Title of Invention


Abstract The invention describes the production of a catalyst for use in the oxidation and selective reduction with properties resembling the catalytic property of the noble metal catalysts, by formation of a crystal surface on catalyst supports from a synthesis crystal of the elements of the rare earths and the metal components cobalt and/or lanthanum produced in multiple stages.
Full Text

The invention describes the method for producing such catalysts and the use in catalytic reaction systems as a substitute for platinum catalysts and redox systems such as for example the DeNOx synthesis.
Such catalysts are known as honeycomb or pouring layer catalysts from DE 198 00 420 A1 and US-A-4,707,341, respectively. Therein, aqueous solutions from a first component of a compound with lanthanum, cerium and cobalt, a second component platinum, a third component rhodium as well as a fourth component from a wash coat of alumina, titanium dioxide and oxalic acid are applied to the catalyst.
The disadvantage of these catalysts is the small surface of the active substance, which is supplemented to a sufficient catalytic effect by the additional use of platinum and rhodium. Thereby, the compounds of lanthanum, cerium and cobalt only act as an improved surface for the platinum, and allow an increased lifetime.
Surprisingly, now, it has been found that the level of platinum is almost completely substituted, the lifetime is increased and the catalytic effect is substantially improved, rf the active substance is crystallized from rare earths and cobalt in multiple stages. Therein, also the substances cobalt and manganese and the rare earths lanthanum, cerium and yttrium are used, but transfomied to crystals with a diameter from 1 to 0.1 pm and a length from 100 to 100,000 pm in a special multistage process.
According to the inventive method, this occurs in the following steps:
The salts of the rare earths lanthanum, cerium and/or yttrium and the salts of the metals cobalt and/or manganese are input into deionised water In the stoichiometric ratio until a 20 to 60 % solution arises. Therein, the stoichiometric

ratio is the amount corresponding to the atomic weight of the involved masses of the reaction partners to the complexes LaCoOa, wherein La can be replaced by cerium and yttrium and cobalt can be replaced by manganese. As the salts, the nitrates, carbonates and acetates are used.
The subsequent burning operation requires a temperature between 500 and 761 °C. The maximum temperature is preset since this temperature is the start of another recrystallization that has to be avoided. The coarse crystal mixture arising in the heating operation is again dissolved in 20 to 60 % oxalic acid until the bottom is low. It is removed from the solution by redecantation. The pure bottom-free solution is again heated to the burning temperature of 500 to 600 and thus processed to a fine powder in crystal form.
Now, another oxalic acid solution is admixed in water with 20 to 40 % oxalic acid. Moleoularty fine alumina (Condea), 10 %, and fine Bayer titanium or equivalent TiOa is now mixed into this solution. The crystal powder produced above is now lastly input into the solution. The thus resulting mixture is intensively stirred to a thin*liquid suspension, possibly with addition of further water.
With this suspension, the actual catalyst production is effected by submerging the support bodies having a honeycomb or pouring layer structure into this suspension. Thereby, it is necessary that the bodies be completely submerged, since else the fusion effects distribute the catalyst unevenly on the surface.
The thus produced wet catalysts are processed to finished catalysts in a 'calcination furnace" at 450 to 550 'C over at least 12 hours. For improved 'initiation" of the catalytic reaction, after the burning process, the catalyst is submerged in a platinum or palladium nitrate solution, such that a concentration of platinum or palladium from 0.1 to 0.5 g/l of catalyst results. Also, the thus resulting finished catalyst is calcined once again over 6 hours at 450 to 550 °C.
The resulting catalyst bodies have a uniform crystal structure or crystal layer, respectively, on the surface, which can be seen in a microscope or scanning

complexes of the rare earths is an important feature of the resulting catalyst crystal. 300 g black catalyst powder result.
This catalyst powder is again dissolved in a solution of 300 g oxalic acid and 3 litres of water while heating and again heated to 500 °C, wherein a similar blak powder arises, but which has a much finer crystal structure and a much more uniform element distribution under the scanning electron microscope. In the case of addition of other rare earths and manganese, the process is repeated a third time until the complete homogeneity is achieved.
The thus resulting black catalyst powder of 300 g needle crystal material, also called perovskite, is now again stirred in 4 litres of deionised water with 105 g oxalic acid. 100 g Condea and 50 g Bayer titanium, a microgranular titanium oxide. The ceramic bodies to be steeped, which are to be conditioned to catalysts by submerging in this solution, are previously dried.
As the catalyst bodies, a honeycomb body, wound metal bodies with continuous channels and porous ceramic extrudates are suitable. As the ceramic material for these bodies, the materials magnesium-aluminium-silicate, the cordierite, Si02 bodies, tItanium-tungsten-oxide-honeycombs and alumina have turned out, wherein the materials magnesium-aluminium-silicate, oordlerite, Si02 bodies, titanium-tungsten-oxide honeycombs are particularly insensitive to expansion and thus particularly suitable.
The catalyst supports are submerged in the catalytic solution such that the porous bodies are uniformly coated, that is, they have to be completely and quickly submerged in order to permit capillary liquid transport within the ceramic as little as possible. If the body is submerged too slowly or on one side, the capillary force of the ceramic body soaks the liquid and the catalytic substance is filtered such that the coating is effected non-uniformly.
After coating by submerging, excessive liquid is separated. This is effected in that the body is placed on a base covered with a screen, which absorbs the excessive

liquid. After complete settling of the liquid at the lower end of the honeycomb bodies, they are freed from the liquid at the lower end by shaking-off or slight blow-out such that the bores of the honeycomb bodies are free.
After coating, the activation of the catalytic coating is effected in that these bodies are calcined at a temperature of 500" over a time period of 2 to 20 hours, that is, the oxalic acid is then completely burned out of the honeycomb body. The burning time depends on the size of the honeycomb bodies. The larger the honey comb body, the longer the burning time.
The honeycomb body thus provided with a crystal layer is not yet completed for the catalytic efficiency. According to the invention, it has been found that small amounts of noble metals, which are applied thereafter in a separate coating operation, develop a particular efficiency. This is because the noble metals are preliminarily deposited on the crystals of the Lao.9Cdo.iCo03 and Lao^gCeoi. This is effected by steeping with a noble metal solution, such as for example platinum nitrate, in such a concentration that 1 gram platinum is dissolved in 1 litre deionised water, and by subsequently burning the ceramic bodies also at 500 ""C.
Thereby* with respect to the usual noble metal coatings, a very stable positioning of the noble metals results, v\^ich achieve a much higher lifetime than upon coating with Condea and Bayer titanium. Moreover, the noble metal brings the coating of LaagCeo.iCoOs and Lao.gCeoi as an "ignition metal" faster to a full catalytic activity, that is, the catalytic activity of the platinum or other noble metals "ignites" the catalytic activity of the ianthanum-cerium-cobattite. This interaction also results with catalyst toxins, which differently poison the two catalytic systems Lao.0CeQ.iCoO3 and noble metals. The respectively less poisoned system activates the other system.
As a result of the inventive coating, the following advantages result, which also establish the economy of the system. The comparable noble metal coating of the same activity necessitates a 20 times higher noble metal amount, has only ca. 5

% of the lifetime compared to the inventive coating, and the catalyst toxins have a reduced influence on the inventive coating.
Moreover, besides the catalytic oxidation of hydrocarbons, the inventive coating gives a completely new, surprising effect. These honeycomb bodies are capable of selectively removing nitrogen oxides from exhaust gases, that is, the nitrogen oxides are also reduced with oxygen containing exhaust gases and the remaining oxygen does not react with the lanthanum-cerium-cobalt surface. However, the process proceeds only as long as until the highest oxidation stage of the catalyst is achieved. Thereafter, the catalyst has to be regenerated again, which is possible with CO and H2 according to today's prior art.

1. Method for producing catalysts for the oxidation of gaseous and vaporous
hydrocarbons (VOC) and the catalytic, selective reduction of DeNOx,
characterized in that
with the compounds of the rare earths and the heavy metals cobalt and manganese, a crystal layer is formed on support bodies as a catalytically active substance in a multi-stage crystallization process.
2. Method according to claim 1,
characterized in that
the reaction partners rare earths and heavy metals, cobalt and/or manganese are formed in super-stoiohiometric ratio such that an excess of rare earths results in the crystal layer.
3. Method according to claims 1 or 2.
characterized in that
the rare earths lanthanum, cerium and yttrium are used collectively or singly.
4. Method according to claims 1 or 2,
characterized in that
as the heavy metals, the metals cobalt and/or manganese are used.
5. Method according to claims 1 or 2,
characterized in that
the starting substances are salts, which are dissolved in water and oxalic acid.
6. Method according to claims 1 or 2,
characterized in that
the fomiation of the complex of rare earths and heavy metals is effected by heating the mixture to 500 to 761 , and this operation is repeated at .least once by dissolving in oxalic acid water,

7. Method according to claims 1,2 or 6,
characterized in that
the catatyticaliy active substance is stirred in an oxalic acid mixture with addition of molecular alumina, Condea and titanium oxide, Bayer titanium to a seeping solution.
8. Method according to claims 1 or 2,
characterized in that
the finished coated catalyst is activated by heating to 500 "C.
9. Method according to claims 1,2,6 or 8,
characterized in that
the finished catalyst is once again seeped in a noble metal solution and subsequently heated to 500 such that the noble metal concentration on the body is between 0.05 and 0.5 g/l.


2241-che-2007 correspondence others 03-06-2011.pdf

2241-che-2007 english translation 03-06-2011.pdf


2241-CHE-2007 AMENDED CLAIMS 26-07-2012.pdf

2241-CHE-2007 AMENDED CLAIMS 12-03-2012.pdf

2241-CHE-2007 CORRESPONDENCE OTHERS 07-04-2011.pdf

2241-CHE-2007 CORRESPONDENCE OTHERS 26-07-2012.pdf

2241-CHE-2007 CORRESPONDENCE OTHRES 12-07-2012.pdf

2241-CHE-2007 FORM-3 12-03-2012.pdf

2241-CHE-2007 OTHER PATENT DOCUMENT 12-03-2012.pdf

2241-CHE-2007 POWER OF ATTORNEY 12-03-2012.pdf






2241-che-2007-form 1.pdf

2241-che-2007-form 3.pdf

2241-che-2007-form 5.pdf

Patent Number 257951
Indian Patent Application Number 2241/CHE/2007
PG Journal Number 48/2013
Publication Date 29-Nov-2013
Grant Date 22-Nov-2013
Date of Filing 04-Oct-2007
Name of Patentee KOCH, CHRISTIAN
Applicant Address SCHULSTRASSE 8 96155 BUTTENHEIM
# Inventor's Name Inventor's Address
PCT International Classification Number B01J 23/10
PCT International Application Number N/A
PCT International Filing date
PCT Conventions:
# PCT Application Number Date of Convention Priority Country
1 10 2006 046 884.8 2006-10-04 Germany