Method for the removal of nitrogen oxides from exhaust gas by selective catalytic reduction in presence of an SCR catalyst comprising a Fe-AEI zeolithic material essentially free of alkali metal

Abstract

A method for the removal of nitrogen oxides from exhaust, flue or off gas by selective catalytic reduction in presence of ammonia as a reductant, comprising the steps of contacting the exhaust gas together with the ammonia or a precursor thereof with an SCR catalyst comprising a Fe-AEI zeolite material essentially free of alkali metal ions (Alk), having the following molar compositions:
SiO.sub.2:oAl.sub.2O.sub.3:pFe:qAlk
wherein o is in the range from 0.001 to 0.2;
wherein p is in the range from 0.001 to 0.2;
wherein Alk is one or more of alkali metal ions and wherein q is below 0.02.

Claims

1. A method for the removal of nitrogen oxides from exhaust, flue or off gas by selective catalytic reduction in presence of ammonia as a reductant, comprising the steps of contacting the exhaust gas together with the ammonia or a precursor thereof with an SCR catalyst comprising a Fe-AEI zeolite material essentially free of alkali metal ions (Alk), having the following molar compositions:
SiO.sub.2:oAl.sub.2O.sub.3:pFe:qAlk wherein o is in the range from 0.001 to 0.2; wherein p is in the range from 0.001 to 0.2; wherein Alk is one or more of alkali metal ions and wherein q is below 0.02.

2. The method according to claim 1, wherein o is in the range from 0.005 to 0.1,p is in the range from 0.005 to 0.1 and q is below 0.005.

3. The method according to claim 1, wherein o is in the range from 0.02 to 0.07,p is in the range from 0.01 to 0.07 and q is below 0.001.

4. The method of claim 1, wherein the exhaust, flue or off gas contains more than about 1% steam.

5. The method of claim 1, wherein the exhaust, flue or off gas is at a temperature of above 200 C.

6. The method of claim 1, wherein the SCR catalyst is coated in or on a porous substrate, which may be a metallic substrate or an extruded ceramic substrate or a corrugated ceramic substrate.

7. The method of claim 6, wherein the substrate is in form of a flow-through monolith, a flow- through honeycomb, or a wall-flow filter.

8. The method of claim 6, wherein the SCR catalyst is coated in an amount of between 10 and 600 g/L calculated on the weight of catalyst material per volume of the total substrate plus the SCR catalyst.

9. The method of claim 8, wherein the amount is between 100 and 300 g/L.

10. The method of 6, wherein the SCR catalyst is coated in or on the porous substrate in form of a wash coat comprising the SCR catalyst and a binder comprising TiO.sub.2, SiO.sub.2, Al.sub.2O.sub.3, ZrO.sub.2, CeO.sub.2, and combinations thereof.

11. The method of claim 6, wherein the SCR catalyst is coated as a layer on the substrate and wherein the substrate comprises one or more further layers comprising a catalyst with a different catalytic activity or on other zeolite catalysts.

12. The method of claim 11, wherein the one or more further layers containing an oxidation catalyst comprising platinum or palladium or combinations thereof.

13. The method of claim 6, wherein the SCR catalyst is zone coated on the substrate, and wherein the substrate optionally comprises a further zone with an oxidation catalyst.

14. The method of claim 6, wherein the substrate comprises a zone with an ammonia slip catalyst.

15. The method of claim 1, wherein the exhaust, flue, or off gas is gas from a gas turbine system or a gas engine exhaust system.

16. The method of claim 15, wherein hydrocarbons and carbon monoxide further contained in the turbine exhaust gas are oxidized to water and carbon dioxide by contact with an oxidation catalyst.

17. The method of claim 16, wherein the oxidation catalyst is arranged up-stream or down-stream of the SCR catalyst.

18. The method of claim 15, wherein the gas turbine system is a system with a single cycle operational mode without any heat recovery system down-stream of a turbine.

19. The method of claim 15, wherein the SCR catalyst is arranged between a gas turbine and a heat recovery system generator.

20. A system for the cleaning of turbine exhaust gas comprising a catalyst unit downstream a gas turbine wherein the catalyst system comprises an SCR catalyst comprising a Fe-AEI zeolite material essentially free of alkali metal ions (Alk), having the following molar compositions:
SiO.sub.2:oAl.sub.2O.sub.3:pFe:qAlk wherein o is in the range from 0.001 to 0.2; wherein p is in the range from 0.001 to 0.2; wherein Alk is one or more of alkali metal ions and wherein q is below 0.02.

Description

BRIEF DESCRIPTION OF THE DRAWING

(1) FIG. 1 is a Powder X-ray diffraction pattern of as-prepared silicoaluminate AEI zeolite synthesized according to Example 1;

(2) FIG. 2 is a Powder X-ray diffraction pattern of as-prepared direct synthesis of Fe- and Na-containing silicoaluminate AEI zeolite synthesized according to the Example 2;

(3) FIG. 3 is a NO.sub.x conversion over Fe-AEI zeolite catalyst with and without Na present;

(4) FIG. 4 is a NO.sub.x conversion over Fe-AEI zeolite catalyst with and without Na present after accelerated hydrothermal aging (conditions given in Example 9);

(5) FIG. 5 is a NO.sub.x conversion over Na-free Fe-AEI compared to state-of-the-art Fe-CHA and Fe-Beta zeolites (also Na-free) after accelerated hydrothermal aging (conditions given in Example 9);

(6) FIG. 6 is a NO.sub.x conversion over Na-free Fe-AEI compared to state-of-the-art Na-free Fe-CHA after severe accelerated hydrothermal aging at 600 C. with 100% H.sub.2O aging; and

(7) FIG. 7 is a SEM image of the Fe-AEI material synthesized according to Example 2.

DETAILED DESCRIPTION OF THE INVENTION

(8) The catalyst according to the invention can preferably prepared by a method, comprising the following steps: (i) preparation of a mixture containing water, a high-silica zeolite as main source of silica and alumina, an alkyl-substituted cyclic ammonium cation as organic structure directing agent (OSDA), a source of iron, and a source of an alkali metal cation [Alk], to obtain a final synthesis mixture having the following molar composition:
SiO.sub.2:a Al.sub.2O.sub.3:b Fe:c OSDA:d Alk:e H.sub.2O wherein a is in the range from 0.001 to 0.2, more preferably in the range from 0.005 to 0.1, and most preferably in the range from 0.02 to 0.07; wherein b is in the range from 0.001 to 0.2; more preferably in the range from 0.005 to 0.1, and most preferably in the range from 0.01 to 0.07; wherein c is in the range from 0.01 to 2; more preferably in the range from 0.1 to 1, and most preferably in the range from 0.1 to 0.6; wherein d is in the range from 0.001 to 2; more preferably in the range from 0.05 to 1, and most preferably in the range from 0.1 to 0.8 and wherein e is in the range from 1 to 200; more preferably in the range from 1 to 50, and most preferably in the range from 2 to 20; (ii) crystallization of the mixture achieved in (i) in a reactor; (iii) recovery of the crystalline material achieved in (ii); (iv) removal of the OSDA occluded in the zeolite structure by calcination of the crystalline material from step (iii); (v) ion exchange of the alkali metal cation present in the crystalline material from step (iv), with ammonium or proton cations to obtain a final crystalline zeolite catalyst material with a low alkali content.

(9) Preferably, the high-silica zeolite structure used as a main source of silica and alumina has a Si/Al ratio above 5. Even more preferable the high silica zeolite has the FAU structure, e.g. Zeolite-Y.

(10) The iron source can be selected from iron oxides or iron salts, such as chlorides and other halides, acetates, nitrates or sulfates, among others, and combinations of them. The iron source can be introduced directly in the mixture of (i), or previously combined with the crystalline source of Si and Al.

(11) Any alkyl-substituted cyclic ammonium cation can be used as OSDA. Preferred are N,N-dimethyl-3,5-dimethylpiperidinium (DMDMP), N,N-diethyl-2,6-dimethylpiperidinium, N,N-dimethyl-2,6-dimethylpiperidinium, N-ethyl-N-methyl-2,6-dimethylpiperidinium, and combinations of them.

(12) In step (i) any alkali cation can be used, such as sodium, potassium, lithium, and cesium and combinations of them.

(13) In the crystallization step (ii), hydrothermal treatment is performed in an autoclave, under static or dynamic conditions. The preferred temperature is in the range of between 100 and 200 C., more preferably in the range of 130 to 175 C.

(14) The preferred crystallization time is ranged from 6 hours to 50 days, more preferably in the range of 1 to 20 days, and more preferably in the range of 1 to 7 days. It should be taken into consideration that the components of the synthesis mixture may come from different sources, and depending on them, times and crystallization conditions may vary.

(15) In order to facilitate the synthesis, crystals of AEI can be added as seeds, in quantities up to 25% by weight respect to the total of oxides, to the synthesis mixture. These can be added before or during the crystallization process.

(16) After the crystallization stage described in (ii), the resultant solids are separated from the mother liquor. The solids can be washed and separated from the mother liquor in (iii) by decantation, filtration, ultrafiltration, centrifugation, or any other solid-liquid separation technique.

(17) Organic material occluded inside the material can be removed by extraction and/or thermal treatment at temperatures over 25 C., preferentially between 400 and 750 C., during a period of time between 2 minutes and 25 hours.

(18) The material essentially free of occluded organic molecules is ion exchanged with ammonium or hydrogen to selectively remove the alkali metal cations by cation exchange procedures. The resulting exchanged AEI material can be calcined with air and/or nitrogen at temperatures between 200 and 700 C.

(19) The catalyst according to the invention can also be prepared by first synthesizing an AEI zeolite SSZ-39 according to known methods as described in U.S. Pat. No. 5,958,370. After synthesis the occluded organic material must be removed as described above. Afterwards the material essentially free of occluded organic molecules is ion exchanged with ammonium or hydrogen ions to selectively remove the alkali metal cations by cation exchange procedures. Instead of including iron compounds in the synthesis mixture, iron can be introduced into the cation exchanged material after step (v) by exchange, impregnation or solid-state procedures to yield a zeolite with the AEI framework containing iron species and essentially free of alkali metals.

(20) The Fe-AEI zeolite catalyst according to the invention is in particular useful in heterogeneous catalytic converter systems, such as when the solid catalyst catalyzes the reaction of molecules in the gas phase. To improve the applicability of the catalyst it can be applied into or onto a substrate that improves contact area, diffusion, fluid and flow characteristics of the gas stream wherein the present invention is applied.

(21) The substrate can be a metal substrate, an extruded substrate or a corrugated substrate made of ceramic paper. The substrate can be designed for the gas as a flow-through design or a wall-flow design. In the latter case the gas should flow through the walls of the substrate and in this way contribute with an additional filtering effect.

(22) The Fe-AEI zeolite catalyst is preferably present on or in the substrate in amounts between 10 and 600 g/L, preferably 100 and 300 g/L, as measured by the weight of the zeolite material per volume of the total catalyst article.

(23) The Fe-AEI zeolite catalyst is coated on or in the substrate using known wash-coating techniques. In this approach the zeolite powder is suspended in a liquid media together with binder(s) and stabilizer(s) where-after the washcoat can be applied onto the surfaces and walls of the substrate.

(24) The washcoat containing the Fe-AEI zeolite catalyst contains optionally binders based on TiO.sub.2, SiO.sub.2, Al.sub.2O.sub.3, ZrO.sub.2, CeO.sub.2 and combinations thereof.

(25) The Fe-AEI zeolite catalyst can also be applied as one or more layers on the substrate in combination with other catalytic functionalities or other zeolite catalysts. One specific combination is a layer with an oxidation catalyst containing for example platinum or palladium or combinations thereof.

(26) The Fe-AEI zeolite catalyst can be additionally applied in limited zones along the gas-flow-direction of the substrate.

(27) One important feature of the method according to the invent is the application of the Fe-AEI zeolite catalyst essentially free of alkali metals in the reduction of nitrogen oxides in the exhaust gas coming from a gas turbine using ammonia as a reductant.

(28) In this application, the catalyst may be placed directly downstream from the gas turbine and thus exposed to an exhaust gas containing water. It may also be exposed to large temperature fluctuations during gas turbine start-up and shut-down procedures.

(29) In certain applications, the Fe-AEI zeolite catalyst is used in a gas turbine system with a single cycle operational mode without any heat recovery system down-stream of the turbine. When placed directly after the gas turbine the catalyst is able to withstand exhaust gas temperatures up to 650 C. with a gas composition containing water.

(30) Further applications are in a gas turbine exhaust treatment system in combination with a heat recovery system such as a Heat Recovery System Generator (HRSG). In such a process design, the Fe-AEI catalyst is arranged in between the gas turbine and the HRSG. The catalyst can be also arranged in several locations inside the HRSG.

(31) Still an application of the Fe-AEI catalyst is the employment in combination with an oxidation catalyst for the abatement of hydrocarbons and carbon monoxide in the exhaust gas from the gas turbine.

(32) The oxidation catalyst, typically composed of precious metals, such as Pt and Pd, can be placed either up-stream or down-stream of the Fe-AEI catalyst and both inside and outside of the HRSG. The oxidation functionality can also be combined with the Fe-AEI catalyst into a single catalytic unit.

(33) The oxidation functionality may be combined directly with the Fe-AEI zeolite by using the zeolite as support for the precious metals. The precious metals can also be supported onto another support material and physically mixed with the Fe-AEI zeolite. The Fe-AEI catalyst and oxidation catalyst may be applied in layers onto a substrate such as a monolithic structure. For example, the zeolite SCR catalyst may be placed in a layer on top of a layer of the oxidation catalyst onto a substrate. The zeolite may also be placed in a downstream layer below an oxidation layer on the substrate.

(34) The Fe-AEI catalyst and oxidation catalyst can furthermore be applied in different zones onto the monolith or down-stream of each other.

(35) The Fe-AEI catalyst can also be combined in zones or layers with other catalytic materials. For example, the catalyst can be combined with an oxidation catalyst or another SCR catalyst.

(36) In all application of the method according to the invention mentioned and described above, the Fe-AEI zeolite catalyst can be applied in or on a substrate such as a monolithic structure or it can be shaped into pellets depending on the requirements of the application.

EXAMPLES

Example 1: Synthesis of AEI Zeolite (Na-containing Material)

(37) 4.48 g of a 7.4% wt aqueous solution of N,N-dimethyl-3,5-dimethylpiperidinium hydroxide was mixed with 0.34 g of a 20% wt aqueous solution of sodium hydroxide (NaOH granulated, Scharlab). The mixture was maintained under stirring 10 minutes for homogenization. Afterwards, 0.386 g of FAU zeolite (FAU, Zeolyst CBV-720 with SiO.sub.2/Al.sub.2O.sub.3=21) was added in the synthesis mixture, and maintained under stirring the required time to evaporate the excess of water until achieving the desired gel concentration. The final gel composition was SiO.sub.2: 0.047 Al.sub.2O.sub.3: 0.4 DMDMP: 0.2 NaOH: 15H.sub.2O. The resultant gel was charged into a stainless steel autoclave with a Teflon liner. The crystallization was then conducted at 135 C. for 7 days under static conditions. The solid product was filtered, washed with abundant amounts of water, dried at 100 C. and, finally, calcined in air at 550 C. for 4 h.

(38) The solid was characterized by Powder X-ray Diffraction, obtaining the characteristic peaks of the AEI structure (see FIG. 1). The chemical analysis of the sample indicates a Si/Al ratio of 9.0.

Example 2: Direct Synthesis of the Fe-containing AEI Structure (Na-containing Material)

(39) 1.98 g of a 7.0% wt aqueous solution of N,N-dimethyl-3,5-dimethylpiperidinium hydroxide was mixed with 0.24 g of a 20% wt aqueous solution of sodium hydroxide (NaOH granulated, Scharlab). The mixture was maintained under stirring 10 minutes for homogenization. Afterwards, 0.303 g of FAU zeolite (FAU, Zeolyst CBV-720 with SiO.sub.2/Al.sub.2O.sub.3=21) was added in the synthesis mixture. Finally, 0.11 g of a 20% wt aqueous solution of iron (III) nitrate [Fe(NO.sub.3).sub.3, Sigma Aldrich, 98%] was added, and the synthesis mixture was maintained under stirring the required time to evaporate the excess of water until achieving the desired gel concentration. The final gel composition was SiO.sub.2: 0.047 Al.sub.2O.sub.3: 0.01 Fe: 0.2 DMDMP: 0.2 NaOH: 15H.sub.2O. The resultant gel was charged into a stainless steel autoclave with a Teflon liner. The crystallization was then conducted at 140 C. for 7 days under static conditions. The solid product was filtered, washed with abundant water, and dried at 100 C. The solid was characterized by Powder X-ray Diffraction, obtaining the characteristic peaks of the AEI structure (see FIG. 2). Finally, the as-prepared solid was calcined in air at 550 C. for 4 h. The solid yield achieved was above 85% (without taking into account the organic moieties). The chemical analysis of the sample indicates a Si/Al ratio of 8.0, an iron content of 1.1% wt and a sodium content of 3.3% wt.

Example 3: Synthesis of Fe-containing Na-free AEI Zeolite by Post-synthetic Ion Exchange

(40) The Na-containing AEI material from Example 1 was first exchanged with a 0.1 M solution of ammonium nitrate (NH.sub.4NO.sub.3, Fluka, 99 wt %) at 80 C. Then, 0.1 g of ammonium-exchanged AEI zeolite was dispersed in 10 ml of deionized water with pH adjusted to 3 using 0.1 M HNO.sub.3. The suspension was heated to 80 C. under nitrogen atmosphere, 0.0002 moles of FeSO.sub.4.7H.sub.2O was then added, and the resultant suspension maintained under stirring at 80 C. for 1 h. Finally, the sample was filtered, washed and calcined at 550 C. for 4 h. The final iron content in the sample was 0.9 wt % and the Na content was below 0.0% wt.

Example 4: Removal of Na from the Direct Synthesis of the Fe-containing AEI Material from Example 2

(41) 200 mg of the calcined Fe-containing AEI material synthesized according to the Example 2, was mixed with 2 ml of a 1 M aqueous solution of ammonium chloride (Sigma-Aldrich, 98% wt), and the mixture was maintained under stirring at 80 C. for 2 h. The solid product was filtered, washed with abundant water, and dried at 100 C. Finally, the solid was calcined in air at 500 C. for 4 h. The chemical analysis of the sample indicates a Si/Al ratio of 8.0, an iron content of 1.1% wt and sodium content below 0.0% wt.

Example 5: Direct Synthesis of the Fe-containing CHA Structure (Na-containing Material)

(42) 0.747 g of a 17.2% wt aqueous solution of trimethyl-1-adamantammonium hydroxide (TMAdaOH, Sigma-Aldrich) was mixed with 0.13 g of a 20% wt aqueous solution of sodium hydroxide (NaOH, Sigma-Aldrich). Then, 0.45 g of a colloidal suspension of silica in water (40% wt, LUDOX-AS, Sigma-Aldrich) and 23 mg of alumina (75% wt, Condea) were added, and the resultant mixture maintained under stirring for 15 minutes. Finally, 0.458 g of a 2.5% wt aqueous solution of iron (III) nitrate [Fe(NO.sub.3).sub.3, Sigma Aldrich, 98%] was added, and the synthesis mixture was maintained under stirring the required time to evaporate the excess of water until achieving the desired gel concentration. The final gel composition was SiO.sub.2: 0.05 Al.sub.2O.sub.3: 0.01 Fe: 0.2 TMAdaOH: 0.2 NaOH: 20H.sub.2O. The resultant gel was charged into a stainless steel autoclave with a Teflon liner. The crystallization was then conducted at 160 C. for 10 days under static conditions. The solid product was filtered, washed with abundant water, and dried at 100 C. The solid was characterized by Powder X-ray Diffraction, obtaining the characteristic peaks of the CHA zeolite. Finally, the as-prepared solid was calcined in air at 550 C. for 4 h. The chemical analysis of the sample indicates a Si/Al ratio of 12.6, an iron content of 1.0% wt and a sodium content of 1.5% wt.

Example 6: Removal of Na from the Direct Synthesis of the Fe-containing CHA Structure from Example 5

(43) 100 mg of the calcined Fe-containing CHA material was mixed with 1 ml of a 1 M aqueous solution of ammonium chloride (Sigma-Aldrich, 98% wt), and the mixture maintained under stirring at 80 C. for 2 h. The solid product was filtered, washed with abundant water, and dried at 100 C. Finally, the solid was calcined in air at 500 C. for 4 h. The chemical analysis of the sample indicates a Si/Al ratio of 12.6, an iron content of 1.10% wt and a sodium content of 0.0% wt.

Example 7: Direct Synthesis of the Fe-containing Beta Structure (Na-free Material)

(44) 0.40 g of a 35% wt aqueous solution of tetraethylammonium hydroxide (TEAOH, Sigma-Aldrich) was mixed with 0.34 g of a 50% wt aqueous solution of tetraethylammonium bromide (TEABr, Sigma-Aldrich). Then, 0.60 g of a colloidal suspension of silica in water (40% wt, LUDOX-AS, Sigma-Aldrich) and 18 mg of alumina (75% wt, Condea) were added, and the resultant mixture maintained under stirring for 15 minutes. Finally, 0.33 g of a 5% wt aqueous solution of iron (III) nitrate [Fe(NO.sub.3).sub.3, Sigma Aldrich, 98%] was added, and the synthesis mixture was maintained under stirring the required time to evaporate the excess of water until achieving the desired gel concentration. The final gel composition was SiO.sub.2: 0.032 Al.sub.2O.sub.3: 0.01 Fe: 0.23 TEAOH: 0.2 TEABr: 20H.sub.2O. The resultant gel was charged into a stainless steel autoclave with a Teflon liner. The crystallization was then conducted at 140 C. for 7 days under static conditions. The solid product was filtered, washed with abundant water, and dried at 100 C. The solid was characterized by Powder X-ray Diffraction, obtaining the characteristic peaks of the Beta zeolite. Finally, the as-prepared solid was calcined in air at 550 C. for 4 h. The chemical analysis of the sample indicates a Si/Al ratio of 13.1, an iron content of 0.9% wt and a sodium content of 0.0% wt.

Example 8: Catalytic Test of Materials in the Selective Catalytic Reduction of Nitrogen Oxides Using Ammonia

(45) The activity of selected samples was evaluated in the catalytic reduction of NO.sub.x using NH.sub.3 in a fixed bed, quartz tubular reactor of 1.2 cm of diameter and 20 cm of length. The catalyst was tested using 40 mg with a sieve fraction of 0.25-0.42 mm. The catalyst was introduced in the reactor, heated up to 550 C. in a 300 NmL/min flow of nitrogen and maintained at this temperature for one hour. Afterwards 50 ppm NO, 60 ppm NH.sub.3, 10% 02 and 10% H.sub.2O was admitted over the catalyst while maintaining a flow of 300 mL/min. The temperature was then decreased stepwise between 550 and 250 C. The conversion of NO was measured under steady state conversion at each temperature using a chemiluminiscence detector (Thermo 62C).

Example 9: Accelerated Hydrothermal Ageing Treatment of Samples

(46) Selected samples were treated in a gas mixture containing 10% H.sub.2O, 10% O.sub.2 and N.sub.2 for 13 hours at 600 C. and afterwards their catalytic performance was evaluated according to Example 8.

Example 10: Influence of Na on Catalytic Performance of Fe-AEI Before Accelerated Aging

(47) The Fe-AEI zeolite containing Na as synthesized in Example 2 was tested according to Example 8. For comparison the Fe-AEI zeolite that was essentially free of Na, prepared according to Example 4, was also evaluated in the NH.sub.3-SCR reaction according to Example 8. The steady state-conversion of NO is shown as a function of temperature for the two catalysts in FIG. 3. The results clearly show the beneficial influence of removing the Na from the Fe-AEI zeolite as the NO.sub.x conversion increases at all temperatures.

Example 11: Influence of Na on Catalytic Performance of Fe-AEI after Accelerated Hydrothermal Aging

(48) The two zeolites that were tested in Example 10 (and prepared in Example 2 and Example 4) were aged under the accelerated aging conditions given in Example 9. The NO.sub.x conversion after aging is shown in FIG. 4.

Example 12: Catalytic Performance of Na-free Fe-AEI Compared to State-of the Art Fe-Beta and Fe-CHA Zeolites after Accelerated Hydrothermal Aging

(49) The NO.sub.x conversion over Na-free Fe-AEI, prepared according to Example 4, was evaluated in the NH.sub.3-SCR reaction after accelerated hydrothermal aging. For comparison Na-free Fe-CHA and Na-free Fe-Beta catalysts (prepared in Example 6 and Example 7, respectively), which represents state-of-the-art iron promoted zeolite catalysts, were also tested after accelerated hydrothermal aging. The measured NO.sub.x conversion is shown in FIG. 5. As can be seen the NO.sub.X conversion is higher over Na-free Fe-AEI compared to the other zeolites.

Example 13: Catalytic Performance of Na-free Fe-AEI Compared to State-of the Art Fe-CHA Zeolites after Severe Accelerated Hydrothermal Aging

(50) A severe accelerated aging of Na-free Fe-AEI and Na-free Fe-CHA prepared in Example 4 and Example 6, respectively, was performed by steaming the catalyst in a muffle furnace with 100% H.sub.2O for 13 h at 600 C. Afterwards the samples were evaluated according to Example 8. The NO.sub.x conversion in the NH.sub.3-SCR reaction over the two Fe-zeolites is shown in FIG. 6. As seen from FIG. 6 the improved stability of Fe-AEI is evident from the higher NO.sub.x seen at all temperatures.

Example 14: Determination of Crystal Size

(51) The Fe-containing AEI zeolite prepared in Example 2 was characterized using scanning electron miscoscopy to determine the size of the primary zeolite crystals. FIG. 7 shows an image of the obtained material that indicates primary crystallite sizes up to 400 nm.

Example 15: Measurement of Porosity Loss During Accelerated Hydrothermal Aging of Fe-AEI Zeolites

(52) The surface area and porosity of a sample prepared according to Example 4 and the same sample hydrothermally aged according to Example 9 using nitrogen adsorption. The results are given in Table 1. As seen the surface area and porosity of the Na-free Fe-AEI catalyst is decreased less than 25% after the accelerated hydrothermal aging treatment.

(53) TABLE-US-00001 TABLE 1 Surface area and porosity measurement of Na-free Fe-AEl before and after accelerated hydrothermal aging (according to Example 9). BET surface Micropore Micropore area area* volume* Material (m.sup.2/g) (m.sup.2/g) (cm.sup.3/g) Na-free Fe-AEl 516 505 0.25 HT AGED Na-free 411 387 0.19 Fe-AEl Percentage loss 20% 23% 24% *calculated using the t-plot method