JP4835043B2 - Exhaust gas purification catalyst - Google Patents

Description

    The present invention relates to an exhaust gas purification catalyst.

    It is known that exhaust gas purification catalysts for internal combustion engines cause S poisoning. This is because S (sulfur) is contained in the fuel and lubricating oil of the internal combustion engine, and this S becomes an oxide or the like and is discharged from the internal combustion engine.

    Regarding this S poisoning problem, Patent Document 1 describes that a sulfur absorbent is provided in the exhaust passage upstream of the NOx absorbent that absorbs NOx in the exhaust gas. As the sulfur absorbent, one in which at least one selected from alkali metals, alkaline earth metals and rare earth elements and a noble metal are supported on an alumina carrier is disclosed. In Patent Document 2, a catalyst for absorbing and decomposing sulfur oxides in exhaust gas is disposed on the upstream side of the exhaust gas flow, and a three-way catalyst having NOx absorption capacity is disposed on the downstream side of the exhaust gas flow. It is described to do. The pre-catalyst, for example, supported on alumina a composite oxide of at least one selected from Na, Mg, Ca, Sr, Ba, Y and La and at least one selected from Fe, Mn, Co and Ni. Consists of things.

By the way, the applicant of the present invention has disclosed a catalyst metal dope type exhaust gas purification in which a catalyst metal is arranged between crystal lattice points or lattice points of CeZr double oxide containing Ce and Zr as metal components and having oxygen storage capacity. Has been proposed (see Patent Document 3). In the case of this catalyst, the catalyst metal is present not only on the surface of the CeZr double oxide particles but also inside thereof, thereby increasing the oxygen storage amount and increasing the oxygen storage rate, thereby improving the exhaust gas purification performance. That is, high exhaust gas purification performance is exhibited even with a small amount of catalyst metal, which is advantageous for cost reduction. Furthermore, since the catalyst metal is disposed between the crystal lattice points of the double oxide or between the lattice points, the aggregation or sintering of the catalyst metal by the high-temperature exhaust gas is suppressed.
JP-A-6-58138 JP 2000-42370 A JP 2004-174490 A

    However, as described above, in the catalyst metal dope type exhaust gas purification catalyst, not all of the catalyst metal is present on the surface of the CeZr mixed oxide. That is, only a part of the catalyst metal exists on the surface of the CeZr double oxide, and the rest exists inside. For this reason, when S poisoning progresses, the catalytic metal that effectively works to purify the exhaust gas on the surface of the CeZr double oxide becomes excessively small. That is, the S component in the exhaust gas reacts with the catalytic metal on the CeZr double oxide surface to generate a compound, and the active sites are reduced.

    Therefore, even if the catalyst metal inside the CeZr double oxide increases the oxygen storage capacity, the catalyst damage is great when S poisoning occurs, and the regeneration treatment from the S poison (oxygen in the exhaust gas) Even if the concentration is lowered and the exhaust gas temperature is increased, the catalyst performance cannot be sufficiently recovered. Of course, if the amount of the catalyst metal is increased, the catalyst performance will not be greatly reduced even if some amount of S poisoning occurs, but this increases the cost.

    That is, an object of the present invention is to take measures against the S poisoning without increasing the amount of catalytic metal.

    In the present invention, in order to solve the above-mentioned problems, the basicity of the CeZr-based double oxide doped with the catalyst metal is increased.

That is, the present invention relates to an exhaust gas purifying catalyst in which a catalytic metal is disposed between crystal lattice points or lattice points of a double oxide having oxygen storage capacity.
In the double oxide, the metal component other than the catalyst metal forming the double oxide is at least one selected from Ce, Zr, alkali metal, alkaline earth metal, La and Pr. It consists of a third metal component M, basic of the mixed oxide by the inclusion of said third metal component M is, basic CeZr mixed oxide containing no said third metal component M, and said third metal component M It is characterized by being higher than the basicity of the CeZr double oxide containing Nd but not containing Nd .

    Therefore, according to the present invention, even if the S component such as sulfur oxide having high acidity in the exhaust gas comes near the catalytic metal appearing on the surface of the double oxide, it is in a site with high basicity around it. Even if it is adsorbed or once adsorbed on the catalyst metal, it is desorbed before forming a strong bond with the catalyst metal and adsorbed on the surrounding highly basic sites. This is because the site of higher basicity than the site where the catalytic metal exists is formed on the surface of the double oxide by addition of the third metal component M, or the basicity of Ce whose valence is easily changed. This is considered to be due to the addition of the third metal component M.

    Thus, the addition of the third metal component M as described above suppresses S poisoning of the catalyst metal, and as a result, the state of the exhaust gas purification performance of the catalyst is maintained over a long period of time. Further, even if the S component is adsorbed on the catalyst metal, the bond is weak, so when the exhaust gas temperature becomes high, especially when the regeneration process for increasing the exhaust gas temperature by lowering the oxygen concentration of the exhaust gas is performed. The recoverability of the catalyst from S poisoning is improved.

    As said 3rd metal component M, it is more preferable that it is a basic thing higher than Ce.

As described above, according to the present invention, in the exhaust gas purifying catalyst in which the catalytic metal is disposed between the crystal lattice points or the lattice points of the double oxide having oxygen storage ability, the double oxide contains the double oxide. The metal component other than the catalyst metal forming the product comprises Ce, Zr, and a third metal component M composed of at least one selected from alkali metals, alkaline earth metals, La and Pr, basic of the mixed oxide by the inclusion of a third metal component M is, basic CeZr mixed oxide containing no said third metal component M, and CeZr mixed oxide containing Nd free of said third metal component M Since it is higher than the basicity of the product, S poisoning of the catalyst metal is suppressed, which is advantageous in maintaining a high exhaust gas purification performance for a long period of time. The effect of good recovery That.

    Hereinafter, embodiments of the present invention will be described with reference to the drawings.

    The exhaust gas purifying catalyst 1 according to the embodiment of the present invention shown in FIG. 1 purifies HC (hydrocarbon), CO (carbon monoxide) and NOx (nitrogen oxide) in the exhaust gas of an automobile engine. It is suitable. This catalyst 1 is obtained by forming a catalyst layer on the wall surface of a cell 3 which is a gas flow path of a honeycomb-shaped carrier 2 formed of an inorganic porous material such as cordierite. That is, as shown in FIG. 2, the catalyst layer 6 is formed on the cell wall 5 separating the cells 3 of the honeycomb-shaped carrier. The catalyst layer 6 is a catalyst metal-doped catalyst in which a catalyst metal is disposed between crystal lattice points or between lattice points of a double oxide containing Ce, Zr, and a third metal component M that increases basicity. It is formed by washing the powder with a binder on a carrier.

    The catalyst layer 6 may further contain a catalyst powder obtained by supporting a catalyst metal on another support material, or may contain Ba or other alkaline earth metal or alkali metal as a NOx absorbent. Alternatively, the catalyst layer 6 and other catalyst layers having different components from the catalyst layer may be formed on the surface of the cell wall 5 in layers.

    Examples of the present invention and comparative examples will be described below.

<Preparation of catalyst powders of Examples and Comparative Examples>
Example 1
This example employs Li as the third metal component M. The method for preparing the catalyst powder is as follows. A predetermined amount of each of zirconium oxynitrate, cerous nitrate, lithium nitrate and rhodium nitrate was mixed with water to make a total of 300 mL, and this mixed solution was stirred at room temperature for about 1 hour. This mixed solution was heated to 80 ° C. and heated, and then vigorously stirred rapidly using a glass rod, and 50 mL of 28% ammonia water prepared in another beaker was added at once and mixed. The addition and mixing of the ammonia water was completed within 1 second. The solution clouded by mixing with aqueous ammonia was allowed to stand overnight, and the resulting cake was centrifuged and washed thoroughly with water. The cake washed with water was dried at a temperature of about 150 ° C. and then calcined under the condition that it was kept at a temperature of 400 ° C. for 5 hours and then kept at a temperature of 500 ° C. for 2 hours.

    Since the catalyst powder obtained as described above is produced by the coprecipitation method with the addition of the Rh component, Rh is arranged at the crystal lattice point of the double oxide in the same manner as Ce, Zr and Li, in other words, It will be in the state couple | bonded strongly with the said double oxide. Or Rh will be in the state arrange | positioned between the lattice points of the said complex oxide. In any case, a part of Rh is uniformly dispersed on the surface and inside of the double oxide crystallite.

    The composition of the metal component excluding Rh in the Rh-doped catalyst powder was Ce: Zr: Li = 17: 75: 8 in mol%, and the Rh amount was 0.116% by mass.

-Examples 2-9-
As the third metal component M, each of the Rh-doped catalyst powders of Examples 2 to 9 adopting Na, K, Ca, Sr, Ba, La, and Pr instead of Li in the same manner as in Example 1. Prepared. The composition of the metal components excluding Rh of these Rh-doped catalyst powders is Ce: Zr: M = 17: 75: 8 in mol%, as in the case where the third metal component M is Li, and the amount of Rh is 0.8. 116% by mass.

    As described above, in each of Examples 1 to 9, the molar ratio of the third metal component M in the double oxide is made smaller than the Ce molar ratio.

-Comparative examples 1 and 2-
An Rh-doped catalyst powder according to Comparative Example 1 employing Nd as the third metal component M was prepared in the same manner as in Example 1. That is, the composition of the metal component excluding Rh in this Rh-doped catalyst powder was Ce: Zr: Nd = 17: 75: 8 in mol%, and the Rh amount was 0.116% by mass.

An Rh-doped catalyst powder according to Comparative Example 2 containing no third metal component was prepared in the same manner as in Example 1. That is, the composition of the Rh-doped catalyst powder excluding Rh is Ce _0.25 Zr _0.75 O ₂ and the amount of Rh is 0.116% by mass.

<Measurement of base amount>
For each of the catalyst powders of Examples 1 to 9 and Comparative Examples 1 and 2, a fixed amount of a sample formed in a pellet form in a fixed bed flow-type temperature rising and desorbing device was charged, and CO ₂ was adsorbed. A method of measuring the amount of CO ₂ desorbed by raising the temperature was adopted.

That is, while passing the carrier gas of He 100% through the temperature-programmed desorption device, the sample temperature was raised to 600 ° C. and held at that temperature for 10 minutes to desorb the adsorbed water. Subsequently, after switching to He gas containing 2% CO ₂ at the same temperature and holding for 10 minutes, the temperature was lowered to room temperature to adsorb CO ₂ to the base point of the sample. Next, by switching to He 100% carrier gas, after exhausting excess CO ₂ , the temperature was raised from room temperature to 600 ° C. at 20 ° C./min while circulating the same gas (SV = 95000 h ⁻¹ ). The total amount of desorbed CO ₂ was quantified and used as the base amount.

The result is shown in FIG. The catalyst powder according to the example employing Li, Na, K, Ca, Sr, Ba, La, Pr as the third metal component M has a larger base amount than the comparative examples (“None” and “Nd”). cage, basic of the mixed oxide by the addition of a third metal component M is, CeZr mixed oxide indicated by "NO" in the figure, and that is higher than CeZr mixed oxide indicated by "Nd" Recognize.

<Evaluation of exhaust gas purification performance>
Samples for measuring exhaust gas purification performance were prepared for each catalyst powder of Examples 1 to 9 and Comparative Example 2 (no third metal component). That is, slurry was prepared by mixing catalyst powder and zirconia binder and adding ion exchange water thereto. The carrier was coated with the slurry by a method of immersing and lifting the honeycomb-like carrier in this slurry and blowing off the excess slurry. Next, this was dried at a temperature of 150 ° C. for 1 hour and calcined at a temperature of 540 ° C. for 2 hours to form the catalyst layer on the surface of the cell wall.

    Then, for each sample, after pre-aging for 24 hours at 1000 ° C. in the air atmosphere, using the model gas flow reactor and the exhaust gas analyzer, when fresh (before S poisoning treatment), The light-off temperature T50 related to the purification of NOx after the S poisoning treatment and after the regeneration treatment was measured.

    In measuring T50 at the time of fresh, a model exhaust gas (temperature 600 ° C.) rich in air-fuel ratio was flowed through the test catalyst for 10 minutes in advance. Then, the measurement was performed by switching to the model exhaust gas for evaluation. T50 is the gas temperature at the catalyst inlet when the temperature of the model gas flowing into the catalyst is gradually increased from room temperature and the purification rate reaches 50%.

The model exhaust gas for evaluation was A / F = 14.7 ± 0.9. That is, the A / F is forcibly oscillated with an amplitude of ± 0.9 by adding a predetermined amount of fluctuation gas in a pulsed manner while constantly flowing the main stream gas of A / F = 14.7. I let you. This frequency was 1 Hz. The space velocity SV is 60000 h ⁻¹ , and the rate of temperature increase of the model gas is 30 ° C./min.

S-poisoning treatment, while circulating _N 2 100% gas sample was heated to 350 ° C. and held at that temperature, then _SO 2 50 ppm at the same _temperature, O 2 10%, the S in the residual _{N 2} The gas is switched to poison gas and allowed to flow for 1 hour (SV = 60000 h ⁻¹ ), and then switched to N ₂ 100% gas to lower the temperature to room temperature. After this S poisoning treatment, T50 was measured by the above model exhaust gas for evaluation in the same manner as when fresh.

In the regeneration treatment, the rich model exhaust gas corresponding to A / F = 14.5 is circulated through the sample after the S poisoning treatment (SV = 120,000 h ⁻¹ ), and the temperature is raised to 600 ° C. at 30 ° C./min. After maintaining at that temperature for 10 minutes, the temperature is switched to room temperature by switching to N ₂ 100% gas. Thereafter, T50 was measured with the model exhaust gas for evaluation in the same manner as in the fresh state.

    The results are shown in Table 1. The S poisoning deterioration rate and regeneration recovery rate in the same table are obtained by the following equations. T50 after S poisoning means T50 after S poisoning treatment, FreshT50 means T50 at fresh time, and T50 after regeneration means T50 after regeneration processing.

S poisoning exacerbation rate = (T50 after S poisoning-FreshT50) / FreshT50
Regeneration recovery rate = (T50 after S poisoning-T50 after regeneration) / (T50 after S poisoning-FreshT50)

    Looking at the T50 at the time of freshness, the example is a little better than the comparative example. This is probably because the oxygen storage capacity or heat resistance of the double oxide was improved by the addition of the third metal element M. In particular, an example in which rare earth elements La and Pr are added is improved.

    Looking at the T50 after the S poisoning treatment, all of the Examples have a lower T50 than the comparative example, and the S poisoning deterioration rate is also small. From this, it can be seen that when the third metal component M is added as in the Examples, the S-toxicity of the catalyst increases.

    Looking at the T50 and regeneration recovery rate after the regeneration treatment, the exhaust gas purification performance recovered to 100% or nearly 100% by the regeneration treatment in all the examples, whereas in the comparative example, only about 50%. It has not recovered. From this, it can be seen that when the third metal component M is added as in the example, the recovery by regeneration after the S poisoning of the catalyst is also high.

To examine the mechanism of S poisoning and regeneration described above, first, FIG. 4 shows a conventional example in which an Rh solution is brought into contact with BaZr oxide (CeZrO to which no third metal component is added) and baked and supported. Show. In this conventional example, as is apparent from the comparative example “No” in FIG. 3, since the basicity of the CeZr double oxide is not so high, the S component (represented by SO ₄ ²⁻ ) in the exhaust gas is , It is considered that when it comes to the vicinity of Rh, it is adsorbed to Rh as it is, becomes rhodium sulfate, binds very strongly to Rh, and is not easily detached. This point is the same as in the comparative example “None”. Therefore, as shown in Table 1, it is considered that the S poisoning deterioration rate is high and the regeneration recovery rate is low.

On the other hand, in the case of the example, as shown in FIG. 5, the Rh-doped double oxide (CeZrMO having the third metal component M) is highly basic due to the action of the third metal component M. ing. For this reason, even if the S component (SO ₄ ²⁻ ) in the exhaust gas comes near Rh on the CeZrMO surface, it is adsorbed on the surrounding highly basic site, or once adsorbed on Rh, It is considered that it is desorbed before forming a compound and adsorbed at a site having a high basicity around it.

    This is because the addition of the third metal component M resulted in the formation of a site having a higher basicity than Rh on the surface of the double oxide, or the basicity of Ce, whose valence is easily changed, is the third metal component. This is thought to be due to the addition of M.

    Further, in the case of the example, the regeneration recovery rate is extremely high compared to the comparative example. This is because even when Rh is poisoned, in the case of the example, the bond between the Rh and the S component is weak. On the other hand, in the case of the comparative example, the bond between Rh and the S component is very strong, which means that the S component is hardly detached.

    In addition, the regeneration recovery rate of the example is about 100%, which means that not only the S component adsorbed to Rh but also the portion other than Rh of the double oxide by the regeneration process. This suggests that most of the components are also detached. That is, rather than the third metal component M forming a highly basic site and the S component adsorbed thereto, the addition of the third metal component increases the basicity of Ce whose valence tends to change, This suggests that the S component is mainly adsorbed on Ce with increased basicity. This is because Ce is easy to desorb the S component by the regeneration process because the valence is likely to change, and therefore, the regeneration recovery rate is considered to be about 100%.

1 is a perspective view of an exhaust gas purifying catalyst according to the present invention. It is sectional drawing which expands and shows a part of the catalyst. It is the graph which compared the amount of bases of CeZr system double oxide which added various third metal ingredients. Rh to S components of the conventional composite oxide CeZrO _(SO ^{4 2-)} is a schematic view showing a state in which the contact. Rh on S component of mixed oxide CeZrMO added a third metal component M according to the present invention _(SO ^{4 2-)} is a schematic view showing a state in which the contact.

DESCRIPTION OF SYMBOLS 1 Exhaust gas purification catalyst 2 Carrier 3 Cell 5 Cell wall 6 Catalyst layer

Claims (1)

In an exhaust gas purifying catalyst in which a catalytic metal is disposed between crystal lattice points or lattice points of a double oxide having oxygen storage capacity,
In the double oxide, the metal component other than the catalyst metal forming the double oxide is at least one selected from Ce, Zr, alkali metal, alkaline earth metal, La and Pr. It consists of a third metal component M, basic of the mixed oxide by the inclusion of said third metal component M is, basic CeZr mixed oxide containing no said third metal component M, and said third metal component M An exhaust gas purifying catalyst characterized by being higher in basicity than a CeZr double oxide containing Nd and containing no Nd .

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