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    • 专利摘要:
    Method for Producing Composite Aluminum Oxide and Mixed Cerium / Zirconium Oxides hereinafter indicated as al / c / zr oxide composite (s) using bohemite and soluble cerium / zirconium salts. the al / c / zr oxide composites produced in such a way have increased thermal stability.
    公开号:BR112014000911B1
    申请号:R112014000911-2
    申请日:2012-07-13
    公开日:2019-06-18
    发明作者:Marcos Schöneborn；Reiner Glöckler；Anja Paeger
    申请人:Sasol Germany Gmbh；
    IPC主号:
    专利说明:

    “METHOD FOR PRODUCING COMPOSITE ALUMINUM OXIDE AND MIXED CERES / ZIRCONIUM OXIDES, AND, AL / CE / ZR OXIDE COMPOSITE” [0001] The present invention relates to a method for producing composites comprising aluminum oxides and mixed oxides of Cerium / Zirconium, then indicated in abbreviated form as Al / Ce / Zr oxide composite (s). The Al / Ce / Zr oxide composite (s) produced in this way have an increased thermal stability.
    [0002] Al / Ce / Zr oxide composite (s) with incorporated catalytically active noble metals are known and are used for post-catalytic exhaust gas treatment, for example, flue gases, in particular, that have been unloaded from the combustion chambers of motor vehicles. Such automotive catalysts generally consist of multiple components. A thermally stable honeycomb-shaped body made of ceramic, usually cordierite, or metal films having a plurality of thin-walled channels is used as the charger. The so-called washable coating, comprising porous aluminum oxide (AI2O3) and oxygen storage components, is applied to the charger. The washable coating also contains catalytically active noble metals incorporated in it. In modern exhaust gas catalysts, these are platinum, rhodium and / or palladium. The ceramic charger is supported in a metal box with the aid of special support mats made of high temperature wool, for example, less often in combination with wire mesh. Washable coatings containing the Al / Ce / Zr oxide composite (s) are known for the exhaust gas post-treatment of combustion engines in which the mixed cerium / zirconium oxides act as oxygen. The Al / Ce / Zr oxide composite (s) according to this invention is / are used in the above automotive catalysts
    2/23 mentioned.
    [0003] WO 2006/070201 A2 describes an improved variant for producing mixed oxides of aluminum oxide, zirconium oxide and optionally at least one representative of CeO 2 , La 2 O3, Nd 2 O 3 , Pr 6 On, Sm 2 O 3 , Y 2 O 3 and possibly other rare earth oxides. Production is based on the combined precipitation of the corresponding salts. Mixed oxides are produced by precipitating together all the oxides involved, starting from a metal salt solution, where the pH is adjusted in the range of 8.5 ± 1 during precipitation.
    [0004] Precipitation is carried out by adding the alkali hydroxides in the particular sodium hydroxide solution.
    [0005] WO 2008/113457 Al describes the production of Al / Ce / Zr oxide composite (s) based on mixtures of aluminum oxide and mixed cerium / zirconium oxides that are separately produced.
    [0006] US 5,883,037 describes the importance of thermal stability for composite materials. The process described here is a multi-step process, in which the salts of Ce, Zr and optionally Pr are first precipitated by raising the pH and then the precipitate is isolated. The precipitate is brought into contact with alumina while mixing, then isolated and subjected to drying and calcination. Alumina is preferably stabilized by external ions from the rare earth group, Ba, Zr or Si. Mixed Ce / Zr oxides and mixed Ce / Zr / Pr oxides produced through precipitation can also be optionally stabilized, for example, by at least one member of group VIII, bismuth or some other element of rare earth. A disadvantage of this production process is due to the low homogeneity of the resulting material.
    [0007] EP 1172139 Al discloses the production of mixed oxides of
    Al 2 O 3 / CeO 2 / ZrO 2 / Y 2 O 3 / La 2 O 3 homogeneous through coprecipitation, as well as their thermal stability. In the process described, the intermediaries of
    3/23 Al-Ce-Zr-Y-La hydroxide resulting from the combined precipitation was calcined and thus converted to oxides.
    [0008] WO 2006/119549 A1 describes a process in which a solution of metal salts is added to a suspension of acid boemite to obtain a second suspension. Precipitation is induced by dropping the drops from the second suspension to an alkaline solution. The WO 2006/119549 A1 method, as also shown by Examples 1 and 2, leads to the development of discrete sheets of a mixed Ce / Zr / rare earth oxide in addition to aluminum oxide. A very similar process is described in Comparative Examples 3, 14 and 15 of US 6,831,036. The residual surface areas described are a maximum of 39 m 2 / g after calcination at 1000 ° C for three hours due to the process.
    [0009] WO 2012/67654 Al describes a process in which the Al / Ce / Zr / rare earth oxide composite is produced by a two-stage precipitation. In a first step, an “aluminum hydrate” and optionally a rare earth hydroxide are produced by the precipitation of aluminum sulfate with sodium aluminate. After renewed acidification of the suspension, then the Ce / Zr / rare earth component is precipitated by adding the saline solution corresponding to this suspension and then increasing the pH again. The Al / Ce / Zr / rare earth oxide composite thus obtained must have a surface area (in m / g) which can be obtained from the formula SA = 0.8235- [Al] + 11.157 after calcining the 1100 ° C for five hours. The residual surface area of the materials after calcining at 1200 ° C for five hours is obtained using the formula SA = 0.3- [Al] +
    7. WO 2012/67654 A1 was subsequently published. The respective request for priority concerns a different main subject than that indicated above.
    [00010] The purpose of the present invention is to provide improved Al / Ce / Zr (optional rare earth) oxide composites having a stability of
    4/23 definitely larger thermal surface, in particular, at temperatures of 1100 ° C or higher (for example, for 24 hours or more). Surface stability in this regard refers to preserving (a lot) the surface at high temperatures as measured according to BET. At the same time, a maximum degree of homogeneity must be obtained. Homogeneity is understood here to be a uniform distribution of the A1 2 O 3 phase and mixed Ce / Zr / rare earth oxide without the formation of discrete islands.
    [00011] This objective is achieved through a method according to claim 1. Preferred embodiments are the main subject of the attached claims and / or are described below.
    [00012] The Al / Ce / Zr oxide composite (s) obtained by the method according to the invention and optionally containing additional rare earth oxide components have been found to contain at least the oxide of Ce / Zr in the form of a solid solution. This can be proved by X-ray powder diffraction analysis. In addition, A1 2 O 3 and mixed Ce / Zr oxides (optionally rare earth) are present in a completely homogeneous distribution side by side, as demonstrated by EDX (the energy dispersion X-ray analysis) and mapping of element. No domains for individual metal oxides were detected. The indication // indicating the mixed oxide components of A1 2 O 3 and Ce / Zr and / or Ce / Zr (optionally rare earth) and / or Al / Ce / Zr oxide composites (optionally rare earth) do not prevent others metal oxides to be components of the mixed oxides or the composite. The composites preferably consist only of A1 2 O 3 and mixed Ce / Zr oxides (optionally rare earth).
    [00013] The process described in this invention differs from the prior art described above in which a suspension of aqueous alkaline bohemite (slurry) is used and precipitation is carried out on the suspension in the presence of soluble metal salts, which form a Ce / Zr (optionally) rare earth)
    5/23 (optionally rare earth) (different from the last solid solution) is distributed homogeneously in the bohemian matrix. The degree of homogeneity and effective separation of the mixed Ce / Zr oxide crystallite (optionally rare earth) by the aluminum oxide that is associated with it is obtained through a very homogeneous precipitation in which the bohemian particles do not settle inside the suspension even in an alkaline environment. The consistently high pH guarantees a uniform precipitation of the Ce / Zr hydroxides (optionally rare earth) so that they are present in the form of a homogeneous solid solution after calcination.
    [0001] In the process described here, the use of alkali, and in particular, sodium hydroxide solution can be omitted. The removal of alkali and / or sodium hydroxide from the composite material is absolutely essential for the application and, therefore, the omission of these components constitutes an important advantage.
    [0002] The inventive method comprises the following steps:
    (a) Provide a suspension comprising bohemite as the precursor to alumina and adjust the pH from 8 to 11.5, preferably 8 to 10.5 or from 9 to 10.5, for example, with an aqueous solution of ammonia. A preferred embodiment involves an aqueous suspension of bohemians that are modified with organic compounds that comprise at least one carboxyl group and one or more additional groups selected from hydroxy (-OH), oxo (-O), carboxy (COO) and / or amine (-NH), for example, tartaric acid or citric acid, preferably in amounts by weight of 0.1% to 50% by weight, in particular from 3% to 12% by weight, based on the dry weight of the bohemian.
    (b) Prepare an aqueous solution of metal salt containing metal salts of cerium and zirconium and optionally one or more rare earth elements. All water-soluble salts (for example,
    6/22 rare earth elements. All water-soluble salts (eg acetates, nitrates, chlorides) are suitable for this production. Soluble in this sense means that a stable solution of at least 5 g of salt (based on the oxidic form of the metal) in 100 g of water is established while stirring at the reaction temperature. In a preferred embodiment, metal nitrates are used. Ammoniacal cerium (IV) nitrate in particular is used as the source of cerium. According to another preferred embodiment, cerium (III) nitrate can be used, if the resulting metal salt solution is oxidized, for example, with an aqueous solution of H2O2.
    (c) Bring the suspension of (a) in contact with the metal salt solution of (b) preferably at a pH of 6.5 to 11, in particular 8 to
    10.5, especially preferably from 8.5 to 10 and independently of this, in particular, at temperatures of 5 to 95 ° C preferably from 80 to 95 ° C or by exposing the resulting slurry to these temperatures, in particular (cl ) Starting with the metal salt solution and adding the alumina precursor suspension to the drops and then adjusting the pH from 6.5 to 11, in particular from 8 to 10.5, especially preferably from 8.5 to 10.
    (c2) Starting with the metal salt solution and added to the drops to the alumina precursor suspension while at the same time adjusting the pH from 6.5 to 11, in particular from 8 to 10.5, especially preferably from 8, 5 to 10.
    (c3) Starting with the alumina precursor and adding to the simultaneous drops of the metal salt solution and the ammonia solution to obtain a pH of 6.5 to 11, in particular, 8 to 10.5, especially preferably 8 , 5 to 10.
    7/23 (d) Separate the aqueous solution and wash the solids from (c) with water.
    (dl) Optionally, the suspension of (c) is matured hydrothermally (subjected to an autoclave), then filtered and the solids washed with deionized water.
    (d2) Dry the solids of (d), for example, by (d2.1) Dry the solids, for example, at 120 ° C for sixteen hours under the influence of heat.
    (d2.2) Redispersize the solids from (d or dl) and then spray dry. In a special embodiment, one or more additional soluble compounds are added before spray drying and, in particular, only after step (c) or after redispersion. Preferred salts are acetates, for example, La acetate and / or salts of alkaline earth elements, rare earth elements, zirconium or silicon.
    (e) calcining the solids of (d or dl or d2), for example, in the temperature range of 550 to 1200 ° C, preferably in the range of 600 to 1000 ° C, in particular, for at least one hour.
    [00016] To adjust the pH, nitrogen bases can be used, including urea or urotropin, for example, in addition to ammonia. The suspension comprising boemite, in particular, is thus adjusted to the required pH.
    [00017] The composite may also comprise one or more elements / compounds of alkaline earth, elements / compounds of rare earth, zirconium and / or silicon, in particular elements / compounds of rare earth, in which these are preferably added before drying , in particular only after step (c) or (d) in the form of one or more additional soluble compounds.
    [00018] According to one embodiment, the suspension of (c) is
    8/23 hydrothermally matured in an aqueous environment, preferably at a temperature of at least 90 ° C for at least an hour, in particular, for at least four hours at a temperature of at least 120 ° C.
    [00019] In particular, water-soluble salts of metals are used to produce the metal salt solution, for example, acetates, nitrates and / or chlorides. In the inventive methods, the addition of alkali salts and / or alkaline earth salts is preferably omitted, excluding barium salts that can be optionally used.
    [00020] Ce / Zr oxide (optionally rare earth) is in the form of a solid solution in the composite, and AI2O3 and the mixed Ce / Zr oxide / solid solution (optionally rare earth) are present in the homogeneous distribution side by side side.
    [00021] The Al / Ce / Zr oxide composite preferably contains from 20% to 80% by weight, preferably from 40% to 70% by weight of aluminum, from 5% to 80% by weight, preferably from 5% to 40% by weight of zirconium, from 5% to 80% by weight, preferably from 5% to 40% by weight of cerium, from 0% to 12% by weight, preferably from 0.1% to 9% by weight of metal rare earth (s), calculated as A1 2 O 3 , ZrO 2 , CeO 2 , RE 2 O 3 . The amount of the other soluble compounds added in step (d2.2) after redispersion is preferably 0.1% to 15% by weight (calculated as oxide) based on the weight of A1 2 O3. Preferred rare earth metals include neodymium, praseodymium, yttrium and / or lanthanum.
    [00022] The Al / Ce / Zr oxide composite (s) preferably still have a surface area of at least 20 m / g, preferably at least 40 m / g after four hours at 1200 ° C.
    [00023] Aluminum / Cerium / Zirconium mixed oxides can be used in automotive catalysts such as three-way catalysts (TWC) or also in other components such as
    9/23 NO X storage, diesel oxidation catalysts (DOC) and diesel carbon black particle filters (DPF). Its structure was described in the introduction.
    [00024] Bohemians in the sense of this invention are the compounds of the general formula AIO (OH) χ H 2 O. Bohemites produced through the hydrolysis of an aluminum alkoxide are preferred; see US Patent 5,055,019 ("Process for the Production of Boehmitic Alumines"). Through this process, bohemic aluminas are obtained in a purity of at least 99.95% of A1 2 O 3 with pore rates defined in a range between 3 and 100 nm through the hydrolysis of salt-free aqueous neutral aluminum alcoholate, where the alumina suspension obtained from the hydrolysis of aluminum alcohol is matured in an autoclave a) at a water vapor pressure of 1 to 30 bar corresponding to a temperature of 100 to 235 ° C, b) in a period of 0 , 5 to 20 hours and c) while stirring at a circumferential speed of 1.0 to 6.0 m / s.
    [00025] According to the invention, aluminum alcoholates are used in the production of bohemian aluminas to obtain products of high purity. Aluminum alcoholates can be synthesized by the Ziegler process, for example, in which a purification step is performed through filtration. To produce aluminum alcoholates, for example, alcohols from C] to C 24 or mixtures thereof can be used, for example.
    [00026] The bohemians that are used are characterized by their especially high purity, among other things (SiO 2 concentrations <approx. 0.01%, Fe 2 O 3 <approx. 0.01%, Na 2 O <approx. 0.002 %, K 2 O <approx. 0.002%, TiO 2 <0.005%, other elements <0.01%). Without taking this into account, in another preferred form, bohemians having a pore volume of 0.4 to 1.2 ml / g and / or crystalline sizes from 4 to 40 nm preferably from 4 to 16 nm measured in the reflection (120) they're used.
    [00027] According to an embodiment especially
    Preferred 10/23, bohemians are modified with organic compounds having at least one carboxy group and one or more additional groups selected from hydroxy (-OH), carboxy (-COO) and / or amine groups (-NH, including -NH 2 ), for example, tartaric acid or citric acid, in particular with from 2 to 12 carbon atoms, especially preferably from 4 to 8 carbon atoms, preferably in amounts by weight of 0.1% to 50% by weight , in particular 5% to 15% by weight, based on the dry weight of the bohemite. This presents agglomeration and sedimentation of bohemites in the alkaline environment. Other substituted carboxylic acids suitable for the purposes of the invention include 2-hydroxypropionic acid, 2-oxopropionic acid, hydroxybutanedicarboxylic acid, dihydroxybutanedicarboxylic acid, 2-hydroxypropane-1,2,3tricarboxylic acid (citric acid), L-aspartic acid, L-serine, glycine, L-leucine, L-tyrosine or L-tryptophan, for example.
    [00028] The composites produced according to the invention comprise aluminum oxide and cerium / zirconium (optionally rare earth) mixed oxides and also have platinum, rhodium and / or palladium as an embodiment according to one embodiment.
    [00029] Based on the present invention, it has also been discovered that precipitation in the presence of an alkaline suspension of a modified bohemite by the addition of the above multifunctional organic acids, in particular in combination with the use of ammoniacal cerium (IV) nitrate according to Cerium source leads to final products with an especially great thermal stability. Surprisingly and independently of this, this effect is especially pronounced when the alkaline suspension is added to the metal salt solution in drops.
    [00030] The invention will now be explained in greater detail based on the illustrations, in which Figure 1 shows the particle size distributions of Examples A1 and A2 in the aqueous suspensions; Figure 2 shows the X-ray powder diffractograms
    11/23
    Example 2 after calcination.
    [00031] The following experimental examples show that [00032] a) larger residual surface areas are obtained compared to the synthesis procedures in EP 1172139 BI and WO 2012/067654 A1, [00033] b) larger residual surface areas are obtained even after calcination under especially different conditions (1150 ° C / 36 h, 1200 ° C / 4h), [00034] c) in Comparative Example 3, the surface areas that are also very high and are within the range of the composites inventives produced by the process described here (Comparative Example 3 and Example 6) are obtained, however, the process described here does not require the use of sodium, which is a significant advantage in process technology because sodium leads to the poisoning of noble metal catalysts .
    [00035] d) in Comparative Example 5, high residual surface areas were also obtained which are also within the range of composites produced through the process described here (Comparative Example 5, Examples 7 and 8).
    [00036] However, in one embodiment, the process described here proposes the use of modified bohemite, which facilitates the ability to disperse in an alkaline medium. Thus, there is no agglomeration or sedimentation of the bohemite, but instead, there is an especially homogeneous precipitation and distribution of the components of CeO2 / Zr €) 2 / (optionally rare earth oxide) at a high pH in the presence of finely dispersed bohemite , which is evident based on the size of the particles in the aqueous suspension at a high pH. This is demonstrated in Examples A1 and A2.
    [00037] Surface area measurements (BET) were performed using a Micromeritics TriStar 3000 according to DIN ISO 9277. The η / 23 X-ray diffractograms were measured using a Panalytical X'Pert Pro MDB diffractometer. Percentage quantities are in percent by weight, unless otherwise indicated. Particle distributions were determined using a Malvem Mastersizer 2000 with the Hydro-S dispersion unit in water. The measurement was performed according to ISO 13320: 2009 using the Fraunhofer method for the analysis.
    Comparative Example 1
    Synthesis according to Example 27 of EP 1172139 BI
    Composition: 61.5% A1 2 O 3 , 21% CeO 2 , 15% ZrO 2 , 2.5% Y 2 O 3 [00038] A mixture consists of 96.43 g of an aqueous nitrate solution zirconyl (ZrO 2 content = 7%), 52.5 g of an aqueous solution of cerium (III) nitrate (CeO 2 content = 18%), 6.32 g of an aqueous solution of yttrium nitrate ( Y 2 O 3 content = 17.80%) and 205.61 g of aluminum nitrate nanohydrate in crystalline form were mixed with 600 ml of water and stirred until a clear solution was obtained.
    [00039] This solution was mixed with 7.47 g of a 35% H 2 O 2 solution (corresponding to 1.2 times the molar amount of cerium) and this mixture was stirred for approx. 25 minutes. The resulting solution was then brought to a pH of 7 by adding a 24% ammonia solution and stirred for 15 minutes. The resulting mixture was filtered and the filter residue was washed with deionized water at 60 ° C. This filter cake was then dried at 120 ° C for sixteen hours. Then, the dry filter cake was first calcined at 300 ° C for five hours and then at 700 ° C for five hours.
    [00040] The measured surface area is shown in Table 1. BET after 300 ° C / 5 hours + 700 ° C / five hours (starting material): [00041] 168 m 2 / g BET after 950 ° C / 5 hours: 109 m 2 / g BET after
    1000 ° C / 4 hours: 84 m 2 / g BET after 1100 ° C / 2 hours: 32 m 2 / g Comparative Example 2
    Synthesis according to Example 1 of EP 1172139 BI
    13/23
    Composition: 41% A1 2 O 3 , 30% CeO 2 , 23% ZrO 2 , 2.5% Y 2 O 3 ,
    3.5% La 2 O 3 [00042] A mixture consisting of 145.93 g of an aqueous solution of zirconyl nitrate (ZrO 2 content = 7%), 72.25 g of an aqueous solution of cerium nitrate ( III) (CeO 2 content = 18%), 6.07 g of an aqueous solution of yttrium nitrate (Y 2 O 3 content = 17.80%), 10.81 g of an aqueous solution of lanthanum nitrate (La 2 O 3 content = 14.57%) and 138.08 g of aluminum nitrate nanohydrate in crystalline form were mixed with 600 ml of water and stirred until a clear solution was obtained.
    [00043] This solution was mixed with 10.71 g of a 35% H 2 O 2 solution (corresponding to 1.2 times the molar amount of cerium) and this mixture was stirred for approx. 25 minutes. The resulting solution was then brought to a pH of 7 by adding a 24% ammonia solution and stirred for 15 minutes. The resulting mixture was filtered and the filter residue was washed with deionized water at 60 ° C.
    [00044] This filter cake was then dried at 120 ° C for sixteen hours. Then, the dry filter cake was first calcined at 300 ° C for five hours and then at 700 ° C for five hours.
    [00045] The measured surface area is shown in Table 2.
    Comparative Example 3
    Synthesis according to Example 6 of WO 2006/070201 A2 Composition: 51% A1 2 O 3 , 14.2% CeO 2 , 34.8% ZrO 2 [00046] An aluminum nitrate solution was prepared by stirring up
    112.5 g of aluminum nitrate monohydrate in 1500 ml of water. To this solution were added 14.77 g of a cerium (III) nitrate solution (CeO 2 content = 28.85%) and 149.16 [g] of a zirconyl nitrate solution (ZrO 2 content = 7%). This mixture was then stirred at room temperature for 15 minutes. A pH of 10 was adjusted by adding a 25% sodium hydroxide solution and this value was maintained during the
    14/23 precipitation. Then 5 g of a 35% H2O2 solution was added and the pH was again adjusted to 10. The resulting suspension was then stirred for 60 minutes. Then, the pH was adjusted to 8 by adding 30% nitric acid and the suspension was again stirred for 30 minutes.
    [00047] The resulting mixture was filtered and the filter residue was washed with deionized water at 60 ° C. This filter cake was then suspended in 850 ml of deionized water and the pH was adjusted to 10 by adding a 25% sodium hydroxide solution.
    [00048] The mixture was then autoclaved for six hours at 120 ° C. The matured suspension was cooled to room temperature, adjusted to a pH of 8 by adding nitric acid and then stirred for 30 minutes.
    [00049] Then, the suspension was again stirred for one hour at 60 ° C and then the liquid was filtered. The resulting filter cake was then washed with deionized water at 60 ° C and then calcined for 4 hours at 850 ° C. The measured surface area is given in Table 3.
    Comparative Example 4
    Synthesis according to Example 12 of WO 2012/067654 Al
    Composition: 50% A1 2 O 3 , 30% CeO 2 , 15% ZrO 2 , 3.5% La 2 O 3 ,
    1.5% Y 2 O 3 [00050] Solution A was prepared by adding 6.0 g of a lanthanum nitrate solution (La2Ü 3 content of 14.57%) to 53 g of a solution of 24% ammonia and 110 g of distilled water.
    [00051] Solution B was prepared by combining 22.19 g of zirconyl nitrate (ZrO 2 content = 33.80%), 35.89 g of cerium (III) nitrate (CeO 2 content = 41, 80%), 4.21 g of a solution of yttrium nitrate (Y2O 3 content =
    4.21%), 100 g of distilled water and hydrogen peroxide with a molar ratio of f ^ C ^ / CeCE of 3.
    [00052] Solution C was prepared by dissolving 46.3 g of aluminate
    15/23 sodium in 200 g of distilled water.
    [00053] Starting with 2 liters of distilled water, it was heated to 65 ° C. Solution A was added to the drops within 25 minutes and the pH was maintained at 7.3 at the same time by adding solution C. After adding all solution A, the rest of solution C was completely added, thereby adjusting the pH up to 9.8. Then the resulting suspension was adjusted to a pH of 4 using diluted nitric acid. Then, solution B was added within 20 minutes. However, the pH was maintained at 4 by adding a 10% ammonia solution. After completely adding solution B, the pH was raised to 8.2 by adding concentrated ammonia solution. The suspension was filtered and the solids were washed with 2 liters of an aqueous solution of ammonium bicarbonate (120 g / liter of H 2 O) heated to 60 ° C. Table 4 lists the resulting surface areas.
    Comparative Example 5
    Synthesis according to Comparative Example 3 of US 6,831,036 and / or Example 7 of WO 2006/119549 Al
    Composition: 50% AI2O3, 30% CeO 2 , 15% Ζ1Ό2, 3.5% La 2 O3,
    1.5% Y 2 O 3 [00054] 15 g CeO 2 , 7.5 g ZrO 2 , 1.75 g La 2 O3 and 0.75 g and 0.75 g Y2O3 in the form of their nitrates were dissolved in water, and then 31.53 g of DISPERAL HP 14 (bohemian AI2O3 content = 79.3%) were added to this acid solution and the resulting suspension was stirred for 30 minutes. The concentrated ammonia solution (300 g) was diluted with 750 ml of water and used as the starting material at room temperature. The acid bohemite / metal nitrate solution was added by dripping slowly to the ammonia solution and stirring was continued for 30 minutes after the addition was completed. The solids were separated by filtration, washed with
    1.5 liters of water and then dried for sixteen hours at 100 ° C.
    16/23 [00055] Table 4 shows the resulting surface areas.
    Example Al - Preparing an alkaline bohemite suspension using pure bohemite [00056] A suspension with an AI2O3 content of 5% was prepared by stirring DISPERAL HP 14 (bohemite) in deionized water at pH 7. Then, the pH was adjusted to 10 by adding a 24% ammonia solution. The particle sizes in the suspension were determined by laser diffraction (Mastersizer):
    [00057] D10 = 0.96 pm; D 50 = 5.11 pm; D 90 - 28.34 pm [00058] The measured particle size distributions are shown in Figure 1.
    Example A2 - Preparing a suspension of alkaline bohemite using a modified bohemite [00059] A suspension with a content of A1 2 O 3 of 5% was prepared by stirring DISPERAL HP 14/7 (bohemite modified with citric acid) in water deionized at pH 7. Then, the pH was adjusted to 10 by adding a 24% ammonia solution. The particle sizes in the suspension were determined by laser diffraction (Mastersizer):
    [00060] D 10 = 0.09 pm; D 50 = 0.23 pm; D 90 = 0.67 pm [00061] The measured particle size distributions are shown in Figure 1.
    Example 1 (according to the invention)
    Composition: 61.5% A1 2 O 3 , 21% CeO 2 , 15% ZrO 2 , 2.5% Y 2 O 3 (corresponds to Comparative Example 1) [00062] A metal salt solution consisting of 81.4 g of an ammoniacal cerium (IV) nitrate solution (CeO 2 content = 12.90%), 103.30 g of a zirconyl nitrate solution (ZrO 2 content = 7.26%) and 7.0 g of a solution of yttrium nitrate (Y 2 O 3 content = 17.80%) was used as the starting material which was heated to 90 ° C.
    17/23 [00063] A suspension consisting of 615.0 g OF DISPERAL HP 14/7 (bohemite modified with citric acid) (A1 2 O 3 content = 5%) was prepared by stirring the solids in deionized water and then a 24% ammonia solution was added to a pH of 10. The suspension was added by dripping slowly to the metal salt solution and after completion, the pH was adjusted to 8.7 by adding ammonia solution to 24%. This mixture was then stirred for 30 minutes at 90 ° C. Then, the mixture was filtered and the filter residue was washed with deionized water at 60 ° C. The filter cake was resuspended in deionized water while stirring and was then spray dried (inlet temperature = 220 ° C, outlet temperature = 110 ° C). The dried material was calcined for four hours at 850 ° C.
    Example 2 (according to the invention)
    Composition: 41% A1 2 O 3 , 30% CeO 2 , 23% ZrO 2 , 2.5% Y 2 O 3 ,
    3.5% La 2 O 3 (corresponds to Comparative Example 2) [00064] A metal salt solution consisting of 96.9 g of an ammoniacal cerium (IV) nitrate solution (CeO 2 content = 12, 90%), 131.96 g of a zirconyl nitrate solution (ZrO 2 content - 7.26%), 10.02 g of a lanthanum nitrate solution (La 2 O 3 content = 14.57% ) and 5.84 g of a solution of yttrium nitrate (Y 2 O 3 content = 17.80%) was used as the starting material which was heated to 90 ° C. A suspension consisting of 341.6 g of DISPERAL HP 14/7 (bohemite modified with citric acid) (A1 2 O 3 content = 5%) was prepared by stirring the solids in deionized water and then adding the ammonia solution 24% to a pH of 10.
    Table 1.
    BET surface areas measured from Comparative Example 1 and Example 1 after calcining (m / g).
    Comparative Example 1 (according to EP 1 172 139) Example 1(according to the invention) 5 h / 300 ° C + 5 h / 700 ° C (starting material) 168 126 5 h / 950 ° C 109 95 4h / 1000 ° C 84 89
    18/23 | 2 h / 1100 ° C I 32 | 70 [00065] The suspension was added dropwise to the metal salt solution and after the addition was complete, the pH was adjusted to 8.5 by adding 24% ammonia solution. This mixture was then stirred for 30 minutes at 90 ° C. Then, the mixture was filtered and the filter residue was washed with deionized water at 60 ° C. The filter cake was resuspended in deionized water while stirring and was then spray dried (inlet temperature = 220 ° C, outlet temperature = 110 ° C). The dry material was calcined for four hours at 850 ° C.
    [00066] In Figure 2 the powder X-ray diffactograms of the material of Example 2 after calcination are shown [00067] a) after calcining 4 h at 850 ° C [00068] b) after calcining 4 h at 850 ° C + 4 ha 1100 ° C [00069] c) after calcining 4 h 850 ° C + 24 h 1100 ° C [00070] d) simulated CeO 2 diffractogram (cubic) [00071] e) simulated CeO 2 diffractogram (tetragonal) Example 3 (according to the invention)
    The composition corresponds exactly to that of Comparative Example 2 41% A1 2 O 3 , 30% CeO 2 , 23% ZrO 2 , 2.5% Y 2 O 3 , 3.5% La 2 O 3 [00072 ] 220.4 g of a suspension of Pural SB (bohemian, A1 2 O 3 content = 9.3%) (pH 9.5) were adjusted to a pH of 9.5 with a 24% ammonia solution and used as the starting material. At room temperature, a mixture consisting of 300 g of a cerium acetate solution (CeO 2 content = 5.0%), 50.3 g of a zirconium acetate solution (ZrO 2 content = 22.88 %), 24.0 g of a lanthanum acetate solution (La 2 O 3 content = 7.3%) and 31.3 g of a yttrium acetate solution (Y 2 O 3 content = 4.0 %) was added slowly at room temperature. The pH value was kept constant at 9.5 by adding a 24% ammonia solution at the same time.
    [00073] The resulting mixture was then stirred for 45 minutes. In
    19/23 then, the suspension was autoclaved for three hours at 140 ° C. The resulting mixture was filtered and the solids were washed with deionized water at 60 ° C. This filter cake was dried for sixteen hours in a drying cabin and then calcined at 850 ° C.
    Example 4 (according to the invention)
    Composition: 41% AI2O3, 30% CeO 2 , 23% ZrO 2 , 2.5% Y 2 O 3 ,
    3.5% La 2 O 3 (corresponding to Comparative Example 2) [00074] A bohemian suspension consisting of 492.0 g of DISPERAL HP 14/7 (bohemian modified with citric acid) (A1 2 O 3 content = 5%) was prepared by stirring the solids in deionized water and then adding the 24% ammonia solution to a pH of 10.
    [00075] At 90 ° C, a metal salt solution consisting of 139.53 g of an ammoniacal cerium (IV) nitrate solution (CeO 2 content = 12.90%),
    190.1 g of a zirconyl nitrate solution (7.26% ZrO 2 content), 14.41 g of a lanthanum nitrate solution (14.57% La 2 O 3 content) and 5.45 g of a solution of yttrium acetate (27.54% Y 2 O 3 content) was slowly added to the drops in this suspension. The pH value was kept constant at 9.0 by adding a 24% ammonia solution at the same time. This mixture was then stirred for 30 minutes at 90 ° C. Then, the mixture was filtered and the filter residue was washed with deionized water at 60 ° C. The filter cake was resuspended in deionized water while stirring and then spray dried (inlet temperature = 220 ° C, outlet temperature = 110 ° C). The dry material was calcined for four hours at 850 ° C.
    Example 5
    Composition: 41% A1 2 O 3 , 30% CeO 2 , 23% ZrO 2 , 2.5% Y 2 O 3 ,
    3.5% La 2 O 3 , corresponds to Comparative Example 2 but using cerium (III) nitrate + H 2 O 2 [00076] A metal salt solution consisting of 58.34 g of a
    20/23 cerium (III) nitrate solution (CeO 2 content - 18.00%), 131.96 g of a zirconyl nitrate solution (ZrO 2 content = 7.26%), 10.02 g of a lanthanum nitrate solution (La 2 O 3 content = 14.57%) and 5.84 g of a yttrium acetate solution (Y 2 O 3 content = 17.80%) was used as the material of departure.
    [00077] At room temperature, 25.74 g of a 30% H 2 O 2 solution cooled to 5 ° C was added. The resulting suspension was stirred for 10 minutes and then heated to 90 ° C. A suspension consisting of 341.6 g of DISPERAL HP 14/7 (bohemite modified with citric acid) (A1 2 O 3 content 5%) was adjusted to a pH of 10 by stirring the solids in deionized water and then adding a 24% ammonia solution.
    [00078] The suspension was added dropwise to the metal salt solution and after the addition was complete, the pH was adjusted to 8.3 by adding 24% ammonia solution. This mixture was then stirred for 30 minutes at 90 ° C. Then, the mixture was filtered and the filter residue was washed with deionized water at 60 ° C. The filter cake was resuspended in deionized water while stirring and was then spray dried (inlet temperature = 220 ° C, outlet temperature = 110 ° C). The dry material was calcined for 4 hours at 850 ° C.
    Table 2.
    Surface areas (BET) measured from Examples 2 to 6 and
    Comparative Example 2 after calcining in m / g.
    Comparative Example 2, according to EP 1 172 139 Example 2 | Example 3 | Example 4 | Example 5 According to the invention 4 h / 850 ° C (starting material) 112 98 89 88 85 4h / 1100 ° C 18 49 34 46 51 24 h / 1100 ° C 12 45 34 39 37 36 h / 1150 ° C20 25 4 h / 1200 ° C16 21
    Example 6 (according to the invention)
    Composition: 51% A1 2 O 3 , 14.2% CeO 2 , 34.8% ZrO 2 (corresponds to Comparative Example 3) [00079] A metal salt solution consisting of 55.0 g of a
    21/23 ammoniacal cerium (IV) nitrate solution (12.90% CeO 2 content) and 239.7 g of a zirconyl nitrate solution (7.26% ZrO 2 content) was used as the starting and heated to 90 ° C.
    [00080] A suspension consisting of 510.0 g DISPERAL HP 14/7 (bohemite modified with citric acid) (A1 2 O 3 content 5%) was adjusted to a pH of 10 by stirring the solids in deionized water and then adding a 24% ammonia solution.
    [00081] This suspension was added slowly to the drops to a solution of metal salt and after the addition was complete, the pH was adjusted to 8.7 by adding 24% ammonia solution. This mixture was then stirred for 30 minutes at 90 ° C. Then, the mixture was filtered and the filter residue was washed with deionized water at 60 ° C. The filter cake was resuspended in deionized water while stirring and was then spray dried (inlet temperature = 220 ° C, outlet temperature = 110 ° C). The dry material was calcined for four hours at 850 ° C.
    [00082] The values of Comparative Example 3 are given in parentheses.
    [00083] BET after 850 ° C / 4 hours (starting material): 97 m 2 / g (107) [00084] BET after 1100 ° C / 2 hours: 62 m 2 / g (47)
    BET after 1100 ° C / 24 hours: 36 m 2 / g (35)
    Table 3.
    Surface areas measured (BET) from Comparative Example 3 and Example 7 after calcining (m / g).
    Comparative Example 3 (according to WO 2006/070201) Example 6(according to the invention) 850 ° C / 4 hours (starting material) 107 97 2 h / 1100 ° C 47 62 24 h / 1100 ° C 35 36
    Example 7 (according to the invention)
    Composition: 50% A1 2 C> 3, 30% CeO 2 , 15% ZrO 2 , 3.5% La 2 Ü3,
    1.5% Y 2 O 3 (corresponds to Comparative Example 4 and 5) [00085] A metal salt solution consisting of 116.3 g of a
    22/23 ammoniacal cerium (IV) nitrate solution (CeO 2 content = 12.90%), 103.3 g of a zirconyl nitrate solution (ZrO 2 content = 7.26%), 12.1 g of a lanthanum nitrate solution (La 2 O 3 content = 14.50%) and 4.2 g of a yttrium acetate solution (Y 2 O 3 content = 17.80%) and heated to 90 ° Ç.
    [00086] A suspension consisting of 500 g of DISPERAL HP 14/7 (bohemite modified with citric acid) (A1 2 O 3 content 5%) was adjusted to a pH of 10 by stirring the solids in deionized water and then adding a 24% ammonia solution.
    [00087] This suspension was added to the drops slowly to a solution of metal salt and after the addition was complete, the pH was adjusted to
    8.3 by adding 24% ammonia solution. This mixture was then stirred for 30 minutes at 90 ° C. Then, the mixture was filtered and the filter residue was washed with deionized water at 60 ° C. The filter cake was dried for sixteen hours at 120 ° C and then calcined for four hours at 850 ° C. Example 8 (according to the invention)
    Composition: 50% A1 2 O 3 , 30% CeO 2 , 15% ZrO 2 , 3.5% La 2 O 3 ,
    1.5% Y 2 O 3 (corresponds to Comparative Examples 4 and 5) [00088] A metal salt solution consisting of 116.3 g of an ammoniacal cerium (IV) nitrate solution (CeO 2 content = 12.90%), 103.3 g of a zirconyl nitrate solution (ZrO 2 content = 7.26%), 12.1 g of a lanthanum nitrate solution (La 2 O 3 content = 14, 50%) and 4.2 g of a solution of yttrium acetate (Y 2 O 3 content = 17.80%) and heated to 90 ° C.
    [00089] A suspension consisting of 500 g of DISPERAL HP 14/7 (citric acid modified bohemite) (A1 2 O 3 content = 5%) was adjusted to a pH of 10 by stirring the solids in deionized water and then adding a 24% ammonia solution. This suspension was added to the drops slowly to a solution of metal salt and after the addition was complete, the pH was adjusted to 9.0 by adding 24% ammonia solution. This mixture was then stirred for 30 minutes at 90 ° C. Then the mixture was
    23/23 filtered and the filter residue was washed with deionized water at 60 ° C. The filter cake was resuspended in deionized water while stirring and was then spray dried (inlet temperature = 220 ° C, outlet temperature = 110 ° C). The dry material was calcined for four hours at 850 ° C.
    Example 9 (according to the invention)
    Composition: 70% A1 2 O 3 , 20% CeO 2 , 7% ZrO 2 , 3.0% La 2 O 3 [00090] A bohemian suspension consisting of 420.0 g of DISPERAL HP 14 / 7 (bohemite modified with citric acid) (A1 2 O 3 content = 5%) was adjusted to a pH of 10 by stirring the solids in deionized water and then adding a 24% ammonia solution. At 90 ° C a metal salt solution consisting of 46.51 g of an ammoniacal cerium (IV) nitrate solution (CeO 2 content = 12.9%), 30.0 g of a zirconyl nitrate solution (ZrO 2 content = 7.0%) and 6.18 g of a lanthanum nitrate solution (La 2 O 3 content = 14.57%) was slowly added to this suspension. The pH was kept constant at 9.0 by adding a 24% ammonia solution at the same time. This mixture was then stirred for 30 minutes at 90 ° C. Then, the mixture was filtered and the filter residue was washed with deionized water at 60 ° C. The filter cake was resuspended in deionized water while stirring and then dried for sixteen hours at 120 ° C. The dry material was then calcined at 850 ° C. Table 4.
    Measured surface areas (BET) of Comparative Examples 4 and 5 and Examples 8 to 10 in m / g.
    Comparative Example4 Calculated* Comparative Example 5 Example 7 Example 8 Example 9 4 h / 850 ° C (starting material) 130 - 96 92 96 101 4 h / 1200 ° C 17 22 (5 h) 23 23 25 40
    * Surface areas calculated based on the formulas given in WO2012 / 067654 Al
    权利要求:
    Claims (18)
    [1]
    1. Method for producing composite aluminum oxide and mixed cerium / zirconium oxides (optionally rare earth), characterized by the fact that it comprises the following steps:
    (a) providing a suspension comprising bohemite as the precursor to alumina and adjusting the pH from 8 to 11.5;
    (b) producing an aqueous solution of metal salt that comprises the metal salts of cerium and zirconium;
    (c) bring the suspension of (a) in contact with the metal salt solution of (b) at temperatures of 5 to 95 ° C or expose the resulting slurry to these temperatures;
    (d) isolating the solids from (c) and (e) calcining the solids from (d);
    on what
    i) the bohemians supplied in the suspension according to step (a) are in an aqueous suspension and are supplied with organic compounds, having at least one carboxyl group (-COO and / or -COOH) and one or more other groups selected from hydroxy (-OH), οχο (-O), carboxy (-COO and / or -COOH) and / or amine groups (-NH and / or -NH 2 ); or ii) the suspension of step (c) is hydrothermally matured in an aqueous environment, at a temperature of at least 90 ° C and for at least one hour, or iii) the measures according to i) and ii) are both applied .
    [2]
    2. Method according to claim 1, characterized in that the isolate comprises separation of the aqueous solution, washing the solids from (c) with water and drying the solids.
    [3]
    Method according to claim 1 or 2, characterized in that the isolate comprises the drying and (re) dispersion of the solids from (c) and the subsequent spray drying.
    2/3
    [4]
    Method according to at least one of the preceding claims, characterized in that the composite also comprises one or more elements / compounds of alkaline earth, elements / compounds of rare earth, zirconium and / or silicon, in particular elements / rare earth compounds, to which these are added before drying and in particular only after step (c) or after (d) in the form of one or more additional soluble compounds.
    [5]
    5. Method according to at least one of the preceding claims, characterized by the fact that bringing in contact comprises:
    (cl) start with the metal salt solution and add the drops of the alumina precursor suspension and then adjust the pH from 6.5 to 11, in particular from 8 to 10.5, especially preferably from 8.5 to 10;
    (c2) start with the metal salt solution and add the drops of the suspension of the alumina precursor and at the same time adjust the pH from 6.5 to 11, in particular from 8 to 10.5, especially preferably 8.5 to 10 or (c3) start with the suspension of alumina precursor and at the same time adding to the drops of the metal salt solution and the ammonia solution to maintain a pH of 6.5 to 11, in particular 8 to 10.5, especially preferably from 8.5 to 10.
    [6]
    6. Method according to at least one of the preceding claims, characterized in that the suspension of (c) is hydrothermally matured in an aqueous environment at a temperature of at least 120 ° C for at least four hours.
    [7]
    Method according to at least one of the preceding claims, characterized in that the water-soluble salts of the metals are used to prepare the metal salt solution, in particular acetates, nitrates and / or chlorides.
    [8]
    8. Method according to at least one of the claims
    3/3, characterized by the fact that Ce / Zr oxide (optionally rare earth) is present as a solid solution in the composite, and AI2O3 and mixed Ce / Zr oxides (optionally rare earth) are homogeneously distributed side by side.
    [9]
    Method according to at least one of the preceding claims, characterized in that the addition of alkali and / or alkaline earth salts is omitted, optionally except for barium salts.
    [10]
    10. Method according to at least one of the preceding claims, characterized by the fact that bohemians are supplied with organic compounds having at least one carboxyl group (-COO and / or COOH) and one or more other groups selected from hydroxy groups ( -OH), oxo (-O), carboxy (-COO and / or -COOH) and / or amine (-NH and / or -NH 2 ), in particular with from 2 to 12 carbon atoms, especially preferably from 4 to 8 carbon atoms, preferably in an amount by weight of 0.1% to 50% by weight, in particular from 5% to 15% by weight based on the dry weight of the bohemite.
    [11]
    11. Method according to at least one of the preceding claims, characterized by the fact that the suspension comprising boemite is adjusted to pH by a nitrogen base, in particular ammonia, urea and / or urotropin.
    [12]
    12. Method according to at least one of the preceding claims, characterized in that the mixed oxide / composite composition comprises 20% to 80% by weight of aluminum, 5% to 80% by weight of zirconium, 5 % to 80% by weight of cerium and optionally from 0% to 12% by weight of rare earth metal (s) (RE), calculated as A1 2 O 3 , ZrO 2 , CeO 2 , RE 2 O 3 .
    [13]
    13. Method according to at least one of the preceding claims, characterized in that the bohemite and / or the bohemite suspension are prepared by hydrolysis of an aluminum alkoxide,
    4/3 preferably with the separation of alcohol.
    [14]
    14. Al / Ce / Zr oxide composite comprising aluminum oxide and mixed cerium / zirconium oxides (optionally rare earth) in the form of a “solid solution”, characterized by the fact that AI2O3 and mixed Ce / Zr oxides (optionally rare earth) are homogeneously distributed side by side, obtainable according to at least one of claims 1 to 13.
    [15]
    15. Al / Ce / Zr oxide composite according to claim 14, characterized by the fact that it comprises:
    • 20% to 80% by weight, preferably 40% to 70% by weight, aluminum, calculated as AI2O3;
    • 5% to 80% by weight, preferably 5% to 40% by weight, Zirconium, calculated as ZrO 2; • 5% to 80% by weight, preferably 5% to 40% by weight, Cerium, calculated as CeO 2; and • 0% to 12% by weight, preferably 0.1% to 9% by weight, rare earth metal (s) (RE) calculated as RE2O3.
    [16]
    16. Al / Ce / Zr oxide composite according to claim 14 or 15, characterized in that even after 4h at 1200 ° C it has a surface area of at least 20m 2 / g, preferably at least 40m 2 / g.
    [17]
    17. Al / Ce / Zr oxide composite according to any of claims 14 to 16, characterized in that the Al / Ce / Zr oxide composite is an Al / Ce / Zr rare earth oxide composite comprising as rare earth oxides are oxides of neodymium, praseodymium, yttrium and / or lanthanum.
    [18]
    18. Al / Ce / Zr oxide composite according to any one of claims 14 to 17, characterized in that it also comprises platinum, rhodium and / or palladium.
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    同族专利:
    公开号 | 公开日
    CN103732320A|2014-04-16|
    US9289751B2|2016-03-22|
    RU2590162C2|2016-07-10|
    BR112014000911A2|2017-02-21|
    EP2545990B1|2018-11-28|
    EP3505241A1|2019-07-03|
    ZA201400121B|2015-06-24|
    RU2014102439A|2015-08-20|
    US10766018B2|2020-09-08|
    KR101900320B1|2018-09-20|
    WO2013007242A1|2013-01-17|
    CA2841803A1|2013-01-17|
    KR20140043938A|2014-04-11|
    US20180272317A1|2018-09-27|
    JP2014534938A|2014-12-25|
    US20140221200A1|2014-08-07|
    DE102011107702A1|2013-01-17|
    CA2841803C|2019-04-16|
    CN103732320B|2017-08-08|
    EP2545990A1|2013-01-16|
    EP2731710B1|2019-09-04|
    JP6185912B2|2017-08-23|
    US20130023410A1|2013-01-24|
    MY168082A|2018-10-11|
    EP2731710A1|2014-05-21|
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    法律状态:
    2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according art. 34 industrial property law|
    2019-04-30| B09A| Decision: intention to grant|
    2019-06-18| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/07/2012, OBSERVADAS AS CONDICOES LEGAIS. (CO) 20 (VINTE) ANOS CONTADOS A PARTIR DE 13/07/2012, OBSERVADAS AS CONDICOES LEGAIS |
    优先权:
    申请号 | 申请日 | 专利标题
    DE102011107702.6|2011-07-14|
    DE102011107702A|DE102011107702A1|2011-07-14|2011-07-14|Process for the preparation of composites of alumina and cerium / zirconium mixed oxides|
    EP11009902.5|2011-12-16|
    EP11009902.5A|EP2545990B1|2011-07-14|2011-12-16|Method for producing composites out of aluminium oxide and cerium/zirconium mixed oxides|
    PCT/DE2012/000700|WO2013007242A1|2011-07-14|2012-07-13|Method for producing composites from aluminium oxide and cerium/zirconium mixed oxides|
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