CN106573273A - 用于涂覆基材主体的工艺 - Google Patents
用于涂覆基材主体的工艺 Download PDFInfo
- Publication number
- CN106573273A CN106573273A CN201580043495.9A CN201580043495A CN106573273A CN 106573273 A CN106573273 A CN 106573273A CN 201580043495 A CN201580043495 A CN 201580043495A CN 106573273 A CN106573273 A CN 106573273A
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- Prior art keywords
- piston
- coating
- base material
- liquid
- speed
- Prior art date
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- 239000003795 chemical substances by application Substances 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
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- 238000002485 combustion reaction Methods 0.000 description 3
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- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
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- 229910052777 Praseodymium Inorganic materials 0.000 description 1
- 229910052773 Promethium Inorganic materials 0.000 description 1
- 229910052772 Samarium Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
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- 229910052775 Thulium Inorganic materials 0.000 description 1
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- 239000002253 acid Substances 0.000 description 1
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- 229940024548 aluminum oxide Drugs 0.000 description 1
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- 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
- 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 1
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- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
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- 230000004048 modification Effects 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
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- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 229910003445 palladium oxide Inorganic materials 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- KZTGQMIOPBMQCK-UHFFFAOYSA-N platinum sulfurous acid Chemical compound S(O)(O)=O.[Pt] KZTGQMIOPBMQCK-UHFFFAOYSA-N 0.000 description 1
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 description 1
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 description 1
- VQMWBBYLQSCNPO-UHFFFAOYSA-N promethium atom Chemical compound [Pm] VQMWBBYLQSCNPO-UHFFFAOYSA-N 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 description 1
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- 239000010703 silicon Substances 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- 239000010959 steel Substances 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 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
- 229910052720 vanadium Inorganic materials 0.000 description 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/22—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to internal surfaces, e.g. of tubes
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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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/19—Catalysts containing parts with different compositions
-
- 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
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- 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
-
- 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
- B01J37/0246—Coatings comprising a zeolite
-
- 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
- B01J37/0248—Coatings comprising impregnated particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C3/00—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material
- B05C3/02—Apparatus in which the work is brought into contact with a bulk quantity of liquid or other fluent material the work being immersed in the liquid or other fluent material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C—APPARATUS FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05C7/00—Apparatus specially designed for applying liquid or other fluent material to the inside of hollow work
- B05C7/04—Apparatus specially designed for applying liquid or other fluent material to the inside of hollow work the liquid or other fluent material flowing or being moved through the work; the work being filled with liquid or other fluent material and emptied
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/18—Processes for applying liquids or other fluent materials performed by dipping
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0006—Honeycomb structures
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
- C04B38/0006—Honeycomb structures
- C04B38/0012—Honeycomb structures characterised by the material used for sealing or plugging (some of) the channels of the honeycombs
-
- 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
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
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- 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
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Abstract
本发明涉及催化涂覆蜂窝状块体、尤其是所谓流通式块体的可靠方法。可通过采用间接涂覆的方法,经由位移主体,可以非常精确地涂覆这些类型的块体。本发明还通过监测某些量度来控制工艺过程,进而对所述方法加以改善。
Description
本发明涉及催化涂覆蜂窝状块体、尤其是所谓流通式块体的可靠方法。通过采用间接涂覆的方法,经由位移主体,可以非常精确地涂覆这些类型的块体。本发明还通过借助某些措施控制工艺过程,来对该方法加以改善。
在内燃机领域中众所周知,燃料燃烧是不完全的,并会产生污染物排放,如未燃烧的碳氢化合物(HC)、一氧化碳(CO)、氮氧化物(NOx)和颗粒物(PM)。为改善空气质量,制定了排放限制法规,以减少来自固定应用和移动源的污染物排放。就客车这样的移动源来说,采取的主要措施能够实现污染物排放减少。改进燃料-空气混合的主要措施大幅减少了污染物排放。然而,由于这些年以来推行更为严格的法规,使用非均相催化剂在所难免。
生产这些非均相催化剂的一个重要方面,是例如在涂覆长度、施涂的涂料量、涂层均匀度和涂覆长度一致性方面,精确地涂覆所使用的基材主体。为实现该目的,截至目前已采用了若干种涂覆策略,试图有利地在尽可能短的时间内提供得到良好涂覆的整块主体。
涂覆基材主体的一种可能是使其一侧上的开口与涂覆介质接触,然后向基材的相对侧施加真空,由此牵引液体涂覆介质穿过基材的开口(例如,通道)。如果只打算在所述通道的部分长度上涂覆,则由于通道与通道之间不可避免地产生单独的流动剖面,所以会出现不同通道的涂覆长度不同的不利现象。
如果涂覆介质被克服重力的压力压入通道,则在完全涂覆通道的情况下,随后需要检查(通常借助传感器)液体何时在顶部出现。在只涂覆通道的部分长度的情况下,通道内涂覆介质液柱的高度通常经由传感器(容量传感器、视觉传感器、红外传感器、振动传感器)通过直接测量或间接测量确定。然而,在这种情况下,块体的通道内也可能产生不均匀的涂覆前沿,例如,如果涂覆是从块体下方的涂覆室中所形成的不均匀浆料表面开始的。具体地讲,如果用很快的速度涂覆,并且涂覆浆料在短时间段内被泵送到涂覆室中时趋向于产生湍流,则会发生后一种情况。
DE102010007499A1中公开了优选的涂覆设备和涂覆方法,其中,圆柱形支撑主体涂覆有液体涂覆介质,所述圆柱形支撑主体各自具有两个端面、一个圆周表面和轴向长度L,还有多个通道自第一端面横穿至第二端面。所考虑的设备具有填充了液体的气缸并具有活塞,其中所述填充了液体的气缸与罐连通,在所述罐内部以这样的方式布置位移主体:即,在活塞移动时,所述位移主体在液体作用下成比例地移动。所述罐与基材的涂覆装置连通,因此所述位移主体作用于液体涂覆介质,从而引起所述涂覆装置中液体涂覆介质的液位成比例地改变(参见该申请的图1)。两个传感器布置在所述涂覆装置中的同一高度上,以便检查涂覆室中浆料表面的位置是否已达到某个液位。
考虑到用这种类型的涂覆装置甚至更进一步加快涂覆进度,一个因素是下述过程的速度:
i.涂覆液体可被递送到基材中,以及
ii.位移主体可再次缩小,以使新的涂覆介质流入涂覆罐。
该速度与活塞在与位移主体连通且填充了液体的气缸中的移动速度直接相关。如果i.和/或ii.的速度增大,则涂覆过程将出现某些缺陷,这可能意味着基材的一些通道中的流动条件和压力条件与其他通道中的大不相同,结果是液体涂覆介质的渗透难度明显增大或明显减小,并且液体涂覆介质在涂覆条件下在个别通道上的沉积长度变短或变长。
例如,已发现液体涂覆介质中可能出现气泡。由于涂覆浆料的粘度有时非常高,所以这些气泡存留下来并且被载往涂覆室,随后进入基材块体,如果气泡最终进入所述块体的通道,则进而导致上文提到的缺陷,例如,导致对产品的涂覆不均匀或不一致。
本发明的目标是消除这个缺点。具体地讲,本发明的目的是提供这样一种方法,其用如上所述的设备涂覆整块基材、而不必担心涂覆浆料不均匀(尤其是由于其中形成了气泡)。另外,应当提出一种用于涂覆整块基材的工艺,其允许在最短的时间内用所设想的装置安全地涂覆这些块体。
该目的通过应用本发明权利要求1所述的工艺来实现。从属权利要求涉及本发明的各种有利方面。
由于在一种涂覆用于生产废气净化催化剂(尤其是机动车辆使用的废气净化催化剂)的基材的工艺中,所述基材为圆柱形支撑主体,并且每个具有两个端面301、一个圆周表面302和轴向长度L,还有容纳液体涂覆介质的多个通道310自第一端面横穿至第二端面,所述基材具有填充了液体103的气缸102并具有活塞101,其中,填充了液体的气缸102与罐112连通,在该罐内部以这样的方式布置位移主体111:即,在活塞101移动时,位移主体111在液体103作用下成比例地移动;并且罐112与基材的涂覆装置122连通,其中位移主体111作用于液体涂覆介质113,从而引起涂覆装置122中的液体涂覆介质113的液位成比例地改变;
活塞101的移动引起位移主体111缩小(所谓“反向行程”),所以采用不超过活塞101的速度并从而避免修补基面涂料(washcoat)中出现气泡的方式控制该移动,本发明相当令人惊讶、但仍然有利地解决了与本发明的涂覆技术相关联的问题,并大大降低了修补基面涂料浆料内形成气体的风险。
显而易见,由于在修补基面涂料贮存器112中施加了过高的负压,导致出现更多气泡。如果活塞101在反向行程阶段中的移动速度过高,则可能引起这种不利的负压。然而,涂覆介质中生成气泡也很大程度取决于浆料和其中存在的组分的特性。因此,必须针对每种涂覆介质(修补基面涂料)分别设置活塞101的反向行程速度的阈值(该阈值不得被超过)。可以在初步试验中确定该阈值,然后相应地将其应用于涂覆装置的控制器单元125。在测试中,已经确定对于普通的修补基面涂料浆料,活塞101引起位移主体111缩小(反向行程)的速度可在0.01m/s至3m/s之间变化,更优选地在0.05m/s至0.25m/s之间变化,最优选地在0.08m/s至0.2m/s之间变化。
导致气泡生成、尤其是影响气泡寿命的主要因素是涂覆到基材主体上的浆料的粘度。如果粘度高,则气泡往往会存留相当长的时间,并损害其在涂覆室中的外观。所以,主张涂覆时间应当尽可能短,以便在确定的时段内涂覆尽可能多的部件,并且有利地将活塞101的反向行程保持在上述时间段内,为此,液体涂覆介质113的粘度应当介于2mPa*s至200mPa*s之间。
还进一步证明,活塞101的反向行程移动的某种概况对修补基面涂料浆料中生成气体有影响。就这一点而言,技术人员可想到几种此类概况。然而,在优选的方面,以如下方式控制活塞101的速度(其导致位移主体111缩小(反向行程)):使活塞首先加速,然后减速直到其反向行程结束。在更优选的模式中,速度的概况接近高斯分布曲线概况。在非常优选的实施例中,活塞101的反向行程的最大速度相比反向行程开始之后活塞101的路径的10%所对应位置处速度,超过的倍数不大于0.5倍,优选1倍,最优选5倍。
检查和控制活塞101的反向行程可通过技术人员已知的装置来完成。活塞的移动通常受控制器单元125控制。正常情况下,根据本发明,控制器单元125可依靠所存储数据用于管理活塞101的移动。然而,活塞125的移动也可通过应用于涂覆装置的某些传感器来实现,据此,用于控制活塞101的速度的传感器选自压力传感器、液位传感器和电导率传感器。
在本发明的非常优选的实施例中,使用所谓的“过程控制”来管理活塞101的反向行程移动。在将活塞101移回其初始位置,并因而在液体涂覆浆料中产生负压时,如果修补基面涂料浆料中出现气泡,则应用于修补基面涂料贮存器(图1中的112;图2中的212)的压力传感器将接收到压力值测量中断。因此,有利的是把压力曲线的这种中断看作是控制活塞101的移动速度的时机。按下述方式进行控制:即,一旦出现中断,在反向行程中移动的活塞101的速度就降低,从而至少最大限度减轻气泡在修补基面涂料浆料中的出现,并且/或者使速度保持低于该中断点以彻底杜绝气泡形成。考虑到修补基面涂料及其物理性质可能在生产活动的整个过程中变化,这种类型的控制不但是首选方案,其优势也最为明显。通常情况下,粘度和如前所述的气泡生成趋势在生产某种催化剂主体的整个时期内不断变化。通过应用该过程控制措施,涂覆介质中产生气体并因而形成气泡的风险大大降低。
为执行本发明的涂覆工艺,请查阅专利公开DE102010007499A1(其全文并入本文),至少参考其中涉及装置特征的各个方面。具体地讲,DE102010007499A1中所提及工艺的优选特征在加以必要的修改后也适用于本发明的工艺。同样应当指出,本文在图1中提及某个方面,被认为是相应地在图2中提及同一个方面。必须指出,图2与图1之所以不同,是因为位移主体111或211分别缩小和膨胀,周期正好相反。因此,在谈到根据图2的实施例时,必须把上文的说法“缩小”更换为“膨胀”。根据上面提到的内容,其他方面可接受类似的解释。
所使用的基材121、221通常是中空基材,其由金属或陶瓷构成,并至少有一个内部通道110、210、310,通常有多个内部通道。所述基材通常是基本上为圆柱形的支撑主体,所述支撑主体每个具有圆柱轴、两个端面、一个圆周表面和轴向长度L,还有多个通道自第一端面横穿至第二端面。此类支撑主体通常也被称为蜂窝状主体。具体地讲,所述基材可为流通式蜂窝状主体或块体,但也可为壁流式过滤器。所述基材可由例如堇青石、莫来石、钛酸铝、碳化硅或金属(诸如钢或不锈钢)构成。所述基材有利地为圆柱形的整块催化剂支撑主体,并且其中有多个与来自内燃机的废气所沿的气缸轴平行的流动通道穿过。此类整块催化剂支撑主体大规模地用于生产汽车废气催化剂。所述催化剂支撑主体的横截面形状取决于对机动车辆的安装要求。横截面为圆形、椭圆形、三角形或六边形的催化剂主体被广泛使用。所述流动通道通常具有正方形、矩形、六边形、三角形、菱形或其他形状的横截面,并且在所述催化剂主体的整个横截面上以间隔狭窄的模式布置。所述流动通道的通道密度(或称单元密度)通常在10至250cm-2之间变化,具体取决于应用。就对汽车进行废气净化来说,时下仍经常使用单元密度为约62cm-2的催化剂支撑主体。壁厚(也就是将基材的通道彼此分隔开的壁的厚度)通常为约0.005cm至约0.25cm。
所述基材有利地以液体密封方式布置在涂覆装置122、222上,该布置可借助至少一个密封件实现。所述密封件可以是中空的,并且在将基材安装到涂覆装置122、222上或将基材插入所述涂覆装置中时,所述密封件可填充有气体或液体,并因而可形成防漏闭合。可借助压力传感器或流量传感器来检查接头的密封性。
液体涂覆介质113、213为例如用于涂覆机动车辆的废气催化剂(流通式块体或过滤器)的悬浮液或分散体(“修补基面涂料”),其包含催化活性组分或其前体与无机氧化物(诸如氧化铝、二氧化钛、氧化锆或这些物质的组合),所述氧化物可能掺杂例如硅或镧。钒、铬、锰、铁、钴、铜、锌、镍或稀土金属(诸如镧、铈、镨、钕、钷、钐、铕、钆、铽、镝、钬、铒、铥、镱)的氧化物或这些氧化物的组合可用作催化活性组分。贵金属诸如铂、钯、金、铑、铱、锇、钌及其组合也可用作催化活性组分。这些金属也可作为彼此的合金、与其他金属的合金或氧化物存在。所述金属也可作为前体存在,诸如所述贵金属的硝酸盐、亚硫酸盐或有机基团及其混合物;具体地讲,硝酸钯、亚硫酸钯、硝酸铂、亚硫酸铂或Pt(NH3)4(NO3)2可用于液体涂覆介质中。随后通过在约400℃至约700℃下煅烧前体,可由所述前体获得催化活性组分。要涂覆用于生产汽车废气催化剂的基材,可首先使用无机氧化物的悬浮液或分散体进行涂覆,接着在后续的涂覆步骤中,可施用含有一种或多种催化活性组分的悬浮液或分散体。然而,液体涂覆介质也可能含有这两种组分。液体涂覆介质的固体含量通常介于35%至52%之间。
适用于生产用于机动车辆的废气催化剂的成品基材(即,经涂覆和热处理或煅烧的基材)具有特别一致的涂层,其特征在于,不同通道的涂覆长度彼此相差不超过5mm、具体地讲是3mm,这一点对于基材所有通道的至少95%、有利地为基材所有通道的至少99%、尤其是基材的所有通道的100%成立。在这种情况下,通道的涂覆长度小于所述轴向长度L。涂覆长度一致的优势在于,用这种方式可以从相应基材的相对两端引入两个涂层。
如果这些涂层是不同的并且必须彼此分开(例如,因为涂层组分以不期望的方式彼此反应或削弱彼此的作用),则必须在两个涂层之间维持间距,并且必须可靠地确保该间距稳定。在此有利的是,可以尽可能准确并可靠地设定涂覆长度,原因在于,以这种方式,只需使用基材上较短的长度来实施涂层之间的间距,使其保持未涂覆,并因而不发挥作用。由此,可改善废气净化效果,或可减少用涂层装填基材的工作量。
因此,可采用特别有利的方式,使用本发明的方法来获得用于生产机动车辆所用的废气催化剂的经涂覆基材,其中设置的通道在内部具有至少一个第一催化活性涂层,在出口具有一个第二催化活性涂层,涂覆有所述第一催化活性涂层和所述第二催化活性涂层的通道长度在每种情况下都小于基材的轴向长度L,并且针对基材至少95%的通道,涂覆有所述第一催化活性涂层和所述第二催化活性涂层的通道长度分别地彼此相差不超过5mm、优选3mm,并且针对基材至少95%的通道,其中所述两个涂层之间的间距不大于5mm,有利地不大于3mm,特别地不大于1mm。
图3A和图3B示出了这种类型的经涂覆基材300。所述基材具有两个端面301、一个圆周表面302和长度L,并且多个通道310在所述两个端面间横穿。在这种情况下,通道在第一部分长度303上具有第一涂层330以及在另一部分长度305上具有第二涂层340,由图3A中的加粗线指示,其形成两个区域,分别具有第一和第二涂层。优选地最小化两个区域303、305之间的间距304,为此,在两个区域303、305中需要尽可能一致的涂层长度以避免重叠。根据本发明,该无涂层间距304不大于5mm,有利地不大于3mm,特别地不大于1mm。在该图3A中,示出了具有圆形端面的基材300。当然,所述端面也可以具有矩形、正方形、椭圆形、三角形、六边形或其他多边形形状,从而产生基材的对应不同三维形状,例如,棱柱体或立方体。所述第一和第二涂层及其具有第一涂层330和第二涂层340的部分长度可以相同或不同,并且可以显示如上所述的间隙或可至少在一定程度上重叠。
所述第一和第二涂层有利地为不同类型的。在本发明的一个实施例中,至少一个涂层是氧化催化剂或SCR催化剂。在本发明的特别有利的实施例中,第一涂层330是SCR催化剂,第二涂层340是用于氧化NH3、HC和CO的氧化催化剂。
有利的是,如果氧化催化剂含有元素周期表第VIII族的贵金属,诸如铂、钯、钌、铑、金、铱或其混合物,则有利地位于多孔的固体支撑物上,通常为多孔无机氧化物,诸如氧化铝或二氧化硅。铂位于作为支撑物的多孔氧化铝和/或沸石上是特别有利的。经涂覆基材上的这种涂层通常含有0.1g/ft3至10g/ft3、优选地0.5g/ft3至5g/ft3的铂。
在本发明的具体实施例中,所述SCR催化剂含有选自以下的氧化物:二氧化钛、五氧化二钒、三氧化钨、氧化铈、氧化锆或其混合物。在本发明的另一具体实施例中,所述SCR催化剂含有作为基质的二氧化钛、至多10重量%的五氧化二钒和至多20重量%的三氧化钨。在本发明的另一具体实施例中,所述第一涂层含有包含五氧化二钒和氧化铝的SCR催化剂,而所述第二涂层含有包含铂、金、钯和氧化铝的氧化催化剂。在这种情况下,所述第二涂层优选地含有0.1g/ft3至10g/ft3、优选地0.5g/ft3至5g/ft3的铂、金或其组合。在本发明的另一个具体实施例中,所述第一涂层含有包含二氧化钛、五氧化二钒和三氧化钨的SCR催化剂,而所述第二涂层含有包含铂和氧化铝和/或沸石的氧化催化剂。在这种情况下,所述第二涂层优选地含有0.1g/ft3至10g/ft3、优选地0.5g/ft3至5g/ft3的铂。
在本发明的另一个具体实施例中,所述第一涂层含有包含沸石或类沸石组合物,例如小孔分子筛(诸如菱沸石或毛沸石或插晶菱沸石或SAPO-34,特别是与铁或铜交换的分子筛)的SCR催化剂,而所述第二涂层含有包含铂和氧化铝和/或如上所述的沸石的氧化催化剂。在这种情况下,所述第二涂层优选地含有0.1g/ft3至10g/ft3、优选地0.5g/ft3至5g/ft3的铂。
在本发明的另一个具体实施例中,所述第一涂层含有SCR催化剂,该SCR催化剂含有与铜交换的菱沸石并且每克催化剂材料具有至少20毫升氨的储氨容量,而所述第二涂层含有包含铂和氧化铝和/或沸石如菱沸石的氧化催化剂。在这种情况下,所述第二涂层优选地含有0.1g/ft3至10g/ft3、优选地0.5g/ft3至5g/ft3的铂。
考虑到过滤器基材要适于根据本发明的工艺生产用于机动车辆的废气过滤器,它们的孔隙率优选地大于40%,通常为40%至75%,特别地为45%至60%。平均孔径为至少7μm,例如7μm至34μm,优选地大于10μm,特别地为10μm至20μm或11μm至19μm。适于生产用于机动车辆的废气过滤器的成品基材具有11μm至33μm的平均孔径和40%至60%的孔隙率是特别有利的。
附图标记列表
图1:
100 致动器
101 活塞
102 气缸
103 液体
104 连接件
110 通道-在基材121内
111 位移主体
112 罐
113 涂覆介质
114 管线部分
115 多通阀
116 管线部分
117 填充流动方向
118 返回流动方向,以去除涂覆介质113
119 排放泵
120 通向涂覆介质的贮存器的连接管线
121 基材
122 涂覆装置
123 用于检测液位130的传感器
124 用于监测位移主体111的位置的传感器
125 控制单元
130 涂覆装置122中113的第一液位
132 基材121中113的第二液位
图2:
200 致动器
201 活塞
202 气缸
203 液体
204 连接件
210 通道-在基材221内
211 位移主体
212 罐
213 涂覆介质
214 管线部分
215 多通阀
216 管线部分
217 填充方向
218 213的抽出流动方向
219 排放和抽出泵
220 通向多余的涂覆介质213的贮存器的连接管线
221 基材
222 涂覆装置
223 用于检测液位230的传感器
224 用于监测位移主体的位置的传感器
225 控制单元
230 涂覆装置222中的第一液位
232 基材221中的第二液位
图3:
300 基材
301 端面
302 圆周表面
303 第一部分长度区域
304 间距-在两个部分长度303和305之间
305 第二部分长度区域
310 通道-在基材300内
330 第一涂层-在通道310内
340 第二涂层-在通道310内
L 基材300的总长度
附图的详细说明
图1示出了用于涂覆基材121内的通道110的布置,该布置在气缸102中具有由致动器100致动的活塞101,所述气缸填充有液体103并且通过气缸102的连接件104连接至位移主体111,这允许致动罐112中的位移主体111,而所述罐填充有液体涂覆介质113并且具有两个管线部分114、116,所述两个管线部分之间具有插入在罐112和涂覆装置122之间的多通阀115,其中涂覆装置122配套提供有基材121和用于确定第一液位130的传感器123。附加传感器124用于监测罐112中涂覆介质113的位移体积和位移主体111的状态。
由传感器123、124确定的值被传输到控制单元125,该控制单元本身控制致动器100并且因此控制活塞101。
一方面,多通阀115切换为在填充流动方向117上用涂覆介质113将涂覆装置122填充至第一液位130;另一方面,在达到基材121中的第二液位132之后,该多通阀切换为在返回流动方向118上连接至排放泵119和通向储罐的连接管线120,所述储罐用于贮存多余的涂覆介质113并将其保存留作后用。
为此目的,所有所需的控制命令优选地同样由中央控制单元125输出。
图2示出了用于涂覆基材221中的通道210的布置,在该布置中,在气缸202中具有由致动器200致动的活塞201,所述气缸填充有液体203并且通过气缸202的连接件204与位移主体211所在的罐212连通,该罐含有液体涂覆介质213并且通过插有多通阀215的两个管线部分214、216连接至涂覆装置222,该涂覆装置配套提供有基材221和用于确定涂覆介质213的第一液位230的传感器223。
借助于罐212上的附加传感器224,监测罐212中涂覆介质的位移体积和位移主体211的状态。由传感器223、224确定的值被传输到控制单元225,该控制单元本身控制致动器200并且因此控制活塞201。
一方面,多通阀215切换为在填充流动方向217上用涂覆介质213将涂覆装置222填充至第一液位230;另一方面,在达到基材221中的第二液位232之后,该多通阀切换为在返回流动方向218上连接至排放泵219和通向储罐的连接管线220,所述储罐用于贮存多余的涂覆介质213并将其保存留作后用。为此目的,所有所需的控制命令优选地同样由中央控制单元225输出。
图3A和图3B以透视图的方式示出了基材300,其具有在其中心部分剖开成为三个平面的剖面,使得可以看到根据本发明的涂层结构。
基材300(其在两个部分长度区域303,305内被涂覆)具有两个端面301、一个圆周表面302和长度L,并且多个通道310在两个端面301之间横穿。
将第一涂层330施加到通道310中的第一部分长度区域303,而另一部分长度区域305具有第二涂层340。
在两个部分长度区域303和305之间或在两个涂层330和340之间存在无涂层区域304,具体地讲如图3B以放大比例示出。
Claims (5)
1.一种涂覆用于生产废气净化催化剂,尤其是机动车辆使用的废气净化催化剂的基材的工艺,所述基材为圆柱形支撑主体,并且每个具有两个端面(301)、一个圆周表面(302)和轴向长度(L),并且还有容纳液体涂覆介质的多个通道(310)自所述第一端面横穿至所述第二端面,所述基材具有填充了液体(103)的气缸(102)并具有活塞(101),其中所述填充了液体的气缸(102)与罐(112)连通,在所述罐内部以这样的方式布置位移主体(111):即,在所述活塞(101)移动时,所述位移主体(111)在所述液体(103)作用下成比例地移动;并且所述罐(112)与所述基材的所述涂覆装置(122)连通,其中所述位移主体(111)作用于所述液体涂覆介质(113),从而引起所述涂覆装置(122)中的液体涂覆介质(113)的液位成比例地改变;
其中所述活塞(101)的移动引起所述位移主体(111)缩小,所以采用如下方式控制所述移动:不超过所述活塞(101)的速度,从而避免修补基面涂料中出现气泡。
2.根据权利要求1所述的工艺,
其特征在于:
引起所述位移主体(111)缩小的所述活塞(101)的速度介于0.01m/s至3m/s之间。
3.根据权利要求2所述的工艺,
其特征在于:
所述液体涂覆介质(113)的粘度介于2mPa*s至200mPa*s之间。
4.根据前述权利要求中任一项所述的工艺,
其特征在于:
所述活塞(101)的速度引起所述位移主体(111)缩小,以如下方式控制所述活塞的速度:使所述活塞首先加速,然后减速直到其反向行程结束。
5.根据前述权利要求中任一项所述的工艺,
其特征在于:
用于控制所述活塞(101)的速度的所述传感器选自压力传感器、光学传感器、电导率传感器和振动传感器。
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CN106573273B (zh) | 2021-01-15 |
PL2985084T3 (pl) | 2017-03-31 |
KR20170042573A (ko) | 2017-04-19 |
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US10441971B2 (en) | 2019-10-15 |
JP6594407B2 (ja) | 2019-10-23 |
RU2017108172A (ru) | 2018-09-14 |
CA2958108A1 (en) | 2016-02-18 |
JP2017532190A (ja) | 2017-11-02 |
BR112017002608A2 (pt) | 2017-12-05 |
RU2693135C2 (ru) | 2019-07-01 |
US20170232472A1 (en) | 2017-08-17 |
EP2985084B1 (en) | 2016-10-12 |
RU2017108172A3 (zh) | 2019-01-30 |
KR102338972B1 (ko) | 2021-12-15 |
EP2985084A1 (en) | 2016-02-17 |
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