CN104475014A - 含活性炭的涂覆基材的制备和使用方法以及由此制得的产品 - Google Patents
含活性炭的涂覆基材的制备和使用方法以及由此制得的产品 Download PDFInfo
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- CN104475014A CN104475014A CN201410549001.1A CN201410549001A CN104475014A CN 104475014 A CN104475014 A CN 104475014A CN 201410549001 A CN201410549001 A CN 201410549001A CN 104475014 A CN104475014 A CN 104475014A
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
本发明涉及含活性炭的涂覆基材的制备和使用方法,以及由此制备的产品。
Description
分案申请说明
本申请系申请日为2010年04月14日、国际申请号为PCT/US2010/031020、进入中国国家阶段后的国家申请号为201080018141.6、题为“含活性炭的涂覆基材的制备和使用方法以及由此制得的产品”的发明专利申请的分案申请。
相关申请的交叉参考
本申请要求于2009.04.20提交的美国申请第12/426,486号的优先权。
技术领域
本发明涉及含活性炭的涂覆基材的制备和使用方法,以及由此制备的产品。
背景技术
可使用含活性炭的成形主体,例如蜂窝体,作为催化剂基材,或者作为用来从流体,例如气流或液流中俘获微粒、液体或气体物质的吸附剂/过滤器。例如,可使用所述成形主体作为吸附剂,用来从气流俘获重金属。
传统上,包含活性炭的成形主体可以通过以下方式制备:首先对未加工的或者“生坯”成形主体进行一次或多次热处理,并且/或者然后对所述处理过的成形主体进行一次或多次受控制的氧化烧制。例如,可以通过以下方式制造蜂窝体:对合成树脂源进行挤出,然后进行烧制,使其碳化和活化。所述蜂窝体可以任选地用硫和/或催化剂进行浸渍。尽管这些传统的方法是令人满意的,但是特别在一些实施方式中,具有一些其它的用来制造含活性炭的成形主体的方法可能是有益的。
本发明人现已发现另外一些含活性炭的涂覆基材和成形主体的新颖的制造和使用方法,以及由此制得的产品。
发明概述
根据本发明的详述以及本文所述的各种示例性的实施方式,本发明涉及包含活性炭的涂覆基材和成形主体的制备和使用方法,以及由此制得的产品。在各种实施方式中,本发明涉及制备包含活性炭的基材的制备方法,所述方法包括,对至少一个基材施涂至少一种吸附剂材料,其中所述吸附剂材料包含活性炭。各种实施方式还涉及一些方法,其中所述涂覆基材可以成形,可以进一步造型为成形主体。本发明还涉及含活性炭的成形主体,涉及使用本文所述的包含活性炭的涂覆基材和成形主体从流体流中吸附至少一种重金属。
附图简要说明
包括的附图提供了对本发明的进一步理解,附图被结合在本说明书中并构成说明书的一部分。附图不是用来对要求保护的本发明构成限制,而是用来图示本发明的实施方式,与说明书一起用来解释本发明的原理。
图1是根据本发明一个实施方式的示例性涂覆基材的截面的SEM显微照片。
图2是根据本发明的一个实施方式制造涂覆和成形的基材的一种示例性方法的示意图;
图3是根据本发明的一个实施方式使用涂覆和成形的基材制造含活性炭的成形主体的一种示例性方法的示意图。
发明详述
应理解,前面的一般性描述和以下的详细描述都只是示例和说明性的,不构成对要求保护的本发明的限制。本领域技术人员通过研究说明书和实施本文所述的本发明将会明显看出本发明的其它实施方式。
本发明涉及含活性炭的涂覆基材以及成形主体的制备方法。在各种实施方式中,所述方法包括对至少一个基材施涂至少一种吸附剂材料,还可以包括对所述涂覆基材进行成形,还可以包括形成成形主体。
如本文所述,所述至少一种吸附剂材料包括活性炭。在各种实施方式中,所述活性炭的形式是例如活性炭粉末、颗粒状活性炭或其组合。在至少一个实施方式中,示例性的活性炭颗粒包括中值粒径未1-100微米的那些。在另一个示例性实施方式中,所述活性炭是中孔与微孔之比约为0.5的活性炭粉末。在另一个实施方式中,所述活性炭的形式是连续的不间断的碳结构。所述连续结构可以通过以下方式获得,例如通过本领域已知的方法,通过碳化将含碳的合成聚合物物质转化为连续的碳结构,然后对该连续的碳结构进行活化。
在各种示例性的实施方式中,所述至少一种吸附剂材料还可以包含:硫,其为任意的氧化态,可以为元素硫或者包含硫的化合物或部分;以及/或者金属催化剂,其为任意的氧化态,例如元素金属或包含金属的化合物或部分。
硫可包括任何氧化态的硫,包括元素硫(0)、硫酸盐(+6)、亚硫酸盐(+4)和硫化物(-2)。如本文中,术语“硫”包括元素硫或者以化合物或部分存在的硫。本领域技术人员可以很容易地确定吸附剂材料中存在的硫的量,可以根据例如具体的金属催化剂(如果存在话)、该吸附剂预期的用途、以及吸附剂所需的污染物去除能力和效率来选择硫的量。在一些实施方式中,所述吸附剂材料可以包含1-20重量%的硫,例如1-15重量%,3-8重量%,2-10重量%,0.1-5重量%,或者2-5重量%的硫。因此,硫的重量百分数是以元素硫为基准计算,为计算吸附剂材料中总硫量,将其他状态的硫转化为元素态。
所述金属催化剂可以包含处于任意氧化态的任意金属元素,可以为元素金属或者包含所述金属的化合物或部分,其所处的形式能够加速从与吸附剂材料接触的流体中除去任意程度的污染物(例如镉,汞,铬,铅,钡,铍,镍,钴,钒,锌,铜,锰,锑,银,铊,砷或硒)。元素金属的非限制性例子包括碱金属、碱土金属、过渡金属、稀土金属(包括镧系元素)以及其它的金属,例如铝、镓、铟、锡、铅、铊和铋。
如上文所述,所述金属催化剂可以以任意的价态存在。例如,如果包含铁,则铁可以+3、+2或0价或以不同价态的混合物存在,并且可以金属铁(0)、FeO、Fe2O3、Fe3O8、FeS、FeCl2、FeCl3、FeSO4等存在。另一个例子是,如果存在锰,则锰可以+4,+2或0价或以不同价态的混合物存在,并且可以金属锰(0)、MnO、MnO2、MnS、MnCl2、MnCl4、MnSO4等存在。
在本发明的一些实施方式中,所述金属催化剂是碱金属,例如锂、钠或钾。在其它的实施方式中,所述金属催化剂是碱土金属,例如镁、钙或钡。在其它的实施方式中,所述金属催化剂是过渡金属,例如铂、钯、银、金、锰或铁。在另外的实施方式中,所述金属催化剂是稀土金属,例如铈。在一些实施方式中,所述金属催化剂是元素形式。在其它的实施方式中,所述金属催化剂以金属硫化物的形式存在。在其它的实施方式中,所述金属催化剂以过渡金属硫化物或氧化物的形式存在。在其它的实施方式中,所述吸附剂主体包含除碱金属、碱土金属或过渡金属或除金属氧化物以外的至少一种催化剂。在其它的实施方式中,所述吸附剂材料包含除以下金属以外的至少一种催化剂:钠、钾、镁、钙、铝、钛、锆、铬、镁、铁和/或锌。在其它的实施方式中,所述吸附剂材料包含除以下金属以外的以元素形式或硫酸盐形式的至少一种金属催化剂:铝、钒、铁、钴、镍、铜或锌。
本领域技术人员可以很容易地确定吸附剂材料中存在的金属催化剂的量,可以根据例如具体使用的金属催化剂、该吸附剂材料预期的用途、以及吸附剂材料所需的污染物去除能力和效率来选择这些金属催化剂的量。在某些实施方式中,所述金属催化剂的量可以为吸附剂材料的1-25重量%,例如占吸附剂材料的1-20重量%,1-15重量%,2-18重量%,3-10重量%,3-5重量%,5-15重量%,或者5-10重量%。
金属催化剂的重量百分数是以元素金属为基准计算,为计算相关材料中金属催化剂的总量,将其他状态的任意金属转化为元素态。以惰性形式存在的金属元素,例如存在于无机粘合剂化合物中的惰性形式的金属元素不看作是金属催化剂,认为它们对金属催化剂的重量百分数没有贡献。可以使用任意合适的分析技术,例如质谱和LECO分析(例如用于硫)测定硫或金属催化剂的量。
在吸附剂中同时包含金属催化剂和硫的示例性实施方式中,金属催化剂的至少一部分可以任选地与至少一部分硫化学结合。在此处以及上下文中,术语“至少一部分”表示描述的材料的一部分或全部。因此,在这些示例性的实施方式中,吸附剂材料中的一部分或全部的金属催化剂可以与吸附剂中一部分或全部的硫化学结合。另外,在一些实施方式中,至少一部分的硫可以与活性炭中的至少一部分碳化学结合。
当金属催化剂与硫化学结合的时候,在一些实施方式中,所述吸附剂材料包含金属硫化物。示例性的金属硫化物包括锰、铜、钙、钯、钼、钨的硫化物,以及它们的组合。但是,金属硫化物中的金属元素不限于这些例子。例如,金属硫化物中的金属元素可选自碱金属、碱土金属、过渡金属、稀土金属(包括镧系元素)和其它金属,例如铝、镓、铟、锡、铅、铊和铋。
在某些实施方式中,所述吸附剂材料包含与硫结合的金属(例如金属硫化物),或者所述吸附剂材料包含与碳结合的硫,所述吸附剂材料还可以包含另外的硫,例如元素硫。在各种其它的实施方式中,至少一部分硫没有与金属催化剂结合,并且/或者至少一部分金属催化剂没有与硫结合。
在各种示例性的实施方式中,硫粉和/或催化剂前体可以与炭粉混合,然后在惰性气氛或还原性气氛中进行烧制。然后可以对制得的炭粉进行研磨,获得所需的粒度或者粒度均匀性。例如,在至少一个实施方式中,将炭粉与硫粉和催化剂前体(例如MnO2)混合,然后在300-900℃的温度下,在惰性气氛或还原性气氛中进行烧制。然后对制得的炭粉进行研磨,以获得更均匀的粒度。
在各种示例性的实施方式中,所述吸附剂材料还可以包含至少一种粘合剂。所述粘合剂可以是聚合物粘合剂,例如苯乙烯-丁二烯、聚氯乙烯、聚乙烯醇、聚乙烯基吡咯烷酮、聚氨酯、聚丙烯、聚四氟乙烯(PTFE)、环氧树脂、酚醛树脂以及其它的热塑性树脂和热固性树脂;可以是干聚合物粘合剂或可溶性粘合剂,例如聚偏二氟乙烯(PVDF)。虽然PVDF是可溶于N-甲基吡咯烷酮(NMP)之类的有机溶剂,但是还可以使用可溶于水的粘合剂。其它的有机粘合剂可以包括硅烷和纤维素粘合剂,例如羧甲基纤维素。所述粘合剂可以是源自无机溶胶-凝胶的,例如源自硅溶胶的SiO2,可溶性玻璃,例如硅酸钠或硅酸钾,以及它们的各种变体。在其它的实施方式中,还可以使用粘合剂的组合,包括有机粘合剂和无机粘合剂。
在各种实施方式中,所述吸附剂材料可以在液体介质中或者以干态的形式施涂。所述液体介质可以包括例如水、NMP、丙酮、异丙醇、甲醇、乙醇、乙腈、四氢呋喃(THF)、二甲氧基乙烷(DME)、碳酸二甲酯(DMC)以及碳酸丙二酯(PC)。在一些实施方式中,至少一种粘合剂可以溶于液体介质中。
本领域技术人员有能力制备施涂于基材的液体介质和/或干吸附剂材料。例如,可以将活性炭和催化剂和/或金属(如果存在的话)加入在溶液中包含至少一种粘合剂的液体介质中,或者悬浮在该介质中。再例如,对于干施涂,所述活性炭和催化剂、金属和/或粘合剂(当存在的时候)可以首先通过机械方法均质混合,或者以另一合适的方式均质混合,然后施涂于基材。
在制备吸附剂材料之后,可以将其施涂于至少一个基材。在本文中,“基材”及其变体是用来表示包括用来接受吸附剂材料的表面的材料。所述基材可以是有机材料、无机材料或金属质/金属材料,可以是多孔的或者非多孔的,并且是处理过的或者未处理过的。在各种示例性的实施方式中,所述基材可以是金属质的(例如金属箔,如铝箔),金属丝网或聚合物丝网,或者是纤维预成形体。用作基材的金属质和/或金属材料包括任意的金属、合金或金属互化物。非限制性的示例包括钢和铝。用作基材的纤维预成形体包括无机材料,例如玻璃纤维和石英毛(quartz wool),有机材料,例如纤维素纤维,以及由任意合成聚合物纤维(如聚乙烯和聚丙烯)制得的那些材料。
在各种示例性的实施方式中,所述基材的厚度可以为10-1000微米,例如其厚度可以为50-150微米。在至少一个实施方式中,所述基材的厚度可以为1-10密耳。所述基材以及基材厚度的选择可以取决于例如复杂的所需形状和耐久性要求,例如温度、寿命、湿度、环境和强度,对于任意特定的实施方式,本领域技术人员有能力根据这些因素以及任何其它的相关因素改变基材的材料和厚度。
在至少一个实施方式中,所述至少一个基材在施涂吸附剂材料之前是基本平坦的。在本文中,术语“基本平坦”是用来表示所述基材在宏观尺度上具有基本平的表面,凹陷或凸起很少或没有。在各种实施方式中,本文所定义的基本平坦的基材还可以在表面具有某种纹理或者使表面变粗糙,或者是多孔的。
在各种示例性的实施方式中,可以在将吸附剂材料施涂于至少一个基材的表面上之前,任选地对该表面进行处理。在至少一些实施方式中,所述基材处理可以改进吸附剂材料和基材之间的粘合。例如,所述处理可以包括在所述至少一个基材的一侧或两侧施涂粘合层。所述粘合材料可以包括例如炭黑和/或石墨,聚合物粘合剂,以及合成橡胶(例如异戊二烯基橡胶,例如聚异戊二烯,丁二烯基橡胶,例如顺-1-4-聚丁二烯,苯乙烯基橡胶,例如苯乙烯-丁二烯橡胶(SBR),腈橡胶,例如腈-丁二烯橡胶(NBR),氯丁橡胶,烯烃基橡胶,例如乙烯-丙烯橡胶,丙烯酸类橡胶,聚氨酯橡胶以及氟橡胶)。在各种实施方式中,所述粘合层可以包含水溶性聚合物和非水溶性粘合剂。
本领域技术人员有能力制备施涂于基材的粘合层材料。例如,在一个实施方式中,可以将炭黑和石墨加入溶液或悬浮液中,通过浸涂、凹槽辊涂覆、喷涂或另一可接受的方法施涂于基材。例如,在至少一个实施方式中,所述粘合层可以是美国密歇根州休伦港的艾奇逊化学品公司(Acheson Chemicals of PortHuron,MI)销售的商品名为DAG EB 012的商业油墨(包含2.5-12.5重量%的PVP,2.5-12.5重量%的炭黑,25-75重量%的石墨,以及交联的金属增粘剂)。
在另一个示例性的实施方式中,所述至少一个基材的一侧或两侧可以进行化学处理和/或机械处理。仅举例来说,一侧或两侧可以进行化学蚀刻或者用机械方法变粗糙,这样形成粗糙的表面,有助于在粘合层与基材之间,或者在吸附剂涂层和基材之间形成粘合。
在各种实施方式中,可以对至少一个基材施涂至少一种吸附剂材料。在本文中,术语“施涂”和“施涂的”以及它们的变化形式是用来表示将吸附剂材料置于至少一个基材上的方法,例如将吸附剂材料施涂在基材表面上,以及/或者对多孔基材进行浸渍。在各种实施方式中,所述吸附剂材料可以通过以下方式施涂:层压、带状浇铸、喷涂、浸涂、狭缝模头涂覆、辊涂、或者本领域技术人员已知的任意其它的技术。在各种示例性的实施方式中,所述吸附剂材料可以是液体介质的形式,可以通过浸涂法、喷涂法或辊涂法沉积,例如可以用包含活性炭颗粒的液体介质对无机纤维基材进行浸渍。在另一个示例性的实施方式中,所述吸附剂材料可以是干燥体系,其可以例如施涂于基材,然后在辊之间或者在平坦表面上通过,从而获得基材和涂层之间的紧密接触。在其它的示例性实施方式中,可以首先将吸附剂材料形成具有特定厚度的膜,然后压制到基材上,即进行层压。
在本文中,提到的在基材上的涂层以及/或者涂覆基材是用来包括施涂在基材上的材料以及/或者包括施涂的材料的基材,例如作为在非多孔基材表面上的层和/或注入或浸渍到多孔基材中的材料。
在各种实施方式中,所述吸附剂材料可以施涂在基材的一个侧面上。在另外的实施方式中,所述吸附剂材料可以施涂在基材的一个以上的侧面上。例如,可以将吸附剂材料施涂于基材的两个侧面上。在各种实施方式中,所述基材的任意一侧的吸附剂材料涂层的厚度可以至少为基材厚度的10%,例如至少50%,至少100%,至少200%,至少300%,至少400%,至少500%,或者至少600%。在本文中,吸附剂材料的厚度是从与吸附剂材料相邻的基材的表面测量的。例如,当用吸附剂材料浸渍基材的时候,吸附剂材料的厚度不包括位于基材的孔内的材料,而是从基材的表面进行测量。本领域技术人员有能力根据例如基材的一个或两个侧面是否进行了涂覆,以及体系的吸附能力要求,确定吸附剂材料的合适厚度。
图1是根据本发明一个实施方式的示例性的涂覆基材的截面的SEM显微照片。图1显示基材101,在该基材的两个侧面上施涂了吸附剂材料102,在基材和吸附剂材料之间插入了粘合层103。
在各种示例性的实施方式中,所述基材可以在施涂了涂层之后成形。在本文中,关于基材,术语“成形”以及其变化形式是用来表示对基材进行处理,从而引起基材结构中的变化。在至少一个实施方式中,所述涂覆基材可以通过一系列的辊,使得基材成形,例如引入各种变化形式,如波纹或起褶。在另一个实施方式中,可以在对基材进行成形之后施涂涂层,在另外的实施方式中,可以对制得的成形涂覆基材进行造型,以制备含活性炭的成形主体,例如用来从液体流吸附至少一种重金属。
图2是根据本发明的一个实施方式制造涂覆和成形的基材的一种示例性方法的示意图。在图2的示例性的方法中,料斗204容纳着半干态的吸附剂材料和粘合剂。使得吸附剂材料的膜通过垂直压延机205,以获得具有所需厚度的预成形膜202。然后,角度片206使得膜202弯折并将其引导到基材201A上,所述基材201A从一卷预涂覆粘合层的基材201同时拉出。将预形成膜202施加在基材201A的两侧,使其通过垂直压延机207,使得基材201A和预形成膜202之间紧密接触。张力辊208将涂覆基材201B引导到驱动辊209,驱动辊在张力下将涂覆基材201B拉出。然后使得涂覆基材201B通过压纹辊210,从而成形得到波纹双面涂覆的基材201C。最后,使用切割设备211将波纹基材201D切割成所需的尺寸。
在各种示例性的实施方式中,可以用本文中称作“增强材料”的至少一种材料对所述至少一个基材进行增强和/或使该材料具有机械稳定性。增强材料可以是有机材料、无机材料或金属质/金属材料,可以是多孔的或者非多孔的,并且是处理过的或者未处理过的。在各种示例性的实施方式中,所述增强材料可以是金属质的(例如金属箔,如铝箔),金属丝网或聚合物丝网,或者是纤维预成形体。用作增强材料的金属质和/或金属材料包括任意的金属、合金或金属互化物。非限制性的示例包括钢和铝。用作增强材料的纤维预成形体包括无机材料,例如玻璃纤维和石英毛,有机材料,例如纤维素纤维,以及由任意合成聚合物纤维(如聚乙烯和聚丙烯)制得的那些材料。所述增强材料可以在其上沉积至少一个基材之前或之后进行成形,在至少一个实施方式中,所述增强材料可以是独立式的。
在各种示例性的实施方式中,可以将至少一种增强材料与至少一个由无机材料和/或纤维材料组成的基材结合使用。例如,可以用金属丝网对玻璃纤维片组成的基材进行增强。在一个示例性的实施方式中,可以将用包含粘合剂的吸附剂材料浸渍的玻璃纤维片在湿时候沉积在金属丝网上。所述粘合剂可以粘附于丝网,将玻璃纤维片保持就位以及/或者保持所需的形状。
在各种实施方式中,所述涂覆基材可以在成形之后进一步造型。在本文中,术语“造型”及其变化形式是用来表示对涂覆的、任选成形的基材进行处理,以形成成形主体。在本文中,“成形主体”包括以任意方式构造的至少一个涂覆的、任选成形的基材,使得所述成形主体包括通道或通路并且/或者以其它的方式允许流体流从该主体流过,例如沿着平行于基材的方向流过所述主体。在本发明的各种实施方式中,所述成形主体可以由至少一个波纹涂覆基材组成。在另外的示例性实施方式中,所述成形主体可以由至少一个波纹涂覆基材以及至少一个基本平坦的涂覆基材组成。所述成形主体可以是蜂窝体结构,其包括入口端和出口端,以及从所述入口端延伸到所述出口端的内部通道。在至少一个示例性的实施方式中,所述蜂窝体结构可以通过对成形涂覆基材进行辊压或堆叠而获得。例如,可以对波纹涂覆基材进行辊压(例如在齿轮压延机上)或与基本平坦的涂覆基材组装,制得蜂窝体结构。再例如,可以在成形主体内,基材和另一基材之间,为涂覆基材提供间隔体或者其它的机械分隔体。
图3是根据本发明的一个实施方式使用涂覆和成形的基材制造含活性炭的成形主体的一种示例性方法的示意图。在图3的示意性方法中,将基本平坦的涂覆基材301B和波纹状涂覆基材301C(此二者都双面涂覆)叠置,形成更高级别的基础单元313。例如,可以将这些基础单元313结合或造型成棱柱形模块314A,或者卷成筒状模块314B。此二者都是蜂窝成形主体的例子。
在各种示例性的实施方式中,在形成成形主体之后,可以使用本领域技术人员已知的任何方法使得所述结构固定,例如通过使用至少一种粘合材料以及/或者至少一种机械接合器件。粘合材料的非限制性例子包括胶和环氧树脂。机械接合器件的非限制性例子包括螺钉,销钉和夹子。在一个示例性的实施方式中,可以用机械接合器件,例如螺钉来固定整个成形主体,例如可以使得单个螺钉穿透成形主体的所有的层并保持这些层。
在各种示例性的实施方式中,制造包含活性炭的涂覆基材和/或成形主体的方法可以按照辊到辊的方式连续进行,并且/或者以高速的方式进行,制得具有所需尺寸的吸附剂结构,包括例如大尺寸的蜂窝体。至少在一些实施方式中,由本发明的方法得到的所述连续和/或高速的制造能够比本领域已知的方法更经济地制造包含活性炭的基材和/或成形主体。
因为炭粉末在施涂之前活化,至少在本发明的一些实施方式中,不会出现与含活性炭的主体,特别是大尺寸蜂窝体相关的潜在的复杂性。例如,在各种实施方式中,可以将活性炭均匀地施涂于基材,制备均匀的涂层和/或不会产生裂纹。因此,本发明还涉及用来改进含活性炭的主体的抗裂纹性以及/或者减少裂纹数量的方法。在本文中,“均匀涂覆的”、“均匀涂层”以及它们的变体是用来表示在特定面积内存在基本均匀数量的碳颗粒。
在本发明的各种实施方式中,所述基材和成形主体可以用来从至少一种流体流吸附至少一种污染物。例如,流体流可以通过涂覆基材,或者通过成形主体的内部通路,所述基材或成形主体上的涂层作为流体流中存在的至少一种污染物的吸附剂。流体流的形式可以为气体或液体。气体或液体还可包含另一相,例如在气流或液流中的固体微粒,或者在气流中的液滴。在一个实施方式,流体流可以是气流,所述气流包括燃煤烟道气(例如来自烟煤和半烟煤类或褐煤),以及在煤的气化工艺中产生的合成气流。
在本文中,术语“吸附”及其变体表示通过物理方式和/或化学方式,用涂覆基材和/或成形主体吸附、吸附或以其他方式俘获至少一种污染物。在本文中,术语“污染物”及其变体包括重金属。术语“重金属”和本文中任何提到名称的具体金属包括金属的元素形式以及氧化态。
因此,重金属的吸附包括吸附元素形式的金属,以及吸附包含该金属的任何有机或无机化合物或组合物。重金属的非限制性例子包括镉、汞、铬、铅、钡、铍、镍、钴、钒、锌、铜、锰、锑、银、铊、砷、硒以及包含这些元素的化合物或组合物。
在本发明的各种实施方式中,本文所述的涂覆基材和成形主体能够从流体流吸附至少一种重金属。在至少一个实施方式中,所述重金属是汞。
在各种示例性的实施方式中,所述涂覆基材和/或成形主体能够吸附流体流中至少5%的至少一种重金属,例如流体流中至少10%,20%,30%,40%,50%,60%,70%,80%,90%的至少一种重金属。
除非另外说明,否则,说明书和权利要求书中使用的所有数值都理解为在所有情况下用术语“约”修饰,而不管是否确有“约”。也应理解,本发明说明书和权利要求书所用的精确数值构成本发明的附加实施方式。已尽力保证本文所揭示的数值的准确度。然而,任何测定的数值必然会含有由各种测定技术中存在的标准偏差所造成的某些误差。
本文所用的“该”、“一个”或“一种”表示至少“一个(一种)”,不应被局限为仅“一个(一种)”,除非有相反的明确说明。因此,例如“所述成形主体”或“一个成形主体”是用来表示至少一个成形主体。
本领域技术人员通过研究说明书和实施本文所述的本发明将会明显看出本发明的其它实施方式。本发明人认为本说明书仅是示例性的,本发明真正的范围和精神由所附权利要求书来限定。
实施例
实施例1
在异丙醇介质中,将包含7重量%的硫和7重量%的MnS的炭粉与PTFE聚合物粉末混合,所述聚合物粉末是以商品名DupontTM 销售的聚四氟乙烯(PTFE)613A,(由美国特拉华州威尔名顿市的杜邦聚合物公司(DuPontPolymers of Wilmington,Delaware)销售),碳与聚合物的重量比为90:10。然后所述粉末在100℃干燥,在室温下通过一组辊对其进行辊压,形成厚度约为12密耳的吸附剂材料带。将该吸附剂材料带层压在铝片的各个侧面之上,所述铝片厚度约为5密耳(125微米),并涂覆有炭黑和石墨的薄粘合层(厚度约为2-5微米)。这两根吸附剂材料带(厚度各为12密耳)完全包封所述铝片和粘合层,所述涂覆片材辊压通过一组钢辊,完成层压工艺。使得涂覆片材的部分辊压通过一组波纹辊,在片材中形成波纹。所述辊压和轧波纹速度大于1毫米/小时,在室温下进行。然后将所述波纹片材和其它的平坦片材叠置,形成上图3所示的蜂窝体结构。
该组装体显示可以通过该方法方便而快捷地制造高质量的蜂窝体结构。
实施例2
使用实施例1的方法制造蜂窝体结构,在150℃对其进行汞去除效率测试。使该样品处于汞浓度为12μg/m3的工业合成烟道气的条件下。所述样品表明在几天时间内的汞去除效率为90%。因此,通过本文所述的方法制造的蜂窝体基材能够有效地从气流除去汞。
实施例3
在本实施例中,用吸附剂材料对一层石英毛进行浸渍,所述石英毛层用作无机纤维基材,所述吸附剂材料包含活性炭粉末在有机溶剂中的悬浮液。所述活性炭粉末包含硫以及金属硫化物催化剂。制备了PVDF在NMP溶剂中的溶液,将活性炭粉末与该溶液混合,使得碳与PVDF的比例为10:1。然后将该悬浮液沉积在所述石英毛层上。所述悬浮液渗入所述多孔层。然后浸渍的基材在150℃干燥,以除去溶剂。该方法制得的基材包括与无机纤维结合的活性炭颗粒,从而增强了片材结构。然后将所述结构成形为所需的构型。在另一个实施方式中,所述构型还可以在干燥过程中形成。
实施例4
在本实施例中,将商业玻璃纤维绝热垫分离成厚度约为1/16英寸的片材。用吸附剂材料浸渍所述片材,所述吸附剂材料包含活性炭在水溶液中的悬浮液,所述水溶液包含由美国纽约州纽约市的普莱德材料国际有限公司(PredMaterials International,Inc.of New York,New York)的以商品名LHB 108 P销售的粘合剂。悬浮液中活性炭与粘合剂的比例维持在10:1。如以上实施例3所述,对玻璃纤维层进行浸渍,然后干燥,成形为所需的形状。用成形金属组成的增强材料对所述浸渍的玻璃纤维层的另一种样品进行增强,干燥形成刚性结构。
实施例3和4证明可以用粘合剂和活性炭、吸附剂材料对基于无机材料的片或层进行浸渍,以形成所需的结构。尽管实施例3和4所述的片材是多孔的,但是在其它的实施方式中,可以对非多孔性片材进行涂覆和成形,以形成所需的结构。
实施例5
在异丙醇介质中,将包含7重量%的硫和7重量%的MnS的吸附剂炭粉与PTFE聚合物粉末混合,所述聚合物粉末是以商品名DupontTM 销售的聚四氟乙烯(PTFE)613A,(由美国特拉华州威尔名顿市的杜邦聚合物公司(DuPont Polymers of Wilmington,Delaware)销售),碳与聚合物的重量比为90:10。然后对所述粉末进行干燥,通过一组辊对其辊压,形成厚度约为12密耳的带。将玻璃纤维垫基材夹在两根这样的带之间,并使其通过辊,对所述带和基材进行压缩。这样形成的复合带强度大,可以将该复合带调节到所需的结构形状。
实施例6
在本实验中,将商业玻璃纤维绝热垫分离成厚度约为1/16英寸的片材。用包含由美国纽约州纽约市的普莱德材料国际有限公司(Pred MaterialsInternational,Inc.of New York,New York)以商品名LHB 108 P销售的粘合剂的水溶液浸渍所述片材。然后将以上实施例5的碳带层压在该处处有粘合剂的玻璃纤维片上。制得的片材强度大,具有高的挠性,包含牢固结合到所述结构中的碳颗粒。
Claims (20)
1.一种制备含活性炭的涂覆基材的方法,该方法包括:
将至少一种包含活性炭的吸附剂材料施涂在至少一个基材的至少一个侧面上,形成涂覆基材;以及
对所述涂覆基材进行成形;
其中所述至少一种吸附剂材料包含元素硫和金属催化剂;并且
至少一部分金属催化剂与至少一部分元素硫化学结合,并且至少一部分元素硫没有与金属催化剂化学结合。
2.如权利要求1所述的方法,其特征在于,所述对涂覆基材进行成形的步骤包括使得涂覆的基材形成波纹。
3.如权利要求1所述的方法,其特征在于,所述至少一种吸附剂材料是通过以下方式施涂的:层压、带状浇铸、喷涂、浸涂、狭缝模头涂覆或辊涂。
4.如权利要求1所述的方法,其特征在于,所述至少一个基材的厚度为10-1000微米。
5.如权利要求1所述的方法,其特征在于,所述至少一个基材包含基本平坦的基材。
6.如权利要求1所述的方法,其特征在于,所述至少一种吸附剂材料还包含至少一种粘合剂。
7.如权利要求6所述的方法,其特征在于,所述至少一种粘合剂是可溶于水的粘合剂、源自无机溶胶-凝胶的粘合剂或其组合。
8.如权利要求1所述的方法,其特征在于,施涂在所述基材的至少一个侧面上的吸附剂材料的厚度至少为所述至少一个基材的厚度的10%。
9.如权利要求1所述的方法,所述方法还包括在施涂所述至少一种吸附剂材料之前对所述至少一个基材进行处理;
其中对所述至少一个基材进行处理的步骤包括以下的至少一种:
(a)在至少一个基材上施涂粘合层;以及
(b)对至少一个基材的表面进行化学处理和/或机械处理。
10.如权利要求1所述的方法,所述方法还包括由涂覆基材形成成形主体。
11.如权利要求10所述的方法,所述方法还包括使用至少一种粘合材料和/或至少一种机械接合器件固定所述成形主体。
12.如权利要求10所述的方法,其特征在于,所述成形主体是蜂窝体。
13.一种含活性炭的主体,其包括至少一个涂覆基材,
其中,所述至少一个涂覆基材由施涂在至少一个基材的至少一个侧面上以形成涂覆基材的至少一种吸附剂材料组成;
所述至少一种吸附剂材料包括活性炭、元素硫和金属催化剂;
至少一部分金属催化剂与至少一部分元素硫化学结合,并且至少一部分元素硫没有与金属催化剂化学结合。
14.如权利要求13所述的含活性炭的主体,其特征在于,所述含活性炭的主体经过成形。
15.如权利要求13所述的含活性炭的主体,其特征在于,施涂在所述基材上的吸附剂材料的厚度为所述至少一个基材的至少一个侧面的厚度的至少10%。
16.如权利要求13所述的含活性炭的主体,其特征在于,所述主体是蜂窝体。
17.如权利要求13所述的含活性炭的主体,其特征在于,所述至少一个基材的厚度为10-1000微米。
18.如权利要求13所述的含活性炭的主体,其特征在于,所述涂覆基材是波纹状的或者是基本平坦的。
19.如权利要求18所述的含活性炭的主体,其特征在于,所述主体包括至少两个波纹状涂覆基材;所述至少两个波纹状涂覆基材被叠置。
20.如权利要求18所述的含活性炭的主体,其特征在于,所述至少一个波纹状涂覆基材是辊压的。
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CN102405101A (zh) | 2012-04-04 |
US20100263533A1 (en) | 2010-10-21 |
US8598073B2 (en) | 2013-12-03 |
CN102405101B (zh) | 2014-11-19 |
WO2010123728A2 (en) | 2010-10-28 |
US8664154B2 (en) | 2014-03-04 |
EP2421642A2 (en) | 2012-02-29 |
TW201107033A (en) | 2011-03-01 |
WO2010123728A3 (en) | 2011-02-24 |
US20130281286A1 (en) | 2013-10-24 |
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