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WO2014202725A1 - Oxyde composite a base d'oxyde de cerium, d'oxyde de silicium et d'oxyde de titane - Google Patents

Oxyde composite a base d'oxyde de cerium, d'oxyde de silicium et d'oxyde de titane Download PDF

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Publication number
WO2014202725A1
WO2014202725A1 PCT/EP2014/062950 EP2014062950W WO2014202725A1 WO 2014202725 A1 WO2014202725 A1 WO 2014202725A1 EP 2014062950 W EP2014062950 W EP 2014062950W WO 2014202725 A1 WO2014202725 A1 WO 2014202725A1
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Prior art keywords
cerium
oxide
oxide precursor
solution
maintaining
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PCT/EP2014/062950
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English (en)
Inventor
Naotaka Ohtake
Toshihiro Sasaki
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Rhodia Operations
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Priority to EP14732863.7A priority Critical patent/EP3010639A1/fr
Priority to CN201480035338.9A priority patent/CN105431228B/zh
Priority to JP2016520492A priority patent/JP6463348B2/ja
Publication of WO2014202725A1 publication Critical patent/WO2014202725A1/fr

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    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • 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
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/08—Silica
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • 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
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/30—Silica
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/90—Physical characteristics of catalysts
    • B01D2255/92—Dimensions
    • B01D2255/9207—Specific surface
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/106—Ozone
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/40—Nitrogen compounds
    • B01D2257/404—Nitrogen oxides other than dinitrogen oxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B01D2257/502—Carbon monoxide
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7022—Aliphatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/702—Hydrocarbons
    • B01D2257/7027—Aromatic hydrocarbons
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
    • B01D2257/708—Volatile organic compounds V.O.C.'s
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/90—Odorous compounds not provided for in groups B01D2257/00 - B01D2257/708
    • 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

Definitions

  • the present invention concerns a composite oxide based on cerium oxide, silicon oxide and titanium oxide.
  • the present invention also concerns a process to obtain these composites, a catalytic system comprising said composite oxides and their use for the treatment of exhaust gases from internal combustion, notably by bringing into contact exhaust gases from internal combustion engines with these catalytic systems.
  • Multifunctional catalysts are currently used for the treatment of exhaust gases from internal combustion engines (automobile afterburning catalysis).
  • the term “multifunctional” is understood to mean catalysts 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, Cerium oxides today appear as constituents which are particularly important and advantageous for thi catalyst, notably for the conversion of noxious gases released by ciiesei engines either from mobiles sources or stationary sources.
  • the subject matter of the invention is thus the development of a composite oxide with simultaneously improved high specific surface area at high temperature and a high, acidity leading to low SOx adsorption and easier "desulfation properties" - ie. a SOx desorption in a lower temperature range than the existing materials.
  • the cerium composite oxide comprising silicon oxide and titanium, oxide of the invention is sufficiently acid, to provide a sulfur resistance and may nota used in the formulation of sulfur resistant diesel. catalyst.
  • the above-described a ler disadvantages of the prior art i!vn overcome by the composition of the invention.
  • the present invention then concerns a cerium, composite oxide comprising at least:
  • oxide in a proportion comprised between 1 and 20 % by weight of oxide, preferably i a proportion comprised between 5 and 15 % by weight of oxide.
  • the present invention also concerns a process to obtain these composite oxides, a catalytic system comprising said composite oxides and the use of them, for the treatment of exhaust gases from internal combustion, notably by bringing into contact exhaust gases from internal combustion engines with these catalytic systems.
  • the present invention concerns a precipitated and calcined composition based on cerium oxide, silicon oxide and titaniuni oxide as described.
  • the term “specific surface” is understood to mean, the RFT specific surface determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 laid down from, the Brunauer-Emmett-Teller method described in. the periodical “The Journal of the American Chemical Society, 60, 309 ( 1 38)" ,
  • the cerium oxide is in the form of eerie oxide (Ce0 2 ).
  • Silicon oxide is SiO : and titanium oxide is T1O2.
  • Composite oxides of the invention may exhibit a pH inferior or equal to 7, more preferably inferior or equal to 6, more preferably a pH comprised, between 1 and 6; wherein pH is measured, in an aqueous solution comprising 3 % by weight of this composition, at 25° C pH may notably be measured according to the following protocol; a composite oxide powder is dried at 2( ) 0°C for 1 hour and the dried oxide powder is hold in a desiccator for 30 minutes.
  • said oxide composites exhibit a specific surface area I ⁇ ⁇ '.
  • I- i i 1 M- calcination at 800°C for 2 hours comprised betwee n " » and 1.20 m 2 /g ; notably comprised between. 5 and I H him g.
  • Said oxide composites may also exhibit a specific surface area (SBET), after calcination at 900°C for 5 hours, comprised between 40 and 85 nr/g, notably comprised between 50 and 70 m /g.
  • Cerium composite oxide of the present invention may also comprise at least one rare earth element oxide, other than cerium oxide, notably in a proportion comprised between 1 and 15 % by weight of oxide, preferably in a proportion comprised between 1 and 10 % by weight of oxide.
  • rare earth element oxides, other than, cerium oxide may be used in the cerium composite oxide of the invention.
  • Rare earth element (REE) or rare earth metal is one of a set of seventeen chemical elements in the periodic table, specifically the fifteen lanthanides plus scandium and yttrium.
  • rare earth element oxide are chosen in the group consisting of: lanthanium oxide (La 2 C1 ⁇ 2) 5 praseodymium oxide (PrgOy)., neodymium oxide (!*3 ⁇ 4(3 ⁇ 4) and yttrium oxide (Y2O3).
  • the cerium composite oxide of the invention comprises at least:
  • oxide preferably in a proportion comprised between 60 and 95 % by weight of oxide ;
  • - a rare earth element oxide, other than cerium, oxide, in a proportion comprised between 1. and 15 % by weight, of oxide, preferably in a proportion comprised between 1 and 10 % by weight of oxide.
  • Cerium, oxide typically accounts for at least 50 % by weight of the oxide. Preferably cerium oxide is at least 60 % by weight. Cerium oxide typically does not exceed 98% by weight of the total weight of the oxide, preferably it does not exceed 95 % by weight.
  • the composite oxides of the present invention may be obtained according to several possible processes.
  • the process consists in a calcination of a precipitate comprising compounds f cerium and other compounds.
  • a precipitate is generally obtained by the addition of a basic compound. It is notably possible to heat the precipitate in an aqueous medium, before to dry and calcine the precipitate.
  • Compounds of silicon and titanium may notably be added before or after the precipitation of the cerium compound.
  • composition o the invention may notably be obtained by a method, for producing a composition comprising the steps of:
  • step (a) providing a cerium solution, in which preferably not less than 90 mol 1 vhich cerium ions are tetravalent, l b) heating and maintaining said cerium solution obtained from step (a) up to and. at not lower than 60°C,
  • a water-soluble cerium, compound which may be used in step (a) may ⁇ be, for example, a eerie nitrate solution or ammonium eerie nitrate, with the eerie nitrate solution being particularly preferred.
  • the initial concentration of the cerium solution may be adjusted to usually 5 to 100 g/L cerium, preferably more preferahl ⁇ 1 0 in 7(1 g I in terms of Ce(3 ⁇ 4.
  • step ( a ) provides a cerium solution in which not less than,. 90 mol % of which cerium ions are tetravalent.
  • a .rare earth element compound for example a rare earth element in the form of nitrate, chloride, oxide, carbonate, halide, oxyhalide, oxynitrate, and/or sulfate.
  • step (b) of heating and maintaining the cerium solution obtained from step (a) up to and at not lower than 60°C is carried out to cause reaction of the cerium solution
  • a reactor to be used in step (b) may either be a sealed- or open-type vessel.
  • An autoclave reactor may preferably be used.
  • the temperature at which the cerium solution is heated and maintained is not lower than 60°C, preferably 60 to 200°C, more preferably 80 to 180°C, most preferably 90 to 160°C.
  • the duration of heating and maintaining is usually 10 minutes to 48 hours, preferably
  • the first method further includes step ) i adding a precipitant to the cerium suspension obtained thr ⁇ heating and maintaining in si * ain a precipitate.
  • the precipitant used in step (c) may be a base, for example, sodium, hydroxide, potassium hydroxide, aqueous ammonia, ammoni gas, or a mixture thereof, with the aqueous ammonia being particularly preferred,
  • the precipitant maybe added, for example, by preparing an aqueous solution of the precipitant at a suitable concentration and adding the solution to the cerium suspension obtained from step (b) under stirring, or in the case of ammonia gas, by bubbling the cerium suspension with the ammonia gas in the reactor under stirring.
  • the amount of the precipitant to be added may easily be determined by monitoring the pH change of the suspension. Usually, the amount for generating a precipitate in the cerium suspension at pff 7 to 9, preferably pH 7 to 8,5 5 is sufficient.
  • Step (c) may be carried out after the cerium suspension obtained through the heating and maintaining in stt is cooled.
  • Such cooling may usually be carried out under stirring according to a commonly knov n method, I he cooling may either be natural, cooling by leaving the suspension to stand, or forced cooling with cooling tubes.
  • the cooling may be carried out down to usually 40°C or lower, preferably a room temperature of .20 to 30°C.
  • step (c) a slurry containing a precipitat of cerium oxide hydrate with grown crystals is obtained.
  • the precipitate may be separated by, for exanipl tsche method, centrifugation, or filter-pressing ; precipitate may optionally be washed, with water as needed. Further, in order to improve the efficiency following step (d), the precipitate may optionally be dried to a suitable level.
  • the first method includes step (d) of calcining the precipitate to obtain a cerium oxide.
  • the temperature for the calcining is usually 250 to 500°C, preferably 280 to 450°C.
  • the cerium, oxide obtained through calcination in step (d) is in the form of a porous body having pores of sufficient volume for impregnation with a solution of a silicon oxide precursor and titanium oxide precursor. This facilitates impregnation with a solution of a silicon oxide precursor and titanium oxide precursor and improves the heat resistance of the ultimate composite oxide.
  • the duration of the calcination may usually be 30 minutes to 36 hours, preferably 1 hour to 24 hours, more preferably 3 hours to 20 hours.
  • the first method includes step (e) of impregnating the cerium oxide obtained through calcination with a solution of a silicon, oxide precursor and a titanium oxide precursor,
  • the silicon, oxide precursor used in. step nay be any compound which may be converted to a silicon oxide through an oxidation, treatment, such as calcining, as long as the calcined cerium oxide porous body may be impregnated with the compound dissolved in a solvent.
  • the precursor may include silicates, such as sodium silicate, silane compounds, such as tetraethyl orthosiiicate, silyl compounds, such a: Ayisilyl. isocyanate, quaternary ajn.rn.on.iiim silicates, such as tetramethyl. ammonium silicate, and colloidal silica.
  • a rare earth element compound for example a rare earth element in. the form oi nitrate, chloride, oxide, carbonate, halide, oxyhalide, oxynitrate, and/or sulfate.
  • a rare earth element compound may be then added in step (a) and/or (e).
  • the first method includes step (f) of calcinating the cerium oxide thus impregnated with the solution of the silicon oxide precursor and titanium oxide precursor.
  • the temperature of the calcination is usually 300 to 900°C, preferably 450 to 750°C.
  • the duration of calcination in step (f) may suitably be determined in view of the calcination temperature, and may usually be 1 to 10 hours.
  • the cerium oxide impregnated with the solution of the silicon oxide precursor and titanium oxide precursor may optionally be dried at about 60 to 200°C, With such a drying step, the efficiency of the calcination in step (0 may be improved.
  • the cerium, oxide impregnated with the solution of the silicon oxide precursor and titanium, oxide precursor may optionally be mi. lied.
  • the milling may usually be catried. out by commonly known method, such as hammer milling or jet milling.
  • inventive composition may be prepared according to a method comprising the steps of:
  • cerium solution in which preferably not less than 90 mol 1 Aiefa cerium ions are tetravalent
  • the second .method according to the present invention includes step ( A) of providing a cerium solution not less than 90 mol % of which cerium ions are tetravalent.
  • a water-soluble cerium compound which may be used in step (A) may be, for example, a eerie nitrate solution or ammonium eerie nitrate, with the eerie nitrate solution being particularly preferred.
  • the initial concentration of the cerium, solution not less than mol % of w hich cerium ions are tetravalent may be adjusted to usually 5 to 100 g/L cerium, preferably 5 to 80 g/L , more preferably 10 to 70 g/L in terms of CeO .
  • water is used for the adjustment of the concentration, of the cerium solution, and deionized water is particularly preferred,
  • step I B of seating and maintaining the cerium, solution obtained from step (A) up to and at not lower than 60° C is carried out next.
  • a reactor to be used in step (B) may either be a sealed- or open-type vessel, and an autoclave reactor may preferably be used.
  • the temperature at which the cerium, solution, is heated and maintained is not lower than 60°C, preferably 60 to 200°C, more preferably 80 to 180°C, most preferably 90 to 160°C.
  • the duration of heating and maintaining is usually 10 minutes to 48 hours, preferably 15 minutes to 36 hours, more preferably 30 minutes to 10 hours.
  • the second method further includes step (C) of adding a silicon oxide precursor aod a titanium oxide precursor to a cerium suspension, obtained from step (B),
  • the silicon oxide precursor to be added to the cerium suspension may be any compound whkh in a be converted in ,i ilicon oxide through an. oxidation treatment, such as calcination, at y be, for example, colloidal silica, siliconate, or quaternary ammonium silicate sol, with the colloidal silica being particularly preferred in view of the production cost and reduction o environmental burden
  • the titanium oxide precursor to be a cerium suspension may be any compound which may be converted to a titanium oxide through an oxidation treatimeiit, such as calcination., and may be, for example, colloidal titania, titanium sulfate, titanium oxysuifate, titanium tetrachloride, titanium oxycMoride, titanium nitrate, titanium tetra-methoxide, titanium tetra-ethoxide, titanium tetra-propoxide, titanium tetra-butoxide, titanium tetra-acety
  • the amount of the silicon oxide precursor is usually 1 to 15 mass % of the silicon, oxide precursor, preferably 5 to 15 mass %, in. terms of SiO : with respect to the total amount of the silicon oxide precursor in terms of Si0 2 , the titanium, oxide precursor in terms of Ti0 2 and the cerium in terms of Ce0 2 .
  • step (C) the amount of the titanium oxide precursor is usually 1 to
  • the titanium oxide precursor preferably 5 to 15 mass %, in terms of Ti0 2 with respect to the total amount o the silicon oxide precursor in terms of SiO . 2, the titanium oxide precursor in terms of TiG 2 and the cerium in terms of Ce0 2 .
  • step (C) before adding the silicon oxide precursor and., the titanium. oxide precursor, the salt concentration, of the cerium suspension, may be adjusted by removing the mother liquor from, the cerium suspension or by adding water.
  • the removal of the mother liquor maybe effected, for example, by decantation, Nutsche method, centrifugation, or filter- pressing.
  • a slight amount of cerium is removed with the mother liquor, so the amount of the silicon, oxide precursor and titanium oxide precursor and water ded next may be adjusted, taking this removed amount of cerium into consideration, te I . ma) i3 ⁇ 4 carried out after the cerium, suspension obtained through the heating and maintaining in step ( 13 ) ⁇ ⁇ a «>ied.
  • Such cooling may usually be carried out under stirring according to a commonly known method.
  • the cooling may either be natural cooling by leaving the suspension to stand, or forced cooling with cooling tubes.
  • the cooling may be carried out down to usually 40°C or lower, preferably a room temperature of 20 to 30°C.
  • a rare earth element compound for example a rare earth element in the form of nitrate, chloride, oxide, carbonate, halide, oxyhalide, oxynitrate, and/or sulfate
  • a rare earth element compound may be then added in step ( ⁇ ) and/or ( ).
  • the second method includes step (D) of heating and maintaining the cerium suspension containing the silicon, oxide precursor and titanium oxide precursor up to and at not lower than 100°C, preferably 100 to 200°C, more preferably 100 to 1 50°C.
  • the duration of the heating and maintaining may be usually utes to 6 hours, preferably 20 minutes to 5 hours, more preferably 30 minutes to 4 hours.
  • step sating and maintaining at lower than 100°C 5 the crystallinity of the precipitate is not sufficiently high, resulting in insufficient heat resistance of the ultimate composite oxide.
  • the second method includes step (E) of adding a precipitant to the cerium suspension containing the silicon oxide precursor and titanium oxide precursor obtained through the heating and maintaining to obtain, a precipitate. commonly known method such as hammer milling or jet milling.
  • composite oxides of the invention as described above or as obtained by means of the preparation process previously described are in the form of powders, but they can optionally be formed so as to be in the form of granules, pellets, foams, beads, cylinders or honeycombs of variable dimensions.
  • composite oxides ca be applied to any support commonly used in the field of catalysis, that is to say in particular thermally inert supports.
  • This support can be chosen from alumina, titanium, oxide, cerium oxide,, zirconium, oxide, silica, spinels, zeolites, silicates, crystalline silicoaluminum phosphates or crystalline aluminum phosphates,
  • the present invention also concerns a composite oxide susceptible to be obtained according to the above mentioned processes o the invention.
  • the composite oxides of the invention may be used in. catalytic systems, These catalytic systems can comprise a coating (wash coat), based on these composite oxides and with catalytic properties, on a substrate of the metal or ceramic monolith type, for example, Such a monolith type can be a filter type based on silicon carbide, cordierite or aluminium titanate, for instance.
  • the coating can itself also comprise a support of the type of those mentioned above. This coating is obtained by mixing the composite oxides with the support, so as to form, a suspension which can subsequently be deposited on the substrate.
  • catalytic systems and more particularly the composite oxides of the invention can. have a great many applications. They are therefore particularly well suited to, and thus usable in, the catalysis of various reactions, such as, for example, dehydration, hydrosulfurization, hydrodenitri fi cation, desul fur ization, hydrodesul furi zation, dehydrohalogenation, reforming, steam reforming, cracking, hydrocracking, hydrogenation, dehydrogenation, isomerization, dismutation, oxychlorination, dehydrocyclization of hydrocarbons or other organic compounds, oxidation, and/or reduction reactions, the Clans reaction, treatment of exhaust gases from internal combustion engines, demetallation, methanation, the shift conversion, oxidation f CO, purification o air by low-temperature oxidation ( ⁇ 200°C, indeed even ⁇ 100°C), catalytic oxidation of the soot emitted by internal combustion engines, such as diesel. engines or petrol engines operating under lean burn conditions.
  • the composite oxides of the invention can be employed in combination with precious metals.
  • the nature of these metals and the techniques for the incorporation of the latter in these compositions are well known to a person skilled in. the art.
  • the metals can be platinum, rhodium, palladium, gold or iridium and they can, in particular, be incorporated in the compositions by impregnation.
  • the treatment of exhaust gases from internal combustion engines is a particularly advantageous application.
  • the compositions of the invention can. thus be used in this case for catalysis. More particularly still in the case of this use in catalysis, the compositions can be employed in combination with an NOx (nitrogen, oxides) trap for the treatment of exhaust gases torn petrol engines operating with a lean burn mixture, for example in the catalysis layer of such a trap.
  • NOx nitrogen, oxides
  • the composite oxides of the invention can be incorporated in oxidation catalysts for diesel engines.
  • the invention also relates very particularly to a process for the treatment of exhaust gases from internal combustion engines which is characterized in that use is made, as catalyst, of a composite oxide or of a catalytic system as described above.
  • the present invention also concerns then, a process for the purification, of air, said air comprising carbon monoxide, ethylene, aldehyde, amine, mercaptan, ozone, volatile organic compounds, atmospheric pollutants, fatty acids, hydrocarbons,, aromatic hydrocarbons, nitrogen, oxides or malodorous compounds, comprising the step of bringing into contact said gases with the catalytic system of the invention, Mention may more particularly be made, as compounds of this type, of ethanethiol, valeric acid and trimethylamine. This treatment is carried out by bringing the air to be treated into contact with a composite oxide or a catalytic system as described above or obtained by the processes described in detail above.
  • This example relates to a composite oxide of cerium, oxide, silicon oxide and titanium oxide at a mass ratio of 92.8:5.1 ;2.1.
  • This example relates to a composite oxide of cerium oxide, silicon oxide and titanium oxide at a mass ratio of 90.0:5.0:5,0 and prepared by a method different from Example 2.
  • a cerium oxide powder was prepared in accordance with the method disclosed in Patent Publication WO2003/022740.
  • This example relates to a composite oxide of cerium oxide and titanium oxide at a mass ratio of 98.0:2.0
  • a composite oxide powder mainly composed of cerium oxide ith 2.0 mass % of titanium oxide was prepared in the same way as in Example 1 except that the amount of a colloidal titania was 2.9 g U .0 g in terns of Ti ( 3 ⁇ 4) and colloidal silica was not added,
  • Thi example relates to a composite oxide of cerium oxide and titanium oxide at a mass ratio of d5.0:5 0
  • a composite oxide powder mainly composed of cerium, oxide with. 5.0 mass % of titanium oxide was prepared in the same way as in Example 1 except that the amount f a colloidal titania w terms of Ti0 2 ) and colloidal silica was riot added.
  • the properties of the composite oxide powder thus obtained were evaluated in the same way as in f aniple 1 and the results are shown in Table 1 , Comparative example 4
  • This example relates to a composite oxide of cerium oxide and titanium oxide at a mass ratio of 90.0:10.0.
  • a composite oxide powder mainly composed f cerium oxide with 10.0 mass % of titanium oxide was prepared in the same way as in Example 1 except that the amount of a colloidal titania was 16.0 g (5.3 g in terms of Ti0 2 ) and colloidal silica was not added.
  • This example relates to a composite oxide of cerium oxide and silicon oxide at a mass ratio of 95.0:5.0,
  • a composite oxide powder mainly composed of cerium oxide with 5.0 mass % of silicon oxide was prepared in the same way as in Example 1 except that colloidal titania was not added.
  • pH in the aqueous suspension The pH in the aqueous solution comprising 3% by weight of the oxide powder is measured in the following way. An oxide powder is dried at 200°C for 1 hour. The dried oxide powder is hold in the desiccator for 30 ' minutes. 3.0 g of thus obtained oxide powder is added into a 100 ml of deionized water under stirring. After 1 minute of stirring, a pH meter (HOR1BA D-51 ) is put into the slurry. The pH value is collected after 3 minutes of putting the pH meter.

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  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Environmental & Geological Engineering (AREA)
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  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Biomedical Technology (AREA)
  • Combustion & Propulsion (AREA)
  • Catalysts (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)

Abstract

La présente invention concerne un oxyde composite à base d'oxyde de cérium, d'oxyde de silicium et d'oxyde de titane. La présente invention concerne également un procédé pour obtenir ces composites, un système catalytique comprenant lesdits oxydes composites et leur utilisation pour le traitement de gaz d'échappement de combustion interne, notamment par la mise en contact des gaz d'échappement de moteurs à combustion interne avec ces systèmes catalytiques.
PCT/EP2014/062950 2013-06-21 2014-06-19 Oxyde composite a base d'oxyde de cerium, d'oxyde de silicium et d'oxyde de titane WO2014202725A1 (fr)

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EP14732863.7A EP3010639A1 (fr) 2013-06-21 2014-06-19 Oxyde composite a base d'oxyde de cerium, d'oxyde de silicium et d'oxyde de titane
CN201480035338.9A CN105431228B (zh) 2013-06-21 2014-06-19 基于氧化铈、氧化硅和氧化钛的复合氧化物
JP2016520492A JP6463348B2 (ja) 2013-06-21 2014-06-19 酸化セリウム、酸化ケイ素および酸化チタンをベースとする複合酸化物

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EPPCT/EP2013/062977 2013-06-21

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CN114751744A (zh) * 2021-01-19 2022-07-15 厦门稀土材料研究所 铈酸稀土基高熵陶瓷材料及其制备方法

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CN110270321A (zh) * 2019-07-04 2019-09-24 南京大学 一种铈硅复合氧化物的制备方法及其产物和应用
CN110302773B (zh) * 2019-07-12 2022-04-29 南京工业大学 一种用于含氯挥发性有机物催化燃烧的催化剂及其制备方法和应用
CN116272980B (zh) * 2023-03-29 2024-06-21 昆明理工大学 一种抗中毒催化剂及其制备方法和应用

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CN114751744A (zh) * 2021-01-19 2022-07-15 厦门稀土材料研究所 铈酸稀土基高熵陶瓷材料及其制备方法

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