CN105503246A - 三维打印具有立体通道的蜂窝型陶瓷氧渗透膜组件的方法 - Google Patents

三维打印具有立体通道的蜂窝型陶瓷氧渗透膜组件的方法 Download PDF

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CN105503246A
CN105503246A CN201510835104.9A CN201510835104A CN105503246A CN 105503246 A CN105503246 A CN 105503246A CN 201510835104 A CN201510835104 A CN 201510835104A CN 105503246 A CN105503246 A CN 105503246A
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ceramic
dimensional
tubes
honeycomb type
membrane
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CN105503246B (zh
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杨乃涛
孟秀霞
石莹
刘少敏
孟波
谭小耀
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Shandong University of Technology
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Abstract

本发明涉及一种三维打印具有立体通道的蜂窝型陶瓷氧渗透膜组件的方法，属于无机膜分离技术领域。本发明基于陶瓷材料三维打印成型技术，以高温氧离子导体陶瓷粉体为原料，使用三维绘图软件设计结构，利用陶瓷三维打印机输出，一步法打印制备成具有立体通道结构的蜂窝型陶瓷氧渗透膜组件的生坯，经烧结处理，获得具有立体通道的蜂窝型陶瓷氧渗透膜组件。本发明不仅制备高效、节约成本，大大提高传质速率，而且自动化程度高、批次稳定。

Description

三维打印具有立体通道的蜂窝型陶瓷氧渗透膜组件的方法
技术领域
本发明涉及一种三维打印具有立体通道的蜂窝型陶瓷氧渗透膜组件的方法，属于无机膜分离技术领域。
背景技术
无机膜反应分离技术是一种重要的化工分离技术。利用高温氧离子导体陶瓷材料制备的陶瓷透氧膜，可以通过高温下氧气在膜表面发生氧化-还原反应，生成活性氧离子，然后在膜两侧氧分压差的驱动下，氧离子在透氧陶瓷膜内部从膜的一侧迁移到另一侧，实现氧的分离和传递。高温陶瓷透氧膜由于采用的是氧离子迁移原理实现分离，理论上可以获得100％纯度的氧气，产品纯度高，过程简单，能耗低。陶瓷透氧膜的结构主要有平板式和管式两种形式。
中国专利CN101869809A公开一种混合导体透氧膜的制备办法，将粉体压成膜片，把生膜烧结，制成混合导体透氧膜。
中国专利CN103638825A公开一种一体化三层结构的无机透氧膜的制备方法，通过流延法分别制备混合导体透氧膜的致密层和多孔层坯体；按多孔层-致密层-多孔层的顺序将坯体叠放在一起，置于80℃的温等静压机里进行压制，制得一体化三层结构透氧膜前驱体；然后将三层结构无机透氧膜前驱体进行烧结即得到一体化的三层结构无机透氧膜。采用该方法可有效降低透氧膜的厚度，提高氧渗透流率。但无论是压片法还是流延方法制得的透氧膜只是一种片状单体膜，并不具有立体通道结构，要将其组装成膜组件，将会增加气体的输送结构和密封构件，难于工业化。
为提高透氧膜渗透率和易于密封，中国专利CN102895886A公开一种利用共纺丝法制备不对称中空纤维透氧膜的方法，但此方法制备的是单根膜组件，要想获得大规模专业化应用，必须将多根膜组装成组件。
中国专利CN101318106公开一种由多根中空纤维陶瓷膜并列连接构成的板状中空纤维陶瓷膜元件及其制备方法，特征是将多根一端封闭、一端开口或两端开口的中空纤维陶瓷膜生坯，两端对齐单层并列，在相互紧密接触的状态下以900～1600℃高温烧结5～20小时；或采用挤出成型制备由中空纤维陶瓷膜单层并列连接构成的板状中空纤维陶瓷膜生坯，干燥后以900～1600℃高温烧结5～20小时。与单根中空纤维陶瓷膜元件相比，本发明元件的机械强度显著提高，有利于制备大尺寸的膜元件，提高陶瓷膜的可靠性和使用寿命，并由于组装分散度的降低，膜组件的填装密度不但不降低，反而可进一步提高；本发明元件可用于制造气体或液体分离提纯装置或高温热交换器。但本方法是先制备单根中空纤维膜，然后再利用一些技术手段，将多根中空纤维进行粘结、固定、密封组装成束。
中国专利CN103349918A公开一种制备多通道陶瓷中空纤维膜的方法，以一定比例将陶瓷粉体、高分子聚合物、有机溶剂和分散剂混合均匀制备铸膜液。铸膜液经过脱气泡处理后，在多通道中空纤维模具以及相转化的协同作用下形成膜生坯。膜生坯经过高温焙烧形成多通道陶瓷中空纤维膜。发明的多通道陶瓷中空纤维膜具有自身非对称结构以及内腔中的骨架结构，能够同时满足陶瓷中空纤维膜强度和通量要求。但此方法制备的多通道中空纤维膜无管间流体流道，如果做成致密的陶瓷透氧膜，传质阻力将会很大，膜有效面积会大大降低。
目前已有的工业技术中，蜂窝型多通道无机膜是一种高效的大规模制膜方法。中国专利CN101456744公开一种蜂窝型陶瓷膜的制备方法。制备过程包括：制备聚合物溶液；制备陶瓷-聚合物铸膜液；制备蜂窝型管状陶瓷膜坯体；制备蜂窝型管状陶瓷膜。采用从内而外依次由内芯管，中套管和外套管镶套构成的专用蜂窝型模具，一次性制得具有多孔支撑层、过渡层及有效分离层非对称结构的蜂窝型管状陶瓷膜。蜂窝型无机膜主要是通过挤出成型技术一步加工而成的多条微管的并联膜组件，因为孔道的壁互相连在一起，不能直接接触外部介质，这种蜂窝型多通道无机膜的每一条蜂窝孔道与外界的传质都严重地受限，只能依靠蜂窝壁的多孔性能与外界进行物质交换。因此蜂窝型无机膜的孔道不能做很多，否则造成蜂窝中心孔道的传质效率大大降低。
三维打印技术作为一种新型的材料成型技术，在制造领域中引起广泛关注。利用三维打印技术可以制备塑料型材，金属型材以及陶瓷型材等，但是真正的工业应用还没有开始，尤其是在无机膜的制备领域还没有受到关注。
目前，采用三维打印具有立体通道的蜂窝型陶瓷氧渗透膜组件的方法未见报道。
发明内容
本发明的目的是提供一种三维打印具有立体通道的蜂窝型陶瓷氧渗透膜组件的方法，解决目前陶瓷氧渗透膜组件制备耗时费力，成本高昂，批次性能不稳定，人工依赖性强，以及蜂窝型膜组件传质效率低的问题。
本发明所述的三维打印具有立体通道的蜂窝型陶瓷氧渗透膜组件的方法，包括以下步骤：
(1)以高温氧离子导体陶瓷粉体为原料，使用三维绘图软件设计结构，利用陶瓷三维打印机输出，一步法打印制备成具有立体通道结构的蜂窝型陶瓷氧渗透膜组件的生坯；
(2)生坯经过烧结后，获得具有立体通道的蜂窝型陶瓷氧渗透膜组件。
所述的高温氧离子导体陶瓷粉体为结构为ABO3-δ的掺杂的钙钛矿型陶瓷、结构为A2B2O5-δ的双钙钛矿型陶瓷、结构为A2BO4-δ的尖晶石型陶瓷或结构为XaY1-aO2-δ的萤石型陶瓷中的一种或多种；其中，
A为镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钙、锶、钡中的一种或多种；
B为钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、镓、铝、钇、锆、铌、钼、铪、钽、钨、铼中的一种或多种；
X为钙、钇、钪、钐、钆、镨金属元素的一种或多种；
Y为锆、铈、铋金属元素的一种或多种；
δ为氧缺位数，0≤a≤1。
所述的高温氧离子导体陶瓷粉体的粒度为0.02～10微米。
所述的三维绘图软件优选ug，catia，pre，3Dmax等。
所述的具有立体通道的蜂窝型陶瓷氧渗透膜组件包括相互平行排列的多组陶瓷微管，每组陶瓷微管均设置在各自的陶瓷筋板上，每组陶瓷微管包含陶瓷微管管口呈直线排列的多个陶瓷微管，平行排列的多组陶瓷微管之间彼此分离，形成管间流体通道；陶瓷微管两端均由陶瓷管板将陶瓷微管固定连接成束，端面为蜂窝状，两块陶瓷管板的两侧分别由两块陶瓷支撑板相连，陶瓷支撑板与陶瓷管板垂直，陶瓷管板、陶瓷支撑板、陶瓷微管与陶瓷筋板均为一体化形成。
所述的管间流体通道为直通道或S型曲折通道。所述的直通道是相邻的两组陶瓷微管的任意两条陶瓷微管的中心线在同一条直线上；所述的S型曲折通道是指相邻的两组陶瓷微管的任意三条陶瓷微管呈三角形分布，即其中一组选1条陶瓷微管，另外一组选2条陶瓷微管。无论怎么排列都可以，只要相邻的两组陶瓷微管之间形成管间流体通道即可。
所述的具有立体通道的蜂窝型陶瓷氧渗透膜组件是指，膜组件具有成束的管通道，但是和挤出成型的蜂窝组件的最大不同之处是：该结构还拥有与管束方向垂直的管间流体通道，整体结构由三维打印一步成型。
所述的烧结是生坯在900～1600℃的温度条件下，于一定气氛中热处理2～10h。
所述的气氛优选氧化性气氛或普通大气气氛。
所述的陶瓷粉体中添加有机物粘结剂或造孔剂，有机物粘结剂或造孔剂的种类为本领域技术人员的常规选择。
更具体的制备过程如下：
首先用三维绘图软件通过计算机辅助设计出膜组件的三维实体模型结构图；然后将干燥、研磨和筛分好的陶瓷粉体与粘结剂混合均匀后，置于三维打印的材料盒中，用计算机控制三维打印机将透氧陶瓷粉体按照设计好的三维实体模型打印成为具有三维通道的无机膜坯体。最后，将此坯体周围附着的陶瓷扫吹干净后，放入程序升温电炉中，先经过低温干燥，中温预热，再经过高温烧结，可得致密的陶瓷氧渗透膜组件。
三维打印技术成型的无机膜组件直接由粉体材料成型为大面积多通道的组件，节省流程，降低成本；性能高，可由三维打印技术直接设计并成型出微管间的立体通道，使得微管外壁的快速传质成为可能；全程设计智能化，制造自动化，批次稳定，降低了人为因素对产品质量的影响。
本发明的有益效果如下：
本发明以具有氧离子传导性的陶瓷粉体为原料，利用三维打印机直接打印成型无机膜组件，解决了无机膜组件制备过程的几个重要难题：
(1)不需要经过单根中空纤维陶瓷膜的制备程序，直接由粉体材料成型为大面积多通道的组件，节省流程，大大提高了生产效率并节约制备成本。本发明制得的陶瓷氧渗透膜组件可用于从含氧混合气中高效选择分离高纯度的氧气；
(2)现有的蜂窝型无机膜组件，通道和通道之间是固体膜壁相连，传质性能差，单个蜂窝体不能拥有太多通道。三维打印技术可以设计并成型出微管间的立体通道，使得微管外壁的快速传质成为可能，提高了膜组件的透氧性能。立体通道的设计既可以提高组件强度，又可以大大提高传质速率；
(3)自动化程度高，批次稳定。三维打印技术可以使用绘图软件一次绘制膜组件的结构图，然后由打印设备输出。一步法成型大面积膜组件，免去了中空纤维陶瓷膜逐条制备和膜组件组装过程带来的批次不稳定，生产过程全部自动化，降低了人为因素对产品质量的影响。
附图说明
图1是计算机设计的膜组件模型的结构示意图；
图2是图1横截面的结构示意图；
图3是本发明制备的膜组件坯体的结构示意图；
图中：1、陶瓷微管管口；2、陶瓷管板；3、陶瓷支撑板；4、陶瓷微管；5、管间流体通道；6、陶瓷筋板。
具体实施方式
以下结合实施例对本发明做进一步描述。
实施例1
将300gLSCF(La0.6Sr0.4Co0.2Fe0.8O3-δ)陶瓷粉体与10g糊精利用混料机均匀混合，过60目筛后置于三维打印机原料盒中。三维打印机采用美国Zcorp公司Z510型陶瓷三维打印机，用ug软件绘制膜组件的三维实体模型结构图，见图1，用计算机控制三维打印机将LSCF陶瓷粉体按照设计好三维实体模型结构图打印成型，得到具有立体通道结构的蜂窝型陶瓷氧渗透膜组件的生坯。该模型外部尺寸为长、宽、高均为4cm，纵向有45条陶瓷微管，提供管程流体通道，横向有8条通道，提供管间流体通道，成型后的坯体照片见图3。该坯体吹扫干净表面粉体残留，置入程序控温电炉，先在80℃干燥2小时，再以2℃/min的升温速度加热到500℃，保温2小时以除去膜中的有机物粘结剂。然后以2℃/min的升温速度加热到1500℃，保温4小时使其充分烧结，最后以2℃/min的降温速率降到室温，获得致密的具有立体通道的蜂窝型陶瓷氧渗透膜组件。
实施例1中具有立体通道的蜂窝型陶瓷氧渗透膜组件包括相互平行排列的多组陶瓷微管4，每组陶瓷微管4均设置在各自的陶瓷筋板6上，每组陶瓷微管4包含陶瓷微管管口1呈直线排列的多个陶瓷微管4，平行排列的多组陶瓷微管4之间彼此分离，形成管间流体通道5；陶瓷微管4两端均由陶瓷管板2将陶瓷微管4固定连接成束，端面为蜂窝状，两块陶瓷管板2的两侧分别由两块陶瓷支撑板3相连，陶瓷支撑板3与陶瓷管板2垂直，陶瓷管板2、陶瓷支撑板3、陶瓷微管4与陶瓷筋板6均为一体化形成。
实施例2
将400gPrBaCo2O5-δ与20g可溶性淀粉利用球磨机机均匀混合，过100目筛后置于三维打印机原料盒中。三维打印机采用美国Zcorp公司Z510型陶瓷三维打印机，用catia软件绘制膜组件的三维实体模型结构图，见图1，用计算机控制三维打印机将陶瓷粉体按照设计好三维实体模型结构图打印成型，得到具有立体通道结构的蜂窝型陶瓷氧渗透膜组件的生坯。该坯体吹扫干净表面粉体残留，置入程序控温电炉，先在85℃干燥2小时，再以2℃/min的升温速度加热到500℃，保温2小时以除去膜中的有机物粘结剂。然后以2℃/min的升温速度加热到1300℃，保温4小时使其充分烧结，最后以2℃/min的降温速率降到室温，获得致密的具有立体通道的蜂窝型陶瓷氧渗透膜组件。
其结构如实施例1。
实施例3
将500gSDC(Sm0.2Ce0.8O2-δ)、20g聚乙烯醇缩丁醛粉体利用球磨机机均匀混合，过60目筛后置于三维打印机原料盒中。三维打印机采用美国Zcorp公司Z510型陶瓷三维打印机，用pre软件绘制膜组件的三维实体模型结构图，见图1，用计算机控制三维打印机将陶瓷粉体按照设计好三维实体模型结构图打印成型，得到具有立体通道结构的蜂窝型陶瓷氧渗透膜组件的生坯。该坯体吹扫干净表面粉体残留，置入程序控温电炉，先在85℃干燥2小时，再以2℃/min的升温速度加热到500℃，保温2小时以除去膜中的有机物粘结剂。然后以5℃/min的升温速度加热到1400℃，保温10小时使其充分烧结，最后以5℃/min的降温速率降到室温，获得致密的具有立体通道的蜂窝型陶瓷氧渗透膜组件。
其结构如实施例1。
实施例4
将450gLa2NiO4-δ、20g聚乙烯醇粉体利用球磨机机均匀混合，过60目筛后置于三维打印机原料盒中。三维打印机采用美国Zcorp公司Z510型陶瓷三维打印机，用3Dmax软件绘制膜组件的三维实体模型结构图，用计算机控制三维打印机将陶瓷粉体按照设计好三维实体模型结构图打印成型，得到具有立体通道结构的蜂窝型陶瓷氧渗透膜组件的生坯。该坯体吹扫干净表面粉体残留，置入程序控温电炉，先在85℃干燥2小时，再以2℃/min的升温速度加热到500℃，保温2小时以除去膜中的有机物粘结剂。然后以3℃/min的升温速度加热到1450℃，保温8小时使其充分烧结，最后以3℃/min的降温速率降到室温，获得致密的具有立体通道的蜂窝型陶瓷氧渗透膜组件。
其结构如实施例1。
实施例5
将200gBSCF(Ba0.5Sr0.5Co0.8Fe0.2O3-δ)、200gGDC(Gd0.2Ce0.8O2-δ)、20g聚乙烯醇粉体利用球磨机机均匀混合，过60目筛后置于三维打印机原料盒中。三维打印机采用美国Zcorp公司Z510型陶瓷三维打印机，用3Dmax软件绘制膜组件的三维实体模型结构图，用计算机控制三维打印机将陶瓷粉体按照设计好三维实体模型结构图打印成型，得到具有立体通道结构的蜂窝型陶瓷氧渗透膜组件的生坯。该坯体吹扫干净表面粉体残留，置入程序控温电炉，先在85℃干燥2小时，再以2℃/min的升温速度加热到500℃，保温2小时以除去膜中的有机物粘结剂。然后以3℃/min的升温速度加热到1200℃，保温8小时使其充分烧结，最后以3℃/min的降温速率降到室温，获得致密的具有立体通道的蜂窝型陶瓷氧渗透膜组件。
其结构如实施例1。

Claims (8)

1.一种三维打印具有立体通道的蜂窝型陶瓷氧渗透膜组件的方法，其特征在于包括以下步骤：
(1)以高温氧离子导体陶瓷粉体为原料，使用三维绘图软件设计结构，利用陶瓷三维打印机输出，一步法打印制备成具有立体通道结构的蜂窝型陶瓷氧渗透膜组件的生坯；
(2)生坯经过烧结后，获得具有立体通道的蜂窝型陶瓷氧渗透膜组件。
2.根据权利要求1所述的方法，其特征在于：高温氧离子导体陶瓷粉体为结构为ABO3-δ的掺杂的钙钛矿型陶瓷、结构为A2B2O5-δ的双钙钛矿型陶瓷、结构为A2BO4-δ的尖晶石型陶瓷或结构为XaY1-aO2-δ的萤石型陶瓷中的一种或多种；其中，
A为镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钙、锶、钡中的一种或多种；
B为钪、钛、钒、铬、锰、铁、钴、镍、铜、锌、镓、铝、钇、锆、铌、钼、铪、钽、钨、铼中的一种或多种；
X为钙、钇、钪、钐、钆、镨金属元素的一种或多种；
Y为锆、铈、铋金属元素的一种或多种；
δ为氧缺位数，0≤a≤1。
3.根据权利要求2所述的方法，其特征在于：高温氧离子导体陶瓷粉体的粒度为0.02～10微米。
4.根据权利要求1～3任一所述的方法，其特征在于：具有立体通道的蜂窝型陶瓷氧渗透膜组件包括相互平行排列的多组陶瓷微管(4)，每组陶瓷微管(4)均设置在各自的陶瓷筋板(6)上，每组陶瓷微管(4)包含陶瓷微管管口(1)呈直线排列的多个陶瓷微管(4)，平行排列的多组陶瓷微管(4)之间彼此分离，形成管间流体通道(5)；陶瓷微管(4)两端均由陶瓷管板(2)将陶瓷微管(4)固定连接成束，端面为蜂窝状，两块陶瓷管板(2)的两侧分别由两块陶瓷支撑板(3)相连，陶瓷支撑板(3)与陶瓷管板(2)垂直，陶瓷管板(2)、陶瓷支撑板(3)、陶瓷微管(4)与陶瓷筋板(6)均为一体化形成。
5.根据权利要求3所述的方法，其特征在于：管间流体通道(5)为直通道或S型曲折通道。
6.根据权利要求1所述的方法，其特征在于：烧结是生坯在900～1600℃的温度条件下，于一定气氛中热处理2～10h。
7.根据权利要求6所述的方法，其特征在于：气氛为氧化性气氛或普通大气气氛。
8.根据权利要求1所述的方法，其特征在于：高温氧离子导体陶瓷粉体中添加有机物粘结剂或造孔剂。
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