CN101564645A - 涂布金属基质 - Google Patents
涂布金属基质 Download PDFInfo
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- CN101564645A CN101564645A CNA2009101416441A CN200910141644A CN101564645A CN 101564645 A CN101564645 A CN 101564645A CN A2009101416441 A CNA2009101416441 A CN A2009101416441A CN 200910141644 A CN200910141644 A CN 200910141644A CN 101564645 A CN101564645 A CN 101564645A
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- 229910052751 metal Inorganic materials 0.000 title claims abstract description 67
- 239000002184 metal Substances 0.000 title claims abstract description 67
- 239000000758 substrate Substances 0.000 title claims abstract description 36
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 39
- 239000003054 catalyst Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 22
- 239000011248 coating agent Substances 0.000 claims abstract description 17
- 238000000576 coating method Methods 0.000 claims abstract description 17
- YKTSYUJCYHOUJP-UHFFFAOYSA-N [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] Chemical compound [O--].[Al+3].[Al+3].[O-][Si]([O-])([O-])[O-] YKTSYUJCYHOUJP-UHFFFAOYSA-N 0.000 claims abstract description 13
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000006185 dispersion Substances 0.000 claims abstract description 10
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 5
- 239000000956 alloy Substances 0.000 claims abstract description 5
- 229910000856 hastalloy Inorganic materials 0.000 claims abstract description 5
- 229910000975 Carbon steel Inorganic materials 0.000 claims abstract description 4
- 229910000604 Ferrochrome Inorganic materials 0.000 claims abstract description 4
- 239000010962 carbon steel Substances 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 4
- 239000010935 stainless steel Substances 0.000 claims abstract description 4
- 229910001220 stainless steel Inorganic materials 0.000 claims abstract description 4
- 239000011159 matrix material Substances 0.000 claims description 28
- 238000001354 calcination Methods 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 12
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 238000010531 catalytic reduction reaction Methods 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 4
- 238000002407 reforming Methods 0.000 claims 2
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000007789 gas Substances 0.000 description 12
- 239000012790 adhesive layer Substances 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 239000005995 Aluminium silicate Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 229910000323 aluminium silicate Inorganic materials 0.000 description 5
- 235000012211 aluminium silicate Nutrition 0.000 description 5
- 238000002485 combustion reaction Methods 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000005507 spraying Methods 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 238000005422 blasting Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 230000035939 shock Effects 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- -1 Sodium potassium aluminum Chemical compound 0.000 description 2
- 230000001133 acceleration Effects 0.000 description 2
- 229920006243 acrylic copolymer Polymers 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000001680 brushing effect Effects 0.000 description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 2
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 2
- QDOXWKRWXJOMAK-UHFFFAOYSA-N dichromium trioxide Chemical compound O=[Cr]O[Cr]=O QDOXWKRWXJOMAK-UHFFFAOYSA-N 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N ferric oxide Chemical compound O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 229910052863 mullite Inorganic materials 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 230000003584 silencer Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- GQPLMRYTRLFLPF-UHFFFAOYSA-N Nitrous Oxide Chemical class [O-][N+]#N GQPLMRYTRLFLPF-UHFFFAOYSA-N 0.000 description 1
- 229910018487 Ni—Cr Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- BNUDRLITYNMTPD-UHFFFAOYSA-N acetic acid;zirconium Chemical compound [Zr].CC(O)=O BNUDRLITYNMTPD-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ITHZDDVSAWDQPZ-UHFFFAOYSA-L barium acetate Chemical compound [Ba+2].CC([O-])=O.CC([O-])=O ITHZDDVSAWDQPZ-UHFFFAOYSA-L 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- VNNRSPGTAMTISX-UHFFFAOYSA-N chromium nickel Chemical group [Cr].[Ni] VNNRSPGTAMTISX-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 239000008199 coating composition Substances 0.000 description 1
- 239000011247 coating layer Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052878 cordierite Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 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 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 230000005484 gravity Effects 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
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 230000010358 mechanical oscillation Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003534 oscillatory effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000011179 visual inspection Methods 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
- B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/63—Platinum group metals with rare earths or actinides
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0225—Coating of metal substrates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/024—Multiple impregnation or coating
- B01J37/0244—Coatings comprising several layers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/16—Clays or other mineral silicates
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
- Y02T10/00—Road transport of goods or passengers
- Y02T10/10—Internal combustion engine [ICE] based vehicles
- Y02T10/12—Improving ICE efficiencies
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/25—Web or sheet containing structurally defined element or component and including a second component containing structurally defined particles
- Y10T428/252—Glass or ceramic [i.e., fired or glazed clay, cement, etc.] [porcelain, quartz, etc.]
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Abstract
用于小型发动机平台的、用于担载尾气排放催化处理催化剂例如三元转化催化剂的涂布金属基质。涂布金属基质包含选自例如不锈钢、碳钢、钛、FeCr合金和哈氏合金等的金属。金属催化剂涂层包括其中分散有氧化铝颗粒的硅酸铝。用含有硅酸铝的分散液涂布并且在涂层依然湿润时将氧化铝颗粒分散于硅酸铝中。随后煅烧涂布金属基质。然后可将包含发动机尾气处理催化剂的修补基面涂层施于涂布金属基质的表面上。
Description
发明领域
本发明涉及用于担载发动机尾气处理催化剂的涂布金属基质。
发明背景
小型内燃机，尤其是两冲程和四冲程火花点燃式发动机，被用来给各种机器例如汽油驱动割草机、链锯、叶片鼓风机、线切割机(string cutter)、叶片鼓风机、小型摩托车、摩托车等提供动力。这样的发动机使催化尾气处理装置处于恶劣环境下工作。这归因于：在小型发动机中，尾气中含有高浓度未燃烧的燃料和未消耗的氧气。
此外，两冲程发动机的振动力可达四冲程发动机的3到4倍。例如，据报道，小型内燃机在150赫兹下能产生70到90重力加速度的震动加速度。小型内燃机的强烈震动和尾气温度条件导致了几种尾气催化处理装置失效的模式，包括通过其将催化剂元件固定在装置中的支撑结构的失效，和作为结果的、机械振动导致的催化剂元件损坏或损毁，以及在高温条件下的尾气的流量波动。
催化剂元件一般含有通常由例如堇青石、多铝红柱石等制成的陶瓷类载体元件，在其上涂有尾气处理催化剂材料。陶瓷类材料将由于过度震动开裂并粉碎。金属载体元件，也就是金属基质，显然可用来替代陶瓷类材料，但有如下所公开的它们自己的问题。
在不远的将来，小型内燃机将受到严格的联邦和各州的排放控制法规的约束。由此，这些小型发动机将需要类似当前用于控制汽车排放的尾气排放控制系统。
对于小型内燃机所用的尾气排放控制系统，通常将控制烃类、一氧化碳和氮氧化物排放的尾气控制处理催化剂如三元转化(“TWC”)催化剂涂在金属基质(在现有技术中也称作金属载体元件)上。所面临的挑战在于，对于寿命有限的各种小型发动机平台，赋予金属基质这样的物理性质，即使得催化剂能够承受剧烈震动下的高温条件和来自油的毒物以及灰分，以及这样的小型发动机平台在宽范围的空气/燃料比和空间速度下运行的需要。贵金属催化剂和金属基质热胀系数上的严重差异会使这个问题更加严重。
尾气排放控制催化剂材料通常以例如直径为10到20微米的微米级颗粒度范围的颗粒形式使用，这样就可以将它们制成浆料，并被用作载体元件上的修补基面涂层。展现出很好的活性和长寿命的已知TWC催化剂含有一种或多种沉积在高表面积的难熔氧化物载体(例如高表面积的氧化铝涂层)上的铂族金属(例如铂或钯，铑，钌和铱)。用尾气排放控制处理催化剂如TWC催化剂涂布金属基质所产生的主要问题是在很宽范围的条件下(在小型发动机平台的运行过程中，涂有催化剂的金属基质将被暴露在这样的条件下)将催化剂粘结到金属基质上。
发明目的
本发明的一个目的是提供涂布组合物和有效地将尾气排放控制处理催化剂固定到涂布金属基质上的方法。
发明综述
本发明涉及发动机尾气排放物催化还原所用的涂布金属基质，包括金属基质和金属基质上的氧化铝-硅酸盐涂层，上述的涂层中分散有氧化铝颗粒。
发明详述
为了本发明的目的，金属基质可包含一种金属如不锈钢、碳钢、钛、FeCr合金或哈氏合金。哈氏合金是非注册商标合金，它的主要组分是镍-铬和钼并含有包含钴、铁和钨的微量组分。
通常用于小型发动机平台的金属基质以膨胀锥体(expansion cone)或废气消音器(exhauset gas silencer)的形式存在，长约为100到约300mm，直径在约30到约100mm的范围内，厚度为约0.5到约3mm以及内表面积为约0.03到0.06mm2。
金属基质表面上的粘合层含有其中分布有氧化铝颗粒的氧化铝-硅酸盐组合物。已经发现氧化铝-硅酸盐组合物与金属基质的表面非常好地粘合。然而，氧化铝-硅酸盐粘合层的表面很光滑，尾气排放物处理催化剂组合物不能很好地附着至粘合层的表面，特别是在小型发动机平台运行过程中涂布金属基质所处的条件下。发明人发现，当氧化铝的颗粒在粘合层还湿润时被分散在其中时，所得到的涂布金属基质经煅烧后，在小型发动机平台的所有运行条件下，尾气排放物处理催化剂都能很好地附着到涂布金属基质上。
施用粘合层和将氧化铝颗粒分散在粘合层中的过程相对简单。如果需要，对金属基质进行喷砂处理以形成粗糙表面并除去任何不需要的颗粒；其后，喷砂处理的金属基质可用30％醋酸洗涤，然后用水冲洗。然后借助例如浸渍、涂刷、海绵辊、空气枪喷雾等方法，将含有水性分散体(其中主要成分是硅酸铝)的粘合层组合物施于金属基质的洁净表面上。其后通过例如浸渍、涂刷等方法在金属基质上的粘合层仍湿润时将氧化铝颗粒施于涂布金属基质上。然后可从粘合表面除去松动的氧化铝颗粒，例如借助温和的空气流，通过在硬表面上轻拍等，而后将所得到的涂布金属基质煅烧。煅烧后，可通过现有技术中已知的常规方法将含有一种或多种贵金属如铂、钯、铑等的尾气排放物处理催化修补基面涂层施于涂布金属基质表面，紧接着干燥和煅烧担载了催化剂的涂布金属基质。
制备本发明的涂布金属基质的方法可总结为包括以下步骤：
(a)用含有硅酸铝的分散液涂布金属基质；
(b)在涂在金属基质上的硅酸铝依然湿润时，用氧化铝颗粒浸渍从步骤(a)所得到的涂布金属基质；以及
(c)煅烧从步骤(b)所得到的涂布金属基质。
含有硅酸铝的分散液在现有技术中是已知的并且可商购。适宜的硅酸铝分散体组成如下：
组分 量，重量％
硅酸钠钾铝 约40到约45
水 约35到约40
丙烯酸共聚物 约1到约5
氧化铬二氧化钛玻璃料 约1到约5
氧化铝 约1到约5
氢氧化钾 约1到约5
无定形氧化硅 约1到约5
氧化钴 约1到约5
另一适宜的硅酸铝分散体组成如下：
组分 量，重量％
碳化硅 约45到约50
水 约20到约26
磷酸铝 约10到约15
无定形氧化硅粘合剂 约2到约6
硼酸 约1到约3
乙醇 约3到约7
多铝红柱石 约4到约6
在方法步骤(b)中，氧化铝颗粒是以粉末状施用的，其中颗粒的颗粒度在约5到约15微米的范围内，优选6到9微米。将氧化铝颗粒以0.01到0.5g/in2用于方法步骤(a)中的硅酸铝涂层的量使用。步骤(c)，即煅烧，在约350到约550℃的温度下进行约0.25到约2小时。
然后将含有发动机尾气处理催化剂的修补基面涂层施于(例如通过喷雾、浸渍、辊涂等)从步骤(c)得到的涂布金属基质上，然后在约60到约100℃的空气中干燥约0.5到约2小时，随后在约350到约550℃的温度下煅烧约0.25到约2小时。
下面的非限制性实施例用于说明本发明实现方案。除非另外指出，所有的份数和百分比都基于重量。
实施例1
在本实施例中所使用的金属基质是由1.3mm规格309锈钢所构成的膨胀锥体。膨胀锥体的长为172mm，内径范围在40.2mm到66.4mm的范围内，计算面积为0.0288m2。将膨胀锥体喷砂处理，用30％醋酸洗涤并用蒸馏水冲洗。
然后用具有下列组成的铝-硅酸盐分散体对洁净的膨胀锥体进行空气枪喷雾：
组分 量，重量％
硅酸钠钾铝 约40到约45
水 约35到约40
丙烯酸共聚物 约1到约5
氧化铬二氧化钛玻璃料 约1到约5
氧化铝 约1到约5
氢氧化钾 约1到约5
无定形氧化硅 约1到约5
氧化钴 约1到约5
然后在450℃的温度下煅烧喷涂过的膨胀锥体30分钟。实验室热冲击试验表明铝-硅酸盐涂层能够容易地耐受超过1000℃的温度循环。
煅烧后，将锥体冷却到室温，然后用手持空气喷枪以1.75g每个锥体的目标比例涂布含有发动机尾气处理催化剂的修补基面涂层，以便给每个锥体施用0.07g贵金属。由发动机尾气处理催化剂的含水浆料(35重量％固体)所组成的修补基面涂层具有下列组成：
组分 量，g/in 3
高表面积氧化铝 0.61
CeZr共沉淀复合物 0.31
醋酸钡 0.04
醋酸锆 0.025
Pt(铵氢氧化物的形式) 0.037
Pd(硝酸盐的形式) 0.0037
然后在80℃下将所得到的锥体空气干燥1小时，然后在450℃的温度下煅烧30分钟。没有对涂布膨胀锥体作进一步研究，因为修补基面涂层浆料没有附着到氧化铝-硅酸盐涂布膨胀锥体上。
实施例2
重复实施例1，以下除外：将同样的铝-硅酸盐分散体用海绵辊子而不是以空气枪喷雾的方式施于膨胀锥体上。然后，在锥体表面被铝-硅酸盐分散体所润湿时，将涂布过的锥体浸入颗粒度范围在2-15微米的氧化铝粉末中。然后在硬表面上轻拍锥体以除去松动的氧化铝颗粒，随后在450℃的温度下煅烧30分钟。涂布锥体含有约0.3g氧化铝颗粒。
煅烧后，将锥体冷却到室温，并用手持空气喷雾枪将与实施例1中所用相同的修补基面涂层以每个锥体1.75g的目标比例施于涂布锥体上，以便给每个锥体施用0.07g贵金属。将所得到的锥体在80℃的温度下空气干燥1小时，然后在450℃的温度下煅烧30分钟。
实施例2的涂布锥体的实验室热冲击试验表明铝-硅酸盐涂层能够容易地耐受超过1000℃的温度循环。实施例2的涂布锥体在固定发电机上刚性连接发动机老化约300小时。老化锥体的目测检查表明涂层没有显著的物理性能恶化。
Claims (11)
1、用于发动机尾气排放物的催化还原的涂布金属基质，其包括其上具有氧化铝-硅酸盐涂层的金属基质，所述氧化铝-硅酸盐涂层中分散有氧化铝颗粒，其中将氧化铝颗粒以0.01到0.5g/in2硅酸铝涂层的量使用。
2、权利要求1的涂布金属基质，其另外包括至少一个包含发动机尾气处理催化剂的顶层。
3、权利要求2的涂布金属基质，所述基质用作三元转化催化剂的基质。
4、权利要求1的涂布金属基质，其中金属基质包含选自不锈钢、碳钢、钛、FeCr合金和哈氏合金的金属。
5、权利要求1的涂布金属基质，其中氧化铝颗粒的颗粒度在5到15微米的范围内。
6、权利要求1的涂布金属基质，其以膨胀锥体或尾气消音器的形式使用。
7、权利要求5的方法生产的涂布金属基质，所述基质用作三元转化催化剂的基质。
8、用于发动机尾气排放物的催化还原的涂布金属基质，所述涂布金属基质由包括以下步骤的方法得到：
(a)用包含硅酸铝的分散液对金属基质进行涂布；
(b)在金属基质上的硅酸铝涂层仍湿润时，用氧化铝颗粒浸渍从步骤(a)所得到的涂布金属基质；以及
(c)煅烧从步骤(b)所得到的涂布金属基质。
9、权利要求8的方法生产的涂布金属基质，其中金属基质包含选自不锈钢、碳钢、钛、FeCr合金和哈氏合金的金属。
10、权利要求8的方法生产的涂布金属基质，其中氧化铝颗粒的颗粒度在5到15微米的范围内。
11、权利要求8的方法生产的涂布金属基质，其以膨胀锥体或尾气消音器的形式使用。
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| US20060079409A1 (en) * | 2004-09-08 | 2006-04-13 | Omniseal, Inc. | Complex mixtures of ions and processes for deposition |
| US20100158775A1 (en) * | 2008-12-18 | 2010-06-24 | Basf Catalysts Llc | Catalyst Systems and Methods for Treating Aircraft Cabin Air |
| US7981390B2 (en) * | 2008-12-23 | 2011-07-19 | Basf Corporation | Small engine palladium catalyst article and method of making |
| CA2750822A1 (en) * | 2009-01-28 | 2010-10-28 | Applied Thin Films Inc. | High temperature stable amorphous silica-rich aluminosilicates |
| US8497018B2 (en) | 2010-01-27 | 2013-07-30 | Applied Thin Films, Inc. | High temperature stable amorphous silica-rich aluminosilicates |
| DE102010022276A1 (de) | 2010-05-31 | 2011-12-01 | Lothar Griesser | Katalysator für die Katalytische Verdampfung und Vergasung flüssiger Brennstoffe |
| CN102631917B (zh) * | 2012-04-09 | 2013-08-07 | 福州大学 | 一种柴油车尾气净化氧化催化剂及其制备方法 |
| CN103657632B (zh) * | 2013-11-27 | 2015-08-26 | 上海纳米技术及应用国家工程研究中心有限公司 | 一种碱液处理整体式氧化铬催化剂及制备方法和应用 |
| US9803139B1 (en) | 2016-06-24 | 2017-10-31 | General Electric Company | Process for removing aluminum-silicon coatings from metallic structures, and related processes for preparing magnetic components |
| CN110293147B (zh) * | 2019-04-26 | 2020-11-10 | 无锡华生精密材料股份有限公司 | 一种高抗氧化电热不锈钢带的生产方法 |
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| WO2005070541A1 (en) | 2005-08-04 |
| EP1713585A1 (en) | 2006-10-25 |
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| US20070082810A1 (en) | 2007-04-12 |
| US7271125B2 (en) | 2007-09-18 |
| JP2007521946A (ja) | 2007-08-09 |
| US7704915B2 (en) | 2010-04-27 |
| CN1909965A (zh) | 2007-02-07 |
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