Method for producing zeolite having controlled aluminum content by adjusting composition of synthesis mixture

Abstract

Provided is a method for producing zeolite having a controlled aluminum content, wherein the sodium hydroxide molar concentration of a zeolite synthesis mixture can be adjusted to adjust the aluminum content in synthesized CHA. The structure of the low aluminum-content CHA produced by the provided method does not collapse even after high-temperature hydrothermal treatment, and thus the catalytic activity of the CHA can be maintained. Moreover, by adjusting the aluminum content in the framework, the properties of the produced CHA significantly change, and thus the CHA can be applied to various fields.

Claims

1. A method of producing a zeolite having a controlled aluminum content, the method comprising: a first step of preparing a synthesis mixture comprising zeolite Y as a raw material of silica and alumina, trimethyladamantylammonium hydroxide (AdaOH) as a structure directing agent, and a sodium hydroxide; and a second step of preparing CHA by subjecting the synthesis mixture to a hydrothermal reaction and calcination; wherein in the synthesis mixture, the sodium hydroxide is included at a molar concentration of 0.2 to 0.4 based on 1 of the silica, wherein the synthesis mixture does not contain CHA seed crystal.

2. The method of claim 1, wherein the CHA has a Si/Al molar ratio of 9.9 to 14.2 from an EDX.

3. The method of claim 1, wherein, in the synthesis mixture, the trimethyladamantylammonium hydroxide is included at a molar concentration of 0.15 based on 1 of the silica.

4. The method of claim 1, wherein the hydrothermal reaction is carried out at 120 C. to 140 C. for 2 days to 6 days under rotation of 0 rpm to 60 rpm, resulting in CHA production.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 is a flowchart illustrating a method of producing a zeolite having a controlled aluminum content according to one embodiment of the present inventive concept.

(2) FIG. 2 shows X-ray diffraction (XRD) patterns of Preparation Examples 1 to 6 of the present inventive concept before and after calcination.

(3) FIG. 3 is nitrogen adsorption isotherms of Preparation Examples 1 to 6 of the present inventive concept.

(4) FIG. 4 shows SEM images of Preparation Examples 1 to 6 of the present inventive concept.

(5) FIG. 5 is XRD patterns of Preparation Examples 7 to 11 of the present inventive concept after a hydrothermal reaction was carried out under the stationary state.

(6) FIG. 6 shows SEM images of Preparation Examples 7 to 11 of the present inventive concept.

(7) FIG. 7 is NMR spectra for determining the chemical state of the aluminum and silicon of Preparation Examples 1 to 6 of the present inventive concept.

(8) FIG. 8 is ammonia temperature-programmed desorption (TPD) curves of Preparation Examples 1 to 6 of the present inventive concept.

(9) FIG. 9 shows correlation curves between the Si/Al molar ratio of the product changes with respect to the Na/Si molar ratio of a synthesis mixture according to one embodiment of the present inventive concept.

(10) FIGS. 10 and 11 shows the hydrothermal stability of Preparation Examples 1, 3, and 6 of the present inventive concept.

(11) FIGS. 12 and 13 are graphs showing the catalytic performance (NH.sub.3-SCR) of Preparation Examples 1, 3, and 6 of the present inventive concept.

(12) FIG. 14 shows graphs illustrating the catalytic performance (methanol-to-olefins (MTO) reaction) of Preparation Examples 1, 3, and 6 of the present inventive concept.

DETAILED DESCRIPTION

(13) Hereinafter, exemplary embodiments of the present inventive concept will be described in detail with reference to the accompanying drawings.

(14) However, the embodiments of the present inventive concept may be modified into various other forms, and the scope of the present inventive concept is not limited to the embodiments described below. In addition, the embodiments of the present inventive concept are provided to more completely explain the present inventive concept to those of ordinary skill in the art. Therefore, the shape, size, and the like of elements may be exaggerated in the drawings for clarity, and the elements denoted by the same reference numerals in the drawings are the same elements.

(15) FIG. 1 is a flowchart illustrating a method of producing a zeolite having a controlled aluminum content according to one embodiment of the present inventive concept.

(16) FIG. 1 discloses a method of producing a zeolite having a controlled aluminum content.

(17) S100 is a first step in which a synthesis mixture is prepared by adjusting the composition of a structure directing agent and sodium hydroxide based on zeolite Y. Here, zeolite Y may be a raw material as silica and alumina source. Examples of silica sources may include zeolites, silicates, silica hydrogels, silicic acid, colloidal silica, fumed silica, tetraalkyl orthosilicates, silica hydroxides, and precipitated silica. In addition, examples of alumina sources may include sodium aluminate (NaAlO.sub.2), AlCl.sub.3, Al.sub.2(SO.sub.4).sub.3, aluminum hydroxide (Al(OH).sub.3), kaolin, clay, and zeolites.

(18) The structure directing agent may be trimethyladamantylammonium hydroxide (AdaOH), benzyl ammonium hydroxide, benzyl ammonium chloride, or choline chloride, and in addition, other materials commonly used in the preparation of CHA may be included.

(19) The synthesis mixture may be a hydrogel in which the molar concentrations of the sodium hydroxide and the structure directing agent have been adjusted. In the synthesis mixture, the sodium hydroxide may be included at a concentration of, for example, 0.1 to 0.7 mole based on 1 mole of silica (SiO.sub.2), in which case the structure directing agent may be included at a concentration of 0.1 to 0.4 mole. Therefore, the aluminum content in the structure of the prepared CHA may vary depending on the usage amount of the sodium hydroxide.

(20) S200 is a second step in which the above-described synthesis mixture is subjected to a hydrothermal reaction and calcination to prepare CHA zeolite. After adding the synthesis mixture to an autoclave, a hydrothermal reaction is carried out at 120 to 140 C. for 2 to 6 days under rotation of 0 to 60 rpm. The product is recovered by centrifugation, washed, and then calcined at 550 C. for 12 h, CHA may be obtained.

MODES OF THE INVENTION

(21) Hereinafter, experimental examples will be provided to facilitate understanding of the present inventive concept. However, the following experimental examples are provided only to facilitate understanding of the present inventive concept and are not intended to limit the present inventive concept.

(22) The following Table 1 summarizes synthesis conditions of the experimental examples for preparing a CHA synthesis mixture.

(23) TABLE-US-00001 TABLE 1 Synthesis conditions Molar composition of Temper- Rotation synthesis mixture ature Time speed (SiO.sub.2:NaOH:AdaOH:H.sub.2O) ( C.) (d) (rpm) Preparation 1.0:0.2:0.15:22 140 4 40 Example 1 Preparation 1.0:0.3:0.15:22 Example 2 Preparation 1.0:0.4:0.15:22 Example 3 Preparation 1.0:0.45:0.15:22 Example 4 Preparation 1.0:0.5:0.15:22 Example 5 Preparation 1.0:0.6:0.15:22 Example 6 Preparation 1.0:0.2:0.14:22 0 Example 7 Preparation 1.0:0.3:0.14:22 Example 8 Preparation 1.0:0.4:0.14:22 Example 9 Preparation 1.0:0.45:0.14:22 Example 10 Preparation 1.0:0.5:0.14:22 Example 11

Preparation Example 1

(24) A synthesis mixture having a molar composition of 1.0 SiO.sub.2:0.2 NaOH:0.15 AdaOH:22 H.sub.2O was subjected to a hydrothermal reaction for 4 days at 140 C. under rotation of 40 rpm. The product was recovered by centrifugation, washed, and calcined at 550 C. for 12 h, and thereby CHA was obtained.

Preparation Example 2

(25) CHA was synthesized in the same manner as in Preparation Example 1 except that a NaOH molar concentration of 0.3 was used for the preparation of a synthesis mixture.

Preparation Example 3

(26) CHA was synthesized in the same manner as in Preparation Example 1 except that a NaOH molar concentration of 0.4 was used for the preparation of a synthesis mixture.

Preparation Example 4

(27) CHA was synthesized in the same manner as in Preparation Example 1 except that a NaOH molar concentration of 0.45 was used for the preparation of a synthesis mixture.

Preparation Example 5

(28) CHA was synthesized in the same manner as in Preparation Example 1 except that a NaOH molar concentration of 0.5 was used for the preparation of a synthesis mixture.

Preparation Example 6

(29) CHA was synthesized in the same manner as in Preparation Example 1 except that a NaOH molar concentration of 0.6 was used for the preparation of a synthesis mixture.

Preparation Example 7

(30) A synthesis mixture having a molar composition of 1.0 SiO.sub.2:0.2 NaOH:0.14 AdaOH:22 H.sub.2O was subjected to a hydrothermal reaction for 4 days at 140 C. in a stationary state without rotation. The product was recovered by centrifugation, washed and then calcined at 550 C. for 12 h, and thereby CHA was obtained.

Preparation Example 8

(31) CHA was synthesized in the same manner as in Preparation Example 7 except that a NaOH molar concentration of 0.3 was used for the preparation of a synthesis mixture.

Preparation Example 9

(32) CHA was synthesized in the same manner as in Preparation Example 7 except that a NaOH molar concentration of 0.4 was used for the preparation of a synthesis mixture.

Preparation Example 10

(33) CHA was synthesized in the same manner as in Preparation Example 7 except that a NaOH molar concentration of 0.45 was used for the preparation of a synthesis mixture.

Preparation Example 11

(34) CHA was synthesized in the same manner as in Preparation Example 7 except that a NaOH molar concentration of 0.5 was used for the preparation of a synthesis mixture.

(35) FIG. 2 shows XRD patterns of Preparation Examples 1 to 6 of the present inventive concept before and after calcination.

(36) Referring to FIG. 2, it can be seen that CHA with excellent crystallinity was produced in all of Preparation Examples 1 to 6 regardless of the molar concentration of sodium hydroxide in the synthesis mixture. In addition, it can be seen that the crystallinity of CHA was well maintained even after calcination.

(37) FIG. 3 is nitrogen adsorption-desorption isotherms of Preparation Examples 1 to 6 of the present inventive concept.

(38) Referring to FIG. 3, it can be seen that CHA having a large surface area and a large pore volume as shown in Table 2 was obtained due to the development of micropores.

(39) TABLE-US-00002 TABLE 2 BET surface area Pore volume.sup.a (m.sup.2g.sup.1) (cm.sup.3g.sup.1) Preparation Example 1 857 0.33 Preparation Example 2 834 0.31 Preparation Example 3 813 0.32 Preparation Example 4 793 0.32 Preparation Example 5 781 0.31 Preparation Example 6 682 0.27 .sup.aTotal pore volume calculated when P/P.sub.0 is 0.99

(40) Referring to Table 2, it can be seen that as the molar concentration (i.e., addition amount) of the sodium hydroxide increased, the surface area decreased but the pore volume did not significantly change, except for the case where CHA was prepared from a synthesis mixture having a high sodium hydroxide molar concentration of 0.6, whose surface area and pore volume were significantly small compared to other Preparation Examples.

(41) FIG. 4 shows SEM images of Preparation Examples 1 to 6 of the present inventive concept.

(42) Referring to FIG. 4, it can be seen that particles of a uniform size were produced in all of Preparation Examples 1 to 6 and that the particle size varied according to the sodium hydroxide concentration of the synthesis mixture. Therefore, by adjusting the sodium hydroxide concentration of the synthesis mixture, it is possible to adjust the particle size over a wide range of 0.1 to 5.0 m.

(43) FIG. 5 is XRD patterns of Preparation Examples 7 to 11 of the present inventive concept after a hydrothermal reaction was carried out in a stationary state.

(44) Referring to FIG. 5, it can be seen that CHA was successfully synthesized even in Preparation Examples 7 to 11, where the hydrothermal reaction was carried out under the stationary state.

(45) FIG. 6 shows SEM images of Preparation Examples 7 to 11 of the present inventive concept.

(46) Referring to FIG. 6, it can be seen that particles of a uniform size were produced even in Preparation Examples 7 to 11, where the hydrothermal reaction was carried out under the stationary state. In addition, it can be seen that even when the hydrothermal reaction was carried out under the stationary state, it is possible to adjust the particle size to a range of 0.1 to 5.0 m similarly to the case where the synthesis was carried out under rotation.

(47) FIG. 7 is NMR spectra for determining the chemical state of the aluminum and silicon of Preparation Examples 1 to 6 of the present inventive concept.

(48) Referring to FIG. 7, it can be seen that all the aluminum and silicon atoms of the CHA prepared in Preparation Examples 1 to 6 were in tetrahedral coordination in the zeolite framework.

(49) The following Table 3 summarizes the values calculated from FIG. 7.

(50) TABLE-US-00003 TABLE 3 Na/Si molar Si/Al molar ratio of Na/Al molar ratio of synthesis ratio of product mixture product.sup.a EDX.sup.a NMR.sup.b Preparation Example 1 0.20 0.40 14.2 12.5 Preparation Example 2 0.30 0.33 12.8 11.4 Preparation Example 3 0.40 0.48 9.9 9.2 Preparation Example 4 0.45 0.53 8.9 9.3 Preparation Example 5 0.50 0.68 5.9 6.7 Preparation Example 6 0.60 0.67 4.5 4.4 Preparation Example 7 0.20 0.36 11.7 Preparation Example 8 0.30 0.45 11.0 Preparation Example 9 0.40 0.48 10.1 Preparation Example 10 0.50 0.74 5.6 Preparation Example 11 0.60 0.86 3.7 .sup.aValues calculated from the EDX result; .sup.bValues calculated from the .sup.29Si MAS NMR spectrum

(51) Referring to Table 3, the Si/Al molar ratios obtained from the EDX result and the .sup.29Si MAS NMR spectrum decreased as the sodium hydroxide concentration of the synthesis mixture increased. This result indicates that the aluminum content in the zeolite framework increased, and shows that by varying the sodium hydroxide concentration of the synthesis mixture, it is possible to adjust the Si/Al molar ratio over a wide range of 4 to 14.

(52) FIG. 8 is ammonia temperature-programmed desorption (TPD) curves of Preparation Examples 1 to 6 of the present inventive concept.

(53) Referring to FIG. 8, it can be seen that as the sodium hydroxide content of the synthesis mixture varies, the aluminum content of the CHA prepared in Preparation Examples 1 to 6 changes and, accordingly, the strength and amount of strong acid sites and weak acid sites are different.

(54) The following Table 4 summarizes the values calculated from FIG. 8.

(55) TABLE-US-00004 TABLE 4 Amount of Amount of Total weak acid strong acid amount of sites sites acid sites (mmol/g) (mmol/g) (mmol/g) Preparation Example 1 0.521 0.443 0.964 Preparation Example 2 0.585 0.441 1.026 Preparation Example 3 0.698 0.440 1.138 Preparation Example 4 0.776 0.463 1.239 Preparation Example 5 1.050 0.678 1.728 Preparation Example 6 0.982 0.513 1.495

(56) In Table 4, the amount of weak acid sites is calculated from the peak area corresponding to a temperature below 300 C. in the TPD curves of FIG. 8, the amount of strong acid sites is calculated from the peak area corresponding to a temperature above 300 C. in the TPD curves of FIG. 8, and the total amount of acid sites is the sum of the amount of weak and strong acid sites, respectively. Here, it can be seen that the higher the sodium hydroxide concentration of the synthesis mixture, the higher the aluminum content of the synthesized CHA, resulting in an increase in the total amount of acid sites.

(57) FIG. 9 shows correlation curves between the Si/Al molar ratio of the product changes with respect to the Na/Si molar ratio of a synthesis mixture according to one embodiment of the present inventive concept.

(58) In FIG. 9, (a) simulates the correlation between the Na/Si molar ratio of the synthesis mixture and the Si/Al molar ratio of the product from the EDX result, and (b) is the correlation curves between the Na/Si molar ratio of the synthesis mixture and the Si/Al molar ratio of the product from the NMR spectra. The correlation between the Na/Si molar ratio of the synthesis mixture and the Si/Al molar ratio of the CHA synthesized can be well simulated as a quadratic function. Therefore, by adjusting the sodium hydroxide concentration of the synthesis mixture, it is possible to easily and reproducibly adjust the aluminum content of CHA to a target value.

(59) FIGS. 10 and 11 shows the hydrothermal stability of Preparation Examples 1, 3, and 6 of the present inventive concept.

(60) Referring to FIGS. 10 and 11, it can be seen that when the addition amount of sodium hydroxide was large (Preparation Example 6), CHA having a high aluminum content was synthesized, in which case, the crystal structure collapsed and the surface area drastically decreased even after 800 C. hydrothermal treatment. On the other hand, it can be seen that in the case of Preparation Example 1 where the aluminum content was relatively low, the amount of nitrogen adsorption hardly decreased even after 800 C. hydrothermal treatment, which indicates that the hydrothermal stability was quite excellent.

(61) FIGS. 12 and 13 are graphs showing the catalytic performance (NH.sub.3-SCR) of Preparation Examples 1, 3, and 6 of the present inventive concept.

(62) Referring to FIGS. 12 and 13, it can be seen that before hydrothermal treatment, CHA having a higher aluminum content (Preparation Example 6) exhibited higher NH.sub.3-SCR activity than other catalysts at high temperatures and lower NH.sub.3-SCR activity than other catalysts at below 400 C. After hydrothermal treatment, the activity at high temperatures was lower as the aluminum content was higher, and particularly in the case of CHA having the highest aluminum content (Preparation Example 6), almost no activity was exhibited over the entire temperature range. Therefore, since the hydrothermal stability of CHA becomes very low when the aluminum content is high, it can be seen that by controlling the sodium hydroxide content in the synthesis mixture, the hydrothermal stability of the produced CHA can be greatly improved.

(63) FIG. 14 shows graphs illustrating the catalytic performance (methanol-to-olefins (MTO) reaction) of Preparation Examples 1, 3, and 6 of the present inventive concept.

(64) Referring to FIG. 14, it can be seen that in the case of Preparation Examples 1 and 3 where the aluminum content was appropriate, high selectivity to ethylene and propylene and a slow deactivation of the MTO reaction were observed, whereas in the case of Preparation Example 6 where the aluminum content was high, a rapid deactivation was observed due to coke formation in the zeolite pores.

(65) Therefore, by properly adjusting the molar concentration of sodium hydroxide in the preparation of a zeolite synthesis mixture, it is possible to adjust the aluminum content of CHA synthesized and, accordingly, improve the activity and hydrothermal stability of zeolite used as a catalyst.

(66) In addition, since the control of the aluminum content in CHA structure causes the properties of the prepared CHA to be significantly changed, the CHA can be applied to various fields.