Bimetal-exchanged zeolite beta from organotemplate-free synthesis and use thereof in the selective catalytic reduction of NOx

Abstract

The present invention relates to a process for the production of a zeolitic material having a BEA-type framework structure comprising YO.sub.2 and X.sub.2O.sub.3, wherein said process comprises the steps of (1) preparing a mixture comprising one or more sources for YO.sub.2 and one or more sources for X.sub.2O.sub.3; (2) crystallizing the mixture obtained in step (1); (3) subjecting the zeolitic material having a BEA-type framework structure obtained in step (2) to an ion-exchange procedure with Cu; and (4) subjecting the Cu ion-exchanged zeolitic material obtained in step (3) to an ion-exchange procedure with Fe; wherein Y is a tetravalent element, and X is a trivalent element, wherein the mixture provided in step (1) and crystallized in step (2) further comprises seed crystals comprising one or more zeolitic materials having a BEA-type framework structure, and wherein the mixture provided in step (1) and crystallized in step (2) does not contain an organotemplate as a structure-directing agent, as well as to the zeolitic material having a BEA framework structure per se, and to its use, in particular in a method for the treatment of NO.sub.x by selective catalytic reduction (SCR).

Claims

1. A process for the production of a zeolitic material having a BEA-type framework structure comprising YO.sub.2 and X.sub.2O.sub.3, the process comprising the following operations in the sequence listed: (1) preparing a mixture comprising one or more sources for YO.sub.2 and one or more sources for X.sub.2O.sub.3; (2) crystallizing the mixture obtained in step (1), wherein a molar ratio YO.sub.2: X.sub.2O.sub.3 of the mixture according to (1) ranges from 5 to 25; (3) subjecting a zeolitic material having a BEA-type framework structure obtained in step (2) to an ion-exchange procedure with Cu, and then calcining the Cu ion-exchanged zeolitic material obtained; and (4) subjecting the calcined Cu ion-exchanged zeolitic material obtained in step (3) to an ion-exchange procedure with Fe, wherein ferrocene is used for the ion-exchange with Fe in (4), wherein (4) is conducted using a solvent or solvent mixture selected from the group consisting of benzene, chlorobenzene, toluene, pentane, hexane, cyclohexane, heptane and combinations of two or more thereof, and then calcining the Fe ion-exchanged zeolitic material obtained; wherein: Y is a tetravalent element; X is a trivalent element; the mixture provided in step (1) and crystallized in step (2) further comprises seed crystals comprising one or more zeolitic materials having a BEA-type framework structure; and the mixture provided in step (1) and crystallized in step (2) does not contain an organotemplate as a structure-directing agent, and wherein: an amount of Cu in the zeolitic material obtained in (4) ranges from greater than 3 to 8 wt.-% calculated as CuO and based on the total weight of the zeolitic material; the amount of Fe in the zeolitic material obtained in (4) ranges from 1.0 to 7.5 wt.-% calculated as Fe.sub.2O.sub.3 and based on the total weight of the zeolitic material; and a molar ratio of Cu:X.sub.2O.sub.3 obtained in (4) ranges from 0.1 to 0.7.

2. The process of claim 1, wherein the seed crystals are zeolite beta.

3. The process of claim 1, wherein the zeolitic material obtained in step (2) comprises one or more alkali metals M.

4. The process of claim 1, wherein Y is selected from the group consisting of Si, Sn, Ti, Zr, Ge, and combinations of two or more thereof.

5. The process of claim 1, wherein the one or more sources for YO.sub.2 provided in step (1) comprises one or more silicates, or both.

6. The process of claim 1, wherein X is selected from the group consisting of Al, B, In, Ga, and combinations of two or more thereof.

7. The process of claim 1, wherein the one or more sources for X.sub.2O.sub.3 comprises one or more aluminate salts.

8. The process of claim 1, wherein the amount of seed crystals comprised in the mixture according to step (1) ranges from 0.1 to 30 wt.-% based on 100 wt.-% of YO.sub.2 in the one or more sources for YO.sub.2.

9. The process of claim 1, wherein the mixture according to step (1) further comprises one or more solvents.

10. The process of claim 9, wherein the molar ratio H.sub.2O:YO.sub.2 of the mixture according to step (1) ranges from 5 to 100.

11. The process of claim 1, wherein the molar ratio M: YO.sub.2 in the mixture according to step (1) ranges from 0.05 to 5.

12. The process of claim 1, wherein the molar ratio of YO.sub.2:X.sub.2O.sub.3:M in the mixture according to step (1) ranges from (1 to 200):1:(0.5 to 100).

13. The process of claim 1, wherein the crystallization in step (2) involves heating of the mixture.

14. The process of claim 13, wherein the crystallization in step (2) is conducted under solvothermal conditions.

15. The process of claim 13, wherein the crystallization in step (2) involves heating of the mixture for a period ranging from 5 to 160 h.

16. The process of claim 1, wherein after step (2) and prior to step (3) the process further comprises one or more of the following steps of: (i) isolating the zeolitic material having a BEA-type framework structure obtained in step (2); and (ii) optionally washing the zeolitic material having a BEA-type framework structure obtained in step (2); and/or (iii) optionally drying the zeolitic material having a BEA-type framework structure obtained in step (2); wherein the steps (i), (ii), (iii), and combinations thereof, can be conducted in any order.

17. The process of claim 1, wherein the ion-exchange of the zeolitic material having a BEA-type framework structure in step (3) comprises the steps of (3a) exchanging one or more of the ionic non-framework elements contained in the zeolitic material having a BEA-type framework structure obtained in step (2) with H.sup.+, NH.sub.4.sup.+, or both; and (3b) subjecting the zeolitic material having a BEA-type framework structure obtained in step (3a) to an ion-exchange procedure with Cu.

18. The process of claim 1, wherein the calcination of the Cu ion-exchanged zeolitic material is conducted at a temperature ranging from 300 to 850 C.

19. The process of claim 1, wherein the zeolitic material having a BEA-type framework structure formed in step (2) comprises zeolite beta.

20. The process of claim 2, wherein the seed crystals comprise a zeolitic material having the BEA-type framework structure.

21. The process of claim 1, wherein the ion-exchange procedure with Cu in step (3) is performed with one or more copper containing compounds, wherein the one or more copper containing compounds are one or more copper(II) salts.

22. The process of claim 1, wherein the ion-exchange procedure with Fe in step (4) is performed with one or more iron containing compounds, wherein the one or more iron containing compounds are selected from the group consisting of iron(II) salts, iron(III) salts, iron complexes and mixtures thereof.

23. The process of claim 1, wherein the ion-exchange procedure with Fe in step (4) comprises the steps of (4a) impregnating the Cu ion-exchanged zeolitic material obtained in step (3) with one or more iron containing compounds, and (4b) calcining the zeolitic material obtained in step (4a).

Description

DESCRIPTION OF THE FIGURES

(1) FIG. 1 displays the NO conversion efficiencies of Examples 4, 5 and 8-10 in a SCR reaction. In the figure, the reaction temperature is shown along the abscissa and the NO conversion efficiency is plotted along the ordinate.

(2) FIG. 2 displays the NO conversion efficiencies of Examples 7, 11 and 12 in a SCR reaction. In the figure, the reaction temperature is shown along the abscissa and the NO conversion efficiency is plotted along the ordinate.

(3) FIG. 3 displays the NO conversion efficiencies of Examples 4, 5 and 7 in a SCR reaction. In the figure, the reaction time is shown along the abscissa and the NO conversion efficiency is plotted along the ordinate.

(4) FIG. 4 displays the TG and DTG curves of Example 4. In the figure, the temperature is shown along the abscissa, while the sample mass and the rate of mass loss are respectively plotted along the left and the right ordinates.

(5) FIG. 5 displays the TG and DTG curves of Example 5. In the figure, the temperature is shown along the abscissa, while the sample mass and the rate of mass loss are respectively plotted along the left and the right ordinates.

(6) FIG. 6 displays the TG and DTG curves of Example 7. In the figure, the temperature is shown along the abscissa, while the sample mass and the rate of mass loss are respectively plotted along the left and the right ordinates.

(7) FIG. 7 displays the time-dependent NO conversion efficiencies of a regenerated catalyst and a fresh catalyst of Example 7. In the figure, the reaction time is shown along the abscissa and the NO conversion efficiency is plotted along the ordinate.

EXAMPLES

Example 1

Organotemplate-free Synthesis of the Sodium Form of Zeolite Beta

(8) 335.1 g of NaAlO.sub.2 were dissolved in 7,314 g of H.sub.2O while stirring, followed by addition of 74.5 g of zeolite beta seeds (Product-Nr. CP814C from Zeolyst International which was converted to the H-form by calcination at 500 C. for 5 h, wherein a heat ramp of 1 C./min was used for reaching the calcination temperature). The mixture was transferred into a 20 L autoclave together with 7,340 g of sodium waterglass solution (26.5-28.5 wt % SiO.sub.2 and 8.0-8.6 wt % Na.sub.2O, from Wllner GmbH & Co. KG) and 1,436 g of Ludox AS40, affording an aluminosilicate gel with a molar ratio of 1.00 SiO.sub.2:0.042 Al.sub.2O.sub.3:0.57 Na.sub.2O:17.5 H.sub.2O. The reaction mixture was heated to a temperature of 120 C., and then maintained at said temperature for 117 h. After having let the reaction mixture cool to room temperature, the solid was separated by filtration, repeatedly washed with deionized water and then dried at 120 C. for 16 h, affording 1,337 g of a white crystalline product.

(9) The chemical analysis indicates that the obtained zeolite has an SiO.sub.2:Al.sub.2O.sub.3 molar ratio of 10.89, and a sodium content (calculated as Na.sub.2O) of 6.69 wt % on the basis of the calcined material. The XRD measurement shows that the obtained crystalline product is zeolite beta.

Example 2

NH4-exchange of the Zeolite Beta from Example 1

(10) 1,000 g of the sodium form of zeolite beta as obtained from Example 1 were added into 10,000 g of an aqueous solution of ammonium nitrate (10 wt %). The suspension was heated to 80 C. and then kept at said temperature under continuous stirring for 2 h. The solid was filtered hot (without additional cooling) over a filter press. The filter cake was washed with distilled water of room temperature until the conductivity of the wash water was below 200 S cm.sup.1. The filter cake was then dried for 16 h at 120 C.

(11) The above procedure was repeated once, thus affording NH.sub.4-exchanged zeolite beta.

Example 3

Preparation of the H-form of Example 2

(12) The NH.sub.4-exchanged zeolitic material from Example 2 was calcined at 500 C. for 5 h to obtain the H-form thereof.

(13) The chemical analysis indicates that the H-form zeolite has a SiO.sub.2:Al.sub.2O.sub.3 ratio of 10.51 and a sodium content (calculated as Na.sub.2O) of 0.08 wt % on the basis of the calcined material.

(14) The specific surface area (BET method) of the H-form product is 458 m.sup.2/g. The temperature-programmed ammonia desorption reveals a total uptake of 1.86 mmol ammonia per gram zeolite.

(15) TABLE-US-00004 TABLE 1 Results of ammonium desorption measurements Temperature at Quantity Peak Number Maximum ( C.) (mmol/g) 1 214.1 1.25 2 340.9 0.61

Example 4

Preparation of Cu-exchanged Zeolite Beta (4.1 wt. %)

(16) 1.0 g of the NH.sub.4-exchanged zeolite beta from Example 2 was further Cu-exchanged with 100 ml of a 0.006 M Cu(CH.sub.3COO).sub.2 aqueous solution at 40 C. for 4 h. After the Cu-exchange process, the zeolite slurry was filtered, washed with deionized water and dried at 110 C. for 6 h. The obtained zeolite product was then calcined at 500 C. for 4 h.

(17) The Cu content of the obtained Cu-exchanged zeolite is 4.1 wt %, as determined by ICP measurement.

Example 5

Preparation of Fe-exchanged Zeolite Beta (2.7 wt.-%)

(18) 1.0 g of the NH.sub.4-exchanged zeolite beta from Example 2 was impregnated (using an incipient wetness method) with a toluene solution of ferrocene (0.1 g of ferrocene in 1.04 g of toluene) at room temperature for 48 h. The zeolite product was then calcined at 500 C. for 4 h so that the Fe species enter into the ion-exchangeable sites of zeolite beta.

(19) The Fe content of the obtained Fe-exchanged zeolite is 2.7 wt %, as determined by ICP measurement.

Example 6

Preparation of Cu(4.0 wt %)/Fe(0.6 wt %) Zeolite Beta by Ion-exchange

(20) 1.0 g of the NH.sub.4-exchanged zeolite beta from Example 2 was Cu-exchanged with 100 ml of a 0.006 M Cu(CH.sub.3COO).sub.2 aqueous solution at 50 C. for 2 h. After the Cu-exchange process, the zeolite slurry was filtered, washed with deionized water and then dried at 110 C. for 6 h. The Cu-exchanged zeolite was then calcined at 500 C. for 4 h.

(21) 0.82 g of the Cu-exchanged zeolite was then impregnated (using an incipient wetness method) with a toluene solution of ferrocene (0.028 g of ferrocene in 0.86 g of toluene) at room temperature for 48 h. After the Fe-impregnation process, the zeolite was finally calcined at 500 C. for 2 h to obtain a Cu/Fe-exchanged zeolite beta.

(22) The Cu and Fe contents of the obtained bimetal-exchanged zeolite beta are 4.0 wt % and 0.6 wt %, respectively, as determined by ICP measurement.

Example 7

Preparation of Cu(3.0 wt %)/Fe(1.3 wt %) Zeolite Beta by Ion-exchange

(23) 1.0 g of the NH.sub.4-exchanged zeolite beta from Example 2 was Cu-exchanged with 100 ml of a 0.0042 M Cu(CH.sub.3COO).sub.2 aqueous solution at 50 C. for 2 h. After the Cu-exchange process, the zeolite slurry was filtered, washed with deionized water and then dried at 110 C. for 6 h. The Cu-exchanged zeolite was then calcined at 500 C. for 4 h.

(24) 0.82 g of the Cu-exchanged zeolite was then impregnated (using an incipient wetness method) with a toluene solution of ferrocene (0.058 g of ferrocene in 0.9 g of toluene) at room temperature for 48 h. After the Fe-impregnation process, the zeolite was finally calcined at 500 C. for 2 h to obtain a Cu/Fe-exchanged zeolite beta.

(25) The Cu and Fe contents of the obtained bimetal-exchanged zeolite beta are 3.0 wt % and 1.3 wt %, respectively, as determined by ICP measurement.

Example 8

Preparation of Cu(4.7 wt %)/Fe(2.0 wt %) Zeolite Beta by Ion-exchange

(26) 1.0 g of the NH.sub.4-exchanged zeolite beta from Example 2 was Cu-exchanged with 100 ml of a 0.01 M Cu(CH.sub.3COO).sub.2 aqueous solution at 50 C. for 2 h. After the Cu-exchange process, the zeolite slurry was filtered, washed with deionized water and then dried at 110 C. for 6 h. The Cu-exchanged zeolite was then calcined at 500 C. for 4 h.

(27) 0.81 g of the Cu-exchanged zeolite was then impregnated (using an incipient wetness method) with a toluene solution of ferrocene (0.055 g of ferrocene in 0.85 g of toluene) at room temperature for 48 h. After the Fe-impregnation process, the zeolite was finally calcined at 500 C. for 2 h to obtain a Cu/Fe-exchanged zeolite beta.

(28) The Cu and Fe contents of the obtained bimetal-exchanged zeolite beta are 4.7 wt % and 2.0 wt %, respectively, as determined by ICP measurement.

Example 9

Preparation of Cu(2.8 wt %)/Fe(2.2 wt %) Zeolite Beta by Ion-exchange

(29) 1.0 g of the NH.sub.4-exchanged zeolite beta from Example 2 was Cu-exchanged with 100 ml of a 0.004 M Cu(CH.sub.3COO).sub.2 aqueous solution at 50 C. for 2 h. After the Cu-exchange process, the zeolite slurry was filtered, washed with deionized water and then dried at 110 C. for 6 h. The Cu-exchanged zeolite was then calcined at 500 C. for 4 h.

(30) 0.85 g of the Cu-exchanged zeolite was then impregnated (using an incipient wetness method) with a toluene solution of ferrocene (0.058 g of ferrocene in 0.89 g of toluene) at room temperature for 48 h. After the Fe-impregnation process, the zeolite was finally calcined at 500 C. for 2 h to obtain a Cu/Fe-exchanged zeolite beta.

(31) The Cu and Fe contents of the obtained bimetal-exchanged zeolite beta are 2.8 wt % and 2.2 wt %, respectively, as determined by ICP measurement.

Example 10

Preparation of Cu(1.9 wt %)/Fe(2.1 wt %) Zeolite Beta by Ion-exchange

(32) 0.5 g of the NH.sub.4-exchanged zeolite beta from Example 2 was Cu-exchanged with 50 ml of a 0.01 M Cu(CH.sub.3COO).sub.2 aqueous solution at 40 C. for 4 h. After the Cu-exchange process, the zeolite slurry was filtered, washed with deionized water and then dried at 110 C. for 6 h. The Cu-exchanged zeolite was then calcined at 500 C. for 4 h.

(33) 0.41 g of the Cu-exchanged zeolite was then Fe-exchanged with 50 ml of 0.05 M FeSO.sub.4 aqueous solution at room temperature for 24 h. After the Fe-impregnation process, the zeolitic slurry was dried at 110 C. for 6 h, and finally calcined in air at 500 C. for 2 h to obtain a Cu/Fe-exchanged zeolite beta.

(34) The Cu and Fe contents of the obtained bimetal-exchanged zeolite beta are 1.9 wt % and 2.1 wt %, respectively, as determined by ICP measurement.

Example 11

Preparation of Fe(1.2 wt %)/Cu(2.7 wt %) Zeolite Beta by Ion-exchange

(35) 1.0 g of the NH.sub.4-form zeolite beta from Example 2 was Fe-exchanged with 100 ml of a 0.003 M FeSO.sub.4 aqueous solution at room temperature for 24 h. After the ion-exchange process, the zeolite slurry was filtered, washed with deionized water and then dried at 110 C. for 6 h. The Fe-exchanged zeolite was then calcined at 500 C. for 4 h.

(36) 0.8 g of the Fe-exchanged zeolite was then impregnated (using an incipient wetness method) with an aqueous solution of Cu(NO.sub.3).sub.2 (0.094 g of Cu(NO.sub.3).sub.2 in 0.64 g of water) at room temperature for 12 h. After the Cu impregnation process, the zeolite was finally calcined at 500 C. for 2 h to obtain a Fe/Cu-exchanged zeolite beta.

(37) The Cu and Fe contents of the obtained bimetal-exchanged zeolite beta are 1.2 wt % and 2.7 wt %, respectively, as determined by ICP measurement.

Example 12

Preparation of a Mixture of Cu-exchanged and Fe-exchanged Zeolite Beta

(38) A comparative sample is prepared by a mechanical mixing of a Cu-exchanged zeolite beta (3.0 wt %) and the Fe-exchanged zeolite beta (1.3 wt %) with an equal mass ratio.

Example 13

Catalytic Testing

(39) The metal(s)-exchanged zeolitic materials chosen from Examples 4-12 were tested in a SCR reaction of reducing NO with NH.sub.3. The SCR reaction was carried out in a fixed-bed quartz reactor (inner diameter 6 mm) using ca. 0.18 g of catalyst (40-60 mesh). The catalyst was pre-treated in a N.sub.2 stream (flow rate=40 ml/min) at 500 C. for 1 h, and then cooled down to room temperature to introduce the reactant gas mixture, which contained 500 ppm NO 500 ppm NH.sub.3, 10% 02, and balance N.sub.2. The total flow rate was 400 ml/min, corresponding to a gas hourly space velocity (GHSV) of ca. 80,000 h.sup.1. The NO, NO.sub.2 and NO.sub.x (=NO+NO.sub.2) concentrations were continually measured by a chemiluminescence analyzer (ML9841AS, Monitor, USA). To avoid errors caused by the conversion of ammonia in the analyzer, an ammonia trap containing phosphoric acid solution was installed upstream. All data were obtained when the SCR reaction reached the steady state at each temperature. Accordingly, the catalytic results for the measured Examples are presented in FIGS. 1 and 2.

(40) FIG. 1 shows the catalytic results of two single-metal-exchanged zeolite beta samples (i.e., Examples 4 and 5) and three bimetal-exchanged zeolite beta samples (i.e., Examples 8-10). All three Cu/Fe-exchanged zeolites exhibit a wide temperature window from 125 C. to 550 C. with a NO conversion efficiency from 70% to 99%. Notably, the bimetal-exchanged zeolites display a higher SCR activity than the single-metal-exchanged zeolites at low temperatures. Or alternatively, said bimetal-exchanged zeolites reach a high catalytic reactivity much faster than the single-metal-exchanged zeolites as a function of an increasing temperature. More specifically, it can be seen from FIG. 1 that the Cu/Fe-exchanged zeolites already reach their maximum catalytic reactivity at about 150 C., whereas the Cu-exchanged zeolite and the Fe-exchanged zeolite need respectively a temperature of about 175 C. and 350 C. for reaching their full catalytic reactivity. Furthermore, the inventive bimetal-exchanged zeolites maintain a higher catalytic reactivity than the Cu-exchanged zeolite in the high temperature range from 300 C. to 550 C. Therefore, it has surprisingly been found that the inventive Cu/Fe-exchanged zeolites are superior to both two single-metal-exchanged zeolites in respect of the catalytic reactivity as well as the working-temperature range.

(41) FIG. 2 shows a comparison of the Cu/Fe-exchanged zeolite beta (Example 7), the Fe/Cu-exchanged zeolite beta (Example 11) and a mixture of Cu-exchanged zeolite and Fe-exchanged zeolite (Example 12) in a SCR reaction. The Cu/Fe-exchanged zeolite (Example 7) displays a higher catalytic reactivity than the mechanical mixture (Example 12) not only in the low temperature range (i.e., below 150 C.) but also in the high temperature range (i.e., above 300 C.). Moreover, it is surprisingly found that the Cu/Fe-exchanged zeolite exhibits a superior catalytic reactivity than the Fe/Cu-exchanged zeolite in particular at temperatures exceeding 350 C. Therefore, the sequence of the ion-exchange with Cu and Fe during the preparation process is essential for achieving the high catalytic performance of the inventive zeolite.

Example 14

Sulfur Resistance

(42) Examples 4, 5 and 7 were further tested with respect to their sulfur resistance during the catalytic reaction. To this effect, the procedure of Example 13 was repeated, wherein the gas mixture further contains 2% H.sub.2O and 100 ppm of SO.sub.2. FIG. 3 shows the time-dependent catalytic reactivities of Examples 4, 5 and 7 in the presence of 2% H.sub.2O and 100 ppm SO.sub.2 at 250 C. in a SCR process.

(43) During the measured reaction period, the Cu/Fe-exchanged zeolite beta (Example 7) maintains a high and stable NO conversion efficiency. In contrast, the Fe-exchanged zeolite beta (Example 5) shows a decrease of about 15% in the NO conversion efficiency in the first 0.5 h of the SCR reaction, and the reactivity of Cu-exchanged zeolite beta (Example 4) is observed to decrease continuously after 4 h of reaction. Therefore, the Cu/Fe-exchanged zeolite displays a much better sulfur resistance than the single-metal-exchanged zeolites in the SCR process.

(44) The above three zeolitic catalysts reacted after sulfation were then analyzed by TG/DTG measurements, the results of which are shown in FIGS. 4-6. The Cu/Fe-exchanged zeolite beta (Example 7) exhibits a relatively small desorption peak of sulfur species at around 430 C. when compared to the single-metal-exchanged zeolites (Examples 4 and 5). Said results of TG/DTG measurements indicate that the bimetal-exchanged zeolite has a low adsorption of sulfur during the catalytic reaction, which is a further proof of its high sulfur resistance.

(45) Furthermore, it is found that the bimetal-exchanged zeolite after sulfation can be effectively regenerated. More specifically, the regeneration of the sulfated catalysts was performed in a N.sub.2 stream (flow rate=40 ml/min) at 450 C. for 1 h to decompose the sulfite/sulfates on the surface. FIG. 7 shows that the regenerated catalyst of Example 7 maintains a high SCR reactivity almost as much as that of the corresponding fresh catalyst.

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