CN101284215A - A kind of preparation method of perovskite hollow fiber membrane - Google Patents
A kind of preparation method of perovskite hollow fiber membrane Download PDFInfo
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- 238000000034 method Methods 0.000 claims abstract description 29
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- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 12
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- 239000000243 solution Substances 0.000 claims description 27
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 25
- 239000000499 gel Substances 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 13
- 210000001161 mammalian embryo Anatomy 0.000 claims description 11
- 108010010803 Gelatin Proteins 0.000 claims description 10
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- 235000020679 tap water Nutrition 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- 229910052745 lead Inorganic materials 0.000 claims description 6
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- 150000003839 salts Chemical class 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052793 cadmium Inorganic materials 0.000 claims description 2
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- 239000008139 complexing agent Substances 0.000 claims description 2
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- 238000001879 gelation Methods 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910021645 metal ion Inorganic materials 0.000 claims description 2
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- 229910052759 nickel Inorganic materials 0.000 claims description 2
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- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims 1
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 229910052719 titanium Inorganic materials 0.000 claims 1
- 239000010936 titanium Substances 0.000 claims 1
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- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
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Abstract
本发明公开了一种钙钛矿中空纤维膜的制备方法，该方法包括液相法制备钙钛矿A1－xBxC1－yDyO3－δ粉体和相转化纺织技术制备钙钛矿中空纤维膜，相转化纺织技术制备钙钛矿中空纤维膜是将聚乙烯吡咯烷酮分散剂溶解在N－甲基吡咯烷酮溶剂中，再加入聚醚砜聚合物，溶解后，加入制备的钙钛矿粉体，真空脱气后，通过喷丝头进入凝胶槽中，在水中放置2～4天，通过吊式烧结的方法吊在管式炉中在1100－1500℃烧结5－24小时得到的钙钛矿中空纤维透氧膜。本发明通过“一步纺织技术”制备出有钙钛矿结构的BCFZ中空纤维膜，与现有技术所采用“多步”制备方法相比，可以省略制备钙钛矿粉体的中间步骤，大大降低制备成本。The invention discloses a method for preparing a perovskite hollow fiber membrane. The method includes preparing perovskite A 1-x B x C 1-y D y O 3-δ powder by a liquid phase method and preparing by phase inversion textile technology Perovskite hollow fiber membrane, phase inversion textile technology to prepare perovskite hollow fiber membrane is to dissolve polyvinylpyrrolidone dispersant in N-methylpyrrolidone solvent, then add polyethersulfone polymer, after dissolving, add the prepared calcium Titanium ore powder, after vacuum degassing, enters the gel tank through the spinneret, puts it in water for 2-4 days, hangs it in a tube furnace by hanging sintering method and sinters it at 1100-1500°C for 5-24 hours The obtained perovskite hollow fiber oxygen-permeable membrane. The present invention prepares BCFZ hollow fiber membranes with a perovskite structure through "one-step textile technology". Preparation costs.
Description
技术领域 technical field
本发明涉及一种钙钛矿中空纤维膜的制备及中空纤维膜在甲烷部分氧化制合成气中的应用。The invention relates to the preparation of a perovskite hollow fiber membrane and the application of the hollow fiber membrane in partial oxidation of methane to synthesis gas.
背景技术 Background technique
混合导体透氧膜是一类同时具有电子和氧离子导电性的无机陶瓷膜。由于在透氧过程中不是以分子氧形式传递而是以离子氧的形式通过氧空穴来传导氧，理论上对氧的扩散选择性为100％，而且某些材料的透氧量可以与微孔膜的渗透量相当。人们普遍认为，若能开发出具有足够高的稳定性和透氧量的膜材料，就可以满足目前多领域的需求，例如从小规模应用于医学方面的氧泵到大规模的燃烧反应等。Mixed conductor oxygen permeable membrane is a kind of inorganic ceramic membrane with both electronic and oxygen ion conductivity. Since oxygen is not transmitted in the form of molecular oxygen but in the form of ionized oxygen through oxygen holes in the process of oxygen transmission, the theoretical diffusion selectivity to oxygen is 100%, and the oxygen transmission rate of some materials can be compared with micro The permeation of the porous membrane is comparable. It is generally believed that if a membrane material with high enough stability and oxygen permeability can be developed, it can meet the current needs of many fields, such as small-scale oxygen pumps used in medicine to large-scale combustion reactions.
混合导体透氧膜的另一个重要应用领域是在化学反应过程中，最为有潜力的工业大规模应用就是用于甲烷部分氧化制合成气。在当今石油资源日渐减少、国际能源急剧动荡的情况下，进一步高效利用天然气资源具有重要的战略意义。Another important application field of the mixed conductor oxygen-permeable membrane is in the chemical reaction process, and the most potential industrial large-scale application is for the partial oxidation of methane to produce syngas. In today's situation where oil resources are dwindling and international energy sources are turbulent, further efficient utilization of natural gas resources is of great strategic significance.
利用混合导体透氧膜反应器可以实现氧分离过程和甲烷部分氧化过程的耦合。这一膜催化过程直接从空气中动态获取纯氧进行甲烷部分氧化反应，从而极大地降低了能耗、设备投资及操作成本。The coupling of oxygen separation process and methane partial oxidation process can be realized by using mixed conductor oxygen permeable membrane reactor. This membrane catalytic process directly dynamically obtains pure oxygen from the air for partial oxidation of methane, thereby greatly reducing energy consumption, equipment investment and operating costs.
目前，钙钛矿透氧膜的制备技术，尤其是在降低膜制备成本方面却没有明显的突破。迄今人们的研究大多数集中在片状膜上，因为片状膜很容易制备。但是片状膜只有很有限的膜面积(通常只有几个平方厘米)，虽然可以采用多层膜片叠在一起使膜面积达到工业应用的规模，但是这样还是有很多问题需要解决：如低的膜面积与体积比从而导致高的生成成本、高温密封问题；另外片状膜的厚度也难以降低，因而气体渗透速率低导致透氧量低，这些问题的存在阻碍了钙钛矿透氧膜在工业上的应用。直径＞5mm的管状膜可以有效地解决一些工程问题，尤其是高温密封问题。但仍然不能从根本上解决单位体积膜面积小，以及膜厚度太大的问题。如Balachandran(Balachandran U，Dusek J T.Maiya P S，et al.，Catal Today，1997，36(3)：265-272.)以La0.2Sr0.8Co0.2Fe0.8O3-δ管状膜为反应器进行了甲烷部分氧化制合成气，但发现当甲烷通入膜管反应几分钟，膜管就碎成几片。在还原气氛下，ABO3型混合导体膜(是管状膜)反应器会出现阴离子缺陷，导致了氧空缺的增多，使得晶格膨胀，从而导致内部应力的产生，当应力达到一定程度时会引起膜管的破裂。At present, there is no obvious breakthrough in the preparation technology of perovskite oxygen-permeable membranes, especially in reducing the cost of membrane preparation. So far, most of people's research has focused on sheet-like membranes, because sheet-like membranes are easy to prepare. However, the sheet membrane has only a very limited membrane area (usually only a few square centimeters). Although multilayer membranes can be stacked together to make the membrane area reach the scale of industrial applications, there are still many problems to be solved: such as low The area-to-volume ratio of the membrane leads to high production costs and high-temperature sealing problems; in addition, the thickness of the sheet-like membrane is difficult to reduce, so the gas permeation rate is low and the oxygen permeability is low. The existence of these problems hinders the perovskite oxygen-permeable membrane in Industrial applications. Tubular membranes with a diameter > 5 mm can effectively solve some engineering problems, especially high-temperature sealing problems. However, it still cannot fundamentally solve the problems of small membrane area per unit volume and too large membrane thickness. For example, Balachandran (Balachandran U, Dusek J T. Maiya P S, et al., Catal Today, 1997, 36(3): 265-272.) reacts with La 0.2 Sr0 .8 Co 0.2 Fe 0.8 O 3-δ tubular film The device has carried out the partial oxidation of methane to produce syngas, but found that when methane is passed into the membrane tube to react for a few minutes, the membrane tube will be broken into several pieces. In a reducing atmosphere, anion defects will appear in the ABO 3 -type mixed conductor membrane (it is a tubular membrane) reactor, which leads to the increase of oxygen vacancies, which makes the lattice expand, which leads to the generation of internal stress. When the stress reaches a certain level, it will cause Rupture of membrane tubes.
中空纤维膜能够有效解决以上问题。中空纤维膜是指外径小于1.0mm，中间为空心的混合导体透氧膜；首先，中空纤维膜具有很大的面积体积比，假设中空纤维膜的直径为0.75mm，在最紧密排列的情况下，1立方米的膜装置，它的有效膜面积将达到5000m2，从而可以大大降低投资成本；其次，中空纤维膜具有特有的多孔指纹结构使得其有效膜厚度很小，这样就可以获得很高的透氧量，同时又不影响膜的机械强度；第三，通过利用长的中空纤维膜，将膜的两端远离高温区，从而可以有效解决无机陶瓷膜的高温密封问题；还有中空纤维膜很容易组装成系统，非常适合工业集成。Hollow fiber membranes can effectively solve the above problems. Hollow fiber membrane refers to a mixed conductor oxygen permeable membrane with an outer diameter of less than 1.0mm and a hollow core in the middle; first, the hollow fiber membrane has a large area-to-volume ratio, assuming that the diameter of the hollow fiber membrane is 0.75mm, in the most closely arranged For a membrane device of 1 cubic meter, its effective membrane area will reach 5000m 2 , which can greatly reduce the investment cost; secondly, the hollow fiber membrane has a unique porous fingerprint structure so that its effective membrane thickness is very small, so that it can obtain a lot of High oxygen permeability without affecting the mechanical strength of the membrane; third, by using a long hollow fiber membrane, the two ends of the membrane are kept away from the high temperature area, which can effectively solve the high temperature sealing problem of the inorganic ceramic membrane; there is also a hollow Fiber membranes are easily assembled into systems that are well suited for industrial integration.
S.M.Liu(S.M.Liu，G.R.Gavalas，Preparation of oxygen ion conducting ceramichollow-fiber membranes，Ind.Eng.Chem.Res.44(2005)7633-7637.)公开了“多步“法制备出钙钛矿中空纤维透氧膜，该方法首先要通过液相法或固相法制备出钙钛矿的粉体，然后粉体筛分，再经过相转化纺织技术或塑性挤压的方法制备中空纤维膜(前驱体)，最后在热处理过程中前驱体就会形成具有钙钛矿结构的中空纤维膜。由此可知，该方法制备过程复杂、成本高。S.M.Liu (S.M.Liu, G.R.Gavalas, Preparation of oxygen ion conducting ceramic hollow-fiber membranes, Ind.Eng.Chem.Res.44(2005) 7633-7637.) disclosed a "multi-step" method to prepare perovskite hollow fibers Oxygen permeable membrane, the method firstly prepares perovskite powder by liquid phase method or solid phase method, then powder sieves, and then prepares hollow fiber membrane (precursor) through phase inversion textile technology or plastic extrusion method ), and finally the precursor will form a hollow fiber membrane with a perovskite structure during heat treatment. It can be seen that the preparation process of this method is complicated and the cost is high.
发明内容 Contents of the invention
本发明的目的在于克服现有技术的缺点，提供一种制备成本低、透氧性能较好的的钙钛矿中空纤维膜的制备方法。The purpose of the present invention is to overcome the shortcomings of the prior art, and provide a method for preparing a perovskite hollow fiber membrane with low preparation cost and good oxygen permeability.
本发明首先采用EDTA-柠檬酸络合法制备钙钛矿A1-xBxC1-yDyO3-δ粉体，然后采用相转化纺织技术制备钙钛矿中空纤维膜。The invention firstly adopts EDTA-citric acid complexation method to prepare perovskite A 1-x B x C 1-y D y O 3-δ powder, and then adopts phase inversion textile technology to prepare perovskite hollow fiber membrane.
本发明目的通过如下技术方案实现：The object of the invention is achieved through the following technical solutions:
一种钙钛矿中空纤维膜的制备方法，包括如下步骤和工艺条件：A preparation method of a perovskite hollow fiber membrane, comprising the following steps and process conditions:
(1)液相法制备钙钛矿A1-xBxC1-yDyO3-δ粉体；按照钙钛矿化学式A1-xBxC1-yDyO3-δ的组成物摩尔比称取起始原料并加水制成溶液后混合，其中A选自Ba，Sr，Ca，Cd，Pb，Ce，Sn，La，Sm，Pr中的一种；B，C分别选自Ca，Ce，Pb，Cr，Cu，Fe，Mn，Ni，Mg，Co中的一种；D选自Zr，Ti，Ce，Zn，Sn，Bi，V，Pb的一种；0＜δ＜1，0＜x＜1，0＜y＜1；起始原料以A、B、C、D的可溶性金属盐引入；在混合溶液中加入EDTA与柠檬酸作为共同络合剂，用硝酸及氨水调节溶液的pH值为6-9，将体系在50-90℃恒温条件下搅拌成明胶体，将胶体在100-200℃固化得凝胶粉，在700-1000℃温度下焙烧1-10小时得到粉体(BCFZ钙钛矿粉体)；所述EDTA、柠檬酸与钙钛矿A1-xBxC1-yDyO3-δ粉体中A、B、C和D金属离子之和的摩尔比为1～2∶1～3∶1～2；(1) Preparation of perovskite A 1-x B x C 1-y D y O 3-δ powder by liquid phase method; according to the perovskite chemical formula A 1-x B x C 1-y D y O 3-δ The composition molar ratio of the starting materials is weighed and mixed with water to make a solution, wherein A is selected from one of Ba, Sr, Ca, Cd, Pb, Ce, Sn, La, Sm, Pr; B, C are respectively One selected from Ca, Ce, Pb, Cr, Cu, Fe, Mn, Ni, Mg, Co; D selected from one of Zr, Ti, Ce, Zn, Sn, Bi, V, Pb; 0<δ<1,0<x<1,0<y<1; starting materials are introduced with soluble metal salts of A, B, C, and D; EDTA and citric acid are added to the mixed solution as co-complexing agents, and nitric acid and ammonia water to adjust the pH of the solution to 6-9, stir the system at a constant temperature of 50-90°C to form gelatin, solidify the gelatin at 100-200°C to obtain gel powder, and roast at 700-1000°C for 1- Obtain powder (BCFZ perovskite powder) in 10 hours; A, B, C and D in the EDTA, citric acid and perovskite A 1-x B x C 1-y D y O 3-δ powder The molar ratio of the sum of metal ions is 1～2:1～3:1～2;
(2)相转化纺织技术制备钙钛矿中空纤维膜；将聚乙烯吡咯烷酮(PVP)分散剂溶解在N-甲基吡咯烷酮(NMP)溶剂中，再加入聚醚砜(Polyethersulfone，简称PESf)聚合物，溶解后，加入步骤(1)制备的钙钛矿粉体，搅拌均匀性，注入纺织设备的料罐中，真空脱气后，在压强为100～120KPa N2驱动下，铸膜液通过喷丝头进入凝胶槽中，通过普通的自来水促进凝胶，所得到的膜在水中放置2～4天以保证其结构稳定性，自然干燥，即可得到稳定的中空纤维膜生胚，生胚通过吊式烧结的方法吊在管式炉中在1100-1500℃烧结5-24小时得到的钙钛矿中空纤维透氧膜；(2) Phase inversion textile technology to prepare perovskite hollow fiber membrane; dissolve polyvinylpyrrolidone (PVP) dispersant in N-methylpyrrolidone (NMP) solvent, and then add polyethersulfone (Polyethersulfone, referred to as PESf) polymer , after dissolving, add the perovskite powder prepared in step (1), stir evenly, inject it into the material tank of the textile equipment, and after vacuum degassing, under the pressure of 100-120KPa N2 , the casting solution is sprayed The silk head enters the gel tank, and the gel is promoted by ordinary tap water. The obtained membrane is placed in water for 2 to 4 days to ensure its structural stability, and it is naturally dried to obtain a stable hollow fiber membrane. The perovskite hollow fiber oxygen permeable membrane obtained by hanging in a tube furnace and sintering at 1100-1500°C for 5-24 hours by hanging sintering method;
所述聚乙烯吡咯烷酮、N-甲基吡咯烷酮和聚醚砜聚合物重量比是1～2∶50～60∶12～15，加入钙钛矿粉体与有机物重量比为6～8∶3～5，所述有机物重量为聚乙烯吡咯烷酮、N-甲基吡咯烷酮和聚醚砜聚合物重量之和。The weight ratio of polyvinylpyrrolidone, N-methylpyrrolidone and polyethersulfone polymer is 1-2:50-60:12-15, and the weight ratio of added perovskite powder to organic matter is 6-8:3-5 , the weight of the organic matter is the sum of the weights of polyvinylpyrrolidone, N-methylpyrrolidone and polyethersulfone polymers.
本发明与现有技术相比，具有如下优点：Compared with the prior art, the present invention has the following advantages:
(1)本发明提供了一种简单、高效、廉价的中空纤维膜制备技术。本发明直接用制备钙钛矿的原材料(如金属硝酸盐)与聚合物混合、搅拌成均匀的铸膜液，通过“一步纺织技术”制备出有钙钛矿结构的BCFZ中空纤维膜。与文献上所采用“多步”制备方法相比，本发明所采用的“一步法”可以省略制备钙钛矿粉体的中间步骤，不仅简化钙钛矿中空纤维透氧膜制备过程，而且大大降低其制备成本。(1) The present invention provides a simple, efficient and cheap hollow fiber membrane preparation technology. The invention directly mixes and stirs the raw material for preparing perovskite (such as metal nitrate) and polymer to form a uniform casting solution, and prepares the BCFZ hollow fiber membrane with perovskite structure through "one-step textile technology". Compared with the "multi-step" preparation method adopted in the literature, the "one-step method" adopted in the present invention can omit the intermediate steps of preparing perovskite powder, which not only simplifies the preparation process of perovskite hollow fiber oxygen permeable membrane, but also greatly reduce its preparation cost.
(2)所制得的中空纤维膜透氧性能较好。制备的中空纤维膜(直径＜1.0mm)具有很大的面积体积比，且中空纤维膜膜壁很薄，氧渗透阻力很小使得其有效膜厚度很小，可以获得很高的透氧量。(2) The prepared hollow fiber membrane has better oxygen permeability. The prepared hollow fiber membrane (diameter < 1.0 mm) has a large area-to-volume ratio, and the hollow fiber membrane wall is very thin, and the oxygen permeation resistance is small so that the effective membrane thickness is small, and a high oxygen permeability can be obtained.
(3)中空纤维膜的致密性很好。本发明钙钛矿粉末很好分散在有机聚合物中，通过高温烧结除去有机聚合物物后，钙钛矿粉末紧密结合在一起形成了致密膜。烧结好的中空纤维膜致密性好，没有空洞。(3) The density of the hollow fiber membrane is very good. The perovskite powder of the present invention is well dispersed in the organic polymer, and after the organic polymer is removed by high-temperature sintering, the perovskite powder is closely combined to form a dense film. The sintered hollow fiber membrane has good density and no voids.
附图说明 Description of drawings
图1为BCFZ粉体及烧结好的中空纤维膜的XRD。Figure 1 is the XRD of BCFZ powder and sintered hollow fiber membrane.
图2为中空纤维生胚的SEM形貌图。Figure 2 is the SEM image of the hollow fiber green embryo.
图3为烧结好的中空纤维膜的SEM形貌图。Figure 3 is the SEM image of the sintered hollow fiber membrane.
具体实施方式 Detailed ways
为更好理解本发明，下面结合实施例对本发明做进一步地说明，但是本发明要求保护的范围并不局限于实施例表示的范围。In order to better understand the present invention, the present invention will be further described below in conjunction with the examples, but the protection scope of the present invention is not limited to the range indicated by the examples.
实施例1Example 1
(1)用液相法制备0.1mol的钙钛矿BaCo0.4Fe0.4Zr0.2O3-δ(BCFZ)粉体(δ为0-0.5，)：称量Ba(NO3)2、Co(NO3)2、Fe(NO3)3、ZrO(NO3)2四种原料，溶于去离子水分别配成1.0mol/lBa(NO3)2、0.4mol/lCo(NO3)2、0.4mol/l Fe(NO3)3和0.2mol/l ZrO(NO3)2的溶液，取100ml 1mol/lBa(NO3)2、100ml 0.4mol/l Co(NO3)2、100ml 0.4mol/l Fe(NO3)3和100ml0.2mol/l ZrO(NO3)2置入耐热大口烧杯搅拌30min，然后加入0.1mol EDTA搅拌30min，再加入0.15mol柠檬酸搅拌30min，用硝酸及氨水调节溶液的pH值为7，将体系加热至85℃，然后恒温下搅拌成明胶体，将胶体在200℃固化得凝胶粉，最后在950℃温度下焙烧8小时得到BCFZ钙钛矿粉体，其中δ＝0-0.5，将得到的粉体进行物相分析，XRD粉末衍射法测定如图1所示。对照标准物质的粉末衍射卡片(即Powder Diffraction File-PDF卡片，该卡片最早是由J.D.Hanawalt于1936年发创立的，1964年由美国材料试验协会(AmerianSociety for Testing Materials)接管，也称ASTM卡片)，其峰值一致，且无杂峰出现，说明本实施例制备的就是BaCo0.4Fe0.4Zr0.2O3-δ。(1) Prepare 0.1mol of perovskite BaCo 0.4 Fe 0.4 Zr 0.2 O 3-δ (BCFZ) powder by liquid phase method (δ is 0-0.5): weigh Ba(NO 3 ) 2 , Co(NO 3 ) 2 , Fe(NO 3 ) 3 , ZrO(NO 3 ) 2 four kinds of raw materials, dissolved in deionized water to make 1.0mol/lBa(NO 3 ) 2 , 0.4mol/lCo(NO 3 ) 2 , 0.4 mol/l Fe(NO 3 ) 3 and 0.2mol/l ZrO(NO 3 ) 2 solution, take 100ml 1mol/lBa(NO 3 ) 2 , 100ml 0.4mol/l Co(NO 3 ) 2 , 100ml 0.4mol/ l Fe(NO 3 ) 3 and 100ml 0.2mol/l ZrO(NO 3 ) 2 were placed in a heat-resistant beaker and stirred for 30 minutes, then added 0.1mol EDTA and stirred for 30 minutes, then added 0.15mol citric acid and stirred for 30 minutes, adjusted with nitric acid and ammonia water The pH value of the solution is 7, the system is heated to 85°C, then stirred at a constant temperature to form gelatin, the gelatin is solidified at 200°C to obtain gel powder, and finally roasted at 950°C for 8 hours to obtain BCFZ perovskite powder. Where δ=0-0.5, the obtained powder is subjected to phase analysis, and XRD powder diffraction method is shown in FIG. 1 . Powder diffraction card against standard substance (i.e. Powder Diffraction File-PDF card, which was first created by JD Hanawalt in 1936 and was taken over by the American Society for Testing Materials (Amerian Society for Testing Materials) in 1964, also known as ASTM card), The peaks are consistent and no miscellaneous peaks appear, indicating that BaCo 0.4 Fe 0.4 Zr 0.2 O 3-δ is prepared in this example.
(2)采用相转化纺织技术制备钙钛矿中空纤维膜。首先配制均一且稳定的铸膜液，具体步骤如下：将4g的聚乙烯吡咯烷酮分散剂溶解在240g N-甲基吡咯烷酮溶剂中，再加入60g聚醚砜聚合物，振荡使其溶解；待其完全溶解后，加入步骤(1)制备的600g BCFZ钙钛矿粉体，强烈搅拌24h以保证其均匀性。将搅拌均匀的铸膜液注入纺织设备(反应设备)的料罐(普通的圆柱形的装配料的罐子)中。真空脱气5min后，在压强为100kPaN2驱动下，铸膜液通过喷丝头(类似自来水的水龙头类似)进入凝胶槽(一个立方体形水槽)中。凝胶槽内通过普通的自来水促进凝胶，所得到的膜在水中放置2天，以保证其结构稳定性，然后在空气中自然干燥，即可得到稳定的中空纤维膜(生胚)。生胚通过吊式烧结(通过悬挂的方式吊着烧结)的方法吊在管式炉中，在1300℃烧结6小时即可得到致密的钙钛矿中空纤维透氧膜。(2) The perovskite hollow fiber membrane was prepared by phase inversion textile technology. First prepare a uniform and stable casting solution, the specific steps are as follows: dissolve 4g of polyvinylpyrrolidone dispersant in 240g of N-methylpyrrolidone solvent, then add 60g of polyethersulfone polymer, shake to dissolve; wait until it is completely After dissolving, add 600g of BCFZ perovskite powder prepared in step (1), and stir vigorously for 24 hours to ensure its uniformity. The uniformly stirred casting solution is injected into the material tank (ordinary cylindrical assembly tank) of the textile equipment (reaction equipment). After vacuum degassing for 5 minutes, under the pressure of 100kPaN2, the casting solution enters the gel tank (a cubic tank) through the spinneret (similar to a faucet of tap water). Ordinary tap water was used to promote gelation in the gel tank, and the obtained membrane was placed in water for 2 days to ensure its structural stability, and then dried naturally in the air to obtain a stable hollow fiber membrane (green embryo). The green embryo is suspended in a tube furnace by hanging sintering (sintering by hanging), and sintered at 1300°C for 6 hours to obtain a dense perovskite hollow fiber oxygen-permeable membrane.
所制备的中空纤维膜的几何形状：外径为800-900μm，内径为500-600μm，中空纤维膜的长度起决于烧结炉子的长度。图2是中空纤维膜生胚的外表面的电镜照片，可以看出钙钛矿粉末很好分散在有机聚合物中，通过高温烧结除去有机聚合物物后，钙钛矿粉末紧密结合在一起形成了致密膜。图3是烧结好的中空纤维膜外表面的电镜照片，图中显示制备的纤维膜致密性好，没有空洞。The geometric shape of the prepared hollow fiber membrane: the outer diameter is 800-900 μm, the inner diameter is 500-600 μm, and the length of the hollow fiber membrane depends on the length of the sintering furnace. Figure 2 is an electron micrograph of the outer surface of the hollow fiber membrane green body. It can be seen that the perovskite powder is well dispersed in the organic polymer. After the organic polymer is removed by high-temperature sintering, the perovskite powder is closely combined to form dense membrane. Figure 3 is an electron micrograph of the outer surface of the sintered hollow fiber membrane, which shows that the prepared fiber membrane has good compactness and no voids.
管状膜(尤其是直径＞5mm管状膜)的发展可以有效地解决一些工程问题，如高温密封问题。但仍然不能从根本上解决单位体积膜面积小，以及膜厚度太大的问题。本实施例在制备的钙钛矿粉体基础上采用的“一步法”制备钙钛矿中空纤维透氧膜，简化钙钛矿中空纤维透氧膜制备过程，且制备的中空纤维膜(直径＜1.0mm)具有很大的面积体积比，从而可以大大降低其投资成本。其次，中空纤维膜膜壁很薄，氧渗透阻力很小使得其有效膜厚度很小，可以获得很高的透氧量。The development of tubular membranes (especially tubular membranes with a diameter > 5 mm) can effectively solve some engineering problems, such as high-temperature sealing problems. However, it still cannot fundamentally solve the problems of small membrane area per unit volume and too large membrane thickness. The "one-step method" used in this example to prepare the perovskite hollow fiber oxygen permeable membrane on the basis of the prepared perovskite powder simplifies the preparation process of the perovskite hollow fiber oxygen permeable membrane, and the prepared hollow fiber membrane (diameter< 1.0mm) has a large area-to-volume ratio, which can greatly reduce its investment cost. Secondly, the membrane wall of the hollow fiber membrane is very thin, and the oxygen permeation resistance is very small, so that the effective membrane thickness is very small, and a high oxygen permeability can be obtained.
实施例2Example 2
(1)用液相法制备0.1mol的钙钛矿LaCo0.5Mn0.4Zr0.1O3-δ粉体：称量La(NO3)2、Co(NO3)2、Mn(NO3)2、ZrO(NO3)2四种原料溶于去离子水分别配成1.0mol/l La(NO3)2、0.5mol/l Co(NO3)2、0.4mol/l Mn(NO3)2、0.2mol/l ZrO(NO3)2的溶液，取100ml 1mol/lLa(NO3)2、100ml 0.5mol/l Co(NO3)2、100ml 0.4mol/l Mn(NO3)2、50ml 0.2mol/l ZrO(NO3)2置入耐热大口烧杯搅拌30min，然后加入0.15mol EDTA搅拌30min，再加入0.2mol柠檬酸搅拌30min，用硝酸及氨水调节溶液的pH值为6.5，将体系加热至50℃，然后恒温下搅拌成明胶体，将胶体在100℃固化得凝胶粉，最后在1000℃温度下焙烧2小时得到粉体，其中δ＝0-0.5。(1) Prepare 0.1mol perovskite LaCo 0.5 Mn 0.4 Zr 0.1 O 3-δ powder by liquid phase method: weigh La(NO 3 ) 2 , Co(NO 3 ) 2 , Mn(NO 3 ) 2 , The four raw materials of ZrO(NO 3 ) 2 were dissolved in deionized water to prepare 1.0mol/l La(NO 3 ) 2 , 0.5mol/l Co(NO 3 ) 2 , 0.4mol/l Mn(NO 3 ) 2 , 0.2mol/l ZrO(NO 3 ) 2 solution, take 100ml 1mol/lLa(NO 3 ) 2 , 100ml 0.5mol/l Co(NO 3 ) 2 , 100ml 0.4mol/l Mn(NO 3 ) 2 , 50ml 0.2 mol/l ZrO(NO 3 ) 2 was placed in a heat-resistant large mouth beaker and stirred for 30 minutes, then added 0.15mol EDTA and stirred for 30 minutes, then added 0.2mol citric acid and stirred for 30 minutes, adjusted the pH value of the solution to 6.5 with nitric acid and ammonia water, and heated the system to 50°C, then stirred at constant temperature to form gelatin, solidified at 100°C to obtain gel powder, and finally fired at 1000°C for 2 hours to obtain powder, wherein δ=0-0.5.
(2)采用相转化纺织技术制备钙钛矿中空纤维膜。首先配制均一且稳定的铸膜液，具体步骤如下：将4g的聚乙烯吡咯烷酮分散剂溶解在220g N-甲基吡咯烷酮溶剂中，再加入55g的聚醚砜聚合物，振荡使其溶解；待其完全溶解后，加入步骤(1)中制备好的LaCo0.5Mn0.4Zr0.1O3-δ钙钛矿粉体400g，强烈搅拌24h以保证其均匀性。将搅拌均匀的铸膜液注入纺织设备的料罐中，真空脱气一段时间后，在压强为110kPaN2驱动下，铸膜液通过喷丝头进入凝胶槽中。内外凝胶液都为普通的自来水，所得到的膜在水中放置2.5天以保证其结构稳定性，然后在空气中自然干燥，即可得到稳定的中空纤维膜(生胚)。生胚通过吊式烧结的方法吊在管式炉中，在1200℃烧结8小时即可得到致密的钙钛矿中空纤维透氧膜。(2) The perovskite hollow fiber membrane was prepared by phase inversion textile technology. First prepare a uniform and stable casting solution, the specific steps are as follows: dissolve 4g of polyvinylpyrrolidone dispersant in 220g of N-methylpyrrolidone solvent, then add 55g of polyethersulfone polymer, shake to dissolve it; After completely dissolving, add 400 g of LaCo 0.5 Mn 0.4 Zr 0.1 O 3-δ perovskite powder prepared in step (1), and stir vigorously for 24 hours to ensure its uniformity. The uniformly stirred casting solution is injected into the material tank of the textile equipment, and after a period of vacuum degassing, driven by a pressure of 110kPaN 2 , the casting solution enters the gel tank through the spinneret. The inner and outer gel liquids are common tap water, and the obtained membrane is placed in water for 2.5 days to ensure its structural stability, and then naturally dried in the air to obtain a stable hollow fiber membrane (green embryo). The green embryo is suspended in a tube furnace by hanging sintering method, and sintered at 1200°C for 8 hours to obtain a dense perovskite hollow fiber oxygen permeable membrane.
实施例3Example 3
(1)用液相法制备0.1mol的钙钛矿SrCo0.5Fe0.4Ti0.1O3-δ粉体：称量Sr(NO3)2、Co(NO3)2、Fe(NO3)3、TiO(NO3)2四种原料溶于去离子水分别配成0.8mol/l Sr(NO3)2、0.5mol/lCo(NO3)2、0.4mol/l Fe(NO3)3、0.2mol/l TiO(NO3)2的溶液，取125ml 0.8mol/l Sr(NO3)2、100ml 0.5mol/l Co(NO3)2、100ml 0.4mol/l Fe(NO3)3、50ml 0.2mol/l TiO(NO3)2置入耐热大口烧杯搅拌30min，然后加入0.1mol EDTA搅拌30min，再加入0.25mol柠檬酸搅拌30min，用硝酸及氨水调节溶液的pH值为9，将体系加热至90℃，然后恒温下搅拌成明胶体，将胶体在200℃固化得凝胶粉，最后在750℃温度下焙烧8小时得到粉体，其中δ＝0-0.5。(1) Prepare 0.1mol perovskite SrCo 0.5 Fe 0.4 Ti 0.1 O 3-δ powder by liquid phase method: weigh Sr(NO 3 ) 2 , Co(NO 3 ) 2 , Fe(NO 3 ) 3 , The four raw materials of TiO(NO 3 ) 2 were dissolved in deionized water to prepare 0.8mol/l Sr(NO 3 ) 2 , 0.5mol/l Co(NO 3 ) 2 , 0.4mol/l Fe(NO 3 ) 3 , 0.2 mol/l TiO(NO 3 ) 2 solution, take 125ml 0.8mol/l Sr(NO 3 ) 2 , 100ml 0.5mol/l Co(NO 3 ) 2 , 100ml 0.4mol/l Fe(NO 3 ) 3 , 50ml Put 0.2mol/l TiO(NO 3 ) 2 in a heat-resistant large mouth beaker and stir for 30min, then add 0.1mol EDTA and stir for 30min, then add 0.25mol citric acid and stir for 30min, adjust the pH value of the solution to 9 with nitric acid and ammonia water, and mix the system Heat to 90°C, then stir at constant temperature to form gelatin, solidify the gelatin at 200°C to obtain gel powder, and finally bake at 750°C for 8 hours to obtain powder, where δ=0-0.5.
(2)采用相转化纺织技术制备钙钛矿中空纤维膜。首先配制均一且稳定的铸膜液，具体步骤如下：将3.8g的聚乙烯吡咯烷酮分散剂溶解在240g N-甲基吡咯烷酮溶剂中，再加入58g的聚醚砜聚合物，振荡使其溶解；待其完全溶解后，加入步骤(1)中制备好的SrCo0.5Fe0.4Ti0.1O3-δ钙钛矿粉体650g，强烈搅拌24h以保证其均匀性。将搅拌均匀的铸膜液注入纺织设备的料罐中，真空脱气一段时间后，在100kPa N2压力驱动下，铸膜液通过喷丝头进入凝胶槽中。内外凝胶液都为普通的自来水，所得到的膜在水中放置4天以保证其结构稳定性，然后在空气中自然干燥，即可得到稳定的中空纤维膜(生胚)。生胚通过吊式烧结的方法吊在管式炉中，在1100℃烧结24小时即可得到致密的钙钛矿中空纤维透氧膜(2) The perovskite hollow fiber membrane was prepared by phase inversion textile technology. First prepare a uniform and stable casting solution, the specific steps are as follows: dissolve 3.8g of polyvinylpyrrolidone dispersant in 240g of N-methylpyrrolidone solvent, then add 58g of polyethersulfone polymer, shake to dissolve; After it is completely dissolved, add 650 g of SrCo 0.5 Fe 0.4 Ti 0.1 O 3-δ perovskite powder prepared in step (1), and stir vigorously for 24 hours to ensure its uniformity. The uniformly stirred casting solution is injected into the material tank of the textile equipment, and after a period of vacuum degassing, under the pressure of 100kPa N2 , the casting solution enters the gel tank through the spinneret. The inner and outer gel liquids are common tap water, and the obtained membrane is placed in water for 4 days to ensure its structural stability, and then naturally dried in the air to obtain a stable hollow fiber membrane (green embryo). The green embryo is suspended in a tube furnace by hanging sintering method, and sintered at 1100°C for 24 hours to obtain a dense perovskite hollow fiber oxygen permeable membrane
实施例4Example 4
(1)用液相法制备0.1mol的钙钛矿Sm0.8Ca0.2Co0.6Ce0.4O3-δ粉体：称量Sm(NO3)2、Ca(NO3)2、Co(NO3)2、Ce(NO3)3四种原料溶于去离子水分别配成1.0mol/l Sm(NO3)2、0.8mol/l Ca(NO3)2、0.5mol/l Co(NO3)2、0.4mol/l Ce(NO3)3的溶液，取80ml 1.0mol/lSm(NO3)2、25ml 0.8mol/l Ca(NO3)2、120ml 0.5mol/l Co(NO3)2、100ml 0.4mol/lCe(NO3)3置入耐热大口烧杯搅拌30min，然后加入0.2mol EDTA搅拌30min，再加入0.3mol柠檬酸搅拌30min，用硝酸及氨水调节溶液的pH值为8.5，将体系加热至85℃，然后恒温下搅拌成明胶体，将胶体在150℃固化得凝胶粉，最后在700℃温度下焙烧10小时得到粉体，其中δ＝0-0.5。(1) Prepare 0.1mol perovskite Sm 0.8 Ca 0.2 Co 0.6 Ce 0.4 O 3-δ powder by liquid phase method: weigh Sm(NO 3 ) 2 , Ca(NO 3 ) 2 , Co(NO 3 ) 2. Ce(NO 3 ) 3 four kinds of raw materials were dissolved in deionized water to make 1.0mol/l Sm(NO 3 ) 2 , 0.8mol/l Ca(NO 3 ) 2 , 0.5mol/l Co(NO 3 ) 2 , 0.4mol/l Ce(NO 3 ) 3 solution, take 80ml 1.0mol/lSm(NO 3 ) 2 , 25ml 0.8mol/l Ca(NO 3 ) 2 , 120ml 0.5mol/l Co(NO 3 ) 2 , 100ml 0.4mol/lCe(NO 3 ) 3 were placed in a heat-resistant large mouth beaker and stirred for 30min, then added 0.2mol EDTA and stirred for 30min, then added 0.3mol citric acid and stirred for 30min, the pH value of the solution was adjusted to 8.5 with nitric acid and ammonia water, and The system is heated to 85°C, then stirred at constant temperature to form gelatin, solidified at 150°C to obtain gel powder, and finally roasted at 700°C for 10 hours to obtain powder, where δ=0-0.5.
(2)采用相转化纺织技术制备钙钛矿中空纤维膜。首先配制均一且稳定的铸膜液，具体步骤如下：将4g的聚乙烯吡咯烷酮分散剂溶解在240g N-甲基吡咯烷酮溶剂中，再加入60g的聚醚砜聚合物，振荡使其溶解；待其完全溶解后，加入步骤(1)中制备好的Sm0.8Ca0.2Co0.6Ce0.4O3-δ钙钛矿粉体580g，强烈搅拌24h以保证其均匀性。将搅拌均匀的铸膜液注入纺织设备的料罐中，真空脱气一段时间后，在压强为120kPa N2驱动下，铸膜液通过喷丝头进入凝胶槽中。内外凝胶液都为普通的自来水，所得到的膜在水中放置3天以保证其结构稳定性，然后在空气中自然干燥，即可得到稳定的中空纤维膜(生胚)。生胚通过吊式烧结的方法吊在管式炉中，在1500℃烧结5小时即可得到致密的钙钛矿中空纤维透氧膜(2) The perovskite hollow fiber membrane was prepared by phase inversion textile technology. First prepare a uniform and stable casting solution, the specific steps are as follows: dissolve 4g of polyvinylpyrrolidone dispersant in 240g of N-methylpyrrolidone solvent, then add 60g of polyethersulfone polymer, shake to dissolve it; After completely dissolving, add 580 g of Sm 0.8 Ca 0.2 Co 0.6 Ce 0.4 O 3-δ perovskite powder prepared in step (1), and stir vigorously for 24 hours to ensure its uniformity. The uniformly stirred casting solution is injected into the material tank of the textile equipment, and after a period of vacuum degassing, driven by a pressure of 120kPa N 2 , the casting solution enters the gel tank through the spinneret. The inner and outer gel liquids are common tap water, and the obtained membrane is placed in water for 3 days to ensure its structural stability, and then dried naturally in the air to obtain a stable hollow fiber membrane (green embryo). The green embryo is suspended in a tube furnace by hanging sintering method, and sintered at 1500°C for 5 hours to obtain a dense perovskite hollow fiber oxygen permeable membrane
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