Method for synthesizing aluminum-rich *MRE framework type molecular sieves

Abstract

Aluminum-rich * This provides a method for synthesizing MRE framework-type molecular sieves. [Solution] The method comprises the step of preparing a synthetic mixture consisting of at least one source of silica, at least one source of alumina having low water solubility, at least one source of hydroxide ions, at least one source of alkali metal and / or alkaline earth metal M, at least one source of diquaternary alkylammonium structure directing agent R, water, and an optional seed crystal.

Description

[Technical Field]

[0001] Bracket, aluminum-rich * A method for synthesizing MRE framework type molecular sieves and the results obtained by this method * Regarding MRE framework-type molecular sieves. [Background technology]

[0002] Zeolites, both naturally occurring and synthetically, have been demonstrated in the past to be useful as adsorbents and to possess catalytic properties for various types of hydrocarbon conversion reactions. Zeolites are regular, porous, crystalline materials with a distinct crystalline structure, as determined by X-ray diffraction (XRD). Within crystalline zeolite materials are numerous cavities, which may be interconnected by numerous channels or pores. These cavities and pores are uniformly sized within a given zeolite material. Because the dimensions of these pores are designed to accept molecules of a specific size for adsorption and reject larger molecules, these materials have become known as "molecular sieves" and are used in a variety of industrial processes, including within refining methods and other methods of manipulating oil flows. Some applications of molecular sieves, or zeolites, are inherently catalytic, while others focus on the zeolite's ability to selectively adsorb molecules in gas flows.

[0003] Zeolite structures used in catalytic treatment of oil flows One example is ZSM-48, which has orthorhombic or pseudoorthorhombic symmetry and possesses 10 discontinuous linear channels with ideal dimensions of 5.5 × 5.6 Å. According to RFLobo et al. (J. Am. Chem. Soc., 2002, 121, 13222-13230), ZSM-48 is not the code for a single material, but rather represents the code for a group of materials with varying degrees of disorder. As a result, *MRE framework molecular sieves may contain zeolites from the ZSM-48 group, such as at least one of COK-8, EU-2, EU-11, IZM-1, SSZ-91, ZBM-30, and ZSM-48.

[0004] For many zeolites, ZSM-48 (or other * The composition of the synthetic mixture used to form the MRE framework molecular sieve can strongly influence the crystalline structure and / or morphology of the resulting zeolite.

[0005] ZSM-48 has shown interesting properties, for example, as a catalyst for dewaxing hydrocarbon feedstocks, see, for example, U.S. Patent Nos. 5,075,269, 6,884,339, and 6,984,309. Consequently, there is great interest in finding new methods for synthesizing ZSM-48, particularly ZSM-48 with high acid activity, i.e., ZSM-48 with a low silica-to-alumina molar ratio.

[0006] ZSM-48 is a structure-directing agent containing C4~C 12 It was first synthesized by Rollmann et al. using organic diamines (see U.S. Patent No. 4,423,021). As synthesized by Rollmann et al., the zeolite contains very little aluminum and therefore has little acid activity.

[0007] U.S. Patent No. 6,923,949 describes a method for forming ZSM-48 crystals using a synthetic mixture comprising an organic linear diquaternary alkylammonium compound, such as hexamethonium chloride, and at least one organic template material selected from linear diaminoalkanes, and a non-ZSM-48 crystal. The presence of the non-ZSM-48 crystal can be detected based on activity testing, but the resulting ZSM-48 crystal may have an X-ray diffraction pattern corresponding to ZSM-48. For crystals with a silica:alumina ratio of about 70:1 to 150:1, ZSM-48 crystals formed using the non-ZSM-48 are described as small, irregularly shaped crystals without fibrous morphology. For crystals with a silica:alumina ratio of less than 70:1, the ZSM-48 crystal is described as a mixture of small, irregularly shaped crystals and acicular crystals.

[0008] U.S. Patent No. 7,482,300 describes a method for forming ZSM-48 crystals without using non-ZSM-48 species in the synthesis mixture. The structure-directing agent used to form the ZSM-48 crystals is described as a hexamethonium salt, such as hexamethonium chloride. The resulting crystals may have a silica:alumina ratio of about 70:1 to about 110:1 and are described as substantially free of fibrous morphology. A preferred range is OH to SiO2. - The molar ratios of and to SiO2 are also described. The preferred range is described as suitable for forming crystals that are substantially free of needle-shaped crystals.

[0009] U.S. Patent No. 8,003,074 describes a method for forming ZSM-48 crystals using a diquaternary ammonium salt structure-directing agent ("diquat-5" structure-directing agent) having a 5-carbon alkyl chain between ammonium ions. The synthesis of ZSM-48 crystals using mixtures of "diquat-5" structure-directing agent and other structure-directing agents such as "diquat-6" structure-directing agent is also described. Various types of synthetic mixtures resulting in the formation of fibrous and / or needle-shaped crystal forms are described.

[0010] U.S. Patent No. 9,873,614 describes a method for forming substantially pure-phase ZSM-48 crystals having a fibrous or needle-like morphology using a synthetic mixture comprising a non-sodium alkali metal ion and a diquaternary alkylammonium salt structure-directing agent ("diquat-6") having a 6-carbon alkyl chain between ammonium ions. The desired morphology may be partially achieved by reducing, minimizing, and / or eliminating the presence of sodium ions in the synthetic mixture.

[0011] As mentioned above, there is great interest in finding a method to synthesize ZSM-48 with high acid activity, i.e., with a low silica / alumina molar ratio. However, previous attempts to make ZSM-48 more alumina often resulted in a significant decrease in the phase purity of the resulting ZSM-48 crystals. Therefore, it is necessary to find a new method to synthesize ZSM-48 with a low silica / alumina molar ratio, for example, from a synthetic mixture having an SiO2:Al2O3 molar ratio of less than 100 or less than 80, while controlling the phase purity of the resulting ZSM-48 crystals. [Prior art documents] [Patent Documents]

[0012] [Patent Document 1] U.S. Patent No. 5,075,269 [Patent Document 2] U.S. Patent No. 6,884,339 [Patent Document 3] U.S. Patent No. 6,984,309 [Patent Document 4] U.S. Patent No. 4,423,021 [Patent Document 5] U.S. Patent No. 6,923,949 [Patent Document 6] U.S. Patent No. 7,482,300 [Patent Document 7] U.S. Patent No. 8,003,074 [Patent Document 8] U.S. Patent No. 9,873,614 [Non-Patent Document]

[0013] [Non-Patent Document 1] R.F. Lobo et al., J. Am. Chem. Soc., 2002, 121, 13222 - 13230 [Summary of the Invention]

[0014] According to the present invention, it has been found that it is possible to synthesize an aluminum-rich MRE framework type molecular sieve using a source of alumina with low water solubility and controlling the phase purity. *

[0015] In a first aspect, the present invention thus comprises: (a) preparing a synthesis mixture comprising at least one source of silica, at least one source of alumina with low water solubility, at least one source of hydroxide ions, at least one source of alkali metal M, at least one source of a diquaternary alkylammonium structure directing agent R, water, and optional seed crystals; (b) heating the synthesis mixture under crystallization conditions * for a time sufficient to form an MRE framework type molecular sieve; and (c) recovering the MRE framework type molecular sieve from the synthesis mixture * comprising an aluminum-rich * ​This invention relates to a method for synthesizing MRE framework-type molecular sieves. The synthesized mixture has the following molar ratio composition: SiO2:Al2O315~100 or less, OH - :SiO2 0.02~0.8, M:SiO2 0.02~0.8 R:SiO2 0.005~0.5, H2O:SiO25~100 It has the following characteristics. Particularly suitable sources of alumina with low water solubility are, for example, aluminum hydroxide and / or kaolin, which are added to the synthesis mixture in solid form.

[0016] In a second embodiment, the present invention also provides an aluminum-rich material that can be obtained by the method of the present invention, or can be obtained by the method of the present invention. * Regarding MRE framework-type molecular sieves.

[0017] In a third embodiment, the present invention relates to an aluminum-rich material that can be obtained by the method of the present invention, or that can be obtained by the method of the present invention. * This relates to the use of MRE framework molecular sieves in hydrocarbon chemical transformation methods. [Brief explanation of the drawing]

[0018] [Figure 1A] This figure shows the XRD spectrum of Example 1. [Figure 1B] This figure shows a scanning electron microscope (SEM) image of Example 1. [Figure 2A] This figure shows the XRD spectrum of Example 2. [Figure 2B] This figure shows a scanning electron microscope (SEM) image of Example 2. [Figure 3A] This figure shows the XRD spectrum of Example 3. [Figure 3B] This figure shows a scanning electron microscope (SEM) image of Example 3. [Figure 4A]This figure shows the XRD spectrum of Example 4. [Figure 4B] This figure shows a scanning electron microscope (SEM) image of Example 4. [Figure 5A] This figure shows the XRD spectrum of Example 5. [Figure 5B] This figure shows a scanning electron microscope (SEM) image of Example 5. [Figure 6A] This figure shows the XRD spectrum of Example 6. [Figure 6B] This figure shows a scanning electron microscope (SEM) image of Example 6. [Figure 7A] This figure shows the XRD spectrum of Example 7. [Figure 7B] This figure shows a scanning electron microscope (SEM) image of Example 7. [Figure 8A] This figure shows the XRD spectrum of Example 8. [Figure 8B] This figure shows a scanning electron microscope (SEM) image of Example 8. [Figure 9A] This figure shows the XRD spectrum of Example 9. [Figure 9B] This figure shows a scanning electron microscope (SEM) image of Example 9. [Figure 10A] This figure shows the XRD spectrum of Example 10. [Figure 10B] This figure shows a scanning electron microscope (SEM) image of Example 10. [Figure 11A] This figure shows the XRD spectrum of Example 11. [Figure 11B] This figure shows a scanning electron microscope (SEM) image of Example 11. [Figure 12A] This figure shows the XRD spectrum of Example 12. [Figure 12B] This figure shows a scanning electron microscope (SEM) image of Example 12. [Figure 13A] This figure shows the XRD spectrum of Example 13. [Figure 13B] This figure shows a scanning electron microscope (SEM) image of Example 13. [Figure 14A] This figure shows the XRD spectrum of Example 14. [Figure 14B] This figure shows a scanning electron microscope (SEM) image of Example 14. [Figure 15] This shows the reaction conditions and molar ratios of the synthesized mixtures for Examples 1 to 14. [Figure 16] The properties of the products obtained in Examples 1 to 14 are summarized below. [Modes for carrying out the invention]

[0019] As used herein, * The MRE framework type molecular sieve includes zeolites from the ZSM-48 group, such as COK-8, EU-2, EU-11, IZM-1, SSZ-91, ZBM-30, and at least one of ZSM-48. Hereafter, the terms "zeolite" and "molecular sieve" can be used interchangeably. Also, the term "ZSM-48 group" can be used interchangeably. * This term is used synonymously with "MRE framework type molecular sieve." The term "ZSM-48 group" materials as used herein refer to the following: A molecular sieve formed from a typical first-degree crystal structure unit cell, wherein the unit cell is * Molecular sieves with MRE framework topology (unit cells are spatial arrangements of atoms that, when arranged in three-dimensional space, describe a crystal structure. Such crystal structures are fully described in the "Atlas of Zeolite Framework Types," 5th edition, 2001, which is incorporated by reference in this specification.) A molecular sieve formed from a common second-degree structural unit, such * MRE framework topology is a two-dimensional tiling of unit cells, forming molecular sieves that form a monolayer with a unit cell thickness of 1 unit cell thickness, preferably 1 c unit cell thickness. A molecular sieve formed from common second-degree constituent units, wherein the molecular sieve is a layer of one or more unit cell thicknesses (the layer of one or more unit cell thicknesses is formed by laminating, packaging, or joining at least two single layers of one unit cell thickness. Such lamination of second-degree constituent units may be regular, irregular, random, or any combination thereof); and * Molecular sieves formed by any regular or random 2D or 3D combination of unit cells having an MRE framework topology Includes one or more of the following.

[0020] For more details, * MRE framework molecular sieves constitute a group of materials having linear channel (or tubular) pores. The pores are formed from a rolled-up honeycomb sheet of fused T6-rings (T=tetrahedrons), and the pore openings contain 10 T-atoms. Adjacent pores are related by a zero shift along the pore direction or by a shift of half the repeating distance along the pore direction. * MRE framework molecular sieves generally have X-ray diffraction patterns with maximum d-intervals at 11.8±0.2, 10.2±0.2, 7.2±0.15, 4.2±0.08, 3.9±0.08, 3.6±0.06, 3.1±0.05, and 2.85±0.05 angstroms. X-ray diffraction data used for material characterization are obtained by standard techniques using a diffractometer with a copper K-α doublet as the incident radiation source and a scintillation counter and associated computer as the collection system.

[0021] The aluminum-rich aluminum according to the present invention *A method for synthesizing an MRE framework type molecular sieve comprises preparing a synthetic mixture according to the prior art, except that the synthetic mixture includes at least one source of alumina having low water solubility. Preferably, the synthetic mixture includes only a source of alumina having low water solubility. The method for synthesizing a molecular sieve according to the present invention further comprises crystallizing the molecular sieve according to the prior art and isolating the molecular sieve according to the prior art.

[0022] More specifically, the present invention provides a step of (a) preparing a synthetic mixture comprising at least one source of silica, at least one source of alumina selected from aluminum hydroxide, clay selected from the kaolin group, and metakaolin, at least one source of hydroxide ions, at least one source of alkali metal and / or alkaline earth metal M, at least one source of linear diquatemary alkylammonium structure directing agent R, water, and an optional seed crystal, and (b) crystallizing the synthetic mixture under crystallization conditions. * (c) heating for a sufficient time to form an MRE framework type molecular sieve; and (c) from the synthetic mixture * The process includes recovering MRE framework-type molecular sieves. * This invention relates to a method for synthesizing MRE framework type molecular sieves. The synthesized mixture has the following molar ratio composition: SiO2:Al2O3 is 15 to less than 100, OH - The composition is as follows: :SiO2 0.02-0.8, M:SiO2 0.02-0.8, R:SiO2 0.005-0.5, H2O:SiO2 5-100. Particularly suitable sources of alumina with low water solubility are, for example, aluminum hydroxide and / or kaolin added to the synthetic mixture in solid form.

[0023] The inventors have improved the control of crystalline phase purity by using at least one source of alumina with low water solubility, resulting in an aluminum-rich material. *We have actually discovered that it is possible to fabricate MRE framework type molecular sieves. While we do not wish to be bound by theory, we have found that by using at least one source of alumina with low water solubility, aluminum is slowly released into the crystallization medium during the hydrothermal treatment process, resulting in aluminum-rich * We believe that this will improve the control of phase purity in MRE framework molecular sieves. Furthermore, while we do not wish to be constrained by theory, we believe that the sustained release of aluminum into the synthetic mixture will help keep the concentration of alkali metals or alkaline earth metals low through the crystallization method. These alkali metals or alkaline earth metals are known as structure-directing agents for more condensed phases, and by keeping their concentrations low through the crystallization method, aluminum-rich phases can be improved. * This enables further improvement in controlling the phase purity of MRE framework-type molecular sieves.

[0024] The present invention also provides an aluminum-rich material obtained by the method of the present invention. * MRE framework type molecular sieves, in particular, with a molar ratio of SiO2:Al2O3 less than 100. * Regarding MRE framework-type molecular sieves.

[0025] synthetic mixture The synthetic mixture can be prepared according to conventional methods, provided that at least one source of alumina is selected from sources of alumina having low water solubility, such as solid aluminum hydroxide or kaolin.

[0026] The SiO2:Al2O3 molar ratio in the synthetic mixture is typically at least 15, most frequently at least 20, particularly at least 25, for example at least 30, at least 40, or at least 50. Alternatively, the SiO2:Al2O3 molar ratio in the synthetic mixture is typically less than 100, preferably less than 80, more preferably less than 75, for example less than 70, most frequently at least 20, particularly at least 25, for example at least 30, at least 40, or at least 50. For example, the SiO2:Al2O3 molar ratio in the synthetic mixture may be between 15 and less than 100, or between 20 and less than 100, or between 25 and less than 100, or between 30 and less than 100, particularly between 15, 20, 25, 30, or 40 and less than 80, or less than 75 or less than 70.

[0027] Effective amounts of various components are added to form a synthetic mixture having the following molar composition: JPEG2026123135000002.jpg52164

[0028] Many sources of alumina are known from the prior art, which generally teach the preferred use of water-soluble sources of alumina, such as aluminates like sodium aluminate, or aluminum salts like aluminum chloride, aluminum nitrate, or aluminum sulfate. The prior art also often discloses the use of aluminum alkoxides or alumina, preferably in hydrated or hydrateable forms, such as colloidal alumina, pseudoboehmite, boehmite, gamma alumina, or trihydrate, or aluminum hydroxide, which are typically added to the synthetic mixture after dissolution in a caustic solution such as sodium hydroxide or potassium hydroxide. Contrary to the general teachings of the prior art, in the method of the present invention, the synthetic mixture comprises at least one source of alumina having low water solubility. In the present invention, the expression “source of alumina having low water solubility” is intended to indicate a source of alumina that does not readily dissolve in the synthetic mixture at room temperature (e.g., 20°C) and near-neutral pH (e.g., pH 7), and that does not dissolve in a caustic solution, for example, before being added to the synthetic mixture. In the method of the present invention, at least one source of alumina having low water solubility is added to the synthesis mixture in solid form, as opposed to addition in solution form in a caustic solution such as sodium hydroxide or potassium hydroxide.

[0029] In the method of the present invention, particularly suitable sources of alumina having low water solubility are aluminum hydroxide, clay selected from the kaolin group, and metakaolin. Typical examples of suitable solid forms include powder form, for example, solid particles having an average particle size of 0.01 to 300 μm, e.g., 0.1 to 200 μm or 1 to 100 μm, as measured by dynamic light scattering (DLS) as a volume-weighted average. Clay selected from the kaolin group is commonly known as Dixie, McNamee, Georgia, and Florida clay, etc., whose main mineral component is kaolinite, halloysite, dickite, naclite, or anorthite. Kaolinite, halloysite, dickite, and naclite are polymorphic clay minerals represented by the empirical formula Al2Si2O5(OH)4. Anorthite is considered to be a mixture of kaolinite and free silica. Metakaolin is obtained by dehydration of kaolin clay, such as from kaolinite, and can be described by the formula Al2Si2O7.

[0030] Other typical sources of alumina may also be present in the synthetic mixture, i.e., sources of alumina that readily dissolve in the synthetic mixture or in the form of a solution in, for example, a caustic solution. Such typical sources of alumina should be present only in trace amounts, i.e., 10 mol% or less, particularly 5 mol% or less, and more particularly 2 mol% or less, of the total amount of alumina sources with respect to the total amount of Al2O3. In a particularly preferred embodiment of the present invention, the synthetic mixture essentially contains no further sources of alumina, except for at least one source of alumina having the low water solubility described above.

[0031] Suitable sources of silica for use in the method of the present invention include any source of silica in the usual use assumed for zeolite synthesis. For example, suitable sources of silica include precipitated silica, e.g., Ultrasil® and Sipemat® 340 (available from Evonik), fumed silica, e.g., Aerosil® (available from Degussa) and Cabosil® (available from DMS), silica gel, silicic acid, silicates, e.g., tetraalkyl orthosilicates such as tetramethyl orthosilicate, alkali metal silicates such as potassium silicate and sodium silicate, or aqueous colloidal suspensions of silica, e.g., sold under the trade name Ludox® by EI du Pont de Nemours.

[0032] Conventionally, various structure directing agents, including linear diquaternary alkylammonium structure directing agents, have been used for the synthesis of ZSM-48 type crystals. In the method of the present invention, the linear diquaternary alkylammonium structure directing agent R is typically the cation moiety of a salt represented by formula R1-R-R2, where R1 and R2 are the same or different, and R1 and R2 are of formula -N + A tetraalkylammonium group having -RR'R", where R3 is of formula (CH2) n The polymethylene group is such that R, R', and R'' are each alkyl groups, which may be the same or different. The R, R', and R'' alkyl groups in the tetraalkylammonium group may each be alkyl groups having 1 to 10 carbon atoms, preferably 4 or fewer carbon atoms, such as a methyl group or an ethyl group, and n is preferably 5 or 6. A particularly preferred linear diquaternary alkylammonium structure directing agent R in the present invention is a pentamethonium cation ((CH3)3N + (CH2)5N + (CH3)3, "Meg-diquat-5-cation"), hexamethonium cation ((CH3)3N + (CH2)6N +It is possible to select from the group consisting of (CH3)3), "Meg-diquat-6-cation") and mixtures thereof. Suitable sources of the linear diquaternary alkylammonium compound include nitrates, sulfates, halides, salts thereof such as chlorides or bromides, and / or hydroxide derivatives thereof.

[0033] In the method of the present invention, the alkali metal or alkaline earth metal M may be selected from the group consisting of Na, K, Li, Ca, Mg and mixtures thereof. In a preferred embodiment, M is an alkali metal cation selected from the group consisting of Na, K, Li and mixtures thereof, more preferably Na and / or K. The alkali metal or alkaline earth metal M generally exists in the synthetic mixture as a hydroxide, but may also exist in the form of salts such as sodium aluminate, sodium silicate, potassium silicate, or NaCl, NaBr, sodium nitrate, KCl, KBr, potassium nitrate, LiCl, LiBr, LiI, lithium nitrate, or lithium sulfate, or combinations thereof. Most frequently, the alkali metal or alkaline earth metal M exists as its hydroxide, for example, sodium hydroxide and / or potassium hydroxide.

[0034] At least one source of hydroxide ions may be selected from alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, and mixtures thereof; for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, and mixtures thereof, most often potassium hydroxide and / or sodium hydroxide. Hydroxides may also be present as counterions of structure directors, i.e., in the form of the structure director R, or by the use of aluminum hydroxide as a source of alumina.

[0035] Synthesis is preferably carried out using seed crystals, typically *The MRE includes zeolite seed crystals of a different or identical framework type, selected from the group consisting of ZSM-48, ZSM-5, ZSM-11, ZSM-12, BEA, Beta, X, and Y type zeolite seed crystals, preferably ZSM-48 or BEA type seed crystals, more preferably BEA type seed crystals. When seed crystals are used, they are most often added to the synthetic mixture in amounts of 50 ppm to 50,000 ppm by weight, based on the total weight of the synthetic mixture. Generally, at least 50 or 100 ppm by weight of seed crystals are used, preferably 100 to 10,000 ppm by weight, more preferably 500 to 6,000 ppm by weight, based on the total weight of the synthetic mixture. The term "seed crystal" means either a seed crystal or an aggregate of seed crystals. For example, the size of the seed crystals introduced into the synthetic mixture may be in the range of 0.01 to 5.0 μm, for example, 0.02 to 1.0 μm. Optionally, seed crystals are included in the synthesis mixture in the form of a colloidal suspension in a liquid medium such as water. As used herein, the term “colloidal suspension” means a suspension containing individual finely divided particles dispersed in a continuous liquid phase, which is preferably stable in the sense that no visible separation occurs and no precipitate forms for a period sufficient for the intended use, advantageously at least 10 hours, more advantageously at least 20 hours, preferably at least 100 hours, and more preferably at least 500 hours, at ambient temperature (23°C). The maximum particle size for which the suspension is maintained stably (peptized) depends to some extent on its shape, the properties and pH of the continuous medium, and the period for which the suspension must remain usable. The particles may be spherical or of other shapes. If the particles are not spherical, the dimensions mentioned are their minimum dimensions. The colloidal species generally have an average diameter (or minimum dimension, corresponding to the number-average primary particle size determined by SEM for 100 or more particles) of 300 nm or less, particularly 200 nm or less, and more particularly 100 nm or less, provided that the colloidal species form a stable suspension in the sense that no visible separation occurs or precipitates are formed for a period sufficient for the intended use.

[0036] The components of the synthetic mixture may be combined in any order. In a preferred modification, if at least one source of alumina contains aluminum hydroxide, the aluminum hydroxide is first mixed with at least a portion of water to form a dispersion before the addition of other components, for example, before the addition of further hydroxide ions, alkali metals or alkaline earth metals M, structure directing agents R, and silica sources. In a preferred modification, if at least one source of alumina contains kaolin, the kaolin may first be mixed with at least a portion of water and / or at least a portion of the hydroxide source and / or at least a portion of the structure directing agent R to form a dispersion before the addition of other components, for example, before the addition of silica sources.

[0037] Crystallization and recovery In the method of the present invention, the crystallization conditions in step (b) may include heating the synthetic mixture at a temperature of 100°C to 220°C, preferably 120°C to 200°C, preferably 140°C to 180°C, and more preferably 150°C to 170°C.

[0038] The synthetic mixture is * The mixture is maintained under effective crystallization conditions until an MRE framework molecular sieve is formed. The crystallization time may vary depending on many factors, ranging from a few minutes to several hours, typically 10 to 200 hours, more typically 12 to 160 hours, for example, 20 to 120 hours, or until the reaction is complete and zeolite crystals are formed. The crystallization time can be determined by methods known in the art, such as sampling the synthetic mixture at various times and determining the yield and X-ray crystallinity of the precipitated solid.

[0039] The crystallization step (b) can be carried out statically or preferably with stirring in any suitable reaction vessel, such as a polypropylene jar or Teflon® bottle, an acid digester, a Teflon®-lined or stainless steel autoclave, a plow shear mixer, or a reaction kettle, preferably a polypropylene jar, Teflon® bottle, Teflon®-lined or stainless steel autoclave, in a continuous or batch configuration.

[0040] In process (c), the manufactured in process (b) * The MRE framework molecular sieves may be recovered from the synthetic mixture by any conventional means such as centrifugation or filtration. * MRE framework molecular sieves are typically washed with deionized water and recovered by centrifugation or filtration. Subsequent operations may include washing with water, drying (usually at temperatures below 250°C, such as 100-200°C), calcination, and ion exchange.

[0041] recovered * MRE Framework Type Molecular Sieve A method that can be obtained or obtained by the method of the present invention * MRE framework molecular sieves are aluminum-rich crystals, such as aluminum-rich ZSM-48 type crystals. In this invention, the expression "aluminum-rich crystal" refers to a crystal having a high aluminum content, typically expressed as a silica:alumina (SiO2:Al2O3) molar ratio of less than 100, particularly less than 80, and more particularly less than 70. Obtained by the method of this invention * The MRE framework type molecular sieve has an SiO2:Al2O3 molar ratio of at least 10, typically at least 15, generally at least 20, more generally at least 25, for example at least 30, at least 40 or even more at least 50. *MRE framework type molecular sieves may therefore have an SiO2:Al2O3 molar ratio of 10 to less than 100, for example, 10 to less than 80 or 10 to less than 70, for example, 15 or 20 to less than 80 or 15 or 20 to less than 70 or 30 or 40 to less than 80 or 30 or 40 to less than 70. The SiO2:Al2O3 molar ratio is understood to be the molar ratio in the molecular sieve framework. Any suitable method can be used to confirm the composition of the molecular sieve material, such as inductively coupled plasma emission spectroscopy (ICP-OES) analysis.

[0042] Obtained from the method of the present invention * MRE framework type molecular sieves are used for materials containing impurities such as amorphous materials; * It will be understood by those skilled in the art that the present invention may contain unit cells having an MRE framework type configuration; unconverted kaolin; and / or other impurities (e.g., heavy metals and / or organic hydrocarbons). * Non-MRE framework-type molecular sieves coexisting * Typical examples of MRE framework molecular sieves include Kenyaite, Magadiite, EU-1, ZSM-50, FAU, Zeolite P, ZSM-12, ZSM-5, Ferrierite, Mordenite, Sodalite, and / or Analcine. Other examples include framework molecular sieves of EUO, MTW, FER, MOR, SOD, ANA, and / or MFI. * MRE framework molecular sieves are preferably substantially free of impurities. As used herein, "substantially free of impurities" means: * MRE framework type molecular sieve (or "non *The MRE framework type molecular sieve (preferably 10% by weight or less, preferably 5% by weight or less, more preferably 2% by weight or less, even more preferably 1% by weight or less, most preferably an amount undetectable by XRD, means that such impurities are present in small proportions, and the weight % value is between the impurities and the pure phase. * This is based on the combined weight of MRE framework type molecular sieves. The amount of impurities can be appropriately determined by powder XRD, rotational electron diffraction, and / or SEM ITEM (e.g., different crystal forms).

[0043] Optionally, the method of the present invention can or can be obtained. * MRE framework type molecular sieves, in their calcined and ion-exchanged forms, have a temperature of 150-500, for example 160-400, for example 170-350 m 2 It has a Sgpy surface area of ​​ / g. Optionally, it can be obtained by the method of the present invention. * MRE framework type molecular sieves, in their calcined and ion-exchanged forms, have a thickness of 0.04–0.2 cm, for example, 0.05–0.1 cm. 3 It has a micropore volume (Vmicro) per g.

[0044] * MRE Successful processing of framework-type molecular sieves As a result of the crystallization process, recovered *MRE framework type molecular sieves contain at least a portion of the structure-directing agent R used in the synthesis within their pores. Preferably, and therefore, this method further includes activating the molecular sieves to remove at least partially the structure-directing agent from them. The activation step is typically achieved by calcining, i.e., essentially heating, the molecular sieves containing the structure-directing agent in the presence of an oxygen-containing gas. In some cases, it may be desirable to heat the molecular sieves in an environment with low or zero oxygen concentration. This type of method can be used to partially or completely remove the structure-directing agent from the crystalline pore system. In other cases, particularly for smaller structure-directing agents, complete or partial removal from the molecular sieves can be achieved by conventional desorption methods. Typically, the recovered molecular sieves are subjected to a calcination step, which includes heating the material at a temperature of at least about 200°C, preferably at least about 300°C, and more preferably at least about 370°C, for at least 1 minute, and generally for 20 hours or less. While subatmospheric pressure may be used for heat treatment, atmospheric pressure is usually preferred for convenience. Heat treatment can be carried out at temperatures of approximately 925°C or lower. For example, heat treatment can be carried out at temperatures of 300-600°C, for example 400-550°C, or for example 500-550°C, in the presence of an oxygen-containing gas, such as air and / or ozone.

[0045] Molecular sieves may be subjected to ion exchange treatment with aqueous ammonium salts, such as ammonium nitrate, ammonium chloride, or ammonium acetate, to remove any remaining alkali metal cations and / or alkaline earth metal cations and replace them with protons, thereby generating the acidic form of the molecular sieve. To a desired extent, the original cations of the as-synthesized material, such as alkali metal cations, can be replaced with other cations by ion exchange. Preferred substitution cations include hydrogen ions, hydrogen precursors, such as ammonium ions, and mixtures thereof. The ion exchange step may be performed after the as-produced molecular sieve has been dried. The ion exchange step may be performed either before or after the calcination step.

[0046] Molecular sieves may also be subjected to other treatments, such as steam treatment and / or washing with solvents. Such treatments are well known to those skilled in the art and are performed to modify the properties of molecular sieves to a desired extent.

[0047] Once molecular sieves are synthesized, they may be incorporated into the product composition by combining them with other materials, such as binders and / or matrix materials, to provide further hardness to the final product. These other materials may be inert or catalytically active. Calcination, ion exchange, steam treatment, and / or washing may be performed on the as-synthesized molecular sieves and / or after the molecular sieves have been incorporated into the product combination.

[0048] A method that can be obtained or obtained by the method of the present invention * When an MRE framework type molecular sieve is used as a catalyst, *It may be desirable to combine MRE framework molecular sieves with other materials that are resistant to the temperatures and other conditions employed during use in organic conversion methods. Such materials include catalytically active and inert materials, as well as synthetic or naturally occurring zeolites, and inorganic materials such as clay and silica, and / or metal oxides such as alumina, yttria, zirconia, gallium oxide, zinc oxide, and mixtures thereof. The metal oxides may be naturally occurring or may be in the form of gelatinous precipitates or gels containing mixtures of silica and metal oxides. * Using catalytically active materials in combination with MRE framework molecular sieves may improve the conversion and / or selectivity of catalysts in certain organic conversion methods. Inert substances preferably serve as diluents to control the amount of conversion in a given method, so that products can be obtained economically without employing other means to control the reaction rate. These materials can be incorporated into naturally occurring clay to improve the fracturing strength of catalysts under commercial operating conditions. * Naturally occurring clays that can be compounded with MRE framework-type molecular sieves include the montmorillonite and kaolinite groups, which include subbentonites and kaolins commonly known as Dixie clay, McNamee clay, Georgia clay, and Florida clay, or others whose dominant mineral component is halloysite, kaolinite, dickite, nacrite, or anauxite. Such clays can be used in their untreated, as-mined state, or after calcination, acid treatment, or chemical modification. *Binders useful for compounding with MRE framework-type molecular sieves include inorganic oxides, particularly alumina. These materials, namely clay, oxides, etc., function as catalyst binders and are resistant to the temperatures and other conditions that occur in various hydrocarbon separation methods, such as mechanical wear. Therefore, the materials prepared by the method of the present invention * MRE framework type molecular sieves may be used in the form of extruded products with a binder. They are typically bonded by forming tablets, spheres, or extruded products. Extruded products are usually formed by extruding molecular sieves in the presence of a binder, and then drying and calcining the resulting extruded products. Further treatments such as steam treatment and / or ion exchange may be performed as needed. Molecular sieves are optionally made of at least 100 m 2 / g, for example, at least 200m 2 / g, optionally at least 300m 2 It may also be bonded with a binder having a surface area of ​​ / g.

[0049] In addition to the materials mentioned above, the following can be obtained by the method of the present invention. * The MRE framework type molecular sieve may be compounded with porous matrix materials, such as silica-alumina, silica-magnesia, silica-zirconia, silica-tria, silica-beryllia, silica-titania, and ternary compositions such as silica-alumina-tria, silica-alumina-zirconia, silica-alumina-magnesia, and silica-magnesia-zirconia.

[0050] * The relative ratio of MRE framework-type molecular sieves to inorganic oxide matrix can vary widely. * The molecular sieve content in MRE frameworks is approximately 1 to 100% by weight, more typically ranging from approximately 2 to 95%, and optionally from approximately 20 to 90% by weight, of the composite, especially when the composite is manufactured in the form of an extruded product.

[0051] * Use of MRE Framework-type Molecular Sieves A method that can be obtained or obtained by the method of the present invention * MRE framework molecular sieves can be used as adsorbents, for example, to separate at least one component from a mixture of gaseous or liquid-phase components that have differential sorption characteristics with respect to the molecular sieve. Thus, by contacting the mixture with the molecular sieve and selectively sorbing one component, it is possible to partially or substantially completely separate at least one component from a mixture of components that have differential sorption characteristics with respect to the molecular sieve.

[0052] Obtained by the method of the present invention, or obtained * MRE framework molecular sieves can also be used in many hydrocarbon chemical transformation processes. Applications of such catalysts include dewaxing, oligomerization, hydrogen isomerization such as the hydrogen isomerization of normal paraffins, and isomerization such as olefin isomerization. These uses are particularly advantageous in terms of their high aluminum content, which provides high activity.

[0053] For catalytic applications, * It is sometimes desirable to use MRE framework molecular sieves in combination with a metal component that can impart hydrogenation-dehydrogenation functionality to the catalyst. Suitable metal components include tungsten, vanadium, molybdenum, rhenium, nickel, cobalt, chromium, manganese, or noble metals such as platinum and palladium. Such components can be exchanged into the composition, impregnated therein, or physically mixed closely with it. Such components can be impregnated into or on the composition, for example, by treating platinum with a solution containing platinum metal ions. Accordingly, suitable platinum compounds include various compounds including chloroplatinic acid, platinumus chloride, and platinumamine complexes.

[0054] Manufactured by the method of the present invention *Catalysts containing MRE framework-type molecular sieves are particularly useful in the dewaxing of lubricating oil substrates (or basestocks). Such feedstocks are wax-containing feedstocks that boil in the range of lubricating oils and typically have a 10% distillation point above 650°F (343°C) as measured by ASTM D 86 or ASTM D 2887. Such feedstocks may be obtained from oils obtained from solvent refining processes such as raffinates, partially solvent-dewaxed oils, dezincified oils, distillates, vacuum gas oils, coker gas oils, slack wax, feet oil, and numerous feedstocks such as Fischer-Tropsch wax. Preferred feedstocks are slack wax and Fischer-Tropsch wax. Slack wax is typically obtained from hydrocarbon feedstocks by solvent or propane dewaxing. Slack wax contains some residual oil and is typically de-oiled. Feet oil is obtained from de-oiled slack wax. Fischer-Tropsch wax is produced by the Fischer-Tropsch synthesis method.

[0055] Dewaxing conditions using such lubricating oil substrates are typically: a temperature below 426°C, e.g., about 250°C to about 400°C, e.g., about 275°C to about 350°C; a pressure of about 791 to about 20786 kPa, e.g., about 1480 to about 17339 kPa; a liquid space-time velocity of about 0.1 to about 10 / hour, e.g., about 0.1 to about 5 / hour; and about 45 to about 1780 m 3 / m 3 (250~10000 scf / B), for example, approximately 89~890 m 3 / m 3 This is the hydrogen treatment gas rate (500~5000 scf / B).

[0056] Manufactured by the method of the present invention *Catalysts containing MRE framework molecular sieves can also be used for the hydrogen isomerization of normal paraffins, especially when they include a hydrogenation component, such as platinum. Typically, hydrogen isomerization occurs at a temperature of about 100°C to about 400°C, for example, about 150°C to about 300°C, using hydrogen with a hydrogen:hydrocarbon molar ratio of about 1:1 to about 5:1, at a liquid space-time velocity of about 0.01 to about 2 / hour, for example, about 0.25 to about 0.50 / hour.

[0057] Manufactured by the method of the present invention * Catalysts containing MRE framework-type molecular sieves are also particularly useful for olefin isomerization. Typical conditions include temperatures of about 250°C to about 750°C, olefin partial pressures of about 30 kPa to about 300 kPa, and WSHV of about 0.5 to about 500 / hour. [Examples]

[0058] The present invention is further illustrated below without limiting its scope.

[0059] In these examples, the X-ray diffraction (XRD) patterns of the as-synthesized materials were recorded using an X-ray powder diffractometer (Bruker, D8 Discover, or STOE, Stadi P Combi) with copper Kα rays in a 20-degree range from 2 to 40 degrees.

[0060] Scanning electron microscope (SEM) images of the as-synthesized material were obtained using a Helios Nanolab G3 UC scanning electron microscope from FEI.

[0061] The zeolite framework type of the as-synthesized material was identified by comparing it with the XRD patterns of known zeolite materials. SEM images were used to aid in assessing the purity of the product. The presence of distinctly different crystalline morphologies in the SEM images may indicate impurities in the form of other crystalline materials. Such approximate analysis is particularly useful in identifying the presence of the formation of relatively small amounts of crystalline impurities that may not be discernible in the XRD patterns of the product.

[0062] The following measurements were performed on samples that underwent ion exchange and calcination. The procedure used for each sample that underwent ion exchange and calcination was as follows: The as-prepared sample was washed twice with 1M ammonium nitrate solution, and then calcined at 538°C for 6 hours.

[0063] The SiO2:AL2O3 molar ratio of the material was determined by inductively coupled plasma (ICP) spectroscopy.

[0064] The total surface area (Sgpy) of the material was determined by nitrogen adsorption-desorption at liquid nitrogen temperature using the BET method described in S. Brunauer, PH. Emmett and E. Teller, J. Am. Chem. Soc., 1938, 60, 309 (incorporated herein by reference).

[0065] The microporous volume of the material was determined by applying a plotting model to an N2 isotherm, as referenced in "Analytical Methods in Fine Particle Technology, PA Webb and C. Orr, Micrometrics Instrument Corporation, ISBN 0-9656783-0-X" (the contents of which are incorporated herein by reference). Comparative Examples 1-5 illustrate the use of sodium aluminate or potassium aluminate solution as a source of alumina. Examples 6-10 describe the use of kaolin as a source of alumina, and Examples 11-13 describe the use of undissolved aluminum hydroxide as a source of alumina.

[0066] Example 1 (Comparative Example): Sodium aluminate aqueous solution - SiO 2 :Al 2 O 3 =81 Sodium aluminate powder was dissolved in water to prepare a sodium aluminate solution (9.1% alumina, 6.6% sodium oxide). 15.50 g of water, 1.40 g of sodium hydroxide solution (20.0% sodium hydroxide), 1.62 g of hexamethonium dichloride solution (24.7% sodium hydroxide), 0.96 g of sodium aluminate solution, 0.75 g of BEA species (16.7% aqueous colloidal suspension, 5000 ppm sodium hydroxide of the synthetic mixture), and 4.76 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. The mixture was stirred for 5 minutes after each addition and for 15 minutes after the last addition. The mixture was then treated under hydrothermal conditions at 165°C for 24 hours while stirring with a U-type stirrer. The solid was then collected, washed several times with water, and dried at 120°C.

[0067] The synthetic mixture was as follows (synthetic mixture / molar ratio): SiO2 / Al2O380.57, OH - / SiO20.13, Na + / SiO2 0.13, R:SiO2 0.02, H2O / SiO2 14.87.

[0068] The recovered material was confirmed to be ZSM-48 with an SiO2 / Al2O3 molar ratio of 67.

[0069] Example 2 (Comparative Example): Sodium aluminate aqueous solution - SiO 2 :Al 2 O 3 =80 A sodium aluminate solution was prepared by dissolving sodium aluminate powder in water (alumina 9.1% by weight, sodium oxide 6.6% by weight). 16.52 g of water, 1.65 g of sodium hydroxide solution (20.0% by weight), 1.34 g of hexamethonium dichloride solution (24.7% by weight), 0.80 g of sodium aluminate solution, 0.75 g of BEA species (16.7% by weight aqueous colloidal suspension, 5000 ppm by weight of the synthetic mixture), and 3.94 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. The mixture was stirred for 5 minutes after each addition and for 15 minutes after the last addition. The mixture was then treated under hydrothermal conditions at 160°C for 28 hours while stirring with a U-type stirrer. The solid was then collected, washed several times with water, and dried at 120°C.

[0070] The synthetic mixture was as follows (synthetic mixture / molar ratio): SiO2 / Al2O380.00, OH - / SiO20.17, Na + / SiO2 0.17, R:SiO2 0.02, H2O / SiO2 18.70.

[0071] The recovered material was confirmed to be ZSM-48 with an SiO2 / Al2O3 molar ratio of 67.

[0072] Example 3 (Comparative Example): Sodium aluminate aqueous solution - SiO 2 :Al 2 O 3 =80 A sodium aluminate solution was prepared by dissolving aluminum hydroxide (Alcoa) in a sodium hydroxide solution. This mixture was heated until a clear solution was obtained. Water was added to obtain the following composition: 3.0% by weight of aluminum hydroxide and 9.1% by weight of sodium hydroxide.

[0073] 14.33 g of water, 0.14 g of sodium hydroxide solution (40.0 wt%), 1.33 g of hexamethonium dichloride solution (25.1 wt%), 3.94 g of sodium aluminate solution, 1.28 g of BEA species (9.8 wt% aqueous colloidal suspension, 5000 wt ppm of the synthetic mixture), and 3.99 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. The mixture was stirred for 5 minutes after each addition and for 15 minutes after the last addition. The mixture was then treated under hydrothermal conditions at 160°C for 28 hours while stirring with a U-type stirrer. The solid was then collected, washed several times with water, and dried at 120°C.

[0074] The synthetic mixture was as follows (synthetic mixture / molar ratio): SiO2 / Al2O380.00, OH - / SiO20.25, Na + / SiO2 0.17, R:SiO2 0.02, H2O / SiO2 18.70.

[0075] The recovered material was confirmed to be ZSM-48 with an SiO2 / Al2O3 molar ratio of 63.

[0076] Example 4 (Comparative Example): Sodium aluminate aqueous solution SiO 2 :Al 2 O 3 =70 A sodium aluminate solution was prepared by dissolving sodium aluminate powder in water (10.0% alumina, 7.4% sodium oxide). 13.01 g of water, 3.24 g of sodium hydroxide solution (10.0% by weight), 1.70 g of hexamethonium dichloride solution (23.4% by weight), 1.01 g of sodium aluminate solution, 1.28 g of BEA species (9.8% by weight aqueous colloidal suspension, 5000 ppm by weight of the synthetic mixture), and 4.75 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. The mixture was stirred for 5 minutes after each addition and for 15 minutes after the last addition. The mixture was then treated under hydrothermal conditions at 165°C for 24 hours while stirring with a U-type stirrer. The solid was then collected, washed several times with water, and dried at 120°C.

[0077] The synthesis mixture was as follows (synthesis mixture / molar ratio): SiO2 / Al2O3 70.00, OH - / SiO2 0.15, Na + / SiO2 0.15, R:SiO2 0.02, H2O / SiO2 14.87.

[0078] The recovered product was identified as Kenyaite.

[0079] Example 5 (Comparative Example): Potassium aluminate solution - SiO 2 :Al 2 O 3 =65 A potassium aluminate solution was prepared by dissolving aluminum hydroxide (Alcoa) in a potassium hydroxide solution. This mixture was heated until a clear solution was obtained. Water was added to obtain the following composition: 3.0 wt% aluminum hydroxide, 5.5 wt% potassium hydroxide.

[0080] 11.91 g of water, 1.10 g of potassium hydroxide solution (7.3 wt%), 1.51 g of hexamethonium dichloride solution (25.0 wt%), 5.26 g of potassium aluminate solution, 0.75 g of BEA seed (16.7 wt% aqueous colloidal suspension, 5000 ppm by weight of the synthesis mixture) and 4.48 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. The mixture was stirred for 5 minutes after each addition and for 15 minutes after the last addition. Thereafter, the mixture was treated under hydrothermal conditions at 160 °C for 125 hours while stirring with a U-shaped stirrer. Thereafter, the solid was recovered, washed several times with water and dried at 120 °C.

[0081] The synthesis mixture was as follows (synthesis mixture / molar ratio): SiO2 / Al2O3 65.00, OH - / SiO2 0.19, K+ / SiO2 0.10, R:SiO2 0.02, H2O / SiO2 16.00.

[0082] The recovered material was identified as a mixture of ZSM-48 containing a significant amount of EU-1 and some amorphous compounds.

[0083] Example 6: Kaolin-SiO 2 :Al 2 O 3 =81 13.75 g of water, 1.81 g of sodium hydroxide solution (20.0 wt%), 1.62 g of hexamethonium dichloride solution (24.7 wt%), 2.42 g of kaolin mixture (10 wt% kaolin powder dispersed in water, particle size approximately 5 μm), 0.75 g of BEA species (16.7 wt% aqueous colloidal suspension, 5000 wt ppm of the synthetic mixture), and 4.64 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. The mixture was stirred for 5 minutes after each addition and for 15 minutes after the last addition. Then, the mixture was hydrothermally treated at 165°C for 24 hours while stirring with a U-type stirrer. After that, the solid was collected, washed several times with water, and dried at 120°C.

[0084] The synthetic mixture was as follows (synthetic mixture / molar ratio): SiO2 / Al2O380.57, OH - / SiO20.13, Na + / SiO2 0.13, R:SiO2 0.02, H2O / SiO2 14.87.

[0085] The recovered material was confirmed to be ZSM-48 with an SiO2 / Al2O3 molar ratio of 76.

[0086] Example 7: Kaolin-SiO 2 :Al 2 O 3 =80 15.06 g of water, 1.99 g of sodium hydroxide solution (20.0 wt%), 1.34 g of hexamethonium dichloride solution (24.7 wt%), 2.02 g of kaolin mixture (10 wt% kaolin powder dispersed in water, particle size approximately 5 μm), 0.75 g of BEA species (16.7 wt% aqueous colloidal suspension, 5000 wt ppm of the synthetic mixture), and 3.84 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. The mixture was stirred for 5 minutes after each addition and for 15 minutes after the last addition. The mixture was then treated under hydrothermal conditions at 160°C for 28 hours while stirring with a U-type stirrer. The solid was then collected, washed several times with water, and dried at 120°C.

[0087] The synthetic mixture was as follows (synthetic mixture / molar ratio): SiO2 / Al2O380.00, OH - / SiO20.17, Na + / SiO2 0.17, R:SiO2 0.02, H2O / SiO2 18.70.

[0088] The recovered material was confirmed to be ZSM-48 with an SiO2 / Al2O3 molar ratio of 68.

[0089] Example 8: Kaolin-SiO 2 :Al 2 O 3 =70 13.15 g of water, 2.10 g of sodium hydroxide solution (20.0 wt%), 1.60 g of hexamethonium dichloride solution (25.0 wt%), 2.80 g of kaolin mixture (10 wt% kaolin powder dispersed in water, particle size approximately 5 μm), 0.75 g of BEA species (16.7 wt% aqueous colloidal suspension, 5000 wt ppm of the synthetic mixture), and 4.61 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. The mixture was stirred for 5 minutes after each addition and for 15 minutes after the last addition. Then, the mixture was hydrothermally treated at 165°C for 24 hours while stirring with a U-type stirrer. After that, the solid was collected, washed several times with water, and dried at 120°C.

[0090] The synthesis mixture was as follows (synthesis mixture / molar ratio): SiO2 / Al2O3 70.00, OH - / SiO2 0.15, Na + / SiO2 0.15, R:SiO2 0.02, H2O / SiO2 14.87.

[0091] The recovered material was confirmed to be ZSM-48 with a SiO2 / Al2O3 molar ratio of 65.

[0092] Example 9: Kaolin-SiO 2 :Al 2 O 3 =65 13.20 g of water, 1.81 g of sodium hydroxide solution (20.0 wt%), 1.60 g of hexamethonium dichloride solution (25.0 wt%), 3.03 g of kaolin mixture (10 wt% kaolin powder dispersed in water, particle size approximately 5 μm), 0.75 g of BEA seeds (16.7 wt% aqueous colloidal suspension, 5000 wt ppm of the synthesis mixture) and 4.61 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. The mixture was stirred for 5 minutes after each addition and for 15 minutes after the last addition. Next, the mixture was hydrothermally treated at 165 °C for 24 hours while stirring with a U-shaped stirrer. Thereafter, the solid was recovered, washed several times with water and dried at 120 °C.

[0093] The synthesis mixture was as follows (synthesis mixture / molar ratio): SiO2 / Al2O3 65.00, OH - / SiO2 0.13, Na + / SiO2 0.13, R:SiO2 0.02, H2O / SiO2 14.87.

[0094] The recovered material was confirmed to be ZSM-48 with a SiO2 / Al2O3 molar ratio of 61, containing trace amounts of mordenite.

[0095] Example 10: Kaolin-SiO 2[[ID=四十三]] :Al 2 O 3=60 12.95 g of water, 1.81 g of sodium hydroxide solution (20.0 wt%), 1.60 g of hexamethonium dichloride solution (25.0 wt%), 3.30 g of kaolin mixture (10 wt% kaolin powder dispersed in water, particle size approximately 5 μm), 0.75 g of BEA species (16.7 wt% aqueous colloidal suspension, 5000 wt ppm of the synthetic mixture), and 4.59 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. The mixture was stirred for 5 minutes after each addition and for 15 minutes after the last addition. Then, the mixture was hydrothermally treated at 165°C for 24 hours while stirring with a U-type stirrer. After that, the solid was collected, washed several times with water, and dried at 120°C.

[0096] The synthetic mixture was as follows (synthetic mixture / molar ratio): SiO2 / Al2O360.00, OH - / SiO20.13, Na + / SiO2 0.13, R:SiO2 0.02, H2O / SiO2 14.87.

[0097] The recovered material was found to contain trace amounts of mordenite and was identified as ZSM-48 with an SiO2 / Al2O3 molar ratio of 55.

[0098] Example 11: Kaolin-SiO 2 :Al 2 O 3 =50 385.60 g of water, 47.57 g of sodium hydroxide solution (19.5 wt%), 41.58 g of hexamethonium dichloride solution (25.0 wt%), 10.29 g of kaolin mixture (10 wt% kaolin powder dispersed in water, particle size approximately 5 μm), 45.69 g of BEA species (7.1 wt% aqueous colloidal suspension, 5000 wt ppm of the synthetic mixture), and 119.38 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. After each addition, the mixture was stirred. Subsequently, a portion of the mixture was treated under hydrothermal conditions at 165°C for 24 hours while stirring with a U-type stirrer. The solid was then collected, washed several times with water, and dried at 120°C.

[0099] The synthetic mixture was as follows (synthetic mixture / molar ratio): SiO2 / Al2O350.00, OH - / SiO20.13, Na + / SiO2 0.13, R:SiO2 0.02, H2O / SiO2 14.87.

[0100] The recovered material was confirmed to be ZSM-48 with an SiO2 / Al2O3 molar ratio of 45.

[0101] Example 12: Aluminum hydroxide-SiO 2 :Al 2 O 3 =65 0.16 g of aluminum hydroxide (particle size approximately 50 μm), 13.49 g of water, 4.90 g of potassium hydroxide solution (7.3 wt%), 1.47 g of hexamethonium dichloride solution (25.0 wt%), 0.80 g of BEA species (9.8 wt% aqueous colloidal suspension, 5000 wt ppm of the synthetic mixture), and 4.27 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. The mixture was stirred for 5 minutes after each addition and for 15 minutes after the last addition. The mixture was then treated under hydrothermal conditions at 160°C for 100 hours while stirring with a U-type stirrer. The solid was then collected, washed several times with water, and dried at 120°C.

[0102] The synthetic mixture was as follows (synthetic mixture / molar ratio): SiO2 / Al2O365.00, OH - / SiO20.19, K + / SiO20.10, R:SiO20.02, H2O / SiO217.00.

[0103] The recovered material was confirmed to be ZSM-48 with an SiO2 / Al2O3 molar ratio of 57.

[0104] Example 13: Aluminum hydroxide-SiO 2 :Al 2 O 3 =50 0.22 g of aluminum hydroxide (particle size approximately 50 μm), 16.38 g of water, 3.83 g of potassium hydroxide solution (7.3 wt%), 1.63 g of hexamethonium dichloride solution (25.0 wt%), 0.82 g of BEA species (9.8 wt% aqueous colloidal suspension, 5000 wt ppm of the synthetic mixture), and 4.71 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. The mixture was stirred for 5 minutes after each addition and for 15 minutes after the last addition. The mixture was then treated under hydrothermal conditions at 160°C for 100 hours while stirring with a U-type stirrer. The solid was then collected, washed several times with water, and dried at 120°C.

[0105] The synthetic mixture was as follows (synthetic mixture / molar ratio): SiO2 / Al2O350.00, OH - / SiO20.19, K+ / SiO20.07, R:SiO20.02, H2O / SiO217.00.

[0106] The recovered material was confirmed to be ZSM-48 with an SiO2 / Al2O3 molar ratio of 53.

[0107] Example 14: Aluminum hydroxide-SiO 2 :Al 2 O 3 =50 0.21 g of aluminum hydroxide (particle size approximately 50 μm), 17.46 g of water, 1.67 g of sodium hydroxide solution (20.0 wt%), 1.67 g of hexamethonium dichloride solution (25.0 wt%), 0.79 g of BEA species (9.8 wt% aqueous colloidal suspension, 5000 wt ppm of the synthetic mixture), and 4.38 g of precipitated silica (Ultrasil® VN3) were added to a Teflon® liner. The mixture was stirred for 5 minutes after each addition and for 15 minutes after the last addition. The mixture was then treated under hydrothermal conditions at 160°C for 100 hours while stirring with a U-type stirrer. The solid was then collected, washed several times with water, and dried at 120°C.

[0108] The synthetic mixture was as follows (synthetic mixture / molar ratio): SiO2 / Al2O350.00, OH - / SiO20.22, Na + / SiO20.10, R:SiO20.02, H2O / SiO217.00.

[0109] The recovered material was confirmed to be ZSM-48 containing trace amounts of impurities, with a SiO2 / Al2O3 molar ratio of 46.

[0110] Example 15: Characterization of the products from Examples 1-14 Figures 1A to 14A show the XRD spectra of each of the Examples 1 to 14 (in their as-synthesized form).

[0111] Figures 1B to 14B show scanning electron microscope (SEM) images of each of Examples 1 to 14 (in their as-synthesized form), respectively.

[0112] Figure 15 summarizes the reaction conditions and molar ratios of the synthesized mixtures for Examples 1 to 14.

[0113] Figure 16 summarizes the properties of the products obtained in Examples 1 to 14, namely their framework type, silica / alumina ratio, total Sgpy surface area, and micropore volume (Vmicro).

[0114] Although the present invention has been described and illustrated with reference to specific embodiments, it will be understood by those skilled in the art that the present invention is suitable for many different modifications not specifically illustrated herein.

[0115] Where any integer or element having known, obvious, or foreseeable equivalents is referred to in the foregoing description, such equivalents are incorporated herein as if they were separately defined. To determine the true scope of the invention, it is necessary to refer to the claims and interpret them to encompass such equivalents. Furthermore, it should be understood by the reader that any integer or feature of the invention described as preferred, advantageous, convenient, etc., is optional and does not limit the scope of the independent claims. Moreover, it should be understood that any such integer or feature may provide possible benefits in some embodiments of the invention while being undesirable and therefore absent in other embodiments.

[0116] Furthermore, or alternatively, the present invention relates to the following:

[0117] [Embodiment 1] (a) A step of preparing a synthetic mixture comprising at least one source of silica, at least one source of alumina selected from aluminum hydroxide, clay selected from the kaolin group, and metakaolin, at least one source of hydroxide ions, at least one source of alkali metal and / or alkaline earth metal M, at least one source of linear diquaternary alkylammonium structure directing agent R, water, and an optional seed crystal. (b) The synthetic mixture is subjected to crystallization conditions. * A step of heating for a sufficient time to form an MRE framework type molecular sieve; and (c) From the synthetic mixture * Process for recovering MRE framework-type molecular sieves Includes, The aforementioned synthetic mixture has the following molar ratio composition: SiO2:Al2O315~100 or less, OH - :SiO2 0.02~0.6, M:SiO2 0.02~0.6 R:SiO2 0.005~0.5, H2O:SiO25~100 It has, At least one source of the alumina is added to the synthesis mixture in solid form. * A method for synthesizing MRE framework-type molecular sieves.

[0118] [Embodiment 2] The aforementioned * The MRE framework type molecular sieve is selected from the group consisting of COK-8, EU-2, EU-11, IZM-1, SSZ-91, ZBM-30, ZSM-48, and mixtures thereof, preferably the above. * The method according to Embodiment 1, wherein the MRE framework type molecular sieve is ZSM-48.

[0119] [Embodiment 3] The method according to Embodiment 1 or 2, wherein at least one source of alumina is in powder form, preferably in the form of solid particles having an average particle size of 0.01 to 300 μm, preferably 0.1 to 200 μm, and more preferably 1 to 100 μm as a volume-weighted average measured by dynamic light scattering (DLS).

[0120] [Embodiment 4] The method according to any one of Embodiments 1 to 3, wherein at least one source of silica is selected from the group consisting of precipitated silica, fumed silica, silica gel, silicic acid, tetraalkyl orthosilicate, alkali metal silicate, and aqueous colloidal suspension of silica.

[0121] [Embodiment 5] The method according to any one of Embodiments 1 to 4, wherein the linear diquaternary alkylammonium structure directing agent R is selected from the group consisting of pentamethonium cations, hexamethonium cations, and mixtures thereof.

[0122] [Embodiment 6] The method according to any one of Embodiments 1 to 5, wherein the alkali metal or alkaline earth metal M is selected from the group consisting of Na, K, Li, Ca, Mg, and mixtures thereof, and is preferably Na and / or K.

[0123] [Embodiment 7] The method according to any one of Embodiments 1 to 6, wherein at least one source of hydroxide ions is selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, aluminum hydroxide, the hydroxide form of the structure directing agent R, and mixtures thereof, preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, aluminum hydroxide, the hydroxide form of the structure directing agent R, and mixtures thereof, more preferably selected from potassium hydroxide and / or sodium hydroxide.

[0124] [Embodiment 8] The method according to any one of Embodiments 1 to 7, wherein the seed crystal is selected from the group consisting of ZSM-48 type, ZSM-5 type, ZSM-11 type, ZSM-12 type, BEA type, beta type, X type, and Y type zeolite seed crystals, preferably ZSM-48 type or BEA type seed crystals.

[0125] [Embodiment 9] The method according to any one of Embodiments 1 to 8, wherein the seed crystal is present in an amount of 0 to 50,000 ppm by weight, preferably 50 to 10,000 ppm by weight, more preferably 100 to 10,000 ppm by weight, and most preferably 500 to 6,000 ppm by weight, based on the total weight of the synthetic mixture.

[0126] [Embodiment 10] The method according to any one of Embodiments 1 to 9, wherein the SiO2:Al2O3 molar ratio in the synthetic mixture is 15 to less than 100, preferably 20 to less than 100, more preferably 30 to less than 100, particularly less than 80, or less than 75, or less than 70.

[0127] [Embodiment 11] The aforementioned synthetic mixture has the following molar ratio composition: OH - SiO2 0.05~0.5, preferably 0.1~0.3, The method according to any one of embodiments 1 to 10, comprising:

[0128] [Embodiment 12] The aforementioned synthetic mixture has the following molar ratio composition: M:SiO2 0.05~0.5, preferably 0.1~0.3 The method according to any one of embodiments 1 to 11, comprising:

[0129] [Embodiment 13] The aforementioned synthetic mixture has the following molar ratio composition: R:SiO2 0.01~0.1, preferably 0.01~0.05. The method according to any one of embodiments 1 to 12, comprising:

[0130] [Embodiment 14] The aforementioned synthetic mixture has the following molar ratio composition: H2O:SiO2 7-50, preferably 10-30 The method according to any one of embodiments 1 to 13, having the characteristics described herein.

[0131] [Embodiment 15] The method according to any one of Embodiments 1 to 14, wherein the crystallization conditions of step (b) include a temperature of 100°C to 220°C, preferably 120°C to 200°C, more preferably 150°C to 170°C, and a time of 10 to 600 hours, particularly 12 to 160 hours, and more particularly 20 to 120 hours.

[0132] [Embodiment 16] Obtained by the method described in any one of Embodiments 1 to 15, having a molar ratio of SiO2:Al2O3 of 10 to less than 100, preferably 15 to less than 80, and more preferably 20 to less than 70. * MRE framework-type molecular sieve.

[0133] [Embodiment 17] Use of molecular sieves as described in Embodiment 16 in a hydrocarbon chemical conversion method, wherein the hydrocarbon chemical conversion method is dewaxing, oligomerization, hydrogen isomerization, or isomerization.

Claims

1. (a) A step of preparing a synthetic mixture comprising at least one source of silica, at least one source of alumina selected from aluminum hydroxide, clay selected from the kaolin group, and metakaolin, at least one source of hydroxide ions, at least one source of alkali metal and / or alkaline earth metal M, at least one source of linear diquaternary alkylammonium structure directing agent R, water, and an optional seed crystal. (b) The synthetic mixture is subjected to crystallization conditions. ＊ A step of heating for a sufficient time to form an MRE framework type molecular sieve; and (c) From the synthetic mixture ＊ Process for recovering MRE framework type molecular sieves Includes, The aforementioned synthetic mixture has the following molar ratio composition: SiO ２ : Al ２ O ３ 15 to less than 100, OH － :SiO ２ 0.02~0.6、 M: Yes ２ 0.02~06、 R:SiO ２ 0.005~0.5、 H ２ O:SiO ２ 5~100 It has, At least one source of the alumina is added to the synthesis mixture in solid form. ＊ A method for synthesizing MRE framework-type molecular sieves.

2. The aforementioned ＊ The MRE framework type molecular sieve is selected from the group consisting of COK-8, EU-2, EU-11, IZM-1, SSZ-91, ZBM-30, ZSM-48, and mixtures thereof, preferably the above ＊ The method according to claim 1, wherein the MRE framework type molecular sieve is ZSM-48.

3. The method according to claim 1 or 2, wherein at least one source of alumina is in powder form, preferably in the form of solid particles having an average particle size of 0.01 to 300 μm, preferably 0.1 to 200 μm, and more preferably 1 to 100 μm as a volume-weighted average measured by dynamic light scattering (DLS).

4. The method according to any one of claims 1 to 3, wherein at least one source of silica is selected from the group consisting of precipitated silica, fumed silica, silica gel, silicic acid, tetraalkyl orthosilicate, alkali metal silicate, and aqueous colloidal suspension of silica.

5. The method according to any one of claims 1 to 4, wherein the linear diquaternary alkylammonium structure directing agent R is selected from the group consisting of pentamethonium cation, hexamethonium cation, and mixtures thereof.

6. The method according to any one of claims 1 to 5, wherein the alkali metal or alkaline earth metal M is selected from the group consisting of Na, K, Li, Ca, Mg, and mixtures thereof, and is preferably Na and / or K.

7. The method according to any one of claims 1 to 6, wherein at least one source of hydroxide ions is selected from the group consisting of alkali metal hydroxides, alkaline earth metal hydroxides, ammonium hydroxide, aluminum hydroxide, the hydroxide form of the structure directing agent R, and mixtures thereof, preferably selected from the group consisting of sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, ammonium hydroxide, aluminum hydroxide, the hydroxide form of the structure directing agent R, and mixtures thereof, more preferably selected from potassium hydroxide and / or sodium hydroxide.

8. The method according to any one of claims 1 to 7, wherein the seed crystal is selected from the group consisting of ZSM-48 type, ZSM-5 type, ZSM-11 type, ZSM-12 type, BEA type, Beta type, X type, and Y type zeolite seed crystals, preferably ZSM-48 type or BEA type seed crystals.

9. The method according to any one of claims 1 to 8, wherein the seed crystal is present in an amount of 0 to 50,000 ppm by weight, preferably 50 to 10,000 ppm by weight, more preferably 100 to 10,000 ppm by weight, and most preferably 500 to 6,000 ppm by weight, based on the total weight of the synthetic mixture.

10. SiO in the aforementioned synthetic mixture ２ : Al ２ O ３ The method according to any one of claims 1 to 9, wherein the molar ratio is 15 to less than 100, preferably 20 to less than 100, more preferably 30 to less than 100, particularly less than 80, or less than 75, or less than 70.

11. The aforementioned synthetic mixture has the following molar ratio composition: OH － SiO ２ 0.05 to 0.5, preferably 0.1 to 0.3, M: SiO ２ 0.05 to 0.5, preferably 0.1 to 0.3, R: SiO ２ 0.01 to 0.1, preferably 0.01 to 0.05, H ２ O: SiO ２ 7 to 50, preferably 10 to 30 The method according to any one of claims 1 to 10, comprising:

12. The method according to any one of claims 1 to 11, wherein the crystallization conditions of step (b) include a temperature of 100°C to 220°C, preferably 120°C to 200°C, more preferably 150°C to 170°C, and a time of 10 to 600 hours, particularly 12 to 160 hours, and more particularly 20 to 120 hours.

13. SiO₂ 10 to less than 100, preferably 15 to less than 80, more preferably 20 to less than 70 ２ : Al ２ O ３ Having a molar ratio, obtained by the method described in any one of claims 1 to 12, ＊ MRE framework-type molecular sieve.

14. Use of molecular sieves according to claim 13 in a hydrocarbon chemical conversion method, wherein the hydrocarbon chemical conversion method is dewaxing, oligomerization, hydrogen isomerization, or isomerization.

Images