Synthesis of zeolites with ferrierite structure

Abstract

Zeolites having a ferrierite framework structure are prepared using one or more of n-propylamine, n-butylamine, isobutylamine and n-amylamine as structure directing agents.

Description

[Technical Field]

[0001] The present disclosure relates to a method for preparing zeolites having an FER framework type. [Background technology]

[0002] Molecular sieve materials are classified by the Structure Commission of the International Zeolite Association according to the IUPAC Zeolite Nomenclature Rules, in which framework-type zeolites and other crystalline microporous materials with established structures are assigned three-letter codes with the meanings set forth in "Atlas of Zeolite Framework Types" by Ch. Baerlocher, LB McCusker and DH Olson (Elsevier, Sixth Revised Edition, 2007).

[0003] One known molecular sieve with an established structure is designated FER, 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 olefin isomerization.

[0004] In accordance with the present disclosure, it has been discovered that FER framework type zeolites can be synthesized using one or more of n-propylamine, n-butylamine, isobutylamine, and n-amylamine as structure directing agents, and in particular using alumina-coated silica as a composite source of silicon and aluminum. Summary of the Invention

[0005] In one aspect, a method for synthesizing a FER framework-type zeolite is provided, the method including: (1) forming a reaction mixture, the reaction mixture including: (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 any combination thereof; (d) a source of alkali metal (M); and (e) a source of hydroxide ions; (f) water; and (g) seed crystals; and (2) treating the reaction mixture under crystallization conditions sufficient to form zeolite crystals.

[0006] In another aspect, a FER framework type zeolite is provided which, in its as-synthesized form, contains within its pores one or more of n-propylamine, n-butylamine, isobutylamine, and n-amylamine. The following is further disclosed in relation to the present invention. [1] 1. A method for synthesizing a zeolite of the FER framework type, said method comprising: (1) forming a reaction mixture, the reaction mixture comprising: (a) a source of silicon; (b) the source of aluminum; (c) a structure directing agent (Q) consisting of n-propylamine, n-butylamine, isobutylamine, n-amylamine, or a combination thereof; (d) a source of alkali metal (M); (e) a source of hydroxide ions; (f) water, and (g) forming a seed crystal; and (2) subjecting said reaction mixture to crystallization conditions sufficient to form crystals of said zeolite. [2] The molar composition of the reaction mixture is as follows: [Table 1A] The method described in [1]. [3] The molar composition of the reaction mixture is as follows: [Table 1B] The method described in [1]. [4] The method of [1], wherein the reaction mixture comprises alumina-coated silica as a combined source of silicon and aluminum. [5] [5] The method according to [5], wherein the alkali metal is sodium, potassium, or a combination thereof. [6] The method according to [1], wherein the seed crystals comprise a FER framework zeolite. [7] The method according to [1], wherein the reaction mixture contains 0.01 ppm by weight to 10,000 ppm by weight of seed crystals. [8] The method according to [1], wherein the crystallization conditions include heating the reaction under autogenous pressure at a temperature of 125°C to 200°C for 24 hours to 240 hours. [9] A zeolite of the FER framework type, which in its as-synthesized form contains within its pores one or more of n-propylamine, n-butylamine, isobutylamine, and n-amylamine.

[10] SiO 2 / Al 2 O 3 The zeolite according to [9], wherein the molar ratio of

[11] SiO 2 / Al 2 O 3 The zeolite according to [9], wherein the molar ratio of

[12] H with a Bronsted acid site density of 350 μmol + / g ~ 500 μmol H + / g of the zeolite according to [9]. [Brief explanation of the drawings]

[0007] [Figure 1] 1 shows the powder X-ray diffraction (XRD) pattern of the as-synthesized zeolite of Example 1.

[0008] [Figure 2] 1 shows the powder XRD pattern of the ammonium-type zeolite of Example 2.

[0009] [Figure 3] 1 shows scanning electron microscope (SEM) images of the ammonium form of the zeolite of Example 2 at various magnifications.

[0010] [Figure 4] 1 shows the powder XRD pattern of the zeolite after synthesis in Example 3.

[0011] [Figure 5] 1 shows the powder XRD pattern of the zeolite after synthesis in Example 4.

[0012] [Figure 6] 1 shows the powder XRD pattern of the zeolite after synthesis in Example 5.

[0013] [Figure 7] 1 shows the powder XRD pattern of the synthesized zeolite of Example 6.

[0014] [Figure 8] 1 shows the powder XRD pattern of the ammonium-type zeolite of Example 7.

[0015] [Figure 9] 1 shows SEM images of the ammonium form of the zeolite of Example 7 at various magnifications.

[0016] [Figure 10] 1 shows the powder XRD pattern of the ammonium-type zeolite of Example 8.

[0017] [Figure 11] 1 shows SEM images of the ammonium form of the zeolite of Example 8 at various magnifications.

[0018] [Figure 12] 1 shows the powder XRD pattern of the synthesized zeolite of Example 9.

[0019] [Figure 13] 1 shows the powder XRD pattern of the synthesized zeolite of Example 10.

[0020] [Figure 14] 1 shows the powder XRD pattern of the synthesized zeolite of Example 11.

[0021] [Figure 15] 1 shows the powder XRD pattern of the synthesized zeolite of Example 12.

[0022] [Figure 16] 1 shows the powder XRD pattern of the synthesized zeolite of Example 13.

[0023] [Figure 17] 1 shows the powder XRD pattern of the synthesized zeolite of Example 14.

[0024] [Figure 18] 1 shows the powder XRD pattern of the synthesized zeolite of Example 15.

[0025] [Figure 19] 1 shows the powder XRD pattern of the synthesized zeolite of Example 16.

[0026] [Figure 20] 1 shows the powder XRD pattern of the synthesized zeolite of Example 17.

[0027] [Figure 21] 1 shows the powder XRD pattern of the synthesized zeolite of Example 18.

[0028] [Figure 22] 1 shows the powder XRD pattern of the synthesized zeolite of Example 19.

[0029] [Figure 23] 1 shows the powder XRD pattern of the synthesized zeolite of Example 20.

[0030] [Figure 24] 2 shows the powder XRD pattern of the synthesized zeolite of Example 21.

[0031] [Figure 25] 1 shows the powder XRD pattern of the synthesized zeolite of Example 22.

[0032] [Figure 26] 1 shows the powder XRD pattern of the ammonium-type zeolite of Example 23.

[0033] [Figure 27] 1 shows SEM images of the ammonium form of the zeolite of Example 23 at various magnifications.

[0034] [Figure 28] 1 shows the powder XRD pattern of the ammonium-type zeolite of Example 24.

[0035] [Figure 29] 1 shows SEM images of the ammonium form of the zeolite of Example 24 at various magnifications.

[0036] [Figure 30] 1 shows the powder XRD pattern of the synthesized zeolite of Example 25.

[0037] [Figure 31] 1 shows the powder XRD pattern of the synthesized zeolite of Example 26.

[0038] [Figure 32] 1 shows the powder XRD pattern of the synthesized zeolite of Example 27.

[0039] [Figure 33] 1 shows the powder XRD pattern of the synthesized zeolite of Example 28.

[0040] [Figure 34] 1 shows the powder XRD pattern of the synthesized zeolite of Example 29. DETAILED DESCRIPTION OF THE INVENTION

[0041] definition As used herein, the term "framework type" has the meaning set forth in "Atlas of Zeolite Framework Types" by Ch. Baerlocher, LB McCusker and DH Olson (Elsevier, Sixth Revised Edition, 2007).

[0042] The term "FER" refers to the FER topological type recognized by the International Zeolite Association Structure Committee.

[0043] The term "post-synthesis" refers to the form of the zeolite after crystallization and before removal of the structure directing agent.

[0044] The term "SiO2 / Al2O3 molar ratio" may be abbreviated as "SAR."

[0045] Zeolite synthesis FER framework-type zeolites are synthesized by (1) forming a reaction mixture containing (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 any combination thereof, (d) a source of alkali metal (M), (e) a source of hydroxide ions, (f) water, and (g) seed crystals; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form zeolite crystals.

[0046] The molar ratio composition of the reaction mixture may be within the ranges shown in Table 1. [Table 1] wherein Q comprises n-propylamine, n-butylamine, isobutylamine, n-amylamine, or a combination thereof.

[0047] Suitable silicon sources include colloidal silica, fumed silica, alkali metal silicates, and tetraalkyl orthosilicates.

[0048] Suitable aluminum sources include hydrated alumina, aluminum hydroxide, alkali metal aluminumates, aluminum alkoxides, and water-soluble aluminum salts (eg, aluminum nitrate).

[0049] Additionally or alternatively, a combined source of silicon and aluminum can be used. The combined source of silicon and aluminum can be alumina-coated silica. The alumina-coated silica can 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-alumina molar ratios can be used. The alumina-coated silica material can be used as the sole or primary source of silicon and aluminum in the reaction mixture. If present, another silicon source (e.g., colloidal silica) can be included.

[0050] The structure directing agent (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].

[0051] The alkali metal (M) is usually introduced into the reaction mixture along with a source of hydroxide ions. Examples of such metals include sodium and / or potassium, as well as lithium, rubidium, and cesium.

[0052] The reaction mixture typically contains seed crystals of the FER framework zeolite, preferably in an amount of 0.01 to 10,000 ppm by weight (e.g., 100 to 5000 ppm by weight) based on the weight of the reaction mixture. Seeding can be advantageous for improving FER selectivity and / or shortening the crystallization process.

[0053] Crystallization of the desired zeolite from the above reaction mixture can be carried out in a suitable reactor vessel (e.g., a polypropylene jar or Teflon-lined or stainless steel autoclave) under static, tumbling, or stirred conditions 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 hours to 240 hours (e.g., 36 hours to 100 hours)). Crystallization is typically carried out under pressure in an autoclave, with the reaction mixture subjected to autogenous pressure.

[0054] Once the desired zeolite crystals have 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 washed with water and then dried for a few seconds to a few 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 as-synthesized zeolite crystals. The drying step can be carried out under vacuum or atmospheric pressure.

[0055] As a result of the crystallization process, the recovered crystalline zeolite product contains within its pores at least a portion of the structure directing agent used in its synthesis.

[0056] The synthesized zeolite can be subjected to heat treatment, ozone treatment, or other treatment to remove some or all of the structure-directing agent used in the synthesis. Removal of the structure-directing agent can be accomplished 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 agent. Although reduced pressure may be used for the heat treatment, atmospheric pressure is preferred for convenience. The heat treatment is carried out at a temperature of at least 370°C (e.g., 400°C to 700°C) for at least 1 minute, typically not exceeding 20 hours (e.g., 1 to 8 hours).

[0057] FER framework zeolites can contain one or more non-framework alkali metals. It is usually desirable to remove the alkali metal cations by ion exchange and replace them with hydrogen, ammonium, or any other metal ion. Thus, the zeolite can be an Na-form zeolite, a K-form zeolite, or a combination of the Na- and K-forms, or an H-form zeolite, an ammonium-form zeolite, or a metal-exchanged zeolite. A typical ion-exchange technique involves contacting the synthetic zeolite with a solution containing the desired replacement cation or salt of the cation. Representative ion-exchange techniques are well known in the art. Ion exchange occurs after synthesis and may be performed either 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 temperatures ranging from 65°C to 315°C (e.g., 80°C to 150°C).

[0058] Zeolite characterization In the as-synthesized and anhydrous form, the FER framework zeolites may have chemical compositions, expressed in molar ratios, within the ranges shown in Table 2. [Table 2] wherein Q comprises n-propylamine, n-butylamine, isobutylamine, n-amylamine, or a combination thereof.

[0059] The FER framework zeolites synthesized by the methods described herein are characterized by their powder XRD patterns. Representative powder XRD patterns of FER framework zeolites can be found in "Collection of Simulated XRD Powder Patterns for Zeolites" by MMJ Treacy and JB Higgins (Elsevier, Fifth Revised Edition, 2007).

[0060] The X-ray diffraction data reported here were collected by standard techniques using copper Kα radiation. Altering the molar ratio of framework species in a particular sample due to changes in lattice parameters can result in subtle changes in the diffraction pattern. Furthermore, sufficiently small crystals can affect peak shape and intensity, causing noticeable peak broadening. Subtle changes in the diffraction pattern can also result from changes in the organic compounds used in preparation. Calcination can also cause slight shifts in the XRD pattern. Despite these small perturbations, the fundamental crystal lattice structure remains unchanged.

[0061] In some embodiments, the FER framework zeolite prepared as described herein has a composition of 350 μmol H as measured by n-propylamine temperature programmed desorption (TPD). + / g ~ 500 μmol H + / g (e.g., 375 μmol H + / g~450μmolH + The polymer may have a total Bronsted acid site density in the range of (1 / g). [Example]

[0062] The following illustrative examples are not intended to be limiting.

[0063] For the synthesis of Examples 1-29 below, the starting materials were loaded into 23 mL Teflon liners. The Teflon liners were then capped and sealed inside steel Parr autoclaves. The autoclaves were then heated in a convection oven at rolling conditions (43 rpm) and a holding temperature of 170°C for 2-3 days. The products were isolated by filtration, washed with copious amounts of deionized water, and finally dried in air at 85°C.

[0064] The molar ratios and conditions used in the synthesis of Examples 1-29 are summarized in Table 3 below.

[0065] Example 1 4.42 g of 1 M NaOH was mixed with 2.43 g of deionized water, and 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35, 24.5% solids) was added. Next, 0.35 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0066] The powder XRD pattern of the product is shown in Figure 1 and indicates that the material is a FER framework type zeolite.

[0067] Example 2 5.53 g of 1 M NaOH was mixed with 5.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35, 24.5% solids). Next, 0.43 g of isobutylamine was added, followed by 0.05 g of zeolite FER seeds.

[0068] The recovered composite was fired in air by placing a thin layer in a firing dish and heating it from room temperature to 120°C at 1°C / min and holding at 120°C for 2 hours. The temperature was then increased to 540°C at 1°C / min and held at 540°C for 5 hours. The temperature was then increased again to 595°C at 1°C / min and held at 595°C for 5 hours. The material was then cooled to room temperature.

[0069] The calcined material was converted to the ammonium form by heating in a solution of ammonium nitrate (typically 1 g NH4NO3 / 1 g zeolite in 10 mL HO at 85 °C for at least 3 hours). The material was then filtered. This was repeated twice for a total of three exchanges. Finally, the material was washed with deionized water to a conductivity of less than 100 μS / cm and dried in air at 85 °C.

[0070] The acid site density was measured using n-propylamine temperature programmed desorption (TPD) and was found to be 423 μmol H + / g.

[0071] Nitrogen micropore volume is 0.14 cm 3 / g (t-plot analysis), and the BET surface area is 324 m 2 / g.

[0072] The material had a SiO2 / Al2O3 molar ratio (SAR) of 30 as determined by inductively coupled plasma-atomic emission spectroscopy (ICP-AES).

[0073] The powder XRD pattern of the ammonium-form material is shown in Figure 2, indicating that the material is a FER framework-type zeolite. SEM images of the material at various magnifications are shown in Figure 3.

[0074] Example 3 4.42 g of 1 M KOH was mixed with 2.45 g of deionized water and 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35, 24.5% solids). Next, 0.35 g of isobutylamine was added, followed by 0.05 g of zeolite FER seeds.

[0075] The powder XRD pattern of the product is shown in Figure 4 and indicates that the material is a FER framework zeolite.

[0076] Example 4 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% solids), and 0.39 g of LUDOX® AS-30 colloidal silica. Next, 0.42 g of isobutylamine was added, followed by 0.05 g of zeolite FER seeds.

[0077] The powder XRD pattern of the product is shown in Figure 5 and indicates that the material is a FER framework type zeolite.

[0078] Example 5 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% solids) and 0.69 g of LUDOX® AS-30 colloidal silica. Next, 0.42 g of isobutylamine was added, followed by 0.05 g of zeolite FER seeds.

[0079] The powder XRD pattern of the product is shown in Figure 6 and indicates that the material is a FER framework zeolite.

[0080] Example 6 In a 23 mL Teflon autoclave, 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% solids), and 1.00 g of LUDOX® AS-30 colloidal silica. Next, 0.37 g of isobutylamine was added, followed by 0.05 g of zeolite FER seeds.

[0081] The powder XRD pattern of the product is shown in Figure 7 and indicates that the material is a FER framework zeolite.

[0082] Example 7 In a 23 mL Teflon autoclave, 4.74 g of 1 M NaOH, 2.86 g of deionized water, 3.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35, 24.5% solids), and 1.00 g of LUDOX® AS-30 colloidal silica were mixed. Next, 0.37 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0083] The recovered composite was calcined and then converted to the ammonium form according to the method of Example 2.

[0084] The acid site density was characterized using n-propylamine TPD and found to be 421 μmol H + / g.

[0085] Nitrogen micropore volume is 0.13 cm 3 / g (t-plot analysis) and the BET surface area is 285 m 2 / g.

[0086] The SiO2 / Al2O3 molar ratio (SAR) was 41 as determined by ICP-AES.

[0087] The powder XRD pattern of the ammonium-form material is shown in Figure 8 and indicates that the material is a FER framework-type zeolite. Figure 9 shows SEM images of the material at various magnifications.

[0088] Example 8 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% solids), and 1.80 g of LUDOX® AS-30 colloidal silica. 0.37 g of isobutylamine was then added, followed by 0.05 g of zeolite FER seed crystals.

[0089] The recovered composite was calcined and then converted to the ammonium form according to the method of Example 2.

[0090] Acid site density was characterized using n-propylamine TPD and 400 μmol H + / g.

[0091] The SiO2 / Al2O3 molar ratio (SAR) was 57 as determined by ICP-AES.

[0092] The powder XRD pattern of the ammonium-form material is shown in Figure 10 and indicates that the material is a FER framework-type zeolite with a small amount of STI. Figure 11 shows SEM images of the material at various magnifications.

[0093] Example 9 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% solids), and 2.20 g of LUDOX® AS-30 colloidal silica. 0.37 g of isobutylamine was then added, followed by 0.05 g of zeolite FER seed crystals.

[0094] The powder XRD pattern of the composite is shown in Figure 12 and indicates that the material is a FER framework type zeolite with a small amount of STI.

[0095] Example 10 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% solids), and 2.59 g of LUDOX® AS-30 colloidal silica. 0.37 g of isobutylamine was then added, followed by 0.05 g of zeolite FER seed crystals.

[0096] The powder XRD pattern of the composite is shown in Figure 13 and indicates that the material is a FER framework type zeolite with a small amount of STI.

[0097] Example 11 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% solids). Next, 0.29 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0098] The powder XRD pattern of the composite shows that the material is a FER framework zeolite with a small amount of STI, as shown in FIG.

[0099] Example 12 4.63 g of 1 M NaOH was mixed with 2.96 g of deionized water and 3.00 g of Nalco alumina-coated silica DVSZN007 (SAR=100, 26.5% solids), followed by the addition of 0.66 g of LUDOX® AS-30 colloidal silica, 0.36 g of isobutylamine, followed by the addition of 0.05 g of zeolite FER seeds.

[0100] The powder XRD pattern of the composite shows that the material is a FER framework zeolite with a small amount of STI, as shown in FIG.

[0101] Example 13 3.71 g of 1 M NaOH was mixed with 2.42 g of deionized water and 2.00 g of Nalco alumina-coated silica DVSZN007 (SAR=100, 26.5% solids), followed by 0.883 g of LUDOX® AS-30 colloidal silica, 0.29 g of isobutylamine, followed by 0.05 g of zeolite FER seeds.

[0102] The powder XRD pattern of the composite shows that the material is a FER framework zeolite with a small amount of STI, as shown in FIG.

[0103] Example 14 4.32 g of 1 M NaOH was mixed with 2.91 g of deionized water and 1.75 g of Nalco alumina-coated silica DVSZN007 (SAR=100, 26.5% solids). Next, 0.34 g of isobutylamine was added, followed by 0.05 g of zeolite FER seeds.

[0104] The powder XRD pattern of the composite shows that the material is a FER framework zeolite with a small amount of STI, as shown in FIG.

[0105] Example 15 6.32 g of 1 M NaOH was mixed with 0.60 g of deionized water and 2.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35, 24.5% solids), followed by 2.93 g of LUDOX® AS-30 colloidal silica, 0.50 g of isobutylamine, followed by 0.05 g of zeolite FER seeds.

[0106] The powder XRD pattern of the composite shows that the material is a FER framework zeolite with a small amount of STI, as shown in FIG.

[0107] Example 16 5.53 g of 1 M KOH was mixed with 0.20 g of deionized water and 3.50 g of Nalco alumina-coated silica DVSZN007 (SAR=35, 24.5% solids), followed by the addition of 1.17 g of LUDOX® AS-30 colloidal silica, 0.43 g of isobutylamine, followed by the addition of 0.05 g of zeolite FER seeds.

[0108] The powder XRD pattern of the composite shows that the material is a pure phase FER framework zeolite, as shown in FIG.

[0109] Example 17 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% solids), and 2.93 g of LUDOX® AS-30 colloidal silica. 0.53 g of isobutylamine was then added, followed by 0.05 g of zeolite FER seed crystals.

[0110] The powder XRD pattern of the composite is shown in Figure 20 and indicates that the material is a FER framework type zeolite with small amounts of STI and layered phases.

[0111] Example 18 5.29 g of 1 M NaOH was mixed with 5.13 g of deionized water, followed by 0.10 g of Reheis F2000 hydrated alumina and mixing thoroughly. 1.13 g of CAB-O-SIL® M-5 fumed silica was added and mixed until uniform. 0.41 g of isobutylamine was then added, followed by 0.05 g of zeolite FER seed crystals.

[0112] The powder XRD pattern of the composite is shown in Figure 21 and indicates that the material is a phase-pure FER framework zeolite.

[0113] Example 19 5.66 g of 1 M NaOH was mixed with 5.51 g of deionized water, then 0.075 g of Reheis F2000 hydrated alumina was added and mixed well. To this mixture, 1.22 g of CAB-O-SIL® M-5 fumed silica was added and mixed until uniform. 0.44 g of isobutylamine was then added, followed by 0.05 g of zeolite FER seed crystals. The molar ratios are shown in Table 2.

[0114] The powder XRD pattern of the composite is shown in Figure 22 and indicates that the material is a phase-pure FER framework zeolite.

[0115] Example 20 5.66 g of 1 M NaOH was mixed with 5.52 g of deionized water, then 0.05 g of Reheis F2000 hydrated alumina was added and mixed well. To this mixture, 1.22 g of CAB-O-SIL® M-5 fumed silica was added and mixed until uniform. 0.44 g of isobutylamine was then added, followed by 0.05 g of zeolite FER seed crystals.

[0116] The powder XRD pattern of the composite is shown in Figure 23 and indicates that the material is a FER framework type zeolite with a small amount of STI.

[0117] Example 21 5.28 g of 1 M NaOH was mixed with 5.16 g of deionized water, then 0.035 g of Reheis F2000 hydrated alumina was added and mixed well. To this mixture, 1.13 g of CAB-O-SIL® M-5 fumed silica was added and mixed until uniform. Next, 0.42 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0118] The powder XRD pattern of the composite is shown in Figure 24 and indicates that the material is a FER framework type zeolite with small amounts of STI and layered phases.

[0119] Example 22 5.29 g of 1 M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=100, 26.5% solids), then 0.39 g of isobutylamine was added, followed by 0.05 g of zeolite FER seeds.

[0120] The powder XRD pattern of the composite is shown in Figure 26 and indicates that the material is a FER framework zeolite with a small amount of STI.

[0121] Example 23 4.94 g of 1 M NaOH was mixed with 0.24 g of deionized water and 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=100, 26.5% solids). 0.39 g of isobutylamine was then added, followed by 0.05 g of zeolite FER seed crystals.

[0122] The recovered composite was calcined and then converted to the ammonium form according to the method of Example 2.

[0123] The acid site density was characterized using n-propylamine TPD and 425 μmol H + / g.

[0124] The nitrogen micropore volume was determined to be 0.06 cm by t-plot analysis. 3 / g and the BET surface area is 147 m 2 / g.

[0125] The SiO2 / Al2O3 molar ratio (SAR) was 77 as determined by ICP-AES.

[0126] The powder XRD pattern of the ammonium-form material is shown in Figure 26 and indicates that the material is a FER framework zeolite with small amounts of impurities. Figure 27 shows SEM images of the material at various magnifications.

[0127] Example 24 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). 0.39 g of isobutylamine was then added, followed by 0.05 g of zeolite FER seed crystals. The molar ratios are shown in Table 2.

[0128] The recovered composite was calcined and then converted to the ammonium form according to the method of Example 2.

[0129] The acid site density was characterized using n-propylamine TPD and found to be 424 μmol H + / g.

[0130] The nitrogen micropore volume was estimated to be 0.05 cm by t-plot analysis. 3 / g and the BET surface area is 134 m 2 / g.

[0131] The SiO2 / Al2O3 molar ratio (SAR) was 81 as determined by ICP-AES.

[0132] The powder XRD pattern of the ammonium-form material is shown in Figure 28 and indicates that the material is a FER framework zeolite with small amounts of impurities. Figure 29 shows SEM images of the material at various magnifications.

[0133] Example 25 3.53 g of 1 M NaOH was mixed with 1.59 g of deionized water and 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=100, 26.5% solids). 0.39 g of isobutylamine was then added, followed by 0.05 g of zeolite FER seed crystals.

[0134] The powder XRD pattern of the composite is shown in Figure 30 and indicates that the material is a FER framework type zeolite with small amounts of STI and layered phases.

[0135] Example 26 4.42 g of 1 M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35, 24.5% solids), followed by 0.28 g of n-propylamine and 0.05 g of zeolite FER seed crystals.

[0136] The powder XRD pattern of the composite is shown in Figure 31 and indicates that the material is a pure FER framework zeolite.

[0137] Example 27 4.42 g of 1 M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35, 24.5% solids), followed by 0.48 g of dipropylamine and 0.05 g of zeolite FER seed crystals.

[0138] The powder XRD pattern of the composite is shown in Figure 32 and indicates that the material is an MFI framework type zeolite.

[0139] Example 28 4.42 g of 1 M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35, 24.5% solids), followed by 0.35 g of n-butylamine and 0.05 g of zeolite FER seed crystals.

[0140] The powder XRD pattern of the composite is shown in Figure 33 and indicates that the material is a pure FER framework zeolite.

[0141] Example 29 4.42 g of 1 M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR=35, 24.5% solids), followed by 0.41 g of n-amylamine and 0.05 g of zeolite FER seed crystals.

[0142] The powder XRD pattern of the composite is shown in Figure 34 and indicates that the material is a mixture of FER and MFI framework-type zeolites. [Table 3] [Table 3] [Table 3] [Table 3] (a) Note: "Nalco(35)" refers to Nalco alumina-coated silica (SAR=35), "Nalco(100)" refers to Nalco alumina-coated silica (SAR=100), "Ludox" refers to LUDOX® AS-30 colloidal silica, "Cabosil" refers to CAB-O-SIL® M-5 fumed silica, and "Reheis" refers to Reheis F2000 hydrated alumina.

Claims

1. 1. A method for synthesizing a FER framework type zeolite, said method comprising: (1) forming a reaction mixture, the reaction mixture comprising: (a) a source of silicon; (b) a source of aluminum; (c) a structure-directing agent (Q) consisting of isobutylamine, n-amylamine, or a combination thereof; (d) a source of alkali metal (M); (e) a source of hydroxide ions; (f) water, and (g) forming a seed crystal; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the zeolite; The method, wherein the molar ratio composition of the reaction mixture is as follows: Table 1B

2. 10. The method of claim 1, wherein the reaction mixture comprises alumina-coated silica as a combined source of silicon and aluminum.

3. The method of claim 1 , wherein the alkali metal is sodium, potassium, or a combination thereof.

4. The method of claim 1 , wherein the seed crystals comprise a FER framework-type zeolite.

5. 10. The method of claim 1, wherein the reaction mixture comprises 0.01 ppm to 10,000 ppm by weight of seed crystals.

6. 10. The method of claim 1, wherein the crystallization conditions include heating the reaction under autogenous pressure at a temperature of 125°C to 200°C for 24 hours to 240 hours.

7. A zeolite of the FER framework type, which in its as-synthesized form contains within its pores one or more of isobutylamine and n-amylamine.

8. SiO ２ / Al ２ O ３ The zeolite according to claim 7, wherein the molar ratio of is in the range of 20 to 100.

9. SiO ２ / Al ２ O ３ The zeolite according to claim 7, wherein the molar ratio of is in the range of 25 to 85.

10. H with a Bronsted acid site density of 350 μmol ＋ / g to 500 μmol H ＋ 8. The zeolite of claim 7, wherein the zeolite has a molecular weight in the range of 1 / g.

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