CN107226709B - 多孔质陶瓷结构体 - Google Patents
多孔质陶瓷结构体 Download PDFInfo
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- CN107226709B CN107226709B CN201710164650.3A CN201710164650A CN107226709B CN 107226709 B CN107226709 B CN 107226709B CN 201710164650 A CN201710164650 A CN 201710164650A CN 107226709 B CN107226709 B CN 107226709B
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- porous ceramic
- ceria
- particles
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- 239000000919 ceramic Substances 0.000 title claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 60
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims abstract description 56
- 239000002245 particle Substances 0.000 claims abstract description 48
- 239000011148 porous material Substances 0.000 claims abstract description 46
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910010293 ceramic material Inorganic materials 0.000 claims abstract description 20
- 229910052878 cordierite Inorganic materials 0.000 claims abstract description 20
- JSKIRARMQDRGJZ-UHFFFAOYSA-N dimagnesium dioxido-bis[(1-oxido-3-oxo-2,4,6,8,9-pentaoxa-1,3-disila-5,7-dialuminabicyclo[3.3.1]nonan-7-yl)oxy]silane Chemical compound [Mg++].[Mg++].[O-][Si]([O-])(O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2)O[Al]1O[Al]2O[Si](=O)O[Si]([O-])(O1)O2 JSKIRARMQDRGJZ-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 15
- 229910010271 silicon carbide Inorganic materials 0.000 claims abstract description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 14
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010419 fine particle Substances 0.000 claims abstract description 12
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 6
- 238000005192 partition Methods 0.000 claims description 21
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 12
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 12
- 239000012530 fluid Substances 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 15
- 239000011248 coating agent Substances 0.000 abstract description 12
- 238000000576 coating method Methods 0.000 abstract description 12
- 238000011282 treatment Methods 0.000 abstract description 12
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 36
- 238000010304 firing Methods 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 16
- 238000001035 drying Methods 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- 239000002994 raw material Substances 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 210000004027 cell Anatomy 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 210000002421 cell wall Anatomy 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 238000005259 measurement Methods 0.000 description 5
- 239000000377 silicon dioxide Substances 0.000 description 5
- 238000011156 evaluation Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 238000000746 purification Methods 0.000 description 4
- 229910002651 NO3 Inorganic materials 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 239000000571 coke Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001125 extrusion Methods 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229920000609 methyl cellulose Polymers 0.000 description 3
- 239000001923 methylcellulose Substances 0.000 description 3
- 235000010981 methylcellulose Nutrition 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- KAKVFSYQVNHFBS-UHFFFAOYSA-N (5-hydroxycyclopenten-1-yl)-phenylmethanone Chemical compound OC1CCC=C1C(=O)C1=CC=CC=C1 KAKVFSYQVNHFBS-UHFFFAOYSA-N 0.000 description 2
- 229910000505 Al2TiO5 Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- JFBZPFYRPYOZCQ-UHFFFAOYSA-N [Li].[Al] Chemical compound [Li].[Al] JFBZPFYRPYOZCQ-UHFFFAOYSA-N 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 238000010306 acid treatment Methods 0.000 description 2
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 2
- 230000004323 axial length Effects 0.000 description 2
- KZHJGOXRZJKJNY-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Si]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O.O=[Al]O[Al]=O KZHJGOXRZJKJNY-UHFFFAOYSA-N 0.000 description 2
- 239000006260 foam Substances 0.000 description 2
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- 239000000395 magnesium oxide Substances 0.000 description 2
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- 229910052863 mullite Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- AABBHSMFGKYLKE-SNAWJCMRSA-N propan-2-yl (e)-but-2-enoate Chemical compound C\C=C\C(=O)OC(C)C AABBHSMFGKYLKE-SNAWJCMRSA-N 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- SBEQWOXEGHQIMW-UHFFFAOYSA-N silicon Chemical compound [Si].[Si] SBEQWOXEGHQIMW-UHFFFAOYSA-N 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- BDAGIHXWWSANSR-NJFSPNSNSA-N hydroxyformaldehyde Chemical compound O[14CH]=O BDAGIHXWWSANSR-NJFSPNSNSA-N 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910000018 strontium carbonate Inorganic materials 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 230000004584 weight gain Effects 0.000 description 1
- 235000019786 weight gain Nutrition 0.000 description 1
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Abstract
本发明涉及一种多孔质陶瓷结构体。本发明的课题是提供一种无需进行γ‑氧化铝之类增大比表面积的涂覆处理就能够担载催化剂的多孔质陶瓷结构体。蜂窝结构体(1)由多孔质的陶瓷材料形成,其在结构体内部具有气孔(5),该陶瓷材料在结构体内部以掺杂的状态存在二氧化铈,至少一部分二氧化铈的粒子(6)暴露在气孔(5)的气孔表面(5a)。陶瓷材料以堇青石质或碳化硅质为主成分,二氧化铈在陶瓷材料中所占的比率为1.0质量%~10.0质量%的范围,铂或钯等铂族元素的催化剂微粒(7)的至少一部分担载于二氧化铈的粒子(6)。
Description
技术领域
本发明涉及多孔质陶瓷结构体。更详细而言,涉及能够用于汽车废气净化用催化剂载体等各种用途的多孔质陶瓷结构体。
背景技术
以往,多孔质陶瓷结构体被用于汽车废气净化用催化剂载体、柴油机微粒除去过滤器或者燃烧装置用蓄热体等广泛的用途。特别是多数使用具有隔壁的蜂窝形状的多孔质陶瓷结构体(以下,称为“蜂窝结构体”。),该隔壁区划形成多个隔室,即从一个端面延伸至另一个端面的流体的流路。该蜂窝结构体是经过挤压成型工序和烧成工序制造而成的,该挤压成型工序中,调制多个陶瓷原料并生坯化,得到成型原料,将该成型原料使用挤压成型机进行挤压成型,该烧成工序中,使挤压成型后的蜂窝成型体干燥后,在规定的烧成条件下进行烧成。
作为构成多孔质陶瓷结构体的陶瓷材料,例如使用碳化硅、硅-碳化硅系复合材料、堇青石、多铝红柱石、氧化铝、尖晶石、碳化硅-堇青石系复合材料、锂铝硅酸盐及钛酸铝等。
此处,由堇青石质形成的蜂窝结构体具有耐冲击性优异等优点。但是,由于蜂窝结构体的隔壁表面等的比表面积较小,所以无法担载足够量的催化剂,直接导致有时无法发挥较高的催化活性。因此,为了增大比表面积,将蜂窝结构体用γ-氧化铝进行涂覆处理。由此,能够增大比表面积,能够将用于发挥较高的催化活性的足够量的催化剂担载于蜂窝结构体(例如参见专利文献1。)。
另一方面,近年来,严格强化了针对由柴油发动机等排出的尾气的各种限制。因此,要求用作汽车废气净化用催化剂载体的蜂窝结构体等多孔质陶瓷结构体高性能化。例如通过将蜂窝结构体的隔壁薄壁化来降低蜂窝结构体整体的热容量,迅速升温至发挥催化剂的催化活性的温度,或者,使隔壁为高气孔率结构。此处,如果蜂窝结构体的气孔率降低,则存在压力损失增大而导致发动机的油耗性能降低等问题(参见专利文献2)。
此处,通过γ-氧化铝来对蜂窝结构体进行涂覆处理有可能堵塞多孔质性的隔壁而导致气孔率降低。因此,研究无需通过γ-氧化铝进行涂覆处理而担载足够量的催化剂的方法。例如已知对堇青石质陶瓷蜂窝结构体进行酸处理,于600℃~1000℃进行热处理后担载催化剂成分(参见专利文献3)。由此,能够增加比表面积,并且,能够不需要通过γ-氧化铝进行涂覆处理(所谓“催化剂载体涂层”)的工序。
现有技术文献
专利文献
专利文献1:日本特许第4046925号公报
专利文献2:国际公开第2013/047908号
专利文献3:日本特公平5-40338号公报
发明内容
如上所述,涂覆处理γ-氧化铝的方法会堵塞蜂窝结构体(多孔质陶瓷结构体)的气孔而导致气孔率降低。因此,具有压力损失增大的问题。
另一方面,如专利文献3所示的、对多孔质陶瓷结构体进行酸处理及热处理由于不需要通过γ-氧化铝进行涂覆处理,所以能够实现多孔质陶瓷结构体的轻量化及耐热冲击性的提高。但是,有可能破坏堇青石质的晶格自身,从而多孔质陶瓷结构体的强度有可能降低。因此,要求开发出一种无需通过γ-氧化铝进行涂覆处理、并且不会导致强度降低就能够担载对于维持较高的催化活性而言足够量的催化剂的多孔质陶瓷结构体。
因此,本发明是鉴于上述实际情况而完成的,其课题是提供一种能够担载对于维持催化活性而言足够量的催化剂的多孔质陶瓷结构体。
根据本发明,提供解决上述课题的多孔质陶瓷结构体。
[1]一种多孔质陶瓷结构体,其由多孔质的陶瓷材料形成,且在结构体内部具有气孔,其中,所述陶瓷材料包含二氧化铈,所述二氧化铈以被引入所述结构体内部的状态存在,并且,所述二氧化铈的至少一部分暴露在所述气孔的气孔表面。
[2]根据上述[1]中记载的多孔质陶瓷结构体,其中,所述二氧化铈在所述陶瓷材料中所占的比率为1.0质量%~10.0质量%的范围。
[3]根据上述[1]或[2]中记载的多孔质陶瓷结构体,其中,所述陶瓷材料以堇青石质或碳化硅质中的任意一者为主成分。
[4]根据上述[1]~[3]中的任意一项中记载的多孔质陶瓷结构体,其中,所述多孔质陶瓷结构体还包含分布在所述气孔表面的铂族元素的催化剂微粒,所述催化剂微粒的至少一部分担载于暴露在所述气孔表面的所述二氧化铈的粒子。
[5]根据上述[4]中记载的多孔质陶瓷结构体,其中,所述铂族元素的催化剂为铂或钯中的任意一者。
[6]根据上述[1]~[5]中的任意一项中记载的多孔质陶瓷结构体,其中,所述多孔质陶瓷结构体为蜂窝结构体。
根据本发明的多孔质陶瓷结构体,二氧化铈暴露在气孔表面,由此,催化剂粒子的一部分选择性地担载于该二氧化铈。因此,能够提高催化剂粒子的担载性能,并且不需要对隔壁进行涂覆。
附图说明
图1是示意性地表示蜂窝结构体的概略构成之一例的立体图。
图2是示意性地表示本发明的一个实施方式的蜂窝结构体的隔壁内部的放大截面图。
图3是示意性地表示在暴露于气孔表面的二氧化铈的粒子上担载有催化剂的状态的放大截面图。
图4是表示暴露在气孔表面的二氧化铈粒子的比例与NO2转化率的相关关系的图表。
图5是表示比较例1、实施例1~3及实施例5的NO2转化率的图表。
图6是表示暴露在气孔表面的二氧化铈及担载于二氧化铈的粒子的催化剂微粒(铂)的SEM图像。
符号说明
1:蜂窝结构体(多孔质陶瓷蜂窝结构体、多孔质陶瓷结构体)、2a:一个端面、2b:另一个端面、3:隔室、4:隔壁、5:气孔、5a:气孔表面、6:粒子、7:催化剂微粒。
具体实施方式
以下,参照附图,对本发明的多孔质陶瓷结构体的实施方式进行详细说明。应予说明,本发明的多孔质陶瓷结构体并不限定于以下的实施方式,只要不脱离本发明的范围,就可以实施各种设计的变更、修正及改良等。
如图1所示,本发明的一个实施方式的多孔质陶瓷结构体为具有格子状的隔壁4的蜂窝形状的大致圆柱状的多孔质陶瓷蜂窝结构体1(以下,仅称为“蜂窝结构体1”。),该格子状的隔壁4区划形成隔室3,该隔室3形成为从一个端面2a延伸至另一个端面2b的流体的流路。此处,蜂窝结构体1的隔壁4由多孔质的陶瓷材料形成,在该隔壁4的内部存在多个气孔5(参照图2及图3)。特别是二氧化铈(CeO2)以被引入该多孔质的蜂窝结构体1的结构体内部的状态存在,并且形成为该二氧化铈中的至少一部分粒子6暴露在隔壁4的内部的气孔5的气孔表面5a。
构成蜂窝结构体1(隔壁4)的陶瓷材料被假定为众所周知的多孔质材料,例如可以举出包含碳化硅、硅-碳化硅(Si/SiC)系复合材料、堇青石、多铝红柱石、氧化铝、尖晶石、碳化硅-堇青石系复合材料、锂铝硅酸盐及钛酸铝等作为主成分的多孔质材料。应予说明,本发明的多孔质陶瓷结构体并不限定于上述的蜂窝结构体1,可以为各种形状。进而,即便是具有蜂窝形状的情况下,也并不限定于大致圆柱状。
构成本实施方式的蜂窝结构体1的多孔质的陶瓷材料中含有的二氧化铈的比率(含有比率)为1.0质量%~10.0质量%的范围,进一步优选为2.5质量%~6.0质量%的范围。二氧化铈的比率低于1.0质量%的情况下,暴露在气孔表面5a的二氧化铈的粒子6变少,从而通过后述的气孔表面5a上的粒子6来担载催化剂微粒7的量变少。结果,难以担载对于得到较高的催化活性而言足够量的催化剂。
另一方面,如果二氧化铈的比率超过10.0质量%,则暴露在气孔表面5a的粒子6变多。因此,气孔5的一部分会被暴露出来的粒子6堵塞,导致隔壁4的气孔率降低,有可能产生压力损失等不良情况。因此,二氧化铈的比率限制在上述的规定范围内。
如上所述,本实施方式的蜂窝结构体1形成为:二氧化铈的粒子6暴露在形成于隔壁4的结构体内部的多个气孔5的表面。由此,催化剂微粒7的一部分选择性地担载于粒子6。即,无需通过以往的利用γ-氧化铝进行涂覆处理(催化剂载体涂层)来增大比表面积,就能够容易地增加催化剂的担载量。因此,不会因γ-氧化铝的涂覆处理而产生压力损失增大等不良情况。
本实施方式的蜂窝结构体1除上述构成以外,还包含分布在隔壁4的内部的气孔表面5a的铂族元素(钌(Ru)、铑(Rh)、钯(Pd)、锇(Os)、铱(Ir)及铂(Pt))的催化剂微粒7。此处,催化剂微粒7的至少一部分选择性地担载于暴露在气孔表面5a的前述二氧化铈的粒子6的粒子表面(参照图3及图6)。此处,如图3示意性所示,相对于催化剂微粒7而言,二氧化铈的粒子6的粒径一般较大。
此处,担载于粒子6的催化剂微粒7如上所述为铂族元素即可,没有特别限定,特别优选使用铂(Pt)或钯(Pd)。这些铂或钯从以往就通常被用作净化处理NO2时的催化剂。另外,如图3所示,催化剂微粒7并不一定需要担载于二氧化铈的粒子6,其中的一部分可以直接担载于气孔5的气孔表面5a。
根据本实施方式的蜂窝结构体1,二氧化铈在构成该蜂窝结构体1(隔壁4)的结构体内部(陶瓷材料中)以按规定的比率被引入的状态存在,并且,该二氧化铈的粒子6暴露在隔壁4的结构体内部的气孔表面5a,且铂等催化剂微粒7的至少一部分选择性地担载于粒子6。由此,在暴露在气孔表面5a的二氧化铈的粒子6上担载有许多催化剂微粒7。结果,将蜂窝结构体1用作NO2净化处理等用的催化剂体的情况下,能够通过所担载的铂等催化剂来发挥较高的催化活性,并且能够提高NO2的净化率(转化率)。因此,可以用作没有压力损失增大等不良情况的催化剂体。
以下,基于下述的实施例,对本发明的多孔质陶瓷结构体(蜂窝结构体)进行说明,但是,本发明的多孔质陶瓷结构体并不限定于这些实施例。
实施例
将构成实施例1~5及比较例1~3的蜂窝结构体的陶瓷材料(包含无机原料及其它原料)及其配合比率等示于下述表1。此处,实施例1~4及比较例1~3是陶瓷成分为堇青石质的蜂窝结构体,实施例5是由硅/碳化硅质(Si/SiC)的复合材料构成的蜂窝结构体。
表1
1.实施例1的蜂窝结构体的制作
(1)生坯的调制
将表1所示的蜂窝结构体的无机原料(滑石39.7质量%、α-氧化铝14.1质量%、氢氧化铝15.3质量%、高岭土17.5质量%、二氧化硅10.7质量%、二氧化铈2.7质量%)混合,相对于得到的无机原料100质量份,加入作为其它原料的焦炭2.0质量份、发泡树脂5.4质量份、吸水性树脂1.5质量份、甲基纤维素树脂5.0质量份。然后,使用捏合机混合10分钟后,加入月桂酸钾1质量份、水33质量份(表1中省略记载)。此处,上述的质量份以混入焦炭等之前的无机原料100质量份为基准。进而,使用捏合机混炼45分钟,制作塑性的生坯。
(2)蜂窝成型体的制作
使用真空练泥机将得到的生坯成型为柱状,然后,导入挤压成型机而制作蜂窝状的蜂窝成型体。此处,蜂窝成型体是蜂窝直径50mm、隔壁厚度12mil(约0.3mm)、隔室密度300cpsi(cell per square inches:46.5隔室/cm2)、外周壁厚度约0.6mm,具备格子状的隔壁,该格子状的隔壁在内部区划形成多个隔室,即流体的流路。
(3)蜂窝成型体的干燥及烧成
对制作的蜂窝成型体进行微波干燥,接下来,进行热风干燥(80℃×12小时),然后,将蜂窝干燥体的两端的端面切断,以使干燥后的蜂窝干燥体的轴向长度为60mm。然后,将蜂窝干燥体在大气中于1400℃的烧成温度进行烧成处理,由此,制作未担载催化剂的蜂窝结构体。
(4)催化剂的担载
将得到的蜂窝结构体在4.0质量%的硝酸四氨合铂水溶液中浸渍后,在大气中于100℃的干燥温度进行4小时干燥。反复进行上述的浸渍及干燥处理,直至铂的重量增加量相对于原来的蜂窝结构体为5g/L。然后,在大气中于550℃的烧成温度进行烧成。由此,得到实施例1的堇青石质的蜂窝结构体。
2.实施例2的蜂窝结构体的制作
将实施例1的无机原料中的二氧化硅的配合比率变更为8.4质量%,将二氧化铈的配合比率变更为5.0质量%,除此以外,以与上述(1)~(4)相同的条件制作实施例2的堇青石质的蜂窝结构体。
3.实施例3的蜂窝结构体的制作
将实施例2的烧成温度变更为1375℃,除此以外,以相同的条件制作实施例3的堇青石质的蜂窝结构体。
蜂窝成型体的制作、蜂窝成型体的干燥及烧成、催化剂的担载
由于与实施例1、2相同,所以省略。由此,得到实施例3的堇青石质的蜂窝结构体。
4.实施例4的蜂窝结构体的制作
(1)生坯的调制
将表1所示的蜂窝结构体的多种无机原料(氧化镁11.9质量%、α氧化铝33.3质量%、二氧化硅49.1质量%、二氧化铈5.7质量%)混合,相对于得到的无机原料100质量份,加入作为其它原料的焦炭2.0质量份、发泡树脂5.4质量份、吸水性树脂1.5质量份、甲基纤维素树脂5.0质量份。然后,使用捏合机混合10分钟后,加入月桂酸钾1质量份、水33质量份(表1中省略记载)。此处,上述的质量份的基准与实施例1相同。进而,使用捏合机混炼45分钟,制作塑性的生坯。
(2)蜂窝成型体的制作、蜂窝成型体的干燥及烧成、催化剂的担载
由于与实施例1、2相同,所以省略。但是,使铂的催化剂量为1g/L。由此,得到实施例4的堇青石质的蜂窝结构体。
5.实施例5的蜂窝结构体的制作
(1)生坯的调制
将表1所示的蜂窝结构体的两种无机原料(碳化硅(SiC)80质量%、硅(Si)20质量%)混合,相对于得到的陶瓷材料100质量份,加入氢氧化铝0.4质量份、碳酸锶1.4质量份、二氧化铈5.0质量份、淀粉3.5质量份、甲基纤维素树脂7.0质量份。然后,使用捏合机混合10分钟后,加入水27质量份(表1中省略记载)。此处,上述的质量份以碳化硅与硅的合计的陶瓷材料100质量份为基准。进而,使用捏合机混炼45分钟,制作塑性的生坯。
(2)蜂窝成型体的制作
由于与实施例1~4相同,所以省略。
(3)蜂窝成型体的干燥及烧成
对制作的蜂窝成型体进行微波干燥,接下来,进行热风干燥(80℃×12小时),然后,将蜂窝干燥体的两端的端面切断,以使干燥后的蜂窝干燥体的轴向长度为60mm。然后,将蜂窝干燥体在氩气氛下于1450℃的烧成温度进行烧成处理,由此,制作未担载催化剂的蜂窝结构体。
(4)催化剂的担载
将得到的蜂窝结构体在4.0质量%的硝酸四氨合铂水溶液中浸渍后,在大气中于100℃的干燥温度进行4小时干燥。反复进行上述的浸渍及干燥处理,直至铂的重量增加量相对于原来的蜂窝结构体为5g/L。然后,在大气中于550℃的烧成温度进行烧成。由此,得到实施例5的硅/碳化硅质(Si/SiC)的蜂窝结构体。
6.比较例1的蜂窝结构体的制作
未添加二氧化铈,使原料中的二氧化硅的配合比率为13.4质量%,将烧成温度设定为1425℃,除此以外,采用与实施例1相同的条件,由此,得到比较例1的堇青石质的蜂窝结构体。
7.比较例2的蜂窝结构体的制作
未添加二氧化铈,使原料中的配合比率为氧化镁11.6质量%、α-氧化铝45.0质量%、二氧化硅43.4质量%,将烧成温度变更为1425℃,除此以外,采用与实施例4相同的条件,由此,得到比较例2的堇青石质的蜂窝结构体。
8.比较例3的蜂窝结构体的制作
(1)催化剂的调制
在水10g中加入4.0质量%的硝酸四氨合铂水溶液24g,用搅拌器搅拌30分钟后,投入二氧化铈粉末,在搅拌下,提高温度而使水分蒸发。水分蒸发后,在大气中于100℃的干燥温度进行4小时干燥,进而,在大气中于550℃的烧成温度进行1小时烧成。将烧成后得到的物质过筛,由此,制成催化剂。
(2)催化剂的担载
相对于水100g,加入得到的催化剂4.5g,用搅拌器搅拌,调制催化剂液后,将与比较例1同样地制作的蜂窝结构体浸渍在该催化剂液中,在大气中于100℃的干燥温度进行4小时干燥。反复进行上述浸渍及干燥处理,直至铂的重量增加量相对于原来的蜂窝结构体为1g/L。然后,在大气中于550℃的烧成温度进行烧成。由此,得到比较例3的堇青石质的蜂窝结构体。
针对所制作的实施例1~5及比较例1~3的蜂窝结构体,就NO2转化率、二氧化铈(CeO2)的粒径及暴露在气孔表面的CeO2粒子的比例的各评价项目进行测定。将测定结果汇总示于下述表2、图4及图5。应予说明,图5给出Pt催化剂量为5g/L时的比较,实施例4及比较例2、3省略图示。
表2
9.评价项目(NO2转化率)
将通过上述操作制作的蜂窝结构体(实施例1~5、比较例1~3)分别加工成直径(=Φ)25.4mm×长度(=L)50.8mm的试样片,将加工后的外周用与基材相同的材料被覆。以其为测定试样,使用汽车废气分析装置进行评价。此时,将上述测定试样放置在升温炉中的反应管上,保持在250℃。另一方面,制作被调整为250℃的气体温度的NO(一氧化氮):200ppm、氧(O2):10%的氮平衡的混合气体,并导入放置在反应管中的测定试样中。此时,使用尾气测定装置(HORIBA制:MEXA-6000FT)分析从测定试样中排出的气体(排出气体),测定各自的排出浓度(NO浓度及NO2浓度)。基于测定结果,计算出NO2转化率(1-NO浓度/(NO浓度+NO2浓度))。此处,铂的担载量为5g/L的情况下,将NO2转化率为45%以上的情形评价为“良”,将NO2转化率为30%以上且低于45%的情形评价为“合格(相当于实施例)”及将NO2转化率低于30%的情形评价为“不合格(相当于比较例)”。
10.评价项目(二氧化铈粒径)
通过图像解析计算出二氧化铈粒径。将此处制作的蜂窝结构体(多孔质陶瓷结构体)用树脂包裹后,使用金刚石浆料等进行镜面研磨,将镜面研磨后的试样用作图像解析用的观察试样。通过扫描型电子显微镜以10000倍的倍率观察该镜面研磨后的截面研磨面,得到多孔质陶瓷结构体的背散射电子图像照片(微结构图像)。将得到的背散射电子图像照片使用图像解析软件(商品名:Image-Pro0.7)调节对比度,区分出堇青石的区域和二氧化铈的区域,并进行二值化处理。通过该二值化处理确定各二氧化铈的截面区域的轮廓,测定二氧化铈粒径。
11.暴露在气孔表面的二氧化铈(CeO2)粒子的比例
与上述10同样地通过图像解析进行计算。此处,通过扫描型电子显微镜以750倍的倍率观察镜面研磨后的截面研磨面,得到多孔质陶瓷结构体的背散射电子图像照片(微结构图像)。使用与上述10同样的图像解析软件进行二值化处理,由此,确定各二氧化铈的截面区域的轮廓,数出背散射电子图像照片中的二氧化铈的个数。进而,数出与气孔表面接触的二氧化铈的个数,计算出配置于(暴露在)气孔表面的二氧化铈的粒子的比例(%)、即、数出的配置于气孔表面的二氧化铈的个数/二氧化铈的总个数×100%。此处,Pt催化剂量为5g/L的情况下,将暴露在气孔表面的二氧化铈粒子的比例为10%以上的情形评价为“良”,将暴露在气孔表面的二氧化铈粒子的比例为3%以上且低于10%的情形评价为“合格(相当于实施例)”及将暴露在气孔表面的二氧化铈粒子的比例低于3%的情形评价为“不合格(相当于比较例)”(不包括实施例4。)。
12.评价结果的考察
如表2所示,确认到:与不含有二氧化铈的比较例1~3相比,含有二氧化铈的实施例1~5表现出较高的NO2转化率(参照图5)。由此,显示出二氧化铈的一部分担载有铂而带来的效果。另外,确认到:暴露在气孔表面的二氧化铈粒子的比例为10%以上的情况下(实施例1、2、5),NO2转化率高达50%以上(参照图4)。
由此说明,二氧化铈在气孔表面暴露出来的比例越高,越有可能发挥出高催化性能。进而确认了:即便是像实施例5那样碳化硅质成分(Si/SiC)的多孔质陶瓷材料也与堇青石质同样具有效果。另外,确认了:像比较例3那样仅将二氧化铈用作催化剂,无法得到本发明的效果,必须是:二氧化铈作为多孔质陶瓷结构体的构成成分以被包含(被引入)在结构体内部的状态存在,且其中的一部分暴露在气孔表面。
关于本发明的多孔质陶瓷结构体,上述实施方式及实施例中给出了优选的多孔质陶瓷结构体,但并不限定于此。例如可以包括:被引入结构体内部的二氧化铈的一部分被置换成稀土元素、过渡金属元素而得到的其它金属氧化物。
产业上的可利用性
本发明的多孔质陶瓷结构体可以优选用作汽车废气净化用催化剂载体等催化剂载体。
Claims (6)
1.一种多孔质陶瓷结构体,其具有格子状的隔壁,所述格子状的隔壁区划形成多个隔室,所述多个隔室形成为从一个端面延伸至另一个端面的流体的流路,
所述隔壁由多孔质的陶瓷材料形成,且在隔壁的内部具有气孔,
所述陶瓷材料包含二氧化铈,所述二氧化铈的粒子以被引入所述隔壁的内部的状态存在,所述二氧化铈的粒子具有0.02μm~3.0μm的粒径,
所述二氧化铈中的至少一部分粒子暴露在所述气孔的气孔表面,暴露在所述气孔表面的所述二氧化铈粒子的比例为5.4%~14.8%。
2.根据权利要求1所述的多孔质陶瓷结构体,其中,
所述二氧化铈在所述陶瓷材料中所占的比率为1.0质量%~10.0质量%的范围。
3.根据权利要求1所述的多孔质陶瓷结构体,其中,
所述陶瓷材料以堇青石质或碳化硅质中的任意一者为主成分。
4.根据权利要求1所述的多孔质陶瓷结构体,其中,
所述多孔质陶瓷结构体还包含分布在所述气孔表面的铂族元素的催化剂微粒,
所述催化剂微粒的至少一部分担载于暴露在所述气孔表面的所述二氧化铈的粒子。
5.根据权利要求4所述的多孔质陶瓷结构体,其中,
所述铂族元素的催化剂为铂或钯中的任意一者。
6.根据权利要求1所述的多孔质陶瓷结构体,其中,
所述多孔质陶瓷结构体为蜂窝结构体。
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