Organotemplate-free synthesis process for producing zeolites of the ton framework type structure

Abstract

An organotemplate-free synthesis process for producing a zeolite of TON framework type structure is provided. The process comprises the steps of: (1) preparing a mixture comprising: (a) alumina-coated silica; (b) an alkali metal source; (c) an alcohol; (d) a source of hydroxide ions; (e) a seed crystal comprising a zeolitic material having a TON framework type structure; and (f) water; and (2) crystallizing the mixture obtained in step (1).

Description

[0001] Cross-references to related applications

[0002] This application claims priority and interest in U.S. Provisional Application Serial No. 63 / 111,828, filed November 10, 2020. Technical Field

[0003] This disclosure relates to a synthetic organic template-free zeolite with a TON framework-type structure, its synthesis, and its uses. Background Technology

[0004] Zeolites are porous crystalline materials composed of repeating SiO4 and AlO4 tetrahedral units. These units connect together to form a framework with regular intracrystalline vacancies and molecular-sized channels. Many types of synthetic zeolites have been synthesized, each with a unique framework based on a specific arrangement of its tetrahedral units. By convention, the International Zeolite Association (IZA) assigns a unique three-letter code to each framework type.

[0005] TON-framework zeolite materials are characterized by one-dimensional elliptical 10-membered ring (10-MR) channels. Examples of TON-framework zeolite materials include ISI-1, KZ-2, NU-10, θ-1, and ZSM-22. TON-framework zeolites can be used as catalysts in various processes, such as dewaxing of hydrocarbon feedstocks.

[0006] Generally, the synthesis of TON framework-type zeolites is carried out in the presence of a nitrogen-containing organic template, which participates in crystallization guidance and micropore filling. Subsequently, it is necessary to remove the organic template from the micropores of the resulting zeolite so that it can be effectively used in applications. The organic template can usually only be removed by processes such as calcination, making recycling impossible. Furthermore, removing the organic template by calcination at high temperatures (typically 450°C to 930°C or even higher) is not only detrimental due to the destruction of the organic template, but also leads to excessive energy consumption and the generation of harmful gases and other undesirable waste products.

[0007] Therefore, there is a need for an organic template-free synthesis process that can provide zeolites with TON-type framework structures. Summary of the Invention

[0008] In a first aspect, an organic template-free synthesis process for producing TON framework-type zeolites is provided, wherein the process comprises the steps of: (1) preparing a mixture comprising: (a) alumina-coated silica; (b) an alkali metal (M) source; (c) an alcohol (Q); (d) a hydroxide ion source; (e) a seed crystal comprising a zeolite material having a TON framework-type structure; and (f) water; and (2) crystallizing the mixture obtained in step (1).

[0009] In a second aspect, a synthetic organic template-free zeolite with a TON framework type structure is provided, wherein the zeolite optionally contains one or more alkali metals (M), and wherein the zeolite is non-calcined.

[0010] In a third aspect, a process is provided for hydroisomerizing a paraffinic hydrocarbon feed stream, the process comprising contacting the hydrocarbon feed stream under hydroisomerization conditions with hydrogen and a catalyst comprising a zeolite of the TON framework type, wherein the zeolite is uncalcined. Attached Figure Description

[0011] Figure 1 The powder X-ray diffraction (XRD) pattern of the zeolite product of Example 6 is shown.

[0012] Figure 2 The powder XRD pattern of the zeolite product of Example 7 is shown.

[0013] Figure 3 The powder XRD pattern of the zeolite product of Example 8 is shown.

[0014] Figure 4 The powder XRD pattern of the zeolite product of Example 10 is shown.

[0015] Figures 5(A) and 5(B) show exemplary scanning electron micrographs (SEM) of the zeolite product of Example 10 at various magnifications.

[0016] Figure 6 This is a graph illustrating the relationship between conversion or yield and temperature during the hydrogenation of n-decane on a Pd / TON catalyst.

[0017] Figure 7 This is a graph illustrating the change in product yield as a function of conversion during the hydrogenation of n-decane on a Pd / TON catalyst.

[0018] Figure 8 This is a graph illustrating the distribution of methyl nonane isomers as a function of conversion during the hydrogenation conversion of n-decane on a Pd / TON catalyst.

[0019] Figures 9(A) to 9(D)This is a diagram illustrating the distribution of cracking products during the hydroconversion of n-decane over a Pd / TON catalyst. Detailed Implementation

[0020] definition

[0021] In this patent specification, the following words and expressions, if used and when used, shall have the meanings given below.

[0022] The term "skeleton type" is known from Ch. Baerlocher, LB McCusker, and DH Olson. Atlas of Zeolite Framework Types The meaning described in "(Elsevier, 6th edition, 2007)".

[0023] The term "organic template" refers to any conceivable nitrogen-containing organic material suitable for template-mediated synthesis of zeolite materials, particularly zeolite materials with TON framework-type structures.

[0024] "Organic template-free" synthesis processes involve synthesis processes in which the materials used in the synthesis process are substantially free of nitrogen-containing organic template materials. The term "substantially" as used in this disclosure with respect to the amount of one or more organic templates contained in one or more materials used in the synthesis process means an amount of 0.1% by weight or less of one or more organic templates (e.g., 0.05% by weight or less, 0.001% by weight or less, 0.0005% by weight or less, or 0.0001% by weight or less). The amount of one or more organic templates (if present in any of the materials used in the synthesis process) may also be expressed as "impurity" or "trace" within the meaning of this disclosure. Furthermore, it should be noted that the terms "organic template" and "organic structure directing agent" are used synonymously in this disclosure.

[0025] The term "alcohol" refers to an alkyl group that has been substituted with at least one hydroxyl group.

[0026] The term "alkyl" refers to a branched, straight-chain, or cyclic saturated hydrocarbon group.

[0027] The term "extra-framework" refers to a cation that is located at an ion-exchangeable site in the zeolite (e.g., on the surface of the zeolite and / or within the cages and / or pores of the zeolite) and thus serves to compensate for the negative charge of the zeolite framework.

[0028] Synthesis of zeolites

[0029] This disclosure provides an organic template-free synthesis process for producing TON framework-type zeolites, wherein the process includes the following steps: (1) preparing a mixture comprising: (a) alumina-coated silica; (b) an alkali metal (M) source; (c) an alcohol (Q); (d) a hydroxide ion source; (e) a seed crystal comprising a zeolite material having a TON framework-type structure; and (f) water; and (2) crystallizing the mixture obtained in step (1).

[0030] The mixture may have a composition in the range of molar ratios listed in Table 1:

[0031] Table 1

[0032]

[0033] Where M is an alkali metal and Q is an alcohol.

[0034] Alumina-coated silica can be obtained from Nalco (Naperville, Illinois) under the trade name DVSZN007 in many different SiO2 / Al2O3 molar ratios (e.g., 35, 80, 100, 127). The alumina-coated silica can comprise two or more types of alumina-coated silica. Typically, the two or more types of alumina-coated silica are materials with different SiO2 / Al2O3 molar ratios. Alumina-coated silica can also be the sole source of silicon and aluminum for forming TON framework-type zeolites.

[0035] Generally, alkali metals (M) can be provided by any suitable compound containing one or more alkali metals. Alkali metals can be provided as alkali metal salts. Alkali metals can contain sodium and / or potassium. Alkali metals can be introduced into the mixture as metal hydroxides (e.g., sodium hydroxide and / or potassium hydroxide) together with a hydroxide ion source.

[0036] Alcohols can be monohydric alcohols, polyhydric alcohols, or mixtures of both or more thereof. Monohydric alcohols can contain one to six carbon atoms (e.g., two, three, four, five, or six carbon atoms). Representative monohydric alcohols include methanol, ethanol, and propanol, such as 1-propanol and 2-propanol. Polyhydric alcohols can contain two to six carbon atoms (e.g., three, four, five, or six carbon atoms) and two to six hydroxyl groups (e.g., two, three, or four hydroxyl groups). Representative polyhydric alcohols include ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, trimethylolpropane, and pentaerythritol. In some aspects, the alcohols include ethanol.

[0037] Without being constrained by any theory, alcohols are believed to act as pore-filling agents during zeolite synthesis. Alcohols themselves are not organic structure-directing agents, but rather provide, enhance, and / or replace the pore-filling and charge-neutralizing functions of known nitrogen-containing organic templates used in the synthesis of TON framework-type zeolites.

[0038] The seed crystal provided in step (1) comprises a zeolite material having a TON framework structure. Generally, the seed crystal can comprise any zeolite material of the TON framework type, provided that the TON framework type zeolite crystallizes in step (2). The zeolite material with a TON framework structure included in the seed crystal can be a zeolite material obtained according to the process disclosed herein. The seed crystal can comprise one or more zeolites selected from the group consisting of ISI-1, KZ-2, NU-10, θ-1, and ZSM-22. In some aspects, the seed crystal comprises ZSM-22. The seed crystal can be added in an amount of 0.1% to 10% (e.g., 0.5% to 5%) by weight of the silica used in the reaction mixture.

[0039] In step (1) according to this disclosure, the mixture can be prepared by any conceivable means, wherein mixing by agitation, such as by stirring.

[0040] Generally, the components of the mixture used to provide step (1) of the process of the present invention can be added in any order, provided that the TON framework-type zeolite crystallizes from the mixture in step (2). The mixture can be prepared in batches or continuously.

[0041] Generally, step (2) of the process according to the invention can be carried out in any conceivable manner, provided that the TON-structured zeolite is crystallized from the mixture according to step (1). The crystallization of the zeolite from the mixture can be carried out under static, tumbling, or stirring conditions in a suitable reactor vessel such as a polypropylene tank or a Teflon-lined or stainless steel autoclave, at a temperature of 100°C to 200°C (e.g., 120°C to 160°C), for a duration sufficient for crystallization to occur at the temperature used (e.g., 1 day to 14 days). Crystallization is typically carried out in an autoclave so that the reaction mixture is subjected to autogenous pressure.

[0042] Generally, the process of this disclosure may optionally include further steps of post-treatment and / or further physical and / or chemical transformation of the TON framework-type zeolite crystallized in step (2) from the mixture provided in step (1). The crystallized material may, for example, undergo separation and / or washing procedures in any order, wherein the zeolite obtained from the crystallization in step (2) preferably undergoes at least one separation and at least one washing procedure.

[0043] The separation of the crystallized products can be achieved by any conceivable means. Preferably, the separation of the crystallized products can be achieved by means of filtration, ultrafiltration, percolation, centrifugation and / or decantation, wherein the filtration method may involve suction filtration and / or pressure filtration steps.

[0044] For one or more optional washing procedures, any conceivable solvent may be used. Washing agents that may be used are, for example, water, alcohols (such as methanol, ethanol, or propanol), or mixtures of two or more of these. Examples of mixtures are mixtures of two or more alcohols (such as methanol and ethanol, or methanol and propanol, or ethanol and propanol, or methanol and ethanol and propanol), or mixtures of water and at least one alcohol (such as water and methanol, or water and ethanol, or water and propanol, or water and methanol and propanol, or water and ethanol and propanol, or water and methanol and ethanol and propanol). Water or a mixture of water and at least one alcohol (preferably water and ethanol) is preferred, and distilled water is particularly preferred as the sole washing agent.

[0045] The separated zeolite can be washed until the conductivity of the detergent (e.g., washing water) is less than 50 µS / cm.

[0046] Furthermore, the process of the present invention may optionally include one or more drying steps. Generally, any conceivable drying means may be used. The drying process may include heating the zeolite and / or applying a vacuum to the zeolite.

[0047] According to the process of the present invention, the zeolite material crystallized in step (2) may optionally undergo at least one step of an ion exchange procedure, wherein the term "ion exchange" generally refers to extra-framework cation elements and / or molecules contained in the zeolite. Preferably, the non-framework cation elements comprise one or more of one or more alkali metals (M) contained in zeolites with a TON framework type structure.

[0048] Generally, apart from organic structure-directing agents specifically used for synthesizing zeolites with TON framework-type structures, any conceivable ion exchange procedure utilizing all possible cationic elements and / or molecules can be performed on zeolites. Suitable alternative cations include hydrogen, ammonium, alkaline earth metals, and transition metals. Representative alkaline earth metals include magnesium, calcium, strontium, and barium. Representative transition metals include titanium, zirconium, vanadium, chromium, molybdenum, tungsten, manganese, iron, ruthenium, osmium, cobalt, iridium, nickel, palladium, platinum, copper, and zinc. Zeolites can first be reacted with H... + and / or NH4 + Ion exchange is performed, followed by a further ion exchange process, which can be carried out using at least one cation and / or cationic element selected from the group consisting of alkaline earth metals and transition metals.

[0049] Generally, the optional washing and / or separation and / or ion exchange procedures included in the process of this invention can be performed in any conceivable order and are frequently repeated as needed. Therefore, the process according to this disclosure optionally includes one or more of the following steps: (3) separating the TON framework-type zeolite obtained in (2); (4) washing the TON framework-type zeolite obtained in (2) or (3); (5) drying the TON framework-type zeolite obtained in (2), (3), or (4); and (6) subjecting the TON framework-type zeolite obtained in (2), (3), (4), or (5) to an ion exchange procedure, wherein the extra-framework cations contained in the zeolite are targeted to H+. + (7) subject the TON framework-type zeolite obtained in (2), (3), (4), (5) or (6) to an ion exchange procedure in which the extra-framework cations contained in the zeolite are ion exchanged against metal cations selected from the group consisting of alkaline earth metals, transition metals and mixtures thereof; (8) dry the TON framework-type zeolite obtained in (7).

[0050] In the process of this disclosure, it is preferred that a calcination step is not employed. Generally, a calcination step involves heating the zeolite crystallized according to step (2) to a temperature above 500°C. More preferably, the process of producing TON framework-type zeolite according to this disclosure without a calcination step refers to a process in which the zeolite crystallized according to step (2) is not subjected to temperatures exceeding 450°C, more preferably 350°C, more preferably 300°C, more preferably 250°C, more preferably 200°C, and even more preferably 150°C in subsequent steps. According to this disclosure, it is particularly preferred that after step (2) of the process of the present invention in which the crystallized zeolite is at ambient temperature, the material is subsequently not subjected to any heating processes normally or appropriately performed for removing the organic template from the TON framework-type zeolite. Within the meaning of this disclosure, "non-calcined" zeolite is zeolite that has not been subjected to any of the aforementioned calcination procedures.

[0051] Generally, the TON framework type zeolite obtained according to the process of the present invention can be any conceivable TON framework type zeolite. In some aspects, the TON framework type zeolite formed in step (2) comprises one or more zeolites selected from the group consisting of ISI-1, KZ-2, NU-10, θ-1 and ZSM-22, wherein the zeolite preferably comprises ZSM-22.

[0052] Characterization of zeolites

[0053] Organic template-free zeolites with TON framework-type structures, prepared as described herein, can have a SiO2 / Al2O3 molar ratio of at least 35 (e.g., 35 to 160, or 60 to 100).

[0054] In some respects, the organic template-free zeolite with a TON framework-type structure contains an alkali metal (M) as an extra-framework cation, and the molar ratio of M / Al2O3 can be in the range of 0.005 to 10 (e.g., 0.05 to 7, 0.5 to 6, or 1 to 5).

[0055] Powder XRD patterns representing TON framework type zeolites can be referenced from MMJ Treacy and JB Higgins's work. Collection of Simulated XRD Powder Patterns for Zeolites (Fifth revised edition, Elsevier, 2007).

[0056] The powder XRD patterns presented in this paper were collected using standard techniques. The radiation is a K-α doublet for copper. Variations in the molar ratio of the framework material in a particular sample can lead to minute changes in the diffraction pattern due to variations in the lattice constant. Furthermore, sufficiently small crystals will affect the shape and intensity of the peaks, resulting in significant peak broadening. Despite these minute perturbations, the basic lattice structure remains unchanged.

[0057] Industrial applicability

[0058] Generally, TON framework-type zeolites produced by the process of this invention can be used as molecular sieves, adsorbents, catalysts, catalyst supports, or binders thereof. For example, zeolites can be used as molecular sieves to dry gases or liquids for selective molecular separation; as ion exchangers; as chemical supports; as adsorbents; or as catalysts.

[0059] In some aspects, TON framework-type zeolites produced by the process of the present invention are used in catalytic processes (e.g., as catalysts and / or catalyst supports). Generally, zeolites can be used as catalysts and / or catalyst supports in any conceivable catalytic process, wherein processes involving the conversion of at least one organic compound are preferred.

[0060] The catalyst containing TON-based zeolite produced by the process of this invention is particularly useful for the hydroisomerization of paraffinic hydrocarbon feedstocks. When the paraffinic hydrocarbon feedstocks are contacted with hydrogen under hydroisomerization conditions in the presence of this catalyst, products with an increased number of branched hydrocarbons relative to the hydrocarbon feedstocks are produced.

[0061] Hydroisomerization conditions include a temperature of 200°C–450°C (e.g., 250°C–400°C), a pressure of 0.5–20 MPa (e.g., 1–15 MPa), and a time of 0.1–10 h. -1(For example, 0.5-5 h) -1 The liquid hourly space velocity (LHSV) is 35.6-1781 Nm. 3 / m 3 (For example, 890-1424 Nm) 3 / m 3 The hydrogen circulation rate.

[0062] If the hydrocarbon feedstock includes n-C8+ hydrocarbons (e.g., n-C10+ hydrocarbons, or n-C15+ hydrocarbons), then the hydrocarbon feedstock is not limited to a specific type. More specifically, examples of such hydrocarbon feedstocks include relatively light distillation fractions, such as kerosene and jet fuel; and high-boiling-point oils, such as fuel fractions or waxy fractions derived from any type of crude oil, atmospheric distillation residues (atmospheric residues), vacuum tower residues, vacuum distillation residues (vacuum residues), cycle oils, synthetic oils (e.g., shale oil, tar, etc.), gas oils, vacuum gas oils, residue oils, and Fischer-Tropsch synthetic oils; and other heavy oils. Other feedstock components that may be used, particularly those that can be used as co-feed components in combination with the feedstocks listed above, include renewable feedstocks derived from plants or animals.

[0063] As with many catalysts, it may be desirable to blend the zeolite of the present invention with another material that is resistant to the temperatures and other conditions used in organic conversion processes. Such materials include active and inactive materials, synthetic or naturally occurring zeolites, and inorganic materials such as clay, silica, and / or metal oxides (such as alumina). The latter may be naturally occurring or in the form of gel-like precipitates or gels (including mixtures of silica and metal oxides). Active materials used in combination with the zeolite of the present invention (i.e., materials combined with the zeolite of the present invention or present during the synthesis of the new material) tend to alter the conversion and / or selectivity of the catalyst in certain organic conversion processes. Inactive materials are suitable as diluents to control the conversion in a given process, allowing the product to be obtained in an economical and orderly manner without resorting to other means of controlling the reaction rate. These materials can be incorporated into naturally occurring clays (e.g., bentonite and kaolin) to improve the crushing strength of the catalyst under commercial operating conditions. These materials (i.e., clay, oxides, etc.) act as a binder for the catalyst. It is desirable to provide catalysts with good crushing strength, because in commercial applications, it is desirable to prevent the catalyst from breaking into powdery material. These clay and / or oxide binders are typically used only for the purpose of improving the crushing strength of the catalyst.

[0064] Naturally occurring clays that can be compounded with the zeolites of this invention include the montmorillonite and kaolinite families, which include sub-bentonite, as well as kaolinite or other clays whose main mineral component is halloysite, kaolinite, dickite, nacrite, or anauxite, commonly known as Dixie, McNamee, Georgia, and Florida clays. Such clays can be used in their original, unprocessed state, or after initial calcination, acid treatment, or chemical modification. Binders that can be used in compounding with the zeolites of this invention also include inorganic oxides such as silica, zirconium oxide, titanium dioxide, magnesium oxide, beryllium oxide, aluminum oxide, and mixtures thereof.

[0065] In addition to the materials mentioned above, the zeolite of the present invention can be combined with porous matrix materials (such as silica-alumina, silica-magnesium oxide, silica-zirconium oxide, silica-thorium oxide, silica-beryllium oxide, silica-titanium dioxide) and ternary compositions (such as silica-alumina-thorium oxide, silica-alumina-zirconium oxide, silica-alumina-magnesium oxide, and silica-magnesium oxide-zirconium oxide).

[0066] The relative proportions of TON-based zeolite and inorganic oxide matrix can vary widely, with the content of TON-based zeolite ranging from 1 wt% to 90 wt% (e.g., 2 wt% to 80 wt%) of the composite material.

[0067] Example

[0068] The following illustrative examples are intended to be non-limiting.

[0069] Example 1 (Comparison)

[0070] According to Q. Wu et al. ( Angew. Chem. Int. Ed The procedure described in 2019, 58, 12138-12142, is used to prepare all-silica TON framework type zeolites.

[0071] 0.51 g of Na₂SiO₃·9H₂O was combined with 1.56 g of silica gel and 0.12 g of seed crystals of a TON-type zeolite composed entirely of silica in a Teflon autoclave. After mixing with a scraper, 1.9 g of methanol was added and rapidly mixed before shutting off the autoclave. The autoclave was heated at 135 °C for 3 days while tumbling at 43 rpm. The product was recovered by filtration and washed with copious amounts of water, then dried in air at 85 °C.

[0072] Powder XRD (not shown) indicates that the product is a TON framework type zeolite.

[0073] Example 2 (Comparison)

[0074] According to Y. Wang et al. ( Catal. Today The procedure described in 2014, 226, 103-108, for the preparation of aluminosilicate TON framework-type zeolites.

[0075] In a Teflon autoclave, 3.2 g of 1 N KOH aqueous solution was combined with 8.8 g of deionized water and 0.096 g of Al2(SO4)3·18H2O and stirred until the alumina dissolved. Then, 3 g of tetraethyl orthosilicate was added, and the mixture was stirred under cover for several hours. Finally, 0.1 g of seed crystals of TON framework-type zeolite was added, the autoclave was closed, and the mixture was heated at 135 °C for 2 days while tumbling at 43 rpm. The product was recovered by filtration and washed with copious amounts of water, then dried in air at 85 °C.

[0076] The material was calcined in air by placing a thin bed in a calcination pan and heating it in a muffle furnace from room temperature to 120°C at a rate of 1°C / min, and holding it at 120°C for 2 hours. The temperature was then ramped up to 540°C at a rate of 1°C / min and held at 540°C for 5 hours. The temperature was then ramped up again to 595°C at a rate of 1°C / min and held at 595°C for 5 hours. The material was then allowed to cool to room temperature.

[0077] The material was converted to ammonium form by heating in an ammonium nitrate solution (e.g., 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. The material was washed with deionized water until a water conductivity of less than 10 µS / cm was obtained.

[0078] Powder XRD (not shown) indicates that the product is a TON framework type zeolite.

[0079] The acid site density of the product was characterized using temperature-programmed desorption (TPD) with n-propylamine, and it was found to be 31.4 µmol H₂. + / g.

[0080] Example 3 (Comparison)

[0081] In a Teflon autoclave, 3.17 g of 1 N KOH was combined with 7.2 g of deionized water and 0.096 g of Al2(SO4)3·18H2O and stirred until the alumina dissolved. Then, 3 g of tetraethyl orthosilicate was added, and the mixture was stirred under cover for several hours. Finally, 0.05 g of seed crystals of TON framework-type zeolite was added. The autoclave was closed and heated at 140 °C for 4 days while tumbling at 43 rpm. The product was recovered by filtration, washed with deionized water, and then dried in air at 85 °C.

[0082] The material was directly converted to ammonium form without calcination by heating in an ammonium nitrate solution (e.g., 1 g NH4NO3 / 1 g zeolite in 10 mL H2O at 85°C for at least 3 hours). This process was repeated twice, for a total of three exchanges. The material was then washed with deionized water.

[0083] Powder XRD (not shown) indicates that the product is a TON framework type zeolite.

[0084] Example 4 (Comparison)

[0085] Example 3 was repeated using 3.60 g of 1 N KOH.

[0086] Powder XRD (not shown) indicates that the product is a TON framework type zeolite.

[0087] Example 5 (Comparative)

[0088] Example 3 was repeated using 2.74 g of 1 N KOH.

[0089] Powder XRD (not shown) indicates that the product is a TON framework type zeolite.

[0090] The acid site density of the product was characterized using n-propylamine TPD, and it was found to be 207 µmol H. + / g.

[0091] Example 6

[0092] In a Teflon autoclave, 2.45 g of 1 N KOH was combined with 4.23 g of deionized water and 3.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 80; 26.9% solids). Then, 0.05 g of seed crystals of TON framework-type zeolite was added. Finally, 2.25 g of denatured ethanol was added and thoroughly mixed. The autoclave was closed and heated at 140 °C for 4 days, while tumbling at 43 rpm. The product was recovered by filtration, washed with water, and dried at 85 °C.

[0093] Powder XRD indicates that the product is a TON framework type zeolite. Figure 1 The powder XRD of the product is shown.

[0094] Example 7

[0095] In a Teflon autoclave, 2.20 g of 1 N KOH was combined with 4.47 g of deionized water and 3.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 80; 26.9% solids). Then, 0.05 g of seed crystals of TON framework-type zeolite was added. Finally, 2.25 g of denatured ethanol was added and thoroughly mixed. The autoclave was closed and heated at 140 °C for 2 days, while tumbling at 43 rpm. The product was recovered by filtration, washed with water, and dried at 85 °C.

[0096] Powder XRD indicates that the product is a TON framework type zeolite. Figure 2 The powder XRD of the product is shown.

[0097] Example 8

[0098] In a Teflon autoclave, 2.45 g of 1 N KOH was combined with 4.24 g of deionized water and 3.00 g of Nalco alumina-coated silica DVSZN007 (SAR = 80; 26.9% solids). Then, 0.05 g of seed crystals of TON framework-type zeolite was added. Finally, 1.13 g of denatured ethanol was added and thoroughly mixed. The autoclave was closed and heated at 140 °C for 2 days, while tumbling at 43 rpm. The product was recovered by filtration, washed with water, and dried at 85 °C.

[0099] Powder XRD indicates that the product is a TON framework type zeolite. Figure 3 The powder XRD of the product is shown.

[0100] Example 9 (Comparative)

[0101] Example 8 was repeated, but without the addition of denatured ethanol, and the reaction time was 4 days.

[0102] Unrecovered crystallized products.

[0103] Example 10

[0104] In a Teflon autoclave, 2.85 g of 1 M KOH aqueous solution was mixed with 4.95 g of water and 3.5 g of Nalco alumina-coated silica DVSZN007 (SAR = 80; 26.9% solids). Then, 0.05 g of seed crystals of zeolite TON was added and thoroughly mixed. Finally, 1.31 g of denatured ethanol was added, mixed, the autoclave was closed, and heated at 140 °C for 2 days while tumbling at 43 rpm. The product was recovered by filtration and washed with copious amounts of water, then dried in air at 85 °C. This procedure was repeated 3 times, for a total of 4 batches, recovering a total of 3.43 g of dried product.

[0105] Powder XRD indicates that the product is a TON framework type zeolite. Figure 4 The powder XRD of the product is shown.

[0106] Figure 5A and Figure 5B Illustrative SEM images of the product at various magnifications are shown.

[0107] The material was directly converted to ammonium form without calcination by heating in an ammonium nitrate solution (typically 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. The material was washed with deionized water until a water conductivity of less than 10 µS / cm was obtained.

[0108] The acid site density of the ammonium-exchanged product was characterized using n-propylamine TPD, and it was found to be 298 µmol H. + / g.

[0109] Example 11

[0110] Palladium exchange

[0111] To exchange palladium to 0.5 wt% Pd based on the original (as-provided) zeolite material, 1.6 g of the ammonium form TON material from Example 10 was combined with 15.3 g of deionized water and 7.0 g of 0.156 N NH4OH solution, and then with 1.6 g of palladium solution prepared by combining a solution of 0.36 g of tetraamine palladium(II) nitrate in 21 g of deionized water with 3 g of 0.148 N NH4OH solution. The pH was then checked and, if necessary, adjusted to 10 by adding concentrated ammonium hydroxide dropwise until the pH reached 10. After standing at room temperature for 3 days, the pH was checked again, and, if necessary, readjusted to 10 and stood for another day. The material was recovered by filtration, washed with deionized water, and air-dried overnight at 85°C. The Pd-exchange material was then calcined in dry air as follows: heated to 120°C at a ramp rate of 1°C / min and held at 120°C for 180 minutes, followed by heating to 482°C at a rate of 1°C / min and holding at 482°C for 180 minutes. Finally, the material was granulated at 5 kpsi, crushed, and sieved to 20-40 mesh.

[0112] Example 12

[0113] Hydrogenation conversion of n-decane

[0114] For catalytic testing, 0.5 g of the Pd / TON catalyst from Example 11 (as determined by thermogravimetric analysis at 600°C as the weight of the dehydrated sample) was loaded in the center of a 23-inch long × ¼-inch outer diameter stainless steel reactor tube, with aluminum powder loaded upstream of the catalyst for preheating the feed (total pressure 1200 psig; downward flow hydrogen rate of 12.5 mL / min when measured at 1 atm and 25°C; and downward flow liquid feed rate of 1 mL / h). The catalyst was first reduced in flowing hydrogen at 315°C for 1 hour. The reaction was carried out from 230°C to 310°C. The products were analyzed by online capillary gas chromatography (GC) approximately every 60 minutes. Raw data from the GC were collected using an automated data collection / processing system, and hydrocarbon conversion was calculated from the raw data. Conversion was defined as the amount of n-decane produced by the reaction, expressed in mol%. The yields of iso-C10 products are expressed as the molar percentage of products other than n-decane. The yields of cracked products (less than C10) are expressed as the molar percentage of n-decane converted to cracked products. Results are as follows: Figure 6 and Figure 7 As shown. Figure 8The figures show the distribution of methylnonane isomers as a function of conversion during the hydrogenation conversion of n-decane. Figures 9(A), 9(B), 9(C), and 9(D) show the cracking product distributions at cracking yields of 10.2 mol.%, 32.1 mol.%, 51.1 mol.%, and 90.1 mol.%, respectively.

[0115] The correction constraint index (CI) will be adjusted. The ratio of 2-methylnonane to 5-methylnonane was calculated as the total isomer yield being approximately 5%, as shown by PA Jacobs et al. ( Zeolites As described in 1984, 4, 98-107. In this embodiment, it was found that at a total isomer yield of 4.8%, the modified constraint index (CI) The value is 5.9.

[0116] Example 16

[0117] Hydroisomerization of n-hexadecane

[0118] 0.5 g of the palladium exchange sample from Example 11 was loaded into the center of a 23-inch long x ¼-inch outer diameter stainless steel reactor tube, with aluminum powder loaded upstream of the catalyst for preheating the feed (total pressure 1200 psig; downward flow hydrogen rate of 160 mL / min when measured at 1 atm and 25°C); downward flow liquid feed rate of 1 mL / h. All materials were first reduced in flowing hydrogen at approximately 315°C for 1 hour. The products were analyzed every thirty minutes by online capillary GC. Raw data from the GC were collected using an automated data collection / processing system, and hydrocarbon conversion was calculated from the raw data.

[0119] Conversion was defined as the amount of n-hexadecane that reacted to produce other products, including the iso-C16 isomer. Yield was expressed as the weight percentage of the product other than n-C16, including the iso-C16 as a yield product. Results at 96% conversion are reported in Table 2.

[0120] Table 2

[0121]

Claims

1. An organic template-free synthesis process for producing zeolites with a TON framework-type structure, wherein the process includes the following steps: (1) Preparing a mixture, the mixture comprising: (a) Silica coated with alumina; (b) Alkali metal M source; (c) Alcohol Q, wherein the alcohol includes ethanol; (d) Hydroxide ion source; (e) Seed crystals containing zeolite materials with a TON framework-type structure; and (f) Water; and (2) Crystallize the mixture obtained in step (1), and The organic template-free synthesis process described herein does not include a calcination step.

2. The process of claim 1, wherein the mixture has the following composition in molar ratio: 。 3. The process of claim 1, wherein the mixture has the following composition in molar ratio: 。 4. The process of claim 1, wherein the alkali metal M comprises sodium, potassium, or a mixture thereof.

5. The process of claim 1, wherein the seed crystal is present in an amount of 0.1-10% by weight of silicon dioxide.

6. The process of claim 1, wherein the seed crystal comprises one or more zeolites selected from the group consisting of ISI-1, KZ-2, NU-10, θ-1, ZSM-22 and mixtures thereof.

7. The process of claim 1, wherein the crystallization in step (2) comprises heating the mixture at a temperature of 100°C to 200°C, under autogenous pressure, and for a period of 1 to 14 days.

8. The process of claim 1, wherein the TON framework-type zeolite formed in step (2) comprises a material selected from the group consisting of ISI-1, KZ-2, NU-10, θ-1, ZSM-22 and mixtures thereof.

9. The process of claim 1, further comprising one or more of the following steps: (3) Separate the TON framework-type zeolite obtained in step (2); (4) Wash the TON framework-type zeolite obtained in step (2) or (3); (5) Dry the TON framework-type zeolite obtained in step (2), (3) or (4); (6) subject the TON framework-type zeolite obtained in steps (2), (3), (4), or (5) to an ion exchange process, wherein the extra-framework cations contained in the zeolite are targeted to H + Ion exchange is performed. (7) subject the TON framework-type zeolite obtained in steps (2), (3), (4), (5) or (6) to an ion exchange procedure, wherein the extra-framework cations contained in the zeolite are ion exchanged with metal cations selected from the group consisting of alkaline earth metals, transition metals and mixtures thereof. (8) Dry the TON skeleton-type zeolite obtained in step (7).

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