Vanadium-free diesel oxidation catalyst and method for its production

Abstract

The invention relates to a method for producing a catalytic composition, wherein the catalytic composition has a high activity and selectivity with regard to the oxidation of CO and a reduced activity with regard to the oxidation of NO. The invention also relates to the catalyst produced using the method according to the invention. Finally, the invention is directed towards an exhaust-gas cleaning system which comprises the catalyst according to the invention.

Claims

1. A method for producing a catalyst, comprising the steps: a) impregnating a metal oxide support material with a platinum compound, b) drying the impregnated metal oxide support material obtained in step a) at a temperature of from 60 to 100 C., c) applying the dried, impregnated metal oxide support material obtained in step b) as a washcoat coating to a catalyst support body which is then dried at a temperature of from 60 to 100 C., and d) calcining the dried catalyst support body obtained in step c) that has not undergone any prior calcining, in a gas stream which consists of CO and inert gas.

2. The method according to claim 1, wherein in step d) a first calcining takes place heating up within 10 minutes and a second calcining takes place within from 10 to 40 minutes under identical calcining conditions.

3. The method according to claim 1, wherein the gas stream contains 0.5 to 3 vol-% CO and 97 to 99.5 vol-% inert gas.

4. The method according to claim 1, wherein N.sub.2, He, Ne or argon is used as inert gas.

5. The method according to claim 1, wherein the calcining takes place at a temperature of from 400 to 650 C.

6. The method according to claim 1, wherein a metallic or ceramic monolith, a non-woven or a metal form is used as catalyst support body.

7. The method according to claim 1, wherein the metal oxide is selected from the group consisting of aluminum oxide, silicon oxide, aluminosilicate, zirconium oxide, titanium oxide, Al/Si mixed oxide or combinations thereof.

8. The method according to claim 4, wherein N.sub.2 is used as inert gas.

9. A method for producing a catalyst, consisting of the steps of: a) impregnating a metal oxide support material with a platinum compound, b) drying the impregnated metal oxide support material obtained in step a) at a temperature of from 60 to 100 C., c) applying the dried, impregnated metal oxide support material obtained in step b) as in the form of a washcoat coating to a catalyst support body which is then dried at a temperature of from 60 to 100 C., and d) calcining the dried catalyst support body obtained in step c) in a gas stream which consists of CO and inert gas.

10. The method according to claim 9, wherein in step d) a first calcining takes place heating up within 10 minutes and a second calcining takes place within from 10 to 40 minutes under identical calcining conditions.

11. The method according to claim 9, wherein the gas stream contains 0.5 to 3 vol-% CO and 97 to 99.5 vol-% inert gas.

12. The method according to claim 9, wherein the calcining takes place at a temperature of from 400 to 650 C.

13. The method according to claim 9, wherein a metallic or ceramic monolith, a non-woven or a metal form is used as catalyst support body.

14. The method according to claim 9, wherein the metal oxide is selected from the group consisting of aluminum oxide, silicon oxide, aluminosilicate, zirconium oxide, titanium oxide, Al/Si mixed oxide or combinations thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 is a graph comparing the CO conversions from the catalysts used.

(2) FIG. 2 is a graph comparing the propylene conversions from the catalysts used.

(3) FIG. 3 is a graph comparing the yield of the oxidation of NO to NO.sub.2 from the catalysts used.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(4) In a preferred embodiment of the invention, the dried, impregnated support material is therefore applied to a catalyst support body prior to the calcining. Particularly preferably, the dried, impregnated support material is applied to the catalyst support body in the form of a washcoat coating and then dried again below the decomposition temperature of the platinum compound.

(5) The drying of the impregnated support material takes place according to the present invention preferably at temperatures of from 60 C. to 100 C., more preferably from 70 to 90 C., most preferably at about 80 C. However, the temperature depends on the platinum compound used, as these can have different decomposition points and thus the temperature must be adapted accordingly. The drying preferably takes place under reduced pressure, particularly preferably under fine vacuum.

(6) For the impregnating, the noble metal (Pt) is usually present as salt solution, for example as chloride, nitrate or sulphate. Normally, all customary salts and complex salts of platinum are suitable, e.g. hexachloroplatinic acid, tetrachloroplatinic acid, dinitro diamine platinate (II), tetraamine platinum (II) chloride, ammonium tetrachloroplatinate (II), ammonium hexachloroplatinate (IV), dichloro(ethylenediamine) platinum, tetraamine platinum (II) nitrate, tetraamine platinum (II) hydroxide, methylethanolamine platinum (II) hydroxide, platinum nitrate, ethanolammonium hexahydroxoplatinate (platinum ethanolamine, PtEA) and similar. Ethanolammonium hexahydroxoplatinate (PtEA) is particularly preferred.

(7) A metal oxide or metal mixed oxide is preferably used as support material. The metal oxide or metal mixed oxide is preferably selected from the group consisting of aluminium oxide, silicon oxide, aluminosilicate, zirconium oxide, titanium oxide, Al/Si mixed oxide or combinations thereof.

(8) The necessary coating techniques for coating a catalyst support body are known to a person skilled in the art. Thus, e.g. the impregnated and dried metal oxide or mixed oxide is processed to an aqueous coating dispersion. This dispersion can be added as binder, e.g. silica sol. The viscosity of the dispersion can be set by the appropriate additives, with the result that it becomes possible to apply the necessary quantity of coating to the walls of the flow channels in a single work step. If this is not possible, the coating can be repeated several times, wherein each freshly applied coating is fixed by an intermediate drying. The finished coating is then calcined at the temperatures given above within the temperature range in less than 10 min, preferably less than 6 min, particularly preferably less than 5 min (first calcining). A second calcining step then takes place, optionally after a short pause, over a period of 10-40 min, preferably 20 min, under the same conditions.

(9) For the exhaust-gas cleaning of diesel engines, coating quantities of from 50 to 500 g/l volume of the catalyst support body are advantageous. The catalyst component is preferably matched such that the catalytically active components are present in the metal oxide in a concentration of from approximately 0.01 to 7 g/l, preferably 2-4 g/l.

(10) A metallic or ceramic monolith, a non-woven or metal foam can be used as catalyst support body. Other catalyst shaped bodies or catalyst support bodies known in the state of the art are also suitable according to the invention. A metallic or ceramic monolith that has a plurality of parallel passage openings which are provided with the washcoat coating is particularly preferred. With this, a uniform and in particular thin application of the washcoat suspension can be guaranteed, which thus supports the calcining.

(11) Metallic honeycomb bodies are often formed from sheet metals or metal foils. The honeycomb bodies are produced for example by alternating arrangement of layers of structured sheets or foils. Preferably, these arrangements consist of one layer of a smooth sheet alternating with a corrugated sheet, wherein the corrugation can be formed for example sinusoidal, trapezoidal, omega-shaped or zigzag-shaped. Suitable metallic honeycomb bodies and methods for their production are described for example in EP 0 049 489 A1 or DE 28 56 030 A1.

(12) In the field of catalyst support bodies, metallic honeycomb bodies have the advantage that they heat up more quickly and thus catalyst support bodies based on metallic substrates normally display a better response behaviour in cold-start conditions.

(13) The honeycomb body preferably has a cell density of from 30 to 1500 cpsi, particularly preferably from 200 to 600 cpsi, in particular 400 cpsi.

(14) The catalyst support body to which the catalyst according to the invention can be applied can be formed from any metal or a metal alloy and be produced e.g. by extrusion or by coiling or stacking or folding of metal foils. In the field of exhaust-gas cleaning, temperature-resistant alloys with the main constituents iron, chromium and aluminium are known. Monolithic catalyst support bodies that can be freely flowed through with or without internal leading edges for the agitation of the exhaust gas or metal foams which have a large internal surface area and to which the catalyst according to the invention adheres very well are preferred for the catalyst according to the invention. However, catalyst support bodies with slits, holes, perforations and impressions in the metal foil can also be used.

(15) In the same way, catalyst support bodies made of ceramic material can be used. Preferably, the ceramic material is an inert material with a small surface area, such as cordierite, mullite or -aluminium oxide. However, the catalyst support used can also consist of support material with a large surface area, such as -aluminium oxide.

(16) A metal foam, for example a metallic open-pored foam material, can also be used as catalyst support body. Within the framework of the present invention, by the term metallic open-pored foam material is meant a foam material made of any metal or of any alloy which can optionally also contain additives and which has a plurality of pores which are connected to each other by conduit, with the result that for example a gas can be conducted through the foam material.

(17) Metallic open-pored foam materials have a very low density because of the pores and cavities, but have a substantial stiffness and strength. The production of metal foams takes place for example by means of a metal powder and a metal hydride. Both powders are normally admixed together and then compacted to a shaped material by hot pressing or extrusion. The shaped material is then heated to a temperature above the melting point of the metals. The metal hydride releases hydrogen gas and the mixture foams.

(18) However, there are also still other possibilities for producing metal foams, for example by blowing gas into a metal melt which has previously been made foamable by adding solid constituents. For aluminium alloys for example, 10 to 20 vol.-% silicon carbide or aluminium oxide is added for the stabilization. In addition, open-pored metallic foam structures with a pore diameter of from 10 ppi to approximately 50 ppi can be produced by special precision casting techniques.

(19) A further subject of the invention is a catalyst which can be obtained using the method according to the invention. The catalyst is characterized by a very good activity and a selective oxidation potential for an oxidation of CO (also HC) and a low activity and selectivity for an oxidation of NO.

(20) The catalyst can accordingly be used as oxidation catalyst. In particular, the oxidation catalyst is to be used for the selective oxidation of CO (and HC).

(21) Preferably, the catalyst is present as coating on a catalyst support body, preferably a metallic or ceramic monolithic shaped body, a non-woven or a metal foam.

(22) The scope of the invention also includes a catalyst component which contains the catalyst according to the invention. The catalyst component is accordingly equipped with a housing in which the catalyst is located. The housing has an inlet and outlet opening for the exhaust gas to be treated.

(23) The catalyst component (or the catalyst according to the invention) can be used as component in an exhaust-gas system. In a preferred embodiment of the invention, the catalyst component (the catalyst according to the invention) is fitted upstream of a diesel particle filter. Through the low activity of the catalyst for the oxidation of NO to NO.sub.2, for example a particle filter is supplied with precisely enough NO.sub.2 to oxidize soot particles, wherein NO.sub.2 itself is reduced. Hardly any excess NO.sub.2 which could be introduced into the environment is thereby left over. In this way, a downstream SCR catalyst can be dispensed with and costs can be reduced.

(24) A subject of the invention is thus also an exhaust-gas system comprising a catalyst according to the invention and a diesel particle filter. The diesel particle filter is fitted downstream of the catalyst according to the invention. The exhaust-gas system is preferably free of an SCR catalyst.

(25) The invention will now be described in more detail with the help of some embodiment examples which are however to be considered as not limiting the scope of the invention. Reference is made in addition to FIGS. 1 to 3.

EMBODIMENT EXAMPLES

Example 1

1. Impregnation

(26) The water absorption of an aluminium oxide (Puralox SCF a-140 L3 from Sasol) stabilized with lanthanum was first determined by weighing the powder, slurrying in water, filtering and then weighing again while wet. It was 50.18 wt.-%.

(27) In a planetary mixer, 110.4 g of a 13.59% solution of platinum ethanolamine (ethanolammonium hexahydroxoplatinate) was added slowly dropwise to 300 g of the dry Puralox powder accompanied by stirring. The powder was dried for 2 days at 80 C. in the vacuum drying cupboard, with the result that 5 wt.-% platinum would be contained on a completely dry powder.

2. Washcoat Production, Coating

(28) 500 g of this vacuum-dried powder (from 2 impregnation batches) was topped up with 2500 g water, de-agglomerated with an Ultra-Turrax stirrer and then milled with a bead mill (4000 rpm, 1.2-mm ZrO.sub.2 beads).

(29) 400-cpsi cordierite honeycombs were coated with this washcoat by immersion and blowing. The honeycombs were then in each case dried again at 80 C. in the vacuum drying cupboard.

(30) As a drying at 80 C. under vacuum does not necessarily take place completely, a loading of 60 g washcoat/1 honeycomb was first produced by repeated coating. When the aluminium oxide is dry, this should correspond to a platinum loading of 3.0 g/l. A honeycomb from a series of identically coated and only vacuum-dried honeycombs was then calcined at 500 C. for 3 h and the platinum content analytically (pulping and ICP analysis) determined. This honeycomb (diameter 3 cm, length 8.8 cm) was coated with 3.68 g washcoat and weighed 33.4 g. With a Pt content of 5 wt.-%, the honeycomb should thus contain 0.55 wt.-% Pt when completely dry. 0.44 wt.-% platinum was determined from the analysis, because the coating with 3.68 g washcoat was not completely dry and still contained water.

(31) The weight of the honeycomb after vacuum drying and the weight of the honeycomb after calcining and the platinum concentration were used to calculate how much platinum must still be coated on the honeycomb for there to be 3.5 g/l platinum on a honeycomb. The platinum quantity which was already on the honeycomb and the washcoat loading after vacuum drying were able to be used to calculate what weight the not completely dry honeycomb vacuum-dried at 80 C. must have at the end in order to have 3.5 g Pt/1 honeycomb volume. The honeycombs were then coated up to this weight, with the result that, at the end, each honeycomb had a platinum content of 3.5 g/l honeycomb volume.

3. Calcining of the Vacuum-Dried Honeycombs Under a Gas Mixture which Contained 1 Vol.-% Co in Nitrogen

(32) The coated honeycombs were introduced into a quartz glass tube using a ceramic fibre blanket for the sealing. A gas mixture of 1 vol.-% CO in nitrogen was conducted over the catalyst in the calcining unit. In front of the quartz glass tube there was a heater which very quickly heated the gas mixture to up to 490 C. immediately before the honeycomb. Around the quartz glass tube there was an IR oven which was also able to heat up the honeycombs quickly by means of IR radiation.

(33) In this structure, the gas stream of 1 vol.-% CO in nitrogen was heated before the honeycomb from room temperature to 450 C. within 50 s and then further via a PID controller to 490 C. within a further minute. At the same time, a heating-up of the IR oven to 600 C. at 100 C./min was started. A measurement with a thermocouple in the honeycomb produced at the end a temperature of 500 C. in the honeycomb. This temperature was reached after 6 min. Under these conditions, after these 6 min, calcining was continued for another 20 min at a gas inlet temperature of 490 C. and an IR oven temperature of 600 C.

Comparison Example 1

1. Impregnation

(34) The water absorption of an aluminium oxide (Puralox SCF a-140 L3 from Sasol) stabilized with lanthanum was first determined by weighing the powder, slurrying in water, filtering and then weighing again while wet. It was 50.18 wt.-%.

(35) In a planetary mixer, 144.2 g of a 13.87% solution of platinum ethanolamine (ethanolammonium hexahydroxoplatinate) was added slowly dropwise to 400 g of the dry Puralox powder accompanied by stirring. The powder was then dried in the drying oven at 80 C. for 3 hours. The powder was then calcined in a calcining oven in air for 3 h at 500 C. (heat-up rate 2 C./min).

2. Washcoat Production, Coating

(36) 140 g of this already calcined powder was topped up to 700 g with water, de-agglomerated with an Ultra-Turrax stirrer and then milled with a bead mill (4000 rpm, 1.2-mm ZrO.sub.2 beads).

(37) 400-cpsi cordierite honeycombs were coated with this washcoat by immersion and blowing. The honeycombs were then in each case dried again and calcined for 3 h at 500 C.

(38) This coating was repeated until a loading of 70 g washcoat/1 honeycomb was reached. As the powder had a platinum content of 5 wt.-%, this meant that the honeycomb also had a platinum content of 3.5 g/l.

Comparison Example 2

1. A Honeycomb Impregnated with Platinum Ethanolamine and Vacuum-Dried was Produced as Described in Example 1

2. Calcining of the Vacuum-Dried Honeycombs Under Air

(39) The coated honeycombs were introduced into a quartz glass tube using a ceramic fibre blanket for the sealing.

(40) In the calcining unit, air was conducted over the catalyst.

(41) In front of the quartz glass tube there was a heater which very quickly heated the air to up to 490 C. immediately before the honeycomb. Around the quartz glass tube there was an IR oven which also heated up the honeycombs quickly by means of IR radiation.

(42) In this structure, the air stream was heated before the honeycomb from room temperature to 450 C. within 50 s and then further via a PID controller to an inlet temperature of 490 C. within a further minute. At the same time, a heating-up of the IR oven to 600 C. at 100 C./min was started. The measurement with a thermocouple in the honeycomb thus produced at the end a temperature of 500 C. in the honeycomb. This temperature was reached after 6 min. Under these conditions, after these 6 min, calcining was continued for another 20 min at a gas inlet temperature of 490 C. and an IR oven temperature of 600 C.

Comparison Example 3

1. A Honeycomb Impregnated with Platinum Ethanolamine and Vacuum-Dried is Produced as Described in Example 1

2. Calcining of the Vacuum-Dried Honeycombs Under 2000 ppm Propylene in Air

(43) The coated honeycombs were introduced into a quartz glass tube using a ceramic fibre blanket for the sealing. The calcining of the vacuum-dried honeycombs took place in a calcining unit with a gas mixture of 2000 ppm propylene in air by conducting the gas stream over the catalyst.

(44) In front of the quartz glass tube there was a heater which very quickly heated the gas mixture to up to 490 C. immediately before the honeycomb. Around the quartz glass tube there was an IR oven which also heated up the honeycombs quickly by means of IR radiation.

(45) In this structure, the gas stream was heated up before the honeycomb from room temperature to 450 C. within 50 s and then further via a PID controller to an inlet temperature of 490 C. within a further minute. At the same time, a heating-up of the IR oven to 600 C. at 100 C./min was started. The measurement with a thermocouple in the honeycomb produced at the end a temperature of 500 C. in the honeycomb. This temperature was reached after 6 min. Under these conditions, after these 6 min, calcining was continued for another 20 min at a gas inlet temperature of 490 C. and an IR oven temperature of 600 C.

Example 4

Comparison Test of the Catalysts

(46) The catalyst honeycombs produced in Example 1 and the comparison examples were tested for the oxidation of CO, propylene and NO in a reactor under the following conditions.

(47) Space Velocity: 70 000 h.sup.1

(48) TABLE-US-00001 CO: 500 ppm NO: 500 ppm Propylene: 500 ppm Oxygen: 5% Water: 10% CO.sub.2: 70-90 ppm Nitrogen: Remainder

(49) The gas stream was heated up before the catalyst. For the test, the catalyst was first operated for 30 min under these gas conditions at 390 C. and then cooled down in steps of 10 C. Each temperature was maintained for 8 min and the product gas composition determined between 7 and 8 min. Below 250 C., the cooling down took place in 5 C. steps in order to be able to more precisely determine in particular the CO light-off temperature (50% CO conversion).

(50) FIG. 1 shows the CO conversion of the catalysts used:

(51) It is clear that the catalyst calcined with CO in N.sub.2 has the best CO light-off temperature with at the same time a very low NO oxidation (see FIG. 3).

(52) FIG. 2 shows the propylene conversion (a hydrocarbon, HC) of the catalysts used. Here too, the catalyst calcined with CO in nitrogen is very good.

(53) The yield for the oxidation of NO to NO.sub.2 is represented in FIG. 3. It is clear that not only is the catalyst which was calcined with CO in nitrogen better for an oxidation reaction, but the catalyst surprisingly oxidizes much less NO to toxic NO.sub.2 under the same conditions in the same test.

(54) In all ranges, the catalyst calcined with propylene in air is at least better than the catalysts calcined only in air.