EP3740312A1 - Procédé de fabrication d'un catalyseur scr à l'aide d'ultrasons - Google Patents

Procédé de fabrication d'un catalyseur scr à l'aide d'ultrasons

Info

Publication number
EP3740312A1
EP3740312A1 EP19701316.2A EP19701316A EP3740312A1 EP 3740312 A1 EP3740312 A1 EP 3740312A1 EP 19701316 A EP19701316 A EP 19701316A EP 3740312 A1 EP3740312 A1 EP 3740312A1
Authority
EP
European Patent Office
Prior art keywords
coating
catalyst
ultrasound
carrier
zeolite
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP19701316.2A
Other languages
German (de)
English (en)
Inventor
Benjamin BARTH
Martin Foerster
Morten Schonert
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Umicore AG and Co KG
Original Assignee
Umicore AG and Co KG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Umicore AG and Co KG filed Critical Umicore AG and Co KG
Publication of EP3740312A1 publication Critical patent/EP3740312A1/fr
Pending legal-status Critical Current

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    • B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
    • B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
    • B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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    • 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
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    • 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
    • B01D53/9418—Processes characterised by a specific catalyst for removing nitrogen oxides by selective catalytic reduction [SCR] using a reducing agent in a lean exhaust gas
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    • F01N2510/063—Surface coverings for exhaust purification, e.g. catalytic reaction zeolites
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/14—Nitrogen oxides
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
    • F01N2570/14—Nitrogen oxides
    • F01N2570/145—Dinitrogen oxide
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
    • F01N2610/00—Adding substances to exhaust gases
    • F01N2610/02—Adding substances to exhaust gases the substance being ammonia or urea
    • 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
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)

Definitions

  • the present invention is directed to a process for the production of autocatalysts, the catalysts themselves and their use.
  • an operating step is used in the production, which leads to a smaller particle size of the catalytically active material used.
  • the exhaust gas from internal combustion engines in motor vehicles typically contains the noxious gases carbon monoxide (CO) and hydrocarbons (HC), nitrogen oxides (NO x ) and optionally sulfur oxides (SO x ), as well as particles consisting predominantly of soot residues and optionally adhering organic agglomerates. These are called primary emissions.
  • CO, HC and particles are products of incomplete combustion of the fuel in the combustion chamber of the engine.
  • Nitrogen oxides are produced in the cylinder from nitrogen and oxygen in the intake air when the combustion temperatures locally exceed 1400 ° C. Sulfur oxides result from the combustion of organic sulfur compounds, which are always present in small amounts in non-synthetic fuels.
  • catalytic exhaust gas purification technologies In order to remove these environmental and health-related emissions from the exhaust gases of motor vehicles, a variety of catalytic exhaust gas purification technologies have been developed, the basic principle of which is usually based on the exhaust gas to be purified via a flow-through or wall-flow honeycomb body, or monolith (wall-flow) with a catalytically active coating applied to it.
  • the catalyst promotes the chemical reaction of various exhaust gas components to form innocuous products such as carbon dioxide and water.
  • the flow or wall flow monoliths just described are also referred to as catalyst supports, supports or substrate monoliths since they carry the catalytically active coating on their surface or in the walls forming this surface.
  • the catalytically active coating is frequently applied to the catalyst support in the form of a suspension in a so-called coating process.
  • US6478874 it is stated that a vacuum is used to draw a washcoat suspension from bottom to top through the channels of a substrate monolith.
  • US4609563 describes a process in which a metered charge system is used for the catalytic coating of a substrate.
  • This system comprises a method of coating a ceramic monolithic carrier with a precisely controlled, predetermined amount of washcoat suspension using a vacuum (hereinafter "metered charge").
  • the monolithic carrier is immersed in a quantified amount of washcoat suspension. Then the washcoat suspension is pulled through the vacuum into the substrate monolith.
  • it is difficult to coat the monolithic support so that the coating profiles of the channels in the monolithic support are uniform.
  • washcoatsuspension (metered charge) is applied to the top of a vertical substrate monolith, this amount being so large that it is retained almost completely within the intended monolith (US6599570).
  • a vacuum / pressure device acting on one of the ends of the monolith, the washcoat suspension is completely sucked / pressed into the monolith without excess suspension coming out at the bottom of the monolith (WO9947260A1). See also JP5378659B2, EP2415522A1 and JP2014205108A2 from Cataler in this connection.
  • the raw exhaust gas of, in particular, diesel engines or lean-burnt gasoline engines contains a relatively high oxygen content of up to 15% by volume.
  • particulate emissions are contained, which consist predominantly of soot residues and, where appropriate, organic agglomerates and result from a partially incomplete fuel combustion in the cylinder.
  • SCR selective catalytic reduction
  • this process is considered to be preferred for denitrification of lean engine exhaust gases.
  • the reduction of the nitrogen oxides contained in the exhaust gas takes place in the SCR process with the aid of a reducing agent metered into the exhaust gas line from an external source.
  • the reducing agent used is ammonia, which converts the nitrogen oxides present in the exhaust gas on the SCR catalyst into nitrogen and water.
  • the ammonia used as the reducing agent can be made available by metering in an ammonia precursor compound, such as urea, ammonium carbamate or ammonium formate, into the exhaust gas line and subsequent hydrolysis.
  • the SCR system can be arranged between a close-coupled diesel oxidation catalyst and a diesel particulate filter in the underbody of the vehicle (DOC-SCR-DPF) according to US20040098979A1 or before a unit of diesel oxidation catalytic converter and diesel particulate filter (SCR-DOC-DPF) according to WO2009156134A1.
  • DOC-SCR-DPF close-coupled diesel oxidation catalyst and a diesel particulate filter in the underbody of the vehicle
  • SCR-DOC-DPF unit of diesel oxidation catalytic converter and diesel particulate filter
  • Zeolites / zeotypes are often subdivided into large, medium and small pore zeolites / zeotypes according to the ring size of their largest pore openings.
  • Large pore zeolites / zeotypes have a maximum ring size of 12 and medium-pore zeolites / zeotype one of 10 tetrahedra atoms.
  • Small pore zeolite / zeotype (abbreviation: SPZ of small pore zeolite / zeotype) have a maximum Ring size of 8 tetrahedra atoms (see also: htp: //europe.iza-structure.org/lZA- SC / ftc table.php; WO2017080722A1).
  • SCR catalysts based on iron-exchanged ⁇ -zeolites ie a large-pore zeolite
  • SCR catalysts based on small-pore zeolites are becoming increasingly important, see, for example, W02008 / 106519A1, W02008 / 1 18434A1 and WO2008 / 132452A2.
  • WO2008 / 132452A2 describes a small-pore zeolite exchanged with copper, for example, which can be coated on a suitable monolithic substrate as washcoat or extruded into a substrate.
  • the washcoat may contain a binder selected from the group consisting of alumina, silica, (non-zeolitic) silica-alumina, natural toners, T1O2, ZrC> 2 and SnC> 2.
  • WO2013 / 060341 A1 describes SCR-active catalyst compositions from a physical mixture of an acidic zeolite or zeotypes in protonic form or in iron-promoted form with, for example, CU / Al 2 O 3.
  • W012075400A1 describes a catalyst composition consisting of a copper or iron containing CHA zeolite for SCR applications in which the average crystal size preferably has a majority of crystal sizes greater than about 0.5 pm.
  • the zeolites are applied to the supports as an aqueous washcoat suspension. Information on setting the grain size, for example by grinding in a ball mill or by means of other grinding methods, can not be found in the application.
  • zeolites or zeotypes are not only used in SCR catalysts. In diesel oxidation catalysts in particular, these often play a major role as hydrocarbon scavengers at low temperatures (HC trap). These have already been described as nitrogen oxides storage.
  • HC trap hydrocarbon scavengers at low temperatures
  • this mixture is applied after previous washing with water with or without admixing of a binder to the support, usually a flow-through carrier or wall-flow filter, by the coating techniques described above.
  • the coating can then be present on the walls of the carriers and / or in the pores of the walls forming the channels of the carriers.
  • Exemplary preparation variants of such catalysts can be found in WO02008 / 106519 A1 or WO02005 / 016497 A1. To homogenize the zeolite suspensions and to destroy powder agglomerates, they are usually treated with high-speed stirrers or ball mills before or after the ion exchange and before the coating process.
  • W008085280A2 describes a catalyst for the selective catalytic reduction of nitrogen oxides with ammonia.
  • a washcoat consisting of 10% aluminum oxide, 50% of a zeolite mixture of H-ZSM-5 and H-beta (1: 1) and 40% Ce0.24Zr0.66La0.04 YO.O6O 2 with water in a ball mill to a mean grain size of 4 - 5 pm ground.
  • a disadvantage of using ball mills for grinding and dispersing components of the washcoat lies in the difficulty of scale-up of ball mills due to the different heat exchange behavior depending on the mill size and geometry.
  • Automotive catalytic converters have to meet ever increasing demands due to the decreasing legal limits for harmful auto emissions. It is therefore a permanent task for research to provide more effective and better car exhaust catalysts.
  • zeolites or zeotypes it is possible in principle to use all types or mixtures thereof which are suitable for the relevant field of application. These include naturally occurring, but preferably synthetically produced zeolites. These may have framework types, for example from the group consisting of beta, ferrierite, Y, USY, ZSM-5, ITQ.
  • Examples of synthetically produced small-pore zeolites and zeotypes which are suitable here are those which correspond to the structure types ABW, ACO, AEI, AEN, AFN, AFT, AFX, ANA, APC, APD, ATN, ATT, ATV, AWO, AWW, BIK, BRE, CAS, CDO, CHA, DDR, DFT, EAB, EDI, EPI, ERI, ESV, GIS, GOO, IHW, ITE, ITW, JBW, KFI, LEV, LTA, LTJ, MER, MON, MTF, NSI, OWE, PAU, PHI, RHO, RTE, RTH, SAS, SAT, SAV, SIV, THO, TSC, UEI, UFI, VNI, YUG and ZON.
  • those of the small pore type are used, which are derived from a type of structure from the group consisting of CHA, LEV, AFT, AEI, AFI, AFX, KFI, ERI, DDR.
  • a type of structure from the group consisting of CHA, LEV, AFT, AEI, AFI, AFX, KFI, ERI, DDR.
  • Particular preference is given here to those which are derived from structural types selected from the group consisting of CHA, LEV, AEI, AFX, AFI or KFI framework or mixtures thereof.
  • Very particular preference is given to zeolite of the AEI or CHA type in this connection. Also mixtures of the species mentioned are possible.
  • the SAR value of the zeolite or the corresponding value for the zeotype should be in the range of 5 to 50, preferably 10 to 45, and most preferably 20 to 40.
  • the zeolites or zeotypes and in particular those of the small-pore type, be exchanged with metal ions, in particular transition metal ions.
  • metal ions in particular transition metal ions.
  • the skilled person can use the metal ions preferably used for the corresponding reaction.
  • metal ions from the group of platinum metals, in particular platinum, palladium and rhodium have crystallized out, while e.g. the SCR reaction has been most effective with zeolites or zeotypes exchanged with iron and / or copper ions.
  • the exchange rate (number of ions at exchange places / total number of exchange places) should be between 0.3 and 0.5. As exchange places here are meant those at which the positive ions compensate negative charges of the grid. It is also possible for further non-exchanged metal ions, in particular Fe and / or Cu ions, to be present in the final SCR catalyst.
  • the ratio of exchanged to non-exchanged ions is> 50:50, preferably 60:40 - 95: 5 and most preferably 70:30 - 90:10.
  • the ions sitting on exchange sites are visible in electron spin resonance analysis and can be quantified (Quantitative EPR, Gareth R.
  • All non-ion exchanged cations are located elsewhere in or outside the zeolite / zeotype. The latter do not compensate for negative charge of the zeolite / zeolite framework. They are invisible in the EPR and can thus be calculated from the difference between the total metal loading (for example, determined by ICP) and the value determined in the EPR.
  • the addition of the corresponding ions to the coating mixture is controlled so that the total amount of metal ions, in particular Fe and / or Cu ions in the final total catalyst at 0.5 to 10 wt .-%, preferably 1-5 wt .-% the coating amount is.
  • the coating suspension may also contain other ingredients. These can be added to the suspension before or after the ultrasonic treatment according to the invention. Binder selected from the group consisting of aluminum oxide, titanium dioxide, zirconium dioxide, silicon dioxide or mixtures have proved advantageous components in this connection. These components can be the catalytic function of the catalytically active material continue to support, but do not actively engage themselves in the reaction. Materials used here are so-called binders. Among other things, the latter ensure that the materials and components involved in the reaction can adhere sufficiently firmly to the corresponding substrate. High-surface-area aluminas are preferably used as such materials here. The binder is used in a certain amount in the coating.
  • the binder is added in a quantity of max. 25% by weight, preferably max. 20 wt .-% and most preferably used in an amount of 5 wt .-% - 15 wt .-%.
  • the viscosity (viscosity: DIN 53019-1: 2008-09 - latest version valid at the filing date) is located at a shear rate of 1 / s advantageously from 0.01 - 10 Pa * s, preferably 0.02 - 2 Pa * s and more preferably 0.05-1.5 Pa * s.
  • the shear rate-dependent viscosity can be measured with a plate-cone rheometer (Malvern, Kinexus or Brookfield, type RST).
  • the coating suspension is applied to the support according to the instructions of the person skilled in the art (see introductory references in this regard).
  • coating accordingly means the application of the frequently aqueous suspension of catalytically active materials and optionally other constituents (also called washcoat) to a largely inert support body, which is a wall-flow filter (wall flow filter) or Flow-through monolith (flow monolith).
  • the coating layer thus assumes the actual catalytic function.
  • the support is dried as described in the literature mentioned above and optionally calcined at elevated temperature.
  • the coating may consist of a layer or be composed of several identical or different layers, which are applied one above the other (multilayered) and / or offset from one another (zoned) onto a support body.
  • a substrate of the wall-flow type (wall-flow filter) or of the flow-through type can serve as the carrier.
  • Flow monoliths are conventional catalyst supports in the prior art, which may consist of metal (corrugated carrier, eg W017153239A1, WO16057285A1, WO15121910A1 and literature cited therein) or ceramic materials. Preference is given to using refractory ceramics such as, for example, cordierite, silicon carbide or aluminum titanate, etc.
  • the number of channels per area is characterized by cell density, which is usually between 300 and 900 cells per cell Square inch (cells per square inch, cpsi).
  • the wall thickness of the channel walls is between 0.5 and 0.05 mm for ceramics.
  • the catalyst material may be in the form of washcoat suspensions in and / or on the porous walls between the inlet and outlet channels. It is also possible to use wall-flow monoliths which have been extruded directly or with the aid of binders from the corresponding catalyst materials, that is to say that the porous walls consist directly of the catalyst material, as in the case of SCR catalysts, for example Zeolite or vanadium base may be the case. Such extruded SCR monoliths may additionally be provided, as described above, with a washcoat suspension in and / or on the porous walls.
  • Preferred substrates to be used can be taken from EP1309775 A1, EP2042225 A1 or EP1663458 A1.
  • the porosity of the wall flow filters is generally more than 40%, generally from 40% to 75%, in particular from 45% to 70% [measured according to DIN 66133 - latest version on the application date].
  • the average pore size is at least 7 pm, e.g. from 7 pm to 34 pm, preferably more than 10 pm, in particular from 10 pm to 20 pm or from 21 pm to 33 pm [measured according to DIN 66134 latest version on the filing date].
  • the finished and th th coated filters with a pore size of usually 10 pm to 33 pm and a porosity of 50% to 65% are particularly preferred. In the present case, it is very particularly preferred to use a corresponding carrier of the wall-flow type.
  • the ultrasound treatment of the coating suspension can be carried out according to the specification of the person skilled in the art.
  • the ultrasound treatment of the washcoat suspension can take place, for example, in a system as outlined in FIG. 1.
  • the plant consists of a storage tank (1) by depending on the batch size between 50 and 1000 I of Washcoatsuspension and are stirred with a stirrer.
  • Over a Pump (2) the aqueous zeolite / zeotyp Airport suspension over a cooling section (4) during the grinding and dispersing process in the circulation through a reactor (5), which is equipped for homogenization and dispersion in the interior with an ultrasonic sonotrode.
  • the system can be equipped with a pulsation damper (3) and flow regulator (6).
  • the deagglomeration, comminution and / or dispersion of the zeolites or zeotypes with ultrasound can also be carried out in a stationary batch process without recirculation.
  • the deagglomeration, comminution and / or dispersion of the particles by the ultrasound is based on the active principle of cavitation.
  • ultrasonic oscillators for example made of piezo zirconate titanate (PZT)
  • PZT piezo zirconate titanate
  • high-frequency electrical energy is converted into mechanical vibrations (ultrasound).
  • ultrasound In the liquid smallest vacuum bubbles are generated, which implode immediately and crush the powder particles by the resulting pressure surges.
  • the comminution effect depends on the amplitude of the ultrasound (energy), the frequency and the duration of the sound.
  • the particle size after the ultrasound treatment of the coating suspension is most preferably below 7 pm (d50), more preferably below 7 pm (d80) and most preferably below 7 pm (d99). These values apply to wall flow filters.
  • the particle sizes (d50) are in the region of less than 20 pm, preferably less than 25 pm (d80) and more preferably less than 30 pm (d99).
  • the lower limit for the particle size is generally> 0.01 pm, more preferably> 0.05 pm and particularly preferably> 0.1 pm.
  • an ultrasound source acts on the coating suspension in such a way that the ultrasound preferably has an amplitude of 5-100 .mu.m, more preferably 10-35 .mu.m, and most preferably 15-25 .mu.m.
  • the frequency of the ultrasound used is advantageously 5 to 30 kHz, more preferably 10 to 25 kHz, and most preferably 15 to 20 kHz.
  • the power radiated in should preferably be from 500 to 50,000 watts, more preferably from 1,000 to 30,000 watts, and most preferably from 2,000 to 20,000 watts.
  • Particle size is usually determined as the average particle size of the particles in the aqueous washcoat suspension by laser diffraction methods. With the values of the grain size indicated in the examples, the particle size is determined by means of the laser diffraction method in an aqueous suspension of the zeolites according to ISO 13320-1 measured (latest version valid on filing date).
  • the ISO 13320-1 Particle size analysis - Laser diffraction method describes the method widely used in the art for determining the particle size distribution of particles in the nanometer and micrometer range by laser diffraction. In laser diffraction, particle size distributions are determined by measuring the angular dependence of the intensity of scattered light from a laser beam passing through a dispersed particulate sample.
  • the essential parameters for characterizing the particle size distribution of the particles are the d 10, d 50 and d 90 or d 99 values based on the number of particles in the sample.
  • the d50 or central or median value indicates the mean value of the particle size and means that 50% of all particles are smaller than the specified value. For the d10 value, 10% of all particles are smaller than this value and 90% larger.
  • the same applies to the d90 / d99 value http://www.horiba.com/scientific/products/particle- characterization / education / qeneral-information / data-interpretation / understandinq-particle-size-distribution-calculations / ).
  • the present invention likewise relates to a catalyst prepared according to the invention for the after-treatment of exhaust gases of a car engine, in particular a corresponding SCR catalyst.
  • the carrier is a wall-flow filter. This has a loading of the dry coating suspension of 30-200 g / l, preferably 50-160 g / l and most preferably 80-145 g / l. This is particularly advantageous for the coating of the wall-flow filter with an SCR catalyst.
  • a catalyst according to the invention for the after-treatment of exhaust gases of a car engine.
  • all exhaust gas aftertreatments which are suitable for this purpose can serve as such.
  • Zeolites and zeotypes as mentioned in the introduction are found, inter alia, in TWCs (three-way catalysts), DOCs (diesel oxidation catalysts), PNAs (passive NOx absorbers), LNTs (nitrogen oxide storage catalysts) and in particular in SCR catalysts.
  • the catalysts prepared by the process according to the invention are suitable. Preference is given to the use of these catalysts for the treatment of exhaust gases of a lean-burn car engine.
  • the catalysts prepared in accordance with the invention are very particularly preferably used in the selective reduction of nitrogen oxides by means of ammonia (SCR treatment).
  • SCR treatment of the preferably lean exhaust gas
  • ammonia or an ammonia precursor compound is injected into this and passed through an SCR catalyst according to the invention.
  • the temperature above the SCR catalyst should be between 150 ° C and 500 ° C, preferably between 200 ° C and 400 ° C or between 180 ° C and 380 ° C, so that the reduction can go as completely as possible.
  • Particularly preferred is a temperature range of 225 ° C to 350 ° C for the reduction.
  • the injection devices used can be chosen as desired by the person skilled in the art. Suitable systems can be found in the literature (T. Mayer, solid SCR system based on ammonium carbamate, dissertation, TU Kaiserslautern, 2005).
  • the ammonia can be introduced via the injection device as such or in the form of a compound in the exhaust gas stream, which gives rise to ammonia in the ambient conditions.
  • aqueous solutions of urea or ammonium formate are suitable, as well as solid ammonium carbamate.
  • the person skilled in the art particularly preferably uses injection nozzles (EP031 1758 A1). By means of this, the optimum ratio of NH 3 / NOx is set so that as complete as possible conversion of the nitrogen oxides to N 2 can be carried out.
  • the process according to the invention is combined with a process step in which the coating suspension is supplied to a predrying after coating of the support.
  • the zeolite used or the zeotype is a metal ion-exchanged zeolite or zeotype, in particular a SPZ and after its coating on and / or in a carrier is pre-dried such that for a sufficient period of time and with a sufficient intensity, a gas stream is passed through the carrier, so that the solids content in the applied Washcoattik to 45% - 60% is adjusted before the support is completely dried and / or calcined, further improved catalysts are obtained.
  • a gas stream preferably an air stream
  • By reducing the moisture content of the coating it is possible to achieve a pseudoplastic state which helps to prevent a less favorable distribution of the coating components.
  • the setting of the solids content on the carrier is carried out in such a way that after its coating on and / or in a carrier, a gas flow is passed through it for a sufficient time and with a sufficient intensity so that the solids content in the applied washcoat layer is 45%. - 60%, more preferably 50% - 60%, before the carrier is completely dried and / or calcined
  • the gas / air stream is passed through the carrier for a certain period of time until the wet weight of the applied washcoat layer has been correspondingly reduced.
  • the gas stream may have a temperature of not more than 60 ° C, preferably not more than 45 ° C.
  • a lower limit to the gas flow is certainly determined by the reduced ability of cold gas streams to absorb moisture. It is at 10 ° C, preferably at 15 ° C and more preferably at 20 ° C.
  • the gas stream is passed through the carrier. He can have a speed. A velocity of the gas flow through the support between 5 - 60 m / s, preferably 10 - 40 m / s is possible, 20 - 30 m / s are preferred.
  • the gas flow is generated by applying a pressure difference of at least 20 mbar between the inlet and outlet side of the carrier.
  • pressure differences of 50-600 mbar, preferably 100-500 mbar and particularly preferably 150-400 mbar are useful for the application of Wandtikfiltern.
  • pressure differences of 20-400 mbar, preferably 50-350 mbar and particularly preferably 80-300 mbar are suitable.
  • a gas flow / air flow is passed for a sufficient period of time in order to preferably adjust the solids content.
  • this should be as short as possible.
  • the period of time should be chosen so that the appropriate solids content can be reliably obtained for all carriers.
  • the time will be between 10 seconds and 2 minutes, preferably between 15 seconds and 1 minute, and most preferably the gas flow will last for a period of 15 to 40 seconds, most preferably> 20- ⁇ 40 seconds.
  • the relative humidity of the gas flowing through the carrier during the method step according to the invention is particularly adapted.
  • the gas all gases which are suitable for the drying process and selected from the group consisting of air, CO 2 , N 2 , noble gases or mixtures thereof can be used. Possibly. Reactive gases can be admixed, such as H 2 or O 2 .
  • air is used. It has proven to be beneficial, especially with respect to the use of air, when relatively dry gas is used for the predrying.
  • the relative humidity of the gas especially air (https://de.wikipedia.org/wiki/Luftfeuchtmaschine), should be reduced to values of less than 5 g of water per kilogram of gas / air. Preference is given to using less than 4 g of water per kilogram of gas / air, more preferably less than 3 g of water per kilogram of gas / air.
  • the additional treatment of the zeolite-coated or zeolite-coated carriers by means of a predrying step can surprisingly further increase the activity of the final catalysts, which was not previously anticipated.
  • the actual drying time can be drastically reduced, which means that the use of the additional predrying step ultimately leads to a net shortening of the overall process duration.
  • the carrier employed is a wall-flow type.
  • the present invention therefore also relates to the catalysts resulting from the combined processes (ultrasound treatment and predrying) and their use in exhaust gas aftertreatment, in particular in the SCR treatment of car exhaust gases of lean-burn engines.
  • the preferred embodiments of the method, the catalyst and its use mentioned above for the ultrasound treatment also apply mutatis mutandis to the objects considered here which are directed to the additional predrying.
  • the present document often refers to lean combustion.
  • the combustion air ratio (A / F ratio, air / fuel ratio) sets the actual air mass mi_, tats available for combustion in relation to the minimum necessary stoichiometric air mass mi_, st required for complete combustion:
  • l ⁇ 1 (eg 0.9) means “lack of air”: rich or rich exhaust gas mixture l> 1 (eg 1, 1) means “excess air”: lean or poor exhaust gas mixture
  • lean-burn car engines or “lean-burn engines” refers to diesel engines predominantly lean burned gasoline engines on average. The latter are mainly on average with lean A / F ratio (air / fuel ratio) powered gasoline engines.
  • lean A / F ratio air / fuel ratio
  • the term “predominantly on average” takes account of the fact that, for example, modern stoichiometric gasoline engines are not operated statically at a fixed air / fuel ratio (A / F ratio; 1 value).
  • a / F ratio; 1 value For example, three-way catalytic converters in the exhaust gas system that contain oxygen storage material are used for gasoline engines that burn "predominantly in the middle stoichiometrically.” These are acted upon by the gasoline engines with exhaust gas with a discontinuous course of the air ratio l.
  • the air ratio l undergoes a periodic change in the air ratio l in a defined manner and thus a periodic change of oxidizing and reducing exhaust gas conditions.
  • This change in the air ratio l is essential in both cases for the exhaust gas purification result.
  • the l-value of the exhaust gas with a very short cycle time (about 0.5 to 5 hertz) and an amplitude Dl of 0.005 ⁇ dl ⁇ 0.07 around the value l 1 (reducing and oxidizing exhaust components are in stoichiometric Relative to each other).
  • the exhaust gas can be described as "on average" stoichiometric.
  • the oxygen storage materials contained in the catalyst balance these deviations to a certain extent by absorbing oxygen from the exhaust gas as required or releasing it into the exhaust gas (Catalytic Air Pollution Control, Commercial Technology, R. Heck et al., 1995, p. 90). Due to the dynamic mode of operation of the engine in the vehicle, however, other deviations from this condition occur at times. For example, during extreme accelerations or when braking in overrun operation operating states of the engine and thus the exhaust gas can be adjusted, which can be over-or under-stoichiometric on average.
  • the stoichiometrically burning gasoline engine has an average of stoichiometric combustion.
  • lean-burn engines this applies mutatis mutandis.
  • These have, for example, a lean-burn gasoline engine and thus an exhaust gas which predominantly, ie in the predominant time of the combustion operation, has an average air / fuel ratio on average over time.
  • Zeolites and zeotypes are defined in WO20150491 10 A1. This definition is also used for this invention. Without being bound to any particular theory, it is believed that conventional milling processes, such as with a ball mill, by attrition and destruction of the crystallites, result in an increase in the fines fraction in the washcoat slurry, and thus usually in an increase in viscosity to lead. In studies by G. Tari et al. (Journal of the European Ceramic Society 18 (1998) 249-253), the influence of the particle size of aluminum oxide particles on the viscosity of suspensions prepared therefrom is shown. It has been found that suspensions with the same solids content have the higher the viscosity values the smaller the average particle size of the suspended aluminum oxide is.
  • FIG. 1 is a diagrammatic representation of FIG. 1:
  • a ceramic filter consisting of a carrier body made of silicon carbide (NGK) with a porosity of 63% and an average pore size of 20 ⁇ m in the dimensions given in Table 1 was used for the present experiments for Examples 1 and 2:
  • NNK silicon carbide
  • a ceramic flow-through substrate consisting of a support made of cordierite (from NGK) in the dimensions indicated in Table 2 was used for the present experiments for Examples 3 and 4:
  • the washcoat has a coating temperature of room temperature, which is usually 20 ° C to 40 ° C, and consists of a suspension of a copper-exchanged zeolite (chabazite) having a solids content of 37%.
  • the suspension is used in Examples 1 and Example 3 using a stirred ball mill (eg Fa. Netzsch or Fa. Hosokawa-Alpine) using zirconia grinding balls with a diameter of 1 mm milled.
  • the loading of the carrier with washcoat is determined by weighing the carrier.
  • the suspension is dispersed with an ultrasonic dispersion unit UiP2000 from Hielscher Ultrasonics to the target particle size. In all examples, the d50 value was within the scope of the claim.
  • Example 2 Washcoat containing zeolite dispersed by means of ultrasound with a d99 ⁇ 6.7 ⁇ m (Hielscher UiP 2000, 2 kW, 3 bar, 100% amplitude) according to the method according to the invention, dried after standing on filter substrate in a convection oven at 120 ° C. for 30 minutes, annealed at 350 ° C for 30 minutes, then calcined at 550 ° C for 2 h.
  • Table 4 presents the results of measurements of exhaust back pressures and NOx conversion rates of differently prepared wall flow filters.
  • Table 5 shows the results of the measurements of the NOx conversion rates of the different manufactured flow monoliths.

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Abstract

La présente invention concerne un procédé de fabrication de catalyseurs d'automobiles, lesdits catalyseurs et leur utilisation. En particulier, lors de la fabrication, on met en œuvre une étape qui entraîne une réduction de la taille des particules de la matière catalytiquement active utilisée.
EP19701316.2A 2018-01-16 2019-01-16 Procédé de fabrication d'un catalyseur scr à l'aide d'ultrasons Pending EP3740312A1 (fr)

Applications Claiming Priority (2)

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DE102018100834.1A DE102018100834A1 (de) 2018-01-16 2018-01-16 Verfahren zur Herstellung eines SCR-Katalysators
PCT/EP2019/051029 WO2019141719A1 (fr) 2018-01-16 2019-01-16 Procédé de fabrication d'un catalyseur scr à l'aide d'ultrasons

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CN (1) CN111601659B (fr)
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FR3123073B1 (fr) * 2021-05-20 2023-11-17 Renault Sas Procédé d’analyse d’un catalyseur à base d’un substrat métallique

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DE102018100834A1 (de) 2019-07-18
CN111601659B (zh) 2023-09-01
WO2019141719A1 (fr) 2019-07-25
US11400443B2 (en) 2022-08-02
CN111601659A (zh) 2020-08-28

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