CN101243025A - 用于脱脂陶瓷蜂窝的改进方法 - Google Patents
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Abstract
采用改进的方法,通过使挤出蜂窝的每个末端与具有不大于外壁透气性的构件接触,从陶瓷蜂窝中除去有机添加剂,所述构件基本覆盖末端,并且加热蜂窝至足以除去有机添加剂的温度。
Description
技术领域
本发明涉及陶瓷蜂窝的形成。本发明特别涉及从挤出陶瓷蜂窝中除去有机粘合剂和添加剂的改进方法。
背景技术
为形成可用于如催化转化器和柴油微粒过滤器(DPFs)应用的陶瓷蜂窝,将陶瓷微粒前体与有机添加剂(例如粘合剂和润滑剂)和液体介质混合,所述液体介质通常为水,以形成塑料材料。然后挤出该塑料材料以形成蜂窝形状,然后将其干燥以除去水。然后加热干燥的蜂窝以除去有机添加剂。除去有机添加剂后,将蜂窝加热到更高的温度以熔化陶瓷晶粒,从而使蜂窝具有可用于催化转化器或DPF的机械整体性(mechanical integrity)和微结构。
用于除去有机添加剂的加热通常在空气或含氧的气氛中进行。然而,有机添加剂总是显示出与其氧化相关的放热反应,其通常导致由局部热梯度引起的坯体(body)开裂。
为避免该类开裂,使用惰性气氛或低含氧气氛(亦即,小于空气的氧含量)(请参见,例如美国专利Nos.6,099,793和6,287,509)。然而,使用该气氛倾向于更慢地除去有机添加剂,并留下有害的含碳残留,其经常妨碍高温下陶瓷晶粒的熔化或导致不希望出现的微结构,如作为缺陷的大孔。
另一种解决方法是使空气、含氧的气氛或其他气氛通过蜂窝以最小化与有机添加剂的氧化相关的热梯度(请参见,例如美国专利No.4,927,577)。该方法昂贵复杂,并且在蜂窝变长时变得更低效。
更近期的解决办法涉及使用两种或两种以上的有机粘合剂,其中一种使用用于其中一种粘合剂的液体进行后续萃取,第二种粘合剂通过使用公知的加热方法如刚刚描述的那些加热方法的一种(请参见,例如美国专利公开No.2004/0079469)加热除去。该方法也复杂,并且需要在其中一种粘合剂的液体萃取过程中处理更易碎的部分。
因此,提供解决现有技术的一个或多个问题(如上述那些问题之一)的形成方法和陶瓷材料是所需的。
发明内容
本发明涉及从陶瓷蜂窝中除去有机添加剂的方法,所述蜂窝具有外壁和从蜂窝的一端延伸到另一端的槽,其中所述槽定义为末端之间许多交错的薄间壁。
a)使挤出蜂窝的每个末端与具有不大于外壁透气性的构件(member)接触,所述构件基本覆盖末端
b)加热蜂窝至足以除去有机添加剂的温度。
令人惊讶的,使用该构件可在氧化气氛如空气中快速从挤出陶瓷蜂窝中除去有机添加剂,而不引起蜂窝的开裂。
例如,可使用该方法制备用作过滤器、热交换器、耐火材料、热和电绝缘器、金属或塑料复合材料体补强、催化剂和催化剂载体的陶瓷蜂窝。
附图说明
图1:对在空气中加热的、两个末端都被基本不透气的板覆盖的蜂窝,由***中间和边缘槽内同一深度的热电偶测定的在蜂窝的中间和边缘的槽内的温度图(实施例)。
图2:对在空气中加热的、一个末端不被覆盖的蜂窝,由***中间和边缘槽内同一深度的热电偶测定的在蜂窝的中间和边缘的槽内的温度图(对比实施例)。
图3:在每个末端都具有板(实施例)和一个末端没有板(对比实施例)的加热炉内在空气中加热的、包含有机粘合剂的蜂窝内,从中央槽到边缘槽的温度差(边缘槽温度减***槽温度)图。
本发明详述
本发明涉及从陶瓷蜂窝中除去有机添加剂的方法。该陶瓷蜂窝可为任意本技术领域公知的使用陶瓷粉和有机添加剂形成的陶瓷蜂窝。示例的陶瓷蜂窝为下述或由加热下述得到的那些:氧化铝、氧化锆、钛酸铌、碳化硅、氮化硅和氮化铝、氮氧化硅和氮碳化硅、莫来石、堇青石、β锂辉石、钛酸铝、硅酸铝锶、硅酸铝锂或其组合。优选的陶瓷蜂窝为下述或由下述得到的那些:碳化硅、堇青石、莫来石或其组合。碳化硅优选为美国专利No.US 6,669,751B1和WO公开EP1142619A1、WO 2002/070106A1中描述的一种。WO 2004/011386A1、WO 2004/011124A1、US 2004/0020359A1和WO 2003/051488A1描述了其它合适的陶瓷蜂窝。
陶瓷蜂窝优选由具有针形微结构的莫来石得到的一种。该蜂窝的例子包括美国专利Nos.5,194,154、5,173,349、5,198,007、5,098,455、5,340,516、6,596,665和6,306,335,美国专利申请公开2001/0038810,和国际PCT公开WO 03/082773描述的那些。
除去的有机添加剂可为任意本领域公知的可用于成形如本领域公知的那些陶瓷蜂窝坯体的有机添加剂。广泛地,有机添加剂可为下述的一种或多种:表面活性剂、润滑剂、粘合剂、溶剂、增塑剂、抗氧化剂、防腐剂、起泡和消泡剂,如Introduction to the Principles of Ceramic Processing,J.S.Reed,John Wiley和Sons,New York,NY,1988的9-12章所述。
特别地,有机添加剂包括有机粘合剂,如一种或多种美国专利Nos.4,001,028、4,162,285、4,929,575、5,286,767、5,344,799、5,568,652、5,925,308、6,080,345、6,241,940和6,680,101描述的那些。在特定的具体实施方式中,有机粘合剂为甲基纤维素、乙基羟乙基纤维素、羟丁基纤维素、羟丁基甲基纤维素、羟乙基纤维素、羟甲基纤维素、羟丙基纤维素、羟乙基甲基纤维素、羧基甲基纤维素钠或其混合物。优选地,纤维素粘合剂为如并入本文作为参考的美国专利No.5,568,652第5栏的49-67行和第6栏的1-21行所述的纤维素粘合剂
陶瓷蜂窝可为任意形状、尺寸和维数,如通常在现有技术中用作媒介的催化剂载体或柴油微粒过滤器的那些。
当其与构件在每个末端接触时,可在接触之前干燥挤出陶瓷蜂窝,或可在挤出时接触。典型地,基本干燥挤出陶瓷蜂窝的液体介质,例如水。基本干燥液体介质,通常意味着已降低挤出蜂窝的可塑性,以致当发生变形时,蜂窝将在塑性形变很小时开裂,(例如,开裂前2%的形变)。典型地,当液体介质含量最大约为蜂窝体积(不包括蜂窝槽体积)的5%时将会如此。
接触(接触构件(contacting member))蜂窝末端的构件可以任意有用的排列安置。例如,蜂窝可垂直或水平取向,用构件接触末端,以使每个末端基本被覆盖。基本被覆盖意味着至少约90%的槽被构件覆盖。优选地,至少约95%,更优选地,至少约98%,最优选地,所有槽均被构件覆盖。
已发现,当在加热以除去有机添加剂的过程中,在蜂窝的每个末端使用具有不大于蜂窝外壁透气性的接触构件时,在有机粘合剂氧化(烧毁)过程中,从蜂窝的中央到蜂窝的边缘的最大温度差基本减小。例如,在燃尽过程中,在对应槽内的相同深度(并且所有其他条件相同),蜂窝的中央和蜂窝的边缘之间的最大温度差减小,例如,当在加热时使用活性气氛除去有机粘合剂的过程中使用板时,减小至少50%,更通常减少70%。令人惊讶地,在有机粘合剂烧毁的过程中,中央的温度甚至可比边缘的温度低,而对于不具有与两个末端接触的该构件的蜂窝,出现相反的结果。
重申,接触构件具有不大于蜂窝外壁的透气性。然而,接触构件的透气性,可具有任意小于外壁的透气性至无透气性。应理解接触构件的透气性是在穿过接触构件的方向上测定的透气性,其中所述接触构件在蜂窝槽方向上。
所述接触构件可以用足以制造具有前述透气性和抵御除去蜂窝内的有机添加剂所必须的加热过程中的温度能力的构件的任意材料制备。合适的材料包括陶瓷和金属。
当使蜂窝与接触构件接触时,除维持接触关系所必须的力之外,不需要任何其它力。例如,重力足以维持在蜂窝末端下面和上面的板。
将接触的蜂窝加热至足以除去有机添加剂的温度。可使用任意合适的加热源进行加热,如本领域公知的那些加热源。例子包括对流,辐射,微波,射频(RF)及其组合。
加热时的气氛可为任意可用于除去有机添加剂的气氛。例如,该气氛可为惰性或活性。然而,当气氛为与有机添加剂反应的一种气氛(如氧化气氛)时,该方法尤其适合。气氛的例子包括氮气、稀有气体、氧气或其组合。优选的气氛为空气。典型地,有机添加剂在约200℃时开始氧化,在空气中400℃可基本除去有机添加剂,但可能需要更高的温度以除去,例如,残留的碳。无需不当反应,开始除去和基本除去有机添加剂的温度可通过本领域的一种普通技术测定。
可以可除去有机添加剂而不损害蜂窝的任意一个或多个加热速率进行加热,如本领域公知的或可由本领域通用技术的一种测定的那些。
具体实施方式
实施例和对比实施例
将包括同样的氧化铝、粘土和有机粘合剂的挤出干燥的陶瓷蜂窝置于同样的两立方尺空气对流烘箱中,并使用表1所示的加热工序同时加热。
表1:加热工序
温度(C) | 升温速率(Ramp rate)(C/hr) | 时间(hr:min) | 时间(hr) |
0-400 | 15 | 26:42:00 | 26.7 |
400-650 | 30 | 8:18:00 | 8.3 |
650-980 | 50 | 6:36:00 | 6.6 |
980 | 0 | 4:00:00 | 4 |
980-300 | 90 | 7:34:00 | 7.56 |
蜂窝为相同尺寸5.66″×6″的长蜂窝,其每平方英寸具有200个孔(cells)。每个蜂窝均垂直取向,其末端被置于ADS-96R氧化铝板上,该板购自Coorstek Inc.,Golden,CO,密度为3.96g/cm3,无透气性,并使用0.05英寸的厚度,整个覆盖底端。一个蜂窝(实施例)具有置于剩余的末端顶部之上,整个覆盖顶端的另一氧化铝板。
将热电偶置入边缘槽(接近外壁)约1.5英寸深,并以同样的深度置入中央槽。
在有机粘合剂氧化(烧毁)开始时,如图2所示,在约10小时(600分钟),对应于约200℃的烘箱温度时,无板时蜂窝中央的温度基本大于具有置于每个末端上的氧化铝板的同样蜂窝的温度上升(图1)。同样地,从蜂窝的中央到边缘的温度差如图3所示。
图3表明,没有板覆盖顶端的对比实施例,得到了最大温度差,其中中央比边缘热约230℃,而当使用氧化铝板完全覆盖两端时,中央实际上更冷约50℃。当冷却后从加热炉移开时,对比实施例裂成三块而实施例不然,在切开实施例蜂窝后,可观察到无残留碳。
Claims (12)
1、一种从陶瓷蜂窝中除去有机添加剂的方法,所述蜂窝具有外壁和从蜂窝的一端延伸到另一端的槽,其中所述槽定义为末端之间许多交错的薄间壁,
a)使挤出蜂窝的每个末端与具有不大于外壁透气性的构件接触,所述构件基本覆盖末端,和
b)加热蜂窝至足以除去有机添加剂的温度。
2、根据权利要求1所述的方法,其中在氧化气氛中进行加热。
3、根据权利要求2所述的方法,其中氧化气氛为空气。
4、根据权利要求1所述的方法,其中构件为陶瓷或金属。
5、根据权利要求3所述的方法,其中构件为陶瓷。
6、根据权利要求1所述的方法,其中构件基本没有透气性。
7、根据权利要求1所述的方法,其中构件为板。
8、根据权利要求1所述的方法,其中在槽内大约相同的深度,从中间的槽到蜂窝***的槽的最大温度差,较之在氧化有机添加剂的温度范围内,没有板覆盖两端的蜂窝的温度至少小50%。
9、根据权利要求8所述的方法,其中温度差至少小70%。
10、根据权利要求1所述的方法,其中在有机添加剂氧化的温度范围内,在蜂窝中间的槽内的温度较之在蜂窝***的槽,具有更低的温度。
11、根据权利要求1所述的方法,其中有机添加剂包括有机粘合剂。
12、根据权利要求11所述的方法,其中有机粘合剂为甲基纤维素、乙基羟乙基纤维素、羟丁基纤维素、羟丁基甲基纤维素、羟乙基纤维素、羟甲基纤维素、羟丙基纤维素、羟乙基甲基纤维素、羧基甲基纤维素钠或其混合物。
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EP1919844B1 (en) | 2010-02-17 |
BRPI0615956A2 (pt) | 2011-05-31 |
US20070045911A1 (en) | 2007-03-01 |
ES2339164T3 (es) | 2010-05-17 |
ZA200801157B (en) | 2009-08-26 |
JP5129137B2 (ja) | 2013-01-23 |
RU2008110950A (ru) | 2009-09-27 |
CA2619598A1 (en) | 2007-10-04 |
CA2619598C (en) | 2013-05-14 |
EP1919844A2 (en) | 2008-05-14 |
KR101360630B1 (ko) | 2014-02-07 |
ATE457965T1 (de) | 2010-03-15 |
JP2009505933A (ja) | 2009-02-12 |
US7635446B2 (en) | 2009-12-22 |
DE602006012331D1 (de) | 2010-04-01 |
CN101243025B (zh) | 2011-05-18 |
RU2420492C2 (ru) | 2011-06-10 |
KR20080038171A (ko) | 2008-05-02 |
WO2007111633A2 (en) | 2007-10-04 |
WO2007111633A3 (en) | 2008-02-28 |
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