Method for preparing alumina-supported perovskite oxide compositions, alumina-supported perovskite oxide compositions, and uses of said compositions

Abstract

The present disclosure relates to methods for preparing alumina-supported perovskite oxide compositions, alumina-supported perovskite oxide compositions, and the use of said alumina-supported perovskite oxide compositions in catalyst systems for emission control applications.

Description

[Technical Field]

[0001] The present disclosure relates to methods for preparing alumina-supported perovskite oxide compositions, alumina-supported perovskite oxide compositions, and the use of such compositions in catalyst systems for emission control applications. [Background technology]

[0002] To reduce the NOx content in the exhaust gas of lean-burn engines, specialized NOx aftertreatment systems are required. Unlike three-way catalysts, which mostly operate under stoichiometric conditions, the reduction of NOx to N2 is not possible under current oxidation conditions. Therefore, specialized exhaust gas aftertreatment catalysts have been developed, containing materials capable of storing NOx, for example, as nitrates / nitrites under lean conditions. By applying simple stoichiometric or sufficient operating conditions, the stored NOx can be converted to nitrogen, and the storage material can be regenerated. Such catalysts are commonly referred to as (lean) NOx trap catalysts. NOx trap catalysts can be installed upstream of a zeolite-based selective catalytic reduction (SCR) catalyst, which becomes more efficient at higher temperatures.

[0003] NOx trap catalysts usually contain CeO2 as a storage component for storing NOx, especially in the low to medium temperature range. The drawback is that during the DeNOx process, e.g., regeneration of rich exhaust gas compositions, most of the reducing agent is consumed due to the redox activity of ceria. 3+ Ce 4+ This results in a substantial fuel penalty.

[0004] Therefore, there is a need to develop materials capable of storing NOx in the low to medium temperature range, where the redox is not active under operating conditions.

[0005] Redox-inactive perovskites with the formula ABO3 (where A is a rare earth, alkaline earth, alkali, or Pb 2+ , and Bi 3+ (wherein B is a cation containing a transition metal, while B is a cation containing a transition metal) are attractive alternatives. However, such compounds usually do not have the surface area required to react with NOx in the bulk state.

[0006] Perovskites and their use in catalytic systems for exhaust gas emissions are disclosed in U.S. Patent No. 5,627,999. The patent discloses a composite of a lanthanum-based perovskite on a support made of alumina or aluminum oxyhydroxide. The composite is produced by a precipitation process, which produces perovskites that are advantageous over the prior art. The necessity and importance of low crystallinity of the perovskite is taught in paragraph 3 of the patent, in that it is stated that the perovskite can be dispersed as finely as possible on the support, in other words, can be provided in the form of fine particles. However, the low crystallinity required for certain catalytic applications cannot be obtained by the method described in the patent.

[0007] Patent Document 2 discloses a two-step process for preparing perovskite mixed oxide supports. In Example 5, LaAlO3 powder is prepared from γ-alumina and lanthanum nitrate in the first step. The LaAlO3 is mixed with an aqueous solution of perovskite precursor compounds, dried, and calcined. Thus, LaAlO3 coexists with the catalytic components of the perovskite material.

[0008] US Patent No. 5,949,999 discloses a two-step process for preparing perovskite mixed oxide supports. In Example 1, γ-alumina is impregnated with lanthanum nitrate in the first step. The stabilized alumina is impregnated three times with an aqueous solution of perovskite precursor compounds, dried, and calcined. Although the crystallite size is not reported, relatively sharp reflections in the X-ray diffraction pattern indicate that the perovskite crystallites are larger than 5 nm. [Prior art documents] [Patent documents]

[0009] [Patent Document 1] US Patent Application Publication No. 2012 / 0046163 [Patent Document 2] U.S. Patent No. 4,921,829 [Patent Document 3] U.S. Patent No. 5,882,616 Summary of the Invention [Problem to be solved by the invention]

[0010] In view of the above, there remains a need to develop a homogeneous perovskite oxide composite with improved properties, where the perovskite structure is on an alumina support. [Means for solving the problem]

[0011] According to a first aspect of the present disclosure, there is provided a method for preparing an alumina supported perovskite oxide composition, the method comprising: (i) providing a doped alumina, the doped alumina comprising: a. Contains alumina and rare earth oxides, b. Containing alumina and alkaline earth oxides, or c. Alumina and mixtures of rare earth oxides and alkaline earth oxides and the doped alumina is (A) preparing a boehmite suspension containing boehmite; (B) preparing an aqueous solution of a salt, the aqueous solution of the salt comprising: a. Rare earth salts or b. alkaline earth salts, or c. Mixtures of rare earth salts and alkaline earth salts and (C) combining the boehmite suspension with an aqueous salt solution to form a boehmite salt mixture; (D) drying the boehmite salt mixture to produce a dried boehmite salt mixture; (E) calcining the dried mixture of boehmite salts to produce doped alumina; and (ii) The doped alumina is dissolved in a water-soluble rare earth salt, a water-soluble alkaline earth salt, a water-soluble alkali salt, a water-soluble Bi 3+ salts, water-soluble Pb 2+ and one of the salts of a water-soluble transition metal salt, or a mixture of such salts, to form an impregnated body of doped alumina; (iii) calcining the doped alumina impregnated body to obtain an alumina-supported perovskite oxide composition; Includes.

[0012] Boehmite is defined as any alumina with the molecular formula AlOOH*xH2O, where x is between 0 and 0.5, and includes boehmite and pseudoboehmite.

[0013] The boehmite suspension may further comprise silica, titania, a water-soluble titanium or zirconium salt, or a mixture thereof.

[0014] The boehmite suspension contains a boehmite precursor and at least water, preferably in a ratio of 2:98 to 20:80. The boehmite suspension optionally contains an additive for adjusting the pH, such as a carboxylic acid or ammonia.

[0015] More preferably, the boehmite suspension is prepared by hydrolysis of an aluminum alkoxide.

[0016] The aqueous salt solution for preparing the doped alumina preferably contains at least water and a water-soluble rare earth salt, a water-soluble alkaline earth salt, or a mixture thereof. The rare earth salt is preferably an acetate or nitrate of an element having an atomic number of 57 to 60, and most preferably an acetate of La. The alkaline earth salt is preferably an acetate or nitrate of an alkaline earth. The alkaline earth salt is preferably an acetate of Ca, Sr, or Ba, and most preferably an acetate of Sr.

[0017] The doped alumina (after calcination) has a maximum content of rare earth oxides, alkaline earth oxides, or mixtures thereof of 20 weight percent or less, preferably less than 12 weight percent, and most preferably less than 10 weight percent. Of the rare earth oxides, alkaline earth oxides, or mixtures thereof present in the alumina-supported perovskite oxide composition, 50 weight percent or more, preferably 90 weight percent or more, and most preferably 100 weight percent is added to the boehmite suspension as a rare earth salt, alkaline earth salt, or mixture thereof. The oxides are produced from the salts by calcination. The doped alumina provides uniformly distributed nucleation sites during the process of impregnating the doped alumina with an aqueous impregnation solution to obtain the alumina-supported perovskite oxide composition.

[0018] In particular, when the doped alumina (after calcination) contains lanthanum oxide, the maximum lanthanum oxide content is 20 weight percent or more, preferably less than 12 weight percent, and most preferably less than 10 weight percent. Lanthanum oxide is produced from lanthanum salts by calcination. Due to the low lanthanum oxide content, LaAlO3 is not produced in the alumina-supported perovskite oxide composition.

[0019] The mixture of boehmite salts is preferably spray dried to produce a dry form of the mixture of boehmite salts.

[0020] The dried mixture of boehmite salts is preferably calcined at a temperature of 450°C to 1200°C, preferably 500°C to 600°C, for at least 0.5 hours, more preferably 0.5 to 5 hours, to produce doped alumina, the temperature and time being independently selected.

[0021] Impregnation of the doped alumina can be carried out by any impregnation method known in the art, preferably by incipient wetness impregnation, which generally impregnates 80-100% of the pore volume of the doped alumina with the aqueous impregnation solution.

[0022] The aqueous impregnation solution contains a mixture of water-soluble salts according to a specific stoichiometric ratio of the perovskite oxide chemical formula ABO3.

[0023] The one or more water-soluble salts of the aqueous impregnation solution are preferably acetates or nitrates of rare earth elements, preferably acetates or nitrates of rare earth elements having atomic numbers of 57 to 60, more preferably acetates or nitrates of La, acetates or nitrates of alkaline earth elements, preferably acetates or nitrates of Sr, Ba, and Ca, more preferably acetates or nitrates of Sr, Pb 2+ and / or Bi 3+ and water-soluble transition metal salts including ammonium iron citrate, ammonium titanium lactate, zirconium acetate, or mixtures thereof. More preferably, the water-soluble salts are zirconium acetate, ammonium iron citrate, and ammonium titanium lactate.

[0024] Step (ii) of the first aspect of the present disclosure provides an aqueous impregnation solution comprising a mixture of water-soluble salts, the salts of which are: (a) acetates or nitrates of rare earth elements, preferably acetates or nitrates of rare earth elements having atomic numbers of 57 to 60, more preferably acetates or nitrates of La; (b) acetates or nitrates of alkaline earth elements, preferably acetates or nitrates of one or more of Sr, Ba, and Ca, more preferably acetates or nitrates of Sr, and (c) Pb 2+ and Bi 3+ One or more acetates or nitrates of and one or more salts of (d) one or more water-soluble transition metal salts, such as transition metal salts of Fe, Ti, and / or Zr, including, for example, ammonium iron citrate, ammonium titanium lactate, ammonium iron citrate, zirconium acetate, or mixtures thereof; and one or more salts of The mixture may include:

[0025] Alternatively, the aqueous impregnation solution can contain only one water-soluble salt, for example, ferric ammonium citrate.

[0026] By using doped alumina, preferably only one impregnation step is applied to obtain a doped alumina impregnated body with high loading capacity upon impregnation.

[0027] The doped alumina impregnated body is preferably calcined at a temperature of 500°C to 1100°C, most preferably at a temperature of 700°C to 1000°C. Calcination can be carried out for a period of at least 0.5 hours, more preferably 0.5 to 5 hours, for example 3 hours. The temperature and time are independently selected. The uniformly dispersed impregnated body obtained in step (ii) results in an alumina-supported perovskite oxide composition having a very low perovskite crystallite size.

[0028] According to a second aspect of the present disclosure, there is provided an alumina supported perovskite oxide composition prepared according to the method of the present disclosure.

[0029] According to a third aspect of the present disclosure, (i) at least 50 weight percent, preferably 75 to 95 weight percent, of doped alumina; (ii) Chemical formula I ABO3(I) 5 to 50 weight percent, preferably 5 to 25 weight percent of a perovskite-type oxide; Including, A is rare earth elements, alkaline earth elements, alkali elements, Pb 2+ , Bi 3+ or mixtures thereof, B comprises one or more transition metals, including mixtures of transition metals; The crystallite size of ABO3 is preferably less than 5 nm after calcination at 850°C for 3 hours, preferably between 4 nm and 5 nm, and is characterized by being less than 2 nm after calcination at 700°C for 4 hours. A composite of an alumina supported perovskite oxide composition is provided.

[0030] Alumina supported perovskite oxide compositions are characterized by a weighted intensity ratio of less than 10, preferably less than 8. The weighted intensity ratio is determined by Equation 1. The X-ray diffraction pattern of the perovskite structure using copper Kα radiation with a wavelength of 1.54 Å contains a strong reflection at 2θ of approximately 32 degrees.

[0031] The X-ray diffraction pattern of transition alumina contains a strong reflection at 2θ about 46.

[0032] The weighted intensity ratio R (see Equation 1) is a measure of the crystallinity of the perovskite material on the alumina support. R=[(I 32 / I 46 )] / m p (Formula 1) I 32 : Reflection intensity at approximately 32 degrees I 46 : Reflection intensity at approximately 46 degrees m p : Mass of perovskite / (Mass of perovskite (calculated as ABO3) + Mass of alumina)

[0033] The doped alumina is defined and prepared under the first aspect of the present disclosure, and the alumina-supported perovskite oxide composition preferably comprises 80 weight percent or more of the doped alumina.

[0034] Preferably, A of the perovskite oxide according to formula I comprises a mixture of an alkaline earth element, more preferably one or more of Sr, Ba or Ca, and a rare earth element, more preferably an element with an atomic number of 57 to 60. Most preferably, A comprises a mixture of Sr and La.

[0035] Preferably, B of the perovskite oxide according to formula I comprises a mixture of two distinct transition metals, preferably Fe and one or more elements from group IVa of the periodic table of the elements, more preferably B comprises a mixture of Fe, Ti and Zr.

[0036] Components A and B are independently selected such that charge balance with the three oxide anions is achieved and the sum of the molar weighted oxidation states of the individual components equals +6.

[0037] The perovskite oxide is preferably uniformly dispersed in the alumina matrix, both of which produce alumina-supported perovskite oxide compositions. Without being bound by theory, Applicants believe that the uniform dispersion of small perovskite oxide crystals allows the alumina matrix to act as a diffusion barrier, resulting in the beneficial properties of the alumina-supported perovskite oxide composite.

[0038] The BET specific surface area of ​​the alumina-supported perovskite oxide composition is 50 m 2 / g~300m 2 / g, preferably 100m 2 / g~200m 2 / g, and the pore volume can be 0.1 ml / g to 1.5 ml / g, preferably 0.5 ml / g to 1.0 ml / g.

[0039] The present disclosure will now be described with reference to the following non-limiting examples and figures. [Brief explanation of the drawings]

[0040] [Figure 1] FIG. 1 shows the X-ray diffraction patterns of Example 1 after calcination at 700° C. for 4 hours and after calcination at 850° C. for 3 hours, with the reflections marked with an asterisk (*) indicating the reflections in the X-ray pattern of the perovskite oxide. [Figure 2] FIG. 2 shows the X-ray diffraction patterns of Example 2 after calcination at 700° C. for 4 hours and after calcination at 850° C. for 3 hours, where the reflections marked with an asterisk (*) indicate the reflections in the X-ray pattern of the perovskite oxide. [Figure 3] FIG. 3 shows the X-ray diffraction patterns of Example 2 and Comparative Example 1 after calcination at 700° C. for 4 hours and after calcination at 850° C. for 3 hours. [Figure 4] FIG. 4 shows the X-ray diffraction patterns of Example 2 and Comparative Example 2 after calcination at 700° C. for 4 hours and after calcination at 850° C. for 3 hours, where reflections marked with an asterisk (*) indicate reflections in the X-ray pattern of perovskite oxide, reflections marked with a hash (#) indicate reflections in the X-ray pattern of SrAlO, and reflections marked with a plus (+) indicate reflections in the X-ray pattern of SrCO. [Figure 5] FIG. 5 shows the X-ray diffraction patterns of Example 3 and Comparative Example 3 after calcination at a temperature of 700° C. for 4 hours, and the reflections marked with an asterisk (*) indicate the X-ray patterns of perovskite oxides. DETAILED DESCRIPTION OF THE INVENTION

[0041] Uniformity is measured by cross-sectional imaging with a scanning electron microscope (SEM), optionally in conjunction with elemental mapping with energy dispersive X-ray analysis (EDX), which reveals the extent of doped alumina and perovskite oxide domains.

[0042] The crystal size of the perovskite oxides is determined using the Debye-Scherrer method, analyzing the (022) reflection (in the Fm-3c space group). The crystal size is less than 5 nm when measured after calcination at 850 °C for 3 h, and less than 2 nm when measured after calcination at 700 °C for 3 h.

[0043] The specific surface area and pore volume are measured at liquid nitrogen temperature by N2 physisorption using common volumetric instruments such as a Quadrasorb from Quantachrome. The specific surface area is determined using the BET theory (DIN ISO 9277) and the pore volume according to DIN 66131. [Example]

[0044] [Example 1] (20 weight percent perovskite La 0.5 Sr 0.5 Fe 0.5 Ti 0.5 O3-based complex) Gamma alumina containing 10 weight percent La2O3 was prepared by mixing an aqueous solution of lanthanum acetate with a 5 weight percent suspension of boehmite in water, then spray-dried and calcined at 500°C for 1 hour.

[0045] La-doped alumina was impregnated by incipient wetness impregnation with a mixed solution of Sr acetate, ammonium iron citrate, and Tyzor LA (titanium solution) to achieve loadings of 4.8 wt. percent SrO, 3.8 wt. percent FeO, and 3.8 wt. percent TiO after calcination. The products were calcined at 850°C for 3 h and 700°C for 4 h, respectively.

[0046] FIG. 1 shows the X-ray diffraction patterns of the material obtained according to Example 1 after calcination at 850° C. for 3 hours and at 700° C. for 4 hours.

[0047] [Example 2] (20 weight percent perovskite La 0.5 Sr 0.5 Fe 0.5 Zr 0.5 O3-based complex) Gamma alumina containing 7.8 weight percent La2O3 was prepared by mixing an aqueous solution of lanthanum acetate with a 5 weight percent suspension of boehmite in water, then spray-dried and calcined at 500°C for 1 hour.

[0048] Doped alumina is ferric ammonium citrate , Zr acetate, The product was impregnated by incipient wetness impregnation with a mixed solution of acetates of Fe and Sr to reach loadings of 3.4 wt. percent FeO, 5.3 wt. percent ZrO, and 4.4 wt. percent SrO. The product was calcined at 850°C for 3 h and 700°C for 4 h, respectively.

[0049] The X-ray diffraction patterns of the material obtained after calcination at 850° C. for 3 hours and after calcination at 700° C. for 4 hours are shown in FIG.

[0050] [Comparative Example 1] (20 weight percent perovskite La 0.5 Sr 0.5 Fe 0.5 Ti 0.5 O3-containing complexes) The complex was prepared according to Example 5 of Patent Document 2.

[0051] First, LaAlO powder was synthesized by adding 100.9 g of gamma alumina to 400 ml of an aqueous solution of 425 g of lanthanum nitrate hexahydrate. The resulting mixture was evaporated and dried. The mixture was then calcined in air at 600 °C for 3 hours and then at 900 °C for 8 hours to obtain LaAlO powder.

[0052] In the next step, the LaAlO powder was mixed with an aqueous solution of strontium, iron, and zirconium nitrates to achieve a loading of 3.4 weight percent FeO, 5.3 weight percent ZrO, 4.4 weight percent SrO, and an additional 6.9 weight percent LaO in the calcined composite. The resulting mixture was dried in air at 110°C for 10 hours and calcined at 700°C for 4 hours and 850°C for 3 hours, respectively.

[0053] The X-ray diffraction patterns of the material obtained after calcination at 850° C. for 3 hours and after calcination at 700° C. for 4 hours are shown in FIG.

[0054] The results show that the resulting product differs from the composition of the present disclosure in the absence of alumina, the larger crystal size of the perovskite, and the substantially smaller specific surface area.

[0055] Comparative Example 2 (20 weight percent perovskite La 0.5 Sr 0.5 Fe 0.5 Ti 0.5 O3-based complex) The complex was prepared according to Example 6 of Patent Document 3.

[0056] 25 g of gamma-alumina beads were impregnated twice with aqueous solutions containing large amounts of lanthanum, strontium, iron, and zirconium nitrates to achieve loadings of 6.9 weight percent La2O3, 3.4 weight percent Fe2O3, 5.3 weight percent ZrO2, and 4.4 weight percent SrO in the calcined composite, 5 g of ethanol, and 10 g of citric acid. The resulting material was dried under vacuum after the first impregnation (to remove the solution). After the second impregnation, the product was calcined at 700°C for 4 hours and 850°C for 3 hours, respectively.

[0057] The X-ray diffraction patterns of the material obtained after calcination at 850° C. for 3 hours and after calcination at 700° C. for 4 hours are shown in FIG.

[0058] Powder X-ray diffraction patterns reveal significantly different phases than the compositions of the present disclosure. Specifically, strontium does not form part of the perovskite structure, but instead exists in the form of SrCO3 after calcination at 700°C and SrAl2O4 after calcination at 850°C. Therefore, it can be concluded that the procedure is not suitable for producing the desired composition. The results are included in Table 1 below.

[0059] [Table 1]

[0060] [Example 3] (Composite with 10 weight percent perovskite LaFeO3) Gamma alumina containing 11.7 weight percent La2O3 was prepared by mixing an aqueous solution of lanthanum acetate with a 5 weight percent suspension of boehmite in water, then spray-dried and calcined at 500 °C for 1 hour.

[0061] The doped alumina was impregnated by incipient wetness impregnation with an aqueous solution of ferric ammonium citrate to reach a loading of 3.3 weight percent Fe2O3. The products were calcined at 850 °C for 3 hours and 700 °C for 4 hours, respectively.

[0062] The X-ray diffraction pattern of the material obtained after calcination at 700° C. for 4 hours is shown in FIG.

[0063] Comparative Example 3 (a composite containing 10 weight percent of the perovskite LaFeO3) The complex was prepared according to Example 3 of Patent Document 1.

[0064] A mixture of 2.2 g of iron acetate in 75 ml of water and 4.46 g of lanthanum acetate in 75 ml of water was mixed and added to a dispersion prepared by mixing 27 g of lanthanum-doped alumina (commercially available as PURALOX TH100 / 150 L4) with 150 ml of water. 11.2 g of 25% NH3 solution was added to the mixture to reach a pH of 10. After stirring for 1.5 hours, the precipitate was filtered, and the resulting powder was calcined at 700°C for 4 hours.

[0065] The X-ray diffraction pattern of the material obtained after calcination at 700° C. for 4 hours is shown in FIG.

[0066] Comparison of the X-ray diffraction patterns of the materials from Example 3 and Comparative Example 3 clearly shows the difference in the crystallinity of the perovskite phase.

[0067] A crystalline perovskite phase is detectable for Comparative Example 3, as indicated by the asterisk in Figure 2, but the perovskite reflection is very weak. It can therefore be concluded that the perovskite phase exists largely in an X-ray amorphous state.

[0068] The results are contained in Table 2 below.

[0069] [Table 2]

Claims

1. 1. A method for preparing an alumina-supported perovskite oxide composition, comprising: (i) providing a doped alumina, said doped alumina comprising: a. Contains alumina and rare earth oxides, b. Containing alumina and alkaline earth oxides, or c. Alumina and a mixture of rare earth oxides and alkaline earth oxides and the doped alumina is (A) preparing a boehmite suspension containing boehmite; (B) preparing an aqueous solution of a salt, the aqueous solution of the salt comprising: a. Rare earth salts, b. an alkaline earth salt, or c. A mixture of rare earth salts and alkaline earth salts and (C) combining the boehmite suspension with the aqueous salt solution to form a boehmite salt mixture; (D) drying the boehmite salt mixture to produce a dried body of the boehmite salt mixture; (E) calcining the dried body of the boehmite salt mixture to produce the doped alumina; and a step provided by a method comprising at least (ii) The doped alumina is dissolved in a water-soluble rare earth salt, a water-soluble alkaline earth salt, a water-soluble alkali salt, a water-soluble Bi ３＋ salts, water-soluble Pb ２＋ and a water-soluble transition metal salt, or a mixture of such salts, to form the doped alumina impregnated body; (iii) calcining the impregnated body of the doped alumina; Including, wherein 50 weight percent or more of the rare earth oxide, the alkaline earth oxide, or the mixture of rare earth oxide and alkaline earth oxide present in the alumina-supported perovskite oxide composition is added to the boehmite suspension as the rare earth salt, the alkaline earth salt, or the mixture of rare earth salt and alkaline earth salt.

2. The boehmite suspension further comprises silica, titania, a water-soluble alkaline earth metal salt, a water-soluble rare earth metal salt, zirconium, or a mixture thereof. The method of claim 1.

3. The aqueous salt solution contains at least water and a water-soluble rare earth salt, a water-soluble alkaline earth salt, or a mixture thereof.

3. The method according to claim 1 or 2.

4. The impregnation of the doped alumina comprises incipient wetness impregnation. The method according to any one of claims 1 to 3.

5. 80-100% of the pore volume of the doped alumina is impregnated with the aqueous impregnation solution. The method according to any one of claims 1 to 4.

6. The water-soluble salt is (a) acetates or nitrates of rare earth elements; (b) acetates or nitrates of alkaline earth elements, and (c) Pb ２＋ and Bi ３＋ One or more acetates or nitrates of and one or more salts of (d) one or more water-soluble transition metal salts, including ammonium iron citrate, ammonium titanium lactate, zirconium acetate, or mixtures thereof; and one or more salts of Contains a mixture of The method according to any one of claims 1 to 5.

7. The impregnated body of the doped alumina is calcined at temperatures between 500°C and 1100°C for at least 0.5 hours each. The method according to any one of claims 1 to 6.

8. (i) 50 weight percent or more of doped alumina; (ii) 5 to 50 weight percent of a compound of the formula ABO ３ Perovskite oxides and Including, A is a rare earth element, an alkaline earth element, an alkali element, or Pb ２＋ , Bi ３＋ or mixtures thereof, B comprises a transition metal, including a mixture of transition metals; ABO ３ The crystallite size of is characterized as less than 5 nm after calcination at 850°C for 3 hours and less than 2 nm after calcination at 700°C for 4 hours. A composite of an alumina-supported perovskite oxide composition.

9. The weighted intensity ratio R is is less than 10, calculated from reflections in an X-ray diffraction pattern of the composition at 2θ of about 32 degrees and 2θ of about 46 degrees, obtained by emitting copper Kα radiation having a wavelength of 1.54 Å; R = [(I ３２ / I ４６ )] / m ｐ (Equation 1) and I ３２ is the intensity of the reflection at about 32 degrees, I ４６ is the intensity of the reflection at about 46 degrees, m ｐ but, Mass of perovskite / ((ABO ３ (calculated as) mass of perovskite + mass of alumina) It is calculated from Equation 1:

9. The alumina-supported perovskite oxide composition of claim 8.

10. A is, one alkaline earth element, One rare earth element and Contains a mixture of 10. The alumina-supported perovskite oxide composition of claim 8 or 9.

11. B contains a mixture of two distinct transition metals The alumina-supported perovskite oxide composition according to any one of claims 8 to 10.

12. Specific surface area: 50 to 300 m ２ / g and further characterized by a pore volume of 0.1 to 1.5 ml / g.

12. The alumina-supported perovskite oxide composition according to any one of claims 8 to 11.

13. The doped alumina is LaAlO ３ does not include 13. The alumina-supported perovskite oxide composition according to any one of claims 8 to 12.

14. in catalytic systems for emission control applications Use of the alumina supported perovskite oxide composition according to any one of claims 8 to 13.

15. In NOx trap catalyst Use of the alumina supported perovskite oxide composition according to any one of claims 8 to 13.

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