EP3448812A1 - Oxyde mixte a base de cérium et de zirconium - Google Patents

Oxyde mixte a base de cérium et de zirconium

Info

Publication number
EP3448812A1
EP3448812A1 EP17725667.4A EP17725667A EP3448812A1 EP 3448812 A1 EP3448812 A1 EP 3448812A1 EP 17725667 A EP17725667 A EP 17725667A EP 3448812 A1 EP3448812 A1 EP 3448812A1
Authority
EP
European Patent Office
Prior art keywords
mixed oxide
cerium
lanthanum
oxide
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
EP17725667.4A
Other languages
German (de)
English (en)
French (fr)
Inventor
Rui Miguel Jorge Coelho Marques
Simon Ifrah
Boris CHABERT
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 EP3448812A1 publication Critical patent/EP3448812A1/fr
Pending legal-status Critical Current

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    • 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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    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G25/00—Compounds of zirconium
    • C01G25/02—Oxides
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    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
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    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the present invention relates to a mixed oxide of zirconium, cerium, lanthanum and at least one oxide of a rare earth other than cerium and lanthanum having a specific porosity and a high specific surface, its preparation process and its use in catalysis.
  • Multifunctional catalysts are used for the treatment of the exhaust gases of internal combustion engines (automotive post-combustion catalysis).
  • Multifunctional means catalysts capable of operating not only the oxidation in particular of carbon monoxide and hydrocarbons present in the exhaust gas but also the reduction in particular nitrogen oxides also present in these gases (catalysts "three ways").
  • the catalyst results from the interaction of a precious metal (eg Pd, Pt, Rh) with a mixed oxide of cerium and zirconium often mixed with alumina.
  • a precious metal eg Pd, Pt, Rh
  • the mixed oxide must have a suitable porosity. Thus, it must have a sufficiently large pore volume and also have pores of sufficiently large size to allow good diffusion of gases.
  • the mixed oxide must also have a surface area high enough to be used in catalysis.
  • the mixed oxide according to the invention as described in claim 1 aims at such a compromise.
  • Figures 1/6 to 6/6 show derived curves (C) giving dV / dlog D as a function of D for several mixed oxides.
  • specific surface is meant the BET specific surface area determined by nitrogen adsorption. This is obtained in accordance with ASTM D3663-03, which is based on the BRUNAUER-EMMETT-TELLER method described in "The Journal of the American Chemical Society, 60, 309 (1938)".
  • the abbreviation ST (° O / x (h) is used to denote the specific surface area of a composition, obtained by the BET method as described above, after calcination of the composition at a temperature T expressed in ° C during a duration of x hours.
  • 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 given temperature and duration correspond, unless otherwise indicated, to calcinations under air at a temperature step over the indicated time.
  • a Micromeritics Tristar II 3020 can be used on samples in accordance with the manufacturer's instructions.
  • the porosities shown are measured by mercury intrusion porosimetry in accordance with ASTM D 4284-83 ("Standard method for determining the 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. Porosimetry by mercury intrusion makes it possible to obtain the pore volume (V) as a function of the pore diameter (D). From these data, it is possible to obtain 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 located ) each at a diameter noted D p .
  • the pores which are considered characteristic of the invention are those having a diameter of less than or equal to 200 nm.
  • 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.
  • cerium oxide is considered to be in the form of ceric oxide (CeO 2)
  • the oxides of the other rare earth elements are in the form TR 2 O 3
  • TR denotes the rare earth (with the exception of praseodymium expressed in the Pr form). 6 ) and that zirconium and hafnium oxide are in ZrO 2 and HfO 2 form.
  • WO 201 1/006780 discloses compositions based on cerium oxide and zirconium oxide having after calcination at 900 ° C for 4 hours, two distinct pore populations.
  • the surface Snoo ° c / 4 h is at least 15 m 2 / g according to one embodiment. In the examples, this area is at most 19 m 2 / g.
  • WO 201 1/138255 discloses compositions based on oxides of zirconium, cerium and yttrium which after calcination at 900 ° C for 4 hours, two distinct pore populations. After calcination at 1100 ° C. for 4 hours, they have a population of pores whose diameter is centered on a value of between 30 and 70 nm, more particularly around 50 nm.
  • the surface Snoo ° c / 4h is at least 25 m 2 / g, more particularly at least 27 m 2 / g. In the examples, the maximum value of Snoo ° C / 4h is 33 m 2 / g and that of Siooo ° C / 4h is 50 m 2 / g.
  • the mixed oxides of the present invention are characterized by a higher SiO o / c surface area of greater than 55 m 2 / g.
  • WO 2012/072439 discloses compositions based on zirconium oxides and a rare earth other than cerium which have a surface Snoo ° c / 4 h of at least 25 m 2 / g, more particularly at least 27 m 2 / g. It is indicated that it is possible to obtain a specific surface of up to 37 m 2 / g. In the examples, the maximum value of Snoo ° c / 4 h is 33 m 2 / g. These compositions do not contain cerium (page 2-line 29).
  • the mixed oxides of the present invention are characterized by a much higher SiO o / c surface area of greater than 55 m 2 / g.
  • WO 201 1/083157 discloses compositions based on oxides of zirconium, cerium and at least one rare earth other than cerium which have a SiO0 ° C / 6 h of at least 45 m 2 / g, more particularly at least 55 m 2 / g.
  • the Snoo ° C / 4 h surfaces of the compositions of Table 1 are less than 25 m 2 / g.
  • WO 2004/002893 describes a composition based on oxides of zirconium, cerium, lanthanum and a rare earth other than cerium.
  • the surface Siooo ° C / 6 hours is at least 40 m 2 / g, more particularly at least 55 m 2 / g.
  • the Si 0 ° C / 6 h surface is at least 20 m 2 / g.
  • the example of this application is a composition ZrO 2 (73.5%) / CeO 2 (20%) / La 2 O 3 (2.5%) / Nd 2 O 3 (4%) has a surface Siooo ° c of 55 m 2 / g and a surface area of 60 m 2 / g.
  • WO 2014/1221402 discloses compositions based on oxides of zirconium, cerium, lanthanum, yttrium or gadolinium and tin (1 -15%) which have a SiO 0 o c at least 45 m 2 / g, or even at least 60 m 2 / g, and a surface Snoo ° c / 6 h of at least 25 m 2 / g, or even at least 40 m 2 / g.
  • WO 07093593 describes compositions based on oxides of zirconium, cerium, yttrium, lanthanum and a rare earth other than cerium and lanthanum which may have, for one of the two variants, a SiO 2 O surface. 4 hours at least 30 m 2 / g. These compositions comprise a proportion by weight of yttrium oxide of between 10 and 25% and a proportion by weight of additional rare earth oxide of between 2 and 15%. All examples include a proportion of rare earth other than cerium and lanthanum that is greater than 15% by weight.
  • WO 2009/130202 discloses compositions based on oxides of zirconium, cerium and yttrium, the proportion of cerium oxide is at most 15% by weight.
  • WO 2012/171947 discloses compositions based on oxides of cerium, zirconium and at least one rare earth other than cerium, having a cerium oxide content greater than 50% by weight.
  • the mixed oxides of the present invention have a cerium content of less than 45%.
  • EP 2868369 describes the preparation of a mixed oxide 40% CeO 2 , 50% ZrO 2 , 5% Pr 2 O 3, 5% La 2 O 3 using a micromixing tool. However, there is no mention of either the specific surface area or the porosity of the mixed oxide in this document.
  • FR 2955098 discloses mixed oxides.
  • the porosity characteristics of the mixed oxide according to claim 1 are not referred to. detailed description
  • this is a mixed oxide of zirconium, of céhum, of lanthanum and possibly of at least one rare earth other than cerium and lanthanum (denoted TR), the proportions by weight of these elements expressed in oxide equivalent relative to the total weight of the mixed oxide being the following:
  • the zirconium supplement characterized in that the mixed oxide has:
  • a BET specific surface area of at least 55 m 2 / g; and in that the derivative curve (dV / dlogD) obtained by mercury porosimetry on the mixed oxide after calcination at a temperature of 1100 ° C. for 4 hours, has in the field pores with a diameter of less than or equal to 200 nm , a peak with a maximum corresponding to a pore diameter D p, noo o c / 4 hours, between 24 and 34 nm, and V D respectively designating the pore volume and pore diameter.
  • the aforementioned elements Ce, La, TR and Zr are generally present in the form of oxides.
  • hydroxides or oxyhydroxides 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 laboratories, especially X-ray fluorescence, for example using the PANalytical Axios-Max spectrometer. The proportions of these elements are given by weight in oxide equivalent relative to the total weight 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 is generally less than 0.1%, expressed by weight relative to the total weight of the mixed oxide.
  • 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 is less than or equal to 2.5%, or even 2.0%, expressed as oxide equivalent relative to the total weight of the mixed oxide.
  • the proportions of the impurities can be determined using Inductively Coupled Plasma Spectrometry (ICP-MS).
  • the mixed oxide consists of a mixture of oxides of zirconium, cerium, lanthanum, and possibly at least one rare earth other than cerium and lanthanum (TR) and optionally hafnium, the proportions by weight deducted oxides being the following:
  • the zirconium oxide supplement characterized in that the mixed oxide has:
  • a BET specific surface area of at least 55 m 2 / g; and in that the derivative curve (dV / dlogD) obtained by mercury porosimetry on the mixed oxide after calcination at a temperature of 1100 ° C. for 4 hours, has in the field pores with a diameter of less than or equal to 200 nm a peak whose maximum corresponds to a pore diameter D p , noo o c / 4 h, between 24 and 34 nm, V and D respectively denoting the pore volume and the pore diameter.
  • the mixed oxide may also comprise tin in the form of SnO 2 oxide in a proportion by weight of oxide equivalent relative to the total weight of the mixed oxide, strictly less than 1.0%, or even less than 0.01%.
  • the mixed oxide does not contain tin.
  • the proportion by weight of cerium is between 8 and 45%, more particularly between 18 and 45%. This proportion can also be between 8 and 12%.
  • the proportion by weight of lanthanum is between 1 and 10%, more particularly between 2 and 9%
  • the mixed oxide may also comprise between 0 and 15% by weight of at least one rare earth other than cerium or lanthanum (TR).
  • the rare earth may be selected from yttriunn, neodymium or praseodymium.
  • the mixed oxide also comprises zirconium.
  • the proportion by weight of zirconium is in addition to 100% of the other elements of the mixed oxide.
  • zirconium is, apart from oxygen, the majority element, that is to say the proportion by weight of oxide equivalent is greater than the proportion by weight in equivalent of oxide of each of the other constituent elements of the mixed oxide (ie Ce, La and optionally TR, Hf, Sn).
  • the proportion by weight of zirconium may be between 40 and 91%.
  • the oxide does not include rare earth other than cerium and lanthanum.
  • the proportion by weight of cerium can be between 30 and 40% and that of lanthanum between 3 and 6%.
  • the zirconium supplement may be between 54 and 67% by weight.
  • the mixed oxide comprises only ytthum as a rare earth other than cerium and lanthanum.
  • the proportion of yttrium can be between 1 and 15%, more especially between 1 and 13%.
  • the proportion of cerium may be between 20 and 40%.
  • the mixed oxide comprises only two rare earths other than cerium and lanthanum which can be yttrium and lenodymium or yttrium and praseodymium.
  • the proportion of yttrium may be between 1 and 10% by weight, and that of neodymium or praseodymium between 2 and 6%.
  • the following constitutive elements of the mixed oxide may be the following: zirconium and optionally hafnium, cerium, lanthanum, yttrium; or
  • the mixed oxide may have only one phase after calcination at 900 ° C./4 h and / or at 1100 ° C./4 h.
  • This single phase can be a cubic or quadratic phase.
  • the mixed oxide has a specific porosity after calcination at 1100 ° C for 4 hours.
  • D p, i ioo ° C / 4 h is between 24 nm and 30 nm, this higher value being excluded (i.e., D p, noo o c / 4 h is greater than or equal to 24 nm and strictly less than 30 nm).
  • the mixed oxide may be such that the pore volume developed by the pores around the diameter D p, i ioo ° C / 4h represents a important part of the pore volume that is developed by pores whose diameter is less than or equal to 200 nm. This can be demonstrated using the ratio R which is defined by the formula below:
  • ⁇ Vi is the pore volume developed by the pores whose diameter is between nm (D p, n 0 o ° c / 4 -15 h) and (D p, n o 0 ° C / 15 h 4);
  • ⁇ V 2 is the pore volume developed by the pores whose diameter is less than or equal to 200 nm;
  • ⁇ Vi and V 2 are determined by mercury porosimetry on the mixed oxide after calcination at 1100 ° C for 4 h.
  • the pore volume that is developed corresponds to the inter and intra-particle porous volume.
  • the pore volume indicated here corresponds to the inter-particle and intra- particle porous volume as deduced from the volume values given by the apparatus.
  • the ratio R makes it possible to appreciate the part of the porous volume developed by the population of "small” pores.
  • the value of 15 nm retained for the ratio R is close to the width at half height of the peaks observed.
  • the higher the R the more the pore volume distribution is around the "small" pores around D p , 100 ° C / 4 h, that is, the diameter in nm is between (D p , noo o c / 4 h - 15) and (D p, i ioo ° C / 4 h + 15).
  • This ratio R is greater than 0.60. It may be greater than 0.65 or even 0.70. It is possible to reach a value R of 0.90 as is visible for example 8.
  • the ratio R can therefore be between 0.60 and 0.90, between 0.65 and 0.90, or between 0.70 and 0.90.
  • the derivative curve (dV / dlogD) obtained by mercury porosimetry on the mixed oxide after calcination at a temperature of 900 ° C. for 4 hours has pore diameter of less than or equal to 200 nm, a peak whose maximum corresponds to a rated pore diameter D p, 90o ° C / 4h and such that the absolute difference D p, noo o c / 4 h - D p, 9oo ° C / 4 h is less than or equal to 15 nm, or even less than or equal to 10 nm.
  • the mixed oxide does not have on the curve (C) two distinct peaks in the range of pores whose diameter is less than or equal to 200 nm.
  • the mixed oxide is also characterized by a high specific surface, in particular because of its specific porosity.
  • it has a surface Snoo ° c / 4 h of at least 30 m 2 / g, more particularly at least 32 m 2 / g, or even at least 35 m 2 / g. It is possible to reach a value of 40 m 2 / g. This specific surface may be between 30 and 40 m 2 / g.
  • the mixed oxide also has a surface area of 100 ° C./4 h of at least 55 m 2 / g, more particularly at least 58 m 2 / g. It is possible to reach a value of 65 m 2 / g.
  • This specific surface may be between 55 and 65 m 2 / g.
  • the surface Sgoo-cw h may be at least 60 m 2 / g, more particularly at least 65 m 2 / g.
  • the surface Sgoo cw-h can be at least 80 m 2 / g when the mixed oxide has never been subjected to a temperature at or above 900 ° C. It is possible to reach a value of 85 m 2 / g.
  • This specific surface may be between 60 and 85 m 2 / g.
  • step (a2) is then introduced into the mixture formed in step (a1) maintained with stirring, an aqueous solution of lanthanum nitrate and rare earth (TR) optionally present in the mixed oxide;
  • step (a3) the suspension obtained at the end of step (a2) is heated with stirring;
  • step (a6) the precipitate obtained at the end of step (a5) is calcined at a temperature between 700 ° C and 1100 ° C to give the mixed oxide;
  • step (a7) the mixed oxide obtained in step (a6) may be optionally milled.
  • step (a1) a solution comprising nitrates of zirconium and cerium (hereinafter referred to as CZ nitrate solution) is used.
  • CZ nitrate solution a solution comprising nitrates of zirconium and cerium
  • crystallized zirconyl nitrate can be dissolved in water.
  • basic zirconium carbonate or zirconium hydroxide with nitric acid This acid attack may be preferably conducted with a molar ratio NO3 ⁇ / Zr between 1.7 and 2.3. In the case of zirconium carbonate, this ratio can be between 1, 7 and 2.0.
  • a usable zirconium nitrate solution resulting from such an attack may have a concentration expressed as ZrO 2 of between 260 and 280 g / l.
  • the zirconium nitrate solution used in Examples 1-16 resulting from such an attack has a concentration of 266 g / L.
  • ceric nitrate For the source of cerium can be used, for example a salt This lv such as nitrate or ceric ammonium nitrate, which particularly suitable here.
  • ceric nitrate is used.
  • An aqueous solution of ceric nitrate may, for example, be obtained by reacting nitric acid with a hydrated ceric oxide prepared in a conventional manner by reacting a solution of a cerous salt, for example cerous nitrate, and an ammonia solution in the presence of hydrogen peroxide. It is also preferable to use a solution of ceric nitrate obtained by the electrolytic oxidation method of a cerous nitrate solution as described in document FR-A-2570087, and which constitutes here an interesting raw material.
  • a solution of ceric nitrate used, resulting from this process may have a concentration, expressed as Ceu 2 between 250 and 265 g / L.
  • the ceric nitrate solution used in Examples 1-16 resulting from this process has a concentration of 259 g / L.
  • the aqueous solution of cerium and zirconium nitrate may have some initial free acidity which can be adjusted by the addition of a base or an acid.
  • the CZ-nitrate solution can be obtained by dissolving the cerium and zirconium compounds in water in any order or by mixing two nitrate solutions.
  • step (a1) the CZ nitrate solution is introduced into a stirred vessel containing a basic aqueous solution so as to react the basic compound and the cerium and zirconium compounds.
  • 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 examples, an aqueous solution of ammonia can be used. As in Example 1, it is possible to use an aqueous solution of ammonia, for example of concentration 12 mol / l.
  • the basic compound can be used with a stoichiometric excess to ensure optimum precipitation of all cations.
  • the stoichiometric excess is preferably at least 40 mol% relative to all the cations present in the CZ-nitrate solution and also in the solution of lanthanum nitrates and rare earth (s) (s). ) (TR) optionally present in the mixed oxide which is added in step (a2).
  • the next step (a2) consists in bringing the medium resulting from the preceding step (a1) into contact with an aqueous solution of lanthanum nitrate and, if appropriate, the nitrate of the rare earth (s). (TR) optionally present in the mixed oxide.
  • This step is done under reduced stirring compared to the stirring of step (a1).
  • the stirring speed used in step (a2) is 25 rpm to obtain the mixed oxides according to the invention of Examples 1 -16.
  • the agitation must make it possible to control the dispersion based on lanthanum and on the rare earth (s) other than cerium and lanthanum within the reaction mixture comprising the precipitate of step (a1).
  • the mechanical stirring power P which is a large macroscopic representative of the quality of the mixture
  • a mechanical stirring power P (a2) used during step (a2) such that the ratio P (a2) / P (a1) is less than or equal to 0.10, or even less than 0.05.
  • This ratio can be between 0.0001 and 0.05.
  • Adapting the process to a new configuration may require to modify by successive tests the speed of step (a2) in order to obtain the mixed oxide of the invention.
  • step (a2) a suspension of a precipitate is obtained.
  • the next step (a3) of the process is the step of heating the precipitate suspension obtained in step (a2).
  • This heating can be carried out directly on the reaction mixture obtained at the end of step (a2) or on a suspension obtained after separation of the precipitate from the reaction mixture of step (a2), optional washing and return to water precipitate.
  • the suspension may be heated to a temperature of at least 100 ° C and even more preferably at least 130 ° C, or even at least 150 ° C.
  • the temperature may be between 100 ° C and 200 ° C, more particularly between 130 ° C and 200 ° C. It can be for example between 100 ° C and 160 ° C.
  • the heating operation can be conducted by introducing the liquid medium into a closed reactor (autoclave type).
  • the pressure in the closed reactor can vary between a value greater than 1 bar (10 5 Pa) and 165 bar (1 bar). , 65 ⁇ 10 7 Pa), preferably between 5 bar (5.10 5 Pa) and 165 bar (1.65 ⁇ 10 7 Pa). It is also possible to carry out heating in an open reactor for temperatures close to 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 1 and 48 hours, preferably between 1 and 24 hours.
  • the rise in temperature is carried out at a speed that is not critical, and one can thus achieve the fixed reaction temperature by heating the medium for example between 30 min and 4 h, these values being given entirely as indicative. It is possible to make several heats.
  • the precipitate obtained after the heating step and possibly a washing may be resuspended in water and then another heating of the medium thus obtained may be carried out. This other heating is done under the same conditions as those described for the first.
  • the next step (a4) of the process consists in adding to the precipitate from the previous step 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.
  • 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.
  • a surfactant which is chosen from those of the type ethoxylates of carboxymethylated fatty alcohols.
  • 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. These products may have the formula: R-O- (CR2R3-CR 4 R 5 -O) n - CH 2 -COOH wherein 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 comprising both -CH 2 -CH 2 -O groups. and -C (CH 3 ) -CH 2 -O-.
  • the addition of the texturing agent can be done in two ways. It can be added directly to the suspension resulting from step (a3). In this case, it is preferably added to a suspension whose temperature is at most 60 ° C. It may also be added to the solid precipitate after separation thereof by any known means from the medium in which the heating took place.
  • the amount of texturizing agent used expressed as a percentage by weight of texturing agent relative to the mixed oxide, is generally between 5% and 100%, more particularly between 15% and 60%.
  • the precipitate before carrying out the last stage of the process (calcination step), the precipitate is washed after having separated it from the medium in which it was in suspension. This washing can be done with water, preferably with water at basic pH, for example ammonia water.
  • step (a6) the recovered precipitate is then calcined to give the mixed oxide according to the invention.
  • This 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.
  • the mixed oxide having good thermal resistance it is possible to perform the calcination at a temperature which is greater than 825 ° C, or even greater than 900 ° C, or even greater than 950 ° C.
  • This temperature may be between 825 ° C. and 1100 ° C., or even between 950 ° C. and 1100 ° C.
  • the duration of the calcination is not critical and depends on the temperature. As a guide only, it may be at least 2 hours, more particularly between 2 and 4 hours.
  • the mixed oxide which is obtained in step (a6) may be optionally milled to obtain powders of the desired particle size.
  • a hammer mill may be used.
  • the powder of the mixed oxide may have a mean diameter d 5 o determined by laser diffraction over a volume distribution of between 0.5 and 50.0 ⁇ .
  • the preparation of the mixed oxide according to the invention may be based on the conditions of Examples 1 -4.
  • 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 in admixture with at least one mineral material.
  • the inorganic material may be chosen from alumina, titanium oxide, cerium oxide, zirconium oxide, silica, spinels, zeolites, silicates, crystalline silicoaluminium phosphates, calcium phosphates and the like. crystalline aluminum.
  • 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 that 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 a catalytic converter comprising a coating layer as described is used.
  • the specific surfaces are determined automatically using a Tristar II 3020 Micromentics device on samples in accordance with the indications recommended by the manufacturer.
  • the samples are pretreated in vacuo for 15 minutes at 300 ° C. It is necessary to desorb the species possibly adsorbed on the surface.
  • the measurement is made on 5 points in the range of relative pressures p / po ranging from 0 to 0.3 inclusive. The equilibrium time for each point is 5 s.
  • a Micromeritics Autopore IV 9500 device was used with a powder penetrometer according to the instructions recommended by the manufacturer.
  • the two solutions previously prepared are stirred constantly.
  • the solution of nitrates of cerium and zirconium is introduced in 45 min into the stirred reactor which contains the ammonia solution and whose stirring is set at a speed of 200 rpm (80 Hz).
  • the solution of lanthanum nitrates and yttrium is introduced in 15 min into the stirred reactor whose stirring is this time set at 25 rpm (10 Hz).
  • a suspension of precipitate is obtained.
  • the suspension is cast in a stainless steel autoclave equipped with a stirrer.
  • the suspension is heated with stirring at 150 ° C for 2 hours.
  • it is allowed to cool to a temperature below 60 ° C. and 1.65 kg of lauric acid are added to the suspension.
  • the suspension is stirred for 1 hour.
  • the solid product obtained is then calcined in air at 950 ° C. for 3 hours to recover about 5 kg of mixed oxide.
  • Example 4 Preparation of 5 kg of mixed oxide ZrO 2 (59%) - CeO 2 (35.5%) - 2 O 3 (5.5%)
  • the two solutions previously prepared are stirred constantly.
  • the solution of nitrates of cerium and zirconium is introduced in 45 min into the stirred reactor which contains the ammonia solution and whose stirring is set at a speed of 200 rpm (80 Hz).
  • the solution of lanthanum nitrates and yttrium is introduced in 15 min into the stirred reactor whose stirring is this time set at 25 rpm (10 Hz).
  • a suspension of precipitate is obtained.
  • the suspension is cast in a stainless steel autoclave equipped with a stirrer.
  • the suspension is heated with stirring at 150 ° C for 2 hours.
  • it is allowed to cool to a temperature below 60 ° C. and 1.65 kg of lauric acid are added to the suspension.
  • the suspension is stirred for 1 hour.
  • the solid product obtained is then calcined in air at 950 ° C. for 3 hours to recover about 5 kg of mixed oxide.
  • Examples 2-3 and 5-16 the mixed oxides according to these examples were prepared in the same way as for example 1 so as to recover 5 kg of mixed oxide. More precisely, an aqueous solution of nitrates of cerium and zirconium is prepared on the one hand and an aqueous solution of lanthanum nitrates and, optionally, rare earths other than cerium and lanthanum, on the other hand. The total volume of the two solutions is 125 liters. The aqueous solution of cerium and zirconium nitrate is introduced in 45 min in the same reactor as that of Example 1, containing 125 liters of aqueous ammonia solution and whose stirring is set at a speed of 200 ° C. / min (80 Hz).
  • the amount of ammonia is such that there is a stoichiometric ammonia excess of 40 mol% relative to the cations that are present in the two solutions of nitrates. Then, the other solution of nitrates is introduced in 15 min into the stirred reactor whose stirring is this time set at 25 rpm (10 Hz). A suspension of precipitate is obtained.
  • the suspension is cast in a stainless steel autoclave equipped with a stirrer.
  • the suspension is heated with stirring at 150 ° C for 2 hours. Then, it is allowed to cool to a temperature below 60 ° C. and 1.65 kg of lauric acid are added to the suspension.
  • the suspension is stirred for 1 hour.
  • the solid product obtained is then calcined under air for 3 hours at a calcination temperature of at least 825 ° C to recover about 5 kg of mixed oxide.
  • Comparative Example 17 15 kg of mixed oxide ZrO 2 (60%) - CeO 2 (30%) - 2 O 3 (5%) - Y 2 O 3 (5%) are prepared
  • the nitrate solution is introduced into the reactor with constant stirring.
  • the solution obtained is placed in a stainless steel autoclave equipped with a stirrer.
  • the temperature of the medium is brought to 150 ° C. for 2 hours with stirring.
  • After cooling to a temperature below 60 ° C. 4.95 kg of lauric acid are added to the suspension thus obtained.
  • the suspension is stirred for 1 hour.
  • the suspension is then filtered, and then the precipitate is washed with ammonia water at a rate of once the volume of the mother liquors filtration.
  • the product obtained is then heated at 825 ° C. for 3 hours to recover about 15 kg of mixed oxide.
  • Comparative Example 18 13 kg of mixed oxide Zr0 2 (60%) - CeO 2 (30%) - 2 O 3 (5%) - Y 2 O 3 (5%) are prepared
  • stirring is introduced with a solution of ammonia (30 liters at 12 mol / L) and then complete with distilled water so as to obtain a total volume of 108.3 liters of basic solution. This makes it possible to ensure a stoichiometric excess of ammonia of 40 mol% relative to the cations to be precipitated.
  • the two solutions previously prepared are stirred constantly.
  • the solution of nitrates of cerium and zirconium is introduced in 45 min into the stirred reactor which contains the ammonia solution and whose stirring is set at a speed of 125 rpm (50 Hz).
  • the solution of lanthanum nitrates and yttrium is introduced in 15 min and stirring in the stirred reactor whose stirring is this time set at 100 rpm (40 Hz).
  • a suspension of precipitate is obtained.
  • the suspension is cast in a stainless steel autoclave equipped with a stirrer.
  • the suspension is heated with stirring at 150 ° C for 2 hours.
  • 4.29 kg of lauric acid are added to the suspension.
  • the suspension is stirred for 1 hour.
  • the suspension is then filtered, and then the precipitate is washed with water.
  • the product obtained is then calcined in air at 825 ° C. for 3 hours to recover the 13 kg.
  • Table 1 describes the prepared oxides.
  • the mixed oxides of Examples 1-16 illustrate the invention and were prepared according to the process of the invention under the conditions of Example 1.
  • the mixed oxides of Examples 17-22 were prepared according to the method of Comparative Example 17 or Comparative Example 18.
  • T ca i designates the temperature at which the recovered precipitates are calcined (step (a6) of process). In any case, the calcination at this stage lasts 3 h.
  • Sicai / 3h therefore denotes the BET specific surface area of the "fresh" mixed oxide as it is obtained at the end of the preparation process.
  • the mixed oxide of Example 8 can be compared directly to that of Comparative Example 21 because the two mixed oxides have the same proportions of oxides and were obtained after calcination at the same temperature of 825 ° C. (Table I) .
  • the mixed oxide of Example 8 has higher specific surface areas, a smaller diameter D p , 100 ° C./4 h and a higher R factor than that of Comparative Example 21.
  • the variation D p , noo ° c / 4h - Dp, 9oo ° c / 4h is less.
  • the mixed oxide of Example 10 can be compared directly to that of Comparative Example 22 because the two mixed oxides have the same proportions of oxides and were obtained after calcination at the same temperature of 950 ° C.
  • Example 10 has higher specific surface areas, a smaller diameter D p , i 100 ° c / 4h and a higher R factor than that of Comparative Example 22.
  • Example 19 impregnation of mixed oxides with a salt of Rh '"
  • the mixed oxides of Examples 1, 17 and 18 (having the same proportions of Zr-Ce-La-Y-Nd 60-30-5-6-0 oxides) are impregnated with Rh m nitrate.
  • the mixed oxide is contacted with a solution of Rh nitrate, the volume thereof being greater than the total pore volume, then the water is evaporated and calcined at 500 ° C. for 4 hours. of rhodium relative to the catalyst as a whole is 0.1% by weight.
  • Example 20 Aging of the mixed oxides impregnated with Example 19
  • the aging is carried out on the aging bench in redox medium, with an alternating injection every 5 min of 2% CO and 2% O2 in the presence of 10% H 2 O (the% CO, O2 and H 2 O are given in volume).
  • the gas flow rate used is 70 cc / min under PTN conditions and the weight of the impregnated mixed oxide tested is 2.5 g.
  • the last injection is oxidizing (2% O2).
  • the aging temperature is 1100 ° C for a total of 6 hours.
  • the programmed temperature reduction makes it possible to determine the volume of hydrogen consumed by a sample when it is subjected to a programmed temperature under a controlled gas flow itself.
  • the device consists of a series of solenoid valves to control the passage of gases, a series of mass flowmeters for fixing the flow rates in the different lines, a series of selection valves to guide the flows gaseous, of a quartz reactor (U-shape) containing the sample and connected to the gas pipes (down flow reactor, the temperature is taken by a thermocouple located in the reactor), a furnace in which the reactor is placed, an H 2 O trap and a katharometer (TCD) which makes it possible to analyze the constituents of the gas mixture.
  • a quartz reactor U-shape
  • TCD a katharometer
  • a computer manages the automatisms with the software MICROMERITICS Autochem II 2920 and makes it possible to collect in real time the data relating to the current experiment. It also performs the processing to translate this data into curves using the Grams / 32 software. Conditions of analysis by TPR
  • the TPR is carried out by carrying the sample at 900 ° C. under a flow of hydrogen (H 2 / Ar at 10% vol H 2 ) according to a temperature ramp of 10 ° C./min from the ambient temperature, after having carried the sample at 500 ° C in the presence of 10% 0 2 .
  • Pr used (° C) (m 2 / g) (nm) (m 2 / g) (m 2 / g) (m 2 / g) (nm)

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EP17725667.4A 2016-04-26 2017-04-25 Oxyde mixte a base de cérium et de zirconium Pending EP3448812A1 (fr)

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FR1653698A FR3050450A1 (fr) 2016-04-26 2016-04-26 Oxyde mixte a base de cerium et de zirconium
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WO2021012107A1 (en) * 2019-07-19 2021-01-28 Rhodia Operations Mixed oxide based on cerium and zirconium
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WO2024033516A1 (en) 2022-08-12 2024-02-15 Rhodia Operations Cerium- and zirconium-based mixed oxide

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WO2017187085A1 (fr) 2017-11-02
CN114715935A (zh) 2022-07-08
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US11547982B2 (en) 2023-01-10
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