Synthesis of zeolites having a ferrierite structure

Abstract

Zeolites having a perierite framework structure are produced using one or more of n-propylamine, n-butylamine, isobutylamine, and n-amylamine as structure guides.

Description

Technology Field

[0001] The present disclosure relates to a method for manufacturing a zeolite having an FER framework type. Background Technology

[0002] Molecular sieve materials are classified by the Structure Committee of the International Zeolite Association according to the rules of the IUPAC Zeolite Nomenclature Committee. According to this classification, three-letter codes are assigned to framework-type zeolites and other crystalline microporous crystalline materials with established structures, as described in Ch. Baerlocher, LB. McCusker, and DH. Olson’s “Atlas of Zeolite Framework Types” (Elsevier, 6th edition, 2007).

[0003] One of the known molecular sieves with an established structure is a material designated as FER, which is a molecular sieve with a unique two-dimensional 10- / 8-membered ring channel system. Examples of FER framework-type zeolites include ferrierite, FU-9, ISI-6, NU-23, and ZSM-35. FER framework-type zeolites are useful catalytic components for various conversion processes, such as the isomerization of olefins.

[0004] According to the present disclosure, it has been revealed that an FER framework type zeolite can be synthesized using one or more of n-propylamine, n-butylamine, isobutylamine, and n-amylamine as a structure directing agent, particularly when alumina-coated silica is used as a combined source of silicon and aluminum. means of solving the problem

[0005] In one embodiment, a method for synthesizing a zeolite of the FER framework type is provided, the method comprising: (1) forming a reaction mixture comprising: (a) a source of silicon; (b) a source of aluminum; (c) a structure-directing agent (Q) comprising n-propylamine, n-butylamine, isobutylamine, n-amylamine, or a combination thereof; (d) a source of an alkali metal (M); (e) a source of hydroxide ions; (f) water; and (g) a seed; and (2) applying the reaction mixture to crystallization conditions sufficient to form crystals of the zeolite.

[0006] In another embodiment, as a zeolite of the FER framework type, a zeolite is provided that comprises one or more of n-propylamine, n-butylamine, isobutylamine, and n-amylamine in the pores in a synthesized state. Brief explanation of the drawing

[0007] Figure 1 shows the powder X-ray diffraction (XRD) pattern of the synthesized zeolite of Example 1. Figure 2 shows the powder XRD pattern of the ammonium-type zeolite of Example 2. Figure 3 shows scanning electron microscope (SEM) images of the ammonium-type zeolite of Example 2 at various magnifications. Figure 4 shows the powder XRD pattern of the synthesized zeolite of Example 3. Figure 5 shows the powder XRD pattern of the synthesized zeolite of Example 4. Figure 6 shows the powder XRD pattern of the synthesized zeolite of Example 5. Figure 7 shows the powder XRD pattern of the synthesized zeolite of Example 6. Figure 8 shows the powder XRD pattern of the ammonium-type zeolite of Example 7. Figure 9 shows SEM images of the ammonium-type zeolite of Example 7 at various magnifications. Figure 10 shows the powder XRD pattern of the ammonium-type zeolite of Example 8. Figure 11 shows SEM images of the ammonium-type zeolite of Example 8 at various magnifications. Figure 12 shows the powder XRD pattern of the synthesized zeolite of Example 9. Figure 13 shows the powder XRD pattern of the synthesized zeolite of Example 10. Figure 14 shows the powder XRD pattern of the synthesized zeolite of Example 11. Figure 15 shows the powder XRD pattern of the synthesized zeolite of Example 12. Figure 16 shows the powder XRD pattern of the synthesized zeolite of Example 13. Figure 17 shows the powder XRD pattern of the synthesized zeolite of Example 14. Figure 18 shows the powder XRD pattern of the synthesized zeolite of Example 15. Figure 19 shows the powder XRD pattern of the synthesized zeolite of Example 16. Figure 20 shows the powder XRD pattern of the synthesized zeolite of Example 17. Figure 21 shows the powder XRD pattern of the synthesized zeolite of Example 18. Figure 22 shows the powder XRD pattern of the synthesized zeolite of Example 19. Figure 23 shows the powder XRD pattern of the synthesized zeolite of Example 20. Figure 24 shows the powder XRD pattern of the synthesized zeolite of Example 21. Figure 25 shows the powder XRD pattern of the synthesized zeolite of Example 22. Figure 26 shows the powder XRD pattern of the ammonium-type zeolite of Example 23. Figure 27 shows SEM images of the ammonium-type zeolite of Example 23 at various magnifications. Figure 28 shows the powder XRD pattern of the ammonium-type zeolite of Example 24. Figure 29 shows SEM images of the ammonium-type zeolite of Example 24 at various magnifications. Figure 30 shows the powder XRD pattern of the synthesized zeolite of Example 25. Figure 31 shows the powder XRD pattern of the synthesized zeolite of Example 26. Figure 32 shows the powder XRD pattern of the synthesized zeolite of Example 27. Figure 33 shows the powder XRD pattern of the synthesized zeolite of Example 28. Figure 34 shows the powder XRD pattern of the synthesized zeolite of Example 29. Specific details for implementing the invention

[0008] definition

[0009] The term “framework type” as used herein has the meaning described in Ch. Baerlocher, LB McCusker and DH Olson’s “Atlas of Zeolite Framework Types” (Elsevier, 6th edition, 2007).

[0010] The term "FER" refers to the FER topology type recognized by the International Zeolite Association Structure Commission.

[0011] The term "as-synthesized" refers to the post-crystallization form of the zeolite before the removal of the structure-directing agent.

[0012] The term "SiO2 / Al2O3 molar ratio" can be abbreviated as "SAR".

[0013] Synthesis of zeolites

[0014] A zeolite of the FER framework type can be synthesized by forming a (1) reaction mixture comprising: (a) a silicon source; (b) an aluminum source; (c) a structure-directing agent (Q) comprising n-propylamine, n-butylamine, isobutylamine, n-amylamine, or any combination thereof; (d) a source of an alkali metal (M); (e) a source of hydroxide ions; (f) water; and (g) a seed; and by applying the (2) reaction mixture to crystallization conditions sufficient to form a zeolite crystal.

[0015] The reaction mixture may have a composition within the range presented in Table 1 in terms of molar ratio:

[0016]

[0017] Here, Q includes n-propylamine, n-butylamine, isobutylamine, n-amylamine, or any combination thereof.

[0018] Suitable sources of silicon include colloidal silica, precipitated silica, fumigated silica, alkali metal silicates, and tetraalkyl orthosilicates.

[0019] Suitable sources of aluminum include hydrated alumina, aluminum hydroxide, alkali metal aluminates, aluminum alkoxides, and water-soluble aluminum salts (e.g., aluminum nitrate).

[0020] Additionally or alternatively, a mixed source of silicon and aluminum may be used. The mixed source of silicon and aluminum may be alumina-coated silica. The alumina-coated silica may have a SiO2 / Al2O3 molar ratio of at least 30 (e.g., 30 to 170, or 35 to 100). Two or more alumina-coated silica materials having different silica-to-alumina molar ratios may be used. The alumina-coated silica material may be used as the sole or predominant source of silicon and aluminum in the reaction mixture. If present, a separate silicon source (e.g., colloidal silica) may be included.

[0021] The structure inducer (Q) comprises one or more of n-propylamine [CH3(CH2)2NH2], n-butylamine [CH3(CH2)3NH2], isobutylamine [(CH3)2CHCH2NH2], and n-amylamine [CH3(CH2)4NH2].

[0022] Alkali metals (M) are typically introduced into the reaction mixture along with a hydroxide ion source. Examples of such metals include sodium and / or potassium, lithium, rubidium, and cesium.

[0023] The reaction mixture also preferably contains seeds of a typical FER framework-type zeolite in an amount of 0.01 to 10,000 ppm by weight (e.g., 100 to 5,000 ppm by weight) of the reaction mixture. Seeding can be advantageous for improving selectivity for FER or shortening the crystallization process.

[0024] Crystallization of the desired zeolite from the above reaction mixture can be carried out under static, tumbling, or stirring conditions in a suitable reactor vessel, such as a polypropylene bottle or a Teflon-lined or stainless steel autoclave, at a temperature of 125°C to 200°C (e.g., 140°C to 185°C) for a time sufficient for crystallization to occur at the temperature used, e.g., about 24 to 240 hours (e.g., 36 to 100 hours). Crystallization is generally carried out by applying pressure in the autoclave so that the reaction mixture is subjected to autogenous pressure.

[0025] Once the desired zeolite crystals are formed, the solid product can be separated from the reaction mixture using standard mechanical separation techniques such as centrifugation or filtration. The recovered crystals are water-washed and then dried for a few seconds to minutes (e.g., 5 seconds to 10 minutes for flash drying) or for several hours (e.g., 4 hours to 24 hours for oven drying at 75°C to 150°C) to obtain the synthesized zeolite crystals. The drying step can be performed under vacuum or atmospheric pressure.

[0026] As a result of the crystallization process, the recovered crystalline zeolite product contains at least a portion of the structure-directing agent used in the synthesis within the pores.

[0027] The zeolite in its synthesized state may undergo heat treatment, ozone treatment, or other treatments to remove some or all of the structure-directing agents used in the synthesis. The removal of the structure-directing agents may be performed using a heat treatment (e.g., calcination) in which the synthesized material is heated in an atmosphere selected from air, nitrogen, or a mixture thereof at a temperature sufficient to remove some or all of the structure-directing agents. Pressures below atmospheric pressure may be used for the heat treatment, but atmospheric pressure is preferred for convenience. The heat treatment may be performed at a temperature of 370°C or higher (e.g., 400°C to 700°C) for at least 1 minute and generally within 20 hours (e.g., 1 to 8 hours).

[0028] FER framework-type zeolites may contain one or more non-framework alkali metals. Generally, it is desirable to remove alkali metal cations through ion exchange and replace them with hydrogen, ammonium, or desired metal ions. Accordingly, the zeolite may be a Na-type zeolite, a K-type zeolite, or a combination of Na- and K-type zeolites, and may be an H-type zeolite, an ammonium-type zeolite, or a metal-exchange type zeolite. A typical ion exchange technique involves contacting the synthesized zeolite with a solution containing a salt of the desired replacement cation. Representative ion exchange techniques are widely known in the field. Ion exchange occurs after synthesis and may take place before or after the zeolite is calcined. After contact with the salt solution of the desired replacement cation, the zeolite is typically washed with water and dried at a temperature ranging from 65°C to 315°C (e.g., 80°C to 150°C).

[0029] Characteristics of zeolite

[0030] In the synthesized anhydrous form, FER framework-type zeolites can have a chemical composition within the ranges presented in Table 2 in terms of molar ratios:

[0031]

[0032] Here, Q includes n-propylamine, n-butylamine, isobutylamine, n-amylamine, or any combination thereof.

[0033] As described in this specification, the synthesized FER framework-type zeolite is characterized by a powder XRD pattern. For a powder XRD pattern representative of the FER framework-type zeolite, refer to MMJ Treacy and JB Higgins' "Collection of Simulated XRD Powder Patterns for Zeolites" (Elsevier, 5th edition, 2007).

[0034] The X-ray diffraction data reported herein were collected by standard techniques using copper K-alpha radiation. Minor variations in the diffraction pattern may occur due to changes in the molar ratio of framework species in a particular sample caused by changes in the lattice constant. Additionally, sufficiently small crystals affect the shape and intensity of the peaks, causing them to broaden significantly. Minor variations in the diffraction pattern may also occur due to changes in the organic compounds used in the preparation. Calcination may also cause minor shifts in the XRD pattern. Despite these minor variations, the underlying crystal lattice structure remains unchanged.

[0035] In some embodiments, the FER framework-type zeolite prepared as described herein contains 350 μmol H of the composition, as determined by n-propylamine temperature-programmed desorption (TPD). + / g to 500μmol H + / g range (e.g., 375 μmol H + / g to 450μmol H + It can have a total Brønsted acid site density of / g.

[0036] example

[0037] The following exemplary examples are intended to be non-limiting.

[0038] In the following synthesis for Examples 1 to 29, the starting material was packed into a 23 mL Teflon liner. The Teflon liner was then capped and sealed inside a steel Parr autoclave. The autoclave was then heated in a convection oven maintained at 170°C for 2 to 3 days under tumbling conditions (43 rpm). The product was filtered to separate it, washed with a large amount of deionized water, and finally dried in air at 85°C.

[0039] The molar ratios and conditions used for the synthesis of Examples 1 to 29 below are summarized in Table 3 below.

[0040] Example 1

[0041] 4.42g of 1M NaOH was mixed with 2.43g of deionized water and 4.00g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content). Then, 0.35g of isobutylamine was added, followed by the addition of 0.05g of zeolite FER seed.

[0042] The powder XRD pattern of the product is shown in Fig. 1, which indicates that the material is an FER framework type zeolite.

[0043] Example 2

[0044] 5.53 g of 1 M NaOH was mixed with 5.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content). Then, 0.43 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed.

[0045] A thin layer of the recovered synthetic material was placed in a calcination dish and calcined in air. It was then heated in a muffle furnace from room temperature to 120°C at a rate of 1°C / min and maintained at 120°C for 2 hours. Next, the temperature was raised to 540°C at a rate of 1°C / min and maintained at 540°C for 5 hours. The temperature was raised again to 595°C at a rate of 1°C / min and maintained at 595°C for 5 hours. Subsequently, the material was cooled to room temperature.

[0046] Then, the calcined material was heated in an ammonium nitrate solution (typically 1 g NH4NO3 / 1 g zeolite in 10 mL of H2O at 85°C for at least 3 hours) to convert it to the ammonium form. The material was then filtered. This was repeated twice for a total of three exchanges. Finally, the material was washed with deionized water and dried in 85°C air until the conductivity was less than 100 μS / cm.

[0047] Acid site density was characterized using n-propylamine temperature-programmed desorption (TPD) and 423 μmol H + It was found to be / g.

[0048] The nitrogen micropore volume is 0.14 cm 3 It was confirmed to be / g (t-plot analysis), and the BET surface area is 324m 2 / g was.

[0049] As determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES), the material had a SiO2 / Al2O3 molar ratio (SAR) of 30.

[0050] The powder XRD pattern of the ammonium-type material is shown in Fig. 2, which indicates that the material is a FER framework type zeolite. SEM images of the material at various magnifications are shown in Fig. 3.

[0051] Example 3

[0052] 4.42g of 1M KOH was mixed with 2.45g of deionized water and 4.00g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solids). Then, 0.35g of isobutylamine was added, followed by the addition of 0.05g of zeolite FER seeds.

[0053] The powder XRD pattern of the product is shown in Fig. 4, which indicates that the material is an FER framework type zeolite.

[0054] Example 4

[0055] In a 23 mL Teflon autoclave, 5.41 g of 1 M NaOH was mixed with 2.45 g of deionized water, 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content), and 0.39 g of LUDOX® AS-30 colloidal silica. Then, 0.42 g of isobutylamine was added, followed by the addition of 0.05 g of zeolite FER seeds.

[0056] The powder XRD pattern of the product is shown in Fig. 5, which indicates that the material is an FER framework type zeolite.

[0057] Example 5

[0058] In a 23 mL Teflon autoclave, 5.41 g of 1 M NaOH and 3.15 g of deionized water were mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content) and 0.69 g of LUDOX® AS-30 colloidal silica. Then, 0.42 g of isobutylamine was added, followed by the addition of 0.05 g of zeolite FER seeds.

[0059] The powder XRD pattern of the product is shown in Fig. 6, which indicates that the material is an FER framework type zeolite.

[0060] Example 6

[0061] 4.74 g of 1 M NaOH was mixed with 2.86 g of deionized water, 3.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content) and 1.00 g of LUDOX® AS-30 in a 23 mL Teflon autoclave. Then, 0.37 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed.

[0062] The powder XRD pattern of the product is shown in Fig. 7, which indicates that the material is an FER framework type zeolite.

[0063] Example 7

[0064] 4.74 g of 1 M NaOH was mixed with 2.86 g of deionized water, 3.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content) and 1.00 g of LUDOX® AS-30 colloidal silica in a 23 mL Teflon autoclave. Then, 0.37 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed.

[0065] The recovered synthetic material was calcined and then converted into an ammonium form according to the method of Example 2.

[0066] The scatter spot density was characterized using n-propylamine TPD and 421 μmol H + It was found to be / g.

[0067] The nitrogen micropore volume is 0.13 cm³ 3 It was confirmed to be / g (t-plot analysis), and the BET surface area is 285m 2 / g was.

[0068] As determined by ICP-AES, the material had a SiO2 / Al2O3 molar ratio (SAR) of 41.

[0069] The powder XRD pattern of the ammonium-type material is shown in Fig. 8, which indicates that the material is a FER framework type zeolite. SEM images of the material at various magnifications are shown in Fig. 9.

[0070] Example 8

[0071] 4.74 g of 1 M NaOH was mixed with 3.05 g of deionized water, 2.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content), and 1.80 g of LUDOX® AS-30 colloidal silica. Then, 0.37 g of isobutylamine was added, followed by the addition of 0.05 g of zeolite FER seed.

[0072] The recovered synthetic material was calcined and then converted into an ammonium form according to the method of Example 2.

[0073] Acid site density was characterized using n-propylamine TPD and 400 μmol H + It was found to be / g.

[0074] As determined by ICP-AES, the material had a SiO2 / Al2O3 molar ratio (SAR) of 57.

[0075] The powder XRD pattern of the ammonium-type material is shown in Fig. 10, which indicates that the material is a FER framework type zeolite having a small amount of STI. SEM images of the material at various magnifications are shown in Fig. 11.

[0076] Example 9

[0077] 4.74 g of 1 M NaOH was mixed with 3.14 g of deionized water, 1.50 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content), and 2.20 g of LUDOX® AS-30 colloidal silica. Then, 0.37 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed.

[0078] The powder XRD pattern of the synthesized product is shown in Fig. 12, which indicates that the material is a FER framework type zeolite having a small amount of STI.

[0079] Example 10

[0080] 4.74 g of 1 M NaOH was mixed with 3.24 g of deionized water, 1.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content), and 2.59 g of LUDOX® AS-30 colloidal silica. Then, 0.37 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed.

[0081] The powder XRD pattern of the synthesized product is shown in Fig. 13, which indicates that the material is a FER framework type zeolite having a small amount of STI.

[0082] Example 11

[0083] 3.71 g of 1 M NaOH was mixed with 2.29 g of deionized water and 3.00 g of Nalco alumina-coated silica DVSZN007 (SAR=100; 26.5% solid content). Then, 0.29 g of isobutylamine was added, followed by the addition of 0.05 g of zeolite FER seed.

[0084] The powder XRD pattern of the synthesized product is shown in Fig. 14, which indicates that the material is a FER framework type zeolite having a small amount of STI.

[0085] Example 12

[0086] 4.63 g of 1 M NaOH was mixed with 2.96 g of deionized water, 3.00 g of Nalco alumina-coated silica DVSZN007 (SAR=100; 26.5% solid content), and 0.66 g of LUDOX® AS-30 colloidal silica. Then, 0.36 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed.

[0087] The powder XRD pattern of the synthesized product is shown in Fig. 15, which indicates that the material is a FER framework type zeolite minor STI.

[0088] Example 13

[0089] 3.71 g of 1 M NaOH was mixed with 2.42 g of deionized water, 2.00 g of Nalco alumina-coated silica DVSZN007 (SAR=100; 26.5% solid content), and 0.883 g of LUDOX® AS-30 colloidal silica. Then, 0.29 g of isobutylamine was added, followed by the addition of 0.05 g of zeolite FER seed.

[0090] The powder XRD pattern of the synthesized product is shown in Fig. 16, which indicates that the material is a FER framework type zeolite having a small amount of STI.

[0091] Example 14

[0092] 4.32g of 1M NaOH was mixed with 2.91g of deionized water and 1.75g ​​of Nalco alumina-coated silica DVSZN007 (SAR=100; 26.5% solids). Then, 0.34g of isobutylamine was added, followed by the addition of 0.05g of zeolite FER seeds.

[0093] The powder XRD pattern of the synthesized product is shown in Fig. 17, which indicates that the material is a FER framework type zeolite having a small amount of STI.

[0094] Example 15

[0095] 6.32 g of 1 M NaOH was mixed with 0.60 g of deionized water, 2.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content), and 2.93 g of LUDOX® AS-30 colloidal silica. Then, 0.50 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed.

[0096] The powder XRD pattern of the synthesized product is shown in Fig. 18, which indicates that the material is a FER framework type zeolite having a small amount of STI.

[0097] Example 16

[0098] 5.53 g of 1 M KOH was mixed with 0.20 g of deionized water, 3.50 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content), and 1.17 g of LUDOX® AS-30. Then, 0.43 g of isobutylamine was added, followed by the addition of 0.05 g of zeolite FER seed.

[0099] The powder XRD pattern of the synthesized product is shown in Fig. 19, which indicates that the material is a pure phase FER framework zeolite.

[0100] Example 17

[0101] 6.32 g of 1 M KOH was mixed with 0.61 g of deionized water, 2.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content), and 2.93 g of LUDOX® AS-30 colloidal silica. Then, 0.53 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed.

[0102] The powder XRD pattern of the synthesized product is shown in FIG. 20, which indicates that the material is a FER framework type zeolite with a small amount of STI and a layered phase.

[0103] Example 18

[0104] 5.29 g of 1 M NaOH was mixed with 5.13 g of deionized water, and then 0.10 g of Reheis F2000 hydrated alumina was added and mixed well. 1.13 g of CAB-O-SIL® M-5 fumed silica was added to this mixture and mixed until homogeneous. Subsequently, 0.41 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed.

[0105] The powder XRD pattern of the synthesized product is shown in Fig. 21, which indicates that the material is a normal-phase FER framework zeolite.

[0106] Example 19

[0107] 5.66 g of 1 M NaOH was mixed with 5.51 g of deionized water, and then 0.075 g of Reheis F2000 hydrated alumina was added and mixed well. 1.22 g of CAB-O-SIL® M-5 fumed silica was added to this mixture and mixed until homogeneous. Subsequently, 0.44 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed. The molar ratios are shown in Table 2.

[0108] The powder XRD pattern of the synthesized product is shown in Fig. 22, which indicates that the material is a normal-phase FER framework type zeolite.

[0109] Example 20

[0110] 5.66 g of 1 M NaOH was mixed with 5.52 g of deionized water, and then 0.05 g of Reheis F2000 hydrated alumina was added and mixed well. 1.22 g of CAB-O-SIL® M-5 fumed silica was added to this mixture and mixed until homogeneous. Then, 0.44 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed.

[0111] The powder XRD pattern of the synthesized product is shown in Fig. 23, which indicates that the material is a FER framework type zeolite having a small amount of STI.

[0112] Example 21

[0113] 5.28 g of 1 M NaOH was mixed with 5.16 g of deionized water, and then 0.035 g of Reheis F2000 hydrated alumina was added and mixed well. 1.13 g of CAB-O-SIL® M-5 fumed silica was added to this mixture and mixed until homogeneous. Subsequently, 0.42 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed.

[0114] The powder XRD pattern of the synthesized product is shown in Fig. 24, which indicates that the material is a FER framework type zeolite having a small amount of STI and a layered structure.

[0115] Example 22

[0116] 5.29 g of 1 M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR= 100; 26.5% solid content). Then, 0.39 g of isobutylamine was added, followed by the addition of 0.05 g of zeolite FER seed.

[0117] The powder XRD pattern of the synthesized product is shown in Fig. 26, which indicates that the material is a FER framework type zeolite having a small amount of STI.

[0118] Example 23

[0119] 4.94g of 1M NaOH was mixed with 0.24g of DI water and 4.00g of Nalco alumina-coated silica DVSZN007 (SAR= 100; 26.5%). Then, 0.39g of isobutylamine was added, followed by the addition of 0.05g of zeolite FER seeds.

[0120] The recovered synthetic material was calcined and then converted into an ammonium form according to the method of Example 2.

[0121] Acid spot density was characterized using n-propylamine TPD and 425 μmol H +It was found to be / g.

[0122] The nitrogen micropore volume is 0.06 cm 3 It was confirmed to be / g (t-plot analysis), and the BET surface area is 147m 2 / g was.

[0123] As determined by ICP-AES, the material had a SiO2 / Al2O3 molar ratio (SAR) of 77.

[0124] The powder XRD pattern of the ammonium-type material is shown in Fig. 26, which indicates that the material is a FER framework type zeolite with a small amount of impurities. Fig. 27 shows SEM images of the material at various magnifications.

[0125] Example 24

[0126] 4.41 g of 1 M NaOH was mixed with 0.75 g of deionized water and 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=100). Then, 0.39 g of isobutylamine was added, followed by the addition of 0.05 g of zeolite FER seeds. The molar ratios are shown in Table 2.

[0127] The recovered synthetic material was calcined and then converted into an ammonium form according to the method of Example 2.

[0128] Acid spot density was characterized using n-propylamine TPD and 424 μmol H + It was found to be / g.

[0129] The nitrogen micropore volume is 0.05 cm 3 It was found to be / g (t-plot analysis), and the BET surface area is 134m 2 / g was.

[0130] As determined by ICP-AES, the material had a SiO2 / Al2O3 molar ratio (SAR) of 81.

[0131] The powder XRD pattern of the ammonium-type material is shown in Fig. 28, which indicates that the material is a FER framework type zeolite with some impurities. Fig. 29 shows SEM images of the material at various magnifications.

[0132] Example 25

[0133] 3.53g of 1M NaOH was mixed with 1.59g of deionized water and 4.00g of Nalco alumina-coated silica DVSZN007 (SAR=100; 26.5% solid content). Then, 0.39g of isobutylamine was added, followed by the addition of 0.05g of zeolite FER seed.

[0134] The powder XRD pattern of the synthesized product is shown in Fig. 30, which indicates that the material is a FER framework type zeolite having a small amount of STI and a layered structure.

[0135] Example 26

[0136] 4.42 g of 1 M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content). Then, 0.28 g of n-propylamine was added, followed by the addition of 0.05 g of zeolite FER seed.

[0137] The powder XRD pattern of the synthesized product is shown in Fig. 31, which indicates that the material is a normal-phase FER framework type zeolite.

[0138] Example 27

[0139] 4.42 g of 1 M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content). Then, 0.48 g of dipropylamine was added, followed by the addition of 0.05 g of zeolite FER seed.

[0140] The powder XRD pattern of the synthesized product is shown in Fig. 32, which indicates that the material is an MFI framework type zeolite.

[0141] Example 28

[0142] 4.42 g of 1 M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solid content). Then, 0.35 g of n-butylamine was added, followed by the addition of 0.05 g of zeolite FER seed.

[0143] The powder XRD pattern of the synthesized product is shown in Fig. 33, which indicates that the material is a normal-phase FER framework type zeolite.

[0144] Example 29

[0145] 4.42 g of 1 M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35; 24.5% solids). Then, 0.41 g of n-amylamine was added, followed by the addition of 0.05 g of zeolite FER seeds.

[0146] The powder XRD pattern of the synthesized product is shown in Fig. 34, which indicates that the material is a mixture of FER and MFI framework-type zeolites.

[0147]

[0148] ( a ) "Nalco(35)" = Nalco alumina-coated silica (SAR=35); "Nalco(100)" = Nalco alumina-coated silica (SAR=100); "Ludox" = LUDOX® AS-30 colloidal silica; "Carbosil" = CAB-O-SIL® M-5 fumed silica; and "Reheis" = Reheis F2000 hydrated alumina.

Claims

Claim 1 A method for synthesizing a zeolite of the FER framework type, wherein the method comprises: (1) forming a reaction mixture comprising: (a) a source of silicon; (b) a source of aluminum; (c) a structure directing agent (Q) comprising isobutylamine, n-amylamine, or a combination thereof; (d) a source of an alkali metal (M); (e) a source of hydroxide ions; (f) water; and (g) a seed; and (2) applying the reaction mixture to crystallization conditions sufficient to form crystals of the zeolite, wherein the reaction mixture has a composition in the following molar ratios: Claim 2 A method according to claim 1, wherein the reaction mixture comprises alumina-coated silica as a mixed source of silicon and aluminum. Claim 3 A method according to claim 1, wherein the alkali metal is sodium, potassium, or a combination thereof. Claim 4 A method according to claim 1, wherein the seed comprises an FER framework type zeolite. Claim 5 The method of claim 1, wherein the reaction mixture comprises 0.01 ppm by weight to 10,000 ppm by weight of seeds. Claim 6 A method according to claim 1, wherein the crystallization condition comprises heating the reaction at a temperature of 125°C to 200°C under autogenous pressure for 24 to 240 hours. Claim 7 A zeolite of the FER framework type, comprising one or more of isobutylamine and n-amylamine in the pores in a synthesized state. Claim 8 In claim 7, a zeolite having an SiO2 / Al2O3 molar ratio in the range of 20 to 100. Claim 9 In claim 7, a zeolite having an SiO2 / Al2O3 molar ratio in the range of 25 to 85. Claim 10 In paragraph 7, 350 μmol H + / g to 500μmol H + Zeolite having a Brønsted scatter point density in the range of / g. Claim 11 delete Claim 12 delete

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