Classifications

• • 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
  • B01D53/9404—Removing only nitrogen compounds
  • B01D53/9409—Nitrogen oxides
  • B01D53/9413—Processes characterised by a specific catalyst
  • B01D53/9422—Processes characterised by a specific catalyst for removing nitrogen oxides by NOx storage or reduction by cyclic switching between lean and rich exhaust gases (LNT, NSC, NSR)
• • 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
  • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
• • 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
  • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/32—Manganese, technetium or rhenium
  • B01J23/34—Manganese
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/20—Metals or compounds thereof
  • B01D2255/202—Alkali metals
  • B01D2255/2022—Potassium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/20—Metals or compounds thereof
  • B01D2255/202—Alkali metals
  • B01D2255/2027—Sodium
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01D—SEPARATION
  • B01D2255/00—Catalysts
  • B01D2255/20—Metals or compounds thereof
  • B01D2255/204—Alkaline earth metals
  • B01D2255/2042—Barium
• • 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
  • B01D2255/2073—Manganese
• • 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
  • B01D2258/012—Diesel engines and lean burn gasoline engines

Definitions

• the present invention relates to compositions which can be used as NOx traps, based on manganese and an alkali or an alkaline earth, and their use in the treatment of exhaust gases.
• NOx nitrogen oxides
• the present invention relates to compositions which can be used as NOx traps, based on manganese and an alkali or an alkaline earth, and their use in the treatment of exhaust gases.
• NOx nitrogen oxides
• the reduction of emissions of nitrogen oxides (NOx) from the exhaust gases of automobile engines in particular is carried out using “three-way” catalysts which use the reducing gases present in the mixture stoichiometrically. Any excess oxygen results in a sudden deterioration in the performance of the catalyst.
• certain engines such as diesel engines or gasoline engines operating in lean burn are fuel efficient but emit exhaust gases which permanently contain a large excess of oxygen of at least 5% for example.
• a standard three-way catalyst therefore has no effect on NOx emissions in this case.
• the limitation of NOx emissions is made imperative by the tight
• NOx traps which are capable of oxidizing NO to NO2 and then adsorbing the NO2 thus formed. Under certain conditions, the NO2 is released and then reduced in 2 by reducing species contained in the exhaust gases.
• These NOx traps still have certain drawbacks, however. Thus, their optimal operating range is located in a relatively low temperature zone, generally between 200 ° C and 270 ° C and they are little or not effective at higher temperatures. It would therefore be interesting to have a system that can operate at temperatures higher than those of current systems. In addition, they may have low thermal stability in a hydrothermal medium or in an oxidizing medium at high temperature. Improving this stability would therefore be an advantage. In addition, they are generally based on precious metals. However, these metals are expensive and their availability can be problematic. It would also be interesting to have catalysts free of precious metals to reduce costs.
• the object of the invention is therefore the development of a composition which can be used as a NOx trap at high temperatures and, possibly, in the absence of precious metal.
• Another object of the invention is to provide a NOx trap with good thermal stability.
• rare earth is understood for the whole of the description the elements of the group constituted by yttrium and the elements of the periodic classification with atomic number included inclusively between 57 and 71.
• the oxygen storage capacity to which reference is made in this description is determined by a test which evaluates the capacity of the support or of the product to successively oxidize injected quantities of oxygen carbon monoxide and to consume injected quantities oxygen to reoxidize the product.
• the method used is said to be alternate.
• the carrier gas is pure helium at a flow rate of 101 / h.
• the injections are made via a loop containing 16ml of gas.
• the injected quantities of CO are carried out using a gas mixture containing 5% of CO diluted in helium while the injected quantities of O2 are made from a gaseous mixture containing 2.5% of ⁇ 2 diluted in l 'helium.
• the gas analysis is carried out by chromatography using a thermal conductivity detector.
• the quantity of oxygen consumed makes it possible to determine the oxygen storage capacity.
• the characteristic value of the oxygen storage capacity is expressed in ml of oxygen (under normal conditions of temperature and pressure) per gram of product introduced and it is measured at 400 ° C.
• the oxygen storage capacity measurements given in the description are made on products pretreated at 900 ° C. in air for 6 hours in a muffle furnace.
• the compositions of the invention comprise a support and an active phase.
• the term support must be taken in a broad sense to designate, in the composition, the majority element (s) and / or either without catalytic activity or own trapping activity, or having a catalytic activity or trapping not equivalent to that of the phase active; and on which or on which the other elements are deposited.
• the active phase is based on manganese and at least one other element A chosen from alkali metals and alkaline earth metals.
• alkaline element mention may be made more particularly of sodium and potassium.
• alkaline earth element there may be mentioned in particular barium.
• the composition may include one or more elements A, any reference in the following description to element A must therefore be understood as being able to also apply in the case where there are several elements A.
• the manganese and A elements are present in the composition of the invention in a chemically bound form.
• a chemically bound form By this is meant that there are chemical bonds between the manganese and the element A resulting from a reaction between them, these two elements not being simply juxtaposed as in a simple mixture.
• the elements manganese and A can be present in the form of a compound or of a phase of mixed oxide type.
• This compound or this phase may in particular be represented by the formula A x Mn y 2 ⁇ ⁇ ⁇ 0) of years which 0.5 ⁇ y / x ⁇ 6, the value of ⁇ depends on the nature of the element A and the oxidation state of manganese.
• phase or compound of formula (1) there may be mentioned by way of example those of the vernadite, hollandite, romanechite or psilomelane, bimessite, todorokite, buserite or lithiophonte type.
• the compound can optionally be hydrated.
• the compound can moreover have a lamellar structure of the Cdl type.
• the formula (1) is given here by way of illustration, it would not be departing from the scope of the present invention if the compound had a different formula insofar as of course the manganese and the element A are well chemically linked.
• the degree of oxidation of manganese can vary between 2 and 7 and, more particularly between 3 and 7.
• this element and manganese can be present in the form of a compound of type K 2 Mn 4 O 8
• barium it can be a compound of type BaMnO
• the invention covers the case where the active phase consists essentially of manganese and one or more other elements A chosen from alkali and alkaline earth metals, manganese and element A being chemically linked.
• consists essentially is meant that the composition of the invention may have a NOx trap activity in the absence in the active phase of any element other than manganese and the element (s) A, such as for example an element of the precious metal or other metal type used usually in catalysis
• compositions of the invention also comprise a support.
• a support any porous support which can be used in the field of catalysis can be used. It is preferable that this support has chemical inertness with respect to the manganese and A elements sufficient to avoid a substantial reaction of one or of these elements with the support which would be likely to hinder the creation of a chemical bond between the manganese and the element A However, in the case of a reaction between the support and these elements, it it is possible to use larger quantities of manganese and of element A to obtain the desired chemical bond between these elements
• This support can be based on alumina Any type of alumina capable of having a specific surface can be used HERE sufficient for application in catalysis.
• aluminas resulting from the rapid dehydration of at least one aluminum hydroxide, such as baye ⁇ te, hydrargillite or gibbsite, nordstrandite, and / or from at least one aluminum oxyhydroxide such as boehmite , pseudoboehmite and diaspore
• stabilizing element mention may be made of rare earths, barium, silicon, titanium and zirconium.
• rare earth mention may be made very particularly of cerium, lanthanum or the lanthanum-neodymium mixture.
• the preparation of the stabilized alumina is carried out in a manner known per se, in particular by impregnating the alumina with solutions of salts, such as nitrates, of the abovementioned stabilizing elements or else by co-drying of an alumina precursor and salts of these elements then calcination
• the support can also be based on an oxide chosen from cerium oxide, zirconium oxide or their mixtures
• this phase corresponds in fact to that of a cenic oxide Ce ⁇ 2 cubic crystallized and whose mesh parameters are more or less offset with respect to a pure ceric oxide, thus reflecting the incorporation of zirconium in the crystal lattice of cerium oxide, and therefore obtaining a true solid solution. Mention may also be made for mixtures of cerium oxide and zirconium oxide based on these two oxides and in addition of scandium oxide or of a rare earth other than cerium, and in particular those described in the application. WO patent
• compositions have a specific surface after calcination for 6 hours at
• the support is based on cerium oxide and it further comprises silica. Supports of this type are described in patent applications EP-A-207857 and EP-A-547924, the teaching of which is incorporated here.
• the total content of manganese, alkaline, and alkaline earth can vary within wide limits. The minimum content is that below which NOx adsorption activity is no longer observed. This content can be in particular between 2 and 50%, more particularly between 5 and 30%, this content being expressed in atomic% by ratio to the sum of the moles of oxide (s) of the support and of the elements concerned in the active phase.
• the respective contents of manganese, alkaline, and alkaline earth can also vary within wide proportions, the manganese content can be in particular equal to, or close to that of alkaline or alkaline earth
• the alkali is potassium in a content (as expressed above) which can be between 10 and 50% and more particularly between 30 and 50%
• compositions of the invention can be prepared by a process in which the support is brought into contact with manganese and at least one other element A or with precursors of manganese and at least one other element A and in which calcination is carried out the whole at a temperature sufficient to create a chemical bond between the manganese and the element A.
• salts one can choose the salts of inorganic acids such as nitrates, sulfates or chlorides.
• the salts of organic acids and in particular the salts of saturated aliphatic carboxylic acids or the salts of hydroxycarboxylic acids.
• the support is then impregnated with the solution or the slip. More particularly, dry impregnation is used. Dry impregnation consists in adding to the product to be impregnated a volume of an aqueous solution of the element which is equal to the pore volume of the solid to be impregnated. It may be advantageous to deposit the elements of the active phase in two stages. Thus, it is advantageous to deposit the manganese in a first step then the element A in a second.
• the support After impregnation, the support is optionally dried and then it is calcined. It should be noted that it is possible to use a support which has not yet been calcined prior to impregnation.
• the deposition of the active phase can also be done by atomization of a suspension based on salts or compounds of the elements of the active phase and of the support.
• the atomized product thus obtained is then calcined.
• compositions for which the support is made of cerium oxide, element A is potassium are excluded from the present invention, in the proportions of Mn and K indicated and where the potassium and manganese precursor used in the preparation process, which has just been described, is potassium permanganate.
• the calcination is carried out, as indicated above, at a temperature sufficient to create a chemical bond between the manganese and the element A.
• This temperature varies according to the nature of the element A but, in the case of a calcination in air , it is generally at least 600 ° C, more particularly at least 700 ° C, it can in particular be between 800 ° C and 850 ° C. Higher temperatures are generally not necessary since the chemical bond between the manganese and the element A is already formed but on the other hand they can cause a reduction in the specific surface of the support likely to decrease the catalytic properties of the composition.
• the duration of the calcination depends in particular on the temperature and it is also fixed so as to be sufficient to create a chemical bond of the elements.
• compositions of the invention as described above are in the form of powders but they can optionally be shaped to be in the form of granules, beads, cylinders or honeycombs of variable dimensions.
• the invention also relates to a gas treatment process for the reduction of nitrogen oxide emissions using the compositions of the invention.
• gases capable of being treated by the present invention are, for example, those from gas turbines, boilers of thermal power stations or even internal combustion engines. In the latter case, they may in particular be diesel engines or of engines operating in lean mixture
• compositions of the invention function as NOx traps when they are brought into contact with gases which have a high oxygen content.
• the value ⁇ is correlated with the air / fuel ratio in a manner known per se, in particular in the field of internal combustion engines.
• Such gases can be those of an engine operating in a lean burn mixture and which have an oxygen content ( expressed in volume) for example at least 2% as well as those which have an even higher oxygen content, for example gases from engines of the diesel type, i.e. e of at least 5% or more than 5%, more particularly of at least 10%, this content being, for example, between 5% and 20%
• the invention also applies to gases of the above type which may further contain water in an amount of the order of 10% for example.
• the invention also relates to a system for the treatment of gases with a view to reducing the emissions of nitrogen oxides, gases which may be of the type of those mentioned above and very particularly those having an excess of oxygen relative to the value stoichiometric
• This system is characterized in that it comprises a composition as described above.
• it can comprise a coating (wash coat) with catalytic properties and based on these compositions, on a substrate of the type, for example metallic monolith or in ceramic
• the invention also relates to the use of the compositions in the manufacture of such a system. Examples will now be given.
• NOx trap evaluation test is carried out as follows:
• 0J5 g of the powdered NOx trap are loaded into a quartz reactor.
• the powder used was previously compacted, then ground and sieved so as to isolate the particle size range between 0J25 and 0.250 mm.
• the reaction mixture at the inlet of the reactor has the following composition (by volume):
• the overall flow rate is 30 Nl / h.
• the WH is around 150,000 h "1 .
• NOx NO + NO2
• NO and NOx signals are given by an ECOPHYSICS NOx analyzer, based on the principle of chemiluminescence.
• NOx traps are evaluated by determining the total amount of NOx adsorbed (expressed in mgNO / g of trap or active phase) until the trap phase is saturated. The experiment is repeated at different temperatures between 250 ° C and 500 ° C. It is thus possible to determine the optimal temperature zone for the operation of the NOx traps.
• Manganese nitrate Mn (N03) 2.4H 2 O, potassium nitrate KNO3 99.5%, barium nitrate Ba (N03) 2 99.5% and sodium nitrate NaNO 3 99.5% are used. .
• the supports used are HSA5 ® of Rhodia cerium oxide, a cerium oxide HSA1 ® of Rhodia, zirconium oxide comprising cerium oxide
• the active phase is based on manganese with another element A which is K, Ba or Na
• the elements are impregnated on the support one after the other.
• the operating protocol is as follows: - Dry impregnation of the first element
• HSA5 ® support for Examples 9 and 10 the HSA514® carrier, for Example 11 the carrier ZrO 2 / CeO 2 and for Example 12 the HSA1® support.
• SBET stands for the specific surface B.E.T. determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 established from the BRUNAUER - EMMETT-TELLER method described in the periodical 'The Journal of the American Chemical Society, 60, 309 (1938) ".
• the RX analysis only shows the CeO 2 phase.
• the RX analysis reveals the CeO 2 phase and a K 2 Mn 4 O 8 type phase referenced in the JCPDS files 16-0205. Analysis by microscopy shows the presence of large crystals formed by Mn and K from 200nm to 300nm approximately. Manganese is in oxidation states III and IV.
• the RX analysis reveals the CeO 2 phase and a BaMnO 3 type phase.
• the RX analysis reveals the CeO 2 phase and a Na 07 MnO 2- ⁇ type phase.
• compositions of the invention there is a significant shift in Tmax towards high temperatures compared to compositions in which the manganese and the other element are not chemically linked. Furthermore, these compositions are effective in storing NOx even in the absence of platinum or another precious metal.
• EXAMPLE 13 This example illustrates the thermal stability of the compositions according to the invention.
• Example 4 The same composition is used as for Example 4, but calcined for 6 hours at 750 ° C. in a nitrogen atmosphere containing 10% by volume of hydrogen.
• the results in catalysis of the composition are given in the table below in which the results of Example 4 have also been reported for comparison: Table 3
• a support based on cerium oxide, zirconium oxide and lanthanum oxide is used in the respective proportions by weight CeO 2 / Zr ⁇ 2 / La 2 O 3 of 67/23/10 calcined 2 hours at 800 ° C.
• the amount of NOx stored is given in table 4 below.
• a support based on alumina calcined for 2 hours at 500 ° C. is used.
• a dry impregnation is carried out with manganese and potassium under the conditions described above and in the following molar proportions:
• the product After impregnation, the product is calcined for 6 hours at 750 ° C. It has an SBET surface of 129m 2 / g.
• the amount of NOx stored is given in table 5 below.

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• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Environmental & Geological Engineering (AREA)
• Health & Medical Sciences (AREA)
• Biomedical Technology (AREA)
• Combustion & Propulsion (AREA)
• Analytical Chemistry (AREA)
• General Chemical & Material Sciences (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Catalysts (AREA)
• Exhaust Gas Treatment By Means Of Catalyst (AREA)
• Treating Waste Gases (AREA)
• Exhaust Gas After Treatment (AREA)
• Solid-Sorbent Or Filter-Aiding Compositions (AREA)

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• 1999
  • 1999-04-12 FR FR9904524A patent/FR2791907B1/fr not_active Expired - Fee Related
• 2000
  • 2000-04-10 WO PCT/FR2000/000909 patent/WO2000061289A1/fr not_active Ceased
  • 2000-04-10 KR KR1020017012982A patent/KR20010108495A/ko not_active Ceased
  • 2000-04-10 EP EP00917174A patent/EP1171236A1/de not_active Withdrawn
  • 2000-04-10 MX MXPA01010287A patent/MXPA01010287A/es unknown
  • 2000-04-10 BR BR0009752-7A patent/BR0009752A/pt not_active IP Right Cessation
  • 2000-04-10 CA CA002367536A patent/CA2367536A1/fr not_active Abandoned
  • 2000-04-10 CN CN008078866A patent/CN1131724C/zh not_active Expired - Fee Related
  • 2000-04-10 JP JP2000610610A patent/JP2002540933A/ja active Pending
• 2001
  • 2001-10-10 NO NO20014931A patent/NO20014931L/no not_active Application Discontinuation

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