CN115487869B - 一种催化臭氧型陶瓷膜的制备方法 - Google Patents
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Abstract
本发明专利涉及分离膜材料技术领域，具体为一种催化臭氧型陶瓷膜的制备方法。本发明通过化学接枝‑配位‑氧化反应在陶瓷膜表面和孔隙壁上接枝纳米二氧化锰粒子，该改性方法对膜的渗透通量影响不明显，且不需要高温煅烧，二氧化锰以纳米颗粒形态接枝在陶瓷膜表面和孔隙壁上，稳定性好。该方法制备的催化臭氧型陶瓷膜制备工艺简单、反应条件温和、催化臭氧效果显著、不影响陶瓷膜的孔隙率和渗透通量、不损伤陶瓷膜的基底等优点，可广泛应用于污水的处理及资源化回用和饮用水的深度净化等领域。
Description
所属技术领域
本发明专利涉及分离膜材料技术领域，具体为一种催化臭氧型陶瓷膜的制备方法。
背景技术
主要污染源为工业废水和生活污水，但是近年来饮用水的污染也成为人们关注的焦点。饮用水污染除了肉眼可见的铁锈和泥沙外，还有导致人体腹泻等病原微生物“两虫”(贾弟鞭毛虫和隐性孢子虫)和新兴污染物内分泌干扰物(EDCs)、药品和个人护理品(PPCPs)等也开始在水体和自来水厂中检出，由此带来的风险更值得重视。
臭氧氧化技术可以有效去除饮用水中的这些新兴微污染物、对印染废水脱色和降解水中有机污染物。但臭氧氧化技术在应用的过程中具有一定的局限性，如臭氧矿化能力低、利用效率低和有机物分解不彻底等。催化臭氧氧化技术是利用催化剂的作用，促进了反应过程中臭氧分子的分解和强氧化性，生成绿色环保和氧化能力更强的羟基自由基，提高了臭氧的利用效率，增加了有机污染物的氧化分解及矿化效率。但在实际应用过程中往往存在这催化剂流失严重以及回收困难的问题。
将臭氧氧化与膜分离集成是一种新颖的催化氧化分离技术，用于污水处理和饮用水的深度净化等领域。膜元件按照材质可分为有机膜和陶瓷膜。与有机膜相比，陶瓷膜具有更好的机械性能和化学稳定性，既能在较高的膜渗透通量下稳定运行，又能承受高的反冲洗强度以取得更好的反冲洗效果，其次陶瓷膜还有一个最重要的特征就是能耐受臭氧氧化。专利(CN 107673504 A)报道过臭氧氧化与陶瓷膜分离技术联用既可以保持稳定的高渗透通量，减缓膜污染进程，又可以氧化降解水中的难降解的污染物，尤其是对EDCs和PPCPs的去除效果十分突出，充分保障产水的生物安全性。
然而，在单纯的臭氧氧化和陶瓷膜过滤集成的技术中，臭氧在大通量的陶瓷膜过滤过程中的传质速率有限，溶解在水中的臭氧浓度低，与污染物的接触不充分，氧化降解效果不是很明显。专利(CN 106630391A)报道将二氧化锰掺杂在陶瓷颗粒中通过高温烧结技术制备具有臭氧催化功能的陶瓷膜，的确明显提高了臭氧的利用效率。但是该掺杂改性法制备的陶瓷膜存在二氧化锰催化剂被包埋现象，导致催化臭氧的效率不是很充分；其次二氧化锰的掺杂导致陶瓷颗粒堆积形成的膜层缺陷增多，膜孔径分布宽，过滤精度差。专利(CN 104803512 A)报道一种通过浸涂法在陶瓷膜表面制备一层钛锰或钛铈的催化功能层，催化溶解在水中的臭氧，实现陶瓷膜的催化自清洁功能。但是存在的问题是该催化功能存在堵塞陶瓷膜孔径的风险，导致膜渗透阻力增加，膜渗透通量变小，跨膜压差增大和过滤效率降低；还有就是该催化功能层可能存在反冲洗脱落的风险，导致膜催化功能层稳定性变差。
发明内容
本发明是针对二氧化锰掺杂共烧改性陶瓷膜和二氧化锰在陶瓷膜表面热沉积改性，制备的催化臭氧型陶瓷膜存在的催化臭氧效果不明显、膜渗透通量小、功能层稳定性差、需要高温煅烧处理等问题，提出一种利用陶瓷膜表面丰富的羟基官能团做活性位点，室温条件下，通过化学接枝-配位-氧化反应在陶瓷膜表面和孔隙壁上接枝纳米二氧化锰粒子，该改性方法对膜的渗透通量影响不明显，且不需要高温煅烧，二氧化锰以纳米颗粒形态接枝在陶瓷膜表面和孔隙壁上，稳定性好。
实现本发明目的的技术解决方案，一种催化臭氧型陶瓷膜的制备方法，包括以下步骤：
步骤1、对陶瓷膜表面预处理：将平板陶瓷膜片在超声波中超声清洗20min，然后在乙醇溶液中浸泡1h，去除其表面和孔隙中的杂质；
步骤2、N,N-二乙基-3-(三甲氧基硅烷基)丙胺接枝到预处理的陶瓷膜上：将步骤1预处理后的陶瓷膜浸泡在含有一定浓度的N,N-二乙基-3-(三甲氧基硅烷基)丙胺的二氯甲烷溶液中1h，然后用二氯甲烷反复冲洗其表面，40℃下真空干燥，得到接枝N,N-二乙基-3-(三甲氧基硅烷基)丙胺的陶瓷膜，其反应过程如下：
步骤3、配位锰离子：将步骤2得到的陶瓷膜浸泡在含有一定浓度的硝酸锰的水溶液中24h，然后用去离子水反复冲洗数次，直到洗液无颜色为止，60℃下真空干燥，得到了表面和孔隙壁上配位了锰离子的平板陶瓷膜，反应过程如下：
步骤4、二氧化锰纳米颗粒制备：将步骤3得到的陶瓷膜浸泡在含有一定浓度的高锰酸钾的水溶液中3h，然后用去离子水反复冲洗数次，直到洗液无颜色为止，60℃下真空干燥，得到了表面和孔隙壁上接枝了二氧化锰纳米颗粒的平板陶瓷膜，反应过程如下：
其中高锰酸根氧化锰离子生成二氧化锰的反应过程如下：
2MnO4-+3Mn2++2H2O＝5MnO2+4H+
作为优选，上述制备方法的步骤1中，所述的陶瓷膜是氧化铝、氧化钛、氧化锆、氧化硅、或碳化硅中的一种或一种以上的复合陶瓷膜。
进一步作为优选，上述制备方法的步骤1中，所述的陶瓷膜是氧化铝和碳化硅。
作为优选，上述制备方法的步骤2中，所述的N,N-二乙基-3-(三甲氧基硅烷基)丙胺的浓度为1～10g/L。
进一步作为优选，上述制备方法的步骤2中，所述的N,N-二乙基-3-(三甲氧基硅烷基)丙胺的浓度为3～8g/L。
作为优选，上述制备方法的步骤3中，所述的硝酸锰的浓度是50％的硝酸锰溶液1～10g/L。
进一步作为优选，上述制备方法的步骤3中，所述的硝酸锰的浓度是50％的硝酸锰溶液3～8g/L。
作为优选，上述制备方法的步骤4中，所述的高锰酸钾的浓度是0.1～1g/L。
进一步作为优选，上述制备方法的步骤4中，所述的高锰酸钾的浓度是 0.3～0.8g/L。
本发明具有以下有益效果：
臭氧是一种绿色环保的氧化剂，其分解产物是氧气，不会对环境产生二次污染。催化臭氧氧化技术是一种高效清洁的高级氧化技术，利用臭氧催化剂催化臭氧产生的具有强氧化性的活性氧物种(如羟基自由基、超氧负离子、单线态氧等) 能够快速地降解有机污染物。将陶瓷膜的分离技术与催化臭氧氧化技术集成，利用催化臭氧氧化过程产生的活性氧物种分解小分子污染物以及被截留在膜表面的污染物，提高小分子污染物去除效率并抑制膜污染。具有以下特点：
(1)该制备方法工艺简单、反应条件温和，室温条件下制备；
(2)陶瓷膜具有耐有机溶剂特性，制备过程不会对膜微结构损伤；
(3)该制备方法是在过滤精度在微滤或超滤的陶瓷膜表面和孔隙壁上接枝纳米二氧化锰颗粒，不会对陶瓷膜孔隙率和渗透通量造成很大影响；
(4)该制备方法是在陶瓷膜表面和孔隙壁上接枝纳米二氧化锰颗粒功能层，催化臭氧效果显著；
(5)该制备方法是采用化学共价键和配位键接枝纳米二氧化锰颗粒功能层，稳定性好；
(6)该制备方法是一种非常新颖的催化臭氧的陶瓷膜改性方法。
附图说明
图1陶瓷膜表面结构示意图
具体实施方式：
下面结合实例进一步说明本发明，但并不是本发明内容范围的任何限制。
实施例1
实验室复配浓度为0.1g/L的4-硝基苯水溶液中，并用没有涂覆膜层的平板碳化硅陶瓷基材做臭氧步气板，给模拟的4-硝基苯废水鼓臭氧，臭氧的浓度是5 mg/L。每间隔5min的时间取样，采用高效液相色谱测膜出水的4-硝基苯的浓度，计算4-硝基苯膜催化降解的去除率。
实施例2
将平板碳化硅陶瓷膜片在超声波中超声清洗20min，然后在乙醇溶液中浸泡 1h，去除其表面和孔隙中的杂质，可得表面如图1所示结构。将膜片浸没在实 验室复配浓度为0.1g/L的4-硝基苯水溶液中，并用没有涂覆膜层的平板碳化硅 陶瓷基材做臭氧步气板，给模拟的4-硝基苯废水鼓臭氧，臭氧的浓度是5mg/L。 采用蠕动泵恒流量负压抽吸平板碳化硅陶瓷膜过滤的液体，并返回反应池中，同 时每间隔5min的时间取样，采用高效液相色谱测膜出水的4-硝基苯的浓度，计 算4-硝基苯膜催化降解的去除率。
实施例3
步骤1、将平板碳化硅陶瓷膜片在超声波中超声清洗20min，然后在乙醇溶液中浸泡1h，去除其表面和孔隙中的杂质；
步骤2、将步骤1预处理后的平板碳化硅陶瓷膜浸泡在浓度为5g/L的N,N- 二乙基-3-(三甲氧基硅烷基)丙胺的二氯甲烷溶液中1h，然后用二氯甲烷反复冲洗其表面，40℃下真空干燥，得到接枝N,N-二乙基-3-(三甲氧基硅烷基)丙胺的平板碳化硅陶瓷膜；
步骤3、将步骤2得到的陶瓷膜片浸泡在浓度是5g/L的硝酸锰的水溶液中 24h，然后用去离子水反复冲洗数次，直到洗液无颜色为止，60℃下真空干燥，得到表面和孔隙壁上配位了锰离子的平板碳化硅陶瓷膜；
步骤4、将步骤3得到的配位了锰离子的陶瓷膜片浸泡在浓度是0.5g/L高锰酸钾的水溶液中3h，然后用去离子水反复冲洗数次，直到洗液无颜色为止，60℃下真空干燥，得到的表面和孔隙壁上接枝了纳米二氧化锰颗粒的平板碳化硅陶瓷膜。
步骤5、将步骤4得到的表面和孔隙壁上接枝了纳米二氧化锰颗粒的平板碳化硅陶瓷膜，浸没在实验室复配浓度为0.1g/L的4-硝基苯水溶液中，并用没有涂覆膜层的平板碳化硅陶瓷基材做臭氧步气板，给模拟的4-硝基苯废水鼓臭氧，臭氧的浓度是5mg/L。采用蠕动泵恒流量负压抽吸平板碳化硅陶瓷膜过滤的液体，并返回反应池中，同时每间隔5min的时间取样，采用高效液相色谱测膜出水的4-硝基苯的浓度，计算4-硝基苯膜催化降解的去除率。
高效液相色谱测试条件:waters-ACQUITY UPLC BEH C18色谱柱2.1×100 mm，1.7μm，柱温为室温，流动相为体积比60/40的甲醇/超纯水，流速1mL/min， 263nm处紫外检测器单波长检测。
表1 对比三种平板陶瓷膜催化降解4-硝基苯的去除效率(％)
结果表明：表面和孔隙壁上接枝了纳米二氧化锰颗粒的平板碳化硅陶瓷膜展现出优异的催化臭氧性能。
实施例5
将实施例2和3中制备的平板陶瓷膜用浙江某景观水的处理，测试其过滤前后COD值、浊度和渗透通量(-0.02MPa下)的变化情况。
水通量(J)定义为：在一定的操作条件下，单位时间(t)内透过单位膜面积(A)的水的体积(V)，其单位为L/m2·h，具体计算公式如下：
COD值的测试采用哈希DR1010-COD测定仪；
浊度值的测试采用哈希TU5200台式浊度仪；
表2 对比实施例2和3过滤30min后景观水的前后参数变化：
结果表明：表面和孔隙壁上接枝了纳米二氧化锰颗粒的平板碳化硅陶瓷膜展现出优异的催化臭氧功能；渗透通量比原膜有减少，但是减少的不是很明显。
以上所述，仅为本发明专利较佳实施例而已，不能依次限定本发明实施的范围，即依本发明专利范围及说明书内容所写的等效变化及修饰，皆应属于本发明涵盖的范围内。
Claims (1)
1.一种催化臭氧型陶瓷膜的制备方法，其特征在于，包括以下步骤：
步骤1、将平板陶瓷膜片在超声波中超声清洗20 min，然后在乙醇溶液中浸泡1 h，去除其表面和孔隙中的杂质；
步骤2、将步骤1预处理后的陶瓷膜浸泡在含有一定浓度的N,N-二乙基-3-（三甲氧基硅烷基）丙胺的二氯甲烷溶液中1 h，然后用二氯甲烷反复冲洗其表面，40 ℃下真空干燥，得到接枝了N,N-二乙基-3-（三甲氧基硅烷基）丙胺的平板陶瓷膜；所述的N,N-二乙基-3-（三甲氧基硅烷基）丙胺的浓度为3~8 g/L；
步骤3、将步骤2得到的陶瓷膜片浸泡在含有一定浓度的硝酸锰的水溶液中24 h，然后用去离子水反复冲洗数次，直到洗液无颜色为止，60 ℃下真空干燥，得到了表面和孔隙壁上配位了锰离子的平板陶瓷膜；所述的硝酸锰的浓度是5g/L；
步骤4、将步骤3得到的陶瓷膜片浸泡在含有一定浓度的高锰酸钾的水溶液中3 h，然后用去离子水反复冲洗数次，直到洗液无颜色为止，60 ℃下真空干燥，得到了表面和孔隙壁上接枝了二氧化锰纳米颗粒的平板陶瓷膜；高锰酸钾的浓度是0.3~0.8g/L；
所述的陶瓷膜是氧化铝、氧化钛、氧化锆、氧化硅、或碳化硅中的一种以上的复合陶瓷膜。
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