WO2018107648A1 - 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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WO2018107648A1
WO2018107648A1 PCT/CN2017/083749 CN2017083749W WO2018107648A1 WO 2018107648 A1 WO2018107648 A1 WO 2018107648A1 CN 2017083749 W CN2017083749 W CN 2017083749W WO 2018107648 A1 WO2018107648 A1 WO 2018107648A1
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metal oxide
composite metal
raw material
coagulation bath
hollow fiber
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PCT/CN2017/083749
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English (en)
French (fr)
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金万勤
朱佳伟
刘郑堃
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南京工业大学
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Priority to US16/466,066 priority Critical patent/US11401213B2/en
Publication of WO2018107648A1 publication Critical patent/WO2018107648A1/zh

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Definitions

  • the invention relates to a method for preparing a composite metal oxide hollow fiber, in particular to a method for preparing a composite metal oxide hollow fiber directly from a raw material.
  • Composite metal oxides such as fluorite, perovskite and pyrochlore
  • the composite metal oxide hollow fiber is mainly prepared by a plurality of processing steps such as high-temperature synthesis of a composite metal oxide powder, preparation of a hollow fiber green body by a phase inversion process, and sintering.
  • Such a preparation process consumes a large amount of labor, energy and time, and the emitted toxic gases and dust can cause environmental pollution to affect human health.
  • the object of the present invention is to provide a method for preparing a composite metal oxide hollow fiber by subverting the defects of the prior art; the invention directly uses the raw material of the composite metal oxide for phase inversion and hot working, and obtains the method.
  • Composite metal oxide hollow fiber The invention successfully solves the problems faced by the traditional method, specifically removes the high-temperature synthesis process of the composite metal oxide powder, successfully avoids the reaction of the composite metal oxide with the phase inversion system, and precisely controls the composite metal oxide. Stoichiometry creates excellent conditions for large-scale application of composite metal oxide hollow fibers.
  • the technical scheme of the present invention is as follows: a method for preparing a composite metal oxide hollow fiber, characterized in that a raw material of a composite metal oxide is directly subjected to phase transformation (spinning) and a one-step heat treatment process (in situ reaction sintering) to obtain a composite
  • the method for metal oxide hollow fiber ; the specific steps are as follows: the composite metal oxide raw material and the polymer binder are added to an organic solvent, and mechanically mixed to obtain a spinning solution with uniform mixing and dispersion; the spinning solution is defoamed After being extruded by the spinneret, the inner core liquid of the spinneret flows out, enters the outer coagulation bath through the dry spinning process, and forms a composite metal oxide hollow fiber green body after solidification; the green body is soaked in the outer coagulation bath, and the organic The solvent is replaced; the green body is naturally dried, placed in a high temperature furnace for temperature rising and sintering, and the composite metal oxide hollow fiber is obtained by undergoing the burning of the
  • the composite metal oxide is a mixture of one or more of a perovskite type, a fluorite type, a K 2 NiF 4 type, a pyrochlore type or a Brownnillerite type.
  • the raw material of the composite metal oxide is a raw material of the composite metal oxide, which is a mixture of two or more of a carbonate or a metal oxide, and does not chemically react with the inner core liquid or the coagulation bath; It is 0.1 to 20 ⁇ m.
  • the polymeric binder is any one of polysulfone, polyethersulfone, polyetherimide, polyvinylidene fluoride or polyvinylcellulose.
  • the organic solvent is any one of N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide.
  • the mass fraction of the polymer binder in the polymer solution is 10% to 25%; the mass fraction of the composite metal oxide raw material in the spinning solution is 40% to 80%;
  • the distance from the silk spinning process is 0-25 cm;
  • the core liquid of the spinneret is water, methanol, ethanol, N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethyl Acetamide or one or a mixture of two or more of dimethyl sulfoxide, the temperature is from 5 ° C to 60 ° C;
  • the external coagulation bath is water, methanol, ethanol, N-methylpyrrolidone, N, N- A mixture of one or two or more of dimethylformamide, N,N-dimethylacetamide or dimethyl sulfoxide at a temperature of from 5 ° C to 60 ° C.
  • the temperature for temperature rising and sintering is preferably 1000 to 1500 ° C, and the holding time is 2 to 20 hours.
  • the process of the invention is extremely simple and energy-saving, and does not require expensive equipment. Compared with the traditional method of preparing composite metal oxide hollow fiber, the time is saved by more than 50%, and the energy consumption is reduced by more than 50%. Moreover, the performance of the hollow fiber is greatly improved.
  • the prepared composite metal oxide hollow fiber has a wide application range and remarkable use value.
  • Figure 1 is a distribution diagram of each metal element in a hollow fiber green body
  • Figure 2 is a topographical view of the hollow fiber
  • Figure 3 is an X-ray diffraction curve of a hollow fiber material
  • Figure 4 is a graph showing the oxygen permeation performance of hollow fibers.
  • Embodiment 1 is a diagrammatic representation of Embodiment 1:
  • Analytically pure SrCO 3 , BaCO 3 , Co 2 O 3 and Fe 2 O 3 were selected as raw materials for the perovskite-type composite metal oxide Ba 0.5 Sr 0.5 Co 0.8 Fe 0.2 O 3- ⁇ , and the particle diameter was about 0.2 ⁇ m.
  • the above raw material having a certain stoichiometry and polyethersulfone are added to N-methylpyrrolidone, and mechanically mixed to obtain a uniformly dispersed spinning solution.
  • the mass ratio of the raw material powder, polymer and organic solution in the spinning solution is 7:1:4; after the defoaming treatment, the spinning solution is extruded by a spinneret and passed through a dry spinning process (0 cm) into the external coagulation bath water.
  • the temperature of the outer coagulation bath is 40 ° C
  • the inner core liquid of the spinneret is water
  • the temperature is 15 ° C
  • the hollow fiber green body is formed after solidification, and the raw materials in the green body are uniformly dispersed (Fig. 1); the green body is soaked in the outer coagulation bath water N-methylpyrrolidone is replaced; the green body is naturally dried, placed in a high-temperature furnace, and heated to 1000 ° C for 5 hours to obtain a complete hollow fiber with a porous dense structure (Fig. 2), which has very good calcium.
  • the titanium ore crystal form (Fig. 3) can be directly used in the process of oxygen separation and catalytic membrane reaction.
  • the oxygen separation performance is shown in Fig. 4.
  • the oxygen flux reaches 12.5 mlmin -1 cm -2 at 900 °C.
  • Embodiment 2 is a diagrammatic representation of Embodiment 1:
  • Analytically pure La 2 O 3 , WO 3 , SrCO 3 and Cr 2 O 3 were selected as raw materials of the composite metal oxide La 5.5 WO 11.25- ⁇ -La 0.87 Sr 0.13 CrO 3- ⁇ , and the particle diameter was about 1 ⁇ m.
  • the above raw materials and polyetherimide having a certain stoichiometry are added to N,N-dimethylformamide, and mechanically mixed to obtain a uniformly dispersed spinning solution.
  • the mass ratio of the raw material powder, polymer and organic solution in the spinning solution is 12:1:3; the spinning solution is defoamed and then extruded by a spinneret and passed through a dry spinning process (5 cm) into the external coagulation bath ethanol.
  • the temperature is 45 ° C
  • the inner core liquid of the spinneret is ethanol
  • the temperature is 55 ° C
  • the hollow fiber green body is formed after solidification, the raw materials in the green body are uniformly dispersed; the green body is soaked in the outer coagulation bath, and N, N - Dimethylformamide is replaced; the green body is naturally dried, placed in a high temperature furnace, and heated to 1350 ° C for 15 hours to obtain a complete dense hollow fiber, which can be directly used for hydrogen separation and catalytic membrane reaction.
  • Embodiment 3 is a diagrammatic representation of Embodiment 3
  • Analytically pure CeO 2 and Sm 2 O 3 were selected as raw materials for the fluorite-type composite metal oxide Ce 0.85 Sm 0.15 O 1.9 , and the particle diameter was about 5 ⁇ m.
  • the above raw materials having a certain stoichiometry and polysulfone are added to N,N-dimethylacetamide, and mechanically mixed to obtain a uniformly dispersed spinning solution.
  • the mass ratio of the raw material powder, polymer and organic solution in the spinning solution is 14:1:4; after the defoaming treatment, the spinning solution is extruded by a spinneret and passed through a dry spinning process (10 cm) into the external coagulation bath methanol.
  • the temperature is 8 ° C
  • the core liquid of the spinneret is a mixture of N-methylpyrrolidone and water (mass ratio is 1:1)
  • the temperature is 12 ° C
  • a hollow fiber green body is formed, in the green body
  • the raw material is evenly dispersed; the green body is immersed in an external coagulation bath, and N,N-dimethylacetamide is replaced; the green body is naturally dried, placed in a high temperature furnace, and heated to 1250 ° C for 10 hours to obtain a complete dense hollow. Fiber, which can be used directly in fuel cells.
  • Embodiment 4 is a diagrammatic representation of Embodiment 4:
  • Analytically pure BaCO 3 , CeO 2 , ZrO 2 , Y 2 O 3 and Yb 2 O 3 were selected as raw materials for perovskite-type composite metal oxide BaCe 0.7 Zr 0.1 Y 0.1 Yb 0.1 O 3- ⁇ with a particle size of approximately 10 ⁇ m.
  • the above raw materials having a certain stoichiometry and polyvinylidene fluoride are added to dimethyl sulfoxide, and mechanically mixed to obtain a uniformly dispersed spinning solution.
  • the mass ratio of the raw material powder, polymer and organic solution in the spinning solution is 9:1:8; after the defoaming treatment, the spinning solution is extruded by a spinneret, and after dry spinning (16 cm), it enters the external coagulation bath N- In the mixture of methylpyrrolidone and water (mass ratio is 1:1), the temperature is 25 ° C, the inner core liquid of the spinneret is water, the temperature is 35 ° C, and the solid fiber hollow body is formed after solidification.
  • the raw material is evenly dispersed; the green body is immersed in the external coagulation bath, and the dimethyl sulfoxide is replaced; the green body is naturally dried, placed in a high temperature furnace, and heated to 1450 ° C for 20 hours to obtain a complete dense hollow fiber, which can be directly Fuel cell for proton conductors.
  • Embodiment 5 is a diagrammatic representation of Embodiment 5:
  • Analytically pure CaCO 3 , CeO 2 , CuO, Fe 2 O 3 , Gd 2 O 3 and La 2 O 3 were selected as fluorite-perovskite heterogeneous composite metal oxides 75 wt.% Ce 0.85 Gd 0.1 Cu 0.05 O 2- ⁇ -25 wt.% La 0.6 Ca 0.4 FeO 3- ⁇ raw material having a particle diameter of about 18 ⁇ m.
  • the above raw material having a certain stoichiometry and polyvinyl cellulose acetate are added to N-methylpyrrolidone, and mechanically mixed to obtain a uniformly dispersed spinning solution.
  • the mass ratio of the raw material powder, polymer and organic solution in the spinning solution is 5:1:5; after the defoaming treatment, the spinning solution is extruded by a spinneret, and after dry spinning (23 cm), it enters the external coagulation bath water.
  • the temperature is 45 ° C
  • the inner core of the spinneret is dimethyl sulfoxide
  • the temperature is 40 ° C
  • the hollow fiber green body is formed after solidification.
  • the raw material in the green body is uniformly dispersed; the green body is immersed in the outer coagulation bath, and the dimethyl sulfoxide is replaced; the green body is naturally dried, placed in a high temperature furnace, and heated to 1150 ° C for 3 hours to obtain a porous hollow fiber. It can be used directly in the CO 2 separation membrane.
  • Analytically pure Pr 2 O 3 , BaCO 3 , CaCO 3 and Co 2 O 3 were selected as raw materials of the Browningerite type composite metal oxide PrBa 0.5 Ca 0.5 Co 2 O 5+ ⁇ , and the particle diameter was about 1 ⁇ m.
  • the above raw material having a certain stoichiometry and polyethersulfone are added to N-methylpyrrolidone, and mechanically mixed to obtain a uniformly dispersed spinning solution.
  • the mass ratio of the raw material powder, polymer and organic solution in the spinning solution is 6:1:4; after the defoaming treatment, the spinning solution is extruded by a spinneret and passed through a dry spinning process (6 cm) into the external coagulation bath water.
  • the temperature of the outer coagulation bath is 25 ° C
  • the inner core liquid of the spinneret is water
  • the temperature is 25 ° C
  • the hollow fiber green body is formed after solidification, the raw materials in the green body are uniformly dispersed; the green body is soaked in the outer coagulation bath water, and N- The methylpyrrolidone is replaced; the green body is naturally dried, placed in a high temperature furnace, and heated to 1100 ° C for 5 hours to obtain a complete hollow fiber with a porous dense structure, which has a very good crystal form and can be directly used for oxygen separation. And processes such as catalytic membrane reactions.
  • the mass ratio of the raw material powder, polymer and organic solution in the spinning solution is 7:1:4; after the defoaming treatment, the spinning solution is extruded by a spinneret and passed through a dry spinning process (2 cm) into the external coagulation bath water.
  • the temperature of the outer coagulation bath is 25 ° C
  • the inner core liquid of the spinneret is water
  • the temperature is 25 ° C
  • the hollow fiber green body is formed after solidification, the raw materials in the green body are uniformly dispersed; the green body is soaked in the outer coagulation bath water, and N- The methylpyrrolidone is replaced; the green body is naturally dried, placed in a high temperature furnace, and heated to 1300 ° C for 5 hours to obtain a complete hollow fiber with a porous dense structure, which has a very good crystal form and can be directly used for oxygen separation. And processes such as catalytic membrane reactions.
  • Analytically pure SrCO 3 and Fe 2 O 3 were selected as the Sr 2 Fe 2 O 7 raw material of the pyrochlore-type composite metal oxide, and the particle diameter was about 0.3 ⁇ m.
  • the above raw material having a certain stoichiometry and polyethersulfone are added to N-methylpyrrolidone, and mechanically mixed to obtain a uniformly dispersed spinning solution.
  • the mass ratio of the raw material powder, polymer and organic solution in the spinning solution is 9:1:4; after the defoaming treatment, the spinning solution is extruded by a spinneret and passed through a dry spinning process (5 cm) into the external coagulation bath water.
  • the temperature of the outer coagulation bath is 25 ° C
  • the inner core liquid of the spinneret is water
  • the temperature is 25 ° C
  • the hollow fiber green body is formed after solidification, the raw materials in the green body are uniformly dispersed; the green body is soaked in the outer coagulation bath water, and N- The methylpyrrolidone is replaced; the green body is naturally dried, placed in a high temperature furnace, and heated to 1400 ° C for 5 hours to obtain a complete hollow fiber with a porous dense structure, which has a very good crystal form and can be directly used for oxygen separation. And processes such as catalytic membrane reactions.

Abstract

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。

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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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115323611A (zh) * 2022-09-02 2022-11-11 南通大学 一种自灭菌高效防寒保暖非织造材料及其制备方法

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110935328B (zh) * 2019-11-12 2022-02-11 南京工业大学 一种有机含氟聚合物掺杂的钙钛矿中空纤维透氧膜的制备方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101905121A (zh) * 2010-08-26 2010-12-08 南京工业大学 一种氧化铝基陶瓷中空纤维膜制备方法
CN103349918A (zh) * 2013-06-19 2013-10-16 南京工业大学 一种制备多通道陶瓷中空纤维膜的方法
CN103768965A (zh) * 2014-01-09 2014-05-07 南京工业大学 一种多通道混合导体中空纤维膜的制备方法

Family Cites Families (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005005467A1 (de) * 2005-02-04 2006-08-10 Fraunhofer-Gesellschaft zur Förderung der angewandten Forschung e.V. Verbunde keramischer Hohlfasern, Verfahren zu deren Herstellung und deren Verwendung
DE102005005464B4 (de) * 2005-02-04 2007-06-14 Uhde Gmbh Verbunde keramischer Hohlfasern, Verfahren zu deren Herstellung und deren Verwendung
US8268041B2 (en) * 2008-06-30 2012-09-18 L'air Liquide Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Hollow organic/inorganic composite fibers, sintered fibers, methods of making such fibers, gas separation modules incorporating such fibers, and methods of using such modules
US20120082922A1 (en) * 2010-10-01 2012-04-05 Kyushu University, National University Corporation Composite electrode material and method of producing the same, negative electrode for metal-air battery, and metal-air battery
US8771404B2 (en) * 2011-07-31 2014-07-08 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Hollow ceramic fibers, precursors for manufacture thereof utilizing nanoparticles, methods of making the same, and methods of using the same
US8741031B2 (en) * 2011-07-31 2014-06-03 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Hollow ceramic fibers, precursors for manufacture thereof utilizing pore formers, methods of making the same, and methods of using the same
CN102284252B (zh) * 2011-08-19 2013-06-12 华南理工大学 一种钙钛矿型中空纤维透氢膜的制备方法
CN105617873A (zh) * 2015-12-29 2016-06-01 合肥工业大学 由无机盐和氧化物一步直接制备中空纤维陶瓷透氧膜的方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101905121A (zh) * 2010-08-26 2010-12-08 南京工业大学 一种氧化铝基陶瓷中空纤维膜制备方法
CN103349918A (zh) * 2013-06-19 2013-10-16 南京工业大学 一种制备多通道陶瓷中空纤维膜的方法
CN103768965A (zh) * 2014-01-09 2014-05-07 南京工业大学 一种多通道混合导体中空纤维膜的制备方法

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN115323611A (zh) * 2022-09-02 2022-11-11 南通大学 一种自灭菌高效防寒保暖非织造材料及其制备方法
CN115323611B (zh) * 2022-09-02 2023-12-08 南通大学 一种自灭菌高效防寒保暖非织造材料及其制备方法

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