CN113413774A - 一种多层生物基纳米纤维重金属过滤膜、制备方法及其用途 - Google Patents

一种多层生物基纳米纤维重金属过滤膜、制备方法及其用途 Download PDF

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CN113413774A
CN113413774A CN202110697053.3A CN202110697053A CN113413774A CN 113413774 A CN113413774 A CN 113413774A CN 202110697053 A CN202110697053 A CN 202110697053A CN 113413774 A CN113413774 A CN 113413774A
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CN113413774B (zh
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吴述平
吴加龙
李亢悔
张自航
陶江涛
蔡佳伟
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Jiangsu University
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Abstract

本发明提供了一种多层生物基纳米纤维重金属过滤膜、制备方法及其用途，以海藻酸钠和聚乙烯醇的混合溶液、聚乙烯亚胺和聚乙烯醇的混合溶液为原料，采用单针头交替进行静电纺丝，两层纤维层交替层叠的多层生物基纳米纤维膜。本发明所制备的多层复合纳米纤维膜具有高效的重金属截留效率、良好的生物降解性、可重复使用，具有较大的市场应用前景；并且制备过程操作简单、易于控制、绿色经济、便于工业化生产。

Description

一种多层生物基纳米纤维重金属过滤膜、制备方法及其用途
技术领域
本发明属于纳米功能材料和环境水处理领域，具体涉及一种多层生物基纳米纤维重金属过滤膜、制备方法及其用途。
背景技术
随着工业的发展，自然界中的金属正被加速开采和利用，伴随着金属的大量消耗，工业能力直线提高。但是在这些金属的使用过程中，必不可少的存在浪费和污染，而一些重金属的处理不得当，会其污染了水环境和土壤环境，让我们的生产和生活受到影响。其次，由于重金属离子是具有积蓄性的环境污染物，很难被微生物降解，最终，随着食物链大量积聚到我们人体，轻则影响我们的身体健康，重则威胁到我们的生命。因此，环境中重金属离子的去除已成为当今世界研究的焦点。
静电纺丝技术是一种高分子流体静电固化工艺，能将高分子聚合物、金属氧化物、碳、金属、复合材料等各类材料固化并生成纤维丝。目前，人们已经可以通过静电纺丝工艺来制备过滤膜、生物发光材料、生物组织支架、电极材料、纳米级电缆、超级电容器等。该工艺因其良好的材料成型能力、快速制备能力和较低的制备成本而在工业界和学术界得到较为广泛的应用。静电纺丝工艺可以在短时间内实现聚合物聚集体以纤维形式形成膜结构，形成的膜具有直径小、均一性好、比表面积大、孔隙率高等特点。生物质高分子因其来源广泛，成本低廉，使用后可被生物降解，绿色可持续，广泛运用于废水中重金属离子的吸附与分离。
近年来，静电纺丝技术在过滤膜领域中的研究已成为国内外热点，但就目前的研究进展上看，国内外对过滤膜的研究大部分都说明了对重金属的高吸附率，在对纳米纤维膜的重复使用上，相关研究内还是较少。对于纳米纤维膜可脱附性是纳米纤维膜能够实现重复使用的关键，脱附的简易性及高脱附率，是纳米纤维膜可重复使用的关键因素。
发明内容
为了解决现有重金属吸附薄膜重复利用次数少、通量低等问题，本发明以生物质海藻酸钠和合成聚合物聚乙烯亚胺、聚乙烯醇为原料，提供一种能够吸附重金属离子的海藻酸钠和聚乙烯亚胺的多层复合纳米纤维超滤膜及其制备方法。该方法操作简单、易于控制、绿色经济、截留率高的特点，在水处理领域具有广阔的应用前景。
本发明解决上述技术问题所采用的技术方案如下：
一种海藻酸钠多层生物基纳米纤维重金属过滤膜的制备方法，其特征在于，包含如下步骤：
(1)原液的配制
将海藻酸钠配置成质量分数为1～5％的水溶液A；将聚乙烯亚胺配置成质量分数为1～10％的水溶液B；将聚乙烯醇配置成质量分数为3～10％的水溶液C；
(2)纺丝混合液的配制
将步骤(1)得到的水溶液A和C在常温下按一定比例配置成混合溶液，得到纺丝液D；将步骤(1)得到的水溶液B和C按一定的比例配置成混合溶液，得到纺丝液E；
(3)多层复合纳米纤维膜的制备
将步骤(2)得到的纺丝液D和E分别注入注射器F和G，注射器F和G交替进行静电纺丝；所述纺丝液D中的海藻酸钠与聚乙烯醇在常温下以氢键的形式结合，在静电纺丝过程中形成纳米纤维层H；所述纺丝液E中的聚乙烯亚胺与聚乙烯醇在常温下以氢键的形式结合，在静电纺丝过程中形成纳米纤维层I；最终获得纳米纤维层H与纳米纤维层I交替层叠的海藻酸钠多层生物基纳米纤维重金属过滤膜。
进一步地，步骤(2)中所述纺丝液D、纺丝液E在配制过程中，水溶液A和C、水溶液B和C混合后，用旋涡混匀器快速混匀，超声去除气泡后开始纺丝。
进一步地，纺丝液D中所述溶液A和C的比例为1:1～1:4。
进一步地，纺丝液E中所述溶液B和C的比例为1:1～1:4。
进一步地，步骤(3)中两种纺丝液交替循环纺丝时，每种纺丝液的每次纺丝所用的注射量为0.5～2mL。
进一步地，步骤(3)中静电纺丝的工艺参数为：电压17～21kV，接收距离5～10cm，溶液挤出速度为1～10μL/min。
所述的制备方法的海藻酸钠多层生物基纳米纤维重金属过滤膜，其特征在于，由纳米纤维层H与纳米纤维层I交替层叠构成。
进一步地，纳米纤维的直径为50-250nm。
所述的海藻酸钠多层生物基纳米纤维重金属过滤膜的用途，其特征在于，用于水环境中重金属离子的吸附分离。
本发明的有益效果是：
本发明制备的多层生物基纳米纤维膜，具有交替的两种纳米纤维层，天然高分子吸附层和合成高分子吸附层层叠设置，纳米纤维层H提供羧基，纳米纤维层I提供羟基，两种官能团通过不同的吸附条件对重金属离子进行吸附，使得吸附效率更高。
混合纺丝液D中的海藻酸钠与聚乙烯醇、纺丝液E中的聚乙烯亚胺与聚乙烯醇在常温下以氢键的形式结合，并缓慢形成沉淀，因此在制备过程中，首先将三种原料配成水溶液，在进行纺丝前，再将其进行混合。同时，在混合的过程中用旋涡混匀器快速混匀，超声去除气泡后开始纺丝；以防纺丝不均匀。
在静电纺丝过程中，严格控制纺丝的工艺及每层纺丝过程中是使用纺丝液的用量，所制得的纤维直径小，比表面积大，孔隙率高，孔径分布均匀。
本发明采用静电纺丝法制备多层生物基纳米纤维膜，整个过程采用可生物降解的药品与水作为溶剂，不产生二次污染，绿色环保，能耗低，操作方便，成本低，易于规模化生产。
附图说明
图1为实施例1的多层纳米纤维SEM图及纤维直径；
图2为不同浓度铜离子的紫外吸收光谱图；
图3为不同浓度铜离子的紫外吸收光标准曲线；
图4为实施例1的多层纳米纤维膜对铜离子过滤效率图；
图5实施例1的多层纳米纤维膜对铜离子循环过滤效率图。
具体实施方式
下面结合附图以及具体实施例对本发明作进一步的说明，但本发明的保护范围并不限于此。
实施例1
称取3g海藻酸钠，溶于97g水中，磁力搅拌8h，完全溶解后得到质量分数为3％的海藻酸钠海藻酸钠溶液；称取3g聚乙烯亚胺，溶于97g水中，磁力搅拌2h，完全溶解后得到质量分数为3％的聚乙烯亚胺溶液；称取5g聚乙烯醇，溶于95g水中，90℃条件下，磁力搅拌4h，完全溶解后得到质量分数为5％的聚乙烯醇溶液。将海藻酸钠和聚乙烯醇溶液以1:3的质量比配成混合溶液，用旋涡混匀器混匀，超声10min得到静电纺丝液D；将聚乙烯亚胺和聚乙烯醇溶液以1:3的质量比配成混合溶液，用旋涡混匀器混匀，超声10min得到静电纺丝液E。将纺丝液D和E分别注入注射器F和G，注射器F和G交替进行静电纺丝，先将注射器F通过自动供液泵控制注射推进速度，设置电压为18.5kV，喷射速度4μL/min，接收距离7cm，进行静电纺丝，当注射器F注射量达到0.5mL时，更换注射器G，采用相同的纺丝参数进行静电纺丝，多层循环，制得多层纳米纤维膜。
图1为本实施例所制备的多层纳米纤维SEM图及纤维直径分布，说明了本发明所制备的纳米纤维直径分布在50-250nm之间，网孔分布密集，提高了纳米纤维膜的孔隙率，为过滤性能提供了支持；图2和图3为通过紫外-可见分光光度法测试的Cu2+的浓度与吸光度的关系，用于计算纳米纤维膜对Cu2+的过滤效率；图4为通过紫外-可见分光光度法测试纳米纤维膜对Cu2+的过滤效率，可达87.3％；图5为多层纳米纤维膜对Cu2+的循环过滤结果，前四次重复使用对Cu2+的过滤效率保持在85％以上，过滤后的脱附采用1mol/L HCl溶液浸泡去除膜上的Cu2+。综上，本发明提供了一种能够吸附重金属离子的多层复合纳米纤维膜，该制备方法操作简单、易于控制、绿色经济，且制备的多层复合纳米纤维膜纤维直径小、截留率高、可重复使用，所制备的纳米纤维膜对重金属离子具有良好的吸附性能。
实施例2
称取6g海藻酸钠，溶于94g水中，磁力搅拌8h，完全溶解后得到质量分数为6％的海藻酸钠海藻酸钠溶液；称取3g聚乙烯亚胺，溶于97g水中，磁力搅拌2h，完全溶解后得到质量分数为3％的聚乙烯亚胺溶液；称取5g聚乙烯醇，溶于95g水中，90℃条件下，磁力搅拌4h，完全溶解后得到质量分数为5％的聚乙烯醇溶液。将海藻酸钠和聚乙烯醇溶液以1:3的质量比配成混合溶液，用旋涡混匀器混匀，超声10min得到静电纺丝液D；将聚乙烯亚胺和聚乙烯醇溶液以1:3的质量比配成混合溶液，用旋涡混匀器混匀，超声10min得到静电纺丝液E。将纺丝液D和E分别注入注射器F和G，注射器F和G交替进行静电纺丝，先将注射器F通过自动供液泵控制注射推进速度，设置电压为19.5kV，喷射速度8μL/min，接收距离10cm，进行静电纺丝，当注射器F注射量达到0.5mL时，更换注射器G，采用相同的纺丝参数进行静电纺丝，多层循环，制得多层纳米纤维膜。
实施例3
称取3g海藻酸钠，溶于97g水中，磁力搅拌8h，完全溶解后得到质量分数为3％的海藻酸钠海藻酸钠溶液；称取6g聚乙烯亚胺，溶于94g水中，磁力搅拌2h，完全溶解后得到质量分数为6％的聚乙烯亚胺溶液；称取5g聚乙烯醇，溶于95g水中，90℃条件下，磁力搅拌4h，完全溶解后得到质量分数为5％的聚乙烯醇溶液。将海藻酸钠和聚乙烯醇溶液以1:3的质量比配成混合溶液，用旋涡混匀器混匀，超声10min得到静电纺丝液D；将聚乙烯亚胺和聚乙烯醇溶液以1:3的质量比配成混合溶液，用旋涡混匀器混匀，超声10min得到静电纺丝液E。将纺丝液D和E分别注入注射器F和G，注射器F和G交替进行静电纺丝，先将注射器F通过自动供液泵控制注射推进速度，设置电压为20kV，喷射速度10μL/min，接收距离12cm，进行静电纺丝，当注射器F注射量达到0.5mL时，更换注射器G，采用相同的纺丝参数进行静电纺丝，多层循环，制得多层纳米纤维膜。
实施例4
称取3g海藻酸钠，溶于97g水中，磁力搅拌8h，完全溶解后得到质量分数为3％的海藻酸钠海藻酸钠溶液；称取3g聚乙烯亚胺，溶于97g水中，磁力搅拌2h，完全溶解后得到质量分数为3％的聚乙烯亚胺溶液；称取5g聚乙烯醇，溶于95g水中，90℃条件下，磁力搅拌4h，完全溶解后得到质量分数为5％的聚乙烯醇溶液。将海藻酸钠和聚乙烯醇溶液以1:3的质量比配成混合溶液，用旋涡混匀器混匀，超声10min得到静电纺丝液D；将聚乙烯亚胺和聚乙烯醇溶液以1:3的质量比配成混合溶液，用旋涡混匀器混匀，超声10min得到静电纺丝液E。将纺丝液D和E分别注入注射器F和G，注射器F和G交替进行静电纺丝，先将注射器F通过自动供液泵控制注射推进速度，设置电压为17kV，喷射速度8μL/min，接收距离5cm，进行静电纺丝，当注射器F注射量达到0.5mL时，更换注射器G，采用相同的纺丝参数进行静电纺丝，多层循环，制得多层纳米纤维膜。
所述实施例为本发明的优选的实施方式，但本发明并不限于上述实施方式，在不背离本发明的实质内容的情况下，本领域技术人员能够做出的任何显而易见的改进、替换或变型均属于本发明的保护范围。

Claims (9)

1.一种海藻酸钠多层生物基纳米纤维重金属过滤膜的制备方法，其特征在于，包含如下步骤：
(1)原液的配制
将海藻酸钠配置成质量分数为1～5％的水溶液A；将聚乙烯亚胺配置成质量分数为1～10％的水溶液B；将聚乙烯醇配置成质量分数为3～10％的水溶液C；
(2)纺丝混合液的配制
将步骤(1)得到的水溶液A和C在常温下按一定比例配置成混合溶液，得到纺丝液D；将步骤(1)得到的水溶液B和C按一定的比例配置成混合溶液，得到纺丝液E；
(3)多层复合纳米纤维膜的制备
将步骤(2)得到的纺丝液D和E分别注入注射器F和G，注射器F和G交替进行静电纺丝；所述纺丝液D中的海藻酸钠与聚乙烯醇在常温下以氢键的形式结合，在静电纺丝过程中形成纳米纤维层H；所述纺丝液E中的聚乙烯亚胺与聚乙烯醇在常温下以氢键的形式结合，在静电纺丝过程中形成纳米纤维层I；最终获得纳米纤维层H与纳米纤维层I交替层叠的海藻酸钠多层生物基纳米纤维重金属过滤膜。
2.根据权利要求1所述的制备方法，其特征在于，步骤(2)中所述纺丝液D、纺丝液E在配制过程中，水溶液A和C、水溶液B和C混合后，用旋涡混匀器快速混匀，超声去除气泡后开始纺丝。
3.根据权利要求1所述的制备方法，其特征在于，纺丝液D中所述溶液A和C的比例为1:1～1:4。
4.根据权利要求1所述的制备方法，其特征在于，纺丝液E中所述溶液B和C的比例为1:1～1:4。
5.根据权利要求1所述的制备方法，其特征在于，步骤(3)中两种纺丝液交替循环纺丝时，每种纺丝液的每次纺丝所用的注射量为0.5～2mL。
6.根据权利要求1所述的制备方法，其特征在于，步骤(3)中静电纺丝的工艺参数为：电压17～21kV，接收距离5～10cm，溶液挤出速度为1～10μL/min。
7.根据权利要求1-6任一项所述的制备方法的海藻酸钠多层生物基纳米纤维重金属过滤膜，其特征在于，由纳米纤维层H与纳米纤维层I交替层叠构成。
8.根据权利要求7所述的方法制备的海藻酸钠多层生物基纳米纤维重金属过滤膜，其特征在于，纳米纤维的直径为50-250nm。
9.根据权利要求7或8所述的海藻酸钠多层生物基纳米纤维重金属过滤膜的用途，其特征在于，用于水环境中重金属离子的吸附分离。
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