CN107983320B - 用于甲醛去除的双功能薄膜的制备方法及其产品和应用 - Google Patents
用于甲醛去除的双功能薄膜的制备方法及其产品和应用 Download PDFInfo
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Abstract
本发明涉及一种用于甲醛去除的双功能薄膜的制备方法及其产品和应用，该薄膜是以稀土元素修饰的活性炭负载锰基催化剂为活性组分，采用静电纺丝的方法制备，包括稀土元素修饰的活性炭的制备、稀土元素修饰的活性炭负载锰基催化剂的制备、静电纺丝溶液的制备和静电纺丝薄膜的制备。该薄膜对于甲醛同时具有吸附和催化氧化的作用，从而能达到去除甲醛的效果。该薄膜制备方法简单，原料价格低廉，对不同浓度甲醛的去除都具有一定的效果，在空气净化领域具有很大的应用前景。
Description
技术领域
本发明属于吸附/催化环保技术领域，特别涉及一种用于甲醛去除的双功能薄膜的制备方法及其产品和应用。
背景技术
甲醛是室内空气污染物中最常见也是毒性最大的污染物之一，主要来源于家具、木制品板材和填料、织物、涂料、墙纸、地毯甚至窗帘。一般新装修的房子其甲醛的含量可超标6倍以上，个别则有可能超标达40倍以上。实测数据说明，一般正常装修的情况下，室内甲醛的释放期会持续3-15年。当甲醛浓度大于 0.08m³ 就会引起喉咙不适、声音嘶哑、胸闷、气喘、皮炎等。长期、低浓度接触甲醛会引起头痛、乏力、感觉障碍、免疫力下降等症状，并且世界卫生组织确定甲醛具有致癌性，长期接触甲醛会增大患上特殊癌症的几率。在大气环境污染日益严重的今天，如何有效去除室内空气污染物中的甲醛是亟待解决的科学难题。
目前针对室内污染物中的甲醛主要是喷射或涂抹处理甲醛的试剂，也有利用植物的吸收作用去除甲醛，但其处理效果均一般，而且甲醛浓度的测定时间也是人工控制的，当甲醛浓度超标时人不能准确的感知到。近年来，对甲醛污染物的控制主要分为两个方向：一个是从源头上减少甲醛污染物的产生；另一方面是采用空气净化设备。从源头上减少控制甲醛污染物主要是开发和使用更环保的材料，其中包括水性涂料、环保粘结剂、环保板材等材料的开发。但目前的技术仍然满足不了市场的需求，需要开发更多的环保材料，从而减少甲醛污染物的产生。
发明内容
针对目前室内空气中甲醛污染严重等问题，本发明目的在于：提供一种用于甲醛去除的双功能薄膜的制备方法。
本发明再一目的在于：提供一种上述方案制备的产品。
本发明又一目的在于：提供一种上述产品的应用。
本发明目的通过下述方案实现：一种用于甲醛去除的双功能薄膜的制备方法，该薄膜以稀土修饰的活性炭负载锰基催化剂作为活性组分，采用静电纺丝的方法制备，包括以下步骤：
第一步：稀土元素修饰的活性炭的制备
称取一定质量的活性炭，按照活性炭：水=1:1.2~1.5的质量比称取一定量的去离子水；按照活性炭：稀土硝酸盐=1:0.1~0.2的质量比称取一定质量的硝酸盐溶于上述去离子水中；向上述硝酸盐的水溶液中滴加氨水直到PH≈8左右；将称取的活性炭加入上述溶液中，室温过夜浸渍，置于50~60oC烘箱中过夜干燥，得到稀土元素修饰的活性炭；
第二步：稀土元素修饰的活性炭负载锰基催化剂的制备
配制0.005mol/L的高锰酸钾溶液，量取1000ml 上述配制的高锰酸钾溶液，称取20~30g第一步中制备的稀土元素修饰的活性炭加入上述量取的高锰酸钾溶液中，搅拌1~3h，过滤，置于50~60 oC烘箱中过夜干燥，得到稀土元素修饰的活性炭负载的锰基催化剂；
第三步：静电纺丝溶液的制备
将聚丙烯腈溶于N-N 二甲基甲酰胺（DMF）中，加入第二步中制备的稀土元素修饰的活性炭负载的锰基催化剂，剧烈搅拌3h，然后超声震荡1h，得到分散均匀的静电纺丝溶液，其中锰基催化剂与聚丙烯腈的质量比为1:12；聚丙烯腈与N-N 二甲基甲酰胺的质量比为1:4；
第四步：静电纺丝薄膜的制备
采用步骤（3）所得的静电纺丝溶液进行静电纺丝，得到一种用于甲醛去除的双功能纳米纤维膜。
所述活性炭为市售的活性炭，所述稀土硝酸盐为硝酸铈、硝酸镧和硝酸锆中的一种。
本发明提供一种用于甲醛去除的双功能薄膜，根据上述任一所述方法制备得到。
本发明提供一种双功能薄膜用于甲醛吸附和催化氧化的应用。本发明所述的薄膜不仅可以用于室内甲醛的净化，同时对于颗粒物的去除也有一定的作用。该双功能薄膜具有多种用途，可以用于室内空气净化产品中，也可以用于房屋墙面装修，家具制造过程中。该薄膜制备方法简单，原料价格低廉，具有很高的实用价值。
本发明采用静电纺丝的方法制备一种用于甲醛去除的双功能薄膜，该薄膜对甲醛去除能同时起到吸附和催化的作用。本发明是将吸附/催化材料负载于高分子纤维上，解决了催化剂在负载到其他材料上易脱落的问题，采用静电纺丝纺织成的纤维薄膜具有多种用途。该薄膜不仅可以用在空气净化产品中，同时可以应用于房屋装修墙面、家具贴面等方面。由于该薄膜具有比表面积大、孔隙率高、孔径直径小等优点，对甲醛的去除有很好的效果。由于该薄膜用途广泛，从而具有很高的实用价值。
本发明中所述一种用于甲醛去除的双功能薄膜及其制备方法相较于现有催化剂，具有以下特点：（1）该薄膜对于甲醛去除同时具有吸附和催化的功能；（2）该薄膜具有多孔结构，对于PM的去除也具有一定的效果；（3）该薄膜以稀土元素修饰的活性炭负载的锰基催化剂为活性组分，采用稀土修饰使活性组分稳定性和活性都得到提高。
具体实施方式
实施例1
称取24g去离子水，向去离子水中2g六水合硝酸铈，待硝酸铈溶解完全后向其中滴加氨水直到PH≈8，称取 20g活性炭溶于上述溶液中，室温过夜浸渍，置于50oC烘箱中过夜干燥，得到铈修饰的活性炭。
配制0.005mol/L的高锰酸钾溶液，量取1000ml 上述配制的高锰酸钾溶液，称取20g上述铈修饰的活性炭加入上述高锰酸钾溶液中，搅拌2h，过滤，置于50oC烘箱中过夜干燥，得到铈修饰的活性炭负载的锰基催化剂。
将12g聚丙烯腈溶于48g N-N 二甲基甲酰胺（DMF）中，加入1g第二步中制备的铈修饰的活性炭负载的锰基催化剂，剧烈搅拌3h，然后超声震荡1h，得到分散均匀的静电纺丝溶液。将此静电纺丝溶液进行静电纺丝，得到本发明所述一种用于甲醛去除的双功能纳米纤维膜。
实施例2
称取56g去离子水，向去离子水中8g六水合硝酸锆，待硝酸铈溶解完全后向其中滴加氨水直到PH≈8，称取 40g活性炭溶于上述溶液中，室温过夜浸渍，置于60oC烘箱中过夜干燥，得到铈修饰的活性炭。
配制0.005mol/L的高锰酸钾溶液，量取1000ml 上述配制的高锰酸钾溶液，称取25g上述铈修饰的活性炭加入上述高锰酸钾溶液中，搅拌2h，过滤，置于60oC烘箱中过夜干燥，得到锆修饰的活性炭负载的锰基催化剂。
将12g聚丙烯腈溶于48g N-N 二甲基甲酰胺（DMF）中，加入1g第二步中制备的锆修饰的活性炭负载的锰基催化剂，剧烈搅拌3h，然后超声震荡1h，得到分散均匀的静电纺丝溶液。将此静电纺丝溶液进行静电纺丝，得到本发明所述一种用于甲醛去除的双功能纳米纤维膜。
实施例3
称取60g去离子水，向去离子水中4g六水合硝酸镧，待硝酸铈溶解完全后向其中滴加氨水直到PH≈8，称取 40g活性炭溶于上述溶液中，室温过夜浸渍，置于60oC烘箱中过夜干燥，得到铈修饰的活性炭。
配制0.005mol/L的高锰酸钾溶液，量取1000ml 上述配制的高锰酸钾溶液，称取30g上述镧修饰的活性炭加入上述高锰酸钾溶液中，搅拌2h，过滤，置于60oC烘箱中过夜干燥，得到锆修饰的活性炭负载的锰基催化剂。
将12g聚丙烯腈溶于48g N-N 二甲基甲酰胺（DMF）中，加入1g第二步中制备的锆修饰的活性炭负载的锰基催化剂，剧烈搅拌3h，然后超声震荡1h，得到分散均匀的静电纺丝溶液。将此静电纺丝溶液进行静电纺丝，得到本发明所述一种用于甲醛去除的双功能纳米纤维膜。
上述实施例为本发明部分实施方式，但本发明并不受上述实施例的限制，其它的任何未背离本发明的精神实质与原理下所作的改变、修饰、替代、组合、简化，均应为等效的置换方式，都包含在本发明的保护范围之内。
Claims (3)
1.一种用于甲醛去除的双功能薄膜的制备方法，其特征在于，该薄膜以稀土修饰的活性炭负载锰基催化剂作为活性组分，采用静电纺丝的方法制备，包括以下步骤：
第一步：稀土元素修饰的活性炭的制备
称取一定质量的活性炭，按照活性炭：水=1:1.2~1.5的质量比称取一定量的去离子水；按照活性炭：稀土硝酸盐=1:0.1~0.2的质量比称取一定质量的硝酸盐溶于上述去离子水中；向上述硝酸盐的水溶液中滴加氨水直到pH ≈8左右；将称取的活性炭加入上述溶液中，室温过夜浸渍，置于50~60℃ 烘箱中过夜干燥，得到稀土元素修饰的活性炭；
第二步：稀土元素修饰的活性炭负载锰基催化剂的制备
配制0.005mol/L的高锰酸钾溶液，量取1000 mL上述配制的高锰酸钾溶液，称取20~30g第一步中制备的稀土元素修饰的活性炭加入上述量取的高锰酸钾溶液中，搅拌1~3h，过滤，置于50~60℃烘箱中过夜干燥，得到稀土元素修饰的活性炭负载的锰基催化剂；
第三步：静电纺丝溶液的制备
将聚丙烯腈溶于N-N 二甲基甲酰胺（DMF）中，加入第二步中制备的稀土元素修饰的活性炭负载的锰基催化剂，剧烈搅拌3h，然后超声震荡1h，得到分散均匀的静电纺丝溶液，其中锰基催化剂与聚丙烯腈的质量比为1:12；聚丙烯腈与N-N 二甲基甲酰胺的质量比为1:4；
第四步：静电纺丝薄膜的制备
采用步骤（3）所得的静电纺丝溶液进行静电纺丝，得到一种用于甲醛去除的双功能纳米纤维膜；
所述稀土硝酸盐为硝酸铈、硝酸镧中的一种。
2.一种用于甲醛去除的双功能薄膜，其特征在于根据权利要求1所述方法制备得到。
3.一种根据权利要求2所述双功能薄膜用于甲醛吸附和催化氧化的应用。
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