WO2022128770A1 - Composition à base d'oxyde de zirconium et d'oxyde de cérium à capacité améliorée de régénération, son procédé de production et son utilisation en tant que catalyseur - Google Patents

Composition à base d'oxyde de zirconium et d'oxyde de cérium à capacité améliorée de régénération, son procédé de production et son utilisation en tant que catalyseur Download PDF

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WO2022128770A1
WO2022128770A1 PCT/EP2021/085154 EP2021085154W WO2022128770A1 WO 2022128770 A1 WO2022128770 A1 WO 2022128770A1 EP 2021085154 W EP2021085154 W EP 2021085154W WO 2022128770 A1 WO2022128770 A1 WO 2022128770A1
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ions
composition according
weight
ion beam
cerium
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PCT/EP2021/085154
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English (en)
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Lionel Ventelon
Simge DANACI
David Fauchadour
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Agc Glass Europe
AGC Inc.
Agc Flat Glass North America, Inc.
Agc Vidros Do Brasil Ltda
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Publication of WO2022128770A1 publication Critical patent/WO2022128770A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
    • B01J23/46—Ruthenium, rhodium, osmium or iridium
    • B01J23/464—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
    • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/56—Platinum group metals
    • B01J23/63—Platinum group metals with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/10—Noble metals or compounds thereof
    • B01D2255/102—Platinum group metals
    • B01D2255/1025—Rhodium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2061—Yttrium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2063—Lanthanum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B01D2255/2065—Cerium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20715—Zirconium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01D2255/407—Zr-Ce mixed oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/01—Engine exhaust gases
    • B01D2258/014—Stoichiometric gasoline engines
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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

  • Zirconium oxide and cerium oxide based composition with improved ability for regeneration, method for the production and use thereof as a catalyst
  • the present invention relates to a composition based on zirconium oxide and cerium oxide with improved ability for regeneration , to its method of preparation and to its use as a catalyst.
  • the present invention relates to a catalyst system, in particular a multifunctional catalyst system, and more particularly, to a multifunctional catalyst regeneration system with enhanced catalyst regeneration effect that may can increase the poisoning removal effect of a catalyst built in an multifunctional catalyst reactor.
  • catalysts are used for the treatment of exhaust gases from internal combustion engines.
  • Multifunctional catalysts are understood to mean those capable of carrying out not only oxidation, in particular of carbon monoxide and hydrocarbons present in exhaust gases, but also reduction, in particular of nitrogen oxides also present in these gases.
  • Such multifunctional catalysts are also called three-way catalysts.
  • Zirconium oxide and cerium oxide appear to be two particularly important and advantageous constituents for this type of catalyst.
  • Catalysts that have improved ability for regeneration have a higher performance, within lower temperature ranges.
  • Catalyst deactivation may be caused by thermal, chemical, and physical factors. There are several deactivation pathways of catalysts, in particular carbon deposition, chemical poisoning, thermal degradation and sintering. Catalyst deactivation leads to an deterioration of the catalyst performance which may be observed as an increase in the reducibil ity temperature.
  • the term "reducibility” is understood to mean, here and for the rest of the description, the capacity of the catalyst to be reduced in a reducing atmosphere and to be reoxidized in an oxidizing atmosphere. This reducibility can be measured by the capacity to capture hydrogen at different temperatures. This is due among others to the cerium in the case of compositions of the type of those of the invention, cerium having the property of being reduced or of being oxidized. When the catalyst is deactivated, reducibility decreases and, as a consequence, higher temperatures are needed to capture hydrogen than before deactivation.
  • reaction temperature for example from 700°C to 800°C then to 700°C.
  • Catalysts deactivated by coke formation or other heavy products may be regenerated by temperature-controlled O2 injection.
  • SCR catalysts particularly in a an industrial environment, may be exposed to a large amount PM (Particulate Matter), such as non-hydrocarbon (HC) and soot, in addition to nitrogen oxides (NOx) and sulfur oxides (SOx).
  • PM Porate Matter
  • NOx nitrogen oxides
  • SOx sulfur oxides
  • the object of the invention is therefore a catalyst with improved ability for regeneration.
  • the present invention relates to catalyst compositions and catalyst systems presenting an improved ability for regeneration.
  • lanthanides is understood to mean elements of the group formed by the elements of the Period Table with an atomic number lying between 57 and 71 included.
  • the present invention concerns catalyst compositions based on zirconium oxide and cerium oxide comprising a zirconium oxide proportion of at least 30% by weight and a cerium oxide proportion of at least 25% by weight, further comprising at least 0.5% by weight, expressed as the oxide, of at least one dopant element, chosen from lanthanides other than cerium and from yttrium.
  • compositions of the present invention are furthermore implanted with ions of nitrogen, argon or oxygen, resulting in the creation of free electrons in the composition’s lattice.
  • the compositions thus comprise ions of nitrogen, argon or oxygen.
  • compositions of the invention may have a temperature at which 50% of NOx conversion is reached after ageing and regeneration Tso(regen) that is at most 1.1 x T 5 O , T50 being the temperature at which 50% of NOx conversion is reached before ageing.
  • Tso(regen) that is at most 1.1 x T 5 O
  • T50 being the temperature at which 50% of NOx conversion is reached before ageing.
  • Tso(regen) is at most 1.08 x T50, advantageously at most 1 .05 x T50 , more advantageously at most 1 .03 x T50.
  • compositions of the invention are of the mixed oxide type, based on zirconium oxide and cerium oxide as main components. They may also include at least one dopant element chosen from lanthanides other than cerium and from Group III elements. In this case, the compositions may therefore be in particular ternary or quaternary compositions.
  • the aforementioned at least one dopant element may more particularly be chosen from lanthanum, neodymium, praseodymium, samarium, yttrium, gadolinium and scandium.
  • the compositions of the invention may in particular be chosen among compositions comprising zirconium, cerium, yttrium and lanthanum or zirconium, cerium, and yttrium.
  • the contents of the various constituents in the compositions of the invention may vary. These contents are expressed here, and for the rest of the description, as mass percentage of the constituent’s oxide (ZrO2, CeO2 and TR2O3, TR denoting the dopant, yttrium and/or a lanthanide other than cerium) relative to the overall composition.
  • the zirconium content is at least 30%, particularly at least 40%, even more particularly at least 45%, and even more particularly at least 47%. Furthermore, the zirconium content is at most 65%, more particularly at most 62% and even more particularly at most 55%.
  • the cerium content is generally at least 25%, more particularly at least 30% and even more particularly at least 35%.
  • cerium content is at most 65%, more particularly at most 62% and even more particularly at most 55%.
  • the content of a dopant is at least 0.5%.
  • the content of a dopant is usually at most 15% and it may be more particularly at most 10%, and it may be between 3% and 10%.
  • compositions of the invention optionally further comprise precious metals.
  • the nature of these metals and the techniques of incorporating them into these compositions are well known to those skilled in the art.
  • the metals may be platinum, rhodium, palladium or iridium, and they may especially be incorporated into the compositions by impregnation.
  • Other methods are also known in the art for preparing metal comprising catalyst compositions, such as coprecipitation, impregnation-precipitation, sol-gel deposition, physical vapor deposition, chemical vapor deposition, atomic layer deposition, electroplating, underpotential deposition, cementation, transmetalation, and flame spray pyrolysis.
  • the inventors have surprisingly found that the ion implanted compositions of the present invention most surprisingly show an improved ability for regeneration, compared to the non-implanted starting material.
  • the process of the present invention allows for the manufacture catalysts that show high performance after regeneration.
  • compositions of the invention that do not comprise precious metals may be essentially characterized by the fact that they have a maximum reducibility temperature of surface Ce(IV) of at most 400° C.
  • This maximum reducibility temperature may be at most 385° C and even more particularly at most 370° C.
  • this maximum temperature may be between 300° C and 400° C and especially between 330° C and 370° C.
  • compositions of the invention that do not comprise precious metals may be essentially characterized by the fact that they have a maximum reducibility temperature of bulk Ce(IV) of at most 550° C.
  • This maximum reducibility temperature may be at most 540° C and even more particularly at most 530° C.
  • this maximum temperature may be between 500° C and 540° C and especially between 530° C and 540° C.
  • compositions of the invention that do comprise precious metals may be essentially characterized by the fact that they have a maximum reducibility temperature of surface Ce(IV) of at most 140° C This maximum reducibility temperature may be at most 120° C and even more particularly at most 110° C. Thus, this maximum temperature may be between 70° C and 140° C and especially between 80° C and 110° C.
  • compositions of the invention that do comprise precious metals may be essentially characterized by the fact that they have a maximum reducibility temperature of bulk Ce(IV) of at most 290° C.
  • This maximum reducibility temperature may be at most 280° C and even more particularly at most 270° C.
  • this maximum temperature may be between 220° C and 290° C and especially between 240° C and 270° C.
  • the reducibility of the compositions is determined by measuring their capacity to capture hydrogen as a function of temperature. This measurement is also used to determine a maximum reducibility temperature that corresponds to the temperature at which hydrogen capture is a maximum and in which, in other words, the reduction of cerium (IV) to cerium (III) is also at a maximum.
  • compositions of the invention are characterized by the fact that they have free electrons trapped in the lattice, in particular due to the implantation of ions.
  • Electron paramagnetic resonance spectroscopy (EPR) is used to determine the number free electrons trapped in the lattice.
  • Electron paramagnetic resonance spectroscopy (EPR) is also called Electron Spin Resonance Spectroscopy (ESR) and is a well-known method for studying unpaired electrons in any materials.
  • compositions of the present invention may be provided with at least 3 x 10 14 free electrons per gram in the lattice.
  • the preparation of the starting material for the compositions of the present invention is well known. Generally it may comprise the following steps: a. a mixture comprising a zirconium compound, a cerium compound and, a compound of an aforementioned dopant element is formed; b. said mixture is brought into contact with a basic compound, by means of which a precipitate is obtained; c. said precipitate is separated and then calcined, forming a calcined precipitate; d. optionally, a precious metal is incorporated into the calcined precipitate; e.
  • the starting material generally obtained as a powder, prepared according to steps (a) to (d) are the implanted with ions of nitrogen, argon or oxygen.
  • the step (a) of the method therefore consists in preparing a mixture in a liquid medium of a zirconium compound, a cerium compound and optionally at least one compound of the additional aforementioned element.
  • the mixing is generally carried out in a liquid medium, which is preferably water.
  • the compounds are preferably soluble compounds. These may especially be zirconium, cerium, lanthanide, and yttrium salts. These compounds may be chosen from nitrates, sulphates, acetates, chlorides and ceric ammonium nitrates.
  • zirconium sulphate zirconyl nitrate or zirconyl chloride.
  • zirconyl nitrate is used.
  • cerium (IV) salts such as, for example, nitrates or ceric ammonium nitrates, which are particularly suitable here.
  • Ceric nitrate may be used. It is advantageous to use salts with a purity of at least 99.5% and more particularly at least 99.9%.
  • An aqueous ceric nitrate solution may for example be obtained by the reaction of nitric acid on a hydrated ceric oxide prepared conventionally by reacting a solution of a cerous salt, for example cerous nitrate, with an ammonia solution in the presence of hydrogen peroxide. It is also possible in particular to use a ceric nitrate solution obtained by the method of electrolytic oxidation of a cerous nitrate solution, as described in the document FR-A-2570087, which constitutes here an advantageous raw material.
  • the aqueous solutions of cerium salts and zirconyl salts may have a certain initial free acidity, which can be adjusted by the addition of a base or an acid.
  • an initial solution of cerium and zirconium salts having actually a certain free acidity as mentioned above and solutions that will have been neutralized beforehand to a greater or lesser extent.
  • This neutralization may be carried out by the addition of a basic compound to the aforementioned mixture so as to limit this acidity.
  • This basic compound may for example be an ammonia solution or a solution of alkali metal (sodium, potassium, etc.) hydroxides, but preferably an ammonia solution.
  • the starting mixture contains a cerium compound in which cerium is in the Ce(lll) form
  • an oxidizing agent for example hydrogen peroxide.
  • This oxidizing agent may be used by being added to the reaction mixture during step (a) or during step (b), especially at the end of the latter step.
  • sol denotes any system consisting of fine solid particles of colloidal dimensions, that is to say dimensions of between about 1 nm and about 500 nm, based on a zirconium or cerium compound, this compound generally being a zirconium or cerium oxide and/or hydrated oxide, in suspension in an aqueous liquid phase, said particles furthermore optionally being able to contain residual amounts of bonded or adsorbed ions, such as for example nitrate, acetate, chloride or ammonium ions.
  • the zirconium or cerium may be either completely in the form of colloids, or simultaneously in the form of ions and in the form of colloids.
  • step (b) of the method said mixture is brought into contact with a basic compound.
  • base or basic compound it is possible to use products of the hydroxide type. Mention may be made of alkali metal or alkaline-earth metal hydroxides. It is also possible to use secondary, tertiary or quaternary amines. However, amines and aqueous ammonia may be preferred in so far as they reduce the risks of contamination by alkali metal or alkaline-earth metal cations. Mention may also be made of urea.
  • the basic compound is generally used in the form of an aqueous solution.
  • the way in which the mixture and the solution are brought into contact with each other is not critical. However, this contacting may be carried out by introducing the mixture into the solution of the basic compound. This variant is preferable in order to obtain compositions in the form of solid solutions.
  • the contacting or the reaction between the mixture and the solution, especially the addition of the mixture into the solution of the basic compound, may be carried out in a single step, gradually or continuously, and it is preferably performed with stirring. It is preferably carried out at room temperature.
  • the product obtained may optionally be dried, by methods well known o the person skilled in the art., before the calcination step. Drying may be performed for example in an oven at a temperature of 100°C for more than 6 hours, for example up to 12 hours.
  • Step (c) of the process is a calcination step.
  • the calcination takes place in an oxidizing atmosphere, for example in air.
  • the calcination is generally carried out at a temperature of between 300 and 1000° C. for a time of generally at least 30 minutes.
  • the calcination is carried out at a temperature of between 300 and 600°C, more advantageously between 400 and 500°C, even more advantageously between 450 and 550°C.
  • the calcination is carried out for a duration of between 2 to 4 hours.
  • a precious metal chosen from platinum, rhodium, palladium or iridium is incorporated into the composition, for example by impregnation, or magnetron sputtering.
  • the compositions of the invention may be employed in combination with precious metals.
  • precious metals The nature of these metals and the techniques of incorporating them into these compositions are well known to those skilled in the art.
  • the metals may be platinum, rhodium, palladium or iridium, and they may especially be incorporated into the compositions by impregnation or magnetron sputtering.
  • the starting material of resulting of steps (a) to (d) is implanted with ions selected among the ions of nitrogen, argon, and oxygen.
  • This ion implantation step comprises providing an ion beam, implanting the starting material with an ion beam dose per weight of starting material, comprised between 4.2 x 1 O 18 ions/g and 4 x 1 O 19 ions/g comprising monocharged or monocharged and multicharged ions with an energy of the monocharged ions in the ion beam from at least 10 keV to at most 100 keV;
  • the ion beam is generated by a plasma filament ion beam source or an electron cyclotron resonance (ECR) plasma source, such as an ECR Plasma Immersion ion implantation (PHI) or preferably an ECR plasma confined with permanent magnets.
  • ECR electron cyclotron resonance
  • PHI ECR Plasma Immersion ion implantation
  • PHI ECR plasma confined with permanent magnets.
  • the catalyst starting material is provided on a support and is mixed intermittently or continuously, so as to uniformly distribute the implanted ions in the catalyst starting material.
  • a carrier or support is used that provides continuous mixed during implantation for example a vibrating plate or bowl, a rotary bowl or a rotary drum.
  • the carrier combines rotating and vibrating movements. It has been observed that the resulting implanted catalyst material is more homogeneously implanted when continuous mixing is provided, such as for example in a rotary bowl or drum.
  • the catalyst starting material on the support shall advantageously form a layer of catalyst starting material having a thickness that is larger than the implantation depth of the ions in the catalyst starting material to avoid implanting ions in the support.
  • At least part of the ions are derived from argon atoms, oxygen atoms and/or nitrogen atoms.
  • At least part of the ions, preferably all ions, are derived from nitrogen atoms.
  • At least 50% of the ions preferably at least 75% of the ions, more preferably at least 90% of the ions, even more preferably at least 95% of the ions and most preferably 100% of the ions are derived from nitrogen atoms.
  • At least part of the ions are derived from argon atoms.
  • At least 50% of the ions preferably at least 75% of the ions, more preferably at least 90% of the ions, even more preferably at least 95% of the ions and most preferably 100% of the ions are derived from argon atoms.
  • the energy E of the monocharged ions in the ion beam is at least 10 keV, preferably at least 20 keV, more preferably at least 30 keV, even more preferably at least 40 keV and most preferably at least 50 keV.
  • the energy E of the monocharged ions in the ion beam is at most 100 keV, preferably at most 90 keV, more preferably at most 80 keV, even more preferably at most 70 keV and most preferably at most 60 keV.
  • the energy E of the monocharged ions in the ion beam is at least 10 keV to at most 100 keV, preferably at least 20 keV to at most 90 keV, more preferably at least 30 keV to at most 80 keV, even more preferably at least 40 keV to at most 70 keV and most preferably at least 50 keV to at most 60 keV.
  • the ion beam comprises a mixture of differently charged ions, and therefore each differently charged ion may have a different energy. This is the result that the energy of the ions in the ion beam is the results of being accelerated by a voltage, preferably the extraction voltage.
  • a nitrogen ion beam may comprise 58% N + ; 32%N 2+; 9%N 3+ and 1 %N +4 .
  • the ion beam is made up of 58% of nitrogen ions with an energy of 40 keV, 32% of nitrogen ions with an energy of 80 keV, 9% of nitrogen ions with an energy of 120 keV and 1 % of nitrogen ions with an energy of 160 keV.
  • the ion beam has an average charge (g avr ) of at least 1.00 to at most 5.00, preferably at least 1.10 to at most 3.00, more preferably at least 1 .20 to at most 2.00, even more preferably at least 1 .30 to at most 1 .75 yet even more preferably at least 1 .40 to at most 1 .60 and most preferably at least 1 .50 to at most 1 .55.
  • g avr is the sum of all the charges in the ion beam divided by the number of ions in the ion beam.
  • the monocharged ions in the ion beam have an average energy (E avr ) of least 10 keV to at most 100 keV, preferably at least 20 keV to at most 90 keV, more preferably at least 30 keV to at most 80 keV, even more preferably at least 40 keV to at most 70 keV and most preferably at least 50 keV to at most 60 keV.
  • E avr is the sum of all the energy values in the ion beam divided by the number of ions in the ion beam. Therefore, an ion beam with an g avr of 1 .53 which is extracted by an extraction voltage of 40 kV has an E a vr of 61 .2 keV.
  • the ions with the highest energy in the ion beam have an energy of at most 200 keV. In some embodiments, the ions with the lowest energy in the ion beam have an energy of at least 10 keV.
  • the ion beam is generated by an ECR plasma confined with permanent magnets.
  • the ion beam source comprises a mono- and multicharged ions plasma confined with permanent magnets which is generated by electron cyclotron resonance (ECR) using a high frequency, such as 2.45, 7.50 or 10.00 GHz.
  • ECR electron cyclotron resonance
  • a monocharged ion is an ion bearing a single positive charge
  • a multicharged ion is an ion bearing more than one positive charge.
  • the ion beam is then extracted to generate mono-multi-energies ions beam penetrating more deeply in the catalytic starting material.
  • Plasma filament ion beam sources and ECR Plasma Immersion ion implantation (PHI) sources generate molecular ions with lower charges states which have the drawbacks to be heavier with less energy, in others words to have reduced depth ranges to treat nanoparticles or catalyst.
  • the ion beam dose is at least 10 13 ions/cm 2 , preferably at least 10 14 ions/cm 2 , even more preferably at least 10 15 ions/cm 2 at the point of contact with the catalyst starting material, where the catalyst starting material is considered to be forming an essentially flat surface
  • the ion beam dose is at most 10 18 ions/cm 2 , preferably at most 10 17 ions/cm 2 , even more preferably at most 10 16 ions/cm 2 at the point of contact with the catalyst starting material, where the catalyst starting material is considered to be forming an essentially flat surface.
  • the ion beam dose is at least 10 13 ions/cm 2 to at most 10 18 ions/cm 2 , preferably at least 10 14 ions/cm 2 to at most 10 17 ions/cm 2 , even more preferably at least 10 15 ions/cm 2 to at most 10 16 ions/cm 2 at the point of contact with the catalyst starting material, where the catalyst starting material is considered to be forming an essentially flat surface.
  • the total ion beam dose is split into m separate doses, and wherein the catalytic starting material is mixed or stirred each time between the m different ion implantation treatments, preferably m is at least 4 to at most 64, more preferably at least 8 to at most 32, even more preferably at least 12 to at most 24 and most preferably at least 16 to at most 18.
  • An amount of powder may be spread over a given area or surface and exposed to the ion beam m times to obtain a total ion dose.
  • the powder may be mixed and may be spread again over the original area to allows to obtain a homogeneous treatment for the powder starting material.
  • m is at least equal to the ratio of the mean thickness of the powder spread over a given area and the mean free path of the ions inside the powder. The free path being the path ions travel inside the powder before they are stopped by the powder.
  • the advancement step of the ion beam is at least 1 % to at most 50%, preferably at least 2% to at most 40%, more preferably at least 5% to at most 30%, even more preferably at least 7% to at most 20% and most preferably at least 10% to at most 15%.
  • the ion beam may move in a series of round trips separated by a distance corresponding to a fraction of the ion beam diameter called advancement step.
  • a step of 10% for a beam with a diameter of 22.5 mm, means that for each round trip a shift of 2.25 mm is performed.
  • the advancement step may result in a high surface homogeneity of the treatment, preferably regardless the intensity distribution of the ion beam, which may be for instance be a Gaussian shape with more intensity at the centre and less intensity at the periphery.
  • the method comprises n different implanting steps with n multiple doses Xi, preferably wherein each dose Xi is X/n, X being the total ion beam dose, i.e. the sum of the n doses .
  • the different implanting steps differ by at least one implantation parameter, e.g. different ions may be used in different steps.
  • n is at most 3, more preferably n is at most 2, and most preferably n is 1 .
  • the method comprises implanting the catalyst starting material with an ion beam that is performed at a pressure of at most 10’ 4 Torr, preferably at most 10’ 5 Torr, more preferably at most 10’ 6 Torr and most preferably at most 10’ 7 Torr.
  • noble gas such as Ar, Kr or Xe
  • lower vacuum levels such as lower than 10’ 4 Torr, preferably lower than 10’ 5 Torr, more preferably lower than 10’ 6 Torr and most preferably lower than 10’ 7 Torr.
  • These noble gasses at least partially supress the static electricity induced by the ion implantation of the catalytic material.
  • the pressure in the treatment chamber is at least 3x1 O’ 6 Torr, preferably at least 5x1 O’ 6 Torr more preferably at least 7x1 O’ 6 Torr, even more preferably at least 10x1 O’ 6 Torr and most preferably at least 20x1 O’ 6 Torr.
  • These vacuum levels help to at least partially neutralize electrostatic barrier induced by the implanted ions.
  • the catalyst starting material is provided on a carrier or support comprising means for dissipating an static charges.
  • the support may comprise or consist of an electrically conducting material, such as a metal, and be electrically grounded.
  • the ion implantation dose is usually expressed using the unit ions/cm 2 .
  • This dosage may be calculated using the following formula (units omitted): wherein D is the dosage [ions/cm 2 ], I is the ion beam current [A], t is the implantation time [s], S is the surface area [cm 2 ], q is the elementary charge 1.6x1 O’ 19 [Coulomb], This formula is easily adapted for mixtures of single charge and multicharge ions.
  • the ion dose is conveniently expressed using the unit ions/g.
  • This dosage may be calculated using the following formula (units omitted): wherein, with the units in square brackets, D is the dosage [ions/cm 2 ], I is the ion beam current [A], t is the implantation time [s], Q is the quantity of implanted catalyst starting material [g], q is the elementary charge 1.6x10’ 19 [Coulomb], This formula is easily adapted for mixtures of single charge and multicharge ions.
  • this dosage can be derived from the dosage expressed in ions/cm 2 and the surface density o , in g/cm 2 , of the evenly distributed catalyst starting material as follows:
  • compositions that are the result of any possible combination of the embodiments hereinabove.
  • compositions of the invention are in the form of powders, but they may optionally be formed into granules, beads, cylinders or honeycombs of varying dimensions. These compositions may be applied to any support normally used in the catalysis field, that is to say, in particular, thermally inert supports. This support may be chosen from alumina, titanium oxide, cerium oxide, zirconium oxide, silica, spinels, zeolites, silicates, crystalline silicon aluminum phosphates and crystalline aluminum phosphates.
  • compositions may also be used in catalytic systems.
  • These catalytic systems may include a wash coat having catalytic properties and based on these compositions, on a substrate for example of the metal or ceramic monolith type.
  • the wash coat may itself include a support of the type of those mentioned above. This wash coat is obtained by mixing the composition with the support so as to form a suspension that may then be deposited on the substrate.
  • catalytic systems and more particularly the compositions of the invention, may have very numerous applications. They are thus particularly well suited to, and therefore usable in, the catalysis of various reactions such as, for example, dehydration, hydrosulfurization, hydrodenitrification, desulfurization, hydrodesulfurization, dehydrohalogenation, reforming, steam reforming, cracking, hydrocracking, hydrogenation, dehydrogenation, isomerization, dismutation, oxychlorination and dehydrocyclization of hydrocarbons or other organic compounds, oxidation and/or reduction reactions, the Claus reaction, the treatment of internal combustion exhaust gases, demetalization, methanation, shift conversion, catalytic oxidation of soot emitted by internal combustion engines, such as diesel or petrol engines operating in lean mode. Finally, the catalytic systems and the compositions of the invention may be used as NOx traps.
  • the invention also relates to the use of a composition or of a catalytic system such as those described above for the manufacture of a catalyst for automobile postcombustion exhaust treatment.
  • Item 1 Composition based on zirconium oxide and cerium oxide comprising a zirconium oxide proportion of at least 30% by weight and a cerium oxide proportion of at least 25% by weight, further comprising at least 0.5% by weight, expressed as the oxide, of at least one dopant element, chosen from lanthanides other than cerium and from yttrium, characterized in that it has a temperature at which 50% of NOx conversion is reached after ageing and regeneration Tso(regen) that is at most 1.1 x T50 , T50 being the temperature at which 50% of NOx conversion is reached before ageing
  • Composition according to item 1 characterized in that it comprises at least one dopant element chosen from lanthanum, neodymium, praseodymium, samarium and yttrium.
  • Item 3 Composition according to any one of the preceding items, characterized in that it comprises a zirconium oxide proportion of at least 40% by weight, more particularly at least 45% by weight.
  • Tso(regen) is at most 1 .08 x T50, preferably at most 1 .05 x T50, more preferably at most 1 .03 x T50.
  • composition according to any one of the preceding items, characterized in that it comprises a cerium oxide proportion by weight of at most 65%, particularly at most 62% and even more particularly at most 55%.
  • composition according any one preceding item characterized in that it comprises no precious metal.
  • Item 7 Composition according to any one of items 1 to 5, characterized in that it comprises a precious metal chosen from platinum, palladium and rhodium.
  • Item 8 Composition according to any one of the preceding items, characterized in that it comprises a cerium oxide proportion by weight of at most 65%, particularly at most 62% and even more particularly at most 55%.
  • Item 9. Composition according to any one preceding item characterized in that it comprises at least 3 x 10 14 free electrons per gram in the composition’s lattice.
  • Item 10 Method of preparing a composition according to one of the preceding items, characterized in that it comprises the following steps: a. providing a starting material based on zirconium oxide and cerium oxide comprising a zirconium oxide proportion of at least 30% by weight and a cerium oxide proportion of at least 25% by weight, further comprising at least 0.5% by weight, expressed as the oxide, of at least one dopant element, chosen from lanthanides other than cerium and from yttrium and optionally further comprising a precious metal chosen from platinum, palladium and rhodium; b. providing an ion beam; c.
  • implanting the starting material with an ion beam dose comprised between 4.2 x 10 18 ions/g and 4 x 10 19 ions/g comprising monocharged or monocharged and multicharged ions with an energy of the monocharged ions in the ion beam from at least 10 keV to at most 100 keV.
  • Item 11 Method according to item 10 characterized in that the starting material comprises at least one dopant element chosen from lanthanum, neodymium, praseodymium, and yttrium.
  • Item 12 Method according to any one of items 10 to 11 characterized in that the starting material comprises a zirconium oxide proportion of at least 40% by weight, more particularly at least 45% by weight.
  • Item 13 Method according to any one of items 10 to 12 characterized in that the starting material comprises a cerium oxide proportion by weight of at most 65%, particularly at most 62% and even more particularly at most 55%.
  • Item 14 Method according to any one of items 10 to 13 characterized in that the starting material comprises characterized in that it comprises no precious metal.
  • Item 15 Method according to any one of items 10 to 13 characterized in that the starting material comprises characterized in that it comprises a precious metal chosen from platinum, palladium and rhodium.
  • Item 16 Method according to any one of items 10 to 15 characterized in that the starting material comprises a cerium oxide proportion by weight of at most 65%, particularly at most 62% and even more particularly at most 55%.
  • Item 17 Method according to any one of items 10 to 16, wherein the ion beam is generated by a plasma source selected from a. a plasma filament ion beam source or b. an electron cyclotron resonance plasma source, selected among c. a ECR Plasma Immersion ion implanter or d. an electron cyclotron resonance plasma confined with permanent magnets.
  • a plasma source selected from a. a plasma filament ion beam source or b. an electron cyclotron resonance plasma source, selected among c. a ECR Plasma Immersion ion implanter or d. an electron cyclotron resonance plasma confined with permanent magnets.
  • Item 18 Method according to any one of items 10 to 17, wherein at least part of the ions or all ions, are derived from argon atoms, oxygen atoms and/or nitrogen atoms.
  • Item 19 Method according to any one of items 10 to 18, wherein the ion beam dose is implanted with an energy of the monocharged ions in the ion beam from at least 15 keV to at most 50 keV.
  • Catalytic system characterized in that it comprises a composition according to one of items 1 to 9.
  • Item 21 Method of treating the exhaust gases of internal combustion engines, characterized in that a catalytic system according to item 19 or in that a composition according to one of items 1 to 9 is used as catalyst.
  • catalytic tests are performed in the following manner: a. 2.5 g catalytic test material is mixed with 10g of inert cordierite powder having a granulometry of ⁇ 60pm; b. The mixture obtained is inserted in a tubular packed bed reactor c. A thermocouple is inserted into the mixture and the tubular reactor is placed in a tubular furnace and provided with a glass inlet at one end and with a gas outlet at the other end d. A rich gas mixture is provide at a gas hourly space velocity of 35000 per hour; e. The temperature is progressively increased and the percentage of NOx conversion is continuously determined at the outlet.
  • Tonset is the temperature at which the NOx conversion starts and 1 -5% of NOx is converted.
  • T10 is the temperature at which 10% of NOx conversion is reached, Tso is the temperature at which 50% of NOx conversion is reached.
  • the ageing of the catalytic material is performed by heating the tubular reactor as prepared herein above at steps a, b, and c of the catalytic test, optionally after one or more NOx conversion measurements, under a flow of air for 2 hours at 900°C. All tested catalytic material show a loss of activity in the catalytic test after this ageing process.
  • the regeneration of the catalytic material is performed by: a. Heating the tubular reactor at a rate of 5°C per minute under flow of rich gas mixture up to 500°C, b. Maintaining the tubular reactor for 1 hour at 500°C under a flow of air, c. Cooling the tubular reactor under a flow of air to room temperature
  • the temperatures and durations may be adapted to simulate real usage conditions of a catalytic system.
  • the regeneration steps can be repeated with or without an intermittent catalytic test.
  • the starting material from 0.5 to 16g, is placed in a microimplantor designed by the company Ionics, including an ECR (Electron Cyclotron Resonance) ion source powered by a 10 GHz and 50 W HF amplifier, and an ion extraction system of 10 kV (kiloVolt).
  • ECR Electro Cyclotron Resonance
  • kV kiloVolt
  • the plasma of the ion source is confined by permanent magnets allowing the production of monocharged and multicharged ions).
  • the starting material, particles agglomerated in powder form, are provided in a vibrating bowl, centered below the ion beam.
  • the diameter of the powder at its surface is slightly larger than the diameter of the diameter of the ion beam.
  • the pressure in the treatment chamber is kept at 10’ 5 mbar.
  • the treatment is done with a mixture of mono and multicharged nitrogen ions, in the case of nitrogen ions for example 58% N + 32%, N 2+ , 9% N 3+ , and 1 % N 4+ , extracted by an extraction voltage of for example 35 kV.
  • nitrogen ions for example 58% N + 32%, N 2+ , 9% N 3+ , and 1 % N 4+
  • an extraction voltage for example 35 kV.
  • the mean charge state is 1.53 and the mean energy E avr equals 53 keV at the extraction voltage above.
  • the total dose can be implanted uniformly, without interruption, while the bowl was kept vibrating.
  • Tonset, T10 and T50 are determined on the starting material and on the ion implanted examples on the freshly prepared sample (T onS et/io/5o(fresh)), then on these samples after one ageing cycle (T onset/10/50 (aged)), and then on these samples, regenerated after ageing (T onset/10/50 (regen.), one regeneration cycle).
  • T onS et/io/5o(fresh) the freshly prepared sample
  • T onset/10/50 (aged) then on these samples after one ageing cycle
  • T onset/10/50 regenerated after ageing
  • T50 after ageing and regeneration is more than 10% higher than T50 before ageing, whereas for Example 1 , T50 after ageing and regeneration is less than 1 .5% higher than T50 before ageing.

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Abstract

La présente invention concerne une composition à base d'oxyde de zirconium et d'oxyde de cérium comprenant une proportion d'oxyde de zirconium d'au moins 30 % en poids et une proportion d'oxyde de cérium d'au moins 25 % en poids, comprenant en outre au moins 0,5 % en poids, exprimé en tant qu'oxyde, d'au moins un élément dopant, choisi parmi les lanthanides autres que le cérium et l'yttrium. La composition est caractérisée en ce qu'elle présente une température à laquelle 50 % de conversion de NOx est atteint après T50(regen) de vieillissement et régénération, c'est-à-dire au plus de 1.1 χ T50, T50 étant la température à laquelle 50 % de conversion de NOx est atteint avant le vieillissement. L'invention concerne également le procédé de fabrication de ladite composition. La présente invention concerne en outre un système catalytique et un procédé de traitement des gaz d'échappement de moteurs à combustion interne utilisant ladite composition.
PCT/EP2021/085154 2020-12-17 2021-12-10 Composition à base d'oxyde de zirconium et d'oxyde de cérium à capacité améliorée de régénération, son procédé de production et son utilisation en tant que catalyseur WO2022128770A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2570087A1 (fr) 1984-09-13 1986-03-14 Rhone Poulenc Spec Chim Procede d'oxydation electrolytique et ensemble d'electrolyse pour sa mise en oeuvre
US20050282698A1 (en) * 2004-06-22 2005-12-22 Southward Barry W Particulate filter device and exhaust treatment system, and methods of regenerating the same
US20130052108A1 (en) * 2010-01-11 2013-02-28 Rhodia Operations Composition containing oxides of zirconium, cerium and another rare earth having reduced maximum reducibility temperature, a process for preparation and use thereof in the field of catalysis
WO2019238701A1 (fr) * 2018-06-12 2019-12-19 Agc Glass Europe Procédé de préparation de nanoparticules catalytiques, de surfaces catalytiques et/ou de catalyseurs

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2570087A1 (fr) 1984-09-13 1986-03-14 Rhone Poulenc Spec Chim Procede d'oxydation electrolytique et ensemble d'electrolyse pour sa mise en oeuvre
US20050282698A1 (en) * 2004-06-22 2005-12-22 Southward Barry W Particulate filter device and exhaust treatment system, and methods of regenerating the same
US20130052108A1 (en) * 2010-01-11 2013-02-28 Rhodia Operations Composition containing oxides of zirconium, cerium and another rare earth having reduced maximum reducibility temperature, a process for preparation and use thereof in the field of catalysis
WO2019238701A1 (fr) * 2018-06-12 2019-12-19 Agc Glass Europe Procédé de préparation de nanoparticules catalytiques, de surfaces catalytiques et/ou de catalyseurs

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
NANCY ARTIOLI ET AL: "Ion beam surface engineering for highly active nanocatalysts OW-403-1", CONFERENCE PROCEEDINGS ARTICLE, 17 June 2015 (2015-06-17), NAM, Pittsburg, USA, XP055524968 *

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