CN1116115C - 催化活性结构物 - Google Patents
催化活性结构物 Download PDFInfo
- Publication number
- CN1116115C CN1116115C CN99804542A CN99804542A CN1116115C CN 1116115 C CN1116115 C CN 1116115C CN 99804542 A CN99804542 A CN 99804542A CN 99804542 A CN99804542 A CN 99804542A CN 1116115 C CN1116115 C CN 1116115C
- Authority
- CN
- China
- Prior art keywords
- metal
- sheet metal
- oxide layer
- metal oxide
- catalytically active
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- 229910052751 metal Inorganic materials 0.000 claims abstract description 145
- 239000002184 metal Substances 0.000 claims abstract description 145
- 238000002485 combustion reaction Methods 0.000 claims abstract description 12
- 150000004706 metal oxides Chemical class 0.000 claims description 77
- 229910044991 metal oxide Inorganic materials 0.000 claims description 75
- 238000007254 oxidation reaction Methods 0.000 claims description 27
- 230000003647 oxidation Effects 0.000 claims description 25
- 239000000463 material Substances 0.000 claims description 16
- 230000003197 catalytic effect Effects 0.000 claims description 15
- 239000011248 coating agent Substances 0.000 claims description 8
- 238000000576 coating method Methods 0.000 claims description 8
- 239000002912 waste gas Substances 0.000 claims description 8
- 229910052725 zinc Inorganic materials 0.000 claims description 7
- 238000009792 diffusion process Methods 0.000 claims description 6
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052719 titanium Inorganic materials 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 241001466460 Alveolata Species 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 230000000717 retained effect Effects 0.000 claims description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 abstract description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 description 10
- 238000000034 method Methods 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 7
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 6
- 239000011701 zinc Substances 0.000 description 6
- 239000011651 chromium Substances 0.000 description 5
- 239000008246 gaseous mixture Substances 0.000 description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011787 zinc oxide Substances 0.000 description 3
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000001413 cellular effect Effects 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 229910001338 liquidmetal Inorganic materials 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910000792 Monel Inorganic materials 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- WYTGDNHDOZPMIW-RCBQFDQVSA-N alstonine Natural products C1=CC2=C3C=CC=CC3=NC2=C2N1C[C@H]1[C@H](C)OC=C(C(=O)OC)[C@H]1C2 WYTGDNHDOZPMIW-RCBQFDQVSA-N 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
- 239000010953 base metal Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000011888 foil Substances 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910001092 metal group alloy Inorganic materials 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Images
Classifications
-
- 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
- B01J37/12—Oxidising
-
- 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
- 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]
- B01D53/9454—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific device
-
- 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
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
-
- 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
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
- F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
- F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
- F01N3/28—Construction of catalytic reactors
- F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
- F01N3/2807—Metal other than sintered metal
- F01N3/281—Metallic honeycomb monoliths made of stacked or rolled sheets, foils or plates
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/30—Honeycomb supports characterised by their structural details
- F01N2330/44—Honeycomb supports characterised by their structural details made of stacks of sheets, plates or foils that are folded in S-form
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2510/00—Surface coverings
- F01N2510/06—Surface coverings for exhaust purification, e.g. catalytic reaction
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Biomedical Technology (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
- Exhaust Gas After Treatment (AREA)
Abstract
为了减少内燃机废气的污染组分，提出一种有金属薄板(2)的结构物，它有催化活性表面(6)。金属薄板(2)的表面(6)至少部分有催化活性金属氧化物层(7)，特别是氧化钛。
Description
技术领域
本发明涉及一种催化活性结构物，具体地说涉及一种蜂窝状结构物，内燃发动机的废气可从该结构物中流过，它由至少一种有催化活性表面的金属薄板制成。
背景技术
为了减少污染组分，例如未燃烧的烃类、一氧化碳和氮氧化物，使用有催化活性表面的结构物，特别是蜂窝状结构物。结构物可由整体的陶瓷蜂窝状物制成。由卷起来的和/或重叠的金属薄板制成的结构物也是已知的。金属结构物用氧化铝薄层(基面涂层)涂覆。氧化铝使结构物的表面积增加。催化活性材料分布在氧化铝层上。催化活性材料包括铂、铑和钯。
为了优化废气催化转化器起作用的方法，需要准确控制废气中的空气-燃料混合比。为此，将λ探针(Lambda probe)安装在相对于废气流向废气催化转化器上游的废气管线中。λ探针与内燃机的控制***连接，用它可控制内燃机的混合气生成。减少废气污染组分的这一***也称为汽车用三元净化催化转化器。
根据Nonnenmann在他的“汽车中的废气催化转化器的金属载体”，MTZ马达技术杂志，第45卷，第12期/1984中的内容，也有由活性金属薄板例如蒙乃尔高强度耐蚀镍铜合金制作的金属催化剂，但是它们没有可渗透性。
同样在小型发动机领域中，例如在有小汽缸容量的割草机、链锯、摩托车等中，也希望用催化活性结构物来减少从这样的内燃机中排出的废气组分。但是，这样的内燃机没有发动机控制***，以及在废气管中没有λ探针，其结果是不可能控制混合气的生成，以便减少污染。
小型发动机在富油混合气条件下运转，也就是说燃料过量。使用这样的内燃机，产生大量未燃烧的烃类到达催化活性结构物并在那里燃烧的问题。在这方面，产生形成所谓过热点的危险，它可使催化活性表面破坏。特别是，当使用有基面涂层的催化活性结构物时，存在基面涂层可能陶瓷化的危险，以致催化活性结构物仅有较短的工作寿命。
发明内容
在此基础上，本发明的目的是提供这样一种催化活性结构物，它也适用于没有控制混合气生成***的内燃机。
根据本发明，这一目的通过具有如下特点的结构物来实现：它由至少一种金属薄板2、3制成，内燃机的废气可通过它流动，金属薄板2、3有催化活性表面6，其中金属薄板2、3的表面6至少部分有催化金属氧化物层7，氧化物层7是由涂覆到金属薄板2’上的金属层10的氧化来制成的，其特征在于，金属氧化物是第4周期的一种金属的氧化物，该金属选自Ti、V、Zn、Fe、Cr、Mn、Ni、Cu、Co。
本发明优选具有蜂窝状设计的结构物由至少一种有至少一催化活性表面的金属薄板制成。金属薄板的表面至少部分有催化活性金属氧化物层。在这种情况下，金属氧化物层的比活性低于选自贵金属族的催化活性金属的比活性，后者如在三元净化催化转化器中使用的。这样的催化活性结构物特别适用于没有控制混合气生成***的内燃机，因为燃料过量的混合气只有一部分在金属氧化物层的表面上被催化转化，所以所谓过热点的生成可避免。
金属氧化物层直接在金属薄板上形成，以致有可能不涂覆基面涂层形式的载体层，从而简化了这样的结构物的生产。
根据本发明结构物的优选实施方案，提出金属氧化物层的金属是金属薄板材料的一种材料组分。这一构型的优点在于，把金属氧化物层的金属结合到金属薄板的材料中，它提供了金属氧化物层对金属薄板的良好结合。这一金属氧化物层可通过在氧化气氛中热处理金属薄板来形成。
根据结构物另一有利的实施方案，提出通过将涂覆到金属薄板上的金属层氧化来形成金属氧化物层。例如，可用滚压在金属薄板上来涂覆金属层。可将基础材料浸泡在液体金属中来涂覆金属层。作为替代方法，可将金属层喷涂到金属薄板上。在这一情况下，形成金属层的金属可以液体的形式或作为粉尘喷涂。视在什么金属上形成金属层而定，也可用电解沉积法形成金属层。将金属层全表面地涂覆到金属薄板上不是绝对必要的。也可将金属层仅涂覆到金属薄板的某些部分。通过涂覆到金属薄板上的金属层的氧化制成金属氧化物层。
也可直接将金属氧化物层涂覆到金属薄板上，以致金属氧化物层一旦涂覆到金属薄板上，金属薄板就具有催化活性。
根据结构物的另一有利的实施方案，提出金属氧化物层的金属比金属薄板的材料组分有更高的氧化势。这样得到的结果是，首先形成催化活性的金属氧化物层。在催化结构物使用过程中常用的温度下，该金属优选不形成稳定的钝化层。
根据结构物的另一有利的实施方案，提出金属氧化物的金属或金属氧化物至多具有适中的扩散到金属薄板中的能力。这就防止金属在金属氧化物形成以前或者金属氧化物扩散到金属薄板中，以致催化活性的金属氧化物层保留在金属薄板上。特别是还必需确保在升温下有适中的扩散。
为了确保金属氧化物层的催化活性不受金属薄板的材料组分扩散到金属氧化物层中的影响或只有较弱的影响，提出这样构成结构物，以致金属薄板的所有材料组分扩散到金属氧化物层的金属中的扩散至多是适中的。这就防止了金属氧化物层被金属薄板的材料组分富集。
根据本发明结构物的有利的实施方案，提出金属氧化物为第4周期金属的氧化物。特别是，金属氧化物为过渡金属的氧化物。金属氧化物优选为选自Ti、V、Zn、Fe、Cr、Mn、Ni、Cu和Co的金属的氧化物。优选的是，金属氧化物为氧化钛，它比所提到的金属的其他氧化物有相对更高的催化活性。金属薄板本身优选由含有钛作为合金组分的材料制成。此外，金属层的材料还可含铁、铬和镍作为合金组分。
金属氧化物优选由在耐腐蚀基础材料上形成的氧化锌构成。对于氧化反应来说，氧化锌的催化活性比较高。它比氧化铁或氧化铬的高。锌层作为金属层可通过将金属薄板浸泡在液体锌中或通过喷涂锌(液体形式或粉尘)或通过从锌盐溶液中电解沉积来涂覆。
附图简要说明
本发明结构物的其他细节和优点将参考附图表示的说明性实施方案来说明，其中：
图1图示说明结构物1，
图2图示说明有金属氧化物层的金属薄板，
图3说明用于制成有金属氧化物层的金属薄板的设备的第一个说明性实施方案，
图4说明用于制成有金属氧化物层的金属薄板的设备的第二个说明性实施方案，
图5说明用于制成有金属氧化物层的金属薄板的设备的第三个说明性实施方案。
实施方式
图1作为例子图示说明结构物1。结构物1基本上具有蜂窝状设计。它由波纹金属薄板2和平金属薄板3制成。将波纹金属薄板2和平金属薄板3重叠，并缠绕成“S”形。波纹金属薄板2和平金属薄板3构成一些孔道，内燃机的废气可通过这些孔道流动。将波纹金属薄板2和平金属薄板3排列在外管4中。
作为例子在图1中表示的结构物1按这样的方式设计，以致它是催化活性的。如果内燃机的废气通过结构物1，那么内燃机废气的组分发生还原和/或氧化。图2为由金属箔制成的金属薄板2的图示放大图。金属薄板2有催化活性表面6。金属薄板2的催化活性表面6由金属氧化物层7构成。金属薄板的整个表面可有金属氧化物层7。波纹金属薄板2和平金属薄板3都可有金属氧化物层。金属氧化物层7为非贵金属氧化形成的氧化物层。
为了生产有金属氧化物层7的金属薄板2，提出根据图3，将不含氧化物的金属薄板2’连续通过氧化设备8。氧化设备8有一室12，它处于适用于生成金属氧化物层的气氛。氧化设备8还有加热器(未示出)，用加热器使室12中达到适用于生成金属氧化物层7的温度。优选将金属薄板2’在氧化设备8中加热到至少350℃，并在这一氧化温度下保持一段预定的时间。氧化温度和氧化时间主要取决于金属薄板2’的材料和室12中的氧化气氛。根据所希望生成的金属氧化物层7，单个的参数可这样设定，以致在金属薄板2上形成所希望的金属氧化物层7。
在图3的金属薄板2中，通过金属薄板2’的材料组分的金属氧化来生成金属氧化物层7。在这种情况下，金属氧化物层的金属优选比金属薄片2的其他材料组分有更高的氧化势。金属薄板2’的氧化优选按这样的方式进行，以致金属薄板2’不完全被形成金属氧化物层的金属沉积。
还应该这样选择金属薄板2’的金属合金，以致金属氧化物层的金属或金属氧化物显示至多中等的扩散到金属薄板中的扩散。这就确保了实际上形成金属氧化物层7。为了达到金属氧化物层的最大活性，如果金属薄板2’的其他材料组分有至多中等的扩散到金属氧化物层中的扩散速率也是有利的。所以，氧化过程比材料组分扩散到金属氧化物层更快，以致防止了混合氧化物生成。金属氧化物层优选为金属氧化物特别是TiO2、V2O5、ZnO、Fe2O3、Cr2O3、MnO2、NiO、CuO和/或CO3O4形成的氧化物层。但是，由氧化钛生成的金属氧化物层是优选的。
代替金属薄板2’的连续氧化过程，也可进行至少一金属薄板2’的断续氧化。但是，由于经济原因，连续生产过程是有利的。
图4图示了用于制作有金属氧化物层7的金属薄板2的设备的第二个说明性实施方案。该设备有涂覆单元9。使用涂覆单元9，将金属10涂覆到金属薄板2上，金属10可为金属箔。金属10在金属薄板2’上形成金属层11。将用这一方法制成的金属薄板2’送入氧化设备8。在有室12的氧化设备8中，金属层11发生氧化。经氧化的金属层11形成本发明含义的金属氧化物层7。室12有氧化气氛。氧化设备8还有加热设备(未示出)，用它将有金属层11的金属薄板加热。除金属层11的氧化外，还发生金属氧化物层7的金属或金属氧化物结合到金属薄板2上。
可用物理方法或化学方法将金属10涂覆到金属薄板2’上。视涂覆金属薄板2’的步骤而定，如果金属10在氧化气氛中涂覆到金属薄板2’上，那么有可能不需要在单独的氧化设备8中进行另外的氧化。例如，可通过液体金属喷雾到氧化气氛中来涂覆金属。
使用涂覆设备9，可用金属在所选的区域内涂覆金属薄板2’。也可能制成这样一种有金属氧化物层7的金属薄板2，这一金属氧化物层含有不同的金属氧化物或含有不同金属氧化物的加工区域。
图5图示说明生产有金属氧化物层7的金属薄板2的可能途径的另一说明性实施方案。通过用金属氧化物膜13滚压在金属薄板2’上来制作有金属氧化物层7的金属薄板2。如果需要，可将生成的有金属氧化物层7的金属薄板2进行进一步处理，特别是热处理，通过这一处理使金属氧化物层7和金属薄板2之间产生永久性结合。优选用大约8微米厚的金属箔制成金属薄板2或2’。特别是该金属箔为钛箔，为了稳定加入铁、铬和钒。这样的钛膜可很容易变形，以致可特别用于制成金属薄板。
作为一种替代方法，也可通过电镀耐腐蚀的无铝金属箔然后将它在氧化气氛中氧化的方法来制作有金属氧化物层的金属薄板。
符号表
1.结构物 12.室
2.波纹金属薄板 13.金属氧化物膜
3.平金属薄板
4.外管
5.孔道
6.表面
7.金属氧化物层
8.氧化设备
9.涂覆单元
10.金属
11.金属层
Claims (3)
1.一种催化活性蜂窝状结构物(1)，它由至少一种金属薄板(2，3)制成，内燃机的废气可通过它流动，金属薄板(2，3)有催化活性表面(6)，其中金属薄板(2，3)的表面(6)至少部分有催化活性金属氧化物层(7)，氧化物层(7)是由涂覆到金属薄板(2’)上的金属层(10)的氧化来制成的，其特征在于，金属氧化物是第4周期的一种金属的氧化物，该金属选自Ti、V、Zn、Fe、Cr、Mn、Ni、Cu、Co。
2.根据权利要求1的结构物，其中金属氧化物层(7)的金属比金属薄板(2’)的材料组分有更高的氧化势。
3.根据权利要求1或2的结构，其中金属氧化物的金属有适中的向金属薄板(2’)中的扩散，其防止了在金属氧化物形成之前金属向金属薄板的扩散，以致催化活性金属氧化物层保留在金属薄板上。
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19815608A DE19815608A1 (de) | 1998-04-07 | 1998-04-07 | Katalytisch wirksame Struktur |
| DE19815608.1 | 1998-04-07 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1295500A CN1295500A (zh) | 2001-05-16 |
| CN1116115C true CN1116115C (zh) | 2003-07-30 |
Family
ID=7863899
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN99804542A Expired - Fee Related CN1116115C (zh) | 1998-04-07 | 1999-03-26 | 催化活性结构物 |
Country Status (14)
| Country | Link |
|---|---|
| US (1) | US6528452B1 (zh) |
| EP (1) | EP1068012B1 (zh) |
| JP (1) | JP2002510546A (zh) |
| KR (1) | KR100564214B1 (zh) |
| CN (1) | CN1116115C (zh) |
| AU (1) | AU3702399A (zh) |
| DE (2) | DE19815608A1 (zh) |
| ES (1) | ES2221378T3 (zh) |
| FR (1) | FR2777040B1 (zh) |
| ID (1) | ID26667A (zh) |
| PL (1) | PL343001A1 (zh) |
| RU (1) | RU2209116C2 (zh) |
| TW (1) | TW556770U (zh) |
| WO (1) | WO1999051346A1 (zh) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010027165A1 (en) * | 1998-05-01 | 2001-10-04 | Michael P. Galligan | Catalyst members having electric arc sprayed substrates and methods of making the same |
| DE19914066A1 (de) * | 1999-03-27 | 2000-10-05 | Celanese Chem Europe Gmbh | Katalysatoren für die Gasphasenoxidation von Ethylen und Essigsäure zu Vinylacetat, Verfahren zu ihrer Herstellung und ihre Verwendung |
| US8062623B2 (en) * | 2004-10-15 | 2011-11-22 | Velocys | Stable, catalyzed, high temperature combustion in microchannel, integrated combustion reactors |
| KR100962082B1 (ko) * | 2008-07-31 | 2010-06-09 | 희성촉매 주식회사 | 수소를 이용한 질소산화물의 환원제거용 촉매 및 이를이용한 질소산화물의 환원제거 방법 |
| DE102008048805A1 (de) * | 2008-09-24 | 2010-03-25 | Emitec Gesellschaft Für Emissionstechnologie Mbh | Vorrichtung zum Reinigen von Abgasen |
| RU2455069C1 (ru) * | 2011-02-17 | 2012-07-10 | Федеральное государственное бюджетное учреждение науки Институт химии Дальневосточного отделения Российской академии наук (ИХ ДВО РАН) | Способ получения катализатора дожига дизельной сажи |
| JP5773514B2 (ja) * | 2011-02-24 | 2015-09-02 | 株式会社不二越 | 水素生成用ニッケルクロム合金触媒およびその製造方法 |
Family Cites Families (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4520124A (en) * | 1981-03-19 | 1985-05-28 | Sakai Chemical Industry Co., Ltd. | Method for producing a catalytic structure for the reduction of nitrogen oxides |
| CA1291743C (en) * | 1986-07-25 | 1991-11-05 | Makoto Imanari | Catalyst for removing nitrogen oxides in exhaust gases |
| JP3113662B2 (ja) * | 1990-02-26 | 2000-12-04 | 株式会社日本触媒 | ディーゼルエンジン排ガス浄化用触媒体 |
| DE69226581T2 (de) * | 1991-09-12 | 1999-02-04 | Cosmo Oil Co. Ltd., Tokio/Tokyo | Katalysator zur Reduktion von Stickoxiden |
| US5234882A (en) * | 1991-10-22 | 1993-08-10 | Pfefferle William C | Catalyst and preparation thereof |
| JPH05168935A (ja) * | 1991-12-19 | 1993-07-02 | Sumitomo Metal Ind Ltd | 脱硝触媒用鋼およびその製造方法 |
| JP3217436B2 (ja) | 1992-03-02 | 2001-10-09 | 高山リード株式会社 | 経揃え装置 |
| DE4416469C1 (de) * | 1994-05-10 | 1995-09-07 | Juergen Dr Koppe | Nickel, Mangan, Chrom und Eisen enthaltender vollmetallischer Oxidationskatalysator |
| EP0727248B1 (en) * | 1995-02-17 | 1998-08-19 | ICT Co., Ltd. | Catalyst for purification of diesel engine exhaust gas |
| DE19536752A1 (de) * | 1995-10-02 | 1997-04-03 | Emitec Emissionstechnologie | Verfahren und Vorrichtung zum Herstellen eines Wabenkörpers aus wärmebehandelten zwei- oder mehrschichtigen Metallfolien |
| DE19736628A1 (de) * | 1997-08-22 | 1999-02-25 | Emitec Emissionstechnologie | Katalysator aus unedlem Metall für einen Kleinmotor |
-
1998
- 1998-04-07 DE DE19815608A patent/DE19815608A1/de not_active Withdrawn
-
1999
- 1999-02-05 FR FR9901389A patent/FR2777040B1/fr not_active Expired - Fee Related
- 1999-02-24 TW TW090221253U patent/TW556770U/zh not_active IP Right Cessation
- 1999-03-26 KR KR1020007011180A patent/KR100564214B1/ko not_active IP Right Cessation
- 1999-03-26 PL PL99343001A patent/PL343001A1/xx unknown
- 1999-03-26 ID IDW20002288A patent/ID26667A/id unknown
- 1999-03-26 WO PCT/EP1999/002066 patent/WO1999051346A1/de active IP Right Grant
- 1999-03-26 DE DE59909529T patent/DE59909529D1/de not_active Expired - Fee Related
- 1999-03-26 CN CN99804542A patent/CN1116115C/zh not_active Expired - Fee Related
- 1999-03-26 JP JP2000542105A patent/JP2002510546A/ja not_active Abandoned
- 1999-03-26 RU RU2000127706/04A patent/RU2209116C2/ru not_active IP Right Cessation
- 1999-03-26 ES ES99919143T patent/ES2221378T3/es not_active Expired - Lifetime
- 1999-03-26 AU AU37023/99A patent/AU3702399A/en not_active Abandoned
- 1999-03-26 EP EP99919143A patent/EP1068012B1/de not_active Expired - Lifetime
-
2000
- 2000-10-10 US US09/685,661 patent/US6528452B1/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| US6528452B1 (en) | 2003-03-04 |
| DE19815608A1 (de) | 1999-10-14 |
| KR100564214B1 (ko) | 2006-03-28 |
| TW556770U (en) | 2003-10-01 |
| DE59909529D1 (de) | 2004-06-24 |
| ES2221378T3 (es) | 2004-12-16 |
| AU3702399A (en) | 1999-10-25 |
| PL343001A1 (en) | 2001-07-30 |
| FR2777040A1 (fr) | 1999-10-08 |
| CN1295500A (zh) | 2001-05-16 |
| ID26667A (id) | 2001-01-25 |
| FR2777040B1 (fr) | 2000-07-28 |
| KR20010052240A (ko) | 2001-06-25 |
| WO1999051346A1 (de) | 1999-10-14 |
| JP2002510546A (ja) | 2002-04-09 |
| EP1068012A1 (de) | 2001-01-17 |
| RU2209116C2 (ru) | 2003-07-27 |
| EP1068012B1 (de) | 2004-05-19 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2931362B2 (ja) | 抵抗調節型ヒーター及び触媒コンバーター | |
| US6107239A (en) | Heat resistant metallic oxide catalyst for reducing pollution emission | |
| US5811064A (en) | Poisoning resistant catalyst for exhaust gas converters | |
| EP2047903A1 (en) | Catalyst for exhaust gas purification | |
| JPH06233918A (ja) | 排ガス浄化用触媒 | |
| CS199526B2 (en) | Formed catalyst and method of its manufacture | |
| JPH01199646A (ja) | 内燃機関の排気ガス処理用触媒の製造方法 | |
| US20090148357A1 (en) | Apparatus and catalyst for purifying exhaust gas | |
| JPH0460108A (ja) | 自動車排ガス浄化用触媒コンバーター装置及び自動車排ガスの浄化方法 | |
| CN1116115C (zh) | 催化活性结构物 | |
| WO1994022577A1 (en) | Catalytic vessel for receiving metal catalysts by deposition from the gas phase | |
| CA2595717A1 (en) | Catalyst for purifying exhaust gases and exhaust-gas purification controller using the same | |
| JP3058995B2 (ja) | ハニカムヒーター | |
| JPH08332350A (ja) | 排ガス浄化用触媒 | |
| CN1184704A (zh) | 一种用于汽车排气净化的三元复合金属氧化物催化剂及其制备方法 | |
| US4465654A (en) | Process for use of a noble metal and rare earth metal catalyst | |
| US4410454A (en) | Noble metal and rare earth metal catalyst | |
| EP0439010A2 (en) | Poisoning-preventive layer-possessing support, poisoning-resistant catalyst, exhaust gas converter device, and poisoning-preventive gasoline composition | |
| US20060140826A1 (en) | Exhaust manifold comprising aluminide on a metallic substrate | |
| JPH05293384A (ja) | 排ガス浄化用触媒及び排ガス浄化方法 | |
| JPH09155205A (ja) | ディーゼル排ガス用酸化触媒 | |
| US8020378B2 (en) | Exhaust manifold comprising aluminide | |
| CN1148251C (zh) | 由非贵金属制成的用于小发动机的催化剂 | |
| JP3433885B2 (ja) | ディーゼル排ガス浄化用触媒 | |
| EP1342499A1 (en) | Multizone catalytic converter |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |