EP2533897A1

EP2533897A1 - Kfi-type copper-containing zeolith and use in the scr-catalyst

Info

Publication number: EP2533897A1
Application number: EP11704589A
Authority: EP
Inventors: Markus Reichinger; Gerd Maletz; Kristof Eisert
Original assignee: Sued Chemie IP GmbH and Co KG
Current assignee: Sued Chemie IP GmbH and Co KG
Priority date: 2010-02-11
Filing date: 2011-02-10
Publication date: 2012-12-19
Also published as: DE102010007626A1; US20170050179A1; WO2011098512A1; US20130089494A1

Abstract

The invention relates to a KFI-type copper-containing zeolithe comprising 1 - 4,5 wt.% copper. The invention also relates to a method for producing the claimed copper-containing zeolithe and to the use thereof in the SCR catalyst. The invention further relates to a wash-coat which contains the claimed zeolith, a SCR catalyst which contains the claimed zeolith and a waste gas cleaning system which contains the SCR catalyst.

Description

Copper-bearing zeolite of the KFI type and use in the SCR

catalysis

The present invention relates to a copper-containing

Zeolites of the KFI type, the zeolite containing from 1 to 4.5% by weight of copper. The invention is also a

A process for preparing the copper-containing zeolite of the invention and directed to the use of the zeolite in SCR catalysis. Further objects of the invention are a washcoat which contains the zeolite according to the invention, an SCR catalyst which contains the zeolite according to the invention and an exhaust gas purification system which comprises the SCR catalyst.

Since the beginning of the exhaust gas cleaning great efforts are made to reduce the pollutant emissions of internal combustion engines ever further. Internal engine measures will no longer be sufficient in the future to meet the legal requirements. For this are modern systems for the

Exhaust gas aftertreatment necessary so that the exhaust gas limits can be met. For example, for the

Exhaust gas aftertreatment of diesel engines, among others the following systems partially already realized or are in the testing: · Selective catalytic reduction (SCR-method)

• ΝΟχ-reduction catalyst (NSR)

• oxidation catalyst (DOC)

• Catalytically coated particle filter • Combinations such as Continuously Regenerating Trap (CRT), SCRT, DPNR.

The surface of those used in these systems

Catalysts has an active coating

Acceleration of the corresponding reactions. When

Catalyst substrate to which the coating is applied, are usually ceramic or metallic

Monoliths.

A special feature of diesel exhaust gases is their relatively low temperature. In partial load operation is the

Exhaust gas temperature in the range between 120 ° C and 250 ° C and reaches only in the full load range a maximum temperature

between 550 ° C and 650 ° C. Therefore, the use of an SCR catalyst having a high cryogenic activity is required. Nevertheless, the materials used should have a high activity even at high temperatures and in particular a high stability against aging.

With selective catalytic reduction (SCR), the selective catalytic reduction of nitrogen oxides from exhaust gases from

Internal combustion engines and also called power plants. With an SCR catalyst, only the nitrogen oxides NO and NO ₂ (commonly referred to as NO _x ) are selectively reduced, with NH ₃ (ammonia) usually added to the reaction. As a reaction product, therefore, only the harmless substances water and

Nitrogen. For use in motor vehicles that is

Carrying ammonia into compressed gas cylinders

Security risk. That's why usually

Precursor compounds of ammonia used in the

Exhaust line of the vehicles are decomposed under ammonia formation. Known in this context, for example, the use of AdBlue ^® , which is an approximately 32.5% eutectic Solution of urea in water. Other sources of ammonia include ammonium carbamate, ammonium formate or urea pellets. Before the actual SCR reaction, ammonia must first be formed from urea. This happens in two

Reaction steps, collectively referred to as hydrolysis reaction. First, H ₃ and isocyanic acid are formed in a thermolysis reaction. Subsequently, in the

actual hydrolysis reaction isocyanic acid with water to ammonia and carbon dioxide reacted.

To avoid solid precipitates, it is necessary that the second reaction be determined by the choice of

Catalysts and sufficiently high temperatures (from 250 ° C) is sufficiently fast. Modern SCR reactors simultaneously take over the function of the hydrolysis catalyst.

The ammonia produced by the thermohydrolysis reacts on the SCR catalyst according to the following equations:

4NO + 4NH ₃ + 0 ₂ -> ■ 4N ₂ + 6H ₂ 0 (1)

NO + NO ₂ + 2NH ₃ -> ■ 2N ₂ + 3H ₂ 0 (2)

6N0 ₂ + 8NH3 -> ■ 7N ₂ + 12H ₂ 0 (3)

At low temperatures (<300 ° C) sales are running

predominantly via reaction (2). For a good one

Low temperature conversion, therefore, it is necessary to set a N0 ₂ : NO ratio of about 1: 1. Under these circumstances, reaction (2) can take place at temperatures as low as 170-200 ° C. The oxidation of NO to NO _x takes place in an upstream oxidation catalyst which is required for optimum efficiency. If more reducing agent is dosed than is reacted during the reduction with ΝΟχ, undesirable NH3 slip may occur. The removal of the NH3 can be done by a

additional oxidation catalyst can be achieved behind the SCR catalyst. This barrier catalyst oxidizes the possibly

occurring ammonia to 2 and H2O. In addition, a careful application of the urea dosage is essential.

An important parameter for SCR catalysis is the so-called feed ratio, defined as the molar ratio of metered NH 3 to the NO _x present in the exhaust gas. In ideal operating conditions (no NH3 slip, no

Side reactions, no NH3 oxidation) is directly proportional to the ΝΟχ reduction rate. If = 1 theoretically a 100% NO _x reduction is achieved. In practical use, an NH3 slip of <20 ppm can achieve a 90% NO _x reduction in stationary and non-stationary operation. Due to the upstream hydrolysis reaction, NO _x conversion> 50% is achieved at temperatures above about 250 ° C. in today's SCR catalysts, optimum conversion rates are achieved in the temperature window of 250-450 ° C. The dosing strategy is of great importance for catalysts with high NH3 storage capacity, since the NH3 storage capacity of SCR catalysts of the prior art

Technique typically decreases with increasing temperature. Currently, both in the power plant sector and in the automotive sector predominantly catalysts based on

Titanium dioxide, vanadium pentoxide and tungsten oxide (VWT catalysts) used.

In addition to the previously used VWT catalysts, metal-exchanged zeolites have been promising

Catalysts in SCR catalysis highlighted. The term "zeolite" is used generally in accordance with

Definition of the International Mineralogical Association (D.S. Coombs et al., Can. Mineralogist, 35, 1997, 1571)

crystalline substance from the group of aluminum silicates with spatial network structure of the general formula

M ^{n +} [(A10 ₂ ) x (Si0 ₂ ) _y ] -z (H ₂ 0) understood, consisting of S1O ₄ / AIO ₄ tetrahedra, which by common oxygen atoms to a regular

three-dimensional network are linked. The ratio of

Si / Al = y / x is always> 1 according to the so-called "Löwenstein rule", which prohibits the adjacent occurrence of two adjacent negatively charged AlC ^ tetrahedra. Although there are more exchange sites for metals available at a low Si / Al ratio, the zeolite is becoming increasingly thermally unstable. In addition, for the purposes of this invention, the term "zeolite" is also to be understood as meaning silicon aluminum phosphate (SAPO) and aluminum phosphates (A1PO), preferably having a KFI structure.

The zeolite structure contains voids and channels characteristic of each zeolite. The zeolites are classified according to their topology into different structures (see above). The zeolite framework contains open cavities in the form channels and cages that are normally occupied by water molecules and extra framework cations that can be exchanged. An aluminum atom has an excess negative charge which is compensated by these cations. The interior of the pore system represents the catalytically active

The more aluminum and the less silicon a zeolite contains, the denser the negative charge in its lattice and the more polar its inner surface. The pore size and structure is in addition to the parameters in the preparation (use or type of templates, pH, pressure,

Temperature, presence of seed crystals) is determined by the Si / Al ratio, which determines much of the catalytic character of a zeolite. Due to the presence of e.g. 3-valent atoms (for example Al or Ga), the zeolite receives a negative lattice charge in the form of so-called anion sites in the vicinity of which the corresponding cation positions are located. The negative

Charge is compensated by the incorporation of cations into the pores of the zeolite material. The zeolites are mainly distinguished by the geometry of the cavities formed by the rigid network of Si0 ₄ / A10 ₄ tetrahedra. The entrances to the cavities are formed by 8, 10 or 12 "rings" (narrow, medium and large pore zeolites). Certain zeolites show a uniform structure (eg ZSM-5 with MFI topology) with linear or zigzagging channels, while others show larger cavities behind the pore openings, eg the Y and A zeolites with the topologies FAU and LTA.

Especially iron or copper containing zeolites of

Framework type MFI or BEA show especially in

Low temperature range high activity in terms of NO _x - implementation. MFI or BEA have relatively large pore diameters. MFI

for example, 5.1 Å x 5.5 Å and 5.3 Å x 5.6 Å and BEA 6.6 x 6.7 Å and 7.1 x 7.3 Å. These large pore openings of the

Zeolites thus allow the absorption of

Hydrocarbons that can penetrate into the pore system. In this case, however, incomplete combustion of the hydrocarbons often takes place, which can lead to soot formation in the pores and thus blocks the active centers of the catalyst. It comes to a sooting of the zeolites.

WO 2008/132452 A2 proposes transition metal-containing zeolites which solve a maximum of this problem

Ring size of 8 tetrahedral atoms have. Here are a variety of possible skeleton structures with

However, only the zeolites SAPO-34, NU-3, SSZ-13, Sigma-1, ZSM-34, and CHA, which either with iron or copper, revealed ring openings with a maximum of 8 tetrahedral atoms

exchanged, were examined in more detail. However, the structural types used have certain disadvantages. Thus, for example, the zeolite SSZ-13 only by means of more expensive

organic template can be prepared, for example with 1-adamantamine, 2 quinuclidinol or 2 exo-Aminonorbornan. Although US 7,597,874 Bl discloses a synthesis of SSZ-13 using a quaternary ammonium salt and use of

Seed crystals. However, the use of quaternary ammonium salts is still more costly than template-free synthesis, and in addition, the seed crystals must first be prepared in an additional process step using organic templates.

SAPO-34 is a silicon-aluminum-phosphate with CHA structure and can indeed be produced without organic template, but the ion exchange, especially in liquid Phase, due to the physical characteristics of the SAPO associated with a considerable effort.

NU-3 shows a good NO _x conversion

Cryogenic activity, which, however, in the higher

Temperature range decreases rapidly. A similar behavior also shows the zeolite Sigma-1 and SSZ-13. The waste at elevated temperatures above approx. 350 ° C is also intensified by aging.

Although the above-mentioned small-pore zeolites show better NO _x conversion and lower N 2 O formation compared to large-pore zeolites such as BEA, as already stated above, many of these zeolites can only be produced using expensive organic templates, show poor performance or are suitable for the use in the exhaust gas catalysis unsuitable because, for example, fibrous, respirable structures are discharged into the environment and thus can cause harm to humans and animals.

The object of the present invention was therefore to provide a material which is suitable for SCR catalysis, which has good low-temperature activity with only minor losses at higher temperatures, exhibits good aging behavior and is also cost-effective

can be produced.

The object was achieved by a copper-containing zeolite of the KFI type, wherein the zeolite 1 to 4.5 wt .-% copper, preferably 1.5 to 4.2 wt .-%, more preferably 2.5 to 4.0 Wt .-%, based on the total weight of the zeolite. Surprisingly, it has been found that a copper-containing KFI-type zeolite containing from 1 to 4.5% by weight of copper is present

excellent for SCR catalysis. The copper-containing zeolite of the KFI type shows a very good

Cryogenic activity, a high activity even in high temperature range and only a low aging behavior. The copper-containing zeolite according to the invention is not prone to sooting, such as large-pore zeolites and is also characterized by a low formation of ₂ O.

Heretofore, in the prior art, a KFI-type zeolite, and particularly a copper-containing KFI-type zeolite, could not be obtained in high purity. Frequently, in addition to the KFI structure type, phase contaminants are found by the

Structure types MER, CHA, ERI and LTL. However, by suitable choice of the reaction conditions, the impurity can be limited to phases of the structure type MER. The MER content can also be obtained by a thermal / hydrothermal treatment

be reduced, so that a higher phase purity of

Zeolites of the KFI type is achieved.

According to one embodiment, it is preferred that the

has copper-containing zeolite primary crystallites, which in the

Range from 0.2 to 10 ym, more preferably 0.25 to 7 ym, most preferably 0.5 to 5 ym.

The primary crystallites preferably have a cuboid morphology. In particular, the primary crystallites have a cubic shape. This is

three-dimensional structures, wherein in the case of cuboid morphology, a length / width ratio + 1, preferably 0.7 to 1.3 and in the case of cubic morphology

Length / width ratio of about 1 is preferred. In addition, two-dimensional structures are also possible, ie with only a small height expansion of the primary crystallites.

These are thus rectangular or square plates. In another embodiment, it is preferred that the copper-containing zeolite contains iron. An advantage of

additional incorporation of iron into the zeolites is a heightened compared to pure copper-containing zeolite

catalytic activity in the high temperature range.

The proportion of iron in the zeolite is preferably 0.01 to 6 wt%, more preferably 0.01 to 3.51 wt%. The proportion of copper and iron together is preferably 1.01 to 10% by weight, more preferably 1.01 to 4.51% by weight, based on the total weight of the zeolite.

In a further advantageous embodiment of the invention, it is preferred that the copper-containing zeolite

Phase shares of a zeolite of structure type MER.

In one embodiment of the invention, it is particularly preferred that the KFI-type copper-containing zeolite contain from 1 to 4.5% by weight of copper, based on the total weight of the

Zeolites, and further having a phase purity> 50%, more preferably> 60% and in particular> 70%. According to an advantageous embodiment of the invention, the zeolite according to the invention is preferably essentially a phase-pure zeolite of the KFI type. "Essentially" here means that phase components of zeolites of others

Structure types, such as MER, may be included, but these have no effect on the properties of the zeolite of the invention of the KFI type. The copper or iron is present in the copper-containing zeolite according to the invention preferably in cationic form, either as a metal cation or as a cationic complex containing copper or iron as the central metal. It is preferred that these cations compensate for the negative charge of the zeolite framework. The cations are present as counter ions to the negative charges in the cavities of the zeolite. A further subject of the invention is a process for the preparation of a copper-containing zeolite characterized by the steps: a) provision of a KFI-type zeolite which may have phase proportions of a MER-type zeolite,

b) Thermal treatment or hydrothermal treatment of the zeolite at a temperature> 500 ° C. Likewise, the thermal and the hydrothermal treatment can be combined with each other, wherein either the thermal or the hydrothermal treatment can be carried out first.

Surprisingly, it was found that by the thermal treatment / hydrothermal treatment of the inventive

Zeolites under hydrothermal conditions, the MER phase slowly decomposes. The S1O ₂ formed during the decomposition of the MER-phase can be referred to as binder content for a

serve to be produced washcoat.

The exchange of copper and possibly iron can in the

process according to the invention before the thermal / hydrothermal treatment or after the thermal / hydrothermal treatment. Preferably, the exchange of copper and possibly Iron by a liquid phase ion exchange. However, all other methods common to the person skilled in the art, such as

For example, a solid-state ion exchange be made.

Before the exchange of copper and possibly iron, the zeolite is preferably converted into the ammonium form. This method is known to the person skilled in the art. The thermal / hydrothermal treatment is preferably carried out over a period of 30 minutes to 50 hours, more preferably 1 hour to 40 hours, and most preferably from 2 hours to 30 hours. However, the

thermal / hydrothermal treatment even over a longer period than 50 hours. The longer the

thermal / hydrothermal treatment takes place, the more parts of the MER phase are decomposed, so that after a certain period of time preferably only a substantially pure KFI phase remains. The course of the increase of the portion of the KFI phase (relative to the MER phase) or the decrease of the

For example, the portion of the MER phase can be tracked via XRD. When all MER signals have disappeared in the XRD spectrum, one can speak of a phase-pure KFI zeolite.

Since the MER phase is not particularly thermally / hydrothermally stable, the temperature can also be varied.

Preferably, temperatures are> 500 ° C, more preferably> 550 ° C, even more preferably> 600 ° C and most preferably> 700 ° C. The temperature should preferably not 1200 ° C, preferably 1100 ° C, even more preferably 1000 ° C, especially 900 ° C not

exceed. The preparation of the KFI-type zeolite is preferably carried out by reacting a reaction mixture containing strontium. In addition, sodium, potassium and / or

Cesium cations are used as a template.

The reaction mixture or the synthesis gel contains in

General:

an aluminum source,

a silicon source,

an alkali metal, preferably potassium, cesium, sodium or

Mixtures of at least two of the named,

- strontium,

- Water.

Particularly preferred zeolites according to the present invention have the following proportions (molar ratios):

(K ₂ O + SrO) / Si0 ₂ 0.10-0.40

H ₂ O / (K ₂ O + SrO) 50-120

Si0 ₂ / Al ₂ O ₃ 4-50

Silica is usually used as the silicon source for the reaction mixture. Most preferred here is a colloidal suspension of Si0 ₂ , for example Ludox HS40 or AM-30, available from EI Dupont de Nemours & Co.

The aluminum source used is preferably Al (OH) 3, which is preferably previously dissolved in alkali solution.

Similarly, A1 ₂ C> 3 x 3H ₂ 0 or it can be used aluminum in the form of metal, which is also dissolved in alkali.

The reaction mixture further preferably contains potassium in the form of potassium hydroxide. The source of strontium is preferred strontium nitrate, although others

Strontium compounds, such as hydroxides,

Carbonates, oxides or sulfates can also be used. The reaction mixture can already during the synthesis of the zeolite of the KFI type, preferably bivalent

Metal cations are added. examples for this are

Calcium, magnesium and other alkaline earth metals, copper,

Manganese, chromium, lead, iron, cobalt, nickel and zinc. Here, the metals are directly in the framework of the zeolite

built-in. However, the proportion of these metals should not be too large, preferably in the range of at most 1 to 1000 ppm. The metals have particular influence on the formation of the zeolite of the KFI type.

The crystallization time also depends on the

Crystallization temperature from. Preferably, the

Crystallization in the range of about 90 to 200 ° C, more preferably 100 to 170 ° C, carried out and crystallization at this temperature over a period of preferably 12 to 240 hours, more preferably 24 to 130 hours,

carried out. Lower temperatures require longer

Reaction times to the same yield of the desired

To achieve product. The crystallization is preferably carried out in a sealed autoclave under autogenous pressure. Lower pressures also require longer crystallization times.

After the synthesis, the obtained KFI-type zeolite is preferably converted to the ammonium form. After that, the

Exchange of copper and possibly iron done. As already stated above, the exchange of copper and possibly iron can already take place after the preparation of the copper-containing zeolite of KFI type, or only after the thermal Treatment / hydrothermal treatment, which leads to the reduction or preferably to the disappearance of the MER phase.

The zeolite prepared according to the invention is suitable as a catalytically active component in SCR catalysis.

The zeolite according to the invention is thus suitable for

Reduction of nitrogen oxide emissions from mobile or

stationary combustion facilities.

Mobile combustion devices in the context of the invention are, for example, internal combustion engines of motor vehicles, in particular diesel engines, power generation units based on internal combustion engines or other units based on internal combustion engines. At the stationary

Incinerators are usually around

Power plants, combustion plants, waste incineration plants and also to heating systems of private households. Thus, the invention also relates to a method for reducing nitrogen oxide emissions in mobile or

stationary combustion devices, wherein the method is characterized in that an exhaust gas stream is passed over a copper-containing zeolite according to the invention.

The copper-containing zeolite according to the invention is advantageously applied to a catalyst support. suitable

Catalyst supports may be metallic or ceramic supports. Preferably, the catalyst support is a monolithic support. One speaks then of a so-called

Coating catalyst.

In general, catalysts can be used in full catalysts and

Coating catalysts are classified. While Full catalysts consist of more than 50% of a catalytically active material, coating catalysts consist of a catalyst support, which consists of a metal or a

Ceramics may be made, the surface of the

Catalyst support is provided with a coating. The coating is treated with a so-called wash-coat suspension, i. a slurry in a fluid medium on the

Catalyst carrier applied. Usually, then the applied wash-coat suspension is dried and

calcined. The coating can then be impregnated with another catalytically active component.

The invention thus also provides a washcoat containing the above-mentioned copper-containing zeolite according to the invention. D is ₅ o-value of the particles contained in the wash-coat approximately 2.5 to 7 .mu.m, preferably, more preferably 3 to 5 ym. The Dgo value is preferably 7 to 12 μm, more preferably 7.5 to 9.5 μm, still more preferably 8 to 9 μm. The Dio value is preferably 0.5 to 2.5 μm, more preferably 1.0 to 2 μm, still more preferably 1.3 to 1.7 μm.

The washcoat may contain a binder. suitable

Binders are known to the person skilled in the art, for example

Silica sols. In a further embodiment, the washcoat is free of additional binder. The binder fraction (here S1O2) is preferably already provided by the decomposition of the MER phase during the thermal treatment of the zeolite according to the invention. The washcoat can be applied to the carrier by conventional methods. Simple methods for this purpose are, for example, immersing the carrier in the washcoat and removing excess washcoat by blowing out with air or sucking off the air. Likewise it is possible the Apply coating using centrifuges by spraying the carrier body with the washcoat.

By applying the washcoat to the support, the finished SCR catalyst is obtained, which is characterized in that it comprises the zeolite according to the invention or the washcoat which contains the zeolite according to the invention. Here, the same preferences apply to the SCR catalyst as above for the zeolite and the washcoat.

Another object of the invention is a

Exhaust gas purification system comprising the SCR catalyst according to the invention. The exhaust gas purification system may further include other components, preferably one

Diesel Oxidation Catalyst (DOC) for Oxidation of

Hydrocarbons, a diesel particulate filter for

Reduction of particle emissions, possibly one

Hydrogenation catalyst for the treatment of urea, and a barrier catalyst subsequent to the SCR catalyst, which serves as an ammonia oxidation catalyst (slip catalyst).

The invention will now be described with reference to some embodiments, which, however, not as limiting the scope of

To understand invention, explained in more detail. In this case, reference is additionally made to the figures. Show it:

1 to 4 XRD spectra of a ZK-5 zeolite in the NH ₄ -form and after calcination at 500 ° C in the H-form.

FIGS. 5 to 8 XRD comparison spectra of a KFI and a MER zeolite. FIGS. 9 and 10 are toluene TPD spectra of an H-MFI (FIG.

and H-ZK5 zeolites (Fig. 10)

11 shows the ΝΟχ conversion and the N ₂ 0 formation

a Cu-ZK-5 according to the invention

Zeolites as a function of temperature.

FIG. 12 shows a TEM image of the

Cu-ZK-5 zeolites according to the invention with cubic morphology.

Exemplary embodiments Example 1

A zeolite Sr, K-ZK-5 was prepared via a synthesis gel in which a solution containing potassium aluminate with a

Silikasol and a Strontiumnitratlösung was mixed. The aluminate solution was prepared by dissolving Al (OH) 3 in aqueous potassium hydroxide (pellets, 85% dissolved in deionized water). This potassium aluminate solution was mixed with the

Strontium nitrate solution and a colloidal silica sol (e.g., AM-30, HS-30, HS-40 or LS-30) (Dupont).

(Gel composition 2.3 K ₂ 0: 0, 2Sr (N0 ₃ ) 2: 1 A1 ₂ 0 ₃ : 12 Si0 ₂ : 160 H ₂ 0).

In a production variant (gel composition 2.3 K ₂ O: 0, l Sr (N0 ₃₎ _2: 1 A1 ₂ 0 _3: 10 Si0 _2: 160 H ₂ 0), the aluminate solution was prepared as follows: 1.149 g of aluminum nitrate were dissolved in a Solution containing 15.0 g of deionized water and 6.463 g of potassium hydroxide pellets. The aluminate solution was allowed to rest at 20 ° C for two days until the wire was dissolved. The strontium nitrate solution was obtained by dissolving 4.455 g strontium-nirate (Sr (NO ₃ ) 2, 99 +%, Fluka) in 13.57 g deionized water. The Sr ²⁺ -containing silica solution was prepared by adding strontium nitrate solution to 240.64 g of Ludox AM-30. This suspension was then mixed with the

Mixed aluminate solution. The resulting gel was shaken for six minutes. The crystallization was at a

Temperature of 100-190 ° C performed in a stainless steel autoclave. The products were filtered, washed with deionized water and air dried at 120 ° C. Each sample was measured with XRD.

The zeolite according to the invention can be prepared very simply and economically, in particular by dispensing with costly organic templates, as opposed to

for example SSZ-13 with CHA structure.

Example 2: Ion exchange on ZK-5 zeolites

First, the zeolite prepared according to the invention was converted to the ammonium form.

130.0 g of ammonium nitrate were dissolved in 1170.0 g of deionized water and 130 g of zeolite powder were added. The suspension was stirred on a magnetic stirrer. Subsequently, the suspension was heated with stirring to 80 ° C and the mixture stirred for one hour. The suspension was then filtered off, the filter cake was washed with demineralized water and the process was repeated twice. Subsequently, the filter cake was dried overnight at 120 ° C.

The KFI-type zeolite used according to the invention is characterized by a problem-free ion exchange in comparison with, for example, SAPO-34. Fig. 1 shows a ZK5 zeolite after ion exchange in the ammonium form, wherein one can still recognize the proportions of the structure type MER. Fig. 1 shows the section for 2 theta of 10 - 20 °. After the zeolite was thermally treated (calcined) at 500 ° C for eight hours, one sees a clear

Decrease in the MER phase, whereas the signals for the KFI phase remain nearly stable. Also in the cutouts for 2 theta from 20 to 30 ° and 30 to 40 ° this decline can be seen (see Figures 2, 3 or 4, which the

full area shows).

Example 3: Copper Exchange

Batch size: 98.73 g

Cu content target value [%]: 4.50

98.73 g of zeolite powder were suspended in 500 ml of deionized water. To this suspension was added 41.52 g of copper terephthalate hydroxide and the reaction was stirred for 16 hours. Subsequently, the suspension was filtered off and the filter cake washed with demineralized water. The process was repeated once.

Subsequently, the filter cake was transferred to a porcelain dish and dried overnight at 120 ° C in. Of the

Copper content was 4.1%.

The KFI-type zeolite used according to the invention is characterized by a problem-free ion exchange in comparison with, for example, SAPO-34.

Example 4: Preparation of a washcoat of the ZK5-Cu type

38.98 g of the produced zeolite powder were suspended in a beaker with 85 g of deionized water. Subsequently were Add 29.2 g silica sol (Bindzil 2034 DI) and 4.8 g nitric acid (65% pa) to the suspension. Thereafter, the suspension was ground in a mill. Example 5: Measurement of NO _x Conversion of Cu-ZK-5

To determine the catalytic activity of the Cu-ZK-5 prepared according to the invention, a flow-through substrate (1 inch × 2 inch, 400 cpsi) was coated with a Cu-ZK-5-based washcoat according to the invention and the catalytic activity was measured. Fig. 11 shows the NO _x conversion of the Cu-ZK-5 under the test conditions: 1.0, NO _x : 500 ppm, GHSV = 84000 1 / h, 0 ₂ , C0 ₂ and H ₂ 0 5 vol. -%, N0 ₂ / NO _x = 0.3).

Example 6: Measurement of N ₂ O formation

Likewise, the formation of N ₂ O on the Cu-ZK-5 according to the invention was investigated. Fig. 11 shows the N ₂ 0 formation of a Cu-ZK-5 according to the invention with 4.1 wt .-% copper. When

Test conditions were chosen: 1.0, NO _x : 500 ppm, GHSV = 84000 1 / h, 0 ₂ , C0 ₂ and H ₂ 0 5 vol% each, N0 ₂ / NO _x = 0.3). One recognizes another distinct advantage of the small pore zeolite as SCR catalyst. The amount of N ₂ O formed is is very small and is of the same order of magnitude as an iron-containing zeolite, while the small- and medium-pore zeolites sometimes produce up to six times the amount of ₂ O. In addition, the copper-containing ZK-5 has significant advantages

towards, for example, a Fe ZK-5 zeolite already known from the literature. Copper-containing zeolites have significantly higher low-temperature activity, which is a crucial

positive factor in SCR catalysis and is. The zeolite according to the invention also has a sufficiently high hydrothermal stability compared to others

small pore zeolites such as MER or zeolite 3A.

Example 7: Adsorption behavior towards hydrocarbons

The zeolite according to the invention shows largely no adsorption of higher due to its molecular sieve effect

Hydrocarbons, e.g. branched long-chain aliphatics or aromatics.

To demonstrate the difference in adsorption behavior, toluene TPD's were measured. An H-MFI and an H-ZK-5 were investigated. The measurement was as follows:

The zeolite was heated in an inert gas stream and then loaded with toluene. Then, the sample was heated and registered by means of a MS at which temperature which amount of toluene was desorbed from the zeolite. The result is summarized in the following table and can also be seen in FIGS. 9 and 10:

Desorption toluene desorption toluene

Sample [μπιοΐ] [μπιοΐ / g sample]

H-MFI 64 636

H-ZK-5 0.518 5 It can be seen that H-ZK-5 adsorbs almost no toluene, whereas in MFI, which has larger pores, about 120 times as much toluene was adsorbed.

Claims

claims

Copper-bearing zeolite of the KFI type, by

in that the zeolite contains from 1 to 4.5% by weight of copper, based on the total weight of the zeolite.

Kupferhaitiger zeolite according to claim 1, characterized

in that the zeolite comprises primary crystallites with a cuboidal structure.

Copper-containing zeolite according to claim 1 or 2, characterized in that the zeolite comprises primary crystallites of cubic structure.

Kupferhaitiger zeolite according to one of claims 1 to 3, characterized in that the zeolite

Primary crystallites having a size in the range of 0.2 to 10 ym.

Copper-containing zeolite according to one of claims 1 to 4, characterized in that the zeolite contains iron.

Kupferhaitiger zeolite according to any one of claims 1 to 5, characterized in that the proportion of copper and iron together 1.01 to 10 wt .-%, preferably 1.01 to 4.51 wt .-%, based on the total weight of the zeolite , is.

Kupferhaitiger zeolite according to one of claims 1 to 6, characterized in that the zeolite has phase proportions of a zeolite of the structure type MER Kupferhaitiger zeolite according to one of claims 1 to 7, characterized in that the zeolite is largely free of phases of the structure types CHA, ERI and LTL. 9. A process for producing a copper-containing zeolite according to any one of claims 1 to 8, comprising the steps:

Providing a KFI-type zeolite which may have phase proportions of a MER-type zeolite,

Thermal treatment or hydrothermal treatment of the zeolite at a temperature> 500 ° C.

10. The method according to claim 9, characterized in that prior to the thermal / hydrothermal treatment or after the thermal / hydrothermal treatment, an exchange of copper and possibly iron takes place.

11. The method according to claim 10, characterized in that the zeolite is transferred before the exchange of copper and optionally iron in the ammonium form.

12. The method according to any one of claims 9 to 11, characterized

characterized in that the thermal / hydrothermal

Treatment over a period of 30 minutes to 50

Hours.

13. Use of a zeolite according to one of claims 1 to 8 in SCR catalysis.

14. Washcoat containing a zeolite according to one of

Claims 1 to 8.

15. SCR catalyst comprising a zeolite according to one of claims 1 to 8 or containing the washcoat according to claim 14.

An exhaust gas purification system containing the SCR catalyst according to claim 15.