CN101287687A - 高比表面的碳化硅基催化载体与过滤器 - Google Patents
高比表面的碳化硅基催化载体与过滤器 Download PDFInfo
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- CN101287687A CN101287687A CNA2006800353312A CN200680035331A CN101287687A CN 101287687 A CN101287687 A CN 101287687A CN A2006800353312 A CNA2006800353312 A CN A2006800353312A CN 200680035331 A CN200680035331 A CN 200680035331A CN 101287687 A CN101287687 A CN 101287687A
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- oxide
- specific surface
- silicon carbide
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- 229910010271 silicon carbide Inorganic materials 0.000 title claims abstract description 35
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 16
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000011148 porous material Substances 0.000 claims abstract description 13
- 238000009826 distribution Methods 0.000 claims abstract description 11
- 230000002902 bimodal effect Effects 0.000 claims abstract description 8
- 229910052574 oxide ceramic Inorganic materials 0.000 claims abstract description 8
- 239000011224 oxide ceramic Substances 0.000 claims abstract description 8
- 230000008021 deposition Effects 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 13
- 239000000843 powder Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 230000001413 cellular effect Effects 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 150000004645 aluminates Chemical class 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000019580 granularity Nutrition 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 4
- 238000007789 sealing Methods 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000011230 binding agent Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 3
- 239000002283 diesel fuel Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000010970 precious metal Substances 0.000 claims description 3
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims description 3
- 239000002002 slurry Substances 0.000 claims description 3
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 239000004902 Softening Agent Substances 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 239000004411 aluminium Substances 0.000 claims description 2
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910052746 lanthanum Inorganic materials 0.000 claims description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 229910052814 silicon oxide Inorganic materials 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 abstract description 4
- 229910010293 ceramic material Inorganic materials 0.000 abstract 2
- 239000007789 gas Substances 0.000 description 20
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 8
- 239000006229 carbon black Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 4
- 229910052753 mercury Inorganic materials 0.000 description 4
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 229910002091 carbon monoxide Inorganic materials 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000007598 dipping method Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000008188 pellet Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 235000019587 texture Nutrition 0.000 description 2
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910001593 boehmite Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229960001866 silicon dioxide Drugs 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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Abstract
本发明涉及一种由多孔陶瓷材料构成的蜂窝状结构,所述结构的特征在于构成其结构的多孔陶瓷材料含有:50-95质量质量%碳化硅SiC、5-50质量%至少一种氧化物陶瓷相;所述结构的特征还在于空隙度高于10%,比表面高于0.5m2/g与至少双峰类型的孔径分布。本发明还涉及这样一种结构的生产方法以及在沉积催化剂后,使用这样一种结构得到的过滤器或催化载体。
Description
本发明涉及催化结构技术领域,它们特别地用于柴油机类型的内燃机排气管道中。优选地,本发明涉及催化过滤器,它们能够同时除去柴油燃料在柴油发动机中燃烧产生的污染气体和炭黑。
能处理来自柴油发动机的一些气体和除去一些炭黑的催化过滤器是本技术领域的技术人员熟知的。这些结构都往往具有蜂窝状结构,该结构的其中一个面能接收待处理的排出气体,另一个面能排掉已处理的排出气体。该结构在接收与排掉面之间还包括一组用多孔壁分开的、其轴彼此平行的邻接管道或管。这些管道在一端或另一端被封闭,以便限定入口沿着接受面开启的室与出口沿着排出面开启的室的范围。这些管按照一定顺序交替地被封闭,例如在通过该蜂窝体的过程中,这些排出气体被约束通过这些入口管侧壁,从而将这些出口管再连接。这样,这些颗粒或炭黑沉积并积累在过滤体的多孔壁上。
人们知道,在其使用期间,该颗粒过滤器经受一系列过滤段(炭黑累积)和再生段(除去炭黑)。这些过滤段时,该发动机放出的炭黑颗粒保留并沉积在该过滤器内。这些再生段时,这些炭黑颗粒在该过滤器被燃烧,从而使它恢复其过滤性能。
往往,这些过滤器是用多孔陶瓷材料,例如碳化硅制成的。
例如专利申请EP 816 065、EP 1 142 619、EP 1 455 923或WO2004/090294和WO 2004/065088描述了催化过滤器实例。
除了处理炭黑的问题外,以气相形式的污染排放物(即主要地氮氧化物(NOx)或硫氧化物(SOx)与一氧化碳(CO),甚至未燃烧的这些烃)转变成无害的气体(例如气态氮(N2)或二氧化碳(CO2))还需要进行补充处理。
为了在同一步骤过程中处理气态和固态污染物,试图使前面描述的颗粒过滤器具有催化功能。根据这些通常采用的方法,让该蜂窝结构浸渍含有催化剂或催化剂前体的溶液。
这样一些方法包括一般包括采用或者在含有溶于水(或其它极性溶剂)的催化剂前体或催化剂的溶液中,或者在催化颗粒水悬浮液中浸没方法的至少一个浸渍步骤。专利US 5 866 210描述了这样一种方法实例。
人们已知,这种浸渍方法可以分一个或多个步骤进行。这个或这些浸渍步骤的目的在于以这种方式使该催化剂尽可能最均匀地沉积在该结构中。
往往,这种催化剂含有活性组分,其中包括贵金属(Pt、Pd、Rh)和任选地稀土氧化物,例如铂与氧化铈混合物Pt/CeO2。根据在异质催化中熟知的一些技术,这种活性组分通常沉积高比表面氧化物载体的空隙中,所述氧化物例如是氧化铝、二氧化钛、二氧化硅、二氧化铈、二氧化锆。
另外,人们知道,在发动机的排气管道中引入如前面描述的颗粒过滤器会造成能改变其性能的负载损失。因此,该过滤器的空隙度应该选择得足够高,以避免这样一种改变,并且一般是20-75%。
该过滤器有催化功能,这种负载损失也就越大。事实上,在该结构的这些壁上和/或在空隙中,该催化涂层,特别是如前面描述的催化剂载体的沉积,由于在该排气管道中有该过滤器还易于增加这种负载损失。由于这种局限性,沉积催化剂的量,结果是排出气体的催化处理效率目前还受到限制。
由此得出还需要获得一种过滤结构,其微结构(空隙度、孔径与孔分布)能够使得催化剂的量增加,从而提高气体处理效率,但还不会导致负载损失很大的增加。
一种可能解决办法在于例如通过在起始混合物中有大量的合成树脂(像丙烯酸树脂)或有机聚合物(像淀粉)类型的造孔剂,提高碳化硅晶粒晶格的空隙度。但是,提高其空隙度同时导致该过滤器的机械性能严重变坏,这样降低其使用能力。
本发明的目的因此是提供一种新型的蜂窝状结构,它能够解决前面公开的问题。
在一般方式中,本发明涉及一种蜂窝状结构,它包括碳化硅和氧化铝晶粒混合物,
a)其空隙度与实际用作单一过滤器(即未催化的)的碳化硅制成的结构的空隙度基本上相等或差别不大,以及
b)高比表面。
在本说明书中,高比表面应该理解是高于0.5m2/克的比表面。作为信息,本申请人进行的试验证明了实际使用的用SiC碳化物制成的过滤器的比表面不超过0.2m2/g。这样增加比表面能够显著减少为增加其比表面而在该结构中沉积之前的载体量,对于根据本发明达到的最高比表面值,甚至使其存在变得无用,这时只是该活性组分按照这个方式沉积。
由欧洲专利EP 1070687B1知道一些蜂窝状的单片结构,它们用作柴油发动机排出气体的颗粒过滤器,它们含有70-97质量%碳化硅和3-30%氧化物粘合剂相,例如氧化铝Al2O3。本发明的目的是提供一种在不超过1650℃的低焙烧温度下获得这样一些单片的方法。然而,由于在这种方法中所描述的高温与中心在5-60微米之间的单模态类型孔分布,得到的这些比表面小于0.5m2/g。特别地,专利EP 1070687 B1没有提到将该结构可能用作载体或催化过滤器。
更具体地,根据第一种实施,本发明涉及由多孔陶瓷材料构成的蜂窝状类型结构,所述结构的特征在于构成该结构的多孔陶瓷材料含有:
-50-95质量%碳化硅SiC,
-5-50质量%至少一种氧化物陶瓷相,
所述结构的特征还在于空隙度高于10%,比表面高于0.5m2/g,优选地高于1m2/g,非常优选地高于1.5m2/g,以及至少双峰类型的孔径分布。
这种氧化物陶瓷相例如是使用一种或多种所述氧化物相前体得到的,其起始比表面高于2m2/g,优选地高于5m2/g,甚至高于10m2/g。
优选地,至少5%一些前体质量是由呈纳米形式的粉末组成的。优选地,使用5-50%纳米粉末质量,例如10-40重量%。本申请人进行的试验证明,在焙烧后,这种纳米粉末的存在能够有利地使其最后的结构达到至少双峰孔分布。
氧化物相实例是铝、稀土氧化物,尤其是铈或镧、锆、钛、硅氧化物和硅-铝酸盐。
优选地,该结构蜂窝状含有:
-50-95质量%碳化硅SiC,
-5-50质量%至少一种单一或混合的氧化物陶瓷相,该氧化物陶瓷相是由至少一种氧化铝和/或至少一种铝酸盐得到的,其初始比表面高于2m2/g,优选地高于5m2/g,甚至高于10m2/g。
有利地,这种构成陶瓷材料的总空隙度是约20-65%,优选地30-60%。
本发明结构中的孔径分布是至少双峰类型的。例如,其中一部分孔的平均直径中心孔径为约5-60微米,优选地5-20微米,另一部分孔的平均直径中心孔径为约1.5-1微米或小于1.5微米,甚至1微米,优选地1.5-0.0015微米。
本发明特别涉及一种引入中心部分的结构,它包括一种蜂窝状过滤元件或多种蜂窝状过滤元件,这些元件彼此通过接合粘合剂连接起来,这个或这些所述元件包括一组由多孔壁分开的、其轴彼此平行的邻接管道或管,这些管道在其一端或另一端被管塞封闭,从而限定入口沿着进气面开启的室与出口沿着排气面开启的室的范围,以便这种气体通过这些多孔壁。
例如,这样一种过滤结构包括每cm2的管数7.75-62根,所述管的截面是0.5-9mm2,将这些管分开的壁的厚度是约0.2-1.0mm,优选地0.2-0.5mm。
按照一种可能性,该结构中这种或这些氧化物陶瓷相的质量比例高于10%,优选地高于20%或甚至高于30%。
本发明还涉及如前面所描述的这样结构的生产方法,其中所述的结构是由单一或混合的碳化硅和氧化物晶粒起始混合物或氧化物混合物得到的,其氧化物比表面高于2m2/g,优选地高于5m2/g,甚至高于10m2/g。这些氧化物例如可以粉末形式加到这种起始混合物中,该混合物含有至少自然聚集的纳米部分(例如像在勃姆石的情况下),或采用利用例如Van der Vaals键的化学合成方法聚集的纳米部分。
例如,所述的氧化物可以包括高比表面的氧化铝或铝酸盐或氧化铝和/或铝酸盐混合物。
一般而言,这些碳化硅晶粒的直径d50小于125微米,典型地5-125微米。
根据一种实施方式,所述的方法包括起始混合物的混合步骤,由此得到呈粘稠浆体形式的均匀产品,所述产品通过适当挤压模的挤压步骤,从而形成峰窝形状的单片,例如通过加热和/或通过微波使得到单片干燥步骤和焙烧步骤。
该焙烧步骤例如可以如下进行:
-在中性气体(例如氩气)的气氛与不超过1700℃,优选地不超过1600℃,优选地1300-1600℃的温度下,或
-在含有氧气的气氛(例如空气)与不超过1400℃,优选地不超过1350℃,优选地1200-1350℃的温度下。
根据该方法的一种可能实施方式,在第一个步骤过程中,将含有至少具有至少一类粒度的碳化硅、一种或多种高比表面氧化物相(例如氧化铝和/或铝酸盐)和任选地造孔剂的混合物进行混合,然后添加至少一种有机增塑剂和/或有机粘合剂和水。
根据该方法的一种可能实施方式,该碳化硅以粉末形式加到具有至少两类粒度的混合物中,例如含有其晶粒尺寸小于10微米的部分和其晶粒尺寸高于10微米部分的颗粒混合物。有利地,这样的方法可能允许更好地控制最后得到结构的孔径。
根据该方法的一种可能实施方式,其目的在于控制构成本发明结构单片材料所寻求的空隙度,使用所有为直径d50为5-125微米的碳化硅晶粒,并且添加比例约0-30%,例如5-20质量%的按照所寻求孔径而选择的造孔剂。
例如,在该干燥步骤中,这些得到认可的陶瓷单片在室温直到110℃的温度下或采用微波进行干燥,其干燥时间足以将非化学结合水含量降到1质量%以下。
在生产颗粒过滤器的情况下,该方法还包括根据熟知的技术在每个单片端封闭两根管中的一根管的步骤。
该焙烧步骤时,一般地,在含有氧的气氛下将该结构单片升到温度约750℃-1400℃,优选地1200-1350℃,或在中性气氛下升到温度约750℃-1700℃,优选地1300-1600℃。
本发明还涉及过滤器或催化载体,它们是由如前面描述的结构与沉积(优选地通过浸渍)至少一种载带或优选地非载带活性催化相后得到的,该相通常含有贵金属,例如Pt、Pd、Rh,以及任选地氧化物,例如CeO2、ZrO2、CeO2-ZrO2。
这样一种结构特别在柴油或汽油发动机排气管道中作为催化载体的用途,或在柴油发动机排气管道中作为颗粒过滤器的用途。
通过阅读下述非限制性实施例将更好地理解本发明及其优点。在这些实施例中,所有百分数是以重量方式给出的。
实施例1:
在混合器中,混合:
-3000g晶粒平均直径d50约40微米的SiC。在本说明书中,直径d50表示50质量%总量以下的颗粒直径,
-1300g呈比表面30m2/g的γ氧化铝形式的氧化铝粉末,其中30质量%呈纳米勃姆石形式,
-150g甲基纤维素类有机粘合剂。
这些质量百分数是SiC为69.8%,氧化铝粉末为30.2%。粘合剂的量是以粉末和晶粒干燥质量计添加3.49%。
添加水,并混合直到得到均匀浆体,其塑性允许通过挤压模挤出蜂窝状结构,其尺寸特征列于表1:
表1
管与单片几何结构 | 平方 |
管密度 | 180cpsi(每平方英寸管数,1英寸=2.54cm)是27.9管/cm2 |
壁厚度 | 350微米 |
长度 | 15.2厘米 |
宽度 | 3.6厘米 |
然后,这些得到认可的单片采用微波进行干燥,其干燥时间足以将非化学结合水含量降到1质量%以下。
根据熟知的技术,例如在申请WO 2004/065088中描述的技术,从每个单片面交替封闭这些管。
该单片在空气中按照20℃/小时升温直到最高温度1300℃进行焙烧,在这个最高温度保持5小时。
最后得到单片,采用汞空隙度测量法测量它的空隙度和平均孔径分别是37%和6微米。
采用扫描电子显微镜分析表明,基本均匀结构的特征在于存在的SiC晶粒围绕着氧化铝,因此在这些所述晶粒之间建立一些接触区域。
使用micromeritics 9500型空隙度测量仪进行的高汞压空隙度测量法分析表明,该孔径分布是双峰类型的。一部分孔的孔径中心是平均直径7微米,而另一部分孔的孔径中心是平均直径0.15微米。单片的BET分析表明,如此得到的单片比表面是1.7m2/g。
实施例2:
在这个实施例中,由与实施例1描述的同样试剂合成单片。在与实施例1描述的同样挤出、干燥与封闭步骤后,这个单片再在氩气下按照20℃/小时升温直到最高温度1600℃进行焙烧,在这个最高温度保持5小时。
最后得到一种单片,采用汞空隙度测量法测定的其空隙度和平均孔径分别是37%和6μm。
采用扫描电子显微镜分析表明,基本均匀结构的特征在于存在的SiC晶粒围绕着氧化铝,因此在这些所述晶粒之间建立一些接触区域。
使用micromeritics 9500型空隙度测量仪进行的高汞压空隙度测量法分析表明,该孔径分布是双峰类型的。一部分孔的孔径中心是平均直径7微米,而另一部分孔的孔径中心是平均直径0.15微米。单片的BET分析表明,如此得到的单片比表面是1.1m2/g。
实施例3(对比):
在这个实施例中,合成现有技术单片,其壁只是由碳化硅构成。为此,将与实施例1中同样试剂进行混合,但没有加入一种或多种氧化铝粉末,以便在氩气下在高于1200℃的温度焙烧后最后得到过滤器,其壁只是由SiC构成。
对这个参比过滤器所测量的空隙度是37%,比表面是0.12m2/g。孔径分布是单峰类型的,孔径的中心是9微米。
实施例1和2与对比实施例3比较表明,根据本发明有可能得到一种其空隙度与用碳化硅制成的过滤器基本相当,但其比表面明显得到改善的结构。
在前面的说明书与实施例中,为了简化起见,描述了与这些催化颗粒过滤器相关的发明,这些过滤器能够除去从柴油发动机排气管道出来的在排出气体中存在的气体污染物和炭黑。
但是,本发明还涉及一些催化载体,它们能够除去从汽油发动机,甚至柴油发动机出来的气体污染物。在这类结构中,这些峰窝管在其一端或另一端没有被封闭。应用于这些载体时,实施本发明的优点是提高该载体的比表面,结果是该载体中活性相的量并不因此而影响该载体的总空隙度。
Claims (22)
1.由多孔陶瓷材料构成的蜂窝状类型结构,所述结构的特征在于构成其结构的多孔陶瓷材料含有:
-50-95质量%碳化硅SiC,
-5-50质量%至少一种氧化物陶瓷相,
所述结构的特征还在于空隙度高于10%,比表面高于0.5m2/g和至少双峰类型的孔径分布。
2.根据权利要求1所述的蜂窝状类型结构,它是由至少一种所述氧化物相前体得到的,该氧化物相初始比表面高于2m2/g,优选地高于5m2/g,甚至高于10m2/g。
3.根据权利要求2所述的蜂窝状结构,其中至少5%一种或多种前体质量是由呈纳米形式的粉末组成的。
4.根据权利要求1-3所述的蜂窝状结构,其中该氧化物相选自铝、稀土氧化物,特别地铈或镧、锆、钛、硅氧化物和硅-铝酸盐。
5.根据权利要求1-3中任一项权利要求所述的蜂窝状结构,它含有:
-50-95质量%碳化硅SiC,
-5-50质量%至少一种单一或混合的氧化物陶瓷相,它是由其初始比表面高于2m2/g,优选地高于5m2/g的至少一种氧化铝和/或至少一种铝酸盐得到的,
所述结构的特征还在于空隙度高于10%,比表面高于0.5m2/g与至少双峰类型的孔径分布。
6.根据上述权利要求中任一项权利要求所述的结构,其中该构成陶瓷材料的总空隙度是20-65%。
7.根据上述权利要求中任一项权利要求所述的结构,其中一部分孔的平均直径中心孔径为5-60微米,优选地5-20微米,另一部分孔的平均直径中心孔径为约1.5微米或小于1.5微米,优选地1.5-0.0015微米。
8.根据上述权利要求中任一项权利要求所述的过滤结构,其中心部分包括一种蜂窝状过滤元件或多种蜂窝状过滤元件,这些元件彼此通过接合粘合剂连接起来,这个或这些所述元件包括一组由多孔壁分开的、其轴彼此平行的邻接管道或管,这些管道在其一端或另一端被管塞封闭,从而限定入口沿着进气面开启的室与出口沿着排气面开启的室的范围,以便这种气体通过这些多孔壁。
9.根据权利要求8所述的过滤结构,它包括每cm2的管数7.75-62根,所述管的截面是0.5-9mm2,将这些管分开的壁的厚度是约0.2-1.0mm,优选地0.2-0.5mm。
10.根据权利要求1-9中任一项权利要求所述结构的生产方法,其中所述的结构是由单一或混合的碳化硅和氧化物晶粒起始混合物或氧化物混合物得到的,其比表面高于2m2/g,优选地高于5m2/g。
11.根据权利要求10所述的生产方法,其中至少5%单一或混合的氧化物或氧化物混合物质量是由呈纳米形式的粉末组成的。
12.根据权利要求10或11所述的方法,其中所述的氧化物包括氧化铝或铝酸盐或氧化铝和/或铝酸盐混合物。
13.根据权利要求10-12所述的方法,其中碳化硅晶粒的直径d50小于125微米,典型地5-125微米。
14.根据权利要求10-13中任一项权利要求所述结构的生产方法,该方法包括起始混合物的混合步骤,由此得到呈粘稠浆体形式的均匀产品,所述产品通过适当挤压模的挤压步骤,从而形成峰窝形状的单片,得到单片干燥步骤,任选地组合步骤和焙烧步骤。
15.根据权利要求14所述的方法,其中在第一个步骤过程中,将含有至少具有至少一类粒度的碳化硅、一种或多种高比表面氧化物相,例如氧化铝和/或铝酸盐,和任选地造孔剂的混合物进行混合,然后添加至少一种有机增塑剂和/或有机粘合剂和水。
16.根据权利要求10-15中任一项权利要求所述的方法,其特征在于把该碳化硅加到具有至少两类粒度的呈粉末形式的混合物中。
17.根据权利要求10-16中任一项权利要求所述的方法,其特征在于使用所有为直径d50为5-125微米的碳化硅晶粒,并且添加比例0-30%的按照所寻求孔径而选择的造孔剂。
18.根据权利要求10-17中任一项权利要求所述的方法,其特征在于在该干燥步骤中,这些得到认可的陶瓷单片采用微波或在一定温度下进行干燥,其干燥时间足以将非化学结合水含量降到1质量%以下。
19.根据权利要求10-18中任一项权利要求所述的方法,它包括还包括在每个单片端封闭两根管中的一根管的步骤。
20.根据权利要求10-19中任一项权利要求所述的方法,其特征在于在该焙烧步骤中,在含有氧的气氛下将该结构单片升到温度约750℃-1400℃,优选地1200-1350℃,或在中性气氛下升到温度约750℃-1700℃,优选地1300-1600℃。
21.由根据权利要求1-9中任一项权利要求所述结构得到的过滤器或催化载体,它们是通过沉积,优选地通过浸渍至少一种载带或优选地非载带活性催化相得到的,该相通常含有至少一种贵金属,例如Pt和/或Rh和/或Pd以及任选地氧化物,例如CeO2、ZrO2、CeO2-ZrO2。
22.根据权利要求21所述的结构作为在柴油或汽油发动机排气管道中作为催化载体的用途,或在柴油发动机排气管道中作为颗粒过滤器的用途。
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CN107446263A (zh) * | 2017-08-09 | 2017-12-08 | 南通矽利康橡塑材料有限公司 | 一种具有多峰孔径分布的泡沫聚合物及其制备方法 |
CN108358652A (zh) * | 2018-01-31 | 2018-08-03 | 天津大学 | 一种具有孔梯度结构的汽油机颗粒捕集器陶瓷滤芯的制备方法 |
CN108947498A (zh) * | 2018-08-17 | 2018-12-07 | 佛山朝鸿新材料科技有限公司 | 一种氧化铝-碳化硅多孔复合陶瓷的制备方法 |
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Cited By (4)
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CN107446263A (zh) * | 2017-08-09 | 2017-12-08 | 南通矽利康橡塑材料有限公司 | 一种具有多峰孔径分布的泡沫聚合物及其制备方法 |
CN107446263B (zh) * | 2017-08-09 | 2020-08-14 | 南通矽利康橡塑材料有限公司 | 一种具有多峰孔径分布的泡沫聚合物及其制备方法 |
CN108358652A (zh) * | 2018-01-31 | 2018-08-03 | 天津大学 | 一种具有孔梯度结构的汽油机颗粒捕集器陶瓷滤芯的制备方法 |
CN108947498A (zh) * | 2018-08-17 | 2018-12-07 | 佛山朝鸿新材料科技有限公司 | 一种氧化铝-碳化硅多孔复合陶瓷的制备方法 |
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ATE417812T1 (de) | 2009-01-15 |
BRPI0614575A2 (pt) | 2016-08-23 |
US20080202080A1 (en) | 2008-08-28 |
JP2009502710A (ja) | 2009-01-29 |
US7985274B2 (en) | 2011-07-26 |
EP1917225B1 (fr) | 2008-12-17 |
ZA200800675B (en) | 2009-01-28 |
AU2006273940A1 (en) | 2007-02-01 |
WO2007012776A3 (fr) | 2007-05-10 |
WO2007012776A2 (fr) | 2007-02-01 |
CA2616730A1 (fr) | 2007-02-01 |
EA200800452A1 (ru) | 2008-06-30 |
FR2889080A1 (fr) | 2007-02-02 |
EP1917225A2 (fr) | 2008-05-07 |
DE602006004358D1 (de) | 2009-01-29 |
FR2889080B1 (fr) | 2007-11-23 |
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