Synthesis of zeolites having a ferrierite structure

Abstract

A zeolite having a ferrierite framework structure produced using one or more of n-propylamine, n-butylamine, isobutylamine, and n-pentylamine as a structure directing agent.

Description

Technical Field

[0001] This disclosure relates to a method for preparing zeolites having a 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. Based on this classification, zeolites with established framework structures and other crystalline microporous materials are assigned three-letter codes and described in the "Atlas of Zeolite Framework Types" by Ch. Baerlocher, LB McCusker, and D. Holson (Elsevier, 6th Revision, 2007).

[0003] One known established molecular sieve structure is that of a material called FER, which is a molecular sieve with a unique two-dimensional 10 / 8-membered ring channel system. Examples of FER-frame type zeolites include magnesium alkali zeolite, FU-9, ISI-6, NU-23, and ZSM-35. FER-frame type zeolites are useful catalyst components for various conversion methods such as olefin isomerization.

[0004] According to this disclosure, it has been found that FER framework-type zeolites can be synthesized using one or more of n-propylamine, n-butylamine, isobutylamine and n-pentylamine as structure-directing agents, especially when alumina-coated silica is used as a combined source of silicon and aluminum. Summary of the Invention

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

[0006] On the other hand, zeolites of the FER framework type and in their post-synthetic form are provided, wherein the zeolite contains one or more of n-propylamine, n-butylamine, isobutylamine and n-pentylamine in its pores. Attached Figure Description

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

[0008] Figure 2 The powder XRD pattern of the ammonium zeolite of Example 2 is shown.

[0009] Figure 3 The images shown are scanning electron micrographs (SEM) of the ammonium zeolite of Example 2 at various magnifications.

[0010] Figure 4 The powder XRD pattern of the synthesized zeolite of Example 3 is shown.

[0011] Figure 5 The powder XRD pattern of the synthesized zeolite of Example 4 is shown.

[0012] Figure 6 The powder XRD pattern of the synthesized zeolite of Example 5 is shown.

[0013] Figure 7 The powder XRD pattern of the synthesized zeolite of Example 6 is shown.

[0014] Figure 8 The powder XRD pattern of the ammonium zeolite of Example 7 is shown.

[0015] Figure 9 SEM images of the ammonium zeolite of Example 7 at various magnifications are shown.

[0016] Figure 10 The powder XRD pattern of the ammonium zeolite of Example 8 is shown.

[0017] Figure 11 SEM images of the ammonium zeolite of Example 8 at various magnifications are shown.

[0018] Figure 12 The powder XRD pattern of the synthesized zeolite of Example 9 is shown.

[0019] Figure 13 The powder XRD pattern of the synthesized zeolite of Example 10 is shown.

[0020] Figure 14 The powder XRD pattern of the zeolite as synthesized in Example 11 is shown.

[0021] Figure 15 The powder XRD pattern of the synthesized zeolite of Example 12 is shown.

[0022] Figure 16 The powder XRD pattern of the synthesized zeolite of Example 13 is shown.

[0023] Figure 17 The powder XRD pattern of the synthesized zeolite of Example 14 is shown.

[0024] Figure 18The powder XRD pattern of the synthesized zeolite of Example 15 is shown.

[0025] Figure 19 The powder XRD pattern of the synthesized zeolite of Example 16 is shown.

[0026] Figure 20 The powder XRD pattern of the synthesized zeolite of Example 17 is shown.

[0027] Figure 21 The powder XRD pattern of the synthesized zeolite of Example 18 is shown.

[0028] Figure 22 The powder XRD pattern of the synthesized zeolite of Example 19 is shown.

[0029] Figure 23 The powder XRD pattern of the synthesized zeolite of Example 20 is shown.

[0030] Figure 24 The powder XRD pattern of the zeolite as synthesized in Example 21 is shown.

[0031] Figure 25 The powder XRD pattern of the synthesized zeolite of Example 22 is shown.

[0032] Figure 26 The powder XRD pattern of the ammonium zeolite of Example 23 is shown.

[0033] Figure 27 SEM images of the ammonium zeolite of Example 23 at various magnifications are shown.

[0034] Figure 28 The powder XRD pattern of the ammonium zeolite of Example 24 is shown.

[0035] Figure 29 SEM images of the ammonium zeolite of Example 24 at various magnifications are shown.

[0036] Figure 30 The powder XRD pattern of the synthesized zeolite of Example 25 is shown.

[0037] Figure 31 The powder XRD pattern of the synthesized zeolite of Example 26 is shown.

[0038] Figure 32 The powder XRD pattern of the synthesized zeolite of Example 27 is shown.

[0039] Figure 33 The powder XRD pattern of the synthesized zeolite of Example 28 is shown.

[0040] Figure 34 The powder XRD pattern of the synthesized zeolite of Example 29 is shown. Detailed Implementation

[0041] definition

[0042] As used herein, the term “frame type” has the meaning described in Ch. Baerlocher, LB McCusker, and D. Holson (Elsevier, 6th revision, 2007) in their “Atlas of Zeolite Framework Types”.

[0043] The term "FER" refers to the FER topology type recognized by the International Zeolite Association's Structural Committee.

[0044] The term "as-synthesized" refers to zeolite in its original form after crystallization and before the removal of the structure-directing agent.

[0045] The term "SiO2 / Al2O3 molar ratio" can be abbreviated as "SAR".

[0046] Synthesis of zeolites

[0047] FER-framework type zeolites can be synthesized by: (1) forming a reaction mixture comprising: (a) a silicon source; (b) an aluminum source; (c) a structure-directing agent (Q) comprising n-propylamine, n-butylamine, isobutylamine, n-pentylamine, or any combination thereof; (d) an alkali metal (M) source; (e) a hydroxide ion source; (f) water; and (g) a seed crystal; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of zeolite.

[0048] The reaction mixture may have a composition in the range listed in Table 1, expressed in molar ratios:

[0049] Table 1

[0050]

[0051]

[0052] Where Q includes n-propylamine, n-butylamine, isobutylamine, n-pentylamine, or any combination thereof.

[0053] Suitable silicon sources include colloidal silica, precipitated silica, pyrolytic silica, alkali metal silicates, and tetraalkyl orthosilicates.

[0054] Suitable sources of aluminum include hydrated alumina, aluminum hydroxide, alkali metal aluminates, aluminum alkoxides, and water-soluble aluminum salts (e.g., aluminum nitrate).

[0055] Alternatively or concurrently, a combination of silicon and aluminum sources may be used. This combination of silicon and aluminum sources 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 with different silica-to-alumina molar ratios may be used. The alumina-coated silica material may be used as the sole or primary source of silicon and aluminum in the reaction mixture. When present, a separate silicon source (e.g., colloidal silica) may be included.

[0056] The structure directing agent (Q) comprises one or more of the following: n-propylamine [CH3(CH2)2NH2], n-butylamine [CH3(CH2)3NH2], isobutylamine [(CH3)2CHCH2NH2], and n-pentylamine [CH3(CH2)4NH2].

[0057] Alkali metals (M) are typically introduced into the reaction mixture along with a hydroxide ion source. Examples of these metals include sodium and / or potassium, as well as lithium, rubidium, and cesium.

[0058] The reaction mixture also contains seed crystals, typically FER framework type zeolites, ideally in an amount of 0.01 to 10,000 ppm by weight of the reaction mixture (e.g., 100 to 5,000 ppm by weight). Adding seed crystals is beneficial for improving the selectivity of FER and / or shortening the crystallization process.

[0059] The crystallization of the desired zeolite from the above reaction mixture can be carried out under static, tumbling, or stirred conditions in a suitable reaction vessel such as, for example, a polypropylene tank 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, for example, about 24 hours to 240 hours (e.g., 36 hours to 100 hours). Crystallization is typically carried out under pressure in an autoclave, subjecting the reaction mixture to autogenous pressure.

[0060] 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 seconds to minutes (e.g., 5 seconds to 10 minutes for rapid drying) or hours (e.g., 4 hours to 24 hours for oven drying at 75°C to 150°C) to obtain the synthesized zeolite crystals as they are. The drying step can be carried out under vacuum or atmospheric pressure.

[0061] 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 its pores.

[0062] The synthesized zeolite can be subjected to heat treatment, ozone treatment, or other treatments to remove some or all of the structure-directing agents used in its synthesis. Removal of the structure-directing agents can be carried out using heat treatment (e.g., calcination), wherein the synthesized undisturbed material is heated in an atmosphere selected from air, nitrogen, or mixtures thereof at a temperature sufficient to remove some or all of the structure-directing agents. Although heat treatment can be performed at pressures below atmospheric pressure, atmospheric pressure is preferred for convenience. Heat treatment can be carried out at a temperature of at least 370°C (e.g., 400°C to 700°C) for at least one minute and typically not longer than 20 hours (e.g., 1 to 8 hours).

[0063] FER-framework zeolites may include one or more non-framework alkali metals. Typically, it is desirable to remove the alkali metal cation by ion exchange and replace it with hydrogen, ammonium, or any desired metal ion. Therefore, the zeolite can be a Na-type zeolite, a K-type zeolite, or a Na, K combination, or it can be a H-type zeolite, an ammonium-type zeolite, or a metal-exchanged zeolite. Typical ion exchange techniques involve contacting the synthesized zeolite with a solution containing one or more desired replacement cations. Representative ion exchange techniques are widely known in the art. Ion exchange occurs post-synthesis and can occur before or after calcination of the zeolite. After contact with the salt solution containing the desired replacement cation, the zeolite is typically washed with water and dried at a temperature of 65°C to 315°C (e.g., 80°C to 150°C).

[0064] Characterization of zeolites

[0065] In their synthesized, as-is and in anhydrous forms, FER framework type zeolites can have chemical compositions in the range of molar ratios listed in Table 2:

[0066] Table 2

[0067] Most widespread secondary <![CDATA[SiO2 / Al2O3]]> 20 to 100 25 to 85 <![CDATA[Q / SiO2]]> >0 to 0.1 >0 to 0.1

[0068] Where Q includes n-propylamine, n-butylamine, isobutylamine, n-pentylamine, or any combination thereof.

[0069] The FER framework-type zeolites synthesized as described in this paper were characterized by their powder XRD patterns. Representative powder XRD patterns of FER framework-type zeolites can be found in "Collection of Simulated XRD Powder Patterns for Zeolites" by MMJ Treacy and JB Higgins (Elsevier, 5th revised edition, 2007).

[0070] The X-ray diffraction data reported in this paper were collected using standard techniques with copper K-α radiation. Minor variations in the diffraction patterns may be due to changes in the lattice constant caused by variations in the molar ratio of the framework material in a particular sample. Additionally, sufficiently small crystals will affect the shape and intensity of the peaks, resulting in significant peak broadening. Minor variations in the diffraction patterns can also be caused by variations in the organic compounds used in the preparation. Calcination may also lead to minor changes in the XRD patterns. Despite these minor perturbations, the basic crystal structure remains unchanged.

[0071] In some respects, the FER framework zeolites prepared as described herein can have a composition with 350 μmol H₂. + / g to 500μmol H + / g (e.g., 375 μmol H) + / g to 450μmol H + The total Brønsted acid site density within the range of (g) was determined by temperature-programmed desorption (TPD) of n-propylamine.

[0072] Example

[0073] The following illustrative examples are intended to be non-limiting.

[0074] In the synthesis of Examples 1-29 below, the starting material was loaded into a 23 mL Teflon-lined container. The Teflon-lined container was then capped and sealed in a Steel Parl autoclave. The autoclave was then heated in a convection oven maintained at 170°C under tumbling conditions (43 rpm) for 2-3 days. The product was separated by filtration, washed with copious amounts of deionized water, and finally dried in air at 85°C.

[0075] The molar ratios and conditions used for the synthesis in Examples 1-29 are summarized in Table 3 below.

[0076] Example 1

[0077] 4.42 g of 1M 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). Then, 0.35 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0078] The powder XRD pattern of the product is shown in Figure 1 The text indicates that the material is a FER framework type zeolite.

[0079] Example 2

[0080] 5.53 g of 1M NaOH was mixed with 5.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids). Then, 0.43 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0081] The recovered synthetic material was calcined in air in a thin bed placed in a calcining dish, and then heated from room temperature to 120°C in a muffle furnace at a rate of 1°C / min, and held at 120°C for 2 hours. The temperature was then increased to 540°C at a rate of 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 allowed to cool to room temperature.

[0082] The calcined material was then converted to ammonium form by heating in an ammonium nitrate solution (typically a solution of 1 g NH4NO3 / 1 g zeolite in 10 mL H2O, at 85°C for at least 3 hours). The material was then filtered. This process was repeated twice, for a total of three exchanges. Finally, the material was washed with deionized water until the conductivity was less than 100 μS / cm and dried in air at 85°C.

[0083] The acid site density was characterized using temperature-programmed desorption (TPD) with n-propylamine and found to be 423 μmol H₂. + / g.

[0084] The nitrogen micropore volume was found to be 0.14 cm³. 3 / g(t-curve analysis) and the BET surface area is 324m² 2 / g.

[0085] The material has a SiO2 / Al2O3 molar ratio (SAR) of 30, as determined by inductively coupled plasma-atomic emission spectrometry (ICP-AES).

[0086] The powder XRD pattern of the ammonium-type material is shown in Figure 2 The image shows that the material is a FER framework type zeolite. SEM images of the material at various magnifications are shown below. Figure 3 middle.

[0087] Example 3

[0088] 4.42 g of 1M 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). Then, 0.35 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0089] The powder XRD pattern of the product is shown in Figure 4The text indicates that the material is a FER framework type zeolite.

[0090] Example 4

[0091] In a 23 mL Teflon autoclave, 5.41 g of 1 M NaOH was mixed with 2.45 g of deionized water and 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids) and 0.39 g of... AS-30 colloidal silica was mixed. Then, 0.42g of isobutylamine was added, followed by 0.05g of zeolite FER seed crystals.

[0092] The powder XRD pattern of the product is shown in Figure 5 The text indicates that the material is a FER framework type zeolite.

[0093] Example 5

[0094] 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... AS-30 colloidal silica was mixed. Then, 0.42g of isobutylamine was added, followed by 0.05g of zeolite FER seed crystals.

[0095] The powder XRD pattern of the product is shown in Figure 6 The text indicates that the material is a FER framework type zeolite.

[0096] Example 6

[0097] In a 23 mL Teflon autoclave, 4.74 g of 1 M NaOH was mixed with 2.86 g of deionized water and 3.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids) and 1.00 g of... AS-30 was mixed. Then, 0.37g of isobutylamine was added, followed by 0.05g of zeolite FER seed crystals.

[0098] The powder XRD pattern of the product is shown in Figure 7 The text indicates that the material is a FER framework type zeolite.

[0099] Example 7

[0100] In a 23 mL Teflon autoclave, 4.74 g of 1 M NaOH was mixed with 2.86 g of deionized water and 3.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids) and 1.00 g of... AS-30 colloidal silica was mixed. Then, 0.37g of isobutylamine was added, followed by 0.05g of zeolite FER seed crystals.

[0101] The recovered material was calcined and then converted into ammonium form according to the method in Example 2.

[0102] The acid site density was characterized using n-propylamine TPD and found to be 421 μmol H. + / g.

[0103] The nitrogen micropore volume was found to be 0.13 cm³. 3 / g(t-curve analysis) and the BET surface area is 285m² 2 / g.

[0104] The material has a SiO2 / Al2O3 molar ratio (SAR) of 41, as determined by ICP-AES.

[0105] The powder XRD pattern of the ammonium-type material is shown in Figure 8 The image shows that the material is a FER framework type zeolite. SEM images of the material at various magnifications are shown below. Figure 9 middle.

[0106] Example 8

[0107] Mix 4.74 g of 1M NaOH with 3.05 g of deionized water and 2.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids) and 1.80 g of... AS-30 colloidal silica was mixed. Then 0.37g of isobutylamine was added, followed by 0.05g of zeolite FER seed crystals.

[0108] The recovered material was calcined and then converted into ammonium form according to the method in Example 2.

[0109] The acid site density was characterized using n-propylamine TPD and found to be 400 μmol H. + / g.

[0110] The material has a SiO2 / Al2O3 molar ratio (SAR) of 57, as determined by ICP-AES.

[0111] The powder XRD pattern of the ammonium-type material is shown in Figure 10 The image shows that the material is a FER framework-type zeolite with a small amount of STI. SEM images of the material at various magnifications are shown below. Figure 11 middle.

[0112] Example 9

[0113] Mix 4.74 g of 1M NaOH with 3.14 g of deionized water and 1.50 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids) and 2.20 g of... AS-30 colloidal silica was mixed. Then, 0.37g of isobutylamine was added, followed by 0.05g of zeolite FER seed crystals.

[0114] The powder XRD pattern of the synthesized product is shown in the figure. Figure 12 The results indicate that the material is a FER framework type zeolite with a small amount of STI.

[0115] Example 10

[0116] 4.74 g of 1M NaOH was mixed with 3.24 g of deionized water and 1.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids) and 2.59 g of... AS-30 colloidal silica was mixed. Then, 0.37g of isobutylamine was added, followed by 0.05g of zeolite FER seed crystals.

[0117] The powder XRD pattern of the synthesized product is shown in the figure. Figure 13 The results indicate that the material is a FER framework type zeolite with a small amount of STI.

[0118] Example 11

[0119] Mix 3.71 g of 1M NaOH with 2.29 g of deionized water and 3.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 100; 26.5% solids). Then, add 0.29 g of isobutylamine, followed by 0.05 g of zeolite FER seed crystals.

[0120] The powder XRD pattern of the synthesized product is shown in the figure. Figure 14 The results indicate that the material is a FER framework type zeolite with a small amount of STI.

[0121] Example 12

[0122] Mix 4.63 g of 1M NaOH with 2.96 g of deionized water and 3.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 100; 26.5% solids) and 0.66 g of... AS-30 colloidal silica was mixed. Then, 0.36g of isobutylamine was added, followed by 0.05g of zeolite FER seed crystals.

[0123] The powder XRD pattern of the synthesized product is shown in the figure. Figure 15The results indicate that the material is a FER-frame type zeolite with a small amount of STI.

[0124] Example 13

[0125] Mix 3.71 g of 1M NaOH with 2.42 g of deionized water and 2.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 100; 26.5% solids) and 0.883 g of... AS-30 colloidal silica was mixed. Then, 0.29g of isobutylamine was added, followed by 0.05g of zeolite FER seed crystals.

[0126] The powder XRD pattern of the synthesized product is shown in the figure. Figure 16 The results indicate that the material is a FER framework type zeolite with a small amount of STI.

[0127] Example 14

[0128] 4.32 g of 1M 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). Then, 0.34 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0129] The powder XRD pattern of the synthesized product is shown in the figure. Figure 17 The results indicate that the material is a FER framework type zeolite with a small amount of STI.

[0130] Example 15

[0131] Mix 6.32 g of 1M NaOH with 0.60 g of deionized water and 2.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids) and 2.93 g of... AS-30 colloidal silica was mixed. Then, 0.50g of isobutylamine was added, followed by 0.05g of zeolite FER seed crystals.

[0132] The powder XRD pattern of the synthesized product is shown in the figure. Figure 18 The results indicate that the material is a FER framework type zeolite with a small amount of STI.

[0133] Example 16

[0134] Mix 5.53 g of 1M KOH with 0.20 g of deionized water and 3.50 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids) and 1.17 g of... AS-30 was mixed. Then, 0.43g of isobutylamine was added, followed by 0.05g of zeolite FER seed crystals.

[0135] The powder XRD pattern of the synthesized product is shown in the figure. Figure 19 The results indicate that the material is a pure-phase FER framework type zeolite.

[0136] Example 17

[0137] Mix 6.32 g of 1M KOH with 0.61 g of deionized water and 2.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids) and 2.93 g of... AS-30 colloidal silica was mixed. Then, 0.53g of isobutylamine was added, followed by 0.05g of zeolite FER seed crystals.

[0138] The powder XRD pattern of the synthesized product is shown in the figure. Figure 20 The results indicate that the material is a FER framework-type zeolite with a small amount of STI and layered phases.

[0139] Example 18

[0140] Mix 5.29 g of 1M NaOH with 5.13 g of deionized water, then add 0.10 g of Reheis F2000 hydrated alumina and mix thoroughly. Add 1.13 g of CAB-O- M-5 pyrolytic silica was mixed until homogeneous. Then, 0.41 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0141] The powder XRD pattern of the synthesized product is shown in the figure. Figure 21 The results indicate that the material is a pure-phase FER framework type zeolite.

[0142] Example 19

[0143] Mix 5.66 g of 1M NaOH with 5.51 g of deionized water, then add 0.075 g of Reheis F2000 hydrated alumina and mix thoroughly. Add 1.22 g of CAB-O- to the mixture. M-5 pyrolytic silica was mixed until homogeneous. Then 0.44 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed crystals. The molar ratios are given in Table 2.

[0144] The powder XRD pattern of the synthesized product is shown in the figure. Figure 22 The results indicate that the material is a pure-phase FER framework type zeolite.

[0145] Example 20

[0146] Mix 5.66 g of 1M NaOH with 5.52 g of deionized water, then add 0.05 g of Reheis F2000 hydrated alumina and mix thoroughly. Add 1.22 g of CAB-O to the mixture. M-5 pyrolytic silica was mixed until homogeneous. Then, 0.44 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0147] The powder XRD pattern of the synthesized product is shown in the figure. Figure 23 The results indicate that the material is a FER framework type zeolite with a small amount of STI.

[0148] Example 21

[0149] Mix 5.28 g of 1M NaOH with 5.16 g of deionized water, then add 0.035 g of Reheis F2000 hydrated alumina and mix thoroughly. Add 1.13 g of CAB-O- to the mixture. M-5 pyrolytic silica was mixed until homogeneous. Then, 0.42 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0150] The powder XRD pattern of the synthesized product is shown in the figure. Figure 24 The results indicate that the material is a FER framework-type zeolite with a small amount of STI and layered phases.

[0151] Example 22

[0152] Mix 5.29 g of 1M NaOH with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 100; 26.5% solids). Then add 0.39 g of isobutylamine, followed by 0.05 g of zeolite FER seed crystals.

[0153] The powder XRD pattern of the synthesized product is shown in the figure. Figure 26 The results indicate that the material is a FER framework type zeolite with a small amount of STI.

[0154] Example 23

[0155] 4.94 g of 1M NaOH was mixed with 0.24 g of DI water and 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 100; 26.5%). Then, 0.39 g of isobutylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0156] The recovered material was calcined and then converted into ammonium form according to the method in Example 2.

[0157] The acid site density was characterized using n-propylamine TPD and found to be 425 μmol H. + / g.

[0158] The nitrogen micropore volume was found to be 0.06 cm³. 3 / g(t-curve analysis) and the BET surface area is 147m² 2 / g.

[0159] The material has a SiO2 / Al2O3 molar ratio (SAR) of 77, as determined by ICP-AES.

[0160] The powder XRD pattern of the ammonium-type material is shown in Figure 26 The results indicate that the material is a FER framework type zeolite with a small amount of impurities. Figure 27 SEM images of the material at various magnifications are shown.

[0161] Example 24

[0162] 4.41 g of 1M 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 0.05 g of zeolite FER seed crystals. The molar ratios are given in Table 2.

[0163] The recovered material was calcined and then converted into ammonium form according to the method in Example 2.

[0164] The acid site density was characterized using n-propylamine TPD and found to be 424 μmol H. + / g.

[0165] The nitrogen micropore volume was found to be 0.05 cm³. 3 / g(t-curve analysis) and the BET surface area is 134m² 2 / g.

[0166] The material has a SiO2 / Al2O3 molar ratio (SAR) of 81, as determined by ICP-AES.

[0167] The powder XRD pattern of the ammonium-type material is shown in Figure 28 The results indicate that the material is a FER framework type zeolite with a small amount of impurities. Figure 29 SEM images of the material at various magnifications are shown.

[0168] Example 25

[0169] Mix 3.53 g of 1M NaOH with 1.59 g of deionized water and 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 100; 26.5% solids). Then, add 0.39 g of isobutylamine, followed by 0.05 g of zeolite FER seed crystals.

[0170] The powder XRD pattern of the synthesized product is shown in the figure. Figure 30 The results indicate that the material is a FER framework-type zeolite with a small amount of STI and layered phases.

[0171] Example 26

[0172] 4.42 g of 1M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids). Then, 0.28 g of n-propylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0173] The powder XRD pattern of the synthesized product is shown in the figure. Figure 31 The results indicate that the material is a pure-phase FER framework type zeolite.

[0174] Example 27

[0175] 4.42 g of 1M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids). Then, 0.48 g of dipropylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0176] The powder XRD pattern of the synthesized product is shown in the figure. Figure 32 The text indicates that the material is an MFI framework type zeolite.

[0177] Example 28

[0178] 4.42 g of 1M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids). Then, 0.35 g of n-butylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0179] The powder XRD pattern of the synthesized product is shown in the figure. Figure 33 The results indicate that the material is a pure-phase FER framework type zeolite.

[0180] Example 29

[0181] 4.42 g of 1M NaOH was mixed with 4.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 35; 24.5% solids). Then, 0.41 g of n-pentylamine was added, followed by 0.05 g of zeolite FER seed crystals.

[0182] The powder XRD pattern of the synthesized product is shown in the figure. Figure 34 The text indicates that the material is a mixture of FER and MFI framework-type zeolites.

[0183] Table 3

[0184]

[0185]

[0186] (a) “Nalco(35)” = Nalco alumina-coated silica (SAR=35); “Nalco(100)” = Nalco alumina-coated silica (SAR=100); “Ludox” = AS-30 colloidal silica; "Cabosil" = CAB-O- M-5 pyrolytic silicon dioxide; and “Reheis” = Reheis F2000 hydrated aluminum oxide.

Claims

1. A method of synthesizing a zeolite of the FER framework type, the 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) comprising isobutylamine, n-pentylamine, or a combination thereof; (d) a source of an alkali metal (M); (e) a source of hydroxide ions; (f) water; and (g) seeds; and (2) subjecting the reaction mixture to crystallization conditions sufficient to form crystals of the zeolite.

2. The method of claim 1, wherein the reaction mixture has a composition in terms of mole ratios as follows: 。 3. The method of claim 1, wherein the reaction mixture has a composition in terms of mole ratios as follows: 。 4. The method of claim 1, wherein the reaction mixture comprises an alumina-coated silica as a combined source of silicon and aluminum.

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

6. The method of claim 1, wherein the seeds comprise a zeolite of the FER framework type.

7. The method of claim 1, wherein the reaction mixture comprises from 0.01 ppm by weight to 10,000 ppm by weight of seeds.

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

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