CN106673636A - 一种复合金属氧化物中空纤维的制备方法 - Google Patents

一种复合金属氧化物中空纤维的制备方法 Download PDF

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CN106673636A
CN106673636A CN201611145840.2A CN201611145840A CN106673636A CN 106673636 A CN106673636 A CN 106673636A CN 201611145840 A CN201611145840 A CN 201611145840A CN 106673636 A CN106673636 A CN 106673636A
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preparation
spinning
composite oxide
metal composite
raw material
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金万勤
朱佳伟
刘郑堃
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Nanjing Tech University
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Nanjing Tech University
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Priority to CN201611145840.2A priority Critical patent/CN106673636A/zh
Priority to PCT/CN2017/083749 priority patent/WO2018107648A1/zh
Priority to US16/466,066 priority patent/US11401213B2/en
Publication of CN106673636A publication Critical patent/CN106673636A/zh
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Abstract

本发明涉及一种复合金属氧化物中空纤维的制备方法，其特征在于由复合金属氧化物的原材料直接进行相转化和一步热处理过程来得到复合金属氧化物中空纤维的方法。具体为将具有一定的化学计量的复合金属氧化物原材料和聚合物粘结剂加入到有机溶剂中，通过机械混合，得到分散均匀的、具有适宜粘度的纺丝液。纺丝液脱泡处理后由喷丝头挤出，经过一定的干纺程进入外凝固浴，此期间发生相转化过程，同时形成复合金属氧化物中空纤维生坯。生坯在外凝固浴中浸泡，置换出有机溶剂，自然干燥后，生坯经热处理工艺，此期间发生聚合物的烧除，原位反应以及原位烧结过程，得到复合金属氧化物中空纤维。本发明工艺极其简便可靠，制成的复合金属氧化物中空纤维膜具有良好的性能。

Description

一种复合金属氧化物中空纤维的制备方法
技术领域
本发明涉及一种复合金属氧化物中空纤维的制备方法，尤其是直接通过原材料制备复合金属氧化物中空纤维的方法。
背景技术
复合金属氧化物(如萤石、钙钛矿和烧绿石)中空纤维具有高的比表面积，快速热循环和高效传质的性质，在能源环境领域(如燃料电池、分离膜及膜反应器)展现出了很好的应用前景。但是，目前复合金属氧化物中空纤维主要通过复合金属氧化物粉体的高温合成、相转化过程制备中空纤维生坯和烧结等多个加工步骤进行制备。这样的一个制备过程消耗了大量的劳动力、能源和时间，而且所排放的有毒气体和粉尘会造成环境污染影响人类的健康。另外，在相转化的过程中，一部分复合金属氧化物会与极性的溶剂或非溶剂发生反应，破坏了其材料本身的物理化学性质，导致中空纤维的性能非常低。因此，亟待开发出极其简便、经济和可靠的复合金属氧化物中空纤维的制备方法。
发明内容
本发明的目的是为了改进现有技术的不足而提供一种颠覆性的制备复合金属氧化物中空纤维的方法；本发明直接将复合金属氧化物的原材料用于相转化和热加工过程，制得了复合金属氧化物中空纤维。该发明成功解决了传统方法所面临的问题，具体为去除了复合金属氧化物粉体的高温合成的过程，成功避免了复合金属氧化物与相转化体系的反应，精确控制了复合金属氧化物的化学计量，为复合金属氧化物中空纤维的大规模应用创造了优异的条件。
本发明的技术方案如下：一种复合金属氧化物中空纤维的制备方法，其特征在于由复合金属氧化物的原材料直接进行相转化(纺丝)和一步热处理过程(原位反应烧结)来得到复合金属氧化物中空纤维的方法；其具体步骤如下：将复合金属氧化物原材料和聚合物粘结剂加入到有机溶剂中，通过机械混合，得到混合分散均匀的纺丝液；纺丝液脱泡处理后由喷丝头挤出，同时流出喷丝头的内芯液，经过干纺程进入外凝固浴，固化后形成复合金属氧化物中空纤维生坯；将生坯在外凝固浴中浸泡，将有机溶剂置换出来；将生坯自然干燥，置于高温炉中升温烧结，通过经历聚合物的烧除，原位反应即固相反应以及原位烧结过程，得到复合金属氧化物中空纤维。
优选所述的复合金属氧化物为为钙钛矿型、萤石型、K2NiF4型、烧绿石型或Brownmillerite型中的一种或几种的混合物。
优选所述的复合金属氧化物的原材料为复合金属氧化物的原材料为碳酸盐或金属氧化物中的两种及以上的混合物，并且不与内芯液或凝固浴发生化学反应；其粒径为0.1～20μm。
优选所述的聚合物粘结剂为聚砜、聚醚砜、聚醚酰亚胺、聚偏氟乙烯或聚醋酸纤维素中的任何一种。
优选所述的有机溶剂为N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或者是二甲基亚砜中的任何一种。
优选所述的聚合物粘结剂在聚合物溶液中的质量分数为10％～25％；所述的纺丝液中复合金属氧化物原材料所占的质量分数为40％～80％；优选喷丝头干纺程的距离范围为0～25cm；喷丝头的内芯液为水、甲醇、乙醇、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或者是二甲基亚砜中的一种或两种及以上的混合物，其温度为5℃-60℃；外凝固浴为水、甲醇、乙醇、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或者是二甲基亚砜中的一种或两种及以上的混合物，其温度为5℃-60℃。
优选升温烧结的温度为1000～1500℃，保温时间为2～20小时。
有益效果：
本发明工艺极其简便节能，无需昂贵设备。与传统制备复合金属氧化物中空纤维的方法相比，节约时间超过50％，耗能降低了50％以上。而且，中空纤维的性能得到大大提升。制备的复合金属氧化物中空纤维应用范围广，使用价值显著。
附图说明
图1为中空纤维生坯中各金属元素的分布图；
图2为中空纤维的形貌图；
图3为中空纤维材料的X射线衍射曲线图；
图4为中空纤维的氧渗透性能图。
具体实施方式
实施例一：
选取分析纯的SrCO3，BaCO3，Co2O3和Fe2O3作为钙钛矿型复合金属氧化物Ba0.5Sr0.5Co0.8Fe0.2O3-δ的原材料，粒径大约为0.2μm。将具有一定的化学计量的以上原材料和聚醚砜加入到N-甲基吡咯烷酮中，通过机械混合，得到分散均匀的纺丝液。纺丝液中原材料粉体、聚合物和有机溶液的质量比为7：1：4；纺丝液脱泡处理后由喷丝头挤出，经过干纺程(0cm)进入外凝固浴水中，外凝固浴温度为40℃，喷丝头的内芯液为水，其温度为15℃，固化后形成中空纤维生坯，生坯中原材料分散均匀(图1)；生坯在外凝固浴水中浸泡，将N-甲基吡咯烷酮置换出来；将生坯自然干燥，置于高温炉中，升温至1000℃保温5小时，得到完整的具有多孔致密结构的中空纤维(图2)，具有非常好的钙钛矿晶型(图3)，可直接用于氧分离以及催化膜反应等过程，其氧分离性能如图4所示，在900℃时氧通量达到了12.5mlmin- 1cm-2。
实施例二：
选取分析纯的La2O3、WO3、SrCO3和Cr2O3作为复合金属氧化物La5.5WO11.25-δ-La0.87Sr0.13CrO3-δ的原材料，粒径大约为1μm。将具有一定的化学计量的以上原材料和聚醚酰亚胺加入到N,N-二甲基甲酰胺中，通过机械混合，得到分散均匀的纺丝液。纺丝液中原材料粉体、聚合物和有机溶液的质量比为12：1：3；纺丝液脱泡处理后由喷丝头挤出，经过干纺程(5cm)进入外凝固浴乙醇中，其温度为45℃，喷丝头的内芯液为乙醇，其温度为55℃，固化后形成中空纤维生坯，生坯中原材料分散均匀；生坯在外凝固浴中浸泡，将N,N-二甲基甲酰胺置换出来；将生坯自然干燥，置于高温炉中，升温至1350℃保温15小时，得到完整的致密中空纤维，可直接用于氢气分离和催化膜反应。
实施例三：
选取分析纯的CeO2和Sm2O3作为萤石型复合金属氧化物Ce0.85Sm0.15O1.9的原材料，粒径大约为5μm。将具有一定的化学计量的以上原材料和聚砜加入到N,N-二甲基乙酰胺中，通过机械混合，得到分散均匀的纺丝液。纺丝液中原材料粉体、聚合物和有机溶液的质量比为14：1：4；纺丝液脱泡处理后由喷丝头挤出，经过干纺程(10cm)进入外凝固浴甲醇中，其温度为8℃，喷丝头的内芯液为N-甲基吡咯烷酮与水的混合物(质量比为1:1)，其温度为12℃，固化后形成中空纤维生坯，生坯中原材料分散均匀；生坯在外凝固浴中浸泡，将N,N-二甲基乙酰胺置换出来；将生坯自然干燥，置于高温炉中，升温至1250℃保温10小时，得到完整的致密中空纤维，可直接用于燃料电池。
实施例四：
选取分析纯的BaCO3、CeO2、ZrO2、Y2O3和Yb2O3作为钙钛矿型复合金属氧化物BaCe0.7Zr0.1Y0.1Yb0.1O3-δ的原材料，粒径大约为10μm。将具有一定的化学计量的以上原材料和聚偏氟乙烯加入到二甲基亚砜中，通过机械混合，得到分散均匀的纺丝液。纺丝液中原材料粉体、聚合物和有机溶液的质量比为9：1：8；纺丝液脱泡处理后由喷丝头挤出，经过干纺程(16cm)进入外凝固浴N-甲基吡咯烷酮与水的混合物(质量比为1:1)中，其温度为25℃，喷丝头的内芯液为水，其温度为35℃，固化后形成中空纤维生坯，生坯中原材料分散均匀；生坯在外凝固浴中浸泡，将二甲基亚砜置换出来；将生坯自然干燥，置于高温炉中，升温至1450℃保温20小时，得到完整的致密中空纤维，可直接用于质子导体的燃料电池。
实施例五：
选取分析纯的CaCO3、CeO2、CuO、Fe2O3、Gd2O3和La2O3作为萤石型-钙钛矿型多相复合金属氧化物75wt.％Ce0.85Gd0.1Cu0.05O2-δ-25wt.％La0.6Ca0.4FeO3-δ的原材料，粒径大约为18μm。将具有一定的化学计量的以上原材料和聚醋酸纤维素加入到N-甲基吡咯烷酮中，通过机械混合，得到分散均匀的纺丝液。纺丝液中原材料粉体、聚合物和有机溶液的质量比为5：1：5；纺丝液脱泡处理后由喷丝头挤出，经过干纺程(23cm)进入外凝固浴水、甲醇、乙醇的混合物(质量比为1:1:1)中，其温度为45℃，喷丝头的内芯液为二甲基亚砜，其温度为40℃，固化后形成中空纤维生坯，生坯中原材料分散均匀；生坯在外凝固浴中浸泡，将二甲基亚砜置换出来；将生坯自然干燥，置于高温炉中，升温至1150℃保温3小时，得到多孔的中空纤维，可直接用于CO2分离膜。
实施例六：
选取分析纯的Pr2O3，BaCO3，CaCO3和Co2O3作为Brownmillerite型复合金属氧化物PrBa0.5Ca0.5Co2O5+δ的原材料，粒径大约为1μm。将具有一定的化学计量的以上原材料和聚醚砜加入到N-甲基吡咯烷酮中，通过机械混合，得到分散均匀的纺丝液。纺丝液中原材料粉体、聚合物和有机溶液的质量比为6：1：4；纺丝液脱泡处理后由喷丝头挤出，经过干纺程(6cm)进入外凝固浴水中，外凝固浴温度为25℃，喷丝头的内芯液为水，其温度为25℃，固化后形成中空纤维生坯，生坯中原材料分散均匀；生坯在外凝固浴水中浸泡，将N-甲基吡咯烷酮置换出来；将生坯自然干燥，置于高温炉中，升温至1100℃保温5小时，得到完整的具有多孔致密结构的中空纤维，具有非常好的晶型，可直接用于氧分离以及催化膜反应等过程。
实施例七：
选取分析纯的Pr2O3，La2O3，NiO，CuO和Ga2O3作为K2NiF4型复合金属氧化物的(Pr0.9La0.1)2(Ni0.74Cu0.21Ga0.05)O4+δ原材料，粒径大约为0.5μm。将具有一定的化学计量的以上原材料和聚醚砜加入到N-甲基吡咯烷酮中，通过机械混合，得到分散均匀的纺丝液。纺丝液中原材料粉体、聚合物和有机溶液的质量比为7：1：4；纺丝液脱泡处理后由喷丝头挤出，经过干纺程(2cm)进入外凝固浴水中，外凝固浴温度为25℃，喷丝头的内芯液为水，其温度为25℃，固化后形成中空纤维生坯，生坯中原材料分散均匀；生坯在外凝固浴水中浸泡，将N-甲基吡咯烷酮置换出来；将生坯自然干燥，置于高温炉中，升温至1300℃保温5小时，得到完整的具有多孔致密结构的中空纤维，具有非常好的晶型，可直接用于氧分离以及催化膜反应等过程。
实施例八：
选取分析纯的SrCO3和Fe2O3作为烧绿石型复合金属氧化物的Sr2Fe2O7原材料，粒径大约为0.3μm。将具有一定的化学计量的以上原材料和聚醚砜加入到N-甲基吡咯烷酮中，通过机械混合，得到分散均匀的纺丝液。纺丝液中原材料粉体、聚合物和有机溶液的质量比为9：1：4；纺丝液脱泡处理后由喷丝头挤出，经过干纺程(5cm)进入外凝固浴水中，外凝固浴温度为25℃，喷丝头的内芯液为水，其温度为25℃，固化后形成中空纤维生坯，生坯中原材料分散均匀；生坯在外凝固浴水中浸泡，将N-甲基吡咯烷酮置换出来；将生坯自然干燥，置于高温炉中，升温至1400℃保温5小时，得到完整的具有多孔致密结构的中空纤维，具有非常好的晶型，可直接用于氧分离以及催化膜反应等过程。

Claims (8)

1.一种复合金属氧化物中空纤维的制备方法，其特征在于由复合金属氧化物的原材料直接进行相转化和一步热处理过程来得到复合金属氧化物中空纤维的方法；其具体步骤如下：将复合金属氧化物原材料和聚合物粘结剂加入到有机溶剂中，通过机械混合，得到混合分散均匀的纺丝液；纺丝液脱泡处理后由喷丝头挤出，同时流出喷丝头的内芯液，经过干纺程进入外凝固浴，固化后形成复合金属氧化物中空纤维生坯；将生坯在外凝固浴中浸泡，将有机溶剂置换出来；将生坯自然干燥，置于高温炉中升温烧结，通过经历聚合物的烧除，原位反应即固相反应以及原位烧结过程，得到复合金属氧化物中空纤维。
2.根据权利要求1所述的制备方法，其特征在于复合金属氧化物为钙钛矿型、萤石型、K2NiF4型、烧绿石型或Brownmillerite型中的一种或几种混合物。
3.根据权利要求1所述的制备方法，其特征在于复合金属氧化物的原材料为碳酸盐或金属氧化物中的两种及以上的混合物，并且不与内芯液或凝固浴发生化学反应；其粒径为0.1～20μm。
4.根据权利要求1所述的制备方法，其特征在于所述的聚合物粘结剂为聚砜、聚醚砜、聚醚酰亚胺、聚偏氟乙烯或聚醋酸纤维素中的任何一种。
5.根据权利要求1所述的制备方法，其特征在于所述的有机溶剂为N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或二甲基亚砜中的任何一种。
6.根据权利要求1所述的制备方法，其特征在于所述的聚合物粘结剂在聚合物溶液中的质量分数为10％～25％；所述的纺丝液中复合金属氧化物原材料所占的质量分数为40％～80％。
7.根据权利要求1所述的制备方法，其特征在于所述喷丝头干纺程的距离范围为0～25cm；喷丝头的内芯液为水、甲醇、乙醇、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或者是二甲基亚砜中的一种或两种及以上的混合物，其温度为5℃-60℃；外凝固浴为水、甲醇、乙醇、N-甲基吡咯烷酮、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺或者是二甲基亚砜中的一种或两种及以上的混合物，其温度为5℃-60℃。
8.根据权利要求1所述的制备方法，其特征在于升温烧结的温度为1000～1500℃，烧结保温时间为2～20小时。
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Application publication date: 20170517