CN110624424A - 一种改性多孔膜材料、制备方法以及二氧化碳的液膜分离方法 - Google Patents
一种改性多孔膜材料、制备方法以及二氧化碳的液膜分离方法 Download PDFInfo
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Abstract
本发明涉及一种用于增强液膜分离二氧化碳的膜改性方法，该方法是将含有胺类基团的有机物接枝在膜材料上，然后在多孔膜的孔道内负载水制得支撑液膜用于二氧化碳的混合气分离实验。本发明通过化学接枝反应引入胺类基团，使水作为膜液时具有一定的碱性，相比较于碱性溶液作为膜液，可以避免有效碱性物质的流失，同时二氧化碳的渗透通量也得到了提高。
Description
技术领域
本发明属于膜材料的改性，具体涉及一种支撑液膜的膜材料的胺化改性及其在增强二氧化碳分离上的应用。
背景技术
近几年来，温室效应是人们最为关心的环境问题之一，而引起温室效应的主要来源是CO2，这主要由发电厂、钢铁厂及化工厂等排放出来。从防止全球变暖的角度考虑，二氧化碳的高效捕集回收技术的开发成为当务之急。除此之外，以CH4为主要成分的天然气开采中也含有CO2，需要从天然气中回收除去CO2，防止CO2等在气体输送过程中对气体管道的腐蚀。此外，还有很多含有CO2且需要除去CO2的待处理体系。
目前，CO2的分离和捕集主要有低温液化分离、吸收剂分离、吸附法捕集、膜分离等等。其中CO2胺类化学吸收法较为成熟，已经实现了工业应用，然而醇胺类吸收CO2之后需要升温解吸，同时温度过高还会导致其的降解（CN103638780A），从而降低吸收剂的再生度和循环率。除此之外，气体解吸塔能耗占了整个CO2捕集成本的~75%，再加上胺类溶剂对设备的强腐蚀作用，已经严重降低了CO2捕集的经济性，胺吸收法也因其自身的特点很难在技术上进一步的突破；低温液化分离虽然原理较为简单，但所需能耗非常巨大，成本较高且所用的装置规模较大；吸附法需要变压、变温或两者连用，所需步骤比较繁琐；膜分离法是比较新型的分离技术，但其所得的CO2纯度有限且难以突破的“Robeson上限”，即膜材料不可以同时达到较高的渗透速率和高选择性。
目前由于支撑液膜在实现高选择性和高渗透性有很好的突破，所以该技术用于气体分离方面的研究逐渐被研究者所重视。离子液体由于其较高的CO2溶解选择性和自身难挥发性在支撑液膜中有很好的应用，但由于其表面张力比较小，对膜孔径分布和大小有很高的要求，不能承受很高的跨膜压差，导致离子液体容易流失，从而对环境造成二次污染且离子液体价格昂贵造成一定的经济损失。
另外，采用现有技术中的采用离子液体的多孔膜自支撑的液膜分离方法时，在实际操作过程中，步骤繁琐。将分离设备更换使用场地之后，需要重新配制液膜，导致了增加了操作步骤，并且也存在着原料的获取等问题。
发明内容
本发明的目的是为了解决支撑液膜膜液流失的问题，同时又要保留离子液体的二氧化碳高效果，提出了一种增强水支撑液膜分离二氧化碳的膜材料胺化改性方法。
本发明的第一个方面，提供了：
一种改性多孔膜材料，所述的膜材料是指无机多孔材料，在膜材料的孔道内修饰有含胺类的基团。
在一个实施方式中，所述的胺类基团为含有伯胺、仲胺或者叔胺基团中的一种。
在一个实施方式中，所述的无机多孔材料为多孔氧化铝、多孔氧化钛、多孔氧化锆或者多孔氧化硅。
在一个实施方式中，所述的膜材料平均孔径为1～200 nm。
在一个实施方式中，所述的膜材料几何结构为平板式或管式。
本发明的第二个方面，提供了：
上述的改性多孔膜材料的制备方法，包括如下步骤：
将含胺类基团的硅烷偶联剂溶解在有机溶剂中，作为改性剂；将多孔膜材料浸没于改性剂中进行接枝反应，反应完成后，经过清洗、烘干，得到改性多孔膜材料。
在一个实施方式中，含胺类基团的硅烷偶联剂：选自例如N，N-二甲基-3-氨丙基三甲氧基硅烷、（3-氨丙基）三甲氧基硅烷等等。
在一个实施方式中，有机溶剂为至少含有乙醇、丙酮、二甲基乙酰胺（DMAC）、四氢呋喃（THF）中的一种。
在一个实施方式中，反应的条件为温度为20～40 ℃，反应时间1～24 h。
本发明的第三个方面，提供了：
一种二氧化碳的液膜分离方法，包括如下步骤：
用水作为溶剂，负载于上述的改性多孔膜材料的孔道中，形成液膜；再与含二氧化碳的混合气接触，使二氧化碳透过膜层。
在一个实施方式中，含二氧化碳的混合气为CO2与至少为N2、CH4、H2、O2、He、CO等气体中的一种。
本发明的第四个方面，提供了：
改性多孔膜材料在用于提高二氧化碳的液膜分离过程中的分离因子或者渗透通量中的应用。
有益效果
本发明中发现通过对多孔陶瓷材料的表面经过修饰胺类基团之后，一方面能够使胺类基团固定于材料表面，另一方面，利用这种结构也能够实现液膜分离二氧化碳的效果。
本发明中，在膜材料上接枝含胺类基团的高分子功能材料既可以满足液膜选择分离和渗透增强的需要，又可以避免因为使用离子液体带来的膜液流失的问题。
本发明是对多孔膜材料进行胺化改性，可以使增强传递的载体以固载的形式接枝在膜表面上，这样可以避免有效碱性物质的流失，并且本实验采用的膜溶剂为环境友好的水。除此之外，在膜液流失的情况下，液膜的修复可以利用膜材料亲水性质和孔结构大小，很容易在含有水汽的二氧化碳混合气条件下，通过毛细冷凝作用进行修复，可以提高支撑液膜的稳定性且操作方便。
采用本发明的方法，直接将胺类基团固载于多孔材料的内部，当需要将分离设备更换使用场地时，直接可以将设备移动位置，并不再需要重新准备复杂的液膜，直接采用简便易得的水作为介质即可，大大提高了装置设备的使用方便性。
附图说明
图1为胺化改性的多孔膜材料的红外图谱。
图2为胺化改性前后的多孔膜材料所制得的水支撑液膜对二氧化碳分离体系中气体渗透率的影响。
图3为未胺化改性的多孔膜，温度对二氧化碳渗透率的影响。
具体实施方式
本发明的技术方案，是将含有胺类基团的硅烷偶联剂滴加到有机溶剂中溶解配成改性溶液，将多孔膜材料浸没在改性溶液中反应，待反应完成后清洗烘干，得到富含胺基基团的膜材料。然后在表面张力的作用下，使水负载在膜孔道内，制得的支撑液膜用于分离二氧化碳混合气。
本发明对支撑材料的改性方法简单易行，可以避免使用离子液体带来的膜液流失问题（对孔径有较高的要求），并且胺类基团的引入可以提高水支撑液膜对二氧化碳的选择分离性。
本发明制备的水支撑液膜所用的膜液为绿色溶剂水，对环境无污染且价格便宜易得。
本发明采用的多孔膜材料自身具有亲水性，便于在二氧化碳混合气中加入水汽，通过毛细冷凝作用实现液膜的修复。
本发明提供的改性多孔膜材料，其膜材料的孔道内修饰有含胺类的基团。
在一个实施方式中，所述的胺类基团为含有伯胺、仲胺或者叔胺基团中的一种。
在一个实施方式中，所述的膜材料的材质是无机多孔膜材料或高分子多孔膜材料。
在一个实施方式中，所述的无机多孔材料为多孔氧化铝、多孔氧化钛、多孔氧化锆或者多孔氧化硅。
在一个实施方式中，所述的膜材料平均孔径为1～200 nm。
在一个实施方式中，所述的膜材料几何结构为平板式或管式。
上述的改性多孔膜材料的制备方法，包括如下步骤：
将含胺类基团的硅烷偶联剂溶解在有机溶剂中，作为改性剂；将多孔膜材料浸没于改性剂中进行接枝反应，反应完成后，经过清洗、烘干，得到改性多孔膜材料。
在一个实施方式中，含胺类基团的硅烷偶联剂：选自例如N，N-二甲基-3-氨丙基三甲氧基硅烷、（3-氨丙基）三甲氧基硅烷等等。
在一个实施方式中，有机溶剂为至少含有乙醇、丙酮、二甲基乙酰胺（DMAC）、四氢呋喃（THF）中的一种。
在一个实施方式中，反应的条件为温度为20～40 ℃，反应时间1～24 h。
实施例1
将平均孔径为100 nm的管式陶瓷膜内膜（几何尺寸：膜有效长度为8cm，外径为12cm、内径为8cm，孔隙率约为40%）洗干净放在干燥箱干燥1～2小时，将含有胺类基团的硅烷偶联剂（N，N-二甲基-3-氨丙基三甲氧基硅烷（DMAPS））滴加到无水乙醇中溶解配成15 mmol/L的改性溶液，将多孔膜材料浸没在改性溶液中，在恒温水浴温度为35℃下反应12h，待充分反应完成后清洗烘干，得到表面带有叔胺基团的膜材料。改性得到的膜材料的表面红外图谱如图1所示。(N,N-二甲基-3-氨丙基)三甲氧基硅烷(DMAPS)的结构如下：
对比改性前后膜的红外光谱图，可以看出改性后的陶瓷膜出现新的特征峰，分别为图中所标注的-CH2-、N-C、-CH3、Si-O-Al的特征峰，尤其是在1610cm-1处的N-C是DMAPS所特有的峰，而且在810cm-1处有证明Si-OH和Al-OH反应生成的Si-O-Al的特征峰。
然后将膜材料放在水中浸泡，通过表面张力的作用使水负载在膜孔里，此过程可以通过抽真空的方式加快，当没有气泡出来的时候，取出来用滤纸轻轻擦去膜表面残留的水，即制得可分离二氧化碳混合气的支撑液膜。
将准备好的水支撑液膜装在膜组件中，用于测定纯气体的渗透率和理想分离因子，在0.6Mpa和25℃的条件下进行渗透测试，结果是：CO2/N2理想分离因子为无穷大，未改性二氧化碳的渗透率约为2.5±0.15GPU，改性后二氧化碳的渗透率约为3.83±0.19GPU，相比于未改性的提高了约为53%。如图2所示。
实施例2
将平均孔径为200nm的管式陶瓷膜内膜（几何尺寸：膜有效长度为8cm，外径为12cm、内径为8cm，孔隙率约为40%）洗干净放在干燥箱干燥1~2小时，将含有胺类基团的硅烷偶联剂（（3-氨丙基）三甲氧基硅烷）滴加到丙酮中溶解配成50 mmol/L的改性溶液，将多孔膜材料浸没在改性溶液中，在恒温水浴温度为30℃下反应24h，待充分反应完成后清洗烘干，得到表面带有叔胺基团的膜材料。将该膜材料用在气液膜接触器的气体吸收中，用水作为吸收剂，发现二氧化碳的传质通量从原来的0.15mol/(m2·h)提高到了0.209 mol/(m2·h)，相对原来通量提高了约40%。
实施例3
考察了不同操作温度条件下对二氧化碳渗透速率的影响，如图3所示。
对于未改性的膜（使用平均孔径为20nm管式陶瓷膜，几何尺寸：膜有效长度为8cm，外径为12.5cm、内径为7.5cm，孔隙率约为30%），采用水为膜液，
支撑液膜中气体的渗透行为符合溶解-扩散模型：D（扩散系数），S(溶解度系数)，J（气体渗透率），l（液膜厚度）
扩散系数随着温度的升高而上升，溶解度系数随着温度的升高而下降，所以气体渗透率J会有一个最佳值点。
Claims (10)
1.一种改性多孔膜材料，其特征在于，所述的膜材料是指无机多孔材料，在膜材料的孔道内修饰有含胺类的基团。
2.根据权利要求1所述的改性多孔膜材料，其特征在于，在一个实施方式中，所述的胺类基团为含有伯胺、仲胺或者叔胺基团中的一种。
3.根据权利要求1所述的改性多孔膜材料，其特征在于，在一个实施方式中，所述的无机多孔材料为多孔氧化铝、多孔氧化钛、多孔氧化锆或者多孔氧化硅。
4.根据权利要求1所述的改性多孔膜材料，其特征在于，在一个实施方式中，所述的膜材料平均孔径为1～200 nm；在一个实施方式中，所述的膜材料几何结构为平板式或管式。
5.权利要求1所述的改性多孔膜材料的制备方法，其特征在于，包括如下步骤：将含胺类基团的硅烷偶联剂溶解在有机溶剂中，作为改性剂；将多孔膜材料浸没于改性剂中进行接枝反应，反应完成后，经过清洗、烘干，得到改性多孔膜材料。
6.根据权利要求5所述的改性多孔膜材料的制备方法，其特征在于，在一个实施方式中，含胺类基团的硅烷偶联剂：选自例如N，N-二甲基-3-氨丙基三甲氧基硅烷、（3-氨丙基）三甲氧基硅烷；有机溶剂为至少含有乙醇、丙酮、二甲基乙酰胺（DMAC）、四氢呋喃（THF）中的一种。
7.根据权利要求5所述的改性多孔膜材料的制备方法，其特征在于，反应的条件为温度为20～40 ℃，反应时间1～24 h。
8.一种二氧化碳的液膜分离方法，其特征在于，包括如下步骤：用水作为溶剂，负载于上述的改性多孔膜材料的孔道中，形成液膜；再与含二氧化碳的混合气接触，使二氧化碳透过膜层。
9.根据权利要求8所述的二氧化碳的液膜分离方法，其特征在于，含二氧化碳的混合气为CO2与至少为N2、CH4、H2、O2、He、CO气体中的一种。
10.权利要求1所述的改性多孔膜材料在用于提高二氧化碳的液膜分离过程中的分离因子或者渗透通量中的应用。
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| CN104801201A (zh) * | 2015-04-10 | 2015-07-29 | 北京工业大学 | 一种用于芳烃/烷烃混合物分离渗透汽化膜的绿色制备方法 |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103534012A (zh) * | 2011-04-08 | 2014-01-22 | 道康宁公司 | 使用环氧官能硅氧烷制备气体选择性膜的方法 |
| CN104801201A (zh) * | 2015-04-10 | 2015-07-29 | 北京工业大学 | 一种用于芳烃/烷烃混合物分离渗透汽化膜的绿色制备方法 |
Non-Patent Citations (1)
| Title |
|---|
| MAYUR OSTWAL等: "3-Aminopropyltriethoxysilane functionalized inorganic membranes for high temperature CO2/N2 separation", 《JOURNAL OF MEMBRANE SCIENCE》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2021031675A1 (zh) * | 2019-08-21 | 2021-02-25 | 南京工业大学 | 一种改性多孔膜材料、制备方法以及二氧化碳的液膜分离方法 |
| US11628410B2 (en) | 2019-08-21 | 2023-04-18 | Nanjing Tech University | Modified porous membrane material and preparation method thereof, and liquid membrane separation method of carbon dioxide |
Also Published As
| Publication number | Publication date |
|---|---|
| US11628410B2 (en) | 2023-04-18 |
| DE112020002779T5 (de) | 2022-02-24 |
| WO2021031675A1 (zh) | 2021-02-25 |
| CN110624424B (zh) | 2021-03-19 |
| US20220362721A1 (en) | 2022-11-17 |
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