EP3558514A1 - Oxyde mixte résistant au vieillissement à base de cérium, de zirconium, d'aluminium et de lanthane pour convertisseur catalytique automobile - Google Patents

Oxyde mixte résistant au vieillissement à base de cérium, de zirconium, d'aluminium et de lanthane pour convertisseur catalytique automobile

Info

Publication number
EP3558514A1
EP3558514A1 EP17838129.9A EP17838129A EP3558514A1 EP 3558514 A1 EP3558514 A1 EP 3558514A1 EP 17838129 A EP17838129 A EP 17838129A EP 3558514 A1 EP3558514 A1 EP 3558514A1
Authority
EP
European Patent Office
Prior art keywords
mixed oxide
cerium
lanthanum
solution
zirconium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP17838129.9A
Other languages
German (de)
English (en)
French (fr)
Inventor
Lama ITANI
Julien Hernandez
Barry SOUTHWARD
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Operations SAS
Original Assignee
Rhodia Operations SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Operations SAS filed Critical Rhodia Operations SAS
Publication of EP3558514A1 publication Critical patent/EP3558514A1/fr
Pending legal-status Critical Current

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    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/945—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific catalyst
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Definitions

  • the present invention relates to a mixed oxide of aluminum, zirconium, cerium, lanthanum and optionally at least one rare earth other than cerium and lanthanum for preparing a catalyst which retains after severe aging good thermal stability and good catalytic activity.
  • the invention also relates to the process for the preparation of this mixed oxide as well as to a process for treating the exhaust gases of internal combustion engines using a catalyst prepared from this mixed oxide.
  • multifunctional catalysts are used for the treatment of the exhaust gases of internal combustion engines (automotive afterburner catalysis).
  • multifunctional is meant catalysts capable of operating not only oxidation in particular carbon monoxide and hydrocarbons present in the gases
  • the catalyst results from the interaction of a precious metal (eg Pd, Pt, Rh) with a coating layer (commonly called “washcoat”) on which it is dispersed.
  • the coating layer is generally obtained from an aqueous dispersion formed from two solid powdery materials, a mixed oxide based on cerium and zirconium and a mineral material which is often alumina.
  • the mixed cerium-zirconium oxide acts as an oxygen reservoir (or "OSC” for Oxygen-Storage-Capacity).
  • An alternative to the physical mixture of the two solid materials for the preparation of the coating layer is to form a composite based on aluminum, cerium and zirconium by a precipitation technique.
  • the composite thus prepared is more homogeneous than the physical mixture and allows during the preparation of the coating layer to save the physical mixing step.
  • the mixed oxide according to the invention can therefore be substituted for the cerium and zirconium compositions conventionally used as well as all or part of the alumina which is mixed with said compositions.
  • the composite as described in claim 1 aims at such a compromise. Other characteristics, details and advantages of the invention will appear even more completely on reading the description and the appended figures.
  • Fig. Fig. 1 shows X-ray images (intensity v. Angle ⁇ ) of the mixed oxide of Example 1 which was calcined at 3 temperatures: (a) 1100 ° C (5 h); (b) 1000 ° C (4 h); (c) 950 ° C (4 h).
  • Fig. 2 shows a porogram (mercury porosimetry) of the mixed oxide of Example 1 which was calcined at 950 ° C for 4 h.
  • Fig. 3 represents the table of relative pressures used for the determination of nitrogen porosity.
  • Porosity data were obtained by mercury or nitrogen porosimetry techniques to define the pore volume (V) as a function of the pore diameter (D).
  • Mercury intrusion porosimetry is obtained in accordance with ASTM D 4284-83 ("Standard method for determining pore volume distribution of catalysts by mercury intrusion porosimetry"). It is possible to use a Micromeritics Autopore IV 9500 device equipped with a powder penetrometer according to the instructions recommended by the manufacturer.
  • specific surface is meant the BET specific surface area obtained by nitrogen adsorption. It is determined from the BRUNAUER - EMMETT-TELLER method. This method is particularly described in the periodical "The Journal of the American Chemical Society, 60, 309 (1938)". The recommendations of standard ASTM D3663-03 can be followed. Subsequently, the abbreviation Sr (° c) / x (h) is used to denote the specific surface area of a composition obtained by the BET method. after calcination of the composition at a temperature T expressed in ° C for a period of x hours. For example, 100 ° C./4 h denotes the BET specific surface area of a composition after calcination thereof at 1000 ° C. for 4 hours. The calcinations for a Temperature and time given, unless otherwise indicated, calcinations under air at a temperature step over the time indicated.
  • the curve (C) representing the derivative (dV / dlogD) of the function V as a function of log D.
  • the derived curve (C) may have one or more peaks each located at a diameter noted D p . It is also possible to obtain from these data the following characteristics relating to the porosity of the mixed oxide:
  • Rare earth means the elements of the group consisting of yttrium and the elements of the Periodic Table with an atomic number inclusive of between 57 and 71.
  • the cerium oxide is in the form of ceric oxide
  • the oxides of the other rare earths are in TR2O3 form, TR denoting the rare earth, with the exception of praseodymium which is expressed in the form Pr 6 On.
  • the zirconium and hafnium oxide are in the form Zr0 2 and HfO2.
  • Aluminum is present in AI2O3 form.
  • the mixed oxide according to the invention is a mixed oxide of aluminum, zirconium, cerium, lanthanum and possibly at least one rare earth other than cerium and lanthanum (noted TR), the proportions in weight of these elements, expressed in oxide equivalent relative to the total weight of the mixed oxide being the following:
  • the X-ray pattern of the mixed oxide does not present to the crystalline phase consisting of cerium oxide and zirconium only one peak whose maximum is located at a 2 ⁇ angle of between 28 and 32 °;
  • the average crystallite size of the crystalline phase consisting of cerium and zirconium oxide is at most 30 nm;
  • the BET specific surface area of the mixed oxide is at least 35 m 2 / g; and in that after being calcined at a temperature of 950 ° C for 4 hours,
  • ⁇ the pore volume of the mixed oxide, developed by pores whose size is less than or equal to 100 nm obtained from the nitrogen porosimetry data is greater than or equal to 0.30 ml / g;
  • ⁇ the total pore volume of the mixed oxide, obtained from the mercury porosimetry data is less than or equal to 2.0 mL / g.
  • the aforementioned elements Al, Ce, La, TR and Zr are generally present in the form of oxides.
  • the mixed oxide can therefore be defined as a mixture of oxides. However, it is not excluded that these elements may be present at least partly in the form of hydroxides or oxyhydroxides.
  • the proportions of these elements can be determined using the usual analysis techniques in the laboratories, in particular the plasma torch and the X-ray fluorescence. The proportions of these elements are given by weight in oxide equivalent with respect to the weight total of the mixed oxide.
  • the mixed oxide comprises the aforementioned elements in the proportions indicated but it may also include other elements, such as for example impurities.
  • the impurities can come from raw materials or starting reagents used.
  • the total proportion of impurities expressed by weight relative to the total weight of the mixed oxide is generally less than 2%, or even less than 1%.
  • the mixed oxide may also comprise hafnium which is generally present in association with zirconium in natural ores.
  • the proportion of hafnium relative to zirconium depends on the ore from which the zirconium is extracted.
  • the mass proportion Zr / Hf in certain ores can thus be of the order of 50/1.
  • baddeleyite contains about 98% zirconium oxide for 2% hafnium oxide.
  • hafnium is usually present as an oxide. However, it is not excluded that it may be present at least partly in the form of hydroxide or oxyhydroxide.
  • the proportion by weight of hafnium in the mixed oxide may be less than or equal to 2.0%, expressed in oxide equivalent relative to the total weight of the mixed oxide.
  • the proportions of impurities and hafnium can be determined using Inductively Coupled Plasma Spectrometry (ICP-MS).
  • ICP-MS Inductively Coupled Plasma Spectrometry
  • the aforementioned elements are intimately mixed, which distinguishes the mixed oxide from a simple mechanical mixture of oxides in solid form.
  • the intimate mixture is obtained by the precipitation of the constituent elements of the mixed oxide in the presence of aluminum hydrate.
  • the proportion by weight of cerium is between 15 and 35%, more particularly between 20 and 33%, more particularly between 20 and 30%, and even between 25 and 30%.
  • the proportion by weight of lanthanum is between 1 and 10%, more particularly between 1 and 6%, or even between 2 and 6%.
  • the mixed oxide may also include one or more rare earth (s) other than cerium or lanthanum (TR).
  • the rare earth may for example be chosen from yttrium, neodymium or praseodymium.
  • the mixed oxide may for example contain only one TR in a proportion of between 0 and 10%.
  • the mixed oxide may also contain more than one TR and in this case the proportion 0-10% then applies to each TR and the sum of the proportions of these lands rare TR remains less than 15%, even less than 10%, or even less than 8%.
  • the mixed oxide also comprises zirconium.
  • the proportion by weight of zirconium may be between 15 and 50%, more particularly between 20 and 45%, more particularly between 25 and 40%, or between 30 and 40%.
  • the mixed oxide also comprises aluminum.
  • the proportion by weight of aluminum may be between 20 and 60%, more particularly between 25 and 60%, more particularly between 25 and 50%, or between 30 and 40%.
  • the mixed oxide comprises aluminum and zirconium, the total proportion of these two elements expressed in oxide form being greater than or equal to 50%.
  • the mixed oxide is characterized by the fact that after calcination at 1100 ° C. for 5 hours, it comprises only a single crystalline phase composed of cerium and zirconium oxide.
  • the crystalline phase composed of cerium and zirconium oxide comprises both cerium and zirconium oxides and may also include lanthanum and optionally rare earth (s) other than cerium and lanthanum.
  • crystallites composed of cerium and zirconium oxide are homogeneous in composition even after a heat treatment carried out at 1100 ° C. This homogeneity generally results in good cerium reducibility properties or good mobility of oxygen.
  • the average crystallite size of this crystalline phase is at most 30 nm, or even at most 25 nm, or even at most 20 nm.
  • the average size of the crystallites is determined by the X-ray diffraction technique and corresponds to the size of the coherent domain calculated from the width of the diffraction line 2 ⁇ between 28 and 32 ° using the Scherrer model:
  • the mixed oxide After being calcined at 1100 ° C for 5 hours, the mixed oxide can also have a ratio R ⁇ 1.0, where R is determined from the X-ray diffraction data by the formula below:
  • ⁇ zz denotes the signal intensity of the crystalline phase composed of cerium and zirconium oxide, the maximum of which is situated at an angle ⁇ between 28 and 32 °;
  • the mixed oxide according to the invention also has a large specific surface area.
  • the surface Snoo ° c / 5h can be at least 35 m 2 / g, more particularly at least 38 m 2 / g, more particularly at least 40 m 2 / g. This surface can reach 65 m 2 / g for a proportion of aluminum greater than 50%, or even greater than 55%. This surface can reach 60 m 2 / g for an aluminum proportion of less than 50%.
  • the surface Sgso-cwh can be at least 75 m 2 / g, more particularly at least 80 m 2 / g. This surface can reach 1 10 m 2 / g.
  • the pore volume developed by the pores whose size is less than or equal to 100 nm obtained from the nitrogen porosimetry data is greater than or equal to 0.30 ml / g or even 0 35 mL / g or even 0.40 mL / g. This pore volume can reach 1, 00 ml / g.
  • the total pore volume obtained from the mercury porosimetry data can be lower or equal to 2.0 mL / g, or even less than or equal to 1.65 mL / g, or even 1.45 mL / g or even 1.25 mL / g.
  • This total pore volume may be 0.70 ml / g.
  • the pore distribution of the mixed oxide determined by mercury porosimetry may, after calcination at 950 ° C. for 4 hours, in the region of pores whose diameter is less than 100 nm, a peak with a diameter at peak D p included between 10 and 30 nm. In this range of pores, this peak may be unique.
  • the mixed oxide also after calcination at 950 ° C for 4 hours, a bulk density of powder greater than or equal to 0.25, or even 0.4, or even 0.5, or even 0.6.
  • the conditions for measuring this density are given below. This density can reach 1, 0.
  • a particular mixed oxide according to the invention based on aluminum, zirconium, cerium, lanthanum and possibly at least one rare earth other than cerium and lanthanum (denoted by TR), the proportions by weight of which are as follows:
  • the average crystallite size of the crystalline phase consisting of cerium and zirconium oxide is at most 20 nm, more particularly between 13 and 20 nm;
  • the pore volume of the mixed oxide developed by the pores whose size is less than or equal to 100 nm obtained from the nitrogen porosimetry data, is greater than or equal to 0.35 mL / g.
  • the surface Snoo ° c / 5 h of this mixed oxide may be between 35 and 42 m 2 / g.
  • the apparent density of powder after calcination at 950 ° C for 4 hours can be between 0.4 and 0.6.
  • This mixed oxide can be based on aluminum, zirconium, cerium, lanthanum, yttrium and neodymium.
  • Another particular mixed oxide according to the invention based on aluminum, zirconium, cerium, lanthanum and possibly at least one rare earth other than cerium and lanthanum (denoted TR), the proportions of which are as follows:
  • the BET surface area of the mixed oxide is at least 50 m 2 / g, more particularly between 50 and 65 m 2 / g;
  • the pore volume of the mixed oxide developed by the pores whose size is less than or equal to 100 nm obtained from the nitrogen porosimetry data, is greater than or equal to 0.40 mL / g, more particularly between 0.40 and 0.70 mL / g.
  • the average crystallite size of the crystalline phase composed of cerium and zirconium oxide can be between 15 and 30 nm.
  • the total pore volume of this other mixed oxide obtained from the mercury porosimetry data can be between 1.20 and 1.70 ml / g.
  • This other mixed oxide may be based on aluminum, zirconium, cerium, lanthanum, yttrium and neodymium.
  • the proportion 3-6% relative to TR applies in the case where the mixed oxide comprises only one TR. In the case where the mixed oxide comprises more than one TR, this proportion 3-6% applies to each of these TRs.
  • the characteristics of the mixed oxide according to the invention as described above apply to a mixed oxide as it is obtained before but also after grinding .
  • grinding is understood to mean the mechanical operation of dividing a solid.
  • the mixed oxide, ground or not may be in the form of a powder having an average diameter d 5 o between 1.0 and 50.0 ⁇ , or even between 5.0 and 40.0 ⁇ , d 5 o being determined by laser diffraction on a volume distribution.
  • d 5 o corresponds to the median diameter as conventionally understood in statistics, determined from a volume distribution of the diameters of the particles obtained using the laser diffraction technique.
  • the Coulter counter LS can be used according to the recommendations and using the manufacturer's software to obtain such a distribution.
  • the measurement can be done in water, possibly in the presence of a dispersant.
  • a1 is introduced into a stirred vessel containing a basic aqueous solution, an aqueous acid solution of cerium precursors, zirconium, lanthanum and optionally at least one rare earth other than cerium and lanthanum in which is dispersed aluminum hydrate;
  • step (a2) the precipitate dispersion obtained at the end of step (a1) is optionally heated;
  • a texturing agent is added to the dispersion obtained in step (a1) or in step (a2);
  • step (a4) the solid of the dispersion of step (a3) is recovered by solid / liquid separation and is optionally washed;
  • step (a5) the solid obtained at the end of step (a4) is optionally dried;
  • step (a6) the solid obtained after step (a4) or step (a5) is calcined at a temperature between 700 ° C and 1100 ° C to yield the mixed oxide;
  • step (a7) the mixed oxide obtained in step (a6) is optionally milled.
  • an aqueous solution comprising precursors of cerium, zirconium, lanthanum and optionally one or more rare earths other than cerium and lanthanum (“precursor solution”) in which is dispersed an aluminum hydrate, for example an aluminum monohydrate. This mixture is referred to hereinafter as "precursor mixture”.
  • the term "precursor" refers to a salt or a compound of the element under consideration.
  • the precursor may be, for example, a nitrate or a chloride of this element.
  • the zirconium precursor may be crystallized zirconyl nitrate.
  • a zirconium precursor can also be obtained by dissolving basic zirconium carbonate or zirconium hydroxide with nitric acid. This acid attack may be preferably conducted with a molar ratio NO3 ⁇ / Zr of between 1.4 and 2.3.
  • a usable zirconium nitrate solution resulting from the attack of the carbonate may have a concentration expressed in ZrO 2 of between 260 and 280 g / l.
  • the zirconyl nitrate solution used in Example 1 resulting from the carbonate attack has a concentration of 268 g / L.
  • a salt of Ce '' or Ce lv such as Ce '' chloride, nitrate or cerium-ammoniac nitrate of Ce '' or Ce lv , which are particularly suitable here.
  • cerous or ceric nitrate may be used
  • An aqueous ceric nitrate solution may for example be obtained by reacting nitric acid with a hydrated ceric oxide prepared in a conventional manner by reaction of a solution of a salt.
  • cerous nitrate and a solution of ammonia in the presence of hydrogen peroxide
  • a solution of ceric nitrate obtained by the electrolytic oxidation process of a nitrate solution cerous as described in the document FR-A-2570087, and which constitutes here a raw material of interest It is possible to obtain with this process a solution of ceric nitrate with a molar ratio Ce lv / total amount of Ce greater than or equal to al at 0.90, which may be an interesting raw material.
  • the lanthanum precursor may be lanthanum chloride or nitrate.
  • the rare earth precursor other than cerium and lanthanum may be a nitrate or a chloride.
  • it may be praseodymium nitrate, neodymium nitrate, yttrium chloride YCl3, yttrium nitrate Y (NO3) 3.
  • the precursor solution is only prepared from precursors in the form of nitrates.
  • the precursor solution comprises a zirconium chloride, a cerium salt, a lanthanum salt and optionally a salt of one or more rare earths other than cerium and lanthanum.
  • the precursor solution is only prepared from precursors in the form of chlorides. Still according to this embodiment, it is possible that the precursor solution also comprises a sulfate anion.
  • the molar ratio of SO 4 2 7 (Ce + Zr) in the precursor solution may be between 0.4 and 2.0, preferably between 0.7 and 1, 5.
  • the anions SO 4 2 " can be provided by adding sulfuric acid or a sulphate salt.
  • the precursor solution has some initial free acidity which can be adjusted by the addition of a base or an acid. Adjusting the free acidity can help disperse the aluminum hydrate in the aqueous solution while avoiding excessive modification of the physicochemical characteristics of the aluminum hydrate.
  • This neutralization can be done by adding a basic compound to the solution so as to limit this acidity but avoiding any precipitation.
  • This basic compound may be for example a solution of ammonia or alkali hydroxides (sodium, potassium, etc.). A solution of ammonia can advantageously be used.
  • the aluminum hydrate is added with stirring in order to obtain the precursor mixture in the form of a dispersion.
  • the precursor mixture contains Ce '' and / or Ce lv
  • an oxidizing agent for example hydrogen peroxide
  • the oxygenated water is added to the precursor mixture or to the precursor solution, the molar ratio H 2 O 2 Ce '"can be between 0.0 and 8.0, preferably between 0.1 and 3.0.
  • the addition of hydrogen peroxide makes it possible to reduce the amount of texturizing agent added in step (a3) to obtain the mixed oxide according to the invention.
  • purity salts of at least 99.0% by weight and more particularly at least 99.5% by weight.
  • the precursor solution can be obtained by dissolving the precursors in water in any order or by mixing precursor solutions.
  • step (a1) the precursor mixture is introduced into a stirred vessel containing a basic aqueous solution so as to obtain a precipitate (so-called "reverse” precipitation).
  • the basic compound dissolved in the basic aqueous solution may be a hydroxide, for example an alkali or alkaline earth hydroxide. It is also possible to use secondary, tertiary or quaternary amines as well as ammonia. As in the example described below, it is possible to use an aqueous solution of ammonia. As in the example, it is possible to use an aqueous solution of ammonia, for example of concentration 2 mol / L.
  • the basic compound can be used with a stoichiometric excess relative to all cations of the precursor solution to ensure optimal and complete precipitation.
  • the stoichiometric excess is preferably at least 20 mol% relative to all the cations of the precursor solution.
  • step (a1) a dispersion of a precipitate is obtained.
  • the aluminum hydrate may be a boehmite or a pseudo-boehmite, optionally doped with at least one dopant, the dopant possibly being, for example, lanthanum or praseodymium.
  • the aluminum hydrate may be in the form of a powder or an aqueous suspension. The powder may have been spray dried.
  • Aluminum hydrate can generally be described by the formula AIOOH-xH 2 O (0 ⁇ x ⁇ 1).
  • Boehmite can be obtained according to the teachings of US Pat. No. 4,154,812, in particular from Example 1 thereof. Boehmite can also be obtained by a so-called alkoxide route.
  • This route used industrially by Sasol and developed by Condea or Vista, uses precursors of the aluminum alkoxide type which are derived as by-products of a Ziegler / Alfol process or directly from an attack. or alcoholic digestion of aluminum in the form of metal. These precursors are hydrolysed in the presence of water, generally at a temperature above 80 ° C., typically 90 ° C., so as to quantitatively precipitate the aluminum hydrate. After separation of a phase containing the liberated alcohol and an aqueous phase containing aluminum hydrate, the aqueous phase is cured at 98 ° C. for 16 hours. A precursor of lanthanum (nitrate or acetate for example) may be added to the aqueous phase. The aqueous phase is then dried, for example by spraying. A boehmite of this type can be synthesized by following the teachings of Example B1 of US 2013/017947.
  • aluminum hydrate H is based on a boemite and can comprise optionally at least one additional element selected from the group formed by lanthanum, praseodymium or a mixture of the two elements, characterized in that after having been calcined in air at a temperature of 900 ° C. for 2 hours, it has:
  • VP o 2 nm-N2 a pore volume in the area of pores whose size is less than or equal to 20 nm
  • x VPT-N 2 is greater than or equal to 10% x VPT-N 2 , more particularly greater than or equal to 15% x VPT-N 2 , or even greater than or equal to 20% x VPT-N 2 , or even greater than or equal to 30% x VPT-N 2 ;
  • - is less than or equal to 60% x VPT-N 2 ;
  • a pore volume in the pore area whose size is between 40 and 100 nm (denoted VP 40 -100 nm-N 2 ), such that VP 40 -100 nm-N 2 is greater than or equal to 20% x VPT -N 2 , more particularly greater than or equal to 25% x VPT-N 2 , or even greater than or equal to 30% x VPT-N 2 ;
  • Boehmite refers in the European nomenclature and in a known manner, gamma oxyhydroxide ( ⁇ - ⁇ ).
  • ⁇ - ⁇ gamma oxyhydroxide
  • Boehmite refers to a variety of aluminum hydrate having a particular crystalline form which is known to those skilled in the art. Boehmite can be characterized by X-ray diffraction.
  • Boehmite also covers "pseudo-boehmite", which according to some authors is similar to a particular variety of boehmite and simply shows a broadening of peaks. characteristics of the boehmite.
  • the aluminum hydrate H can optionally comprise at least one additional element selected from the group formed by lanthanum, praseodymium or a mixture of the two elements.
  • the proportion of this element or the total proportion of these elements may be between 0% and 15% by weight, more particularly between 0% and 10% by weight, more particularly between 0% and 8%. This proportion can be between 2% and 8%.
  • This proportion is given by weight of the element or elements expressed as oxide with respect to the total weight of elements Al, La and / or Pr also expressed in the form of oxides. For the calculation of this proportion, it is considered that the lanthanum oxide is in the La 2 O 3 form, the praseodymium oxide is in the Pr 6 O 2 form and the aluminum oxide is in the Al 2 O 3 form.
  • an aluminum hydroxide H comprising 7% lanthanum is such that it contains the equivalent of 7% La 2 O 3 and the equivalent of 93% Al 2 O 3.
  • the proportion of additional element (s) can be determined by calcining the hydrate of aluminum in air so as to convert it to alumina and oxide (s) of the additional element (s), then attacking the product thus calcined, for example with a concentrated nitric acid solution, so as to dissolve its elements in a solution which can then be analyzed by the techniques known to man such as ICP.
  • the boehmite contained in the aluminum hydrate H may have an average crystallite size of at most 6.0 nm, or even at most 4.0 nm, more particularly at most 3.0 nm.
  • the average size of the crystallites is determined by the X-ray diffraction technique and corresponds to the size of the coherent domain calculated from the width at half height of the line (020).
  • Aluminum hydrate H may be in the form of a mixture of a boehmite, identifiable as previously described by the X-ray diffraction technique, and a non-visible phase in X-ray diffraction, in particular an amorphous phase.
  • the aluminum hydrate H can have a% crystalline phase (boehmite) which is less than or equal to 60%, more particularly less than or equal to 50%. This% can be between 40% and 55%, or between 45% and 55%, or even between 45% and 50%. This% is determined in a manner known to those skilled in the art.
  • this%:% crystallinity peak intensity (120) / peak intensity (120) of the reference x 100 in which the peak intensity (120) of the hydrate is compared.
  • aluminum and peak intensity (120) of a reference The reference used in the present application is the product corresponding to the example B1 of the application US 2013/017947.
  • the intensities measured correspond to the areas of the peaks (120) above the baseline. These intensities are determined on the diffractograms with respect to a baseline taken over the angle range 2 ⁇ between 5.0 ° and 90.0 °.
  • the baseline is determined automatically from the diffractogram data analysis software.
  • Aluminum hydrate H has a particular porosity. Thus, after calcination under air at 900 ° C.
  • VP20 nm-N2 a pore volume in the pore area whose size is less than or equal to 20 nm (denoted VP20 nm-N2) such that VP 2 o nm-N2 is greater than or equal to 20% x VPT-N 2 , more particularly greater than or equal to 25% x VPT-N 2 , or even greater than or equal to 30% x VPT-N 2 .
  • VP 20 nm -N 2 is less than or equal to 60% x VPT-N 2 .
  • the aluminum hydrate H has a pore volume in the pore area whose size is between 40 and 100 nm (denoted VP 40 -100 nm-N 2 ), such that VP 40 -100 nm-N2 is greater than or equal to 15% x VPT-N 2 , more particularly greater than or equal to 20% x VPT-N 2 , or even greater than or equal to 25% x VPT-N 2 , or even greater than or equal to 30% x VPT-N 2 .
  • VP 40 -100 nm-N 2 may be less than or equal to 65% x VPT-N 2 .
  • the aluminum hydrate H may have a total pore volume (VPT-N 2 ) of between 0.65 and 1, 20 ml / g, more particularly between 0, 70 and 1, 15 mL / g, or even between 0.70 and 1.10 mL / g. It will be noted that the pore volume thus measured is mainly developed by pores whose diameter is less than or equal to 100 nm.
  • Aluminum hydrate H may have a specific surface area of at least 200 m 2 / g, more particularly at least 250 m 2 / g. This specific surface may be between 200 and 400 m 2 / g.
  • the pore volumes given in the present application are determined by the nitrogen porosimetry technique.
  • the samples are pretreated before heat and / or under vacuum to eliminate volatile surface species (such as for example H 2 O, ).
  • volatile surface species such as for example H 2 O, .
  • the sample may be heated to 200 ° C for 2 hours.
  • the aluminum hydrate H may have a specific surface area (BET) of at least 130 m 2 / g, more particularly at least 150 m 2 / g. This specific surface may be between 130 and 220 m 2 / g.
  • BET specific surface area
  • the aluminum hydrate H may have a specific surface area (BET) of at least 80 m 2. g, more particularly at least 100 m 2 / g. This specific surface may be between 80 and 120 m 2 / g.
  • the aluminum hydrate H may have a high thermal resistance.
  • the aluminum hydrate after calcination in air at 940 ° C. for 2 hours, followed by calcination under air at 1200 ° C. for 5 hours, the aluminum hydrate can have a specific surface area (BET) of minus 45 m 2 / g, more particularly at least 50 m 2 / g. This specific surface may be between 45 and 75 m 2 / g.
  • BET specific surface area
  • the expression "after calcination under air at the temperature x ° C. for y hours, the aluminum hydrate present" is used to characterize the aluminum hydrate even if the measured property (specific surface or porous volume) is the same. the product resulting from the calcination of aluminum hydrate.
  • Aluminum hydrate H may be obtained by the process comprising the following steps:
  • an aqueous solution (A) comprising aluminum sulphate, optionally the additional components in the form of nitrate (s) and nitric acid;
  • the aqueous solution (A) being introduced continuously throughout step (a) and the rate of introduction of the solution (B) being regulated so that the average pH of the reaction mixture is equal to a value a target of between 4.0 and 6.0, more particularly between 4.5 and 5.5;
  • the aqueous solution (B) is continued to reach a target pH of between 8.0 and 10.5, preferably between 9.0 and 10.0;
  • step (d) the solid resulting from step (c) is then dried to give aluminum hydrate H.
  • the next optional step (a2) of the process is the step of heating the precipitate suspension obtained in step (a1).
  • This heating can be carried out directly on the reaction mixture obtained at the end of step (a1) or on a suspension obtained after separation of the precipitate from the reaction mixture of step (a1), optional washing and return to water precipitate.
  • the suspension can be heated to a temperature of at least 60 ° C.
  • the temperature can be between 60 ° C and 180 ° C.
  • the heating operation can be carried out by introducing the mixture into a closed reactor (of the autoclave type).
  • the pressure in the closed reactor can vary between a value greater than 1 Bar (10 5 Pa) and 165 Bar (1.65 ⁇ 10 7 Pa), preferably between 5 Bar (5.10 5 Pa) and 165 Bar (1.65 ⁇ 10 7 Pa).
  • the heating can also be carried out in an open reactor for temperatures below 100 ° C.
  • the heating may be conducted either in air or in an atmosphere of inert gas, preferably nitrogen.
  • the duration of the heating can vary within wide limits, for example between 20 minutes and 48 hours, preferably between 20 minutes and 3 hours.
  • the rise in temperature is carried out at a speed which is not critical, and it is thus possible to reach the reaction temperature set by heating the medium, for example between 30 minutes and 4 hours, these values being given for all purposes. indicative fact.
  • the mixture is then cooled to a temperature below 50 ° C. This cooling is performed by allowing the mixture to cool naturally or using a cooling means known to those skilled in the art.
  • the next step (a3) of the process consists in adding to the dispersion obtained in step (a1) or in step (a2), a texturing agent whose function is to control the porosity of the mixed oxide.
  • a texturizing agent includes polar chemical groups that interact with the chemical groups on the surface of the precipitate. The texturizing agent is subsequently removed in the calcination step (a6).
  • the texturing agent may be chosen from anionic surfactants, nonionic surfactants, polyethylene glycols and carboxylic acids and their salts, as well as surfactants of the ethoxylate type of carboxymethylated fatty alcohols. Regarding this additive, reference may be made to the teaching of the application WO-98/45212 and use the surfactants described herein.
  • ethoxycarboxylates ethoxylated fatty acids
  • sarcosinates phosphate esters
  • sulphates such as alcohol sulphates, ether alcohol sulphates and sulphated alkanolamide ethoxylates
  • sulphonates such as sulphosuccinates.
  • alkyl benzene or alkyl naphthalene sulfonates are examples of surfactants of the anionic type, of ethoxycarboxylates, ethoxylated fatty acids, sarcosinates, phosphate esters, sulphates such as alcohol sulphates, ether alcohol sulphates and sulphated alkanolamide ethoxylates, sulphonates such as sulphosuccinates.
  • alkyl benzene or alkyl naphthalene sulfonates are examples of surfactants of the anionic type, of ethoxycar
  • nonionic surfactants there may be mentioned acetylenic surfactants, alcohol ethoxylates, alkanolamides, amine oxides, ethoxylated alkanolamides, long chain ethoxylated amines, ethylene oxide / propylene oxide copolymers, sorbiatan derivatives, ethylene glycol, propylene glycol, glycerol, polyglyceryl esters and their ethoxylated derivatives, alkylamines, alkylimidazolines, ethoxylated oils and alkylphenol ethoxylates.
  • carboxylic acids it is possible to use, in particular, aliphatic mono- or dicarboxylic acids and, among these, more particularly saturated acids. These include formic, acetic, propionic, butyric, isobutyric, valeric, caproic, caprylic, capric, lauric, myristic and palmitic acids.
  • dicarboxylic acids there may be mentioned oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid and sebacic acid.
  • fatty acids and more particularly saturated fatty acids can be in particular linear and saturated acids of formula CH 3 - (CH 2 ) m - COOH, m being an integer between 6 and 20, more particularly between 9 and 15.
  • the salts of all the acids mentioned can also be to be used, especially the ammoniacal salts.
  • ammoniacal salts By way of example, there may be mentioned more particularly lauric acid and ammonium laurate.
  • carboxymethylated fatty alcohol ethoxylates is understood to mean products consisting of ethoxylated or propoxylated fatty alcohols comprising at the end of the chain a CH 2 --COOH group.
  • R means a carbon chain, saturated or unsaturated, whose length is generally at most 22 carbon atoms, preferably of at least 12 carbon atoms
  • R2, R3, R4 and R 5 can be identical and represent hydrogen, or R2 may be CH 3 and R 3, R and R 5 are hydrogen
  • n is a non-zero integer of up to 50 and more particularly between 5 and 15, these values being included.
  • a surfactant may consist of a mixture of products of the above formula for which R 1 may be saturated and unsaturated respectively or products containing both -CH 2 -CH 2 -O- and -C (CH 3 ) -CH 2 -O- groups.
  • the texturing agent may be added to the dispersion resulting from step (a1) or from step (a2). It is preferably added to a dispersion whose temperature is at most 40 ° C.
  • the proportion of texturizing agent used is generally between 1% and 60%, more particularly between 10% and 50%, this proportion being expressed as a percentage by weight of texturing agent relative to the mixed oxide.
  • step (a4) the solid of the dispersion of step (a3) is recovered by solid / liquid separation.
  • a vacuum filter for example of the Nutsche type, a centrifugal separation or a filter press.
  • step (a4) is followed by washing the precipitate after separating it from the medium in which it was in suspension.
  • the washing operation involves contacting the solid with water. This washing can be done with water, preferably with water at pH> 7, for example ammonia water.
  • the washing operation may be to circulate water through the solid retained on the filter or to redisperse the solid in water and recover it by solid / liquid separation.
  • step (a5) the solid obtained at the end of step (a4) is optionally dried.
  • This step can be performed for example using an atomizer.
  • step (a6) the solid obtained at the end of step (a4) or of step (a5) is calcined to yield the mixed oxide.
  • the solid may be dry or still wet, that is to say that the solid contains residual water.
  • the calcination makes it possible to develop the crystallinity of the product formed.
  • the specific surface of the product is even lower than the calcination temperature used is higher.
  • the calcination is generally carried out under air, but a calcination carried out for example under an inert gas or under a controlled atmosphere (oxidizing or reducing) is not excluded.
  • the calcining temperature is generally between 700 ° C and 1100 ° C. This temperature may be between 800 ° C. and 1100 ° C., or even between 900 ° C. and 1100 ° C.
  • the duration of the calcination is adapted to the calcination temperature. As a guide only, it may be at least 2 h, more particularly between 2 and 5 h.
  • the mixed oxide which is obtained in step (a5) may be optionally milled to obtain a powder of the desired particle size.
  • a powder of the desired particle size For example, a hammer mill or mortar grinding may be used.
  • the powder can also be sieved to control the particle size.
  • the preparation of the mixed oxide according to the invention may be based on the conditions of Example 1 given below
  • the invention also relates to a mixed oxide obtainable by the process just described. As regards the use of the mixed oxide according to the invention, this falls within the field of automobile pollution remediation.
  • the mixed oxide according to the invention can be used in the manufacture of a catalytic converter ("catalytic converter") whose function is to treat automotive exhaust.
  • the catalytic converter comprises a catalytically active coating layer prepared from the mixed oxide and deposited on a solid support. The function of the coating layer is to transform certain pollutants of the exhaust gas, in particular carbon monoxide, unburned hydrocarbons and nitrogen oxides, into chemical products that are less harmful to the environment.
  • the solid support may be a metal monolith, for example FerCralloy, or ceramic.
  • the ceramic may be cordierite, silicon carbide, alumina titanate or mullite.
  • a commonly used solid support consists of a generally cylindrical monolith comprising a multitude of small parallel porous wall channels. This type of support is often cordierite and presents a compromise between a large specific surface area and a limited pressure drop.
  • the coating layer commonly called "washcoat” is deposited on the surface of the solid support.
  • the coating layer is formed from a composition comprising the mixed oxide according to the invention mixed with at least one mineral material.
  • the inorganic material may be chosen from alumina, boehmite or pseudo-boehmite, titanium oxide, cerium oxide, zirconium oxide, silica, spinels, zeolites, silicates, crystalline silicoaluminum phosphates, crystalline aluminum phosphates.
  • the composition may also comprise other additives which are specific to each formulator: H 2 S trap, organic or inorganic modifier whose function is to facilitate the coating, colloidal alumina, etc.
  • the coating layer thus comprises such composition.
  • Alumina is a mineral material commonly used, this alumina possibly being doped, for example by an alkaline earth metal such as barium.
  • the coating layer also comprises at least one precious metal (such as for example Pt, Rh, Pd) dispersed.
  • the amount of precious metal is generally between 1 and 400 g, based on the volume of the monolith expressed in ft 3 .
  • the precious metal is catalytically active.
  • a salt of the precious metal may be added to a suspension of the mixed oxide or mineral material or the mixture of the mixed oxide and the inorganic material.
  • the salt may be, for example, a chloride or a nitrate of the precious metal (eg, rhodium nitrate) .
  • the water is removed from the suspension to fix the precious metal, the solid is dried and calcined under air at room temperature. typically between 300 and 800 ° C.
  • An example of a precious metal dispersion can be found in Example 1 of US 7,374,729.
  • the coating layer is obtained by applying the suspension to the solid support.
  • the coating layer therefore has a catalytic activity and can serve as a depollution catalyst.
  • the depollution catalyst can be used to treat the exhaust gases of internal combustion engines.
  • the catalytic systems and mixed oxides of the invention can finally be used as NO x traps or to promote the reduction of NO x even in an oxidizing medium.
  • the invention also relates to a method for treating the exhaust gases of internal combustion engines which is characterized in that uses a catalytic converter comprising a coating layer as described.
  • BET specific surfaces specific surfaces are determined automatically using a Tristar II 3020 Micromeritics device on samples in accordance with the manufacturer's instructions. The samples are pretreated for 2 hours at 200 ° C. The measurement is made on 5 points in the range of relative pressures p / po ranging from 0.05 to 0.3 inclusive. The equilibrium time for each point is 5 s.
  • mercury porosity a Micromeritics Autopore IV 9500 was used with a powder penetrometer according to the manufacturer's instructions.
  • the following parameters can be used: penetrometer used: 3.2 ml; capillary volume: 0.412 ml; head pressure: 4.68 psi; contact angle: 130 °; superficial mercury tension: 485 dynes / cm; Mercury density: 13.5335 g / ml.
  • penetrometer used 3.2 ml
  • capillary volume 0.412 ml
  • head pressure 4.68 psi
  • contact angle 130 °
  • superficial mercury tension 485 dynes / cm
  • Mercury density 13.5335 g / ml.
  • a vacuum of 50 mmHg is applied to the sample for 5 minutes.
  • the equilibrium times are as follows: low pressure range (1, 3-30 psi): 20 s - high pressure range (30-60,000 psi): 30 s.
  • the samples Prior to the measurement, the samples are degassed in an oven at 100 ° C for at least 15 min. Nitrogen porosity: Micromeritics Tristar II 3020 was used.
  • the porous nitrogen distribution measurement is done on 85 points using a pressure table (47 points between 0.05 and 0.995 for adsorption and 38 points for desorption between 0.995 and 0.2) [cf. Fig. 3].
  • the equilibrium time for a relative pressure between 0.05 and 0.995 excluded is 5 s.
  • the equilibrium time for a relative pressure greater than or equal to 0.995 is 600 s.
  • Tolerances on pressures are 5 mmHg for absolute pressure and 5% for relative pressure.
  • the po is measured at regular intervals during the analysis (2 h).
  • the method of Barett, Joyner and Halenda (BJH) with the law of Harkins & Jura is used for the determination of mesoporosity.
  • the analysis of the results is done on the desorption curve.
  • a Panalytical X Per Pro goniometer with a copper source and a spinner sample holder was used and a X Celerator 1D detector with an angular width of 2.122 °.
  • the unit is equipped with a nickel filter at the front and programmable slots to illuminate a constant square surface of 10 mm side.
  • An acquisition lasts about 30 minutes.
  • the intensities are determined on the diffractograms with respect to a baseline taken at the angle range 29 between 5.0 ° and 90.0 °.
  • the baseline is determined automatically from the diffractogram data analysis software.
  • apparent density of powder the apparent density of the mixed oxide powder corresponds to the weight of a certain amount of powder relative to the volume occupied by this powder:
  • the apparent density of powder is determined by the method described below. Firstly, the volume of a specimen without a spout having a cylindrical shape of approximately 25 ml is determined first. To do this, we weigh the empty test piece (tare T). Distilled water is then poured into the test tube to the edge but without exceeding the edge (no meniscus). The test tube filled with distilled water (M) is weighed. The mass of water contained in the test tube is therefore:
  • the density of water is by density of water at the measurement temperature
  • the mixed oxide powder is carefully poured through a funnel to reach the edge of the test tube. Excess powder is leveled with a spatula. The powder should not be compacted or compacted during filling. The test specimen containing the powder is then weighed.
  • Viscometer (mL) qranulometry measured using Coulter counter LS.
  • the mixed oxide is dispersed in an aqueous solution of sodium hexametaphosphate at a concentration 10 g / L.
  • the measurement could be carried out after an ultrasound treatment at an energy ranging from 5 to 500 W for a duration of 25 seconds to 5 minutes.
  • Example H1 preparation of an aluminum hydrate of composition 93.8% A Oa - 6.2% LapC
  • a solution (A) is prepared by introducing 34.7 kg of deionized water, 10.95 kg of a solution of aluminum sulphate with a concentration of 8.31% by weight of alumina (Al 2 O 3). 1.43 kg of a solution of lanthanum nitrate of concentration 26.9% by weight of La 2 O 3 and 4.97 kg of a solution of nitric acid at 68% by weight.
  • Solution (B) is a solution of sodium aluminate with a concentration of 24.9% by weight of alumina (Al2O3).
  • a step (a) the solution (A) and the solution (B) are simultaneously introduced into the reactor stirred by introduction rods close to the stirring device.
  • Solution (A) is introduced at a rate of 1.05 kg / min.
  • Solution (B) is introduced at a flow rate to reach a pH of 5 in 3 min.
  • the flow rate of the solution (A) remains constant at 1.05 kg / min and the flow rate of the solution (B) is regulated so as to maintain the pH at a value of 5.1 for 46 min.
  • a step (b) the introduction of the solution A is stopped and the solution (B) is added until a pH of 10 is reached in 15 minutes.
  • step (c) the reaction slurry is then poured onto a vacuum filter. At the end of the filtration, the cake is washed with deionized water at 60 ° C. The cake has a solids content of 11% by weight of oxide (Al 2 O 3 - La 2 O 3 ). The cake is then redispersed in deionized water to obtain a suspension of concentration close to 8% by weight of oxide (Al 2 O 3 - La 2 O 5).
  • step (d) the suspension is atomized to obtain a dry powder of lanthanum-doped aluminum hydrate. The loss on ignition of the powder is obtained by the loss of mass after calcination at 950 ° C-2 hours. It is 31.2% by mass.
  • the aluminum hydrate powder contains an equivalent of 64.5% by weight of Al 2 O 3 and 4.2% by weight of La 2 O 3. This powder has a BET surface area of 344 m 2 / g.
  • Example H2 preparation of an aluminum hydrate of composition 93.8% AI9O3 - 6.2% LapC
  • a solution (A) is prepared by introducing 34.7 kg of deionized water, 10.95 kg of a solution of aluminum sulphate with a concentration of 8.31% by weight of alumina (Al 2 O 3). 1.43 kg of a solution of lanthanum nitrate with a concentration of 26.9% by weight of La 2 O 3 and 4.96 kg of a solution of 68% nitric acid.
  • Solution (B) is a solution of sodium aluminate with a concentration of 24.9% by weight of alumina.
  • a step (a) the solution (A) and the solution (B) are simultaneously introduced into the reactor stirred by introduction rods close to the stirring device.
  • Solution (A) is introduced at a rate of 1.05 kg / min.
  • Solution (B) is introduced at a flow rate to reach a pH of 4.4 in 3 min.
  • the flow rate of the solution (A) remains constant at 1.05 kg / min and the flow rate of the solution (B) is regulated so as to maintain the pH at a value of 4.4 for 46 minutes.
  • a step (b) the introduction of the solution (A) is stopped and solution B is added until a pH of 10 is reached in 15 minutes.
  • a step (c) the reaction slurry is then poured onto a vacuum filter. At the end of the filtration, the cake is washed with deionized water at 60 ° C. The cake has a solids content of 13% by weight of oxide (Al 2 O 3 - La 2 O 3). The cake is then redispersed in deionized water to obtain a suspension of concentration close to 8% by weight of oxide (Al 2 O 3 - La 2 Os).
  • a step (d) the suspension is atomized to obtain a lanthanum doped aluminum hydrate powder.
  • the loss on ignition of the powder is obtained by the loss of mass after calcination at 950 ° C-2 hours. It is 38.5% by weight.
  • the aluminum hydrate powder contains an equivalent of 57.8% by weight of Al 2 O 3 and 3.8% by weight of La 2 O 3. This powder has a BET surface area of 259 m 2 / g. Characterizations of aluminum hydrates H1 and H2
  • Example 1 Preparation of a mixed oxide Al 2 O 3 (30%) - ZrO 2 (35%) - CeO 2 (27%) - 2 O 3 (4%) - Y 2 O 3 (4%) ( % in weight)
  • a nitrate-based solution of the precursors is prepared by introducing 361 g of water, 11 g of a solution of zirconyl nitrate into a stirred tank with the aid of a four-blade mobile inclined at 45 °.
  • the precursor mixture is introduced over 60 min into a stirred reactor with a 45 ° (575 rpm) 45 ° slant mobile, containing 500 mL of a 2 mol / L ammonia solution at room temperature.
  • the mixture is heated to a temperature of 95 ° C. and maintained at this temperature for 30 min.
  • the mixture is then cooled to a temperature below 40 ° C.
  • To this cooled mixture was added 12 g of lauric acid with stirring at 650 rpm. This stirring is maintained for 30 minutes.
  • the wet cake obtained is then introduced into a muffle furnace.
  • the temperature of the oven is raised with a speed of 4 ° C / min until reaching 950 ° C, this temperature is then maintained for 4 hours.
  • the mixed oxide is obtained.
  • the recovered mixed oxide is then ground with a mortar.
  • Porous volume (pore sizes ⁇ 100 nm) by N 2 porosimetry after calcination under air at 950 ° C / 4 h: ⁇ 00 nm, N2 ⁇ 0.58 mL / g
  • Example 2 Preparation of a mixed oxide Al 2 O 3 (30%) - ZrO 2 (35% ) - CeO 2 (27%) - 2 O 3 (4%) - Y 2 O 3 (4%) (% by weight)
  • the precursor mixture is introduced over 60 min into a stirred reactor with a 45 ° (575 rpm) 45 ° slant mobile, containing 500 mL of a 2 mol / L ammonia solution at room temperature.
  • the mixture is heated to a temperature of 95 ° C. and maintained at this temperature for 30 min.
  • the mixture is then cooled to a temperature below 40 ° C.
  • To this cooled mixture was added 12 g of lauric acid with stirring at 650 rpm. This stirring is maintained for 30 minutes.
  • the precursor mixture is introduced in 60 min into a stirred reactor with a 45 ° (575 rpm) 45 ° slant mobile, containing 500 ml of a 1.8 mol / L ammonia solution at room temperature. .
  • the reaction medium is heated to a temperature of 95 ° C. and maintained at this temperature for 30 min.
  • the reaction medium is then cooled to a temperature below 40 ° C.
  • the reaction mixture is again heated in an autoclave at a temperature of 150 ° C. and maintained at this temperature for 2 hours.
  • the reaction medium is then cooled to a temperature below 40 ° C.
  • To this cooled mixture was added 23 g of lauric acid with stirring at 500 rpm. This stirring is maintained for 30 minutes.
  • the reaction medium is heated to a temperature of 95 ° C. and maintained at this temperature for 30 min.
  • the reaction medium is then cooled to a temperature below 40 ° C.
  • To this cooled mixture was added 12 g of lauric acid with stirring at 850 rpm. This stirring is maintained for 30 minutes.
  • the wet cake obtained is then introduced into a muffle furnace.
  • the temperature of the oven is raised with a speed of 4 ° C / min to 950 ° C, this temperature is maintained for 4 hours.
  • the mixed oxide is obtained.
  • the recovered mixed oxide is then ground with a mortar.
  • Example 5 Preparation of a mixed oxide Al 2 O 3 (30%) - ZrO 2 (35%) - CeO 2 (27%) - 2 O 3 (4%) - Y 2 O 3 (4%)
  • a nitrate solution of the precursors is prepared by introducing into a stirred tank using a Rushton turbine (200 rpm), 96.5 kg of water, 18.3 kg of a nitrate solution.
  • a stirred reactor 125 rpm, mobile type Mixell TT
  • 125 L of a solution of ammonia to 1, 6 mol / L The precursor mixture is introduced in 60 min into the stirred reactor. It operates at room temperature.
  • the reaction medium is heated to a temperature of 90 ° C. and maintained at this temperature for 30 min.
  • the suspension is then heated at 150 ° C in an autoclave for 120 minutes and then cooled to a temperature of 40 ° C.
  • To this cooled mixture was added 4 kg of lauric acid with stirring at 100 rpm. This stirring is maintained for 60 minutes.
  • the reaction medium is heated to a temperature of 95 ° C. and maintained at this temperature for 30 min.
  • the reaction medium is then cooled to a temperature below 40 ° C.
  • To this cooled mixture was added 6 g of lauric acid with stirring at 650 rpm. This stirring is maintained for 30 minutes.
  • the wet cake obtained is then introduced into a muffle furnace.
  • the temperature of the oven is raised with a speed of 4 ° C / min to 950 ° C, this temperature is maintained for 4 hours.
  • the mixed oxide is obtained.
  • the recovered mixed oxide is then ground with a mortar.
  • Example 7 Preparation of a mixed oxide Al 2 O 3 (30%) - ZrO 2 (35%) - CeO 2 (27%) - 2 O 3 (4%) - Y 2 O 3 (4%)
  • a stirred reactor 600 rpm, mobile four pale inclined at 45 °
  • 500 mL of a solution of ammonia 3 mol / L 500 mL of a solution of ammonia 3 mol / L.
  • the precursor mixture is introduced in 60 min into the stirred reactor. It operates at room temperature.
  • the reaction medium is heated to a temperature of 95 ° C. and maintained at this temperature for 30 min.
  • the reaction medium is then cooled to a temperature below 40 ° C.
  • To this cooled mixture was added 1.18 g of lauric acid with stirring at 500 rpm. This stirring is maintained for 30 minutes.
  • the wet cake obtained is then introduced into a muffle furnace.
  • the temperature of the oven is raised with a speed of 4 ° C / min to 950 ° C, this temperature is maintained for 4 hours. At the end of this calcination under air, the mixed oxide is obtained. The recovered mixed oxide is then ground with a mortar.
  • Example 8 Preparation of a mixed oxide Al 2 O 3 (30%) - ZrO 2 (35%) - CeO 2 (27%) - 2 O 3 (4%) - Y 2 O 3 (4%)
  • a solution based on the nitrates of the precursors is prepared by introducing into a stirred tank with a 45 ° -standard, 458.4 g of water, 75.8 g of a nitrate solution.
  • the wet cake obtained is then introduced into a muffle furnace.
  • the temperature of the oven is raised with a speed of 4 ° C / min to 950 ° C, this temperature is maintained for 4 hours.
  • the mixed oxide is obtained.
  • the recovered mixed oxide is then ground with a mortar.
  • Example 9 Preparation of a mixed oxide Al 2 O 3 (30%) - ZrO 2 (35%) - CeO 2 (27%) - 2 O 3 (4%) - Y 2 O 3 (4%)
  • a stirred reactor 600 rpm, mobile four pale inclined at 45 °
  • 500 mL of a solution of ammonia 2 mol / L 500 mL of a solution of ammonia 2 mol / L.
  • the precursor mixture is introduced in 60 min into the stirred reactor. It operates at room temperature.
  • the reaction medium is heated to a temperature of 95 ° C. and maintained at this temperature for 30 min.
  • the reaction medium is then cooled to a temperature below 40 ° C.
  • To this cooled mixture was added 12 g of lauric acid with stirring at 500 rpm. This stirring is maintained for 30 minutes.
  • the wet cake obtained is then introduced into a muffle furnace.
  • the temperature of the oven is raised with a speed of 4 ° C / min to 950 ° C, this temperature is maintained for 4 hours. At the end of this calcination under air, the mixed oxide is obtained. The recovered mixed oxide is then ground with a mortar.
  • the basic aqueous solution is introduced into the precursor mixture while in the process of the invention, the precursor mixture is introduced into a basic aqueous solution.
  • a solution based on the nitrates of the precursors is prepared by introducing 362 g of water, 14 g of a solution of zirconyl nitrate ([1]) into a stirred reactor (600 rpm, moving at four pale angles inclined at 45 °).
  • the wet cake obtained is then introduced into a muffle furnace.
  • the temperature of the oven is raised with a speed of 4 ° C / min to 950 ° C, this temperature is maintained for 4 hours.
  • the mixed oxide is obtained.
  • the recovered mixed oxide is then ground with a mortar.
  • the reaction medium is heated to a temperature of 95 ° C. and maintained at this temperature for 30 min.
  • the reaction medium is then cooled to a temperature below 40 ° C.
  • the wet cake obtained is then introduced into a muffle furnace.
  • the temperature of the oven is raised with a speed of 4 ° C / min to 950 ° C, this temperature is maintained for 4 hours.
  • the mixed oxide is obtained.
  • the recovered mixed oxide is then ground with a mortar.
  • a solution based on the nitrates of the precursors is prepared by introducing into a stirred tank with a 45 ° -standard, 458.4 g of water, 75.8 g of a nitrate solution.
  • the wet cake obtained is then introduced into a muffle furnace.
  • the temperature of the oven is raised with a speed of 4 ° C / min to 950 ° C, this temperature is maintained for 4 hours.
  • the mixed oxide is obtained.
  • the recovered mixed oxide is then ground with a mortar.
  • the aluminum hydrate is dispersed in the basic aqueous solution while in the process of the invention it is dispersed in an aqueous acidic solution.
  • a solution based on the nitrates of the precursors is prepared by introducing into a stirred tank with the aid of a four-blade mobile inclined at 45 °, 394.2 g of water, 75.8 g of a nitrate solution.
  • the solution based on the nitrates of precursors is kept stirring.
  • the wet cake obtained is then introduced into a muffle furnace.
  • the temperature of the oven is raised with a speed of 4 ° C / min to 950 ° C, this temperature is maintained for 4 hours.
  • the mixed oxide is obtained.
  • the recovered mixed oxide is then ground with a mortar.

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EP17838129.9A 2016-12-23 2017-12-22 Oxyde mixte résistant au vieillissement à base de cérium, de zirconium, d'aluminium et de lanthane pour convertisseur catalytique automobile Pending EP3558514A1 (fr)

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CN110124659B (zh) * 2019-06-20 2021-03-23 中自环保科技股份有限公司 一种铈锆铝基复合材料、cGPF催化剂及其制备方法
WO2021012107A1 (en) * 2019-07-19 2021-01-28 Rhodia Operations Mixed oxide based on cerium and zirconium
WO2021020104A1 (ja) * 2019-07-30 2021-02-04 第一稀元素化学工業株式会社 ジルコニア系複合酸化物、及び、ジルコニア系複合酸化物の製造方法
US20220410124A1 (en) * 2019-11-29 2022-12-29 Rhodia Operations Alumina with a particular pore profile
US20220410128A1 (en) * 2019-11-29 2022-12-29 Rhodia Operations Alumina with a particular pore profile
US20240075462A1 (en) * 2020-12-24 2024-03-07 Mitsui Mining & Smelting Co., Ltd. Complex oxide and method of producing the same
WO2022248205A1 (en) 2021-05-28 2022-12-01 Rhodia Operations Composition of aluminium oxide and cerium oxide with a particular porosity profile
CN113275000B (zh) * 2021-07-23 2021-11-09 山东国瓷功能材料股份有限公司 耐高温的铈锆复合氧化物及其制备方法与应用
JP2024529561A (ja) 2021-07-30 2024-08-06 ローディア オペレーションズ 酸化アルミニウム及び酸化セリウムの組成物
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WO2024196581A1 (en) * 2023-03-20 2024-09-26 Pacific Industrial Development Corporation Thermally stable oxygen storage material (osm) and method of making the same
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