CN105008050B - 陶瓷蜂窝结构体及其制造方法 - Google Patents
陶瓷蜂窝结构体及其制造方法 Download PDFInfo
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- CN105008050B CN105008050B CN201480009653.4A CN201480009653A CN105008050B CN 105008050 B CN105008050 B CN 105008050B CN 201480009653 A CN201480009653 A CN 201480009653A CN 105008050 B CN105008050 B CN 105008050B
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- ceramic honeycomb
- micropore
- structural body
- honeycomb structural
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- 239000000919 ceramic Substances 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 55
- 238000004519 manufacturing process Methods 0.000 title claims description 10
- 239000011148 porous material Substances 0.000 claims abstract description 82
- 238000009825 accumulation Methods 0.000 claims abstract description 58
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 31
- 230000035515 penetration Effects 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims description 48
- 239000000463 material Substances 0.000 claims description 31
- 229910052878 cordierite Inorganic materials 0.000 claims description 25
- 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 description 25
- 238000009826 distribution Methods 0.000 claims description 25
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 23
- 230000001186 cumulative effect Effects 0.000 claims description 23
- 239000002994 raw material Substances 0.000 claims description 17
- 230000008569 process Effects 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 11
- 238000013022 venting Methods 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 9
- 239000002689 soil Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 230000001413 cellular effect Effects 0.000 claims description 3
- 239000003054 catalyst Substances 0.000 description 54
- 239000002912 waste gas Substances 0.000 description 30
- 238000000746 purification Methods 0.000 description 22
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 11
- 238000002425 crystallisation Methods 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000011347 resin Substances 0.000 description 7
- 229920005989 resin Polymers 0.000 description 7
- 230000009467 reduction Effects 0.000 description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000000635 electron micrograph Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 3
- 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 3
- 239000007789 gas Substances 0.000 description 3
- 238000010191 image analysis Methods 0.000 description 3
- 230000008676 import Effects 0.000 description 3
- 239000000395 magnesium oxide Substances 0.000 description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 229910052863 mullite Inorganic materials 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 239000004215 Carbon black (E152) Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
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- 235000013339 cereals Nutrition 0.000 description 2
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- 150000002430 hydrocarbons Chemical class 0.000 description 2
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
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- 230000000007 visual effect Effects 0.000 description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- 241000256844 Apis mellifera Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 241000237903 Hirudo Species 0.000 description 1
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- 229910052581 Si3N4 Inorganic materials 0.000 description 1
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 241000209140 Triticum Species 0.000 description 1
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- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 1
- 229910021502 aluminium hydroxide Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000006837 decompression Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 235000013312 flour Nutrition 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
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- 229910002804 graphite Inorganic materials 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007373 indentation Methods 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
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 1
- 229920000609 methyl cellulose Polymers 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000001923 methylcellulose Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000008520 organization Effects 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
- 239000005022 packaging material Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000013618 particulate matter Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
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- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
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- 238000002459 porosimetry Methods 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
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- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
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- 229910052682 stishovite Inorganic materials 0.000 description 1
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- 229910052623 talc Inorganic materials 0.000 description 1
- 235000012222 talc Nutrition 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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Abstract
一种陶瓷蜂窝结构体,其特征在于,其为具有被多孔质的隔壁隔开的多个孔道的陶瓷蜂窝结构体,对于所述隔壁而言,(a)气孔率为50~80%,(b)利用水银压入法测定的中值微孔直径为25~50μm,(c)(i)利用水银压入法测定的微孔直径20μm以下的累积微孔容积为总微孔容积的25%以下,(ii)利用水银压入法的测定的微孔直径大于20μm且50μm以下的累积微孔容积为总微孔容积的50%以上,以及(iii)利用水银压入法测定的微孔直径大于50μm的累积微孔容积为总微孔容积的12%以上。
Description
技术领域
本发明涉及汽车等内燃机的废气净化所使用的陶瓷蜂窝结构体、及其制造方法。
背景技术
为了削减由建设机械用内燃机、产业用内燃机排出的废气中所包含的PM(Particulate Matter:微粒状物质)、NOx(氮氧化物)、HC(烃)、CO(一氧化碳)、SOx(硫氧化物)等有害物质,而使用陶瓷蜂窝结构体作为废气净化用的催化剂载体或微粒子捕集用的过滤器。该陶瓷蜂窝结构体1如图1(a)和图1(b)所示,具有被多孔质的隔壁12隔开且在废气流通的方向上延伸的多个孔道13。作为催化剂载体使用的陶瓷蜂窝结构体在其隔壁的表面、隔壁内部所存在的微孔中负载净化用的催化剂,穿过陶瓷蜂窝结构体的废气与这些催化剂接触,由此进行废气的净化。
使用这种陶瓷蜂窝结构体净化废气时,为了提高净化效率,需要使废气所含的有害物质与隔壁中负载的催化剂高效地接触。因此,通常采用减小孔道开口面积、增加孔道密度,进而增大与催化剂的接触面积的方法。然而,若增加孔道密度,则存在压力损失增加的问题。
对于这样的问题,日本特表2006-517863号公开了催化剂支承体,其由蜂窝结构体构成,所述蜂窝结构体由多孔质陶瓷材料构成、且包含由入口端贯穿至出口端的多个平行的孔道,所述催化剂支承体具有超过45容积%的总体的气孔率和连通孔的网状组织,该连通孔的网状组织具备具有大于5μm且小于30μm的中值微孔直径的窄微孔直径分布。日本特表2006-517863号中记载有:该催化剂支承体(陶瓷蜂窝结构体)能够实现更高的催化剂装填率而不伴有压力降低。
WO2007/026803公开了一种陶瓷蜂窝结构体,其具备:以形成将两个端面间连通的多个孔道的方式而配置的、具有多个微孔的多孔质的隔壁;和以在任一端面或孔道的内部中对上述孔道进行网眼密封的方式来配置的网眼密封部,其中,所述隔壁的透过性为7×10-12~4×10-8m2,WO2007/026803中记载有该陶瓷蜂窝结构体的净化效率优异且压力损失小。
然而,对于日本特表2006-517863号和WO2007/026803号中记载的陶瓷蜂窝结构体,在催化剂负载于隔壁的表面或隔壁内部的微孔的情况下,有时隔壁内部的微孔被催化剂堵塞,从而催化剂负载后的陶瓷蜂窝结构体的压力损失变大,隔壁内部的微孔中负载的催化剂难以被有效地活用,有时无法提高净化效率。尤其是,在如日本特表2006-517863号中记载的催化剂支承体那样不具备网眼密封部的陶瓷蜂窝结构体(催化剂载体)的情况下,有时废气难以在隔壁内部的负载有催化剂的微孔中流通,有时净化效率无法提高。此外,由于WO2007/026803号中记载的陶瓷蜂窝结构体的隔壁的透过性大,因此隔壁自身的强度小,陶瓷蜂窝结构体的强度存在问题。
发明内容
发明所要解决的课题
因此,本发明的目的在于提供一种废气净化用的陶瓷蜂窝结构体,该废气净化用的陶瓷蜂窝结构体即便不具备网眼密封部,也能够在维持强度的同时确保废气向隔壁内部的微孔的流通性,此外,通过负载催化剂,从而催化剂所带来的有害物质的除去能力高,且压力损失小。
用于解决课题的手段
本发明人鉴于上述目的而进行了深入研究,其结果发现:在具有被多孔质的隔壁隔开的多个孔道的陶瓷蜂窝结构体中,当上述隔壁满足(a)具有50~80%的气孔率、(b)利用水银压入法测定的中值微孔直径为25~50μm、(c)利用水银压入法测定的微孔直径20μm以下的累积微孔容积为总微孔容积的25%以下、(d)利用水银压入法的测定的微孔直径大于20μm且50μm以下的累积微孔容积为总微孔容积的50%以上、以及(e)利用水银压入法测定的微孔直径大于50μm的累积微孔容积为总微孔容积的12%以上的条件时,可以得到兼顾高强度和废气向微孔的高流通性的蜂窝结构体,从而想到本发明。
即,本发明的陶瓷蜂窝结构体的特征在于,具有被多孔质的隔壁隔开的多个孔道,
对于上述隔壁而言,
(a)气孔率为50~80%,
(b)利用水银压入法测定的中值微孔直径为25~50μm,
(c)(i)利用水银压入法测定的微孔直径20μm以下的累积微孔容积为总微孔容积的25%以下,
(ii)利用水银压入法的测定的微孔直径大于20μm且50μm以下的累积微孔容积为总微孔容积的50%以上,以及
(iii)利用水银压入法测定的微孔直径大于50μm的累积微孔容积为总微孔容积的12%以上。
优选为,在上述隔壁表面开口的微孔的开口面积率(隔壁表面的每单位面积中开口的微孔的总开口面积)为30%以上。
优选为,以等效圆直径表示在上述隔壁表面开口的微孔时,中值开口直径为60μm以上。
优选为,以等效圆直径表示在上述隔壁表面开口的微孔时,开口直径30μm以下的累积开口面积为总开口面积的20%以下。
优选为,以等效圆直径表示在上述隔壁表面开口的微孔时,开口直径100μm以上的累积开口面积为总开口面积的30~70%。
优选为,上述隔壁的通气度为10×10-12~30×10-12m2。
优选为,上述陶瓷蜂窝结构体的A轴压缩强度为1.0MPa以上。
制造上述陶瓷蜂窝结构体的本发明的方法的特征在于,
其包括:将包含堇青石化原料和造孔材料的原料粉末混炼而得到坯土的工序;将上述坯土挤出成形而得到蜂窝状的成形体的工序;以及对上述成形体进行干燥和烧成而得到陶瓷蜂窝结构体的工序,
(a)上述堇青石化原料包含具有10~60μm的中值粒径的二氧化硅10~25质量%,
(b)对于上述造孔材料,
(i)具有大于70μm且200μm以下的中值粒径,
(ii)在表示粒径与累积体积(累积特定粒径以下的粒子体积而得的值)的关系的曲线中,与总体积的90%相当的累积体积下的粒径D90为90~250μm,以及与总体积的10%相当的累积体积下的粒径D10为15~160μm,
(iii)粒度分布偏差SD为0.3以下,
(c)上述造孔材料的含量相对于堇青石化原料为1~20质量%。
发明效果
本发明的陶瓷蜂窝结构体即便在不具备网眼密封部的情况下,也能够在维持强度的同时确保废气向隔壁内部的微孔的高流通性,因此,通过负载催化剂,可以得到催化剂所带来的有害物质的除去能力高、并且压力损失小的废气净化用的陶瓷蜂窝结构体。
附图说明
图1(a)为示意性地表示本发明的陶瓷蜂窝结构体的一例主视图。
图1(b)为示意性地表示本发明的陶瓷蜂窝结构体的一例的部分剖面图。
图2为表示本发明的陶瓷蜂窝结构体的隔壁的表面的电子显微镜照片。
具体实施方式
以下,具体对本发明的实施方式进行说明,但本发明并不限于以下的实施方式,在不脱离本发明的主旨的范围内,可以基于本领域技术人员的通常的知识而适当地实施设计的变更、改良等。
本发明的陶瓷蜂窝结构体的特征在于,其为具有被多孔质的隔壁隔开的多个孔道的陶瓷蜂窝结构体,
对于上述隔壁而言,
(a)气孔率为50~80%,
(b)利用水银压入法测定的中值微孔直径为25~50μm,
(c)(i)利用水银压入法测定的微孔直径20μm以下的累积微孔容积为总微孔容积的25%以下,
(ii)利用水银压入法的测定的微孔直径大于20μm且50μm以下的累积微孔容积为总微孔容积的50%以上,以及
(iii)利用水银压入法测定的微孔直径大于50μm的累积微孔容积为总微孔容积的12%以上。
通过催化剂负载于本发明的陶瓷蜂窝结构体,从而废气能够容易地在隔壁内部的微孔中流通,因此能够得到催化剂所带来的有害物质的除去能力高、且压力损失小的废气净化用的陶瓷蜂窝结构体。
(a)隔壁的气孔率
隔壁的气孔率为50~80%。隔壁的气孔率小于50%时,在负载催化剂后的陶瓷蜂窝结构体中,无法维持低的压力损失,另一方面,若气孔率超过80%,则变得无法确保使用时能够经受的强度。上述气孔率优选为55~75%,进一步优选为58~72%。
(b)隔壁的中值微孔直径
利用水银压入法测定的中值微孔直径为25~50μm。上述中值微孔直径小于25μm时,在负载了催化剂后的陶瓷蜂窝结构体中,有时压力损失特性降低,另一方面,若中值微孔直径超过50μm,则由于强度降低而有时在使用上成为问题。中值微孔直径优选为28~45μm,进一步优选为30~40μm。
(c)隔壁的微孔直径分布
对于隔壁而言,利用水银压入法测定的(i)微孔直径20μm以下的累积微孔容积为总微孔容积的25%以下,(ii)微孔直径大于20μm且50μm以下的累积微孔容积为总微孔容积的50%以上,以及(iii)微孔直径大于50μm的累积微孔容积为总微孔容积的12%以上。通过使隔壁具有这样的微孔直径分布,从而稳定地维持陶瓷蜂窝结构体的强度,并且在负载催化剂后的陶瓷蜂窝结构体中,废气能够更容易地在隔壁内部的微孔中流通,由此,催化剂所带来的有害物质的除去能力更高,并且压力损失进一步变小。
微孔直径20μm以下的累积微孔容积超过总微孔容积的25%时,微孔直径大于20μm的微孔的比例相对变少,因此压力损失变差。微孔直径20μm以下的累积微孔容积的比例优选为3~22%,进一步优选为5~18%。
微孔直径大于20μm且50μm以下的累积微孔容积小于总微孔容积的50%时,在负载催化剂后的陶瓷蜂窝结构体中,微小微孔及粗大微孔的比例变大,导致压力损失特性的恶化和强度的降低。微孔直径大于20μm且50μm以下的累积微孔容积的比例优选为55~80%,进一步优选为60~75%。
微孔直径大于50μm的累积微孔容积小于总微孔容积的12%时,在负载催化剂后的陶瓷蜂窝结构体中,压力损失特性降低。微孔直径大于50μm的累积微孔容积的比例优选为15~30%,进一步优选为18~25%。
优选微孔分布偏差σ为0.35以下。若微孔分布偏差σ大于0.35,则给压力损失及强度带来不良影响的微孔的比例变多。优选为0.32以下,进一步优选为0.30以下。在此,微孔分布偏差σ=log(d20)-log(d80),d20在表示微孔直径与累积微孔容积(对最大的微孔直径至特定的微孔直径为止的微孔容积进行累积而得的值)之间的关系的曲线中,表示相当于总微孔容积的20%的微孔容积下的微孔直径(μm),d80同理表示相当于总微孔容积的80%的微孔容积下的微孔直径(μm)。d80<d20。上述微孔直径与累积微孔容积之间的关系可以通过水银压入法进行测定。特别优选通过水银孔隙计进行测定。
(d)在隔壁表面开口的微孔的开口面积率
优选在隔壁表面开口的微孔的开口面积率(隔壁表面的每单位面积中开口的微孔的总面积)为30%以上。上述开口面积率小于30%时,废气变得难以在隔壁内部的微孔中流通,因此废气与隔壁的表面、内部的微孔中负载的催化剂的接触变少,有时净化效率降低。
在此,在隔壁表面开口的微孔的开口面积率如下计算:例如,由如图2所示的、以隔壁厚度的2倍以上的视野面积(例如,隔壁厚度为300μm时,600μm×600μm以上的视野)拍摄隔壁的表面而得的电子显微镜照片,利用图像解析装置(例如,Media Cybernetics公司制Image-Pro Plus ver.6.3)求出各微孔的开口面积的合计,再除以测定视野面积而算出开口面积率。
(e)在隔壁表面开口的微孔的中值开口直径
以等效圆直径表示在隔壁表面开口的微孔时的中值开口直径优选为60μm以上。上述中值开口直径小于60μm时,在负载催化剂后的陶瓷蜂窝结构体中,有时压力损失变大。
在此,在隔壁表面开口的微孔的中值开口直径是指:相对于开口的微孔的等效圆直径(具有与微孔的开口面积相同的面积的圆的直径),在对隔壁表面开口的微孔的累积面积(对特定的等效圆直径以下的微孔的开口面积进行累积而得的值)进行绘制而得图表中,达到与总微孔面积的50%相当的累积面积的微孔的等效圆直径。上述微孔的开口面积和等效圆直径可如下求得:由拍摄隔壁的表面而得的电子显微镜照片,使用图像解析装置(例如,Media Cybernetics公司制Image-Pro Plus ver.6.3)进行解析而求得。
(f)隔壁表面的微孔直径分布
(i)在隔壁表面开口的微孔的开口直径30μm以下的累积开口面积
以等效圆直径表示在隔壁表面开口的微孔时的开口直径30μm以下的累积开口面积优选为总开口面积的20%以下。上述开口直径30μm以下的累积开口面积大于总开口面积的20%时,在负载催化剂后的陶瓷蜂窝结构体中,有时压力损失变大。上述开口直径30μm以下的累积开口面积优选为总开口面积的17%以下,进一步优选为15%以下。
(ii)在隔壁表面开口的微孔的开口直径100μm以上的累积开口面积
以等效圆直径表示在隔壁表面开口的微孔时的开口直径100μm以上的累积开口面积优选为总开口面积的30~70%。上述开口直径100μm以上的累积开口面积小于总开口面积的30%时,废气变得难以在隔壁内部的微孔中流通,因此废气与隔壁的表面、内部的微孔中负载的催化剂的接触变少,有时净化效率降低,超过70%时,导致强度的降低。上述开口直径100μm以上的累积开口面积优选为总开口面积的33~65%,进一步优选为35~60%。
(g)通气度
隔壁的通气度优选为10×10-12~30×10-12m2。由于隔壁的通气度为10×10-12~30×10-12m2,因此可以得到催化剂所带来的有害物质的除去能力更高、且即使在负载催化剂后压力损失也较小的废气净化用的陶瓷蜂窝结构体。隔壁的通气度小于10×10-12时,负载催化剂后的陶瓷蜂窝结构体的压力损失增加,另一方面,超过30×10-12m2时,有时隔壁的强度降低。隔壁的通气度优选为12×10-12~28×10-12m2。
(h)A轴压缩强度
陶瓷蜂窝结构体的A轴压缩强度优选为1.0MPa以上。由于陶瓷蜂窝结构体的A轴压缩强度为1.0MPa以上,因此可以得到催化剂所带来的有害物质的除去能力更高、且即使在负载催化剂后压力损失也较小的废气净化用的陶瓷蜂窝结构体。陶瓷蜂窝结构体的A轴压缩强度小于1.0MPa时,有时无法维持使用时能够经受的强度。上述A轴压缩强度优选为1.2MPa以上。
(i)热膨胀系数
陶瓷蜂窝结构体的20~800℃间的热膨胀系数优选为15×10-7/℃以下。具有这种热膨胀系数的陶瓷蜂窝结构体具有高的耐热冲击性,因此作为由内燃机排出的废气的净化用催化剂载体、微粒捕集用过滤器,可足以经受实用。上述热膨胀系数优选为3×10-7/℃~13×10-7/℃。
(j)其他的构成
优选为,陶瓷蜂窝结构体的平均隔壁厚度为0.10~0.50mm,平均孔道密度为150~500cpsi。由于陶瓷蜂窝结构体具有这样的平均隔壁厚度和平均孔道密度,因此能够得到可维持强度且压力损失小的废气净化用的陶瓷蜂窝结构体。平均隔壁厚度小于0.10mm时,隔壁的强度降低,另一方面,大于0.50mm时,将难以维持低的压力损失。平均隔壁厚度优选为0.15~0.45mm。另外,平均孔道密度小于150cpsi(23.3孔道/cm2)时,隔壁的强度降低,另一方面,超过500cpsi(77.5孔道/cm2)时,将难以维持低的压力损失。平均孔道密度优选为170~300cpsi,进一步优选为160~280cpsi。
作为陶瓷蜂窝结构体的材质,从陶瓷蜂窝结构体用作废气净化用的催化剂载体、微粒捕集用的过滤器的方面考虑,优选为具有耐热性的陶瓷、即以氧化铝、莫来石、堇青石、碳化硅、氮化硅、氧化锆、钛酸铝、锂铝硅酸盐等作为主结晶的陶瓷。其中,优选以耐热冲击性优异的低热膨胀的堇青石作为主结晶。主结晶相为堇青石时,可以含有尖晶石、莫来石、假蓝宝石等其他结晶相,还可以含有玻璃成分。
陶瓷蜂窝结构体的制造方法
制造本发明的陶瓷蜂窝结构体的方法的特征在于,包括:将包含堇青石化原料和造孔材料的原料粉末混炼而得到坯土的工序;将所述坯土挤出成形而得到蜂窝状的成形体的工序;以及对所述成形体进行干燥和烧成而得到陶瓷蜂窝结构体的工序,
(a)上述堇青石化原料包含具有10~60μm的中值粒径的二氧化硅10~25质量%,
(b)对于上述造孔材料而言,
(i)具有大于70μm且200μm以下的中值粒径,
(ii)在表示粒径与累积体积(累积特定的粒径以下的粒子体积而得的值)的关系的曲线中,与总体积的90%相当的累积体积下的粒径D90为90~250μm,以及与总体积的10%相当的累积体积下的粒径D10为15~160μm,
(iii)粒度分布偏差SD为0.3以下,
(c)上述造孔材料的含量相对于堇青石化原料为1~20质量%。
通过这样的方法,可以得到如下的陶瓷蜂窝结构体,
其隔壁的气孔率为50~80%,
利用水银压入法测定的上述隔壁的中值微孔直径为25~50μm,
利用水银压入法测定的(i)微孔直径20μm以下的累积微孔容积为总微孔容积的25%以下,(ii)微孔直径大于20μm且50μm以下的累积微孔容积为总微孔容积的50%以上,以及(iii)微孔直径大于50μm的累积微孔容积为总微孔容积的12%以上。
(a)堇青石化原料
堇青石化原料是指,以使主结晶为堇青石(主成分的化学组成为42~56质量%的SiO2、30~45质量%的Al2O3和12~16质量%的MgO)的方式配合二氧化硅源成分、氧化铝源成分和氧化镁源成分的各原料粉末而得的原料。在以堇青石为主结晶的陶瓷中形成的微孔主要具有:烧成二氧化硅而产生的微孔和造孔材料燃烧而产生的微孔。
在堇青石化原料中使用中值粒径为10~60μm的二氧化硅10~25%。二氧化硅的中值粒径小于10μm时,使压力损失特性变差的微小微孔变多,另一方面,在超过60μm时,使强度降低的粗大微孔变多。二氧化硅的中值粒径优选为35~55μm。
(b)造孔材料
造孔材料具有大于70μm且200μm以下的中值粒径。造孔材料的中值粒径为70μm以下时,隔壁的表面和内部所形成的微孔相对变小,将难以与催化剂有效地接触,有时净化效率降低。另外,若中值粒径超过200μm,则形成的微孔变得粗大,强度降低。造孔材料的中值粒径优选为75~180μm,进一步优选为80~150μm。
在表示造孔材料的粒径与累积体积(累积特定的粒径以下的粒子体积而得的值)之间的关系的曲线中,与总体积的90%相当的累积体积下的粒径D90为90~250μm,与总体积的10%相当的累积体积下的粒径D10为15~160μm,并且粒度分布偏差SD为0.3以下。
在造孔材料具有这样的粒径分布的情况下,容易得到具有上述的微孔结构的隔壁。在此,粒径D10与粒径D90满足D90>D10的关系。
上述粒度分布偏差是以SD=log(D80)-log(D20)定义的值。其中,D20为在表示粒径与累积体积(表示特定的粒径以下的粒子体积为总体的多少%)的关系的曲线(累积粒度分布曲线)中与20%的累积体积相当的粒径(μm),D80同理为与80%的累积体积相当的粒径(μm)。D20<D80。粒度分布偏差SD优选为0.27以下,进一步优选为0.25以下。造孔材料的粒径(粒子分布)可以使用日机装(株)制Micro Trak粒度分布测定装置(MT3000)进行测定。
作为造孔材料,可以使用小麦粉、石墨、淀粉粉末、中实或中空的树脂(聚甲基丙烯酸甲酯、聚甲基丙烯酸丁酯、聚丙烯酸酯、聚苯乙烯、聚乙烯、聚对苯二甲酸乙二醇酯、甲基丙烯酸酯甲酯-丙烯腈共聚物等)等。它们之中,优选中空的树脂粒子,其中,优选由甲基丙烯酸甲酯-丙烯腈共聚物形成的中空的树脂粒子。对于中空的树脂粒子而言,优选内包有烃等气体、且外壳厚度为0.1~2μm的中孔的树脂粒子,优选含有70~95%的水分的中空的树脂粒子。通过含有上述水分,从而树脂粒子的滑动性得到改善,在混合、混炼和成形中,树脂粒子不易被压碎。
(c)制造工序
陶瓷蜂窝结构体通过如下工序来制造,所述工序包括:在具有堇青石化原料和造孔材料的原料粉末中添加粘合剂、水等并进行混炼而得到坯土的工序;通过公知的方法将所得的坯土从模具挤出,由此形成蜂窝结构的成形体的工序;以及将上述成形体干燥后,根据需要实施端面和外周等的加工,再进行烧成的工序。
使用连续炉或间歇炉,边调整升温和冷却的速度边进行烧成。陶瓷原料为堇青石化原料时,在1350~1450℃下保持1~50小时,堇青石主结晶充分生成后,冷却至室温,得到主结晶相为堇青石的陶瓷蜂窝结构体。需要说明的是,也可以含有尖晶石、莫来石、假蓝宝石等其他的结晶相,还可以含有玻璃成分。对于上述升温速度而言,尤其是在制造外径150mm以上、以及全长150mm以上的大型的陶瓷蜂窝结构体的情况下,为了在烧成过程不使成形体发生皲裂,优选在粘合剂发生分解的温度范围(例如150~350℃)中为0.2~10℃/hr,在堇青石化反应进行的温度区域(例如1150~1400℃)中为5~20℃/hr。冷却特别优选在1400~1300℃的范围内以20~40℃/h的速度进行。
使所得的蜂窝陶瓷结构体的隔壁上负载含有选自Pt、Rh、Pd中的一种以上的贵金属的催化剂,从而可制成废气净化用催化剂载体。
对于所得的蜂窝陶瓷结构体而言,也可以通过公知的方法对所希望的流路的端部或流路内部进行网眼密封而制成陶瓷蜂窝过滤器。需要说明的是,该网眼密封部也可以在烧成前形成。
实施例
(1)陶瓷蜂窝结构体的制作(实施例1~16和比较例1~10)
将具有表1所示粒径的二氧化硅、高岭土、滑石、氧化铝、氢氧化铝的原料粉末以表3所示的添加量进行调整,制成具有包含50质量%的SiO2、35质量%的Al2O3、和13质量%的MgO的化学组成的堇青石化原料粉末。相对于该堇青石化原料粉末,添加表2所示的造孔材料和甲基纤维素并混合后,添加水并进行混炼,制作出包含具有可塑性的堇青石化原料的陶瓷坯土。使用挤出成形管头对该坯土进行挤出成形,得到隔壁厚度13mil(0.33mm)、孔道密度255cpsi(39.5孔道/cm2)的蜂窝结构的成形体,干燥后,对蜂窝结构的干燥体的边缘部进行除去加工,利用烧成炉在最高温度1410℃的条件下按照200小时的时间表进行烧成,得到主结晶为堇青石的陶瓷蜂窝结构体。在烧成后的陶瓷蜂窝结构体的外周,涂敷包含非晶质二氧化硅和胶体二氧化硅的外皮材料并使其干燥,得到外径266.7mm、全长304.8mm的实施例1~16和比较例1~10的陶瓷蜂窝结构体各2个。
(2)陶瓷蜂窝结构体的隔壁结构、通气度和强度的测定
对于实施例1~16和比较例1~10中得到的陶瓷蜂窝结构体各1个,将其切割为试样,进行利用水银压入法的隔壁的微孔分布的测定、在隔壁表面开口的微孔直径及其分布的测定、通气度、以及A轴压缩强度的测定。将它们的结果示于表4。
利用水银压入法的测定如下进行:将由陶瓷蜂窝过滤器切割而得到的试验片(10mm×10mm×10mm)收纳于Micromeritics公司制Auto pore III的测定设备内,使孔道内减压后,导入水银并进行加压,求出加压时的压力、与压入试验片内所存在的微孔中的水银的体积之间的关系。根据上述压力与体积之间的关系,求出微孔直径与累积微孔容积之间的关系(累积微孔容积分布曲线)。将导入水银的压力设为0.5psi(0.35×10-3kg/mm2),由压力计算微孔直径时的常数使用接触角=130°和表面张力=484dyne/cm的值。
根据利用水银压入法求得的累积微孔容积分布曲线、即微孔直径与累积微孔容积之间的关系,求出气孔率、微孔直径以及其分布。气孔率是根据总微孔容积的测定值,将堇青石的真比重设为2.52g/cm3,通过计算而求出的。微孔的中值微孔直径、以及规定的微孔直径分布(微孔直径20μm以下的累积微孔容积、微孔直径大于20μm且50μm以下的累积微孔容积、和微孔直径大于50μm的累积微孔容积)根据累积微孔容积分布曲线而求出。
在隔壁表面开口的微孔直径及其分布通过在800μm×800μm的视野中,根据拍摄隔壁的表面而得的电子显微镜照片,利用图像解析装置(例如,Media Cybernetics公司制Image-Pro Plus ver.6.3)进行解析而求得。算出在隔壁表面开口的微孔的开口面积率、在隔壁表面开口的微孔的中值开口直径、以等效圆直径表示在隔壁表面开口的微孔时的中值开口直径、开口直径30μm以下的累积开口面积、以及开口直径100μm以上的累积开口面积。
通气度设为使用Perm Automated Porometer(注册商标)6.0版(PorousMaterials公司),边使空气流量从30cc/sec增加至400cc/sec边进行测定而得的通气度的最大值。
A轴压缩强度按照社团法人汽车技术会规定的标准M505-87“汽车废气净化用陶瓷整体载体的试验方法”进行测定。
20~800℃间的热膨胀系数(CTE)使用由蜂窝过滤器切割而成的另外的试验片进行测定。
(3)过滤器性能的评价
使实施例1~16和比较例1~10中得到的陶瓷蜂窝结构体中的剩余的各1个如下操作而负载催化剂,对所得的过滤器的压力损失和催化剂效果进行了评价。
(a)催化剂的负载
将含有活性氧化铝、作为贵金属的铂(Pt)和作为助催化剂的铈(Ce)的氧化物(CeO2)的催化剂浆料利用吸引法导入陶瓷蜂窝结构体的隔壁表面和隔壁内部的微孔而形成涂布层,进行加热干燥,制作出负载有催化剂的陶瓷蜂窝结构体。
(b)压力损失
向固定于压力损失试验架的陶瓷蜂窝结构体以10Nm3/min的流量送入空气,求出此时的流入侧与流出侧之间的压差作为初期压力损失。其结果是将压力损失相对于比较例1的压力损失为
0.9倍以上的情形设为(×)
大于0.7倍且0.9倍以下的情形设为(△)、
大于0.5倍且0.7倍以下的情形设为(○)、及
0.5倍以下的情形设为(◎),
由此来评价压力损失。将结果示于表4。
(c)催化剂效果
向负载有催化剂的陶瓷蜂窝结构体导入废气温度为300℃、且包含400ppm的NOx的废气,添加于废气中的NOx量为等量的柴油燃料(HC),测定负载有催化剂的陶瓷蜂窝结构体出口处的废气中的NOx量,测定催化剂所带来的净化效果。其结果是将NOx量相对于比较例1的NOx量为
0.9倍以上的情形设为(×)
大于0.7倍且0.9倍以下的情形设为(△)、
大于0.5倍且0.7倍以下的情形设为(○)、及
0.5倍以下的情形设为(◎),
由此来评价催化剂所带来的净化效果。将结果示于表4。
表1
表2
表3
续表3
表4
续表4
续表4
根据表4可知,本发明的实施例1~16的陶瓷蜂窝结构体可维持强度,并且在负载催化剂后的陶瓷蜂窝结构体中,催化剂所带来的有害物质的除去能力高,且压力损失小。另一方面,对于比较例1~10的陶瓷蜂窝结构体而言,在强度、负载催化剂后的陶瓷蜂窝结构体中催化剂所带来有害物质的除去能力、压力损失方面存在问题。
Claims (8)
1.一种陶瓷蜂窝结构体,其特征在于,
其为具有被多孔质的隔壁隔开的多个孔道的陶瓷蜂窝结构体,
对于所述隔壁,
(a)气孔率为50~80%,
(b)利用水银压入法测定的中值微孔直径为25~50μm,
(c)(i)利用水银压入法测定的微孔直径20μm以下的累积微孔容积为总微孔容积的25%以下,
(ii)利用水银压入法的测定的微孔直径大于20μm且50μm以下的累积微孔容积为总微孔容积的50%以上,以及
(iii)利用水银压入法测定的微孔直径大于50μm的累积微孔容积为总微孔容积的12%以上。
2.根据权利要求1所述的陶瓷蜂窝结构体,其特征在于,
在所述隔壁表面开口的微孔的开口面积率、即隔壁表面的每单位面积中开口的微孔的总开口面积为30%以上。
3.根据权利要求1所述的陶瓷蜂窝结构体,其特征在于,
以等效圆直径表示在所述隔壁表面开口的微孔时,中值开口直径为60μm以上。
4.根据权利要求1所述的陶瓷蜂窝结构体,其特征在于,
以等效圆直径表示在所述隔壁表面开口的微孔时,开口直径30μm以下的累积开口面积为总开口面积的20%以下。
5.根据权利要求1所述的陶瓷蜂窝结构体,其特征在于,
以等效圆直径表示在所述隔壁表面开口的微孔时,开口直径100μm以上的累积开口面积为总开口面积的30~70%。
6.根据权利要求1所述的陶瓷蜂窝结构体,其特征在于,
所述隔壁的通气度为10×10-12~30×10-12m2。
7.根据权利要求1~6中任一项所述的陶瓷蜂窝结构体,其特征在于,
所述陶瓷蜂窝结构体的A轴压缩强度为1.0MPa以上。
8.一种陶瓷蜂窝结构体的制造方法,其特征在于,其是权利要求1所述的陶瓷蜂窝结构体的制造方法,
包括:将包含堇青石化原料和造孔材料的原料粉末混炼而得到坯土的工序;将所述坯土挤出成形而得到蜂窝状的成形体的工序;以及对所述成形体进行干燥和烧成而得到陶瓷蜂窝结构体的工序,
(a)所述堇青石化原料包含具有10~60μm的中值粒径的二氧化硅10~25质量%,
(b)对于所述造孔材料,
(i)具有大于70μm且200μm以下的中值粒径,
(ii)在表示粒径与累积体积的关系的曲线中,与总体积的90%相当的累积体积下的粒径D90为90~250μm,以及与总体积的10%相当的累积体积下的粒径D10为15~160μm,
(iii)粒度分布偏差SD为0.3以下,
(c)所述造孔材料的含量相对于堇青石化原料为1~20质量%,
其中,累积体积是累积特定粒径以下的粒子体积而得的值。
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