CN1262517C - 用作催化剂载体的多孔陶瓷基体 - Google Patents
用作催化剂载体的多孔陶瓷基体 Download PDFInfo
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Abstract
一种由水、难熔颗粒和成孔材料以及聚合分散剂构成的分散体。加入一种水敏性破稳剂用于提高混合体的粘度使其固化形成一个生坯，将其从模具中脱模出来，随后加热和烧结。
Description
技术领域
本发明涉及一种制备多孔陶瓷基体的方法，所述的基体可用于催化剂材料和类似目的。
背景技术
EP-A-0353669公开了一种通过压制由水、陶瓷粉末、可燃烧有机物质(椰子壳颗粒和/或纤维素颗粒)、粘合剂和选择性的润滑剂组成的一种易流动混合物，干燥压制体和燃烧以分解有机物质而制得制品的方法。
EP-A-0767154公开了从选自于金属、金属互化物、硬金属、金属陶瓷和/或陶瓷的粉末形成固态的、均相或多孔的成型体的方法，其包括下列步骤：
a)制备由所述粉末和蛋白质物质组成的水性浆体，所述的蛋白质物质在室温下是溶于水且在90℃的温度下能够形成不可逆的凝胶。
b)通过模铸、流延成型或模压成型将所述浆体制成所需形状的物体；和
c)加热至至少相当于蛋白质的凝胶温度。
蛋白质的含量适宜地是基于水相的10-15重量％，这使得分散体的加工是困难的且限制了可分散的固体的量。在本申请的实施例1，2和3中，固体的含量分别是32体积％，20体积％且37体积％。
发明内容
本发明的一个目的是提供一种制备具有不同工业用途的多孔陶瓷基体的有效方法。
根据本发明的一方面，本发明提供了一种制造多孔陶瓷基体的方法，该方法包括：
i)形成一分散体，该分散体包括水、难熔颗粒、至少一种成孔有机材料和一种聚合分散剂；
ii)向该分散体中以每克分散体为1-10×10-5摩尔的浓度加入一种水敏性环酯，形成混合物；
iii)将所述的混合物置入模具中；
iv)允许或促使所述的环酯水解，使混合物的粘度增加，并使其凝固并形成一生坯；
vii)从模具中移出所述的生坯；并且
iii)加热所述的生坯以除去水，并通过燃烧除去有机材料。
难熔颗粒可以从一很宽的金属和非金属范围内选取。这些颗粒可以是所谓的小比表面积、中等比表面积和大比表面积材料。这些表面积的代表值分别为大约0.1～20m2/g；20～200m2/g；200～1000m2/g。中等比表面积材料包括过渡性矾土、硅藻土和活化粘土。小比表面积颗粒的实例有α-氧化铝、莫来石、堇青石、熔化的硅石、氧化锆、二氧化钛；γ-氧化铝、一些碳、硅和铝的水合物如勃姆石、大水铝石和三水铝石是大比表面积材料的代表。其它材料是铜、锌、羟基碳酸盐；金属氧化物如氧化镍(可以还原成金属以提供镍海绵体)；硅铝石、碳化硅、氮化硅以及类似物。
聚合分散剂可以是适合于此目的的任何一种物质。其实例包括丙烯酸盐、聚丙烯酸酯和类似物。一个具体实例是聚丙烯酸胺。
优选地，成孔材料是颗粒状，其尺寸的选择决定了孔的大小。优选地，颗粒具有不同的尺寸和形状，这样易于互相连接。成孔材料可以从大量的天然或合成的有机物中选取。实例包括碳纤维或粉末；杏仁壳、椰子壳颗粒、橄榄石粉末、木粉、切碎的棉花纤维；切碎的聚酯纤维、尼龙、聚合物珠粒、硬脂酸盐、挤出物、聚苯乙烯或聚丙烯的颗粒；或类似物。成孔材料的含量和性质通常可用于控制基体的孔隙率和孔分布。
为了适合于本发明的目的，破稳剂必须能与其它成分形成基本上均匀的分散体，并且可在适当的时间内水解，形成成型体，该物体在生坯的状态下应足够硬以便从模具中脱模出来。
选择水解速率以便使可脱模的混合体在大约10分钟至数小时内形成。如果太慢，该项技术在工业上是不可接受的，如果太快，组合物会在浇铸过程中固化，缺陷就会在生坯内形成。
水敏性破稳剂可以从很宽范围的物质中选取。优选的试剂是一种酯，更优选的试剂是环酯，例如羧酸内酯和交酯。适合于本发明的可选物质包括：
特快反应剂，例如：δ-葡萄糖内脂、3，6-二甲基-1，4-二氧杂环己烷-3，5-二酮和其他的6元环内脂和交脂；
快速反应剂，例如：α-D-葡庚糖-γ-内脂、D-葡萄糖-6，3-内脂、L-古洛糖-γ-内脂、D-古洛糖-1，4-内脂、L-甘露糖-γ-内脂、D-赤糖酸-γ-内脂、α-羟基-γ-丁内脂、δ-戊内酯、α-当归内酯、以及其他五元环内脂，其侧链不超过3个甲基。
中速反应剂，例如：β-丁内酯和其他四员环内酯；
慢速反应剂，例如：全内酯、ε-己内酯、γ-丁内酯、γ-戊内酯、已及其他侧链为不超过3个甲基的高元环内酯。
反应剂浓度典型为大约每克分散体为1～10×10-5摩尔，优选为2～5×10-5摩尔。提高浓度将会缩短混合物固化的周期。
混合物的温度优选是降到环境温度以下，以减缓水解速度，进而在加入反应剂后改进分散体的均匀性。加入破稳剂后，粘度开始上升。在较低温度下，粘度上升的速度非常慢。因为反应动力学常数较小。在较低的温度下工作(不宜太低否则系统中的水会结冰)使得在反应剂中以较长的时间混合。参考温度范围在大约0～20℃之间，在加入破稳剂之前温度优选在0～10℃之间。
混合阶段会混入空气。因此，若需要，此方法中可包括抽真空的步骤以除去混合过程中带入的空气泡。
一个优选的实施方案中，在将组合物浇入到模具后进行混合和清除空气。由此，可以由可铸模的组合物形成模品，然后将其从模具中脱模出来。
另一个优选的实施方案中，所述的方法包括了加热混合物以加快水解速度的后续步骤。在控制方式下加热，将促使进一步水解，粘度上升，从而促进模制品的生成。
形成的陶瓷基体的表观孔隙率优选在20％至70％的范围内，这取决于具体的应用。
另一个优选的实施方案中，加热除去水并通过燃烧除去成孔材料以烧结陶瓷基体。
本发明的一个优点是，复杂形状的基体可以用简单的方法生产。复杂的形状增加了几何表面积。这种性质可以在大量的工业过程中得到良好的应用。例如，基体可以用于装载催化剂，由于高催化剂金属负载可使基体高效，提高几何表面积和减少气流阻力。一项具体的用途是作为催化剂的载体，催化活性组分被导入载体的孔内和外表面。清洗涂层技术可能被应用。隔离剂和/或促进剂也可以同时引入。本发明多孔陶瓷基体的其它用途是两相陶瓷颗粒/陶瓷基体的组合物的预加工；通风扩散板；气液过滤器；交叉流微过滤元件；以及类似物。
此处所用的术语“催化活性组分”是指一种金属或化合物，在形成或还原时或在活化状态下具有催化活性。术语“隔离剂”是指一种有助于稳定金属催化剂的细小微晶的物质，例如，通过阻止这些颗粒积聚，而术语“促进剂”是指一种使催化剂具有与无促进剂时不同的选择性的物质，例如通过抑制不利的副反应，如结焦进行等。
本发明方法的另一个具体的优点在于，试剂损失最少，与其他沉淀或浸渍方法相比较，活性相几乎专门限定于基体孔内。
多孔载体可以用酸或碱进行预处理，以改善催化活性材料与孔壁的相互作用。壁表面可以在加入活性相之前，通过增加“隔离剂/载体”材料如在陶瓷基体孔内的氧化铝得到改善。这可以通过将多孔基体简单浸渍在“隔离剂/载体”材料如硝酸铝的溶盐中，或使用均匀沉淀技术来完成。用任一种方法，浸渍的陶瓷基体的烧结温度都必须严格控制，以得到所需的表面性质。
优选在多孔陶瓷载体中置入活性相。基体优选在真空中条件下，浸渍在含有所需的催化组分和可水解材料的可溶盐溶液中。陶瓷基体随后从溶液中取出，并排水。排水后，将陶瓷基体加热至合适温度，以控制水解材料的水解，因此，可提高被吸收的溶液的PH值，并导致孔内不溶氧化物的沉积。这有效地阻止了孔的进一步浸渍。
催化剂的金属负载可以通过重复上述步骤来增加。在重新浸渍催化剂之前，孔必须被打开。按照该方法的一个方面，孔可以通过孔内材料的热分解来打开。催化剂可选用水或弱碱溶液清洗，然后在合适的高温下干燥。所需金属负载的催化剂最终在大约450℃温度下烧结。
当基体由大比表面积的颗粒组成时，它可以用于形成催化剂泡沫，具有质量轻和高活性的优点。本发明的基体可以用于形成热交换器。
本发明通过以下实施例进行进一步的说明。
实施例1
将85g氧化铝(A16SG，Alcoa，Bauxite，Arkansas，72011，USA)，15g杏仁壳粉末(100目)，0.05g 4，5-二羟基-1，3-苯磺酸二钠盐一水合物，0.2ml氨水(35％NH3)，和25g水混合而制备悬浮液。悬浮液的PH值在9～10之间。在室温下放置2小时后，向悬浮液中混入1.0g(相当于4.5×10-5mol/g)D-古洛糖-1，4-内酯。然后将混合物浇入一塑料或金属模具中，在22℃下保持三小时。将其从模具中脱模卸出，干燥并且在1520℃烧结30分钟。生坯的密度为1.76g/cm3，而烧结后的密度为2.36g/cm3，相当于40％的孔隙率。
实施例2
将180g氧化铝(A16SG)，20g橄榄石粉末(颗粒尺寸为100目)，0.6g DISPEX A40(DISPEX是一个商标)，0.3ml氨水和50g水混合制备成一悬浮液，其PH值约为9.5，粘度小于1Pa.s。在室温下保持一小时后，悬浮液进一步与2.0g D-古洛糖-1，4-内酯混合1分钟，然后将混合物浇入橡胶模具中。2～3小时后，卸下固化的混合物，在室温下干燥1天，接着在40℃的炉子干燥两天以上。以4℃/min的升温速度，加热生坯至1520℃，并浸渍30分钟。烧结的物体具有35％的孔隙率。
实施例3
在一个含有适量的成型剂的模具中，用实施例1的配方制备如附图1中所示的柱状体10。该柱状体有一个主孔11，具有多边形状。所有的边或延伸12都是对称的。径向空间的分开的侧孔13基本是不规则的。这些孔(包括内部互联)的形状和空间排列是经过设计的用于增加几何表面积和改善气流的均匀性，同时保持基体的机械强度。形成体的堆积密度为0.9g/cm3。几何表面积比相同尺寸的拉西环增加约55％，比沟槽环载体增加了约30％。
Claims (11)
1、一种制备多孔陶瓷基体的方法，该方法包括：
i)形成一分散体，该分散体包括水、难熔颗粒、至少一种成孔有机材料和一种聚合分散剂；
ii)向该分散体中以每克分散体为1-10×10-5摩尔的浓度加入一种水敏性环酯，形成混合物；
iii)将所述的混合物置入模具中；
iv)允许或促使所述的环酯水解，使混合物的粘度增加，并使其凝固并形成一生坯；
v)从模具中移出所述的生坯；并且
vi)加热所述的生坯以除去水，并通过燃烧除去有机材料。
2、根据权利要求1所述的方法，其中所述环酯的浓度为对每克分散体为2-5×10-5摩尔。
3.根据权利要求1或2所述的方法，其中所述的环酯是羧酸内酯或交酯。
4、根据权利要求1或2所述的方法，其中降低混合物的温度以减缓水解速度，并由此改善形成的组合物的均匀性。
5、根据权利要求1或2所述的方法，包括抽真空以除去由加入所述水敏性环酯的步骤带入的空气泡的步骤。
6.根据权利要求1或2所述的方法，其中调节孔成形材料的含量来控制基体的孔隙率。
7.根据权利要求1或2所述的方法，包括加热混合物以提高水解的速率的后续步骤。
8、一种制备催化剂的方法，其包括下列步骤：使用权利要求1-7任一项中所述的方法制备多孔陶瓷基体；和将催化剂颗粒装载至所形成的多孔陶瓷基体的孔内，或装载至所形成的多孔陶瓷基体的孔内和外表面上。
9、根据权利要求8所述的方法，其中所述的多孔陶瓷基体由具有小比表面积的颗粒制成。
10.根据权利要求1或2所述的方法，其中所述的多孔陶瓷基体由具有大比表面积的颗粒制成。
11.根据权利要求8所述的方法，其中所述的多孔陶瓷基体由具有大比表面积的颗粒制成。
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| GB9825109.3 | 1998-11-16 |
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| CN1262517C true CN1262517C (zh) | 2006-07-05 |
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| JP2004516214A (ja) | 2000-12-21 | 2004-06-03 | コーニング インコーポレイテッド | 溶融シリカ製造炉のための耐火物 |
| US6872677B2 (en) * | 2002-10-02 | 2005-03-29 | Oil Dri Corporation | Brick additives and methods for using same |
| KR100687695B1 (ko) * | 2003-02-12 | 2007-02-27 | 도아고세이가부시키가이샤 | 다공성 세라믹의 제조 방법 |
| FR2873685B1 (fr) * | 2004-07-28 | 2007-06-22 | Saint Gobain Ct Recherches | Procede d'obtention de ceramiques poreuses |
| ATE518575T1 (de) * | 2004-12-31 | 2011-08-15 | Fiat Ricerche | Herstellung eines filterelements zur beseitigung von feststoffpartikelemissionen |
| EP1785408A1 (fr) * | 2005-11-15 | 2007-05-16 | L'AIR LIQUIDE, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | Procédé d'élaboration de supports poreux céramiques de microstructure contrôlée |
| FR2896797B1 (fr) | 2006-02-01 | 2008-08-08 | Saint Gobain Ct Recherches | Mousse ceramique en carbure de silicium recristallise impregnee. |
| CA2728253C (en) | 2008-06-13 | 2015-04-07 | Saint-Gobain Abrasives, Inc. | Self-bonded foamed abrasive articles and machining with such articles |
| CN101745432B (zh) * | 2008-12-03 | 2011-06-29 | 中国科学院金属研究所 | 一种湿化学制备max相多孔催化剂载体材料的方法 |
| CH702511A1 (fr) | 2010-01-13 | 2011-07-15 | Haute Ecole Du Paysage D Ingenierie Et D Architecture Hepia | Module pour vegetaliser des surfaces. |
| WO2014186769A1 (en) * | 2013-05-17 | 2014-11-20 | Uram Stuart | Molds for ceramic casting |
| US10525448B2 (en) | 2015-07-22 | 2020-01-07 | Basf Corporation | High geometric surface area catalysts for vinyl acetate monomer production |
| FR3071248B1 (fr) | 2017-09-19 | 2020-09-25 | Saint Gobain Ct Recherches | Mousse ceramique |
| FR3124181B1 (fr) | 2021-06-17 | 2024-03-29 | Saint Gobain Ct Recherches | Procédé de fabrication d’une mousse céramique frittée |
| FR3130794A1 (fr) | 2021-12-17 | 2023-06-23 | Saint-Gobain Centre De Recherches Et D'etudes Europeen | Mousse céramique à dispersion de taille de cellules réduite |
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| GB1109140A (en) * | 1964-10-21 | 1968-04-10 | Sanyo Chemical Industry Compan | Soil treating composition and process |
| JPS59137376A (ja) * | 1983-01-26 | 1984-08-07 | 九州耐火煉瓦株式会社 | 自硬性耐熱組成物 |
| GB8510143D0 (en) * | 1985-04-20 | 1985-05-30 | Foseco Trading Ag | Pouring tubes |
| DE3826220A1 (de) * | 1988-08-02 | 1990-02-08 | Hoechst Ceram Tec Ag | Verfahren zur herstellung keramischer formkoerper |
| GB9409258D0 (en) * | 1994-05-10 | 1994-06-29 | Dytech Corp Ltd | Production of ceramic articles |
| SE515393C2 (sv) * | 1995-10-03 | 2001-07-23 | Skf Nova Ab | Sätt att forma kroppar av en uppslamning av pulver i vatten med ett irreversibelt gelbildande protein |
| GB2317887A (en) * | 1996-10-04 | 1998-04-08 | Dytech Corp Ltd | Porous ceramic articles; bone cell growth and drug carriers |
| US5746957A (en) * | 1997-02-05 | 1998-05-05 | Alliedsignal Inc. | Gel strength enhancing additives for agaroid-based injection molding compositions |
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1998
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1999
- 1999-11-15 ES ES99954257T patent/ES2190268T3/es not_active Expired - Lifetime
- 1999-11-15 AU AU10669/00A patent/AU1066900A/en not_active Abandoned
- 1999-11-15 CN CN99813369.8A patent/CN1262517C/zh not_active Expired - Fee Related
- 1999-11-15 BR BR9915169-3A patent/BR9915169A/pt not_active Application Discontinuation
- 1999-11-15 DE DE69905610T patent/DE69905610T2/de not_active Expired - Lifetime
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- 1999-11-15 US US09/831,953 patent/US6617270B1/en not_active Expired - Lifetime
- 1999-11-15 GB GB9927001A patent/GB2343675A/en not_active Withdrawn
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| GB9927001D0 (en) | 2000-01-12 |
| DE69905610T2 (de) | 2003-10-02 |
| EP1140731A2 (en) | 2001-10-10 |
| GB2343675A (en) | 2000-05-17 |
| AU1066900A (en) | 2000-06-05 |
| GB9825109D0 (en) | 1999-01-13 |
| CN1332708A (zh) | 2002-01-23 |
| WO2000029353A2 (en) | 2000-05-25 |
| ATE233232T1 (de) | 2003-03-15 |
| BR9915169A (pt) | 2001-08-14 |
| EP1140731B1 (en) | 2003-02-26 |
| DE69905610D1 (de) | 2003-04-03 |
| US6617270B1 (en) | 2003-09-09 |
| ES2190268T3 (es) | 2003-07-16 |
| WO2000029353A3 (en) | 2000-10-05 |
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