化-氢氧化铝的粒径为15-80纳米,比表面积200-800平方米/克。本发明15-30g的净水材料可连续使用710-1430h左右,然后将使用过的纳米净水材料取出,经过再生后仍可继续使用。本发明的纳米净水材料具有体积小,寿命长,成本低,效果好,用途广的优点,因此可广泛用于净水领域。

权利要求书

1: 1、一种纳米净水材料,其形状包括层状圆形、卷曲筒状及片状,其主要成份为 铝的氧化-氢氧化相:30-60%,玻璃纤维:10-35%,纤维素:15-40%, 其中氧化-氢氧化铝的粒径为15-80纳米,比表面积200-800平方米/克。 2、权利要求1所述纳米净水材料的制备方法,包括如下步骤: (1)将浓度为0.5-10.5g/l的酸性溶液10-100ml加入玻璃纤维的水悬浮液 中,其中玻璃纤维0.5-15.8g,蒸馏水100-500ml,将混合物加热至 20-120℃; (2)将加热后的混合物取出并向其中投入粒径为15-70nm的铝粉 0.2-10.2g,然后置于超声发生器中,在20-150℃温度下超声 0.3-5.5h,之后加入0.5-20g/l的四乙基正硅酸酯的醇溶液 10-110ml继续振荡5-55min,然后取出,在室温下冷却; (3)将浓度为0.04-5.64g/l的聚乙烯醇-[-CH 2 CHOH-]- n 溶液20-120ml 加入0.5-10.5g纤维素的水悬浮液中,其中纤维素
2: 0-11g,蒸馏水 200-600ml,浸泡、均质1-8h; (4)将步骤(2)、(3)制得的混合物用布氏漏斗进行过滤; (5)将滤料在40 180℃温度下在干燥箱中干燥1.5-10h得到白色圆形、 卷曲筒状及片状的本发明的纳米净水材料。 3、如权利要求2所述的纳米净水材料的制备方法,其特征在于:酸性溶液可以 是硼酸或水杨酸钠。 4、如权利要求2所述的纳米净水材料的制备方法,其特征在于:玻璃纤维可以 是C-玻璃纤维或E-玻璃纤维。 5、如权利要求2所述的纳米净水材料的制备方法,其特征在于:纤维素可以是 活性碳纤维丝或聚乙烯,聚乙烯为乙醇悬浮液,聚乙烯1.0-11g溶于 50-150ml乙醇。 6、权利要求1所述纳米净水材料在去除水中重金属方面的应用。 7、权利要求2-5任何一项制备方法所制备的纳米净水材料在去除水中重金属方 面的应用。

说明书


去除重金属的纳米净水材料、制备方法及应用

    【技术领域】

    本发明属于水的净化领域,具体涉及一系列以高分子材料为填充剂、纳米材料为过滤体,能够将污水中的重金属完全去除的纳米净水材料,以及纳米净水材料的制备方法。

    技术背景

    近年来,伴随着全球经济的迅速发展,水质污染日益严重,水中有毒、有害物质明显增加,各类水体中重金属污染也日趋加剧,已经对人们的生活和健康造成了巨大的威胁。就我国来说,据有关部门近五年来对我国纵多河流、湖泊及水库等几类水体的监测发现,汞的污染是十分突出的。城市河流有35.11%的河段出现总汞超过地面水III类水体标准,21.43%地河段年均值超标。北方地区超标最高的济南小清河,超标8倍;南方城市河流中污染最重的上海苏州河超标22倍;而在对作为饮用水源的城市河流污染物监测中发现,镉污染仅次于汞污染,城市河流有18.46%的河段面总镉超过III类水体标准,9.23%的河段年均值超过III类水体标准;镉和铅也是比较普遍的重金属污染物,近年来在对我国各大湖泊的调查中发现,这两种金属一直呈现上升趋势,已经开始影响到水体的质量;重金属污染不仅存在于地表水体,在地下水体中也是一个不容忽视的问题。据调查,我国绝大多数城市的地下水都不同程度的存在着较突出的水质问题,而城市生活污染、工业污染、饮用未经处理的污水灌溉农田以及地质条件恶化等是造成污染的主要原因。据统计,全国地下水水质超标(III类地下水体标准)面积大于200km2的城市有11.1%,超标面积在100-200km2的有18.5%,20--100km2的有48.2%,其主要污染物为重金属(如六价铬、汞等)。由以上所述可以看出,解决地表水体、地下水体、饮用水源中日益突出的重金属污染问题,对于提高水质、保护人民健康与安全有着十分重要的意义。

    目前去除重金属的水质净化技术主要有:沉淀法、螯合树脂法、高分子捕集剂法、天然沸石吸附法、膜技术、活性炭吸附工艺、离子交换法等。由国内外的研究可以看出,对水中重金属离子的去处确实有许多不同的方法,这些工艺方法普遍存在着对重金属离子选择性差、效率低、成本高等的缺点。

    【发明内容】

    本发明的目的是:提供一系列由以高分子材料为填充剂、纳米材料为过滤体能够对水中的重金属有效去除的纳米净水材料。

    本发明的另一个目的是提供上述纳米净水材料的制备方法。

    如图1所示,为本发明所述的纳米净水材料,其形状包括层状圆形、卷曲筒状及片状其主要成份为铝的氧化—氢氧化相:30-60%,玻璃纤维:10-35%,纤维素:15-40%,其中氧化—氢氧化铝的粒径为15-80纳米,比表面积200-800平方米/克。

    纳米净水材料的制备方法如下:

    1.将浓度为0.5-10.5g/l的酸性溶液10-100ml加入玻璃纤维(1.5-15.5g)的水悬浮液(其中玻璃纤维0.5-15.8g,蒸馏水100-500ml)中,将混合物加热至20-120℃;

    2.将加热后的混合物取出并向其中投入粒径为15-70nm的铝粉0.2-10.2g,然后置于超声发生器(K-100型超声波清洗器)中,在20-150℃温度下超声0.3-5.5h,之后加入0.5-20g/l的四乙基正硅酸酯的醇溶液10-110ml继续振荡5-55min,然后取出,在室温下冷却;

    3.将浓度为0.04-5.64g/l的聚乙烯醇-[-CH2CHOH-]-n溶液20-120ml加入0.5-10.5g纤维素(活性碳纤维、聚乙烯)的水悬浮液中(聚乙烯为乙醇悬浮液),其中纤维素(活性碳纤维、聚乙烯)1.0-11g,蒸馏水200-600ml(50-150ml乙醇),中,浸泡、均质1-8h;

    4.将步骤2、3制得的混合物用布氏漏斗进行过滤;

    5.将滤料在40-180℃温度下在干燥箱中干燥1.5-10h得到白色圆形、卷曲筒状及片状的本发明的纳米净水材料。

    本发明的纳米净水材料可广泛地应用于净水器等领域。例如若将本发明的纳米净水材料15--30g装在某小型净水器的净水装置中,用其处理各种污水,可连续使用710--1430h左右,然后将使用过的纳米净水材料取出,经过再生后仍可继续使用。当纳米净水材料重复再生使用8-10次,可重新更换新的材料。由此看来,本发明的纳米净水材料具有体积小,寿命长,成本低,效果好,用途广的优点,因此可广泛用于净水领域。

                 表一  去除Cd2+的实验数据

      45min    -0.002    0.000    0.000    -0.001    0.000    0.000  50min    0.000    0.000    0.000    -0.001    -0.002    0.000  60min    -0.001    0.000    -0.002    -0.001    0.000    -0.001  70min    0.000    -0.001    -0.001    -0.001    -0.001    -0.002  80min    0.000    0.000    -0.001    0.000    0.000    -0.001  90min    -0.001    -0.001    0.000    0.000    -0.002    0.000  100min    0.001    0.001    0.001    0.001    0.001    0.001  110min    0.001    0.002    0.001    0.002    0.003    0.002  120min    0.003    0.003    0.002    0.002    0.004    0.002  130min    0.004    0.003    0.003    0.003    0.003    0.003  140min    0.005    0.004    0.003    0.004    0.004    0.003  150min    0.005    0.004    0.004    0.002    0.004    0.004  165min    0.006    0.005    0.004    0.003    0.005    0.004  180min    0.007    0.006    0.005    0.004    0.005    0.005  195min    0.005    0.006    0.006    0.004    0.006    0.003  210min    0.006    0.004    0.006    0.005    0.006    0.005  225min    0.007    0.006    0.005    0.005    0.007    0.006  240min    0.007    0.007    0.006    0.006    0.005    0.006  255min    0.008    0.005    0.007    0.006    0.006    0.006  270min    0.009    0.007    0.008    0.007    0.007    0.007  285min    0.009    0.007    0.008    0.007    0.007    0.007  300min    0.010    0.008    0.009    0.008    0.009    0.008  320min    0.013    0.11    0.010    0.008    0.010    0.008  340min    0.017    0.014    0.012    0.012    0.013    0.011  360min    0.017    0.015    0.015    0.015    0.014    0.013  380min    0.020    0.018    0.017    0.016    0.015    0.015  400min    0.025    0.020    0.019    0.017    0.015    0.017  420min    0.023    0.022    0.021    0.023    0.024    0.020  440min    0.024    0.024    0.024    0.021    0.024    0.023

      460min    0.029    0.027    0.025    0.026    0.024    0.025  480min    0.031    0.029    0.023    0.028    0.026    0.027  500min    0.033    0.031    0.030    0.032    0.033    0.030  515min    0.037    0.034    0.035    0.034    0.035    0.032  530min    0.042    0.037    0.039    0.038    0.035    0.036  545min    0.045    0.041    0.043    0.042    0.043    0.040  560min    0.047    0.045    0.046    0.044    0.045    0.044  575min    0.050    0.048    0.049    0.046    0.047    0.046  590min    0.053    0.051    0.052    0.051    0.050    0.049  605min    0.055    0.054    0.055    0.053    0.053    0.051  620min    0.058    0.057    0.058    0.056    0.055    0.054  635min    0.061    0.059    0.060    0.058    0.059    0.057  650min    0.064    0.061    0.063    0.062    0.063    0.061  660min    0.065    0.061    0.059    0.063    0.060    0.063  670min    0.063    0.064    0.065    0.065    0.062    0.064  680min    0.067    0.066    0.067    0.065    0.065    0.067  690min    0.069    0.068    0.069    0.067    0.068    0.066  700min    0.071    0.069    0.070    0.068    0.070    0.069  710min    0.075    0.073    0.074    0.072    0.073    0.071  720min    0.078    0.076    0.071    0.075    0.076    0.074    730min    0.074    0.076    0.073    0.074    0.076    0.072  740min    0.073    0.078    0.075    0.078    0.076    0.073  750 min    0.079    0.074    0.077    0.079    0.071    0.075  755min    0.081    0.079    0.079    0.078    0.075    0.070  760min    0.083    0.080    0.081    0.082    0.077    0.072  765min    0.085    0.084    0.085    0.082    0.079    0.075  770min    0.088    0.085    0.087    0.086    0.079    0.080  775min    0.087    0.087    0.089    0.088    0.081    0.077  780min    0.088    0.089    0.091    0.088    0.083    0.079

      785min    0.092    0.087    0.090    0.091    0.083    0.081  790min    0.091    0.089    0.091    0.087    0.086    0.081  795min    0.093    0.088    0.093    0.009    0.088    0.083  800min    0.095    0.090    0.092    0.091    0.082    0.085  802min    0.098    0.090    0.095    0.093    0.085    0.085  804min    0.101    0.088    0.097    0.095    0.088    0.086  806min    0.100    0.091    0.099    0.094    0.089    0.086  808min    0.102    0.091    0.099    0.095    0.092    0.086  810min    0.102    0.091    0.099    0.095    0.092    0.086

    注:表中各样品的质量和厚度分别为:

                 A:0.2688g,2.2mm    B:0.2653g,2.6mm

                 C:0.2690g,2.8mm    D:0.2744g,2.7mm

                 E:0.2687g,2.6mm    F:0.2751g,2.8mm

    表一为使用本发明的纳米净水材料处理含有Cd2+的实验数据。据生活饮用水卫生标准,Cd2+的出水标准为0.01mg/l(见《水和废水监测分析方法》P575)。而从表中明显看出,本发明的纳米净水材料在10s就可将Cd2+完全除去,在实验的前100min去除效率均可达到100%,100min后去除效率逐渐降低,材料A在300min、材料B、C、E在320min、材料D、F在340min出水中的Cd2+达到或已超过标准,而在808min(材料B、C在806min,c,材料F在804min)后材料的去除能力达到最大饱和。由表中可以看出,本发明的材料对于重金属(Cd2+)具有去除能力大、效率高的特点,并且具有很大的饱和度。

    另外,表中实验数据是使用如备注中所列的质量和厚度的材料,若将其厚度增加(即质量也增加),则对于处理与表中同样的水,其去除能力、使用时间及饱和度也相应的增加。(这已经过了实验证明,不再详细列举数据)。

         表二  去除Cd2+的实验数据(使用再生过的纳米净水材料)

      110min  0.001    0.003    0.002    0.002   0.001   0.001  120min  0.003    0.004    0.002    0.002   0.002   0.002  130min  0.004    0.004    0.003    0.003   0.003   0.002  140min  0.005    0.005    0.003    0.004   0.003   0.003  150min  0.005    0.005    0.004    0.002   0.004   0.003  165min  0.004    0.006    0.004    0.003   0.005   0.004  180min  0.007    0.006    0.005    0.004   0.005   0.004  195min  0.005    0.006    0.006    0.004   0.006   0.003  210min  0.006    0.004    0.006    0.005   0.006   0.005  225min  0.007    0.006    0.005    0.005   0.007   0.006  240min  0.007    0.007    0.006    0.006   0.005   0.005  255min  0.008    0.005    0.007    0.006   0.006   0.006  270min  0.008    0.007    0.009    0.007   0.007   0.007  285min  0.009    0.007    0.010    0.007   0.007   0.007  300min  0.010    0.008    0.009    0.008   0.009   0.008  320min  0.012    0.11    0.010    0.009   0.010   0.009  340min  0.016    0.014    0.012    0.012   0.013   0.011  360min  0.017    0.015    0.015    0.015   0.014   0.013  380min  0.020    0.018    0.017    0.016   0.015   0.015  400min  0.021    0.020    0.019    0.017   0.015   0.017  420min  0.023    0.022    0.021    0.023   0.024   0.020  440min  0.024    0.024    0.024    0.021   0.024   0.023  460min  0.029    0.027    0.025    0.026   0.024   0.025  480min  0.031    0.029    0.023    0.028   0.026   0.027  500min  0.033    0.031    0.031    0.032   0.033   0.030  515min  0.036    0.034    0.035    0.034   0.035   0.032  530min  0.040    0.037    0.039    0.038   0.035   0.034  545min  0.045    0.041    0.043    0.042   0.043   0.036  560min  0.047    0.045    0.046    0.044   0.045   0.039

      575min    0.050    0.048    0.049    0.046    0.047    0.041  590min    0.053    0.051    0.052    0.051    0.050    0.043  605min    0.055    0.054    0.055    0.053    0.053    0.045  620min    0.057    0.057    0.058    0.056    0.055    0.047  635min    0.060    0.059    0.061    0.058    0.059    0.048  650min    0.064    0.061    0.063    0.062    0.063    0.050  660min    0.065    0.061    0.059    0.063    0.060    0.052  670min    0.063    0.064    0.065    0.065    0.062    0.054  680min    0.067    0.066    0.067    0.065    0.065    0.056  690min    0.069    0.068    0.069    0.067    0.068    0.058  700min    0.071    0.069    0.070    0.068    0.070    0.059  710min    0.075    0.073    0.074    0.072    0.073    0.060  720min    0.077    0.076    0.071    0.075    0.076    0.062  730min    0.074    0.077    0.073    0.074    0.076    0.064  740min    0.073    0.078    0.075    0.078    0.076    0.065  750min    0.079    0.074    0.077    0.079    0.071    0.067  755min    0.081    0.079    0.079    0.078    0.075    0.068  760min    0.083    0.080    0.081    0.082    0.077    0.069  765min    0.085    0.084    0.085    0.084    0.079    0.070  770min    0.085    0.085    0.087    0.086    0.079    0.071  775min    0.087    0.087    0.087    0.088    0.081    0.073  780min    0.088    0.087    0.091    0.088    0.082    0.05  785min    0.092    0.087    0.090    0.091    0.083    0.077  790min    0.091    0.089    0.091    0.087    0.086    0.078  795min    0.093    0.088    0.093    0.009    0.088    0.080  800min    0.095    0.090    0.092    0.091    0.082    0.082  802min    0.098    0.090    0.095    0.093    0.085    0.083  804min    0.100    0.089    0.097    0.095    0.088    0.085  806min    0.101    0.090    0.098    0.094    0.089    0.085

      808min    0.102    0.091    0.099    0.095    0.092    0.086  810min    0.102    0.091    0.099    0.095    0.092    0.086

    注:表中各样品的质量和厚度分别为:

                A:0.2687g,2.2mm    B:0.26531g,2.6mm

                C:0.2688g,2.7mm    D:0.2743g,2.7mm

                E:0.2686g,2.5mm    F:0.2751g,2.8mm

    表二为使用再生过的纳米净水材料处理含有Cd2+的污水的实验数据。将使用过的纳米净水材料在高压釜中进行再生,然后将其再应用于处理含有Cd2+的污水。从表中的实验数据来看,其总体效果与再生前几乎没有差别,由此可以看出,材料再生简单、彻底,可重复使用。

                        表三  去除Cr6+的实验数据

      16min    0.000   -0.001   0.000   -0.002   0.000   0.000  19min    -0.001   0.000   -0.001   -0.001   -0.002   -0.001  22min    -0.001   -0.001   -0.001   0.000   0.000   0.000  25min    0.000   0.000   0.000   0.000   -0.001   0.000  30min    -0.002   0.000   -0.002   -0.001   0.000   -0.001  35min    0.000   0.000   0.000   0.000   0.000   0.000  40min    0.000   0.000   0.000   0.000   0.000   0.000  45min    -0.002   0.000   0.000   -0.001   0.000   0.000  50min    0.000   0.000   0.000   -0.001   -0.002   0.000  60min    -0.001   0.000   -0.002   -0.001   0.000   -0.001  70min    0.000   0.000   0.000   0.000   0.000   0.000  80min    0.000   0.001   0.000   0.000   -0.001   0.000  90min    0.001   0.002   0.001   0.001   0.001   0.001  100min    0.002   0.003   0.002   0.002   0.002   0.001  110min    0.003   0.004   0.003   0.002   0.003   0.002  120min    0.003   0.005   0.004   0.003   0.004   0.002  130min    0.004   0.006   0.005   0.004   0.004   0.003  140min    0.005   0.007   0.006   0.005   0.005   0.004  150min    0.006   0.008   0.007   0.006   0.005   0.005  165min    0.008   0.010   0.009   0.008   0.006   0.006  180min    0.011   0.012   0.011   0.010   0.010   0.008  195min    0.013   0.014   0.013   0.012   0.012   0.010  210min    0.016   0.016   0.015   0.014   0.013   0.012  225min    0.020   0.021   0.019   0.019   0.018   0.016  240min    0.023   0.025   0.024   0.023   0.021   0.020  255min    0.027   0.029   0.028   0.027   0.025   0.023  270min    0.029   0.031   0.030   0.028   0.027   0.026  285min    0.032   0.034   0.033   0.031   0.029   0.028  300min    0.035   0.037   0.036   0.034   0.032   0.031

      320min    0.040    0.42    0.041    0.039    0.039    0.037  340min    0.045    0.048    0.047    0.044    0.043    0.041  360min    0.049    0.050    0.049    0.048    0.048    0.047  380min    0.055    0.056    0.056    0.055    0.053    0.052  400 min    0.061    0.063    0.062    0.060    0.060    0.059  420min    0.068    0.070    0.069    0.068    0.067    0.065  440min    0.074    0.076    0.075    0.074    0.073    0.071  460min    0.080    0.84    0.082    0.080    0.079    0.078  480min    0.087    0.091    0.089    0.088    0.086    0.084  500min    0.093    0.100    0.096    0.094    0.092    0.090  515min    0.101    0.109    0.106    0.102    0.101    0.099  530min    0.108    0.121    0.111    0.107    0.107    0.105  545min    0.116    0.129    0.125    0.115    0.114    0.112  560min    0.122    0.138    0.131    0.121    0.120    0.119  575min    0.129    0.147    0.144    0.128    0.126    0.124  590min    0.135    0.155    0.151    0.134    0.132    0.131  605min    0.141    0.160    0.158    0.139    0.137    0.136  620min    0.150    0.169    0.163    0.150    0.147    0.145  625min    0.159    0.178    0.170    0.157    0.155    0.152  650min    0.174    0.182    0.179    0.172    0.170    0.168  660min    0.197    0.201    0.200    0.196    0.195    0.194  670min    0.215    0.219    0.217    0.214    0.212    0.210  680min    0.232    0.235    0.233    0.230    0.228    0.227  690min    0.258    0.260    0.259    0.254    0.253    0.254  700min    0.273    0.276    0.275    0.271    0.269    0.268  710min    0.296    0.302    0.298    0.295    0.293    0.292  720min    0.315    0.317    0.316    0.314    0.313    0.312  730min    0.337    0.340    0.339    0.336    0.335    0.333  740min    0.354    0.359    0.356    0.354    0.352    0.350

      750min  0.373  0.381  0.378  0.372  0.370  0.368  755min  0.389  0.399  0.394  0.387  0.385  0.383  760min  0.401  0.412  0.410  0.400  0.399  0.396  765min  0.418  0.430  0.427  0.418  0.417  0.415  770min  0.432  0.443  0.441  0.431  0.430  0.427  775min  0.440  0.447  0.445  0.441  0.440  0.436  780min  0.449  0.454  0.452  0.449  0.447  0.444  785min  0.459  0.461  0.460  0.457  0.456  0.451  790min  0.466  0.468  0.467  0.464  0.464  0.462  795min  0.474  0.475  0.474  0.473  0.472  0.471  800min  0.483  0.486  0.484  0.482  0.480  0.480  802min  0.491  0.494  0.492  0.490  0.491  0.489  804min  0.495  0.499  0.498  0.494  0.493  0.491  806min  0.499  0.503  0.501  0.497  0.494  0.491  808min  0.499  0.504  0.503  0.498  0.495  0.492  810min  0.500  0.505  0.503  0.499  0.495  0.492

    注:表中各样品的质量和厚度分别为:

               A:0.2712g,2.7mm    B:0.2677g,2.6mm

               C:0.2710g,2.6mm    D:0.2644g,2.5mm

               E:0.2698g,2.7mm    F:0.2738g,2.8mm

    表三为使用本发明的纳米净水材料处理含有Cr6+的实验数据。据生活饮用水卫生标准,Cr6+的出水标准为0.05mg/l(见《水和废水监测分析方法》P575)。而从表中明显看出,本发明的纳米净水材料在10s就可将Cr6+完全除去,在实验的前90min(材料B在前80min)去除效率均可达到100%,90min后(材料B在80min后)去除效率逐渐降低,各材料在380min(材料B在360min),出水中的Cr6+达到或已超过标准,而在810min(材料C、F在808min)后材料的去除能力达到最大饱和。由表中可以看出,本发明的材料对于重金属(Cr6+)具有去除能力大、效率高的特点,并且具有很大的饱和度。

    另外,表中实验数据是使用如备注中所列的质量和厚度的材料,若将其厚度增加(即质量也增加),则对于处理与表中同样的水,其去除能力、使用时间及饱和度也相应的增加。(这已经过了实验证明,不再详细列举数据)。

        表四  去除Cr6+的实验数据(使用再生过的纳米净水材料)

      45min    -0.002    0.000    0.000    -0.001    0.000    0.000  50min    0.000    0.000    0.000    0.000    -0.002    -0.001  60min    0.000    0.000    -0.001    0.000    0.000    -0.001  70min    0.001    0.001    0.001    0.000    0.000    0.000  80min    0.001    0.001    0.001    0.001    0.001    0.000  90min    0.002    0.002    0.002    0.001    0.001    0.001  100min    0.002    0.003    0.002    0.002    0.003    0.001  110min    0.003    0.005    0.003    0.003    0.003    0.002  120min    0.004    0.006    0.004    0.003    0.004    0.002  130min    0.005    0.007    0.005    0.004    0.004    0.003  140min    0.006    0.008    0.006    0.005    0.005    0.004  150min    0.008    0.009    0.007    0.006    0.006    0.005  165min    0.010    0.011    0.010    0.009    0.007    0.007  180min    0.012    0.013    0.011    0.010    0.009    0.009  195min    0.014    0.015    0.014    0.012    0.011    0.010  210min    0.016    0.017    0.015    0.015    0.014    0.014  225min    0.019    0.020    0.018    0.019    0.018    0.017  240min    0.022    0.025    0.023    0.022    0.020    0.020  255min    0.026    0.029    0.027    0.026    0.024    0.024  270min    0.028    0.033    0.031    0.027    0.026    0.025  285min    0.031    0.035    0.034    0.030    0.029    0.029  300min    0.035    0.038    0.035    0.034    0.032    0.031  320min    0.040    0.042    0.040    0.039    0.037    0.036  340min    0.044    0.047    0.046    0.044    0.042    0.043  360min    0.049    0.050    0.048    0.048    0.047    0.045  380min    0.054    0.057    0.054    0.053    0.051    0.050  400min    0.061    0.063    0.063    0.060    0.059    0.057  420min    0.069    0.071    0.068    0.068    0.067    0.065  440min    0.075    0.077    0.076    0.074    0.073    0.071

      460min    0.080    0.83    0.081    0.080    0.078    0.076  480min    0.087    0.091    0.089    0.086    0.084    0.082  500min    0.094    0.100    0.098    0.093    0.092    0.090  515min    0.101    0.109    0.107    0.102    0.101    0.098  530min    0.108    0.121    0.114    0.106    0.105    0.103  545min    0.115    0.127    0.125    0.114    0.113    0.112  560min    0.121    0.136    0.133    0.120    0.119    0.118  575min    0.128    0.145    0.144    0.126    0.124    0.122  590min    0.133    0.153    0.151    0.132    0.132    0.131  605min    0.140    0.162    0.158    0.139    0.137    0.135  620min    0.151    0.169    0.166    0.150    0.147    0.144  635min    0.158    0.178    0.172    0.157    0.155    0.152  650min    0.172    0.182    0.180    0.171    0.170    0.168  660min    0.195    0.202    0.201    0.194    0.192    0.189  670min    0.211    0.218    0.217    0.210    0.212    0.210  680min    0.230    0.235    0.233    0.230    0.228    0.226  690min    0.257    0.260    0.258    0.254    0.253    0.252  700min    0.272    0.275    0.275    0.271    0.269    0.267  710min    0.295    0.302    0.298    0.295    0.293    0.291  720min    0.314    0.319    0.317    0.314    0.313    0.311  730min    0.337    0.341    0.340    0.336    0.335    0.332  740min    0.349    0.359    0.356    0.354    0.352    0.350  750min    0.370    0.381    0.378    0.372    0.370    0.368  755min    0.390    0.399    0.396    0.387    0.385    0.383  760min    0.403    0.412    0.411    0.400    0.399    0.396  765min    0.420    0.430    0.428    0.418    0.417    0.415  770min    0.435    0.443    0.441    0.431    0.430    0.427  775min    0.444    0.447    0.445    0.441    0.440    0.436  780min    0.449    0.454    0.452    0.449    0.447    0.444

      785min   0.458   0.461   0.460   0.457   0.456   0.451  790min   0.465   0.468   0.467   0.464   0.463   0.462  795min   0.473   0.475   0.474   0.473   0.472   0.479  800min   0.481   0.486   0.484   0.485   0.480   0.485  802min   0.494   0.498   0.492   0.494   0.490   0.489  804min   0.497   0.501   0.499   0.496   0.493   0.491  806min   0.499   0.503   0.501   0.498   0.494   0.491  808min   0.499   0.505   0.503   0.499   0.495   0.492  810min   0.500   0.505   0.503   0.499   0.495   0.492

    注:表中各样品的量和厚度分别为:

              A:0.2711g,2.7mm    B:0.2675g,2.6mm

              C:0.2708g,2.6mm    D:0.2643g,2.5mm

              E:0.2697g,2.7mm    F:0.2736g,2.8mm

    表四为使用再生过的纳米净水材料处理含有Cr6+的污水的实验数据。将使用过的纳米净水材料在高压釜中进行再生,然后将其再应用于处理含有Cr6+的污水。从表中的实验数据来看,其总体效果与再生前几乎没有差别,由此可以看出,材料再生简单、彻底,可重复使用。

                     表五  去除Pb2+的实验数据

        60s    0.000    0.000    0.000    0.0000    0.000    0.000    2min    0.000    -0.001    0.000    -0.002    0.000    0.000    4min    -0.001    0.000    -0.001    -0.001    -0.002    -0.001    6min    -0.001    -0.001    -0.001    0.000    0.000    0.000    8min    0.000    0.000    0.000    0.000    -0.001    0.000    10min    -0.001    0.000    -0.002    -0.001    0.000    -0.001    13min    0.000    0.000    0.000    0.000    0.000    0.000    16min    0.000    0.000    0.000    0.000    0.000    0.000    19min    -0.002    0.000    0.000    -0.001    0.000    0.000    22min    0.000    0.000    0.000    -0.001    -0.002    0.000    25min    0.000    0.000    0.000    -0.001    -0.002    0.000    30min    0.000    -0.001    0.000    -0.002    0.000    0.000    35min    -0.001    0.000    -0.001    -0.001    -0.002    -0.001    40min    -0.001    -0.001    -0.001    0.000    0.000    0.000    45min    0.000    0.000    0.000    0.000    -0.001    0.000    50min    -0.001    0.000    -0.002    -0.001    0.000    -0.001    60min    -0.001    0.000    -0.001    -0.001    -0.001    -0.001    70min    0.000    -0.001    -0.001    0.000    0.000    0.000    80min    0.001    0.001    0.001    0.001    0.000    0.000    90min    0.001    0.002    0.002    0.001    0.001    0.001    100min    0.002    0.002    0.003    0.002    0.001    0.002    110min    0.003    0.003    0.003    0.003    0.002    0.002    120min    0.005    0.004    0.004    0.003    0.003    0.003    130min    0.006    0.005    0.005    0.004    0.004    0.003    140min    0.008    0.007    0.007    0.006    0.005    0.004    150min    0.010    0.009    0.008    0.007    0.007    0.006    165min    0.013    0.012    0.010    0.010    0.009    0.008    180min    0.016    0.015    0.015    0.014    0.012    0.011    195min    0.020    0.019    0.019    0.018    0.017    0.016

      210min    0.024    0.022    0.022    0.020    0.20    0.020  225min    0.029    0.028    0.027    0.024    0.023    0.024  240min    0.031    0.031    0.030    0.029    0.028    0.028  255min    0.035    0.034    0.034    0.033    0.031    0.030  270min    0.039    0.039    0.038    0.037    0.035    0.035  285min    0.042    0.041    0.041    0.040    0.039    0.039  300min    0.046    0.045    0.045    0.044    0.044    0.043  320min    0.053    0.050    0.051    0.049    0.048    0.048  340min    0.062    0.059    0.057    0.056    0.054    0.052  360min    0.108    0.104    0.101    0.101    0.100    0.099  380min    0.154    0.153    0.152    1.151    0.150    0.150  400min    0.197    0.196    0.195    0.193    0.191    0.190  420min    0.239    0.238    0.237    0.236    0.235    0.234  440min    0.288    0.286    0.285    0.284    0.282    0.281  460min    0.327    0.325    0.324    0.323    0.321    0.320  480min    0.346    0.345    0.344    0.342    0.341    0.340  500min    0.373    0.372    0.371    0.369    0.368    0.366  515min    0.398    0.396    0.395    0.394    0.393    0.392  530min    0.421    0.421    0.420    0.419    0.418    0.417  545min    0.444    0.443    0.442    0.441    0.440    0.439  560min    0.472    0.471    0.470    0.468    0.467    0.466  575min    0.499    0.499    0.498    0.497    0.496    0.495  590min    0.520    0.518    0.517    0.515    0.514    0.513  605min    0.537    0.535    0.536    0.534    0.533    0.532  620min    0.566    0.563    0.562    0.561    0.559    0.558  635min    0.598    0.596    0.595    0.594    0.592    0.591  650min    0.629    0.625    0.624    0.622    0.620    0.619  660min    0.651    0.649    0.647    0.646    0.645    0.644  670min    0.676    0.675    0.674    0.673    0.672    0.671

      680min   0.693   0.691   0.690   0.688   0.686   0.685  690min   0.710   0.707   0.706   0.704   0.703   0.702  700min   0.726   0.724   0.723   0.722   0.720   0.719  710min   0.747   0.745   0.744   0.743   0.741   0.740  720min   0.765   0.763   0.762   0.761   0.760   0.759  730min   0.787   0.784   0.782   0.780   0.779   0.778  740min   0.809   0.807   0.805   0.804   0.802   0.801  750min   0.821   0.819   0.818   0.817   0.816   0.815  755min   0.838   0.834   0.833   0.832   0.831   0.830  760min   0.855   0.853   0.852   0.851   0.850   0.849  765min   0.873   0.872   0.871   0870   0.869   0.868  770min   0.896   0.894   0.893   0.892   0.891   0.890  775min   0.919   0.916   0.915   0.914   0.913   0.912  780min   0.937   0.935   0.934   0.933   0.928   0.930  785min   0.952   0.951   0.950   0.949   0.947   0.946  790min   0.988   0.986   0.985   0.983   0.954   0.950  795min   1.004   1.003   1.001   0.985   0.960   0.954  800min   1.011   1.010   1.009   0.988   0.966   0.961  803min   1.014   1.012   1.011   0.991   0.971   0.966  806min   1.020   1.019   1.013   0.996   0.975   0.970  809min   1.025   1.023   1.015   1.000   0.980   0.973  812min   1.031   1.029   1.018   1.002   0.982   0.976  815min   1.036   1.034   1.020   1.002   0.986   0.979  817min   1.039   1.037   1.022   1.003   0.991   0.982  819min   1.044   1.042   1.023   1.006   0.992   0.985  821min   1.048   1.043   1.026   1.006   0.993   0.987  823min   1.051   1.044   1.028   1.008   0.994   0.987  825min   1.051   1.044   1.028   1.009   0.994   0.988

    注:表中各样品的量和厚度分别为:

          A:0.2738g,2.7mm    B:0.2705g,2.7mm

          C:0.2685g,2.6mm    D:0.2677g,2.6mm

          E:0.2727g,2.7mm    F:0.2702g,2.7mm

    表五为使用本发明的纳米净水材料处理含有Pb2+的实验数据。据生活饮用水卫生标准,Pb2+的出水标准为0.05mg/l(见《水和废水监测分析方法》P575)。而从表中明显看出,本发明的纳米净水材料在10s就可将Pb2+完全除去,在实验的前70min(材料E、F为前80min)去除效率均可达到100%,70min后(材料E、F为前80min后)去除效率逐渐降低,材料A、B、C、在320min,材料D、E、F在340min出水中的Pb2+达到或已超过标准,而在823min(材料D、F在825min)后材料的去除能力达到最大饱和。由表中可以看出,本发明的材料对于重金属(Pb2+)具有去除能力大、效率高的特点,并且具有很大的饱和度。

    另外,表中实验数据是使用如备注中所列的质量和厚度的材料,若将其厚度增加(即质量也增加),则对于处理与表中同样的水,其去除能力、使用时间及饱和度也相应的增加。(这已经过了实验证明,不再详细列举数据)。

         表六  去除Pb2+的实验数据(使用再生过的纳米净水材料)

      6min   0.000   0.000   -0.001   0.000   0.000   0.000  8min   0.000   -0.002   0.000   0.000   0.000   0.000  10min   -0.001   -0.001   -0.001   0.001   -0.001   -0.001  13min   0.000   0.000   0.000   -0.002   0.000   0.000  16min   0.001   -0.001   0.001   -0.001   -0.001   -0.001  19min   0.000   0.000   0.000   0.000   0.000   0.000  22min   0.000   0.000   -0.002   0.000   0.000   0.000  25min   0.000   0.000   0.000   0.000   0.000   0.000  30min   -0.001   0.001   -0.001   -0.001   -0.001   -0.001  35min   0.000   0.000   0.000   0.000   0.000   0.000  40min   -0.001   -0.001   0.001   -0.001   -0.001   0.001  45min   -0.001   0.001   -0.001   0.001   -0.001   -0.001  50min   0.000   0.000   0.000   0.000   0.000   0.000  60min   -0.001   0.001   -0.001   -0.001   0.001   -0.001  70min   0.000   -0.001   0.000   0.000   0.000   -0.002  80min   0.001   0.001   0.001   0.001   0.001   0.001  90min   0.002   0.002   0.002   0.001   0.001   0.001  100min   0.002   0.002   0.002   0.002   0.002   0.002  110min   0.003   0.003   0.003   0.003   0.002   0.001  120min   0.005   0.004   0.004   0.004   0.003   0.003  130min   0.006   0.005   0.005   0.004   0.003   0.003  140min   0.008   0.007   0.007   0.006   0.006   0.005  150min   0.010   0.009   0.007   0.007   0.007   0.006  165min   0.013   0.012   0.010   0.010   0.009   0.009  180min   0.016   0.015   0.015   0.015   0.013   0.012  195min   0.020   0.019   0.019   0.017   0.017   0.016  210min   0.024   0.022   0.022   0.021   0.020   0.019  225min   0.029   0.028   0.027   0.026   0.024   0.022  240min   0.031   0.031   0.030   0.029   0.029   0.028

      255min    0.035    0.034    0.034    0.033    0.032    0.030  270min    0.039    0.039    0.038    0.037    0.036    0.036  285min    0.042    0.041    0.040    0.040    0.039    0.038  300min    0.046    0.045    0.045    0.044    0.044    0.044  320min    0.053    0.050    0.050    0.048    0.048    0.048  340min    0.062    0.059    0.057    0.056    0.055    0.053  360min    0.108    0.104    0.101    0.100    0.100    0.099  380min    0.154    0.153    0.152    1.151    0.151    0.150  400min    0.197    0.196    0.195    0.194    0.192    0.190  420min    0.239    0.238    0.237    0.236    0.235    0.234  440min    0.288    0.286    0.285    0.284    0.283    0.281  460min    0.327    0.325    0.324    0.322    0.321    0.320  480min    0.346    0.344    0.344    0.342    0.340    0.340  500min    0.373    0.372    0.371    0.370    0.368    0.367  515min    0.398    0.396    0.395    0.394    0.394    0.392  530min    0.421    0.421    0.420    0.419    0.418    0.417  545min    0.444    0.443    0.442    0.441    0.441    0.439  560min    0.472    0.471    0.470    0.469    0.468    0.466  575min    0.499    0.499    0.498    0.497    0.497    0.495  590min    0.520    0.518    0.517    0.516    0.514    0.513  605min    0.537    0.535    0.535    0.534    0.533    0.532  620min    0.566    0.564    0.562    0.561    0.560    0.558  635min    0.598    0.596    0.595    0.594    0.593    0.590  650min    0.629    0.627    0.625    0.623    0.621    0.619  660min    0.651    0.649    0.647    0.646    0.645    0.644  670min    0.676    0.675    0.674    0.673    0.672    0.671  680min    0.693    0.691    0.690    0.688    0.687    0.685  690min    0.710    0.708    0.707    0.705    0.703    0.702  700min    0.726    0.724    0.723    0.722    0.721    0.719

      710min   0.747   0.745   0.744   0.743   0.742   0.740  720min   0.765   0.764   0.762   0.761   0.761   0.759  730min   0.787   0.785   0.783   0.781   0.779   0.778  740min   0.809   0.807   0.805   0.803   0.802   0.801  750min   0.821   0.819   0.818   0.817   0.816   0.815  755min   0.838   0.836   0.834   0.832   0.831   0.830  760min   0.855   0.853   0.852   0.851   0.850   0.849  765min   0.873   0.872   0.871   0.870   0.869   0.868  770min   0.896   0.895   0.893   0.892   0.891   0.890  775min   0.919   0.917   0.915   0.914   0.913   0.912  780min   0.937   0.936   0.934   0.933   0.931   0.930  785min   0.952   0.951   0.950   0.949   0.947   0.946  790min   0.988   0.986   0.985   0.984   0.954   0.952  795min   1.004   1.003   1.001   0.985   0.960   0.954  800min   1.011   1.010   1.009   0.988   0.965   0.961  803min   1.014   1.012   1.011   0.991   0.971   0.966  806min   1.020   1.019   1.017   0.996   0.975   0.970  809min   1.025   1.022   1.018   1.000   0.980   0.973  812min   1.031   1.029   1.018   1.002   0.982   0.975  815min   1.036   1.033   1.021   1.002   0.984   0.978  817min   1.039   1.035   1.022   1.003   0.990   0.982  819min   1.044   1.042   1.023   1.006   0.992   0.985  821min   1.048   1.043   1.025   1.007   0.993   0.987  823min   1.051   1.044   1.028   1.009   0.994   0.988  825min   1.051   1.044   1.028   1.009   0.994   0.988

    表六为使用再生过的纳米净水材料处理含有Pb2+的污水的实验数据。将使用过的纳米净水材料在高压釜中进行再生,然后将其再应用于处理含有Pb2+的污水。从表中的实验数据来看,其总体效果与再生前几乎没有差别,由此可以看出,材料再生简单、彻底,可重复使用。

    综上所述,将本发明的纳米净水材料用于处理含重金属的污水,与现已有的水处理技术相比具有如下的优点:

    1.制备方法简单,价格便宜,使用方便,效果显著;

    2.去除能力强,除净度高,对水中的重金属可达到100%的去除,并具有

    相当大的饱和度;

    3.再生简单,并且没有二次污染。

    【附图说明】

    图1(a)层状的纳米净水材料;

    图1(b)卷曲筒状的纳米净水材料;

    图1(c)片状的纳米净水材料

    【具体实施方式】

    实施例1:

    取7.5g E-玻璃纤维在400ml蒸馏水中混合均匀后,加入2.0g/l的硼酸50ml,然后加热至40℃,加入5.5g铝粉(粒径为20nm),然后置于超声槽中在25℃下超声振荡30min,然后向混合物中加入5.5g/l四己基正硅酸酯的醇溶液100ml继续超声振荡55min,之后取出在室温下冷却;将6.0g活性碳纤维放入450ml蒸馏水中,浸泡、均质1h,加入4.5g/l聚乙烯醇溶液30ml混合均匀;将上述制得的两种混合液过滤,将滤料在干燥箱中,温度90℃干燥1.5h,即得到34.2g本发明的纳米净水材料,其组成为:铝的氧化—氢氧化相:46.5%,玻璃纤维:21.9%,活性碳纤维:22.2%,其中氧化—氢氧化铝的粒径为25纳米,比表面积705平方米/克。

    实施例2:

    将1.0g活性碳纤维用200ml蒸馏水浸泡、均质50min,加入5g/l聚乙烯醇溶液混合均匀;取1.8gC--玻璃纤维加入280ml蒸馏水中混合均匀后,加入4g/l的水杨酸钠14ml,然后加热至80℃,加入0.7g铝粉(粒径为15nm),然后置于超声槽中在55℃超声振荡50min,然后向混合物中加入15g/l四己基正硅酸酯的醇溶液10ml继续超声振荡30min,取出,在室温下冷却;将上述制得的两种混合液过滤,将滤料在干燥箱中于温度150℃下干燥5h,即得到5.15g本发明的纳米净水材料,其组成为:铝的氧化—氢氧化相:39.3%,玻璃纤维:35%,活性碳纤维:19.4%,其中氧化—氢氧化铝的粒径为20纳米,比表面积725平方米/克。

    实施例3:

    将3.1g聚乙烯用50ml乙醇浸泡、均质60min,加入3g/l聚乙烯醇溶液40ml混合均匀;取2.0gE--玻璃纤维放入310ml蒸馏水中混合均匀后,加入1.2g/l的水杨酸钠15ml,然后加热至45℃,加入1.5g铝粉(粒径30nm),然后置于超声槽中在100℃下超声振荡1.5h,然后向混合物中加入15g/l四己基正硅酸酯的醇溶液继续超声振荡50min,取出,在室温下冷却;将上述制得的两种混合液过滤,将滤料在干燥箱中于温度120℃下干燥3h,即得到11.3g本发明的纳米净水材料。其组成为:铝的氧化—氢氧化相:38.3%,玻璃纤维:17.7%,聚乙烯:27.4%,其中氧化—氢氧化铝的粒径为35纳米,比表面积645平方米/克。

    实施例4:

    将2.6微晶纤维素加入420ml蒸馏水中,浸泡、均质3h,加入2.8g/l聚乙烯醇溶液44ml混合均匀;取3.0g的C--玻璃纤维在420ml蒸馏水中混合均匀后,加入1.4g/l的水杨酸钠60ml,然后加热至50℃,加入1.8g铝粉(粒径为15nm),然后置于超声槽中在55℃超声振荡0.5h,然后向混合物中加入5g/l四己基正硅酸酯的醇溶液20ml继续超声振荡50min,之后取出在室温下冷却;将上述制得的两种混合液过滤,将滤料在干燥箱中,温度120℃干燥4h,即得到12.7g本发明的纳米净水材料。其组成为:铝的氧化—氢氧化相:40.9%,玻璃纤维:23.6%,纤维素:20.5%,其中氧化—氢氧化铝的粒径为20纳米,比表面积720平方米/克。

    实施例5:

    取6.6g E-玻璃纤维在500ml蒸馏水中混合均匀后,加入1.5g/l的水杨酸钠溶液20ml,然后加热至30℃,加入5.4g铝粉(粒径为15nm),然后置于超声槽中在55℃超声振荡65min,然后向混合物中加入2.1g/l四己基正硅酸酯的醇溶液110ml继续超声振荡45min,之后取出在室温下冷却;将6.0g活性碳纤维放入450ml蒸馏水中,浸泡、均质1h,加入3g/l聚乙烯醇溶液40ml混合均匀;将上述制得的两种混合液过滤,将滤料在干燥箱中,温度90℃干燥2.5h,即得到31.8g本发明的纳米净水材料,其组成为:铝的氧化—氢氧化相:49.1%,玻璃纤维:20.8%,活性碳纤维:18.9%,其中氧化—氢氧化铝的粒径为20纳米,比表面积730平方米/克。

    实施例6:

    取7.0g E--玻璃纤维放入500ml蒸馏水中混合均匀后,加入0.2g/l的水杨酸钠100ml,然后加热至25℃,加入6.5g铝粉(粒径20nm),然后置于超声槽中在50℃超声振荡2.5h,然后向混合物中加入9.4g/l四己基正硅酸酯的醇溶液40ml继续超声振荡15min,取出,在室温下冷却;将8.5g聚乙烯用105ml乙醇浸泡、均质5min,加入5g/l聚乙烯醇溶液30ml混合均匀;将上述制得的两种混合液过滤,将滤料在干燥箱中于温度00℃下干燥5h,即得到38.8g本发明的纳米净水材料,其组成为:铝的氧化—氢氧化相:48.4%,玻璃纤维:18.0%,聚乙烯:21.9%,其中氧化—氢氧化铝的粒径为25纳米,比表面积690平方米/克。

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本发明属于水的净化领域,具体涉及一系列以高分子材料为填充剂、纳米材料为过滤体,能够对水中的重金属进行有效处理的高分子纳米净水材料以及该材料的制备方法。其形状包括层状圆形、卷曲筒状及片状,其主要成分为铝的氧化氢氧化相:3060,玻璃纤维:1035,纤维素:1540,其中氧化氢氧化铝的粒径为1580纳米,比表面积200800平方米/克。本发明1530g的净水材料可连续使用7101430h左右,然后将使。

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