CN115487871B - 一种催化还原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，具体为一种催化还原型陶瓷膜的制备方法。本发明通过共价键接枝均苯酰氯到陶瓷膜表面和孔隙壁上，然后通过酰氯水解后形成的羧基接枝配位贵金属离子，最后在将贵金属离子还原成贵金属纳米颗粒，与羧基官能团通过配位键固定在陶瓷膜表面和孔隙壁上，制备了一种由贵金属纳米颗粒构成的催化还原功能层。该方法制备的催化还原型陶瓷膜制备工艺简单、反应条件温和、分散均匀和稳定、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，可广泛应用于化工生产等领域。
Description
所属技术领域
本发明专利涉及膜材料技术领域，具体为一种催化还原型陶瓷膜的制备方法。
背景技术
膜分离作为一种分离、纯化、浓缩的重要支撑技术，被广泛应用于化工生产、生物制药、食品加工和废水处理及污水资源化回用、饮用水深度净化等领域。在这些应用场景中，膜所担当的角色主要是选择型的分离，截留固体颗粒、胶体、大分子物质，溶质等，让小分子物质或溶剂透过的物理分割的过程。从而体现出膜法技术的功能单一性。
将膜分离技术与催化氧化或者还原技术集成一直是人们关注的焦点。单纯将流态床催化氧化或还原过程及膜分离耦合，反应效率的确得到明显提升。悬浮在液态流体中的粉末催化剂被分离膜截留，反应生成物透过分离膜，实现了催化剂与反应产物的高效分离。但是纳米颗粒的粉体在分离膜表面不断沉积，参与催化反应的催化剂在膜表面形成厚厚的滤饼层，阻碍反应产物透过膜的孔隙，降低了膜的分离效率，同时也降低了催化反应的效率。看来只是单纯的将两种工艺耦合，得不到催化与分离共同协作的效果。
因此，以多孔膜作为载体，将具有催化功能的催化剂负载在膜表面和孔隙壁上，催化反应在膜孔隙中进行，即解决催化反应的传质问题，又实现了催化剂与反应产物的分离，最重要的是可以形成“微纳米孔隙反应器”，催化反应效率可以提升千倍。基于以上思路，对膜材料的要求是，孔隙率高，耐溶剂性好，表面有活性位点官能团，便于接枝纳米颗粒的催化剂。相比于有机聚合物膜，陶瓷膜更具备做催化剂载体的要求，孔隙率高、耐有机溶剂、表面丰富的羟基官能团作为活性位点。
目前催化陶瓷膜的研究主要采用的是热沉积法，将陶瓷膜浸渍在过渡金属硝酸盐溶液中或者过渡金属醇盐的溶胶中，达到饱和吸附后，再高温煅烧成氧化物颗粒。存在的问题是陶瓷膜孔隙形成的毛细管作用力，充分吸收过渡金属硝酸盐或醇盐后，高温蒸发和煅烧后，晶体分布不均匀，并且晶格生长成大颗粒，催化效果不理想；最主要的是长大的晶体填充陶瓷膜孔隙，导致膜孔隙率降低，渗透通量降低，过滤效率降低。
发明内容
本发明是针对当前依靠陶瓷膜浸渍过渡金属硝酸盐或醇盐，通过热沉积法制备的催化陶瓷膜，催化效果不理想、膜孔隙率降低、膜渗透通量降低等问题，提出一种通过接枝-配位-还原的方法将具有催化还原功能的贵金属纳米颗粒接枝到管式陶瓷膜表面和孔隙壁上，制备一种催化还原型陶瓷膜。
实现本发明目的的技术解决方案，一种催化还原型陶瓷膜的制备方法，包括以下步骤：
步骤1、对陶瓷膜预处理：将管式陶瓷膜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、均苯酰氯接枝到陶瓷膜上：将步骤1预处理后的陶瓷膜浸泡在含有一定浓度的均苯酰氯的异构烷烃溶液中5min，得到了接枝均苯酰氯的陶瓷管式膜，其反应过程如下：
步骤3、金离子接枝到陶瓷膜上：将步骤2得到的陶瓷膜浸泡在含有一定浓度的四氯金酸的pH值为4的盐酸水溶液中24h，用去离子水反复冲洗，陶瓷膜表面和孔隙壁上接枝的酰氯基团水解成羧酸基团，得到了接枝间苯二甲酸的陶瓷膜，接着羧酸中的氢质子被金离子置换，得到了接枝间苯二甲酸金的管式陶瓷膜，反应过程如下：
步骤4、陶瓷膜上的金离子还原成金纳米颗粒：将步骤3得到的陶瓷膜浸泡在含有一定浓度的硼氢化钠的水溶液中10min，用去离子水反复冲洗，得到了接枝金纳米颗粒的管式陶瓷膜，反应过程如下：
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，所述的陶瓷膜材质是氧化铝和碳化硅。
作为优选，上述制备方法的步骤2和步骤4中，所述的均苯酰氯的浓度为 0.1～1g/L。
进一步作为优选，上述制备方法的步骤2和步骤4中，所述的均苯酰氯的浓度为0.3～0.8g/L。
作为优选，上述制备方法的步骤3中，所述的四氯金酸的浓度为0.1～2.0g/L。
进一步作为优选，上述制备方法的步骤3中，所述的四氯金酸的浓度为 0.5～1.5g/L。
作为优选，上述制备方法的步骤3中，所述的贵金属盐是四氯金酸、硝酸银、硝酸钯、醋酸钯中的一种或者一种以上复合物。
作为优选，上述制备方法的步骤4中，所述的硼氢化钠的浓度为0.1～1g/L。
进一步作为优选，上述制备方法的步骤4中，所述的硼氢化钠的浓度为 0.3～0.8g/L。
本发明具有以下有益效果：
(1)该制备方法工艺简单、反应条件温和，都是在室温下进行；
(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和配位纳米颗粒，不会对陶瓷膜孔隙率造成很大的影响；
(4)该制备方法是在陶瓷膜表面和孔隙壁上接枝和配位贵金属纳米颗粒，颗粒分布均匀，不会发生颗粒团聚；
(5)该制备方法是采用接枝和配位技术将贵金属纳米颗粒通过共价键和配位键修饰在陶瓷膜所有表面积上，具有很好的稳定性；
(6)该制备方法不需要高温煅烧处理。
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
将管式碳化硅陶瓷膜在超声波中超声清洗20min，然后在乙醇溶液中浸泡1 h，去除其表面和孔隙中的杂质；
实施例2
步骤1、将管式碳化硅陶瓷膜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预处理后的陶瓷膜浸泡在浓度为0.5g/L的均苯酰氯的异构烷烃溶液中5min，得到了接枝均苯酰氯的管式碳化硅陶瓷膜；
步骤3、将步骤2得到的碳化硅陶瓷膜浸泡在浓度为1.0g/L的四氯金酸的 pH值为4的盐酸水溶液中24h，用去离子水反复冲洗，得到了接枝了间苯二甲酸金的管式碳化硅陶瓷膜；
步骤4、将步骤3得到的陶瓷膜浸泡在浓度为0.5g/L的硼氢化钠的水溶液中10min，用去离子水反复冲洗，得到了接枝金纳米颗粒的管式碳化硅陶瓷膜；
实施例3
将实施例2的步骤3中的四氯金酸更换成硝酸银，其他参数和条件不变。
实施例4
将实施例2的步骤3中的四氯金酸更换成硝酸钯，其他参数和条件不变。
实施例5
将实施例1、2、3、4制备的管式碳化硅陶瓷膜，安装到膜组件中，采用错流循环恒压(1bar)过滤模式，过滤浓度为2.0g/L的4-硝基苯酚和2.0g/L的硼氢化钠的混合水溶液，回流液和渗透液都返回反应罐。随着反应的进行，每隔3 min取样测紫外光谱，观察波长400nm处的吸光度变化情况，判断催化还原型管式碳化硅陶瓷膜将4-硝基苯酚还原成4-氨基苯酚的进展情况。同时将取来的样品稀释20倍后，用高效液相测试定量检测4-硝基苯酚转化率和4-氨基苯酚的产率。测试条件:waters-ACQUITY UPLC BEH C18色谱柱2.1×100mm，1.7μm，柱温为室温，流动相为体积比80/20的甲醇/超纯水，流速1mL/min，263nm处紫外检测器单波长检测。其催化还原4-硝基苯酚的反应过程如下：
表1:实施例1～4比较四种管式碳化硅陶瓷膜催化还原4-硝基苯酚100％转化所需要的时间及膜的渗透通量：
| 实施例 | 1 | 2 | 3 | 4 |
| 时间(min) | - | 14.2 | 21.8 | 19.5 |
| 膜的渗透通量(LMH) | 1285 | 1197 | 1237 | 1208 |
结果发现：实施例1中的4-硝基苯酚转化率只有38.2％，实施例2、3和4 均催化还原膜都展现出优异的催化还原4-硝基苯酚的性能。相比于原膜，实施例 2、3和4陶瓷膜的渗透通量稍微减小，但是减少的不是很明显，说明接枝的纳米贵金属颗粒不影响膜的渗透通量。
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)
1.一种催化还原型陶瓷膜的制备方法，其特征在于，包括以下步骤：
步骤1、将管式陶瓷膜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预处理后的管式陶瓷膜浸泡在含有一定浓度的均苯酰氯的异构烷烃溶液中5 min，得到了接枝均苯酰氯的管式陶瓷膜：所述的均苯酰氯的浓度为0.3~0.8 g/L；
步骤3、将步骤2得到的陶瓷膜浸泡在含有一定浓度的四氯金酸的pH值为4的盐酸水溶液中24 h，用去离子水反复冲洗，得到了接枝间苯二甲酸金的管式陶瓷膜：所述的四氯金酸的浓度为0.5~1.5 g/L；
步骤4、将步骤3得到的陶瓷膜浸泡在含有一定浓度的硼氢化钠的水溶液中10 min，用去离子水反复冲洗，得到了接枝贵金属纳米颗粒的管式陶瓷膜；所述的硼氢化钠的浓度为0.3~0.8 g/L；
所述的陶瓷膜是氧化铝、氧化钛、氧化锆、氧化硅、或碳化硅中一种以上的复合陶瓷膜。
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