Source: http://www.google.com/patents/US5210062?ie=ISO-8859-1&dq=7751826
Timestamp: 2014-04-19 08:18:03
Document Index: 733152287

Matched Legal Cases: ['art 1', 'art 3', 'art 4', 'art 1', 'art 3', 'art 4']

Patent US5210062 - Aluminum oxide catalyst supports from alumina sols - Google PatentsSearch Images Maps Play YouTube News Gmail Drive More »Sign inAdvanced Patent SearchPatentsThis invention is directed to a method of providing a channeled substrate with a porous washcoat used as a supporting structure for a catalyst. The substrate is coated with a reactive mixture made of components comprising aluminum alkoxide, water, and acid or the alkoxide in an alcohol. The aluminum...http://www.google.com/patents/US5210062?utm_source=gb-gplus-sharePatent US5210062 - Aluminum oxide catalyst supports from alumina solsAdvanced Patent SearchPublication numberUS5210062 APublication typeGrantApplication numberUS 07/750,174Publication dateMay 11, 1993Filing dateAug 26, 1991Priority dateAug 26, 1991Fee statusLapsedAlso published asCA2115041A1, DE69206152D1, DE69206152T2, EP0600971A1, EP0600971B1, WO1993003840A1Publication number07750174, 750174, US 5210062 A, US 5210062A, US-A-5210062, US5210062 A, US5210062AInventorsChaitanya K. Narula, Mordecai Shelef, William L. H. WatkinsOriginal AssigneeFord Motor CompanyExport CitationBiBTeX, EndNote, RefManPatent Citations (13), Non-Patent Citations (12), Referenced by (13), Classifications (12), Legal Events (5) External Links: USPTO, USPTO Assignment, EspacenetAluminum oxide catalyst supports from alumina solsUS 5210062 AAbstract This invention is directed to a method of providing a channeled substrate with a porous washcoat used as a supporting structure for a catalyst. The substrate is coated with a reactive mixture made of components comprising aluminum alkoxide, water, and acid or the alkoxide in an alcohol. The aluminum alkoxide contains hydrolyzable alkoxy groups and has the chemical formula: Al(OR).sub.3, where R is an alkyl or branched alkyl group of 3 to 6 carbon atoms. The method also includes drying and calcining the coating to form a γ-alumina washcoat.
We claim: 1. A method of providing a washcoat uniformly comprising oxides uniformly distributed in γ-alumina on a channeled substrate as a supporting structure for an exhaust gas conversion catalyst comprising:(a) applying a coating of a reactive mixture, consisting of aluminum alkoxide, at least one salt of barium and cerium, a solvent, and a complexing acid to promote a clear sol to said channeled substrate, said aluminum alkoxide having a chemical formula of Al(OR).sub.3, wherein R comprises an alkyl group of branched alkyl group having between 3 and 6 carbon atoms; (b) after removing excess coating from said channels by blowing gas through said channels, hydrolizing said coating; (c) drying said coating on said channeled substrate at a temperature sufficient to remove solvent; and (d) calcining said coating at a temperature to density said coating to form said washcoat comprising γ-alumina. 2. The method according to claim 1 wherein said method comprises repeating steps (a) through (c) until a coating of desired surface area is obtained and then calcining the resultant coating.
11. A method of providing a γ-alumina comprising washcoat on a channeled substrate as a supporting structure for an exhaust gas conversion catalyst comprising:(a) applying a coating of a reactive mixture made from aluminum alkoxide, at least one of barium or cerium alkoxide and alcohol vaporizable at or below 100 having a chemical formula of Al(OR).sub.3, wherein R comprises an alkyl group or branched alkyl group having between 3 and 6 carbon atoms; (b) removing excess coating from said channels by blowing gas through said channels; (c) exposing said coating to water vapor; (d) drying said coating on said channeled substrate at a temperature sufficient to remove alcohol and/or water; and (e) calcining said coating at a temperature to densify said coating to form said washcoat comprising γ-alumina and barium or cerium oxides. 12. The method according to claim 11 wherein said method comprises repeating steps (a) through (d) until a coating of desired surface area is obtained and then calcining the resultant coating.
DETAILED DESCRIPTION AND BEST MODE The invention is directed to a method for providing a washcoat comprising γ-alumina on a channeled substrate, e.g., a ceramic honeycomb structure used in catalytic converters. The washcoat is used as a supporting structure for an exhaust gas catalyst.
According to a first embodiment of the invention, a reactive mixture is made by combining a certain type of liquid aluminum alkoxide containing hydrolyzable alkoxy groups with water and acid, generally with stirring, wherein a suspension is formed. The aluminum alkoxide useful with this invention has the chemical formula: Al(OR).sub.3, wherein R comprises an alkyl group, branched alkyl group, or aryl group having between 3 and 6 carbon atoms. Exemplary of suitable aluminum alkoxides which may be used in this invention include, but are not limited to, ethoxides, (n-, or iso) propoxides, (n, sec, or tert-) butoxides, or (n, sec, or tert-) amyloxides such as tris(2-propoxide), tris(2-amyloxide, tris tert-butoxide), and tris(sec-butoxide), with the latter butoxide being preferred. Compatible mixtures of such alkoxides may also be employed.
The aluminum alkoxide is combined with the water in at least an amount sufficient to allow for essentially complete hydrolysis of the alkoxide. Preferably, the ratio of water to alkoxide employed to form the mixture is between about 1.8 and 2.2 liters of water to moles of alkoxide, more preferably this ratio is about 2. This ratio can be varied, however, outside that disclosed above. Using greater amounts of water per mole of alkoxide results in an alumina of smaller particle size as would be apparent to one skilled in the art. When the alkoxide is added to water, the alkoxide hydrolyzes. The parent alcohol of the alkoxide may also be employed as a partial solvent in the reaction mixture. After mixing the alkoxide with the water, the mixture is allowed to stand, for example at room temperature, during which time further hydrolysis takes place. It may be desirable to heat the reactive mixture to encourage hydrolysis of the aluminum alkoxide. Preferably the alkoxide is added to water which is at an elevated temperature, e.g, 80
The mixture may be applied to the substrate by any suitable technique, including spraying or dipping. If the substrate is dipped into the mixture, after withdrawing it from the mixture, the channels of the honeycomb structure would generally be gas (e.g., air/nitrogen) blown to open the channels and remove excess coating. This leaves a very thin coating of the reactive mixture on the substrate. The coating is then subjected to drying at a temperature suitable to evaporate any solvents including water from the coating, that temperature preferably being about 100 the coating. Thereafter, the coating is calcined to densify the coating and form aluminum oxide. The calcination temperature generally is between about 300 catalyst support is to be used for automotive applications. Generally, in order to provide a supporting structure for the catalyst of sufficient surface area, the substrate would be subjected to repeated coating and drying and then afterwards to a final calcining. If the substrate is rested on its side during drying, the substrate is preferably rotated 90 side to obtain the most uniform washcoat. Alternately, the dipping, drying and calcining can be repeated in sequence until a washcoat of desired surface area is obtained. Generally, it is then desirable to subject the resultant coating to a lengthier calcination.
According to a second embodiment of the present invention, the reaction mixture is made from the certain type of liquid aluminum alkoxide disclosed above dissolved in alcohol vaporizable at or below about 100 example, one such reaction mixture comprises aluminum tris-(2-propoxide) dissolved in 2-propanol. The reaction mixture comprises the alkoxide and alcohol preferably in amounts which provide 0.8 to 1.2 molar solutions, more preferably about 1.0 molar solutions of the alkoxide. The reactive mixture may further comprise other components, e.g., compatible salts of materials like barium and cerium as disclosed for the first embodiment. Preferably, in either embodiment if barium and/or cerium are to be incorporated in the γ-alumina washcoat, they would be incorporated by subjecting the calcined γ-alumina washcoat on the substrate to a solution of a barium or cerium salt, e.g., cerium nitrate. Afterwards, the washcoat would again be calcined.
Because the reactive mixture of aluminum alkoxide is sensitive to moisture, its formation is desirably carried out in a substantially moisture free environment. The reactive mixture is applied to a channeled substrate of type described previously herein by any suitable technique, including spraying or dipping. After application of the reactive mixture, the channels of the structure would preferably be gas blown (e.g., nitrogen) to remove excess reaction mixture. The reactive mixture coating is subsequently exposed to water vapor, e.g., moist air, sufficient to cause hydrolysis of the alkoxide. The coating is then subjected to drying along the lines of the procedure used in the first embodiment disclosed herein. During both exposure to humidity and drying, the substrate is preferably rested on a different consecutive side to encourage uniform coating. Thereafter, the coating is calcined to densify the coating and form aluminum oxide. The calcination temperature generally is between about 300 catalyst support is to be used for automotive applications. The substrate may be subjected to repeated coating, humidity, drying and afterwards to a final calcining. Alternately, the dipping, drying, exposing to water vapor, and calcining can be repeated in sequence until a washcoat of desired surface area is obtained. Generally, it is then desirable to subject the resultant coating to a lengthier calcination.
Coatings according to the present invention desirably have surface areas of at least 25 m.sup.2 /g in order to provide adequate surface area for the catalyst. Advantageously, according to the present invention such high surface area is provided with less loading of washcoat on the substrate. For example, while 33% by weight of a conventional washcoat made by dipping the substrate in a dispersion of γ-alumina, baria and ceria is required to achieve a desired surface area of 25-30 m.sup.2 /g of total substrate/washcoat weight, a washcoat made according to the present invention method of 14.7% by weight provides the same surface area. Consequently, the invention washcoat provides decreased washcoat material without a corresponding decrease in the surface area of the washcoat. Hence, the channels of a honeycomb substrate uniformly coated according to the present invention will maintain markedly more of their openness while at the same time providing a desired surface area of washcoat so that catalyst effectiveness is maintained. The back pressure problem associated with the narrowing of the channels thus is substantially eliminated for more efficient operation of the catalytic converter.
EXAMPLE 1 Aluminum tris(sec-butoxide), 9.85 g, is added to distilled water, 80 ml, at 80 remains in suspension with stirring. The suspension is kept at 90 C. for 1 hour, and then nitric acid (2.8 ml of 1M) solution is added to the suspension. The alumina sol so formed is boiled in an open flask to evaporate sec-butonal which forms from the hydrolysis of the butoxide. After removal of the butanol from the flask, the sol is kept at 90 C. for 16 hours.
A piece of honeycomb substrate is dipped into the sol and after withdrawing the substrate, the channels are emptied by blowing air through them. The coating is converted to a gel on the substrate when it is dried at 80 repeated until no further weight increase is recorded. This appears to be due to the equilibrium between the gel on the substrate and the sol into which the substrate is being dipped. After calcination at 600 for 4 hours (which can be as short as 30 minutes), the coated substrate is cooled to room temperature. On calcination, the gel coating densifies and converts to γ-alumina. The process of dipcoating and calcination was repeated to obtain a washcoat of 14.7% by weight. The coating is then further calcined for 12 hours at 600 resulting washcoat is found to be 25 m.sup.2 /g. The coating is substantially uniform in thickness.
A commercial platinum/palladium catalyst is placed on the washcoat by dipping the calcined washcoat in an aqueous solution of the nitrates of the catalyst. Thereafter the impregnated washcoat is calcined at 500 reactor for hydrocarbon and carbon monoxide oxidation and nitrogen oxide reduction. FIG. 3 shows an R-curve (explained below) for the washcoat/catalyst prepared according to this example. In contrast, FIG. 4 shows an R-curve for a commercially available washcoat/catalyst using the same catalyst. The R in these figures is obtained by dividing the sum of the equivalent reducing components of the mixture by the sum of the oxidizing components and can be calculated according to the following formula: ##EQU1## R=1 is a stoichiometric gas mixture. The R curves of FIGS. 3 and 4 are comparable showing that an equally effective catalysis was obtained from the present invention thinner washcoat. An improvement is seen in hydrocarbon oxidation in the present invention system. Due to the more open channels of the present invention system, problems with back pressure typical of conventionally washcoated honeycomb catalyst systems is avoided.
EXAMPLE 2 A γ-alumina washcoat is provided on a honeycomb substrate according to the procedure of Example 1. Afterwards the coated substrate is dipped into a barium nitrate solution. The coating is dried at 100 30 minutes and then calcined at 600 the mixture of washcoat to 5% barium oxide and 95% of the alumina. Barium is known to provide high temperature stabilization to alumina materials. The small amount of barium does not change the channels in honeycomb substrate significantly and the channels remain similar to the one described in Example 1.
EXAMPLE 3 A solution of freshly distilled aluminum tris-(2-propoxide) (1.0M) is prepared in 2-propanol. A honeycomb substrate is dipped into the solution. After blowing-out excess solution using nitrogen gas, the substrate is exposed to atmospheric humidity, dried at 80 2-propanol and calcined at 600 thickness as in Example 1.
BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is an optical micrograph of a washcoat/catalyst on a honeycomb substrate where the washcoat is provided according to a first embodiment the present invention.
SUMMARY OF THE INVENTION This invention overcomes the above disadvantages and is directed to a method of providing a particular washcoat on a channeled substrate as a supporting structure for an exhaust gas conversion catalyst. The method includes first applying a coating of a reactive mixture on the channeled substrate. The coating on the substrate is dried at a temperature suitable to remove water present in the coating, preferably at or below about 100 temperature greater than about 300 300 γ-alumina. The method may comprise repeatedly applying and drying the coating followed by calcining or doing all three steps until a coating of desired surface area is obtained. Preferably, the γ-alumina washcoat additionally comprises barium oxide, cerium oxide or mixtures thereof.
The reactive mixture is made according to a first embodiment from aluminum alkoxide dissolved in alcohol vaporizable at or below 100 preferably its parent alcohol, and according to a second embodiment from aluminum alkoxide, water, and acid. The aluminum alkoxide has a chemical formula of Al(OR).sub.3, wherein R comprises an alkyl group, branched alkyl group, or aryl group of between 3 and 6 carbon atoms. In the second embodiment wherein the reactive mixture is made from aluminum alkoxide and alcohol, the coating is exposed to water vapor prior to drying. In either situation, after the step of applying a coating to the channeled substrate the channels are gas blown to remove excess coating.
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